期刊
ACCOUNTS OF CHEMICAL RESEARCH
卷 42, 期 12, 页码 1995-2004出版社
AMER CHEMICAL SOC
DOI: 10.1021/ar900253e
关键词
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资金
- NSF Center for Chemical Innovation [CHE-0802907, CHE-0947829]
- Arnold and Mabel Beckman Foundation
- CCSER (Gordon and Betty Moore Foundation)
- BP MC2 program
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0802907] Funding Source: National Science Foundation
Natural photosynthesis uses sunlight to drive the conversion of energy-poor molecules (H2O, CO2) to energy-rich ones (O-2, (CH2O)(n)). Scientists are working hard to develop efficient artificial photosynthetic systems toward the Holy Grail of solar-driven water splitting. High on the list of challenges is the discovery of molecules that efficiently catalyze the reduction of protons to H-2. In this Account, vie report on one promising class of molecules: cobalt complexes with diglyoxime ligands (cobaloximes). Chemical, electrochemical, and photochemical methods all have been utilized to explore proton reduction catalysis by cobaloxime complexes. Reduction of a Co-II-diglyoxime generates a Col species that reacts with a proton source to produce a Co-III-hydride. Then, in a homolytic pathway, two Co-III-hydricles react in a bimolecular step to eliminate H-2. Alternatively, in a heterolytic pathway, protonation of the Co-III-hydricle produces H-2 and Co-III. A thermodynamic analysis of H-2 evolution pathways sheds new light on the barriers and driving forces of the elementary reaction steps involved in proton reduction by Co-I-diglyoximes. In combination with experimental results, this analysis shows that the barriers to H-2 evolution along the heterolytic pathway are, in most cases, substantially greater than those of the homolytic route. In particular, a formidable barrier is associated with Co-III-diglyoxime formation along the heterolytic pathway. Our investigations of cobaloxime-catalyzed H-2 evolution, coupled with the thermodynamic preference for a homolytic route, suggest that the rate-limiting step is associated with formation of the hydride. An efficient water splitting device may require the tethering of catalysts to an electrode surface in a fashion that does not inhibit association of Co-III-hydricles.
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