Metalloporphyrins as Catalytic Models for Studying Hydrogen and Oxygen Evolution and Oxygen Reduction Reactions

作者：Xialiang Li, Haitao Lei, Lisi Xie, Ni Wang, Wei Zhang, Rui Cao · 发表于：Accounts of Chemical Research · 年份：2022 · DOI：10.1021/acs.accounts.1c00753 · 被引用次数：359 · 研究领域：Electrocatalysts for Energy Conversion、Metalloenzymes and iron-sulfur proteins、Advanced battery technologies research

Conspectus The hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) are involved in biological and artificial energy conversions. H–H and O–O bond formation/cleavage are essential steps in these reactions. In nature, intermediates involved in the H–H and O–O bond formation/cleavage are highly reactive and short-lived, making their identification and investigation difficult. In artificial catalysis, the realization of these reactions at considerable rates and close to their thermodynamic reaction equilibria remains a challenge. Therefore, the elucidation of the reaction mechanisms and structure–function relationships is of fundamental significance to understand these reactions and to develop catalysts. This Account describes our recent investigations on catalytic HER, OER, and ORR with metalloporphyrins and derivatives. Metalloporphyrins are used in nature for light harvesting, energy conversion, electron transfer, O 2 activation, and peroxide degradation. Synthetic metal porphyrin complexes are shown to be active for these reactions. We focused on exploring metalloporphyrins to study reaction mechanisms and structure–function relationships because they have stable and tunable structures and characteristic spectroscopic properties. For HER, we identified three H–H bond formation mechanisms and established the correlation between these processes and metal hydride electronic structures. Importantly, we provided direct experiment...