期刊
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS
卷 1827, 期 8-9, 页码 1123-1139出版社
ELSEVIER SCIENCE BV
DOI: 10.1016/j.bbabio.2013.01.003
关键词
Hydrogen; Electrochemistry; Hydrogenase mimic; Homogeneous catalysis; Proton transport
资金
- Center for Molecular Electrocatalysis, an Energy Frontier Research Center
- US Department of Energy, Office of Science, Office of Basic Energy Sciences.
- DOE Office of Science Early Career Research Program through the Office of Basic Energy Sciences
This review discusses the development of molecular electrocatalysts for H-2 production and oxidation based on nickel. A modular approach is used in which the structure of the catalyst is divided into first, second, and outer coordination spheres. The first coordination sphere consists of the ligands bound directly to the metal center, and this coordination sphere can be used to control such factors as the presence or absence of vacant coordination sites, redox potentials, hydride donor abilities and other important thermodynamic parameters. The second coordination sphere includes functional groups such as pendent acids or bases that can interact with bound substrates such as H-2 molecules and hydride ligands, but that do not form strong bonds with the metal center. These functional groups can play diverse roles such as assisting the heterolytic cleavage of H-2, controlling intra-and intermolecular proton transfer reactions, and providing a physical pathway for coupling proton and electron transfer reactions. By controlling both the hydride donor ability of the catalysts using the first coordination sphere and the proton donor abilities of the functional groups in the second coordination sphere, catalysts can be designed that are biased toward H-2 production, oxidation, or bidirectional (catalyzing both H-2 oxidation and production). The outer coordination sphere is defined as that portion of the catalytic system that is beyond the second coordination sphere. This coordination sphere can assist in the delivery of protons and electrons to and from the catalytically active site, thereby adding another important avenue for controlling catalytic activity. Many features of these simple catalytic systems are good models for enzymes, and these simple systems provide insights into enzyme function and reactivity that may be difficult to probe in enzymes. This article is part of a Special Issue entitled: Metals in Bioenergetics and Biomimetics Systems. (C) 2013 Elsevier B.V. All rights reserved.
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