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Synthesis of Ultrathin High-Entropy Oxides with Phase Controllability
具有相位可控性的超薄高熵氧化物的合成Click to copy article link
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- Jingjing Liang 梁晶晶Jingjing LiangThe Institute for Advanced Studies, Wuhan University, Wuhan 430072, ChinaMore by Jingjing Liang
- Junlin Liu 刘俊林Junlin LiuCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, ChinaMore by Junlin Liu
- Huiliu Wang 王慧琉Huiliu WangCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, ChinaMore by Huiliu Wang
- Zeyuan Li 李泽元Zeyuan LiSchool of Electrical Engineering and Automation, Wuhan University, Wuhan 430072, ChinaSchool of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, ChinaMore by Zeyuan Li
- Guanghui Cao 曹光辉Guanghui Cao 曹光辉College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China
武汉大学化学与分子科学学院， 湖北 430072More by Guanghui Cao
更多 Guanghui Cao 的产品 - Ziyue Zeng 曾子悦Ziyue ZengCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, ChinaMore by Ziyue Zeng
- Sheng Liu 刘胜Sheng LiuSchool of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, ChinaMore by Sheng Liu
- Yuzheng Guo 郭玉正Yuzheng GuoSchool of Electrical Engineering and Automation, Wuhan University, Wuhan 430072, ChinaMore by Yuzheng Guo
- Mengqi Zeng* 曾梦琪*Mengqi Zeng*Email: zengmq_lan@whu.edu.cnCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, ChinaMore by Mengqi Zeng
- Lei Fu* 她是*Lei Fu*Email: leifu@whu.edu.cnThe Institute for Advanced Studies, Wuhan University, Wuhan 430072, ChinaCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, ChinaMore by Lei Fu
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Abstract 抽象
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High-entropy oxides (HEOs) with an ultrathin geometric structure are especially expected to exhibit extraordinary performance in different fields. The phase structure is deemed as a key factor in determining the properties of HEOs, rendering their phase control synthesis tempting. However, the disparity in intrinsic phase structures and physicochemical properties of multiple components makes it challenging to form single-phase HEOs with the target phase. Herein, we proposed a self-lattice framework-guided strategy to realize the synthesis of ultrathin HEOs with desired phase structures, including rock-salt, spinel, perovskite, and fluorite phases. The participation of the Ga assistor was conducive to the formation of the high-entropy mixing state by decreasing the formation energy. The as-prepared ultrathin spinel HEOs were demonstrated to be an excellent catalyst with high activity and stability for the oxygen evolution reaction in water electrolysis. Our work injects new vitality into the synthesis of HEOs for advanced applications and undoubtedly expedites their phase engineering.
具有超薄几何结构的高熵氧化物 （HEO） 尤其有望在不同领域表现出非凡的性能。相结构被认为是决定 HEO 性质的关键因素，使其相控合成具有诱人性。然而，多种组分的本征相结构和物理化学性质的差异使得与目标相形成单相 HEO 具有挑战性。在此，我们提出了一种自晶格框架引导策略，以实现具有所需相结构的超薄 HEO 的合成，包括岩盐、尖晶石、钙钛矿和萤石相。Ga 辅助体的参与有利于通过降低形成能来形成高熵混合态。所制备的超薄尖晶石 HEO 已被证明是一种优异的催化剂，具有高活性和稳定性，可用于水电解中的析氧反应。我们的工作为用于高级应用的 HEO 综合注入了新的活力，无疑加快了它们的阶段工程。
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Copyright © 2024 American Chemical Society
版权所有 © 2024 美国化学会
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Benefited from nearly limitless elemental combination, high stability, and synergistic interaction between each component, (1) high-entropy oxides (HEOs) with excellent properties have been attracting extensive attention in various fields, including catalysis, (2−4) supercapacitor, (5) battery, (6,7) magnetism, (8) and so on. The functionality and performance of oxides are closely related to their phase structure, which can significantly influence the electronic configuration and ion diffusion. (9−12) Therefore, the synthesis of HEOs with the desired phase is highly pursued, which undoubtedly provides promising access to promote material design, performance optimization, and advanced applications.
得益于近乎无限的元素组合、高稳定性和各组分之间的协同作用，（1） 具有优异性能的高熵氧化物 （HEO） 在各个领域引起了广泛关注，包括催化、（2-4） 超级电容器、（5） 电池、（6,7） 磁性、（8） 等等。氧化物的功能和性能与其相结构密切相关，这会显着影响电子构型和离子扩散。（9−12） 因此，具有所需相的 HEO 的合成受到高度追求，这无疑为促进材料设计、性能优化和高级应用提供了有前途的途径。
The type of the incorporated metal cation correlates with the category of attainable phase structure of the metal oxide. (13) The cation radius and valence state play a crucial role in the coordination and bonding of metal cations and oxygen anions, thus affecting the natural tendency of phase formation of metal oxide. This means the single phase control in the HEOs is a huge challenge due to the intrinsic complexities between metal elements (e.g., differences in ionic radius, oxidation potential, and bonding force with oxygen) easily lead to phase separation.
掺入的金属阳离子的类型与金属氧化物可达到的相结构类别相关。（13） 阳离子半径和价态在金属阳离子和氧阴离子的配位和键合中起着至关重要的作用，从而影响金属氧化物成相的自然趋势。这意味着 HEO 中的单相控制是一个巨大的挑战，因为金属元素之间的内在复杂性（例如，离子半径、氧化电位和与氧的结合力的差异）很容易导致相分离。
The decrease of energy thermodynamically is beneficial to overcoming elemental immiscibility to form a high-entropy state. (2,14−17) Recently, we reported that utilizing Ga with relatively negative mixing enthalpy to reduce Gibbs free energy can realize uniform elemental mixing in high-entropy alloys under relatively mild reaction conditions. (14) Therefore, it provides an idea to construct a high-entropy mixing state in oxides. Although several studies have been reported to realize the preparation of HEOs, (2,18−21) the universal phase-controlled synthesis of HEOs is still rare, let alone further accessibility in ultrathin geometry morphology.
热力学能量的减少有利于克服元素不混溶性以形成高熵状态。（2,14−17） 最近，我们报道了利用具有相对负混合焓的 Ga 来降低吉布斯自由能，可以在相对温和的反应条件下实现高熵合金中的元素均匀混合。（14） 因此，它提供了一种在氧化物中构建高熵混合态的想法。尽管已经有几项研究实现了 HEO 的制备，（2,18−21） HEO 的通用相位控制合成仍然很少见，更不用说在超薄几何形态学中进一步可及了。
Herein, the self-lattice framework with a mixing assistor guided strategy was proposed for phase control synthesis of ultrathin HEOs (Figure 1), including rock-salt, spinel, perovskite, and fluorite phase structures. In a representative synthesis protocol, metal salts, glucose, and glycine were uniformly premixed and then annealed under an air atmosphere to produce HEO nanosheets (Figure S1), where glucose and glycine are utilized to generate the carbon template for guiding the formation of nanosheets. As for the phase structure, the intrinsic property of the element is in favor of forming specific coordination polyhedrons to construct related phase structures, which is something like utilizing the natural mixing features among different elements to diminish casting segregation in the field of high-entropy alloys. (22)
在此，提出了具有混合辅助器引导策略的自晶格框架，用于超薄 HEO 的相位控制合成（ 图 1），包括岩盐、尖晶石、钙钛矿和萤石相结构。在代表性合成方案中，金属盐、葡萄糖和甘氨酸均匀预混合，然后在空气气氛下退火以产生 HEO 纳米片（ 图 S1），其中葡萄糖和甘氨酸用于生成碳模板以指导纳米片的形成。至于相结构，元素的本征性质有利于形成特定的配位多面体来构建相关的相结构，这就像在高熵合金领域利用不同元素之间的自然混合特性来减少铸件偏析。（22）
Figure 1 图 1
Figure 1. Schematic illustration of a self-lattice-framework with Ga mixing assistor for HEO synthesis.
图 1.用于 HEO 合成的带有 Ga 混合辅助器的自晶格框架的示意图。
As a result, oriented by the target phase structure, elements with suitable intrinsic properties (i.e., cation radii and valence state) are combined to generate the required ion arrangement, which could be figuratively regarded as the self-lattice framework. Such natural preference for bonding constitutes the structural basis of oxides, modulating the ions to arrange on the basis of the crystal structure. Meanwhile, the introduced Ga component could be regarded as an assistor, which was beneficial to the occupancy of various metal elements into the cation site under relatively mild conditions. The relatively low reaction temperature also ensured the functionality of the template for producing HEO ultrathin morphology, which can exhibit facile electron and ion transport behavior and high exposure of active sites. (23,24) Additionally, the ionic radius of Ga resembles that of the 3d transition metals, which would reduce the effect of lattice distortion on phase stability. (8) Therefore, the self-lattice framework with a Ga assistor can modulate the structure and mixing state of the system to form the HEO with the desired phase and high-entropy mixing state (Figure 1).
结果，在目标相结构的导向下，具有适当本征性质（即阳离子半径和价态）的元素被组合以产生所需的离子排列，这可以形象地视为自晶格框架。这种对键合的自然偏好构成了氧化物的结构基础，调节离子在晶体结构的基础上排列。同时，引入的 Ga 组分可以看作是一种辅助剂，有利于在相对温和的条件下各种金属元素进入阳离子位点。相对较低的反应温度还确保了模板用于生产 HEO 超薄形态的功能，其可以表现出简单的电子和离子传输行为以及活性位点的高暴露。（23,24） 此外，Ga 的离子半径类似于 3d 过渡金属的离子半径，这将减少晶格畸变对相稳定性的影响。（8） 因此，带有 Ga 辅助器的自晶格框架可以调制系统的结构和混合状态，以形成具有所需相位和高熵混合状态的 HEO（ 图 1）。
The scanning electron microscopy and atomic force microscopy characterizations of the generated HEO (GaFeCoNiCr oxide) are shown in Figure S2, exhibiting curled and flexible nanosheets with micrometer-scale lateral size and ultrathin thickness characteristics. The Brunauer–Emmett–Teller and Barrett–Joyner–Halenda analyses demonstrated that the HEO nanosheets exhibited a surface area of 77.5 m2/g and contained the mesopore with a size of about 10 nm (Figure S3). The carbon–sulfur analyzer test indicated the content of carbon was about 0.6 wt %, indicating a very small quantity of carbon residues. Besides, both the increase in the reaction time and the decrease in the amount of glucose and glycine would lead to an increase in the thickness of the HEO nanosheets (Figures S4 and S5).
生成的 HEO（GaFeCoNiCr 氧化物）的扫描电子显微镜和原子力显微镜特性如图 S2 所示，展示了具有微米级横向尺寸和超薄厚度特性的卷曲和柔性纳米片。Brunauer-Emmett-Teller 和 Barrett-Joyner-Halenda 分析表明，HEO 纳米片的表面积为 77.5 m2/g，包含大小约为 10 nm 的中孔（ 图 S3）。碳硫分析仪测试表明，碳含量约为 0.6 wt %，表明碳残留物的数量非常少。此外，反应时间的增加以及葡萄糖和甘氨酸量的减少都会导致 HEO 纳米片厚度的增加（ 图 S4 和 S5）。
The strategy showed applicability to four types of oxide phase structures (Figures 2, S6, and S7). As a demonstration of the rock-salt structure, the HEO system containing Co, Mg, Ni, Cu, Zn, Li, and Ga elements was synthesized considering that most of them have the ability to form metal–oxygen octahedrons and have an oxidation state of +2. The X-ray diffraction (XRD) pattern revealed that the product belonged to the cubic rock-salt structure (Figure 2a). According to energy-dispersive spectroscopy (EDS) elemental mappings obtained by transmission electron microscopy (TEM), high-entropy mixing characteristics of the oxide were verified where all elements exhibited uniform distribution. Considering the Li element is too light to detect by the TEM-EDS technique, its existence was confirmed by X-ray photoelectron spectroscopy (XPS) (Figure S8). The selected-area electron diffraction (SAED) pattern displayed multiple diffraction rings (Figure S9a), matching the interplanar spacings of the rock-salt structure. It also indicated the polycrystalline characteristic structure of the HEO nanosheet.
该策略显示适用于四种类型的氧化物相结构（ 图 2、S6 和 S7）。作为岩盐结构的示范，合成了含有 Co、Mg、Ni、Cu、Zn、Li 和 Ga 元素的 HEO 体系，考虑到它们中的大多数具有形成金属-氧八面体的能力并且具有 +2 的氧化态。X 射线衍射 （XRD） 图谱显示，该产物属于立方岩盐结构（ 图 2a）。根据透射电子显微镜 （TEM） 获得的能量色散光谱 （EDS） 元素映射，验证了氧化物的高熵混合特性，其中所有元素均表现出均匀分布。考虑到 Li 元素太轻，无法通过 TEM-EDS 技术检测，其存在通过 X 射线光电子能谱 （XPS） 证实（ 图 S8）。选定区域电子衍射 （SAED） 图样显示了多个衍射环（ 图 S9a），与岩盐结构的面间距相匹配。它还表明了 HEO 纳米片的多晶特征结构。
Figure 2 图 2
Figure 2. Structural and elemental characterizations of HEO nanosheets with different crystal structures. (a–d) XRD profiles (left) and elemental mappings (right) of the rock-salt (a), spinel (b), perovskite (c), and fluorite (d) structures, respectively. The inset of the XRD profile is a crystal structure diagram. Scale bar: (a) 1 μm, (b) 1 μm, (c) 500 nm, and (d) 300 nm.
图 2.具有不同晶体结构的 HEO 纳米片的结构和元素表征。（一至四）岩盐 （a）、尖晶石 （b）、钙钛矿 （c） 和萤石 （d） 结构的 XRD 剖面（左）和元素映射（右）。XRD 剖面的插图是晶体结构图。比例尺：（a） 1 μm、（b） 1 μm、（c） 500 nm 和 （d） 300 nm。
When the system contains elements with valence states of +2 and +3, and metal–oxygen tetrahedron and octahedron, it would be inclined to form a spinel structure. The homogeneous elemental distribution, only one set of diffraction patterns in the XRD result, and the matched SAED pattern demonstrated the successful synthesis of spinel structure in the HEO system consisting of Mg, Zn, Ni, Co, Mn, and Ga elements (Figures 2b and S9b).
当系统包含价态为 +2 和 +3 的元素以及金属-氧四面体和八面体时，它会倾向于形成尖晶石结构。均匀的元素分布、XRD 结果中只有一组衍射图谱以及匹配的 SAED 图谱表明，尖晶石结构在由 Mg、Zn、Ni、Co、Mn 和 Ga 元素组成的 HEO 系统中成功合成（ 图 2b 和 S9b）。
When the system contains elements with valence states of +3, 12-fold coordination of oxygen, and metal–oxygen octahedron, it would tend to form a perovskite structure. The perovskite-type HEO including La, Fe, Mn, Ni, Co, Cr, and Ga elements was prepared as shown in Figure 2c. The dispersion of each element was uniform. The XRD profile and diffraction rings in the SAED pattern (Figure S9c) could be indexed to the standard XRD pattern of the perovskite crystal structure.
当系统包含价态为 +3、氧的 12 倍配位和金属-氧八面体的元素时，它往往会形成钙钛矿结构。如图 2c 所示，制备了包括 La、Fe、Mn、Ni、Co、Cr 和 Ga 元素的钙钛矿型 HEO。各元素的分散度均匀。SAED 图谱（ 图 S9c）中的 XRD 剖面和衍射环可以与钙钛矿晶体结构的标准 XRD 图谱进行索引。
As for the fluorite structure, the elements usually have an 8-fold coordination of oxygen and an oxidation state of four. Figures 2d and S9d indicated that Zr, Fe, Mn, Co, and Ga elements were homogeneously incorporated into the fluorite structure. Therefore, most likely, the Zr element with a stable oxidation state of +4 could be regarded as a host to stabilize the fluorite lattice for accepting the other elements, which is similar to the effect of Ce ion in the previous report. (25)
至于萤石结构，元素通常具有 8 倍氧配位和 4 氧化态。 图 2d 和 S9d 表明 Zr、Fe、Mn、Co 和 Ga 元素均匀地掺入萤石结构中。因此，最有可能的是，具有稳定氧化态 +4 的 Zr 元素可以被视为稳定萤石晶格以接受其他元素的主体，这与上一份报告中 Ce 离子的作用相似。（25）
The XPS analysis further corroborated that all elements of the four systems were in the oxidation state (Figures S8 and S10–S12). Some elements of the system exhibited multiple valence states to better self-adapting to the disorder of multiple cations, which was commonly observed in the ever-reported HEOs. (26,27) The specific chemical compositions of the HEOs are shown in Tables S1 and S2. In addition, the utilization of glucose and glycine would not affect the phase structure (Figure S13). Furthermore, HEO containing the noble metal was also synthesized (Figure S14).
XPS 分析进一步证实，四个系统的所有元素都处于氧化态（ 图 S8 和 S10-S12）。该系统的一些元素表现出多种价态，以更好地自我适应多种阳离子的无序，这在不断报道的 HEO 中很常见。（26,27） HEO 的具体化学成分如表 S1 和 S2 所示。此外，葡萄糖和甘氨酸的利用不会影响相结构（ 图 S13）。此外，还合成了含有贵金属的 HEO（ 图 S14）。
To illustrate the effect of structure and mixing modulation for HEO synthesis, the oxide system the same as that of Figure 2a was synthesized without the Ga assistor addition. As shown in Figure 3a, the major diffraction peaks could be indexed to the standard patterns of the rock-salt phase. The existence of the main phase and its structural consistency with the HEO system containing Ga assistor (Figure 2a) indicated the elements could spontaneously form a specific lattice framework to modulate the structure of the system toward the target phase. However, there were some extra diffraction peaks and elemental aggregations in the product (Figure 3a,b). The formation energy of multicomponent oxides was calculated by density functional theory, indicating that the formation energy of the system with Ga assistor participation was lower than that of the assistor-free system (Figure 3c). Additionally, the multiple-component oxides still exhibited phase separation under the circumstance that they had the same element number as the HEO systems containing Ga (Figures S15 and S16). These results indicated that the presence of the Ga assistor would be beneficial to achieve high-entropy mixing by decreasing the formation energy. The absence of the assistor failed mixing modulation, leading to nucleation and growth of impurity phases (Figure 3d). Similar phenomena, that is, elemental aggregations and the coexistence of the main phase and impure phases, could also be observed in the other three HEO systems without assistor addition (Figures S17–19). Therefore, both the structure and mixing modulation are of great importance to the formation of single-phase HEO, where structure and mixing modulation are closely related to the attainable phase structure and high-entropy mixing state.
为了说明结构和混合调制对 HEO 合成的影响，合成了与图 2a 相同的氧化物体系，而没有添加 Ga 辅助器。如图 3a 所示，主要衍射峰可以与岩盐相的标准模式进行索引。主相的存在及其与含有 Ga 辅助子的 HEO 系统的结构一致性（ 图 2a）表明这些元素可以自发形成特定的晶格框架，以将系统的结构调节到目标相。然而，产物中有一些额外的衍射峰和元素聚集体（ 图 3a、b）。通过密度泛函理论计算多组分氧化物的形成能，表明有 Ga 助焊器参与的体系的形成能低于无助焊体系的形成能（ 图 3c）。此外，多组分氧化物在与含有 Ga 的 HEO 系统具有相同的元素数的情况下仍然表现出相分离（ 图 S15 和 S16）。这些结果表明，Ga 辅助子的存在有利于通过降低形成能来实现高熵混合。辅助子的缺失使混合调制失败，导致成核和杂质相生长（ 图 3d）。类似的现象，即元素聚集以及主相和不纯相的共存，也可以在其他三个 HEO 系统中观察到，而无需添加辅助器（ 图 S17-19）。 因此，结构和混频调制对于单相 HEO 的形成都非常重要，其中结构和混频调制与可实现的相结构和高熵混频态密切相关。
Figure 3 图 3
Figure 3. Effect of structural and mixing modulation on the formation of single-phase HEO. (a,b) XRD pattern and EDS mapping of the HEO without a Ga assistor. Scale bar: 500 nm. (c) Formation energy of single-phase HEO before and after introducing Ga assistor. (d) Schematic illustration of multiphase oxide formation without Ga assistor.
