清华大学章名田团队报道了用于光催化CO₂还原的异双金属NiFe配合物——NiFe双位点共同作用。相关研究成果发表在2024年10月8日出版的《美国化学会杂志》。

催化二氧化碳减排对二氧化碳转化为化学品和燃料提出了重大挑战。Ni-Fe一氧化碳脱氢酶（[NiFe]-CODH）在接近热力学平衡电位下有效地介导了CO₂和CO的可逆转化，突出了CO₂还原催化剂设计中的异双金属合作。然而，许多NiFe仿生模型复合物在二氧化碳还原催化方面收效甚微，这突显了精确的双金属结构和功能的关键作用。

该文中，研究人员提出了一种用于光催化还原CO₂为CO的异双金属NiFe复合物，与同核NiNi催化剂相比，其催化性能显著提高。光催化和机理研究表明，在氧化还原活性邻菲咯啉配体的帮助下，NiFe通过关键中间体Ni^II（μ-CO₂^2--κC:κO）Fe^II实现了CO₂的双位点活化，其中Fe^II位点的路易斯酸性起着重要作用，这在同核FeFe系统中得到了证实。

该研究介绍了第一种能够有效催化CO₂还原为CO的异核NiFe分子催化剂，深化了对异双金属合作的理解，并为设计高活性和选择性的CO₂还原催化剂提供了一种新策略。

附：英文原文

Title：Heterobimetallic NiFe Complex for Photocatalytic CO2 Reduction: United Efforts of NiFe Dual Sites

Author: Yao Xiao, Hong-Tao Zhang, Ming-Tian Zhang

Issue&Volume: October 8, 2024

Abstract: Catalytic CO2 reduction poses a significant challenge for the conversion of CO2 into chemicals and fuels. Ni–Fe carbon monoxide dehydrogenase ([NiFe]-CODH) effectively mediates the reversible conversion of CO2 and CO at a nearly thermodynamic equilibrium potential, highlighting the heterobimetallic cooperation for the design of CO2 reduction catalysts. However, numerous NiFe biomimetic model complexes have realized little success in CO2 reduction catalysis, which underscores the crucial role of precise bimetallic configuration and functionality. Herein, we presented a heterobimetallic NiFe complex for the photocatalytic reduction of CO2 to CO, demonstrating significantly enhanced catalytic performance compared to the homonuclear NiNi catalyst. Photocatalytic and mechanistic investigations revealed that with the assistance of a redox-active phenanthroline ligand, NiFe achieves dual-site activation of CO2 through a pivotal intermediate, NiII(μ-CO22–-κC:κO)FeII, where the Lewis acidity of the FeII site plays an important role, as corroborated in the homonuclear FeFe system. This study introduces the first heteronuclear NiFe molecular catalyst capable of efficiently catalyzing the reduction of CO2 to CO, deepening insights into heterobimetallic cooperation and offering a novel strategy for designing highly active and selective CO2 reduction catalysts.

DOI: 10.1021/jacs.4c08510

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c08510