Spin states of metal centers in electrocatalysis

Abstract

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, e.g., 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.