图 3.结构和混合调制对单相 HEO 形成的影响。（一、二）没有 Ga 辅助器的 HEO 的 XRD 图谱和 EDS 映射。比例尺：500 nm。（c） 引入 Ga 辅助器前后单相 HEO 的形成能量。（d） 无 Ga 助剂的多相氧化物形成示意图。
Metal oxides are one of the most excellent electrocatalysts for oxygen evolution reaction (OER). (21,28,29) Considering Fe, Co, and Ni are usually the active elements for the OER, (29,30) they were included in the chemical composition of HEOs. Herein, the quinary GaFeCoNiMo and GaFeCoNiCr, quaternary GaFeCoNi oxides, were synthesized and tested toward the OER, all of which exhibited the high-entropy mixing state and single-phase spinel structure (Figure S20).
金属氧化物是析氧反应 （OER） 最优异的电催化剂之一。（21,28,29） 考虑到 Fe、Co 和 Ni 通常是 OER 的活性元素，（29,30） 它们被包含在 HEO 的化学成分中。在此，合成了四元 GaFeCoNiMo 和 GaFeCoNiCr，并针对 OER 进行了测试，它们都表现出高熵混合态和单相尖晶石结构（ 图 S20）。
In the polarization curves of Figure 4a, two quinary HEOs exhibited superior OER activity compared to the RuO2 catalyst and the quaternary oxide, indicating that entropy engineering could enhance the catalytic performance. As shown in Figure 4b,c, GaFeCoNiMo oxide exhibited the lowest value of both overpotential and Tafel slope, indicating that it possessed the highest catalytic activity and fastest OER reaction kinetics among the catalysts. The smaller value of charge-transfer resistances of GaFeCoNiMo oxide than other systems further verified the best electrocatalytic kineties (Figure S21), which accords with the result of Tafel slopes. Moreover, the double-layer capacitance analysis indicated the most electrochemically active sites for GaFeCoNiMo oxide (Figures S22 and S23). The high OER activity of GaFeCoNiMo oxide may be because the alloying of Mo with variable valence states and large ionic radius could modulate the electronic structure of the active site and induce strain to boost the activity. (31−33) Additionally, the XPS analysis indicated there were abundant oxygen vacancies (Figure S24), which has been demonstrated to promote the catalytic performance. (5,33,34) According to the chronopotentiometry curve (Figure 4d), the GaFeCoNiMo oxide catalyst exhibited no obvious deterioration after the 250 h test, reflecting excellent stability.
在图 4a 的极化曲线中，与 RuO2 催化剂和季氧化物相比，两个五元 HEO 表现出优异的 OER 活性，表明熵工程可以提高催化性能。如图 4b，c 所示，GaFeCoNiMo 氧化物的过电位和塔菲尔斜率均表现出最低值，表明它在催化剂中具有最高的催化活性和最快的 OER 反应动力学。GaFeCoNiMo 氧化物的电荷转移电阻值小于其他系统，进一步验证了最佳的电催化基质（ 图 S21），这与 Tafel 斜率的结果一致。此外，双层电容分析表明 GaFeCoNiMo 氧化物的电化学活性位点最强（ 图 S22 和 S23）。GaFeCoNiMo 氧化物的高 OER 活性可能是因为具有可变价态和大离子半径的 Mo 合金化可以调节活性位点的电子结构并诱导应变以增强活性。（31−33） 此外，XPS 分析表明存在丰富的氧空位（ 图 S24），这已被证明可以促进催化性能。（5,33,34） 根据计时电位曲线（ 图 4d），GaFeCoNiMo 氧化物催化剂在 250 h 测试后没有表现出明显的劣化，反映了优异的稳定性。
Figure 4 图 4
Figure 4. Electrocatalytic performance of HEO nanosheets toward the OER. (a) Polarization curves. (b) Comparison of overpotential of different samples at 10 mA cm–2. (c) Tafel slopes. (d) Chronopotentiometric curve of the HEO (GaFeCoNiMo oxide) at 10 mA cm–2. The curves and columns with different colors in (a–d) represent different HEO systems. Red: GaFeCoNiMo oxide. Blue: GaFeCoNiCr oxide. Gray: GaFeCoNi oxide. Orange: RuO2.
图 4.HEO 纳米片对 OER 的电催化性能。（a） 极化曲线。（b） 不同样品在 10 mA cm–2 下的过电位比较。（c） 塔菲尔斜坡。（d） HEO（GaFeCoNiMo 氧化物）在 10 mA cm–2 下的计时电位曲线。（a–d） 中具有不同颜色的曲线和列表示不同的 HEO 系统。红色：GaFeCoNiMo 氧化物。蓝色：GaFeCoNiCr 氧化物。灰色：GaFeCoNi 氧化物。橙色：RuO2。
In conclusion, we demonstrate the self-lattice framework with the mixing assistor for realizing the synthesis of ultrathin HEOs. With the assistance of Ga to decrease the formation energy, the self-lattice framework generated by the element bonding preference can accomplish the structure and mixing dual modulation in a high-entropy scenario, resulting in the formation of single-phase HEO. The maintenance of the main phase yet the appearance of the impurity phase and local element aggregation in the oxide systems without the assistor addition demonstrated the dual-modulation of our strategy. The approach showed broad applicability in the construction of rock-salt, spinel, perovskite, and fluorite high-entropy structures. The as-obtained HEO nanosheets exhibited great activity and stability for electrocatalytic OER. This strategy provides new insight into the controlled synthesis of high-entropy materials and provides a platform for developing advanced catalysts.
总之，我们展示了带有混合辅助器的自晶格框架，用于实现超薄 HEO 的合成。在 Ga 降低形成能的辅助下，元素键合偏好产生的自晶格框架可以在高熵情景下完成结构和混频双调制，从而形成单相 HEO。在没有添加辅助剂的情况下，氧化物系统中保持主相但出现杂质相和局部元素聚集，证明了我们策略的双重调制。该方法在构建岩盐、尖晶石、钙钛矿和萤石高熵结构方面显示出广泛的适用性。所获得的 HEO 纳米片对电催化 OER 表现出很好的活性和稳定性。该策略为高熵材料的受控合成提供了新的见解，并为开发高级催化剂提供了平台。
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Experimental and characterization details; details of theoretical calculations; schematic diagram of the ultrathin HEO synthesis; morphology characterization and thickness regulation of the HEO nanosheet; OM, SEM, AFM, XPS, SAED, TEM-EDS, and ICP-OES characterizations of the HEOs with four type phase structures; structural and elemental analysis of the HEOs without glucose and glycine addition, multicomponent oxide systems without assistor addition, and the HEO containing the noble metal; TEM, XRD, and XPS characterizations of the HEO catalyst; impedance and double-layer capacitance measurement of all OER catalysts (PDF)
实验和表征细节;理论计算的细节;超薄 HEO 合成示意图;HEO 纳米片的形貌表征和厚度调节;具有四种类型相结构的 HEO 的 OM、SEM、AFM、XPS、SAED、TEM-EDS 和 ICP-OES 表征;对不添加葡萄糖和甘氨酸的 HEO、不添加辅助剂的多组分氧化物系统以及含有贵金属的 HEO 进行结构和元素分析;HEO 催化剂的 TEM、XRD 和 XPS 表征;所有 OER 催化剂的阻抗和双电层电容测量 （PDF）
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Author Information 作者信息
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- Mengqi Zeng - College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China;
https://orcid.org/0000-0002-1442-052X;
Mengqi Zeng - 武汉大学化学与分子科学学院，中国 430072; https://orcid.org/0000-0002-1442-052X; - Lei Fu - The Institute for Advanced Studies, Wuhan University, Wuhan 430072, China; College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, China;https://orcid.org/0000-0003-1356-4422;
Lei Fu - 武汉大学高等研究院，中国武汉 430072; 武汉大学化学与分子科学学院， 中国 武汉 430072; https://orcid.org/0000-0003-1356-4422;
- Yuzheng Guo - School of Electrical Engineering and Automation, Wuhan University, Wuhan 430072, China;https://orcid.org/0000-0001-9224-3816
郭玉峥 - 武汉大学电气工程与自动化学院，中国 430072 武汉; https://orcid.org/0000-0001-9224-3816
J. Liang and J. Liu contributed equally to this work.
J. Liang 和 J. Liu 对这项工作做出了同样的贡献。
Acknowledgments 确认
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The research was supported by the Natural Science Foundation of China (22025303) and the National Key Research and Development Program of China (2022YFA1402501). The authors acknowledge the Center for Electron Microscopy at Wuhan University for their substantial support to TEM characterization. The authors thank the Core Facility of Wuhan University for the measurement of XPS, SEM, TEM, and BET analysis. The authors also thank the Core Research Facilities of the College of Chemistry and Molecular Sciences at Wuhan University for the SEM and XRD characterizations.
该研究得到了国家自然科学基金 （22025303） 和国家重点研发计划 （2022YFA1402501） 的支持。作者感谢武汉大学电子显微镜中心对 TEM 表征的大力支持。作者感谢武汉大学核心设施对 XPS、SEM、TEM 和 BET 分析的测量。作者还感谢武汉大学化学与分子科学学院的核心研究机构对 SEM 和 XRD 表征。
References 引用
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This article references
34 other publications.
本文引用了其他 34 种出版物。
- 2Li, T.; Yao, Y.; Huang, Z.; Xie, P.; Liu, Z.; Yang, M.; Gao, J.; Zeng, K.; Brozena, A. H.; Pastel, G. Denary oxide nanoparticles as highly stable catalysts for methane combustion. Nat. Catal. 2021, 4, 62– 70, DOI: 10.1038/s41929-020-00554-1
阿拉伯数字李 T.;姚 Y.;黄 Z.;谢 P.;刘 Z.;杨 M.;高 J.;曾 K.;布罗泽纳，AH;粉状 G.Denary 氧化物纳米颗粒作为高度稳定的甲烷燃烧催化剂。Nat. Catal.2021， 4， 62– 70， DOI： 10.1038/s41929-020-00554-1Google Scholar 谷歌学术2Denary oxide nanoparticles as highly stable catalysts for methane combustionLi, Tangyuan; Yao, Yonggang; Huang, Zhennan; Xie, Pengfei; Liu, Zhenyu; Yang, Menghao; Gao, Jinlong; Zeng, Kaizhu; Brozena, Alexandra H.; Pastel, Glenn; Jiao, Miaolun; Dong, Qi; Dai, Jiaqi; Li, Shuke; Zong, Han; Chi, Miaofang; Luo, Jian; Mo, Yifei; Wang, Guofeng; Wang, Chao; Shahbazian-Yassar, Reza; Hu, LiangbingNature Catalysis (2021), 4 (1), 62-70CODEN: NCAACP; ISSN:2520-1158. (Nature Research)Oxide nanoparticles with elemental and structural diversity are widely studied for catalysis and energy applications. While compositional control holds great promise for materials discovery, current oxide nanoparticles are typically limited to a few cations due to the intrinsic complexity in nanoscale multi-element mixing. Here we report the rational design and synthesis of single-phase multi-element oxide nanoparticles with tunable compn., size and structure. We have identified temp.-, oxidn.- and entropy-driven synthesis strategies to mix a range of elements with largely dissimilar oxidn. potentials (including palladium), thus greatly expanding the compositional space. Through rapid synthesis and screening, we obtained a denary multi-element oxide catalyst showing high performance and superior stability for catalytic methane combustion over 100 h due to the high-entropy design and stabilization. Our work therefore provides a viable synthesis route with clear guidelines for multi-element oxide nanoparticles and enables materials design in the multi-element space towards highly stable catalysts. - 3Xu, H.; Zhang, Z.; Liu, J.; Do-Thanh, C.; Chen, H.; Xu, S.; Lin, Q.; Jiao, Y.; Wang, J.; Wang, Y. Entropy-stabilized single-atom Pd catalysts via high-entropy fluorite oxide supports. Nat. Commun. 2020, 11, 3908, DOI: 10.1038/s41467-020-17738-9
3 徐 H.;张 Z.;刘 J.;Do-Thanh， C.;陈 H.;徐 S.;林 Q.;焦 Y.;王 J.;Wang， Y.通过高熵萤石氧化物载体的熵稳定单原子 Pd 催化剂。Nat. Commun.2020， 11， 3908， DOI： 10.1038/s41467-020-17738-9Google Scholar 谷歌学术3Entropy-stabilized single-atom Pd catalysts via high-entropy fluorite oxide supportsXu, Haidi; Zhang, Zihao; Liu, Jixing; Do-Thanh, Chi-Linh; Chen, Hao; Xu, Shuhao; Lin, Qinjing; Jiao, Yi; Wang, Jianli; Wang, Yun; Chen, Yaoqiang; Dai, ShengNature Communications (2020), 11 (1), 3908CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Single-atom catalysts (SACs) have attracted considerable attention in the catalysis community. However, fabricating intrinsically stable SACs on traditional supports (N-doped carbon, metal oxides, etc.) remains a formidable challenge, esp. under high-temp. conditions. Here, we report a novel entropy-driven strategy to stabilize Pd single-atom on the high-entropy fluorite oxides (CeZrHfTiLa)Ox (HEFO) as the support by a combination of mech. milling with calcination at 900°C. Characterization results reveal that single Pd atoms are incorporated into HEFO (Pd1@HEFO) sublattice by forming stable Pd-O-M bonds (M = Ce/Zr/La). Compared to the traditional support stabilized catalysts such as Pd@CeO2, Pd1@HEFO affords the improved reducibility of lattice oxygen and the existence of stable Pd-O-M species, thus exhibiting not only higher low-temp. CO oxidn. activity but also outstanding resistance to thermal and hydrothermal degrdn. This work therefore exemplifies the superiority of high-entropy materials for the prepn. of SACs. - 4Li, Y.; Bai, X.; Yuan, D.; Yu, C.; San, X.; Guo, Y.; Zhang, L.; Ye, J. Cu-based high-entropy two-dimensional oxide as stable and active photothermal catalyst. Nat. Commun. 2023, 14, 3171, DOI: 10.1038/s41467-023-38889-5
4 李英;白，X.;袁 D.;于，C.;桑，X.;郭 Y.;张 L.;Ye， J.Cu 基高熵二维氧化物作为稳定且有效的光热催化剂。Nat. Commun.2023， 14， 3171， DOI： 10.1038/s41467-023-38889-5Google Scholar 谷歌学术4Cu-based high-entropy two-dimensional oxide as stable and active photothermal catalystLi, Yaguang; Bai, Xianhua; Yuan, Dachao; Yu, Chenyang; San, Xingyuan; Guo, Yunna; Zhang, Liqiang; Ye, JinhuaNature Communications (2023), 14 (1), 3171CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)Cu-based nanocatalysts are the cornerstone of various industrial catalytic processes. Synergistically strengthening the catalytic stability and activity of Cu-based nanocatalysts is an ongoing challenge. Herein, the high-entropy principle is applied to modify the structure of Cu-based nanocatalysts, and a PVP templated method is invented for generally synthesizing six-eleven dissimilar elements as high-entropy two-dimensional (2D) materials. Taking 2D Cu2Zn1Al0.5Ce5Zr0.5Ox as an example, the high-entropy structure not only enhances the sintering resistance from 400 °C to 800 °C but also improves its CO2 hydrogenation activity to a pure CO prodn. rate of 417.2 mmol g-1 h-1 at 500 °C, 4 times higher than that of reported advanced catalysts. When 2D Cu2Zn1Al0.5Ce5Zr0.5Ox are applied to the photothermal CO2 hydrogenation, it exhibits a record photochem. energy conversion efficiency of 36.2%, with a CO generation rate of 248.5 mmol g-1 h-1 and 571 L of CO yield under ambient sunlight irradn. The high-entropy 2D materials provide a new route to simultaneously achieve catalytic stability and activity, greatly expanding the application boundaries of photothermal catalysis. - 5Meng, Z.; Gong, X.; Xu, J.; Sun, X.; Zeng, F.; Du, Z.; Hao, Z.; Shi, W.; Yu, S.; Hu, X. A general strategy for preparing hollow spherical multilayer structures of oxygen-rich vacancy transition metal oxides, especially high entropy perovskite oxides. Chem. Eng. J. 2023, 457, 141242, DOI: 10.1016/j.cej.2022.141242
5 孟，Z.;龚 X.;徐 J.;Sun， X.;曾， F.;杜 Z.;郝，Z.;石 W.;俞 S.;胡， X.制备富氧空位过渡金属氧化物的空心球形多层结构的一般策略，特别是高熵钙钛矿氧化物。化学工程杂志 2023， 457， 141242， DOI： 10.1016/j.cej.2022.141242Google Scholar 谷歌学术5A general strategy for preparing hollow spherical multilayer structures of Oxygen-Rich vacancy transition metal Oxides, especially high entropy perovskite oxidesMeng, Zeshuo; Gong, Xiliang; Xu, Jian; Sun, Xucong; Zeng, Fanda; Du, Zhengyan; Hao, Zeyu; Shi, Wei; Yu, Shansheng; Hu, Xiaoying; Tian, HongweiChemical Engineering Journal (Amsterdam, Netherlands) (2023), 457 (), 141242CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)The development of excellent synthetic strategies and exploration of the synthesis mechanisms of active site-rich high-entropy oxides are crucial for high-entropy materials. Herein, a universal synthetic method was designed to prep. La(Co0.2Mn0.2Fe0.2Ni0.2Cu0.2)O3 (HSM-HEPs) with hollow spherical multilayer structure (HSM) and rich oxygen vacancies. The tracking characterization was used during the synthesis of HSM-HEPs to clarify the formation of multi-shell, multi-vacancy, and single-phase crystal structures of HSM-HEPs. Three basic conditions were proposed to obtain vacancy-rich high-entropy materials. The exptl. data showed excellent electrochem. activity and extraordinary stability of HSM-HEPs electrode materials owing to the formation of HSM structure, abundant oxygen vacancies, abundant elemental compn., and high sp. surface area. When used as supercapacitor electrode materials, HSM-HEPs exhibited a high specific capacity of 625 F g-1 with an excellent capacity retention rate of 88% after 10,000 cycles. Besides, HSM-HEPs achieved efficient water oxidn. with an overpotential of 309 mV at 10 mA cm-2. Furthermore, the proposed strategy can be extended to the synthesis of metal oxides with various representative HSM crystal structures. Overall, the designed and tuned synthetic method looks promising for the formation of more active sites-high-entropy materials. - 6Lun, Z.; Ouyang, B.; Kwon, D.; Ha, Y.; Foley, E. E.; Huang, T.; Cai, Z.; Kim, H.; Balasubramanian, M.; Sun, Y. Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries. Nat. Mater. 2021, 20, 214– 221, DOI: 10.1038/s41563-020-00816-0
6 伦，Z.;欧阳 B.;权，D.;哈，Y.;弗利，E. E.;黄 T.;蔡，Z.;金 H.;Balasubramanian， M.;Sun， Y.用于锂离子电池的阳离子无序岩盐型高熵阴极。Nat. Mater.2021， 20， 214– 221， DOI： 10.1038/s41563-020-00816-0Google Scholar 谷歌学术6Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteriesLun, Zhengyan; Ouyang, Bin; Kwon, Deok-Hwang; Ha, Yang; Foley, Emily E.; Huang, Tzu-Yang; Cai, Zijian; Kim, Hyunchul; Balasubramanian, Mahalingam; Sun, Yingzhi; Huang, Jianping; Tian, Yaosen; Kim, Haegyeom; McCloskey, Bryan D.; Yang, Wanli; Clement, Raphaele J.; Ji, Huiwen; Ceder, GerbrandNature Materials (2021), 20 (2), 214-221CODEN: NMAACR; ISSN:1476-1122. (Nature Research)High-entropy (HE) ceramics, by analogy with HE metallic alloys, are an emerging class of solid solns. composed of a large no. of species. These materials offer the benefit of large compositional flexibility and can be used in a wide variety of applications, including thermoelecs., catalysts, superionic conductors and battery electrodes. It is shown here that the HE concept can lead to very substantial improvements in performance in battery cathodes. Among lithium-ion cathodes, cation-disordered rocksalt (DRX)-type materials are an ideal platform within which to design HE materials because of their demonstrated chem. flexibility. By comparing a group of DRX cathodes contg. two, four or six transition metal (TM) species, it is shown that short-range order systematically decreases, whereas energy d. and rate capability systematically increase, as more TM cation species are mixed together, despite the total metal content remaining fixed. A DRX cathode with six TM species achieves 307 mAh g-1 (955 Wh kg-1) at a low rate (20 mA g-1), and retains > 170 mAh g-1 when cycling at a high rate of 2,000 mA g-1. To facilitate further design in this HE DRX space, a compatibility anal. is presented of 23 different TM ions, and a phase-pure HE DRX compd. contg. 12 TM species is synthesized as a proof of concept. - 7Zhao, C.; Ding, F.; Lu, Y.; Chen, L.; Hu, Y. High-entropy layered oxide cathodes for sodium-ion batteries. Angew. Chem., Int. Ed. 2020, 59, 264– 269, DOI: 10.1002/anie.201912171
