Zhang Yuwei, Wu Qian, Seow Justin Zhu Yeow, Jia Yingjie, Ren Xiao, Xu Zhichuan J
School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore.
Energy Research Institute@NTU (ERI@N), Interdisciplinary Graduate Programme, Nanyang Technological University, 639798, Singapore.
Chem Soc Rev. 2024 Aug 12;53(16):8123-8136. doi: 10.1039/d3cs00913k.
Understanding the electronic structure of active sites is crucial in efficient catalyst design. The spin state, spin configurations of d-electrons, has been frequently discussed recently. However, its systematic depiction in electrocatalysis is lacking. In this tutorial review, a comprehensive interpretation of the spin state of metal centers in electrocatalysts and its role in electrocatalysis is provided. This review starts with the basics of spin states, including molecular field theory, crystal field theory, and ligand field theory. It further introduces the differences in low spin, intermediate spin, and high spin, and intrinsic factors affecting the spin state. Popular characterization techniques and modeling approaches that can reveal the spin state, such as X-ray absorption microscopy, electron spin resonance spectroscopy, Mössbauer spectroscopy, and density functional theory (DFT) calculations, are introduced as well with examples from the literature. The examples include the most recent progress in tuning the spin state of metal centers for various reactions, , the oxygen evolution reaction, oxygen reduction reaction, hydrogen evolution reaction, carbon dioxide reduction reaction, nitrogen reduction reaction, nitrate reduction reaction, and urea oxidation reaction. Challenges and potential implications for future research related to the spin state are discussed at the end.
了解活性位点的电子结构对于高效催化剂设计至关重要。自旋态，即d电子的自旋构型，近来经常被讨论。然而，在电催化中缺乏对其系统的描述。在本教程综述中，提供了对电催化剂中金属中心自旋态及其在电催化中作用的全面解释。本综述从自旋态的基础知识开始，包括分子场理论、晶体场理论和配体场理论。进一步介绍了低自旋、中自旋和高自旋的差异以及影响自旋态的内在因素。还介绍了能够揭示自旋态的常用表征技术和建模方法，如X射线吸收显微镜、电子自旋共振光谱、穆斯堡尔光谱和密度泛函理论（DFT）计算，并列举了文献中的实例。这些实例包括在调节金属中心自旋态以用于各种反应方面的最新进展，即析氧反应、氧还原反应、析氢反应、二氧化碳还原反应、氮还原反应、硝酸盐还原反应和尿素氧化反应。最后讨论了与自旋态相关的未来研究面临的挑战和潜在影响。
