Identifying and Interpreting Geometric Configuration-Dependent Activity of Spinel Catalysts for Water Reduction,Journal of the American Chemical Society

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Identifying and Interpreting Geometric Configuration-Dependent Activity of Spinel Catalysts for Water Reduction
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-10-04 , DOI: 10.1021/jacs.2c08726
Jing Wu _{1,

2} , Xin Wang _{1,

2} , Wenhao Zheng _{1,

2} , Yu Sun _{1,

2} , Yong Xie _{1,

2} , Kaikai Ma _{1,

2} , Zheng Zhang _{1,

2} , Qingliang Liao _{1,

2} , Zhen Tian _{1,

2} , Zhuo Kang _{1,

2} , Yue Zhang _{1,

2}

Affiliation

The catalytic activity of transition metal-based catalysts is overwhelmingly dependent on the geometric configuration. Identification and interpretation of different geometric configurations’ contributions to catalytic activity plays a pivotal role in catalytic performance elevation. Spinel structured AB₂X₄, consisting of tetrahedral (A²⁺–X)_{T_d} and octahedral (B³⁺–X)_{O_h} geometric configurations, is a prototypical category of multi-geometric-configuration featured catalysts. However, it is still under debate about the predominant geometric configuration responsible for spinel catalyst activity, and the mechanistic origin of specific activity discrepancy among varied geometric configurations also remains ambiguous. Herein, Co_{T_d}²⁺ and Co_{O_h}³⁺ in Co₃O₄ are replaced by catalytically inert Zn²⁺ and Al³⁺ to yield ZnCo₂O₄ and CoAl₂O₄, respectively, thus ensuring the manipulable exposure of monotypic active configurations. By means of pulse voltammetry and in situ extended X-ray absorption fine structure, (Co³⁺–O)_{O_h} is identified to be dominant for alkaline HER. In-depth theoretical investigation in combination with X-ray absorption spectroscopy further interprets the synergistic effect between Co and O sites in (Co³⁺–O)_{O_h} configuration on water reduction kinetics upon both water dissociation and hydrogen desorption steps. Furthermore, specific facet dependence of catalytic activity is also deciphered based on precise facet exposure identification and serial theoretical analysis. This work unambiguously figures out the subtle geometric configuration dependence of spinel catalyst activity for water reduction and highlights the synergistic relationship among different components confined in geometric configuration, thereby shedding new light on the rational design of advanced catalysts from the atomic level of geometric configuration optimization.

中文翻译：

识别和解释与几何构型相关的尖晶石催化剂的减水活性

过渡金属基催化剂的催化活性很大程度上取决于几何构型。识别和解释不同几何构型对催化活性的贡献在催化性能提升中起着关键作用。尖晶石结构 AB ₂ X ₄，由四面体 (A ²⁺ –X) _{T _d}和八面体 (B ³⁺ –X) _{O _h组成}几何构型，是多几何构型特征催化剂的原型类别。然而，关于尖晶石催化剂活性的主要几何构型仍然存在争议，并且不同几何构型之间比活性差异的机制起源也仍然模棱两可。在此，Co ₃ O _4中的Co_{T _d}²⁺和Co _{O _h}³⁺被催化惰性的Zn ²⁺和Al ³⁺代替，得到ZnCo ₂ O ₄和CoAl ₂ O ₄，分别，从而确保单型有源配置的可操作曝光。通过脉冲伏安法和原位扩展 X 射线吸收精细结构，(Co ³⁺ -O) _{O _h}被确定为碱性 HER 的主要成分。结合 X 射线吸收光谱的深入理论研究进一步解释了 (Co ³⁺ -O) _{O _{h中 Co 和 O 位点之间的协同效应}}水分解和氢解吸步骤中水还原动力学的配置。此外，还基于精确的刻面暴露识别和系列理论分析破译了催化活性的特定刻面依赖性。该工作明确地揭示了尖晶石催化剂活性对减水的细微几何构型依赖性，并突出了几何构型受限的不同组分之间的协同关系，从而为从原子级几何构型优化的先进催化剂的合理设计提供了新的思路。

更新日期：2022-10-04

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