7 赵 C.;丁 F.;卢 Y.;陈，L.;胡， Y.钠离子电池用高熵层状氧化物阴极.安格。化学，国际版 2020,59,264– 269，DOI ： 10.1002/anie.201912171Google Scholar 谷歌学术7High-Entropy Layered Oxide Cathodes for Sodium-Ion BatteriesZhao, Chenglong; Ding, Feixiang; Lu, Yaxiang; Chen, Liquan; Hu, Yong-ShengAngewandte Chemie, International Edition (2020), 59 (1), 264-269CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Material innovation on high-performance Na-ion cathodes and the corresponding understanding of structural chem. still remain a challenge. Herein, a new concept is reported of high-entropy strategy to design layered oxide cathodes for Na-ion batteries. An example of layered O3-type NaNi0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2 has been demonstrated, which exhibits the longer cycling stability (ca. 83% of capacity retention after 500 cycles) and the outstanding rate capability (ca. 80% of capacity retention at the rate of 5.0 C). A highly reversible phase-transition behavior between O3 and P3 structures occurs during the charge-discharge process, and importantly, this behavior is delayed with > 60% of the total capacity being stored in O3-type region. Possible mechanism can be attributed to the multiple transition-metal components in this high-entropy material which can accommodate the changes of local interactions during Na+ (de)intercalation. This strategy opens new insights into the development of advanced cathode materials. - 8Johnstone, G. H. J.; Gonzalez-Rivas, M. U.; Taddei, K. M.; Sutarto, R.; Sawatzky, G. A.; Green, R. J.; Oudah, M.; Hallas, A. M. Entropy engineering and tunable magnetic order in the spinel high-entropy oxide. J. Am. Chem. Soc. 2022, 144, 20590– 20600, DOI: 10.1021/jacs.2c06768
8 约翰斯通，G. H. J.;冈萨雷斯-里瓦斯，M.U.;塔代，KM;苏塔托，R.;佐治亚州萨瓦茨基;格林，RJ;欧达，M.;Hallas， A. M. 尖晶石高熵氧化物中的熵工程和可调磁序。J. Am. Chem. Soc.2022， 144， 20590– 20600， DOI： 10.1021/jacs.2c06768Google Scholar 谷歌学术8Entropy Engineering and Tunable Magnetic Order in the Spinel High-Entropy OxideJohnstone, Graham H. J.; Gonzalez-Rivas, Mario U.; Taddei, Keith M.; Sutarto, Ronny; Sawatzky, George A.; Green, Robert J.; Oudah, Mohamed; Hallas, Alannah M.Journal of the American Chemical Society (2022), 144 (45), 20590-20600CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Spinel oxides are an ideal setting to explore the interplay between configurational entropy, site selectivity, and magnetism in high-entropy oxides (HEOs). In this work, we characterize the magnetic properties of the spinel (Cr, Mn, Fe, Co, Ni)3O4 and study the evolution of its magnetism as a function of nonmagnetic gallium substitution. Across the range of compns. studied here, from 0 to 40% Ga, magnetic susceptibility and powder neutron diffraction measurements show that ferrimagnetic order is robust in the spinel HEO. However, we also find that the ferrimagnetic order is highly tunable, with the ordering temp., satd. and sublattice moments, and magnetic hardness all varying significantly as a function of Ga concn. Through X-ray absorption and magnetic CD, we are able to correlate this magnetic tunability with strong site selectivity between the various cations and the tetrahedral and octahedral sites in the spinel structure. In particular, we find that while Ni and Cr are largely unaffected by the substitution with Ga, the occupancies of Mn, Co, and Fe are each significantly redistributed. Ga substitution also requires an overall redn. in the transition metal valence, and this is entirely accommodated by Mn. Finally, we show that while site selectivity has an overall suppressing effect on the configurational entropy, over a certain range of compns., Ga substitution yields a striking increase in the configurational entropy and may confer addnl. stabilization. Spinel oxides can be tuned seamlessly from the low-entropy to the high-entropy regime, making this an ideal platform for entropy engineering. - 9Joshi, A.; Chakrabarty, S.; Akella, S. H.; Saha, A.; Mukherjee, A.; Schmerling, B.; Ejgenberg, M.; Sharma, R.; Noked, M. High-entropy Co-free O3-type layered oxyfluoride: A promising air-stable cathode for sodium-ion batteries. Adv. Mater. 2023, 35, 2304440, DOI: 10.1002/adma.202304440
9 乔希，A.;查克拉巴蒂，S.;阿克拉，SH;萨哈，A.;穆克吉，A.;施默林，B.;埃根伯格，M.;夏尔马，R.;Noked， M.高熵无钴 O3 型层状氟氧化合物：一种很有前途的空气稳定阴极，用于钠离子电池。Adv. Mater.2023， 35， 2304440， DOI： 10.1002/adma.202304440Google Scholar 谷歌学术9High-Entropy Co-Free O3-Type Layered Oxyfluoride: A Promising Air-Stable Cathode for Sodium-Ion BatteriesJoshi, Akanksha; Chakrabarty, Sankalpita; Akella, Sri Harsha; Saha, Arka; Mukherjee, Ayan; Schmerling, Bruria; Ejgenberg, Michal; Sharma, Rosy; Noked, MalachiAdvanced Materials (Weinheim, Germany) (2023), 35 (51), 2304440CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Sodium-ion batteries have recently emerged as a promising alternative to lithium-based batteries, driven by an ever-growing demand for electricity storage systems. The present workproposes a cobalt-free high-capacity cathode for sodium-ion batteries, synthesized using a high-entropy approach. The high-entropy approach entails mixing more than five elements in a single phase; hence, obtaining the desired properties is a challenge since this involves the interplay between different elements. Here, instead of oxide, oxyfluoride is chosen to suppress oxygen loss during long-term cycling. Supplement to this, lithium is introduced in the compn. to obtain high configurational entropy and sodium vacant sites, thus stabilizing the crystal structure, accelerating the kinetics of intercalation/deintercalation, and improving the air stability of the material. With the optimization of the cathode compn., a reversible capacity of 109 mAh g-1 (2-4 V) and 144 mAh g-1 (2-4.3 V) is obsd. in the first few cycles, along with a significant improvement in stability during prolonged cycling. Furthermore, in situ and ex situ diffraction studies during charging/discharging reveal that the high-entropy strategy successfully suppresses the complex phase transition. The impressive outcomes of the present work strongly motivate the pursuit of the high-entropy approach to develop efficient cathodes for sodium-ion batteries. - 10Zhao, B.; Du, Y.; Yan, Z.; Rao, L.; Chen, G.; Yuan, M.; Yang, L.; Zhang, J.; Che, R. Structural defects in phase-regulated high-entropy oxides toward superior microwave absorption properties. Adv. Funct. Mater. 2023, 33, 2209924, DOI: 10.1002/adfm.202209924
10 赵 B.;杜 Y.;严，Z.;饶，L.;陈 G.;袁 M.;杨 L.;张 J.;Che， R.相控高熵氧化物中的结构缺陷具有优异的微波吸收性能。Adv. Funct.Mater.2023， 33， 2209924， DOI： 10.1002/adfm.202209924Google Scholar 谷歌学术10Structural Defects in Phase-Regulated High-Entropy Oxides toward Superior Microwave Absorption PropertiesZhao, Biao; Du, Yiqian; Yan, Zhikan; Rao, Longjun; Chen, Guanyu; Yuan, Mingyue; Yang, Liting; Zhang, Jincang; Che, RenchaoAdvanced Functional Materials (2023), 33 (1), 2209924CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)High-entropy (HE) oxides have become increasingly popular as electromagnetic wave-absorbing materials owing to their customizable structure and unique HE effects. However, the weak loss property of single-phase HE ceramics and the approaches implemented to improve them based on semi-empirical rules severely limit their development. Herein, two biphasic HE oxides are prepd. by simple sintering to realize accurate regulation of crystal phases and structural defects. It is verified that HE effects cause various defects that are beneficial for microwave dissipation within complex-phase ceramics. In spinel/perovskite HE oxides, around the interface of spinel (111) and perovskite (110) planes, notable stress concns. and lattice distortions are directly obsd., inducing numerous point defects and stacking faults. Interestingly, besides the existing heterogeneous interface of rock salt (220)/spinel (220) plane and defects, rock salt/spinel HE oxides enabled synergistic effects via the precise regulation of components' phase. Driven by structural defects and multi-phases in HE complexes, the intense polarization is evidently found, confirmed by the first-principles calcns. Accordingly, the two complex-phase HE oxides demonstrate excellent microwave absorption performance, and the minimal reflection loss of -54.5 dB is achieved. Therefore, this study provides valuable guidelines for the design of microwave absorbers using HE oxides. - 11Li, Y.; Yu, Z.; Wang, L.; Weng, Y.; Tang, C.; Yin, X.; Han, K.; Wu, H.; Yu, X.; Wong, L. Electronic-reconstruction-enhanced hydrogen evolution catalysis in oxide polymorphs. Nat. Commun. 2019, 10, 3149, DOI: 10.1038/s41467-019-11124-w
11 李英;俞 Z.;王 L.;翁 Y.;唐 C.;尹 X.;韩，K.;吴 H.;于，X.;Wong， L.氧化物多晶型物中的电子重建增强析氢催化。Nat. Commun.2019， 10， 3149， DOI： 10.1038/s41467-019-11124-wGoogle Scholar 谷歌学术11Electronic-reconstruction-enhanced hydrogen evolution catalysis in oxide polymorphsLi Yangyang; Wang Ling; Wu Haijun; Wang John; Pennycook Stephen J; Venkatesan Thirumalai; Xue Jun Min; Chen Jingsheng; Yu Zhi Gen; Zhang Yong-Wei; Weng Yakui; Tang Chi Sin; Yin Xinmao; Wee Andrew T S; Venkatesan Thirumalai; Tang Chi Sin; Wee Andrew T S; Pennycook Stephen J; Venkatesan Thirumalai; Yin Xinmao; Yu Xiaojiang; Breese Mark B H; Han Kun; Wang Xiao Renshaw; Wong Lai Mun; Chai Jianwei; Wang Shijie; Wan Dongyang; Pennycook Stephen J; Venkatesan Thirumalai; Dong ShuaiNature communications (2019), 10 (1), 3149 ISSN:.Transition metal oxides exhibit strong structure-property correlations, which has been extensively investigated and utilized for achieving efficient oxygen electrocatalysts. However, high-performance oxide-based electrocatalysts for hydrogen evolution are quite limited, and the mechanism still remains elusive. Here we demonstrate the strong correlations between the electronic structure and hydrogen electrocatalytic activity within a single oxide system Ti2O3. Taking advantage of the epitaxial stabilization, the polymorphism of Ti2O3 is extended by stabilizing bulk-absent polymorphs in the film-form. Electronic reconstructions are realized in the bulk-absent Ti2O3 polymorphs, which are further correlated to their electrocatalytic activity. We identify that smaller charge-transfer energy leads to a substantial enhancement in the electrocatalytic efficiency with stronger hybridization of Ti 3d and O 2p orbitals. Our study highlights the importance of the electronic structures on the hydrogen evolution activity of oxide electrocatalysts, and also provides a strategy to achieve efficient oxide-based hydrogen electrocatalysts by epitaxial stabilization of bulk-absent polymorphs. - 12Li, Q.; Wu, J.; Wu, T.; Jin, H.; Zhang, N.; Li, J.; Liang, W.; Liu, M.; Huang, L.; Zhou, J. Phase engineering of atomically thin perovskite oxide for highly active oxygen evolution. Adv. Funct. Mater. 2021, 31, 2102002, DOI: 10.1002/adfm.202102002
12 李 Q.;吴 J.;吴 T.;金 H.;张 N.;李 J.;梁 W.;刘 M.;黄 L.;周，J.用于高活性氧析出的原子薄钙钛矿氧化物的相工程。Adv. Funct.Mater.2021， 31， 2102002， DOI： 10.1002/adfm.202102002Google Scholar 谷歌学术12Phase Engineering of Atomically Thin Perovskite Oxide for Highly Active Oxygen EvolutionLi, Qun; Wu, Jiabin; Wu, Tao; Jin, Hongrun; Zhang, Nian; Li, Jia; Liang, Wenxi; Liu, Meilin; Huang, Liang; Zhou, JunAdvanced Functional Materials (2021), 31 (38), 2102002CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)Ultrathin perovskite oxides with tailored crystal structures are promising catalysts for O evolution reaction (OER) owing to their high intrinsic catalytic activity and large exposed active surface area. However, the synthesis of phase-controllable perovskite oxide nanosheets with thickness down to a few nanometers remains a challenge since the formation of a perovskite phase often requires long-time calcination at high temps. Here, a salt-templated strategy for fabrication of atomically thin perovskite oxide of LaMnO3 with tailored phase structure for highly active OER catalysts is reported. The orthorhombic structure of LaMnO3 nanosheets demonstrates much higher electrochem. activity than the tetragonal or hexagonal phase and the benchmark IrO2 catalyst, exhibiting extremely small onset overpotential (≈70 mV) and a low overpotential (≈324 mV at 10 mA cm-2disk) in alk. soln. The remarkable OER activity of this catalyst is attributed to the desired surface binding energetics (or the unique electronic structures) inherent to the orthorhombic phase, as predicted by d. functional theory calcns. and confirmed by exptl. measurements. Further, it is believed that this study paves a new path toward rational the design of perovskite oxide nanosheets with desired phase structures for many applications. - 13Amiri, A.; Shahbazian-Yassar, R. Recent progress of high-entropy materials for energy storage and conversion. J. Mater. Chem. A 2021, 9, 782– 823, DOI: 10.1039/D0TA09578H
13 阿米里，A.;Shahbazian-Yassar， R.用于储能和转换的高熵材料的最新进展。J. 马特。化学 A2021， 9， 782– 823， DOI： 10.1039/D0TA09578HGoogle Scholar 谷歌学术13Recent progress of high-entropy materials for energy storage and conversionAmiri, Azadeh; Shahbazian-Yassar, RezaJournal of Materials Chemistry A: Materials for Energy and Sustainability (2021), 9 (2), 782-823CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)A review. The emergence of high-entropy materials (HEMs) with their excellent mech. properties, stability at high temps., and high chem. stability is poised to yield new advancement in the performance of energy storage and conversion technologies. This review covers the recent developments in catalysis, water splitting, fuel cells, batteries, supercapacitors, and hydrogen storage enabled by HEMs covering metallic, oxide, and non-oxide alloys. Here, first, the primary rules for the proper selection of the elements and the formation of a favorable single solid soln. phase in HEMs are defined. Furthermore, recent developments in different fields of energy conversion and storage achieved by HEMs are discussed. Higher electrocatalytic and catalytic activities with longer cycling stability and durability compared to conventional noble metal-based catalysts are reported for high-entropy materials. In electrochem. energy storage systems, high-entropy oxides and alloys have shown superior performance as anode and cathode materials with long cycling stability and high capacity retention. Also, when used as metal hydrides for hydrogen storage, remarkably high hydrogen storage capacity and structural stability are obsd. for HEMs. In the end, future directions and new energy-related technologies that can be enabled by the application of HEMs are outlined. - 14Cao, G.; Liang, J.; Guo, Z.; Yang, K.; Wang, G.; Wang, H.; Wan, X.; Li, Z.; Bai, Y.; Zhang, Y. Liquid metal for high-entropy alloy nanoparticles synthesis. Nature 2023, 619, 73– 77, DOI: 10.1038/s41586-023-06082-9
14 曹 G.;梁 J.;郭 Z.;杨 K.;王 G.;王 H.;万，X.;李 Z.;白，Y.;Zhang， Y.用于高熵合金纳米颗粒合成的液态金属。自然 2023， 619， 73– 77， DOI： 10.1038/s41586-023-06082-9Google Scholar 谷歌学术14Liquid metal for high-entropy alloy nanoparticles synthesisCao, Guanghui; Liang, Jingjing; Guo, Zenglong; Yang, Kena; Wang, Gang; Wang, Huiliu; Wan, Xuhao; Li, Zeyuan; Bai, Yijia; Zhang, Yile; Liu, Junlin; Feng, Yanpeng; Zheng, Zhenying; Lu, Cai; He, Guangzhi; Xiong, Zeyou; Liu, Ze; Chen, Shengli; Guo, Yuzheng; Zeng, Mengqi; Lin, Junhao; Fu, LeiNature (London, United Kingdom) (2023), 619 (7968), 73-77CODEN: NATUAS; ISSN:1476-4687. (Nature Portfolio)High-entropy alloy nanoparticles (HEA-NPs) show great potential as functional materials1-3. However, thus far, the realized high-entropy alloys have been restricted to palettes of similar elements, which greatly hinders the material design, property optimization and mechanistic exploration for different applications4,5. Herein, we discovered that liq. metal endowing neg. mixing enthalpy with other elements could provide a stable thermodn. condition and act as a desirable dynamic mixing reservoir, thus realizing the synthesis of HEA-NPs with a diverse range of metal elements in mild reaction conditions. The involved elements have a wide range of at. radii (1.24-1.97 Å) and m.ps. (303-3,683 K). We also realized the precisely fabricated structures of nanoparticles via mixing enthalpy tuning. Moreover, the real-time conversion process (i.e., from liq. metal to cryst. HEA-NPs) is captured in situ, which confirmed a dynamic fission-fusion behavior during the alloying process. - 15Nie, S.; Wu, L.; Zhao, L.; Zhang, P. Enthalpy-change driven synthesis of high-entropy perovskite nanoparticles. Nano Res. 2022, 15, 4867– 4872, DOI: 10.1007/s12274-021-3803-3
