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论文类型：期刊论文

发表时间：2019-04-10

发表刊物：Journal of the American Chemical Society

收录刊物：EI

卷号：141

期号：14

页面范围：5565-5580

ISSN号：00027863

关键字：Artificial photosynthesis; Carboxylation; Ligands; Metal complexes; Oxidation; Transition metal compounds; Transition metals, Carboxylate groups; Carboxylate ligands; Conversion reactions; Intrinsic activities; Molecular catalysts; Regular configuration; Small molecule activation; Water oxidation catalysts, Catalyst activity

摘要：A water-oxidation catalyst with high intrinsic activity is the foundation for developing any type of water-splitting device. To celebrate its 10 years anniversary, in this Perspective we focus on the state-of-the-art molecular water-oxidation catalysts (MWOCs), the Ru-bda series (bda = 2,2 ?bipyridine-6,6 ?dicarboxylate), to offer strategies for the design and synthesis of more advanced MWOCs. The O - O bond formation mechanisms, derivatives, applications, and reasons behind the outstanding catalytic activities of Ru-bda catalysts are summarized and discussed. The excellent performance of the Ru-bda catalyst is owing to its unique structural features: the distortion induced 7-coordination and the carboxylate ligands with coordination flexibility, proton-transfer function as well as small steric hindrance. Inspired by the Ru-bda catalysts, we emphasize that the introduction of negatively charged groups, such as the carboxylate group, into ligands is an effective strategy to lower the onset potential of MWOCs. Moreover, distortion of the regular configuration of a transition metal complex by ligand design to generate a wide open site as the catalytic site for binding the substrate as an extra-coordination is proposed as a new concept for the design of efficient molecular catalysts. These inspirations can be expected to play a great role in not only water-oxidation catalysis but also other small molecule activation and conversion reactions involving artificial photosynthesis, such as CO2 reduction and N2 fixation reactions. © 2019 American Chemical Society.