期刊
INORGANIC CHEMISTRY
卷 56, 期 4, 页码 1783-1793出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.6b01707
关键词
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资金
- Ministry of New and Renewable Energy, India [103/180/2010-NT]
- DST India [SB/S1/IC-25/2013]
Iron porphyrin complexes with second-sphere distal triazole residues show a hydrogen evolution reaction (HER) catalyzed by the Fe(I) state in both organic and aqueous media, whereas an analogous iron porphyrin complex without the distal residues catalyzes the HER in the formal Fe(0) state. This activation of the Fe(I) state by the second sphere residues lowers the overpotential of the HER by these iron porphyrin complexes by 50%. Experimental data and theoretical calculations indicate that the distal triazole residues, once protonated, enhance the proton affinity of the iron center via formation of a dihydrogen bond with an Fe(III)-H(-)intermediate.
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