15 聂，S.;吴 L.;赵 L.;Zhang， P.焓变驱动的高熵钙钛矿纳米粒子的合成。纳米研究 2022， 15， 4867– 4872， DOI： 10.1007/s12274-021-3803-3Google Scholar 谷歌学术15Enthalpy-change driven synthesis of high-entropy perovskite nanoparticlesNie, Siyang; Wu, Liang; Zhao, Lingci; Zhang, PengfeiNano Research (2022), 15 (6), 4867-4872CODEN: NRAEB5; ISSN:1998-0000. (Springer GmbH)Due to their diverse and tunable compn., distorted lattice and excellent stability, high-entropy ceramics (HECs) hold great promise for catalysis, esp. when they present as nanoparticles (NPs). However, current HECs are typically limited to bulky materials with none or fewer defects, because high synthetic temp. (e.g., 1,000-1,200 °C) is usually required to highlight the entropic contribution (TΔS) in ΔG = ΔH - TΔS. Being different with previous strategies, a neg. Gibbs free energy for HECs crystn. is obtained by dramatically decreasing the mixing enthalpy (ΔH). Guided by this principle, single-phase high-entropy La(Ni0.2Mn0.2Cu0.2Fe0.2Co0.2)O3-δ perovskite (HE-LMO) NPs were prepd. at a relatively low temp. (≤ 500 °C). Interestingly, abundant oxygen vacancies were directly created within HE-LMO NPs, which exhibited good activity in catalytic oxidn. Meanwhile, the high-entropy structure endows as-made HE-LMO with robust stability even with 5 vol.% water in feeding gas. D. functional theory (DFT) calcns. revealed that the defective sites in HE-LMO NPs facilitated the charge transfer from HE-LMO to CO, thus activating the adsorbed CO gas. The current work may inspire future design and synthesis of HECs NPs. [graphic not available: see fulltext]. - 16Xie, H.; Qin, M.; Hong, M.; Rao, J.; Guo, M.; Luo, J.; Hu, L. Rapid liquid phase-assisted ultrahigh-temperature sintering of high-entropy ceramic composites. Sci. Adv. 2022, 8, eabn8241 DOI: 10.1126/sciadv.abn8241
16 谢 H.;秦 M.;洪，M.;饶，J.;郭 M.;罗 J.;胡 L.快速液相辅助超高温烧结高熵陶瓷复合材料.科学 Adv.2022， 8， eabn8241 DOI： 10.1126/sciadv.abn8241 - 17Zheng, X.; Gao, X.; Vila, R. A.; Jiang, Y.; Wang, J. Y.; Xu, R.; Zhang, R.; Xiao, X.; Zhang, P.; Greenburg, L. C. Hydrogen-substituted graphdiyne-assisted ultrafast sparking synthesis of metastable nanomaterials. Nat. Nanotechnol. 2023, 18, 153– 159, DOI: 10.1038/s41565-022-01272-4
17 郑 X.;高 X.;维拉，RA;江 Y.;王，JY;徐 R.;张 R.;肖 X.;张 P.;Greenburg， LC 氢取代石墨二炔辅助的亚稳态纳米材料的超快火花合成。纳米技术.2023， 18， 153– 159， DOI： 10.1038/s41565-022-01272-4Google Scholar 谷歌学术17Hydrogen-substituted graphdiyne-assisted ultrafast sparking synthesis of metastable nanomaterialsZheng, Xueli; Gao, Xin; Vila, Rafael A.; Jiang, Yue; Wang, Jingyang; Xu, Rong; Zhang, Rui; Xiao, Xin; Zhang, Pu; Greenburg, Louisa C.; Yang, Yufei; Xin, Huolin L.; Zheng, Xiaolin; Cui, YiNature Nanotechnology (2023), 18 (2), 153-159CODEN: NNAABX; ISSN:1748-3387. (Nature Portfolio)Metastable nanomaterials, such as single-atom and high-entropy systems, with exciting phys. and chem. properties are increasingly important for next-generation technologies. Here, we developed a hydrogen-substituted graphdiyne-assisted ultrafast sparking synthesis (GAUSS) platform for the prepn. of metastable nanomaterials. The GAUSS platform can reach an ultra-high reaction temp. of 3,286 K within 8 ms, a rate exceeding 105 K s-1. Controlling the compn. and chem. of the hydrogen-substituted graphdiyne aerogel framework, the reaction temp. can be tuned from 1,640 K to 3,286 K. We demonstrate the versatility of the GAUSS platform with the successful synthesis of single atoms, high-entropy alloys and high-entropy oxides. Electrochem. measurements and d. functional theory show that single atoms synthesized by GAUSS enhance the lithium-sulfur redox reaction kinetics in all-solid-state lithium-sulfur batteries. Our design of the GAUSS platform offers a powerful way to synthesize a variety of metastable nanomaterials. - 18Wu, H.; Lu, Q.; Li, Y.; Zhao, M.; Wang, J.; Li, Y.; Zhang, J.; Zheng, X.; Han, X.; Zhao, N. Structural framework-guided universal design of high-entropy compounds for efficient energy catalysis. J. Am. Chem. Soc. 2023, 145, 1924– 1935, DOI: 10.1021/jacs.2c12295
18 吴 H.;卢 Q.;李英;赵 M.;王 J.;李英;张 J.;郑 X.;韩 X.;Zhao， N.用于高效能量催化的高熵化合物的结构框架引导通用设计。J. Am. Chem. Soc.2023， 145， 1924– 1935， DOI： 10.1021/jacs.2c12295Google Scholar 谷歌学术18Structural Framework-Guided Universal Design of High-Entropy Compounds for Efficient Energy CatalysisWu, Han; Lu, Qi; Li, Yajing; Zhao, Menghan; Wang, Jiajun; Li, Yingbo; Zhang, Jinfeng; Zheng, Xuerong; Han, Xiaopeng; Zhao, Naiqin; Li, Jiajun; Liu, Yanhui; Deng, Yida; Hu, WenbinJournal of the American Chemical Society (2023), 145 (3), 1924-1935CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)High-entropy compds. with extraordinary properties due to the synergistic effect of multiple components have exhibited great potential and attracted extensive attention in various fields, including physics, mech. property anal., and energy storage. Achieving universal stability and synthesis of high-entropy compds. with a wide range of components and structures continues to be difficult due to the high complexity of multicomponent mixing. Here, we propose a design strategy with high generality for realizing the stability and synthesis of high-entropy compds. that one metal site like the framework in the compd. structures with bimetallic sites stabilizes another site to accommodate different elements. Several typical metal compds. with bimetallic sites, including perovskite hydroxides, layered double hydroxide, spinel sulfide, perovskite fluoride, and spinel oxides, have been synthesized into high-entropy compds. High-entropy perovskite hydroxides (HEPHs) as representative compds. have been synthesized with a highly wide range of components even a septenary component and exhibit great oxygen evolution activity. Our work provides a design platform to develop more high-entropy compd. systems with promising development potential for electrocatalysts. - 19Wu, H.; Lu, Q.; Li, Y.; Wang, J.; Li, Y.; Jiang, R.; Zhang, J.; Zheng, X.; Han, X.; Zhao, N. Rapid joule-heating synthesis for manufacturing high-entropy oxides as efficient electrocatalysts. Nano Lett. 2022, 22, 6492– 6500, DOI: 10.1021/acs.nanolett.2c01147
19 吴 H.;卢 Q.;李英;王 J.;李英;江 R.;张 J.;郑 X.;韩 X.;Zhao， N.用于制造高熵氧化物作为高效电催化剂的快速焦耳热合成。纳米 Lett.2022， 22， 6492– 6500， DOI： 10.1021/acs.nanolett.2c01147Google Scholar 谷歌学术19Rapid Joule-Heating Synthesis for Manufacturing High-Entropy Oxides as Efficient ElectrocatalystsWu, Han; Lu, Qi; Li, Yajing; Wang, Jiajun; Li, Yingbo; Jiang, Rui; Zhang, Jinfeng; Zheng, Xuerong; Han, Xiaopeng; Zhao, Naiqin; Li, Jiajun; Deng, Yida; Hu, WenbinNano Letters (2022), 22 (16), 6492-6500CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)High-entropy oxide (HEO) including multiple principal elements possesses great potential for various fields such as basic physics, mech. properties, energy storage, and catalysis. However, the synthesis method of high-entropy compds. through the traditional heating approach is not conducive to the rapid properties screening, and the current elemental combinations of HEO are also highly limited. Herein, the authors report a rapid synthesis method for HEO through the Joule-heating of Ni foil with dozens of seconds. High-entropy rocksalt oxides (HERSO) with the new elemental combination, high-entropy spinel oxides (HESO), and high-entropy perovskite oxide (HEPO) were synthesized through the Joule-heating. The synthesized HERSO with new elemental combinations proves to be a great promotion of OER activity due to the synergy of multiple components and the continuous electronic structure exptl. and theor. The demonstrated synthesis approach and the new component combination of HERSO provide a broad platform for the development of high-entropy materials and catalysts. - 20Wei, J.; Rong, K.; Li, X.; Wang, Y.; Qiao, Z.; Fang, Y.; Dong, S. Deep eutectic solvent assisted facile synthesis of low-dimensional hierarchical porous high-entropy oxides. Nano Res. 2022, 15, 2756– 2763, DOI: 10.1007/s12274-021-3860-7
20 魏 J.;荣 K.;李 X.;王 Y.;乔 Z.;方 Y.;Dong， S.深度共熔溶剂辅助简单合成低维多级多孔高熵氧化物。纳米研究 2022， 15， 2756– 2763， DOI： 10.1007/s12274-021-3860-7Google Scholar 谷歌学术20Deep eutectic solvent assisted facile synthesis of low-dimensional hierarchical porous high-entropy oxidesWei, Jiale; Rong, Kai; Li, Xiaolong; Wang, Yuchen; Qiao, Zhen-An; Fang, Youxing; Dong, ShaojunNano Research (2022), 15 (3), 2756-2763CODEN: NRAEB5; ISSN:1998-0000. (Springer GmbH)High-entropy-oxides (HEOs), a new class of solids that contain five or more elemental species, have attracted increasing interests owing to their unique structures and fascinating physicochem. properties. However, it is a huge challenge to construct various nanostructured, esp. low-dimensional nanostructured HEOs under the high temp. synthetic conditions. Herein, a facile strategy using glucose-urea deep eutectic solvent (DES) as both a solvent and the carbon source of structure-directed template is proposed for the synthesis of various HEOs with two-dimentional (2D) nanonets and one-dimentional (1D) nanowires, including rock-salt (Co, Cu, Mg, Ni, Zn)O, spinel (Co, Cr, Fe, Mn, Ni)3O4, and perovskite La(Co, Cr, Fe, Mn, Ni)O3. The as-prepd. HEOs possessed five or more uniformly dispersed metal elements, large sp. surface areas (more than 25 m2·g-1), and a pure single-phase structure. In addn., high cooling rate (cooling in air or liq-N2-quenching) was indispensable to obtain a single-phase rock-salt (Co, Cu, Mg, Ni, Zn)O because of phase sepn. caused by copper. By taking advantage of unique features of HEOs, rock-salt (Co, Cu, Mg, Ni, Zn)O can function as a promising candidate for lithium-ion batteries (LIBs) anode material, which achieved excellent cycling stability. This work provides a feasible synthetic strategy for low-dimensional hierarchical HEOs, which creates new opportunities for the stable HEOs being highly active functional materials. - 21Liu, K.; Jin, H.; Huang, L.; Luo, Y.; Zhu, Z.; Dai, S.; Zhuang, X.; Wang, Z.; Huang, L.; Zhou, J. Puffing ultrathin oxides with nonlayered structures. Sci. Adv. 2022, 8, eabn2030 DOI: 10.1126/sciadv.abn2030
21 刘 K.;金 H.;黄 L.;罗 Y.;朱 Z.;戴，S.;庄 X.;王 Z.;黄 L.;周， J.具有非层状结构的普芬超薄氧化物。Sci. Adv.2022， 8， eabn2030 DOI： 10.1126/sciadv.abn2030 - 22Wei, S.; Kim, S.; Kang, J.; Zhang, Y.; Zhang, Y.; Furuhara, T.; Park, E. S.; Tasan, C. C. Natural-mixing guided design of refractory high-entropy alloys with as-cast tensile ductility. Nat. Mater. 2020, 19, 1175– 1181, DOI: 10.1038/s41563-020-0750-4
22 魏 S.;金，S.;康 J.;张 Y.;张 Y.;古原，T.;公园，ES;Tasan， C. C.具有铸态拉伸延展性的难熔高熵合金的自然混合导向设计。Nat. Mater.2020， 19， 1175– 1181， DOI： 10.1038/s41563-020-0750-4Google Scholar 谷歌学术22Natural-mixing guided design of refractory high-entropy alloys with as-cast tensile ductilityWei, Shaolou; Kim, Sang Jun; Kang, Jiyun; Zhang, Yong; Zhang, Yongjie; Furuhara, Tadashi; Park, Eun Soo; Tasan, Cemal CemNature Materials (2020), 19 (11), 1175-1181CODEN: NMAACR; ISSN:1476-1122. (Nature Research)Metallic alloys contg. multiple principal alloying elements have created a growing interest in exploring the property limits of metals and understanding the underlying phys. mechanisms. Refractory high-entropy alloys have drawn particular attention due to their high m.ps. and excellent softening resistance, which are the two key requirements for high-temp. applications. Their compositional space is immense even after considering cost and recyclability restrictions, providing abundant design opportunities. However, refractory high-entropy alloys often exhibit apparent brittleness and oxidn. susceptibility, which remain important challenges for their processing and application. Here, utilizing natural-mixing characteristics among refractory elements, we designed a Ti38V15Nb23Hf24 refractory high-entropy alloy that exhibits >20% tensile ductility in the as-cast state, and physicochem. stability at high temps. Exploring the underlying deformation mechanisms across multiple length scales, we observe that a rare β'-phase plays an intriguing role in the mech. response of this alloy. These results reveal the effectiveness of natural-mixing tendencies in expediting high-entropy alloy discovery. - 23Xie, J.; Zhang, X.; Zhang, H.; Zhang, J.; Li, S.; Wang, R.; Pan, B.; Xie, Y. Intralayered Ostwald ripening to ultrathin nanomesh catalyst with robust oxygen-evolving performance. Adv. Mater. 2017, 29, 1604765, DOI: 10.1002/adma.201604765
23 谢 J.;张 X.;张 H.;张 J.;李 S.;王 R.;潘，B.;Xie， Y.层内 Ostwald 成熟为具有强大析氧性能的超薄纳米网状催化剂。Adv. Mater.2017， 29， 1604765， DOI： 10.1002/ADMA.201604765 - 24Wang, S.; Yang, L.; He, G.; Shi, B.; Li, Y.; Wu, H.; Zhang, R.; Nunes, S.; Jiang, Z. Two-dimensional nanochannel membranes for molecular and ionic separations. Chem. Soc. Rev. 2020, 49, 1071– 1089, DOI: 10.1039/C9CS00751B
24 王 S.;杨 L.;他，G.;石 B.;李英;吴 H.;张 R.;努内斯，S.;江， Z.用于分子和离子分离的二维纳米通道膜。Chem. Soc. Rev.2020， 49， 1071– 1089， DOI： 10.1039/C9CS00751BGoogle Scholar 谷歌学术24Two-dimensional nanochannel membranes for molecular and ionic separationsWang, Shaofei; Yang, Leixin; He, Guangwei; Shi, Benbing; Li, Yifan; Wu, Hong; Zhang, Runnan; Nunes, Suzana; Jiang, ZhongyiChemical Society Reviews (2020), 49 (4), 1071-1089CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. Two-dimensional (2D) nanosheets have emerged as promising functional materials owing to their at. thickness and unique phys./chem. properties. By using 2D nanosheets as building blocks, diverse kinds of two-dimensional nanochannel membranes (2DNCMs) are being actively explored, in which mass transport occurs in the through-plane and interlayer channels of 2D nanosheets. The rational construction and phys./chem. microenvironment regulation of nanochannels are of vital significance for translating these 2D nanosheets into mol. sepn. membranes and ionic sepn. membranes. Focusing on the recent advances of 2DNCMs, in this review, various porous/nonporous 2D nanosheets and their derived nanochannels are first briefly introduced. Then we discuss the emerging top-down and bottom-up methods to synthesize high-quality 2D nanosheets and to prep. high-performance 2DNCMs. As the major part of this review, we focus on three types of nanochannels, which are based on nonporous nanosheets, intrinsically porous nanosheets and perforated nanosheets. The strategies for regulating the phys. and chem. microenvironments in the nanochannels are emphasized. The representative applications of 2DNCMs in mol. sepns. (gas sepn., liq. sepn.) and ionic sepns. are presented. Finally, the current challenges and future perspectives are highlighted. - 25Djenadic, R.; Sarkar, A.; Clemens, O.; Loho, C.; Botros, M.; Chakravadhanula, V. S. K.; Kubel, C.; Bhattacharya, S. S.; Gandhi, A. S.; Hahn, H. Multicomponent equiatomic rare earth oxides. Mater. Res. Lett. 2017, 5, 102– 109, DOI: 10.1080/21663831.2016.1220433
25 杰纳迪奇，R.;萨卡，A.;克莱门斯，O.;洛霍，C.;博特罗斯，M.;Chakravadhanula， VSK;库贝尔，C.;巴塔查里亚，SS;甘地，A. S.;Hahn， H.多组分双原子稀土氧化物。母公司。Res. Lett.2017， 5， 102– 109， DOI： 10.1080/21663831.2016.1220433Google Scholar 谷歌学术25Multicomponent equiatomic rare earth oxidesDjenadic, Ruzica; Sarkar, Abhishek; Clemens, Oliver; Loho, Christoph; Botros, Miriam; Chakravadhanula, Venkata S. K.; Kuebel, Christian; Bhattacharya, Subramshu S.; Gandhi, Ashutosh S.; Hahn, HorstMaterials Research Letters (2017), 5 (2), 102-109CODEN: MRLAC4; ISSN:2166-3831. (Taylor & Francis Ltd.)Multicomponent rare earth oxide (REO) nanocryst. powders contg. up to seven equiat. rare earth elements were successfully synthesized in a single-phase CaF2-type (Fm-3 m) structure. The addn. of more than six elements resulted in the formation of a secondary phase. Annealing at 1000°C for 1 h led to the formation of a single-phase (Ia-3) even in the 7-component system. In the absence of cerium (Ce4+), secondary phases were obsd. irresp. of the no. of cations or the extent of thermal treatment indicating that cerium cations played a crucial role in stabilizing the multicomponent REOs into a phase pure structure. - 26Gu, K.; Wang, D.; Xie, C.; Wang, T.; Huang, G.; Liu, Y.; Zou, Y.; Tao, L.; Wang, S. Defect-rich high-entropy oxide nanosheets for efficient 5-hydroxymethylfurfural electrooxidation. Angew. Chem., Int. Ed. 2021, 60, 20253– 20258, DOI: 10.1002/anie.202107390
26 顾 K.;王 D.;谢 C.;王 T.;黄 G.;刘 Y.;邹 Y.;陶，L.;Wang， S.用于高效 5-羟甲基糠醛电氧化的富含缺陷的高熵氧化物纳米片。安格。化学， 国际版.2021， 60， 20253– 20258， DOI： 10.1002/anie.202107390Google Scholar 谷歌学术26Defect-Rich High-Entropy Oxide Nanosheets for Efficient 5-Hydroxymethylfurfural ElectrooxidationGu, Kaizhi; Wang, Dongdong; Xie, Chao; Wang, Tehua; Huang, Gen; Liu, Yanbo; Zou, Yuqin; Tao, Li; Wang, ShuangyinAngewandte Chemie, International Edition (2021), 60 (37), 20253-20258CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)High-entropy oxides (HEOs), a new concept of entropy stabilization, exhibit unique structures and fascinating properties, and are thus important class of materials with significant technol. potential. However, the conventional high-temp. synthesis techniques tend to afford micron-scale HEOs with low surface area, and the catalytic activity of available HEOs is still far from satisfactory because of their limited exposed active sites and poor intrinsic activity. Here the authors report a low-temp. plasma strategy for prepg. defect-rich HEOs nanosheets with high surface area, and for the 1st time employ them for 5-hydroxymethylfurfural (HMF) electrooxidn. Owing to the nanosheets structure, abundant O vacancies, and high surface area, the quinary (FeCrCoNiCu)3O4 nanosheets deliver improved activity for HMF oxidn. with lower onset potential and faster kinetics, outperforming that of HEOs prepd. by high-temp. method. The authors' method opens new opportunities for synthesizing nanostructured HEOs with great potential applications. - 27Zhao, J.; Bao, J.; Yang, S.; Niu, Q.; Xie, R.; Zhang, Q.; Chen, M.; Zhang, P.; Dai, S. Exsolution-dissolution of supported metals on high-entropy Co3MnNiCuZnOx: toward sintering-resistant catalysis. ACS Catal. 2021, 11, 12247– 12257, DOI: 10.1021/acscatal.1c03228
27 赵 J.;鲍 J.;杨 S.;牛，Q.;谢 R.;张 Q.;陈 M.;张 P.;Dai， S.高熵 Co3MnNiCuZnOx 上负载金属的溶解：走向耐烧结催化。ACS Catal.2021， 11， 12247– 12257， DOI： 10.1021/acscatal.1c03228Google Scholar 谷歌学术27Exsolution-Dissolution of Supported Metals on High-Entropy Co3MnNiCuZnOx: Toward Sintering-Resistant CatalysisZhao, Jiahua; Bao, Jiafeng; Yang, Shize; Niu, Qiang; Xie, Rongyong; Zhang, Qiuyue; Chen, Mingshu; Zhang, Pengfei; Dai, ShengACS Catalysis (2021), 11 (19), 12247-12257CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)Herein, in situ generation of CuCoNi nanoalloys over a high-entropy oxide Co3MnNiCuZnOx matrix has been employed to generate a sintering-resistant metal-oxide interface for the CO2 hydrogenation reaction. The high-entropy Co3MnNiCuZnOx catalyst with a single reverse spinel structure was synthesized by a mechanochem. redox-based process and thermal treatment just at 600°C. Interestingly, the entropy-driven force allows the exsoln. and dissoln. of CuCoNi alloys under reductive and oxidative recycles, which results in the dynamics confinement of the supported metals. With high temp. (500°C) CO2 hydrogenation as a model reaction, the restriction of CuCoNi nanoparticles over a high-entropy Co3MnNiCuZnOx matrix guaranteed long-term thermal stability (>100 h). In comparison, binary CoMnOx as a control catalyst deactivated in 10 h. This high-entropy stabilization may inspire a no. of sintering-resistant catalysts in the near future. - 28An, L.; Zhang, H.; Zhu, J.; Xi, S.; Huang, B.; Sun, M.; Peng, Y.; Xi, P.; Yan, C. Balancing activity and stability in spinel cobalt oxides through geometrical sites occupation towards efficient electrocatalytic oxygen evolution. Angew. Chem., Int. Ed. 2023, 62, e202214600 DOI: 10.1002/anie.202214600
28 安，L.;张 H.;朱 J.;习， S.;黄 B.;孙，M.;彭 Y.;习，P.;Yan， C.通过几何位点占据实现高效电催化析氧来平衡尖晶石钴氧化物的活性和稳定性。安格。Chem.， Int. Ed.2023， 62， e202214600 DOI： 10.1002/anie.202214600Google Scholar 谷歌学术28Balancing Activity and Stability in Spinel Cobalt Oxides through Geometrical Sites Occupation towards Efficient Electrocatalytic Oxygen EvolutionAn, Li; Zhang, Hong; Zhu, Jiamin; Xi, Shibo; Huang, Bolong; Sun, Mingzi; Peng, Yong; Xi, Pinxian; Yan, Chun-HuaAngewandte Chemie, International Edition (2023), 62 (3), e202214600CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Designing active and stable oxygen evolution reaction (OER) catalysts are vitally important to various energy conversion devices. Herein, we introduce elements Ni and Mn into (Co)tet(Co2)octO4 nanosheets (NSs) at fixed geometrical sites, including Mnoct, Nioct, and Nitet, to optimize the initial geometrical structure and modulate the CoCo2O4 surface from oxygen-excess to oxygen-deficiency. The pristine (Ni,Mn)-(Co)tet(Co2)octO4 NSs shows excellent OER activity with an overpotential of 281.6 mV at a c.d. of 10 mA cm-2. Moreover, without damaging their initial activity, the activated (Act)-(Ni,Mn)-(Co)tet(Co2)octO4 NSs after surface reconstruction exhibit long-term stability of 100 h under 10 mA cm-2, 50 mA cm-2, or even 100 mA cm-2. The optimal balance between electroactivity and stability leads to remarkable OER performances, providing a pivotal guideline for designing ideal electrocatalysts and inspiring more works to focus on the dynamic change of each occupation site component. - 29Yu, M.; Budiyanto, E.; Tuysuz, H. Principles of water electrolysis and recent progress in cobalt-, nickel-, and iron-based oxides for the oxygen evolution reaction. Angew. Chem., Int. Ed. 2022, 61, e202103824 DOI: 10.1002/anie.202103824
29 余，M.;布迪扬托，E.;Tuysuz， H.水电解原理以及用于析氧反应的钴、镍和铁基氧化物的最新进展。安格。化学， 国际版.2022， 61， e202103824 DOI： 10.1002/anie.202103824Google Scholar 谷歌学术29Principles of Water Electrolysis and Recent Progress in Cobalt-, Nickel-, and Iron-Based Oxides for the Oxygen Evolution ReactionYu, Mingquan; Budiyanto, Eko; Tueysuez, HarunAngewandte Chemie, International Edition (2022), 61 (1), e202103824CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Water electrolysis that results in green hydrogen is the key process towards a circular economy. The supply of sustainable electricity and availability of oxygen evolution reaction (OER) electrocatalysts are the main bottlenecks of the process for large-scale prodn. of green hydrogen. A broad range of OER electrocatalysts have been explored to decrease the overpotential and boost the kinetics of this sluggish half-reaction. Co-, Ni-, and Fe-based catalysts have been considered to be potential candidates to replace noble metals due to their tunable 3d electron configuration and spin state, versatility in terms of crystal and electronic structures, as well as abundance in nature. This Review provides some basic principles of water electrolysis, key aspects of OER, and significant criteria for the development of the catalysts. It provides also some insights on recent advances of Co-, Ni-, and Fe-based oxides and a brief perspective on green hydrogen prodn. and the challenges of water electrolysis. - 30Han, L.; Dong, S.; Wang, E. Transition-metal (Co, Ni, and Fe)-based electrocatalysts for the water oxidation reaction. Adv. Mater. 2016, 28, 9266– 9291, DOI: 10.1002/adma.201602270
30 韩 L.;董，S.;Wang， E.用于水氧化反应的过渡金属（Co、Ni 和 Fe）基电催化剂。Adv. Mater.2016， 28， 9266– 9291， DOI： 10.1002/ADMA.201602270Google Scholar 谷歌学术30Transition-Metal (Co, Ni, and Fe)-Based Electrocatalysts for the Water Oxidation ReactionHan, Lei; Dong, Shaojun; Wang, ErkangAdvanced Materials (Weinheim, Germany) (2016), 28 (42), 9266-9291CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Increasing energy demands and environment awareness have promoted extensive research on the development of alternative energy conversion and storage technologies with high efficiency and environmental friendliness. Among them, water splitting is very appealing, and is receiving more and more attention. The crit. challenge of this renewable-energy technol. is to expedite the oxygen evolution reaction (OER) because of its slow kinetics and large overpotential. Therefore, developing efficient electrocatalysts with high catalytic activities is of great importance for high-performance water splitting. In the past few years, much effort has been devoted to the development of alternative OER electrocatalysts based on transition-metal elements that are low-cost, highly efficient, and have excellent stability. Here, recent progress on the design, synthesis, and application of OER electrocatalysts based on transition-metal elements, including Co, Ni, and Fe, is summarized, and some invigorating perspectives on the future developments are provided. - 31Abdelhafiz, A.; Tanvir, A. N. M.; Zeng, M.; Wang, B.; Ren, Z.; Harutyunyan, A. R.; Zhang, Y.; Li, J. Pulsed light synthesis of high entropy nanocatalysts with enhanced catalytic activity and prolonged stability for oxygen evolution reaction. Adv. Sci. 2023, 10, 2300426, DOI: 10.1002/advs.202300426
31 阿卜杜勒哈菲兹，A.;坦维尔，ARM;曾 M.;王 B.;任，Z.;Harutyunyan， A. R.;张 Y.;Li， J.高熵纳米催化剂的脉冲光合成，具有增强的催化活性和延长的析氧反应稳定性。Adv. Sci.2023， 10， 2300426， DOI： 10.1002/ADVS.202300426Google Scholar 谷歌学术31Pulsed Light Synthesis of High Entropy Nanocatalysts with Enhanced Catalytic Activity and Prolonged Stability for Oxygen Evolution ReactionAbdelhafiz, Ali; Tanvir, A. N. M.; Zeng, Minxiang; Wang, Baoming; Ren, Zhichu; Harutyunyan, Avetik R.; Zhang, Yanliang; Li, JuAdvanced Science (Weinheim, Germany) (2023), 10 (18), 2300426CODEN: ASDCCF; ISSN:2198-3844. (Wiley-VCH Verlag GmbH & Co. KGaA)The ability to synthesize compositionally complex nanostructures rapidly is a key to high-throughput functional materials discovery. In addn. to being time-consuming, a majority of conventional materials synthesis processes closely follow thermodn. equil., which limit the discovery of new classes of metastable phases such as high entropy oxides (HEO). Herein, a photonic flash synthesis of HEO nanoparticles at timescales of milliseconds is demonstrated. By leveraging the abrupt heating and cooling cycles induced by a high-power-d. xenon pulsed light, mixed transition metal salt precursors undergo rapid chem. transformations. Hence, nanoparticles form within milliseconds with a strong affinity to bind to the carbon substrate. Oxygen evolution reaction (OER) activity measurements of the synthesized nanoparticles demonstrate two orders of magnitude prolonged stability at high current densities, without noticeable decay in performance, compared to com. IrO2 catalyst. This superior catalytic activity originates from the synergistic effect of different alloying elements mixed at a high entropic state. It is found that Cr addn. influences surface activity the most by promoting higher oxidn. states, favoring optimal interaction with OER intermediates. The proposed high-throughput method opens new pathways toward developing next-generation functional materials for various electronics, sensing, and environmental applications, in addn. to renewable energy conversion. - 32Hooch Antink, W.; Lee, S.; Lee, H. S.; Shin, H.; Yoo, T. Y.; Ko, W.; Shim, J.; Na, G.; Sung, Y.-E.; Hyeon, T. High-valence metal-driven electronic modulation for boosting oxygen evolution reaction in high-entropy spinel oxide. Adv. Funct. Mater. 2024, 34, 2309438, DOI: 10.1002/adfm.202309438
32 酒 安廷克，W.;李，S.;李，HS;辛，H.;Yoo， T. Y.;高，W.;沈 J.;娜，G.;Sung， Y.-E.;Hyeon， T.高价金属驱动的电子调制，用于促进高熵尖晶石氧化物中的析氧反应。Adv. Funct.Mater.2024， 34， 2309438， DOI： 10.1002/adfm.202309438Google Scholar 谷歌学术32High-Valence Metal-Driven Electronic Modulation for Boosting Oxygen Evolution Reaction in High-Entropy Spinel OxideHooch Antink, Wytse; Lee, Seongbeom; Lee, Hyeon Seok; Shin, Heejong; Yoo, Tae Yong; Ko, Wonjae; Shim, Jaehyuk; Na, Geumbi; Sung, Yung-Eun; Hyeon, TaeghwanAdvanced Functional Materials (2024), 34 (1), 2309438CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)High-entropy spinel oxides (HESOs) are a promising class of electrocatalysts whose material properties and catalytic activity can be finely tuned by controlling the elemental compn. Although numerous HESOs are already reported, their compns. are primarily limited to the first-row transition metals. Herein, the synthesis of a high-entropy spinel (CrFeCoNiMo)3O4 nanosheet (HEO-NS) and its application as oxygen evolution reaction (OER) catalyst are reported. The high-entropy spinel displays a low overpotential of 255.3 mV at a c.d. of 10 mA cm-2 and excellent stability, outperforming the IrO2 benchmark. Careful anal. with XPS and X-ray absorption spectroscopy (XAS) reveals that the incorporation of high-valence Cr and Mo can activate the lattice oxygen by weakening the metal-oxygen bond and promoting the lattice oxygen mechanism (LOM). Furthermore, the catalyst can achieve a high c.d. of 1 A cm-2 at 1.71 V in a lab-scale electrolyzer, demonstrating the potential of HESOs for practical application. - 33Huang, Y.; Li, M.; Pan, F.; Zhu, Z.; Sun, H.; Tang, Y.; Fu, G. Plasma-induced Mo-doped Co3O4 with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting. Carbon Energy 2023, 5, e279 DOI: 10.1002/cey2.279
33 黄 Y.;李 M.;潘，F.;朱 Z.;孙，H.;唐 Y.;Fu， G.等离子体诱导的 Mo 掺杂 Co3O4 具有富氧空位，用于分解水中的电催化析氧。碳能源 2023， 5， e279 DOI： 10.1002/CEY2.279Google Scholar 谷歌学术33Plasma-induced Mo-doped Co3O4 with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splittingHuang, Yujie; Li, Meng; Pan, Fei; Zhu, Zhuoya; Sun, Huamei; Tang, Yawen; Fu, GengtaoCarbon Energy (2023), 5 (3), e279CODEN: CEANFS; ISSN:2637-9368. (John Wiley & Sons Australia, Ltd.)Heteroat. substitution and vacancy engineering of spinel oxides can theor. optimize the oxygen evolution reaction (OER) through charge redistribution and d-band center modification but still remain a great challenge in both the prepn. and catalytic mechanism. Herein, we proposed a novel and efficient Ar-plasma (P)-assisted strategy to construct heteroatom Mo-substituted and oxygen vacancies enriched hierarchical spinel Co3O4porous nanoneedle arrays in situ grown on carbon cloth (denoted P-Mo-Co3O4@CC) to improve the OER performance. Ar-plasma technol. can efficiently generate vacancy sites at the surface of hydroxide, which induces the anchoring of Mo anion salts through electrostatic interaction, finally facilitating the substitution of Mo atoms and the formation of oxygen vacancies on the Co3O4surface. The P-Mo-Co3O4@CC affords a low overpotential of only 276 mV at 10 mA cm-2 for the OER, which is 58 mV superior to that of Mo-free Co3O4@CC and surpasses com. RuO2 catalyst. The robust stability and satisfactory selectivity (nearly 100% Faradic efficiency) of P-Mo-Co3O4@CC for the OER are also demonstrated. Theor. studies demonstrate that Mo with variable valance states can efficiently regulates the at. ratio of Co3+/Co2+ and increases the no. of oxygen vacancies, thereby inducing charge redistribution and tuning the d-band center of Co3O4, which improve the adsorption energy of oxygen intermediates (e.g., *OOH) on P-Mo-Co3O4@CC during OER. Furthermore, the two-electrode OER//HER electrolyzer equipped with P-Mo-Co3O4@CC as anode displays a low operation potential of 1.54 V to deliver a c.d. of 10 mA cm-2, and also exhibits good reversibility and anticurrent fluctuation ability under simulated real energy supply conditions, demonstrating the great potential of P-Mo-Co3O4@CC in water electrolysis. - 34Feng, D.; Dong, Y.; Zhang, L.; Ge, X.; Zhang, W.; Dai, S.; Qiao, Z. Holey lamellar high-entropy oxide as an ultra-high-activity heterogeneous catalyst for solvent-free aerobic oxidation of benzyl alcohol. Angew. Chem., Int. Ed. 2020, 59, 19503– 19509, DOI: 10.1002/anie.202004892
34 冯 D.;董 Y.;张 L.;葛 X.;张 W.;戴，S.;Qiao， Z.Holey 层状高熵氧化物作为苯甲醇无溶剂有氧氧化的超高活性非均相催化剂。安格。化学，国际版 2020,59,19503– 19509，DOI ： 10.1002/anie.202004892Google Scholar 谷歌学术35Holey Lamellar High-Entropy Oxide as an Ultra-High-Activity Heterogeneous Catalyst for Solvent-free Aerobic Oxidation of Benzyl AlcoholFeng, Danyang; Dong, Yangbo; Zhang, Liangliang; Ge, Xin; Zhang, Wei; Dai, Sheng; Qiao, Zhen-AnAngewandte Chemie, International Edition (2020), 59 (44), 19503-19509CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)The development of noble-metal-free heterogeneous catalysts is promising for selective oxidn. of arom. alcs.; however, the relatively low conversion of non-noble metal catalysts under solvent-free atm. conditions hinders their industrial application. Now, a holey lamellar high entropy oxide (HEO) Co0.2Ni0.2Cu0.2Mg0.2Zn0.2O material with mesoporous structure is prepd. by an anchoring and merging process. The HEO has ultra-high catalytic activity for the solvent-free aerobic oxidn. of benzyl alc. Up to 98% conversion can be achieved in only 2 h, to our knowledge, the highest conversion of benzyl alc. by oxidn. to date. By regulating the catalytic reaction parameters, benzoic acid or benzaldehyde can be selectively optimized as the main product. Anal. characterizations and calcns. provide a deeper insight into the catalysis mechanism, revealing abundant oxygen vacancies and holey lamellar framework contribute to the ultra-high catalytic activity.
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董一林 ， 张丽华 ， 吴彤 ， 詹银波 ， 周博伟 ， 魏飞 ， 张东亮 ， 霞龙 . 用于能量转换反应的多维高熵材料：现状和未来趋势。 化学化学 2025， 18 （1） https://doi.org/10.1002/cssc.202401261 - Xiaomin Han, Ran Zhao, Jingjing Yang, Yahui Wang, Anqi Zhang, Zhifan Hu, Mengge Lv, Chuan Wu, Ying Bai. High-entropy materials for aqueous zinc metal batteries. Energy & Environmental Science 2025, 18
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韩晓敏 ， 赵然 ， 杨晶晶 ， 王亚辉 ， 张安琪 ， 胡志凡 ， 吕梦哥 ， 吴川 ， 白英 . 用于水性锌金属电池的高熵材料。 能源与环境科学 2025， 18 （1） ， 97-129.https://doi.org/10.1039/D4EE04442H - Kai Zhou, Shuanqiang Liu, Le Li. Recent advances of high-entropy materials as electrocatalysts for rechargeable Zn-air batteries. Journal of Alloys and Compounds 2025, 1011 , 178435. https://doi.org/10.1016/j.jallcom.2024.178435
周凯 ， 刘爽强 ， 李乐 . 高熵材料作为可充电锌空气电池电催化剂的最新进展。 合金与化合物杂志 2025， 1011 ， 178435.https://doi.org/10.1016/j.jallcom.2024.178435 - Jiahui Feng, Tao Zhang, Zhen Yang, Kunyan Qian, Xin Wang, Wanqing Song, Panzhe Qiao, Jia Ding, Wenbin Hu. Sub-5 nm amorphous iridium oxide nanosheets with synergistic multi-element doping for enhanced acidic oxygen evolution electrocatalysis. Chemical Engineering Journal 2025, 503 , 158213. https://doi.org/10.1016/j.cej.2024.158213
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李欣伟 ， 王正汉 ， 杨璐峰 ， 刘子玉 ， 黄胜驰 ， 何蓓贤 ， Howard Hsueh， 陈杰 ， 何伦华 ， 郭再平 ， 刘美林 ， 李文武 . 高熵合金负极的元素筛选工程：实现快速、稳健的储锂，具有最佳工作潜力。 先进材料 2024， 36 （48） https://doi.org/10.1002/adma.202409278 - Zhi-Jie Zhang, Ning Yu, Yi-Lin Dong, Guanqun Han, Han Hu, Yong-Ming Chai, Bin Dong. High entropy catalysts in electrolytic water splitting: A review from properties to applications. Chemical Engineering Journal 2024, 498 , 155736. https://doi.org/10.1016/j.cej.2024.155736
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Abstract 抽象
Figure 1 图 1
Figure 1. Schematic illustration of a self-lattice-framework with Ga mixing assistor for HEO synthesis.
图 1.用于 HEO 合成的带有 Ga 混合辅助器的自晶格框架的示意图。Figure 2 图 2
Figure 2. Structural and elemental characterizations of HEO nanosheets with different crystal structures. (a–d) XRD profiles (left) and elemental mappings (right) of the rock-salt (a), spinel (b), perovskite (c), and fluorite (d) structures, respectively. The inset of the XRD profile is a crystal structure diagram. Scale bar: (a) 1 μm, (b) 1 μm, (c) 500 nm, and (d) 300 nm.
Figure 3
Figure 3. Effect of structural and mixing modulation on the formation of single-phase HEO. (a,b) XRD pattern and EDS mapping of the HEO without a Ga assistor. Scale bar: 500 nm. (c) Formation energy of single-phase HEO before and after introducing Ga assistor. (d) Schematic illustration of multiphase oxide formation without Ga assistor.
Figure 4
Figure 4. Electrocatalytic performance of HEO nanosheets toward the OER. (a) Polarization curves. (b) Comparison of overpotential of different samples at 10 mA cm–2. (c) Tafel slopes. (d) Chronopotentiometric curve of the HEO (GaFeCoNiMo oxide) at 10 mA cm–2. The curves and columns with different colors in (a–d) represent different HEO systems. Red: GaFeCoNiMo oxide. Blue: GaFeCoNiCr oxide. Gray: GaFeCoNi oxide. Orange: RuO2.
References
This article references 34 other publications.
- 1Sun, Y.; Dai, S. High-entropy materials for catalysis: A new frontier. Sci. Adv. 2021, 7, eabg1600 DOI: 10.1126/sciadv.abg1600There is no corresponding record for this reference.
- 2Li, T.; Yao, Y.; Huang, Z.; Xie, P.; Liu, Z.; Yang, M.; Gao, J.; Zeng, K.; Brozena, A. H.; Pastel, G. Denary oxide nanoparticles as highly stable catalysts for methane combustion. Nat. Catal. 2021, 4, 62– 70, DOI: 10.1038/s41929-020-00554-12Denary oxide nanoparticles as highly stable catalysts for methane combustionLi, Tangyuan; Yao, Yonggang; Huang, Zhennan; Xie, Pengfei; Liu, Zhenyu; Yang, Menghao; Gao, Jinlong; Zeng, Kaizhu; Brozena, Alexandra H.; Pastel, Glenn; Jiao, Miaolun; Dong, Qi; Dai, Jiaqi; Li, Shuke; Zong, Han; Chi, Miaofang; Luo, Jian; Mo, Yifei; Wang, Guofeng; Wang, Chao; Shahbazian-Yassar, Reza; Hu, LiangbingNature Catalysis (2021), 4 (1), 62-70CODEN: NCAACP; ISSN:2520-1158. (Nature Research)Oxide nanoparticles with elemental and structural diversity are widely studied for catalysis and energy applications. While compositional control holds great promise for materials discovery, current oxide nanoparticles are typically limited to a few cations due to the intrinsic complexity in nanoscale multi-element mixing. Here we report the rational design and synthesis of single-phase multi-element oxide nanoparticles with tunable compn., size and structure. We have identified temp.-, oxidn.- and entropy-driven synthesis strategies to mix a range of elements with largely dissimilar oxidn. potentials (including palladium), thus greatly expanding the compositional space. Through rapid synthesis and screening, we obtained a denary multi-element oxide catalyst showing high performance and superior stability for catalytic methane combustion over 100 h due to the high-entropy design and stabilization. Our work therefore provides a viable synthesis route with clear guidelines for multi-element oxide nanoparticles and enables materials design in the multi-element space towards highly stable catalysts.
- 3Xu, H.; Zhang, Z.; Liu, J.; Do-Thanh, C.; Chen, H.; Xu, S.; Lin, Q.; Jiao, Y.; Wang, J.; Wang, Y. Entropy-stabilized single-atom Pd catalysts via high-entropy fluorite oxide supports. Nat. Commun. 2020, 11, 3908, DOI: 10.1038/s41467-020-17738-93Entropy-stabilized single-atom Pd catalysts via high-entropy fluorite oxide supportsXu, Haidi; Zhang, Zihao; Liu, Jixing; Do-Thanh, Chi-Linh; Chen, Hao; Xu, Shuhao; Lin, Qinjing; Jiao, Yi; Wang, Jianli; Wang, Yun; Chen, Yaoqiang; Dai, ShengNature Communications (2020), 11 (1), 3908CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Single-atom catalysts (SACs) have attracted considerable attention in the catalysis community. However, fabricating intrinsically stable SACs on traditional supports (N-doped carbon, metal oxides, etc.) remains a formidable challenge, esp. under high-temp. conditions. Here, we report a novel entropy-driven strategy to stabilize Pd single-atom on the high-entropy fluorite oxides (CeZrHfTiLa)Ox (HEFO) as the support by a combination of mech. milling with calcination at 900°C. Characterization results reveal that single Pd atoms are incorporated into HEFO (Pd1@HEFO) sublattice by forming stable Pd-O-M bonds (M = Ce/Zr/La). Compared to the traditional support stabilized catalysts such as Pd@CeO2, Pd1@HEFO affords the improved reducibility of lattice oxygen and the existence of stable Pd-O-M species, thus exhibiting not only higher low-temp. CO oxidn. activity but also outstanding resistance to thermal and hydrothermal degrdn. This work therefore exemplifies the superiority of high-entropy materials for the prepn. of SACs.
- 4Li, Y.; Bai, X.; Yuan, D.; Yu, C.; San, X.; Guo, Y.; Zhang, L.; Ye, J. Cu-based high-entropy two-dimensional oxide as stable and active photothermal catalyst. Nat. Commun. 2023, 14, 3171, DOI: 10.1038/s41467-023-38889-54Cu-based high-entropy two-dimensional oxide as stable and active photothermal catalystLi, Yaguang; Bai, Xianhua; Yuan, Dachao; Yu, Chenyang; San, Xingyuan; Guo, Yunna; Zhang, Liqiang; Ye, JinhuaNature Communications (2023), 14 (1), 3171CODEN: NCAOBW; ISSN:2041-1723. (Nature Portfolio)Cu-based nanocatalysts are the cornerstone of various industrial catalytic processes. Synergistically strengthening the catalytic stability and activity of Cu-based nanocatalysts is an ongoing challenge. Herein, the high-entropy principle is applied to modify the structure of Cu-based nanocatalysts, and a PVP templated method is invented for generally synthesizing six-eleven dissimilar elements as high-entropy two-dimensional (2D) materials. Taking 2D Cu2Zn1Al0.5Ce5Zr0.5Ox as an example, the high-entropy structure not only enhances the sintering resistance from 400 °C to 800 °C but also improves its CO2 hydrogenation activity to a pure CO prodn. rate of 417.2 mmol g-1 h-1 at 500 °C, 4 times higher than that of reported advanced catalysts. When 2D Cu2Zn1Al0.5Ce5Zr0.5Ox are applied to the photothermal CO2 hydrogenation, it exhibits a record photochem. energy conversion efficiency of 36.2%, with a CO generation rate of 248.5 mmol g-1 h-1 and 571 L of CO yield under ambient sunlight irradn. The high-entropy 2D materials provide a new route to simultaneously achieve catalytic stability and activity, greatly expanding the application boundaries of photothermal catalysis.
- 5Meng, Z.; Gong, X.; Xu, J.; Sun, X.; Zeng, F.; Du, Z.; Hao, Z.; Shi, W.; Yu, S.; Hu, X. A general strategy for preparing hollow spherical multilayer structures of oxygen-rich vacancy transition metal oxides, especially high entropy perovskite oxides. Chem. Eng. J. 2023, 457, 141242, DOI: 10.1016/j.cej.2022.1412425A general strategy for preparing hollow spherical multilayer structures of Oxygen-Rich vacancy transition metal Oxides, especially high entropy perovskite oxidesMeng, Zeshuo; Gong, Xiliang; Xu, Jian; Sun, Xucong; Zeng, Fanda; Du, Zhengyan; Hao, Zeyu; Shi, Wei; Yu, Shansheng; Hu, Xiaoying; Tian, HongweiChemical Engineering Journal (Amsterdam, Netherlands) (2023), 457 (), 141242CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)The development of excellent synthetic strategies and exploration of the synthesis mechanisms of active site-rich high-entropy oxides are crucial for high-entropy materials. Herein, a universal synthetic method was designed to prep. La(Co0.2Mn0.2Fe0.2Ni0.2Cu0.2)O3 (HSM-HEPs) with hollow spherical multilayer structure (HSM) and rich oxygen vacancies. The tracking characterization was used during the synthesis of HSM-HEPs to clarify the formation of multi-shell, multi-vacancy, and single-phase crystal structures of HSM-HEPs. Three basic conditions were proposed to obtain vacancy-rich high-entropy materials. The exptl. data showed excellent electrochem. activity and extraordinary stability of HSM-HEPs electrode materials owing to the formation of HSM structure, abundant oxygen vacancies, abundant elemental compn., and high sp. surface area. When used as supercapacitor electrode materials, HSM-HEPs exhibited a high specific capacity of 625 F g-1 with an excellent capacity retention rate of 88% after 10,000 cycles. Besides, HSM-HEPs achieved efficient water oxidn. with an overpotential of 309 mV at 10 mA cm-2. Furthermore, the proposed strategy can be extended to the synthesis of metal oxides with various representative HSM crystal structures. Overall, the designed and tuned synthetic method looks promising for the formation of more active sites-high-entropy materials.
- 6Lun, Z.; Ouyang, B.; Kwon, D.; Ha, Y.; Foley, E. E.; Huang, T.; Cai, Z.; Kim, H.; Balasubramanian, M.; Sun, Y. Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries. Nat. Mater. 2021, 20, 214– 221, DOI: 10.1038/s41563-020-00816-06Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteriesLun, Zhengyan; Ouyang, Bin; Kwon, Deok-Hwang; Ha, Yang; Foley, Emily E.; Huang, Tzu-Yang; Cai, Zijian; Kim, Hyunchul; Balasubramanian, Mahalingam; Sun, Yingzhi; Huang, Jianping; Tian, Yaosen; Kim, Haegyeom; McCloskey, Bryan D.; Yang, Wanli; Clement, Raphaele J.; Ji, Huiwen; Ceder, GerbrandNature Materials (2021), 20 (2), 214-221CODEN: NMAACR; ISSN:1476-1122. (Nature Research)High-entropy (HE) ceramics, by analogy with HE metallic alloys, are an emerging class of solid solns. composed of a large no. of species. These materials offer the benefit of large compositional flexibility and can be used in a wide variety of applications, including thermoelecs., catalysts, superionic conductors and battery electrodes. It is shown here that the HE concept can lead to very substantial improvements in performance in battery cathodes. Among lithium-ion cathodes, cation-disordered rocksalt (DRX)-type materials are an ideal platform within which to design HE materials because of their demonstrated chem. flexibility. By comparing a group of DRX cathodes contg. two, four or six transition metal (TM) species, it is shown that short-range order systematically decreases, whereas energy d. and rate capability systematically increase, as more TM cation species are mixed together, despite the total metal content remaining fixed. A DRX cathode with six TM species achieves 307 mAh g-1 (955 Wh kg-1) at a low rate (20 mA g-1), and retains > 170 mAh g-1 when cycling at a high rate of 2,000 mA g-1. To facilitate further design in this HE DRX space, a compatibility anal. is presented of 23 different TM ions, and a phase-pure HE DRX compd. contg. 12 TM species is synthesized as a proof of concept.
- 7Zhao, C.; Ding, F.; Lu, Y.; Chen, L.; Hu, Y. High-entropy layered oxide cathodes for sodium-ion batteries. Angew. Chem., Int. Ed. 2020, 59, 264– 269, DOI: 10.1002/anie.2019121717High-Entropy Layered Oxide Cathodes for Sodium-Ion BatteriesZhao, Chenglong; Ding, Feixiang; Lu, Yaxiang; Chen, Liquan; Hu, Yong-ShengAngewandte Chemie, International Edition (2020), 59 (1), 264-269CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Material innovation on high-performance Na-ion cathodes and the corresponding understanding of structural chem. still remain a challenge. Herein, a new concept is reported of high-entropy strategy to design layered oxide cathodes for Na-ion batteries. An example of layered O3-type NaNi0.12Cu0.12Mg0.12Fe0.15Co0.15Mn0.1Ti0.1Sn0.1Sb0.04O2 has been demonstrated, which exhibits the longer cycling stability (ca. 83% of capacity retention after 500 cycles) and the outstanding rate capability (ca. 80% of capacity retention at the rate of 5.0 C). A highly reversible phase-transition behavior between O3 and P3 structures occurs during the charge-discharge process, and importantly, this behavior is delayed with > 60% of the total capacity being stored in O3-type region. Possible mechanism can be attributed to the multiple transition-metal components in this high-entropy material which can accommodate the changes of local interactions during Na+ (de)intercalation. This strategy opens new insights into the development of advanced cathode materials.
- 8Johnstone, G. H. J.; Gonzalez-Rivas, M. U.; Taddei, K. M.; Sutarto, R.; Sawatzky, G. A.; Green, R. J.; Oudah, M.; Hallas, A. M. Entropy engineering and tunable magnetic order in the spinel high-entropy oxide. J. Am. Chem. Soc. 2022, 144, 20590– 20600, DOI: 10.1021/jacs.2c067688Entropy Engineering and Tunable Magnetic Order in the Spinel High-Entropy OxideJohnstone, Graham H. J.; Gonzalez-Rivas, Mario U.; Taddei, Keith M.; Sutarto, Ronny; Sawatzky, George A.; Green, Robert J.; Oudah, Mohamed; Hallas, Alannah M.Journal of the American Chemical Society (2022), 144 (45), 20590-20600CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Spinel oxides are an ideal setting to explore the interplay between configurational entropy, site selectivity, and magnetism in high-entropy oxides (HEOs). In this work, we characterize the magnetic properties of the spinel (Cr, Mn, Fe, Co, Ni)3O4 and study the evolution of its magnetism as a function of nonmagnetic gallium substitution. Across the range of compns. studied here, from 0 to 40% Ga, magnetic susceptibility and powder neutron diffraction measurements show that ferrimagnetic order is robust in the spinel HEO. However, we also find that the ferrimagnetic order is highly tunable, with the ordering temp., satd. and sublattice moments, and magnetic hardness all varying significantly as a function of Ga concn. Through X-ray absorption and magnetic CD, we are able to correlate this magnetic tunability with strong site selectivity between the various cations and the tetrahedral and octahedral sites in the spinel structure. In particular, we find that while Ni and Cr are largely unaffected by the substitution with Ga, the occupancies of Mn, Co, and Fe are each significantly redistributed. Ga substitution also requires an overall redn. in the transition metal valence, and this is entirely accommodated by Mn. Finally, we show that while site selectivity has an overall suppressing effect on the configurational entropy, over a certain range of compns., Ga substitution yields a striking increase in the configurational entropy and may confer addnl. stabilization. Spinel oxides can be tuned seamlessly from the low-entropy to the high-entropy regime, making this an ideal platform for entropy engineering.
- 9Joshi, A.; Chakrabarty, S.; Akella, S. H.; Saha, A.; Mukherjee, A.; Schmerling, B.; Ejgenberg, M.; Sharma, R.; Noked, M. High-entropy Co-free O3-type layered oxyfluoride: A promising air-stable cathode for sodium-ion batteries. Adv. Mater. 2023, 35, 2304440, DOI: 10.1002/adma.2023044409High-Entropy Co-Free O3-Type Layered Oxyfluoride: A Promising Air-Stable Cathode for Sodium-Ion BatteriesJoshi, Akanksha; Chakrabarty, Sankalpita; Akella, Sri Harsha; Saha, Arka; Mukherjee, Ayan; Schmerling, Bruria; Ejgenberg, Michal; Sharma, Rosy; Noked, MalachiAdvanced Materials (Weinheim, Germany) (2023), 35 (51), 2304440CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Sodium-ion batteries have recently emerged as a promising alternative to lithium-based batteries, driven by an ever-growing demand for electricity storage systems. The present workproposes a cobalt-free high-capacity cathode for sodium-ion batteries, synthesized using a high-entropy approach. The high-entropy approach entails mixing more than five elements in a single phase; hence, obtaining the desired properties is a challenge since this involves the interplay between different elements. Here, instead of oxide, oxyfluoride is chosen to suppress oxygen loss during long-term cycling. Supplement to this, lithium is introduced in the compn. to obtain high configurational entropy and sodium vacant sites, thus stabilizing the crystal structure, accelerating the kinetics of intercalation/deintercalation, and improving the air stability of the material. With the optimization of the cathode compn., a reversible capacity of 109 mAh g-1 (2-4 V) and 144 mAh g-1 (2-4.3 V) is obsd. in the first few cycles, along with a significant improvement in stability during prolonged cycling. Furthermore, in situ and ex situ diffraction studies during charging/discharging reveal that the high-entropy strategy successfully suppresses the complex phase transition. The impressive outcomes of the present work strongly motivate the pursuit of the high-entropy approach to develop efficient cathodes for sodium-ion batteries.
- 10Zhao, B.; Du, Y.; Yan, Z.; Rao, L.; Chen, G.; Yuan, M.; Yang, L.; Zhang, J.; Che, R. Structural defects in phase-regulated high-entropy oxides toward superior microwave absorption properties. Adv. Funct. Mater. 2023, 33, 2209924, DOI: 10.1002/adfm.20220992410Structural Defects in Phase-Regulated High-Entropy Oxides toward Superior Microwave Absorption PropertiesZhao, Biao; Du, Yiqian; Yan, Zhikan; Rao, Longjun; Chen, Guanyu; Yuan, Mingyue; Yang, Liting; Zhang, Jincang; Che, RenchaoAdvanced Functional Materials (2023), 33 (1), 2209924CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)High-entropy (HE) oxides have become increasingly popular as electromagnetic wave-absorbing materials owing to their customizable structure and unique HE effects. However, the weak loss property of single-phase HE ceramics and the approaches implemented to improve them based on semi-empirical rules severely limit their development. Herein, two biphasic HE oxides are prepd. by simple sintering to realize accurate regulation of crystal phases and structural defects. It is verified that HE effects cause various defects that are beneficial for microwave dissipation within complex-phase ceramics. In spinel/perovskite HE oxides, around the interface of spinel (111) and perovskite (110) planes, notable stress concns. and lattice distortions are directly obsd., inducing numerous point defects and stacking faults. Interestingly, besides the existing heterogeneous interface of rock salt (220)/spinel (220) plane and defects, rock salt/spinel HE oxides enabled synergistic effects via the precise regulation of components' phase. Driven by structural defects and multi-phases in HE complexes, the intense polarization is evidently found, confirmed by the first-principles calcns. Accordingly, the two complex-phase HE oxides demonstrate excellent microwave absorption performance, and the minimal reflection loss of -54.5 dB is achieved. Therefore, this study provides valuable guidelines for the design of microwave absorbers using HE oxides.
- 11Li, Y.; Yu, Z.; Wang, L.; Weng, Y.; Tang, C.; Yin, X.; Han, K.; Wu, H.; Yu, X.; Wong, L. Electronic-reconstruction-enhanced hydrogen evolution catalysis in oxide polymorphs. Nat. Commun. 2019, 10, 3149, DOI: 10.1038/s41467-019-11124-w11Electronic-reconstruction-enhanced hydrogen evolution catalysis in oxide polymorphsLi Yangyang; Wang Ling; Wu Haijun; Wang John; Pennycook Stephen J; Venkatesan Thirumalai; Xue Jun Min; Chen Jingsheng; Yu Zhi Gen; Zhang Yong-Wei; Weng Yakui; Tang Chi Sin; Yin Xinmao; Wee Andrew T S; Venkatesan Thirumalai; Tang Chi Sin; Wee Andrew T S; Pennycook Stephen J; Venkatesan Thirumalai; Yin Xinmao; Yu Xiaojiang; Breese Mark B H; Han Kun; Wang Xiao Renshaw; Wong Lai Mun; Chai Jianwei; Wang Shijie; Wan Dongyang; Pennycook Stephen J; Venkatesan Thirumalai; Dong ShuaiNature communications (2019), 10 (1), 3149 ISSN:.Transition metal oxides exhibit strong structure-property correlations, which has been extensively investigated and utilized for achieving efficient oxygen electrocatalysts. However, high-performance oxide-based electrocatalysts for hydrogen evolution are quite limited, and the mechanism still remains elusive. Here we demonstrate the strong correlations between the electronic structure and hydrogen electrocatalytic activity within a single oxide system Ti2O3. Taking advantage of the epitaxial stabilization, the polymorphism of Ti2O3 is extended by stabilizing bulk-absent polymorphs in the film-form. Electronic reconstructions are realized in the bulk-absent Ti2O3 polymorphs, which are further correlated to their electrocatalytic activity. We identify that smaller charge-transfer energy leads to a substantial enhancement in the electrocatalytic efficiency with stronger hybridization of Ti 3d and O 2p orbitals. Our study highlights the importance of the electronic structures on the hydrogen evolution activity of oxide electrocatalysts, and also provides a strategy to achieve efficient oxide-based hydrogen electrocatalysts by epitaxial stabilization of bulk-absent polymorphs.
- 12Li, Q.; Wu, J.; Wu, T.; Jin, H.; Zhang, N.; Li, J.; Liang, W.; Liu, M.; Huang, L.; Zhou, J. Phase engineering of atomically thin perovskite oxide for highly active oxygen evolution. Adv. Funct. Mater. 2021, 31, 2102002, DOI: 10.1002/adfm.20210200212Phase Engineering of Atomically Thin Perovskite Oxide for Highly Active Oxygen EvolutionLi, Qun; Wu, Jiabin; Wu, Tao; Jin, Hongrun; Zhang, Nian; Li, Jia; Liang, Wenxi; Liu, Meilin; Huang, Liang; Zhou, JunAdvanced Functional Materials (2021), 31 (38), 2102002CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)Ultrathin perovskite oxides with tailored crystal structures are promising catalysts for O evolution reaction (OER) owing to their high intrinsic catalytic activity and large exposed active surface area. However, the synthesis of phase-controllable perovskite oxide nanosheets with thickness down to a few nanometers remains a challenge since the formation of a perovskite phase often requires long-time calcination at high temps. Here, a salt-templated strategy for fabrication of atomically thin perovskite oxide of LaMnO3 with tailored phase structure for highly active OER catalysts is reported. The orthorhombic structure of LaMnO3 nanosheets demonstrates much higher electrochem. activity than the tetragonal or hexagonal phase and the benchmark IrO2 catalyst, exhibiting extremely small onset overpotential (≈70 mV) and a low overpotential (≈324 mV at 10 mA cm-2disk) in alk. soln. The remarkable OER activity of this catalyst is attributed to the desired surface binding energetics (or the unique electronic structures) inherent to the orthorhombic phase, as predicted by d. functional theory calcns. and confirmed by exptl. measurements. Further, it is believed that this study paves a new path toward rational the design of perovskite oxide nanosheets with desired phase structures for many applications.
- 13Amiri, A.; Shahbazian-Yassar, R. Recent progress of high-entropy materials for energy storage and conversion. J. Mater. Chem. A 2021, 9, 782– 823, DOI: 10.1039/D0TA09578H13Recent progress of high-entropy materials for energy storage and conversionAmiri, Azadeh; Shahbazian-Yassar, RezaJournal of Materials Chemistry A: Materials for Energy and Sustainability (2021), 9 (2), 782-823CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)A review. The emergence of high-entropy materials (HEMs) with their excellent mech. properties, stability at high temps., and high chem. stability is poised to yield new advancement in the performance of energy storage and conversion technologies. This review covers the recent developments in catalysis, water splitting, fuel cells, batteries, supercapacitors, and hydrogen storage enabled by HEMs covering metallic, oxide, and non-oxide alloys. Here, first, the primary rules for the proper selection of the elements and the formation of a favorable single solid soln. phase in HEMs are defined. Furthermore, recent developments in different fields of energy conversion and storage achieved by HEMs are discussed. Higher electrocatalytic and catalytic activities with longer cycling stability and durability compared to conventional noble metal-based catalysts are reported for high-entropy materials. In electrochem. energy storage systems, high-entropy oxides and alloys have shown superior performance as anode and cathode materials with long cycling stability and high capacity retention. Also, when used as metal hydrides for hydrogen storage, remarkably high hydrogen storage capacity and structural stability are obsd. for HEMs. In the end, future directions and new energy-related technologies that can be enabled by the application of HEMs are outlined.
- 14Cao, G.; Liang, J.; Guo, Z.; Yang, K.; Wang, G.; Wang, H.; Wan, X.; Li, Z.; Bai, Y.; Zhang, Y. Liquid metal for high-entropy alloy nanoparticles synthesis. Nature 2023, 619, 73– 77, DOI: 10.1038/s41586-023-06082-914Liquid metal for high-entropy alloy nanoparticles synthesisCao, Guanghui; Liang, Jingjing; Guo, Zenglong; Yang, Kena; Wang, Gang; Wang, Huiliu; Wan, Xuhao; Li, Zeyuan; Bai, Yijia; Zhang, Yile; Liu, Junlin; Feng, Yanpeng; Zheng, Zhenying; Lu, Cai; He, Guangzhi; Xiong, Zeyou; Liu, Ze; Chen, Shengli; Guo, Yuzheng; Zeng, Mengqi; Lin, Junhao; Fu, LeiNature (London, United Kingdom) (2023), 619 (7968), 73-77CODEN: NATUAS; ISSN:1476-4687. (Nature Portfolio)High-entropy alloy nanoparticles (HEA-NPs) show great potential as functional materials1-3. However, thus far, the realized high-entropy alloys have been restricted to palettes of similar elements, which greatly hinders the material design, property optimization and mechanistic exploration for different applications4,5. Herein, we discovered that liq. metal endowing neg. mixing enthalpy with other elements could provide a stable thermodn. condition and act as a desirable dynamic mixing reservoir, thus realizing the synthesis of HEA-NPs with a diverse range of metal elements in mild reaction conditions. The involved elements have a wide range of at. radii (1.24-1.97 Å) and m.ps. (303-3,683 K). We also realized the precisely fabricated structures of nanoparticles via mixing enthalpy tuning. Moreover, the real-time conversion process (i.e., from liq. metal to cryst. HEA-NPs) is captured in situ, which confirmed a dynamic fission-fusion behavior during the alloying process.
- 15Nie, S.; Wu, L.; Zhao, L.; Zhang, P. Enthalpy-change driven synthesis of high-entropy perovskite nanoparticles. Nano Res. 2022, 15, 4867– 4872, DOI: 10.1007/s12274-021-3803-315Enthalpy-change driven synthesis of high-entropy perovskite nanoparticlesNie, Siyang; Wu, Liang; Zhao, Lingci; Zhang, PengfeiNano Research (2022), 15 (6), 4867-4872CODEN: NRAEB5; ISSN:1998-0000. (Springer GmbH)Due to their diverse and tunable compn., distorted lattice and excellent stability, high-entropy ceramics (HECs) hold great promise for catalysis, esp. when they present as nanoparticles (NPs). However, current HECs are typically limited to bulky materials with none or fewer defects, because high synthetic temp. (e.g., 1,000-1,200 °C) is usually required to highlight the entropic contribution (TΔS) in ΔG = ΔH - TΔS. Being different with previous strategies, a neg. Gibbs free energy for HECs crystn. is obtained by dramatically decreasing the mixing enthalpy (ΔH). Guided by this principle, single-phase high-entropy La(Ni0.2Mn0.2Cu0.2Fe0.2Co0.2)O3-δ perovskite (HE-LMO) NPs were prepd. at a relatively low temp. (≤ 500 °C). Interestingly, abundant oxygen vacancies were directly created within HE-LMO NPs, which exhibited good activity in catalytic oxidn. Meanwhile, the high-entropy structure endows as-made HE-LMO with robust stability even with 5 vol.% water in feeding gas. D. functional theory (DFT) calcns. revealed that the defective sites in HE-LMO NPs facilitated the charge transfer from HE-LMO to CO, thus activating the adsorbed CO gas. The current work may inspire future design and synthesis of HECs NPs. [graphic not available: see fulltext].
- 16Xie, H.; Qin, M.; Hong, M.; Rao, J.; Guo, M.; Luo, J.; Hu, L. Rapid liquid phase-assisted ultrahigh-temperature sintering of high-entropy ceramic composites. Sci. Adv. 2022, 8, eabn8241 DOI: 10.1126/sciadv.abn8241There is no corresponding record for this reference.
- 17Zheng, X.; Gao, X.; Vila, R. A.; Jiang, Y.; Wang, J. Y.; Xu, R.; Zhang, R.; Xiao, X.; Zhang, P.; Greenburg, L. C. Hydrogen-substituted graphdiyne-assisted ultrafast sparking synthesis of metastable nanomaterials. Nat. Nanotechnol. 2023, 18, 153– 159, DOI: 10.1038/s41565-022-01272-417Hydrogen-substituted graphdiyne-assisted ultrafast sparking synthesis of metastable nanomaterialsZheng, Xueli; Gao, Xin; Vila, Rafael A.; Jiang, Yue; Wang, Jingyang; Xu, Rong; Zhang, Rui; Xiao, Xin; Zhang, Pu; Greenburg, Louisa C.; Yang, Yufei; Xin, Huolin L.; Zheng, Xiaolin; Cui, YiNature Nanotechnology (2023), 18 (2), 153-159CODEN: NNAABX; ISSN:1748-3387. (Nature Portfolio)Metastable nanomaterials, such as single-atom and high-entropy systems, with exciting phys. and chem. properties are increasingly important for next-generation technologies. Here, we developed a hydrogen-substituted graphdiyne-assisted ultrafast sparking synthesis (GAUSS) platform for the prepn. of metastable nanomaterials. The GAUSS platform can reach an ultra-high reaction temp. of 3,286 K within 8 ms, a rate exceeding 105 K s-1. Controlling the compn. and chem. of the hydrogen-substituted graphdiyne aerogel framework, the reaction temp. can be tuned from 1,640 K to 3,286 K. We demonstrate the versatility of the GAUSS platform with the successful synthesis of single atoms, high-entropy alloys and high-entropy oxides. Electrochem. measurements and d. functional theory show that single atoms synthesized by GAUSS enhance the lithium-sulfur redox reaction kinetics in all-solid-state lithium-sulfur batteries. Our design of the GAUSS platform offers a powerful way to synthesize a variety of metastable nanomaterials.
- 18Wu, H.; Lu, Q.; Li, Y.; Zhao, M.; Wang, J.; Li, Y.; Zhang, J.; Zheng, X.; Han, X.; Zhao, N. Structural framework-guided universal design of high-entropy compounds for efficient energy catalysis. J. Am. Chem. Soc. 2023, 145, 1924– 1935, DOI: 10.1021/jacs.2c1229518Structural Framework-Guided Universal Design of High-Entropy Compounds for Efficient Energy CatalysisWu, Han; Lu, Qi; Li, Yajing; Zhao, Menghan; Wang, Jiajun; Li, Yingbo; Zhang, Jinfeng; Zheng, Xuerong; Han, Xiaopeng; Zhao, Naiqin; Li, Jiajun; Liu, Yanhui; Deng, Yida; Hu, WenbinJournal of the American Chemical Society (2023), 145 (3), 1924-1935CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)High-entropy compds. with extraordinary properties due to the synergistic effect of multiple components have exhibited great potential and attracted extensive attention in various fields, including physics, mech. property anal., and energy storage. Achieving universal stability and synthesis of high-entropy compds. with a wide range of components and structures continues to be difficult due to the high complexity of multicomponent mixing. Here, we propose a design strategy with high generality for realizing the stability and synthesis of high-entropy compds. that one metal site like the framework in the compd. structures with bimetallic sites stabilizes another site to accommodate different elements. Several typical metal compds. with bimetallic sites, including perovskite hydroxides, layered double hydroxide, spinel sulfide, perovskite fluoride, and spinel oxides, have been synthesized into high-entropy compds. High-entropy perovskite hydroxides (HEPHs) as representative compds. have been synthesized with a highly wide range of components even a septenary component and exhibit great oxygen evolution activity. Our work provides a design platform to develop more high-entropy compd. systems with promising development potential for electrocatalysts.
- 19Wu, H.; Lu, Q.; Li, Y.; Wang, J.; Li, Y.; Jiang, R.; Zhang, J.; Zheng, X.; Han, X.; Zhao, N. Rapid joule-heating synthesis for manufacturing high-entropy oxides as efficient electrocatalysts. Nano Lett. 2022, 22, 6492– 6500, DOI: 10.1021/acs.nanolett.2c0114719Rapid Joule-Heating Synthesis for Manufacturing High-Entropy Oxides as Efficient ElectrocatalystsWu, Han; Lu, Qi; Li, Yajing; Wang, Jiajun; Li, Yingbo; Jiang, Rui; Zhang, Jinfeng; Zheng, Xuerong; Han, Xiaopeng; Zhao, Naiqin; Li, Jiajun; Deng, Yida; Hu, WenbinNano Letters (2022), 22 (16), 6492-6500CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)High-entropy oxide (HEO) including multiple principal elements possesses great potential for various fields such as basic physics, mech. properties, energy storage, and catalysis. However, the synthesis method of high-entropy compds. through the traditional heating approach is not conducive to the rapid properties screening, and the current elemental combinations of HEO are also highly limited. Herein, the authors report a rapid synthesis method for HEO through the Joule-heating of Ni foil with dozens of seconds. High-entropy rocksalt oxides (HERSO) with the new elemental combination, high-entropy spinel oxides (HESO), and high-entropy perovskite oxide (HEPO) were synthesized through the Joule-heating. The synthesized HERSO with new elemental combinations proves to be a great promotion of OER activity due to the synergy of multiple components and the continuous electronic structure exptl. and theor. The demonstrated synthesis approach and the new component combination of HERSO provide a broad platform for the development of high-entropy materials and catalysts.
- 20Wei, J.; Rong, K.; Li, X.; Wang, Y.; Qiao, Z.; Fang, Y.; Dong, S. Deep eutectic solvent assisted facile synthesis of low-dimensional hierarchical porous high-entropy oxides. Nano Res. 2022, 15, 2756– 2763, DOI: 10.1007/s12274-021-3860-720Deep eutectic solvent assisted facile synthesis of low-dimensional hierarchical porous high-entropy oxidesWei, Jiale; Rong, Kai; Li, Xiaolong; Wang, Yuchen; Qiao, Zhen-An; Fang, Youxing; Dong, ShaojunNano Research (2022), 15 (3), 2756-2763CODEN: NRAEB5; ISSN:1998-0000. (Springer GmbH)High-entropy-oxides (HEOs), a new class of solids that contain five or more elemental species, have attracted increasing interests owing to their unique structures and fascinating physicochem. properties. However, it is a huge challenge to construct various nanostructured, esp. low-dimensional nanostructured HEOs under the high temp. synthetic conditions. Herein, a facile strategy using glucose-urea deep eutectic solvent (DES) as both a solvent and the carbon source of structure-directed template is proposed for the synthesis of various HEOs with two-dimentional (2D) nanonets and one-dimentional (1D) nanowires, including rock-salt (Co, Cu, Mg, Ni, Zn)O, spinel (Co, Cr, Fe, Mn, Ni)3O4, and perovskite La(Co, Cr, Fe, Mn, Ni)O3. The as-prepd. HEOs possessed five or more uniformly dispersed metal elements, large sp. surface areas (more than 25 m2·g-1), and a pure single-phase structure. In addn., high cooling rate (cooling in air or liq-N2-quenching) was indispensable to obtain a single-phase rock-salt (Co, Cu, Mg, Ni, Zn)O because of phase sepn. caused by copper. By taking advantage of unique features of HEOs, rock-salt (Co, Cu, Mg, Ni, Zn)O can function as a promising candidate for lithium-ion batteries (LIBs) anode material, which achieved excellent cycling stability. This work provides a feasible synthetic strategy for low-dimensional hierarchical HEOs, which creates new opportunities for the stable HEOs being highly active functional materials.
- 21Liu, K.; Jin, H.; Huang, L.; Luo, Y.; Zhu, Z.; Dai, S.; Zhuang, X.; Wang, Z.; Huang, L.; Zhou, J. Puffing ultrathin oxides with nonlayered structures. Sci. Adv. 2022, 8, eabn2030 DOI: 10.1126/sciadv.abn2030There is no corresponding record for this reference.
- 22Wei, S.; Kim, S.; Kang, J.; Zhang, Y.; Zhang, Y.; Furuhara, T.; Park, E. S.; Tasan, C. C. Natural-mixing guided design of refractory high-entropy alloys with as-cast tensile ductility. Nat. Mater. 2020, 19, 1175– 1181, DOI: 10.1038/s41563-020-0750-422Natural-mixing guided design of refractory high-entropy alloys with as-cast tensile ductilityWei, Shaolou; Kim, Sang Jun; Kang, Jiyun; Zhang, Yong; Zhang, Yongjie; Furuhara, Tadashi; Park, Eun Soo; Tasan, Cemal CemNature Materials (2020), 19 (11), 1175-1181CODEN: NMAACR; ISSN:1476-1122. (Nature Research)Metallic alloys contg. multiple principal alloying elements have created a growing interest in exploring the property limits of metals and understanding the underlying phys. mechanisms. Refractory high-entropy alloys have drawn particular attention due to their high m.ps. and excellent softening resistance, which are the two key requirements for high-temp. applications. Their compositional space is immense even after considering cost and recyclability restrictions, providing abundant design opportunities. However, refractory high-entropy alloys often exhibit apparent brittleness and oxidn. susceptibility, which remain important challenges for their processing and application. Here, utilizing natural-mixing characteristics among refractory elements, we designed a Ti38V15Nb23Hf24 refractory high-entropy alloy that exhibits >20% tensile ductility in the as-cast state, and physicochem. stability at high temps. Exploring the underlying deformation mechanisms across multiple length scales, we observe that a rare β'-phase plays an intriguing role in the mech. response of this alloy. These results reveal the effectiveness of natural-mixing tendencies in expediting high-entropy alloy discovery.
- 23Xie, J.; Zhang, X.; Zhang, H.; Zhang, J.; Li, S.; Wang, R.; Pan, B.; Xie, Y. Intralayered Ostwald ripening to ultrathin nanomesh catalyst with robust oxygen-evolving performance. Adv. Mater. 2017, 29, 1604765, DOI: 10.1002/adma.201604765There is no corresponding record for this reference.
- 24Wang, S.; Yang, L.; He, G.; Shi, B.; Li, Y.; Wu, H.; Zhang, R.; Nunes, S.; Jiang, Z. Two-dimensional nanochannel membranes for molecular and ionic separations. Chem. Soc. Rev. 2020, 49, 1071– 1089, DOI: 10.1039/C9CS00751B24Two-dimensional nanochannel membranes for molecular and ionic separationsWang, Shaofei; Yang, Leixin; He, Guangwei; Shi, Benbing; Li, Yifan; Wu, Hong; Zhang, Runnan; Nunes, Suzana; Jiang, ZhongyiChemical Society Reviews (2020), 49 (4), 1071-1089CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)A review. Two-dimensional (2D) nanosheets have emerged as promising functional materials owing to their at. thickness and unique phys./chem. properties. By using 2D nanosheets as building blocks, diverse kinds of two-dimensional nanochannel membranes (2DNCMs) are being actively explored, in which mass transport occurs in the through-plane and interlayer channels of 2D nanosheets. The rational construction and phys./chem. microenvironment regulation of nanochannels are of vital significance for translating these 2D nanosheets into mol. sepn. membranes and ionic sepn. membranes. Focusing on the recent advances of 2DNCMs, in this review, various porous/nonporous 2D nanosheets and their derived nanochannels are first briefly introduced. Then we discuss the emerging top-down and bottom-up methods to synthesize high-quality 2D nanosheets and to prep. high-performance 2DNCMs. As the major part of this review, we focus on three types of nanochannels, which are based on nonporous nanosheets, intrinsically porous nanosheets and perforated nanosheets. The strategies for regulating the phys. and chem. microenvironments in the nanochannels are emphasized. The representative applications of 2DNCMs in mol. sepns. (gas sepn., liq. sepn.) and ionic sepns. are presented. Finally, the current challenges and future perspectives are highlighted.
- 25Djenadic, R.; Sarkar, A.; Clemens, O.; Loho, C.; Botros, M.; Chakravadhanula, V. S. K.; Kubel, C.; Bhattacharya, S. S.; Gandhi, A. S.; Hahn, H. Multicomponent equiatomic rare earth oxides. Mater. Res. Lett. 2017, 5, 102– 109, DOI: 10.1080/21663831.2016.122043325Multicomponent equiatomic rare earth oxidesDjenadic, Ruzica; Sarkar, Abhishek; Clemens, Oliver; Loho, Christoph; Botros, Miriam; Chakravadhanula, Venkata S. K.; Kuebel, Christian; Bhattacharya, Subramshu S.; Gandhi, Ashutosh S.; Hahn, HorstMaterials Research Letters (2017), 5 (2), 102-109CODEN: MRLAC4; ISSN:2166-3831. (Taylor & Francis Ltd.)Multicomponent rare earth oxide (REO) nanocryst. powders contg. up to seven equiat. rare earth elements were successfully synthesized in a single-phase CaF2-type (Fm-3 m) structure. The addn. of more than six elements resulted in the formation of a secondary phase. Annealing at 1000°C for 1 h led to the formation of a single-phase (Ia-3) even in the 7-component system. In the absence of cerium (Ce4+), secondary phases were obsd. irresp. of the no. of cations or the extent of thermal treatment indicating that cerium cations played a crucial role in stabilizing the multicomponent REOs into a phase pure structure.
- 26Gu, K.; Wang, D.; Xie, C.; Wang, T.; Huang, G.; Liu, Y.; Zou, Y.; Tao, L.; Wang, S. Defect-rich high-entropy oxide nanosheets for efficient 5-hydroxymethylfurfural electrooxidation. Angew. Chem., Int. Ed. 2021, 60, 20253– 20258, DOI: 10.1002/anie.20210739026Defect-Rich High-Entropy Oxide Nanosheets for Efficient 5-Hydroxymethylfurfural ElectrooxidationGu, Kaizhi; Wang, Dongdong; Xie, Chao; Wang, Tehua; Huang, Gen; Liu, Yanbo; Zou, Yuqin; Tao, Li; Wang, ShuangyinAngewandte Chemie, International Edition (2021), 60 (37), 20253-20258CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)High-entropy oxides (HEOs), a new concept of entropy stabilization, exhibit unique structures and fascinating properties, and are thus important class of materials with significant technol. potential. However, the conventional high-temp. synthesis techniques tend to afford micron-scale HEOs with low surface area, and the catalytic activity of available HEOs is still far from satisfactory because of their limited exposed active sites and poor intrinsic activity. Here the authors report a low-temp. plasma strategy for prepg. defect-rich HEOs nanosheets with high surface area, and for the 1st time employ them for 5-hydroxymethylfurfural (HMF) electrooxidn. Owing to the nanosheets structure, abundant O vacancies, and high surface area, the quinary (FeCrCoNiCu)3O4 nanosheets deliver improved activity for HMF oxidn. with lower onset potential and faster kinetics, outperforming that of HEOs prepd. by high-temp. method. The authors' method opens new opportunities for synthesizing nanostructured HEOs with great potential applications.
- 27Zhao, J.; Bao, J.; Yang, S.; Niu, Q.; Xie, R.; Zhang, Q.; Chen, M.; Zhang, P.; Dai, S. Exsolution-dissolution of supported metals on high-entropy Co3MnNiCuZnOx: toward sintering-resistant catalysis. ACS Catal. 2021, 11, 12247– 12257, DOI: 10.1021/acscatal.1c0322827Exsolution-Dissolution of Supported Metals on High-Entropy Co3MnNiCuZnOx: Toward Sintering-Resistant CatalysisZhao, Jiahua; Bao, Jiafeng; Yang, Shize; Niu, Qiang; Xie, Rongyong; Zhang, Qiuyue; Chen, Mingshu; Zhang, Pengfei; Dai, ShengACS Catalysis (2021), 11 (19), 12247-12257CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)Herein, in situ generation of CuCoNi nanoalloys over a high-entropy oxide Co3MnNiCuZnOx matrix has been employed to generate a sintering-resistant metal-oxide interface for the CO2 hydrogenation reaction. The high-entropy Co3MnNiCuZnOx catalyst with a single reverse spinel structure was synthesized by a mechanochem. redox-based process and thermal treatment just at 600°C. Interestingly, the entropy-driven force allows the exsoln. and dissoln. of CuCoNi alloys under reductive and oxidative recycles, which results in the dynamics confinement of the supported metals. With high temp. (500°C) CO2 hydrogenation as a model reaction, the restriction of CuCoNi nanoparticles over a high-entropy Co3MnNiCuZnOx matrix guaranteed long-term thermal stability (>100 h). In comparison, binary CoMnOx as a control catalyst deactivated in 10 h. This high-entropy stabilization may inspire a no. of sintering-resistant catalysts in the near future.
- 28An, L.; Zhang, H.; Zhu, J.; Xi, S.; Huang, B.; Sun, M.; Peng, Y.; Xi, P.; Yan, C. Balancing activity and stability in spinel cobalt oxides through geometrical sites occupation towards efficient electrocatalytic oxygen evolution. Angew. Chem., Int. Ed. 2023, 62, e202214600 DOI: 10.1002/anie.20221460028Balancing Activity and Stability in Spinel Cobalt Oxides through Geometrical Sites Occupation towards Efficient Electrocatalytic Oxygen EvolutionAn, Li; Zhang, Hong; Zhu, Jiamin; Xi, Shibo; Huang, Bolong; Sun, Mingzi; Peng, Yong; Xi, Pinxian; Yan, Chun-HuaAngewandte Chemie, International Edition (2023), 62 (3), e202214600CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)Designing active and stable oxygen evolution reaction (OER) catalysts are vitally important to various energy conversion devices. Herein, we introduce elements Ni and Mn into (Co)tet(Co2)octO4 nanosheets (NSs) at fixed geometrical sites, including Mnoct, Nioct, and Nitet, to optimize the initial geometrical structure and modulate the CoCo2O4 surface from oxygen-excess to oxygen-deficiency. The pristine (Ni,Mn)-(Co)tet(Co2)octO4 NSs shows excellent OER activity with an overpotential of 281.6 mV at a c.d. of 10 mA cm-2. Moreover, without damaging their initial activity, the activated (Act)-(Ni,Mn)-(Co)tet(Co2)octO4 NSs after surface reconstruction exhibit long-term stability of 100 h under 10 mA cm-2, 50 mA cm-2, or even 100 mA cm-2. The optimal balance between electroactivity and stability leads to remarkable OER performances, providing a pivotal guideline for designing ideal electrocatalysts and inspiring more works to focus on the dynamic change of each occupation site component.
- 29Yu, M.; Budiyanto, E.; Tuysuz, H. Principles of water electrolysis and recent progress in cobalt-, nickel-, and iron-based oxides for the oxygen evolution reaction. Angew. Chem., Int. Ed. 2022, 61, e202103824 DOI: 10.1002/anie.20210382429Principles of Water Electrolysis and Recent Progress in Cobalt-, Nickel-, and Iron-Based Oxides for the Oxygen Evolution ReactionYu, Mingquan; Budiyanto, Eko; Tueysuez, HarunAngewandte Chemie, International Edition (2022), 61 (1), e202103824CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Water electrolysis that results in green hydrogen is the key process towards a circular economy. The supply of sustainable electricity and availability of oxygen evolution reaction (OER) electrocatalysts are the main bottlenecks of the process for large-scale prodn. of green hydrogen. A broad range of OER electrocatalysts have been explored to decrease the overpotential and boost the kinetics of this sluggish half-reaction. Co-, Ni-, and Fe-based catalysts have been considered to be potential candidates to replace noble metals due to their tunable 3d electron configuration and spin state, versatility in terms of crystal and electronic structures, as well as abundance in nature. This Review provides some basic principles of water electrolysis, key aspects of OER, and significant criteria for the development of the catalysts. It provides also some insights on recent advances of Co-, Ni-, and Fe-based oxides and a brief perspective on green hydrogen prodn. and the challenges of water electrolysis.
- 30Han, L.; Dong, S.; Wang, E. Transition-metal (Co, Ni, and Fe)-based electrocatalysts for the water oxidation reaction. Adv. Mater. 2016, 28, 9266– 9291, DOI: 10.1002/adma.20160227030Transition-Metal (Co, Ni, and Fe)-Based Electrocatalysts for the Water Oxidation ReactionHan, Lei; Dong, Shaojun; Wang, ErkangAdvanced Materials (Weinheim, Germany) (2016), 28 (42), 9266-9291CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. Increasing energy demands and environment awareness have promoted extensive research on the development of alternative energy conversion and storage technologies with high efficiency and environmental friendliness. Among them, water splitting is very appealing, and is receiving more and more attention. The crit. challenge of this renewable-energy technol. is to expedite the oxygen evolution reaction (OER) because of its slow kinetics and large overpotential. Therefore, developing efficient electrocatalysts with high catalytic activities is of great importance for high-performance water splitting. In the past few years, much effort has been devoted to the development of alternative OER electrocatalysts based on transition-metal elements that are low-cost, highly efficient, and have excellent stability. Here, recent progress on the design, synthesis, and application of OER electrocatalysts based on transition-metal elements, including Co, Ni, and Fe, is summarized, and some invigorating perspectives on the future developments are provided.
- 31Abdelhafiz, A.; Tanvir, A. N. M.; Zeng, M.; Wang, B.; Ren, Z.; Harutyunyan, A. R.; Zhang, Y.; Li, J. Pulsed light synthesis of high entropy nanocatalysts with enhanced catalytic activity and prolonged stability for oxygen evolution reaction. Adv. Sci. 2023, 10, 2300426, DOI: 10.1002/advs.20230042631Pulsed Light Synthesis of High Entropy Nanocatalysts with Enhanced Catalytic Activity and Prolonged Stability for Oxygen Evolution ReactionAbdelhafiz, Ali; Tanvir, A. N. M.; Zeng, Minxiang; Wang, Baoming; Ren, Zhichu; Harutyunyan, Avetik R.; Zhang, Yanliang; Li, JuAdvanced Science (Weinheim, Germany) (2023), 10 (18), 2300426CODEN: ASDCCF; ISSN:2198-3844. (Wiley-VCH Verlag GmbH & Co. KGaA)The ability to synthesize compositionally complex nanostructures rapidly is a key to high-throughput functional materials discovery. In addn. to being time-consuming, a majority of conventional materials synthesis processes closely follow thermodn. equil., which limit the discovery of new classes of metastable phases such as high entropy oxides (HEO). Herein, a photonic flash synthesis of HEO nanoparticles at timescales of milliseconds is demonstrated. By leveraging the abrupt heating and cooling cycles induced by a high-power-d. xenon pulsed light, mixed transition metal salt precursors undergo rapid chem. transformations. Hence, nanoparticles form within milliseconds with a strong affinity to bind to the carbon substrate. Oxygen evolution reaction (OER) activity measurements of the synthesized nanoparticles demonstrate two orders of magnitude prolonged stability at high current densities, without noticeable decay in performance, compared to com. IrO2 catalyst. This superior catalytic activity originates from the synergistic effect of different alloying elements mixed at a high entropic state. It is found that Cr addn. influences surface activity the most by promoting higher oxidn. states, favoring optimal interaction with OER intermediates. The proposed high-throughput method opens new pathways toward developing next-generation functional materials for various electronics, sensing, and environmental applications, in addn. to renewable energy conversion.
- 32Hooch Antink, W.; Lee, S.; Lee, H. S.; Shin, H.; Yoo, T. Y.; Ko, W.; Shim, J.; Na, G.; Sung, Y.-E.; Hyeon, T. High-valence metal-driven electronic modulation for boosting oxygen evolution reaction in high-entropy spinel oxide. Adv. Funct. Mater. 2024, 34, 2309438, DOI: 10.1002/adfm.20230943832High-Valence Metal-Driven Electronic Modulation for Boosting Oxygen Evolution Reaction in High-Entropy Spinel OxideHooch Antink, Wytse; Lee, Seongbeom; Lee, Hyeon Seok; Shin, Heejong; Yoo, Tae Yong; Ko, Wonjae; Shim, Jaehyuk; Na, Geumbi; Sung, Yung-Eun; Hyeon, TaeghwanAdvanced Functional Materials (2024), 34 (1), 2309438CODEN: AFMDC6; ISSN:1616-301X. (Wiley-VCH Verlag GmbH & Co. KGaA)High-entropy spinel oxides (HESOs) are a promising class of electrocatalysts whose material properties and catalytic activity can be finely tuned by controlling the elemental compn. Although numerous HESOs are already reported, their compns. are primarily limited to the first-row transition metals. Herein, the synthesis of a high-entropy spinel (CrFeCoNiMo)3O4 nanosheet (HEO-NS) and its application as oxygen evolution reaction (OER) catalyst are reported. The high-entropy spinel displays a low overpotential of 255.3 mV at a c.d. of 10 mA cm-2 and excellent stability, outperforming the IrO2 benchmark. Careful anal. with XPS and X-ray absorption spectroscopy (XAS) reveals that the incorporation of high-valence Cr and Mo can activate the lattice oxygen by weakening the metal-oxygen bond and promoting the lattice oxygen mechanism (LOM). Furthermore, the catalyst can achieve a high c.d. of 1 A cm-2 at 1.71 V in a lab-scale electrolyzer, demonstrating the potential of HESOs for practical application.
- 33Huang, Y.; Li, M.; Pan, F.; Zhu, Z.; Sun, H.; Tang, Y.; Fu, G. Plasma-induced Mo-doped Co3O4 with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splitting. Carbon Energy 2023, 5, e279 DOI: 10.1002/cey2.27933Plasma-induced Mo-doped Co3O4 with enriched oxygen vacancies for electrocatalytic oxygen evolution in water splittingHuang, Yujie; Li, Meng; Pan, Fei; Zhu, Zhuoya; Sun, Huamei; Tang, Yawen; Fu, GengtaoCarbon Energy (2023), 5 (3), e279CODEN: CEANFS; ISSN:2637-9368. (John Wiley & Sons Australia, Ltd.)Heteroat. substitution and vacancy engineering of spinel oxides can theor. optimize the oxygen evolution reaction (OER) through charge redistribution and d-band center modification but still remain a great challenge in both the prepn. and catalytic mechanism. Herein, we proposed a novel and efficient Ar-plasma (P)-assisted strategy to construct heteroatom Mo-substituted and oxygen vacancies enriched hierarchical spinel Co3O4porous nanoneedle arrays in situ grown on carbon cloth (denoted P-Mo-Co3O4@CC) to improve the OER performance. Ar-plasma technol. can efficiently generate vacancy sites at the surface of hydroxide, which induces the anchoring of Mo anion salts through electrostatic interaction, finally facilitating the substitution of Mo atoms and the formation of oxygen vacancies on the Co3O4surface. The P-Mo-Co3O4@CC affords a low overpotential of only 276 mV at 10 mA cm-2 for the OER, which is 58 mV superior to that of Mo-free Co3O4@CC and surpasses com. RuO2 catalyst. The robust stability and satisfactory selectivity (nearly 100% Faradic efficiency) of P-Mo-Co3O4@CC for the OER are also demonstrated. Theor. studies demonstrate that Mo with variable valance states can efficiently regulates the at. ratio of Co3+/Co2+ and increases the no. of oxygen vacancies, thereby inducing charge redistribution and tuning the d-band center of Co3O4, which improve the adsorption energy of oxygen intermediates (e.g., *OOH) on P-Mo-Co3O4@CC during OER. Furthermore, the two-electrode OER//HER electrolyzer equipped with P-Mo-Co3O4@CC as anode displays a low operation potential of 1.54 V to deliver a c.d. of 10 mA cm-2, and also exhibits good reversibility and anticurrent fluctuation ability under simulated real energy supply conditions, demonstrating the great potential of P-Mo-Co3O4@CC in water electrolysis.
- 34Feng, D.; Dong, Y.; Zhang, L.; Ge, X.; Zhang, W.; Dai, S.; Qiao, Z. Holey lamellar high-entropy oxide as an ultra-high-activity heterogeneous catalyst for solvent-free aerobic oxidation of benzyl alcohol. Angew. Chem., Int. Ed. 2020, 59, 19503– 19509, DOI: 10.1002/anie.20200489235Holey Lamellar High-Entropy Oxide as an Ultra-High-Activity Heterogeneous Catalyst for Solvent-free Aerobic Oxidation of Benzyl AlcoholFeng, Danyang; Dong, Yangbo; Zhang, Liangliang; Ge, Xin; Zhang, Wei; Dai, Sheng; Qiao, Zhen-AnAngewandte Chemie, International Edition (2020), 59 (44), 19503-19509CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)The development of noble-metal-free heterogeneous catalysts is promising for selective oxidn. of arom. alcs.; however, the relatively low conversion of non-noble metal catalysts under solvent-free atm. conditions hinders their industrial application. Now, a holey lamellar high entropy oxide (HEO) Co0.2Ni0.2Cu0.2Mg0.2Zn0.2O material with mesoporous structure is prepd. by an anchoring and merging process. The HEO has ultra-high catalytic activity for the solvent-free aerobic oxidn. of benzyl alc. Up to 98% conversion can be achieved in only 2 h, to our knowledge, the highest conversion of benzyl alc. by oxidn. to date. By regulating the catalytic reaction parameters, benzoic acid or benzaldehyde can be selectively optimized as the main product. Anal. characterizations and calcns. provide a deeper insight into the catalysis mechanism, revealing abundant oxygen vacancies and holey lamellar framework contribute to the ultra-high catalytic activity.
Supporting Information
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.3c10868.
Experimental and characterization details; details of theoretical calculations; schematic diagram of the ultrathin HEO synthesis; morphology characterization and thickness regulation of the HEO nanosheet; OM, SEM, AFM, XPS, SAED, TEM-EDS, and ICP-OES characterizations of the HEOs with four type phase structures; structural and elemental analysis of the HEOs without glucose and glycine addition, multicomponent oxide systems without assistor addition, and the HEO containing the noble metal; TEM, XRD, and XPS characterizations of the HEO catalyst; impedance and double-layer capacitance measurement of all OER catalysts (PDF)
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