Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 18, Pages 5457-5462Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201510001
Keywords
bimetallic reactions; electrocatalysis; homolysis; hydrogen evolution; nickel porphyrins
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Funding
- National Natural Science Foundation of China [21101170, 21573139]
- Fundamental Research Funds for the Central Universities
- Renmin University of China
- Thousand Young Talents program in China
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A nickel(II) porphyrin Ni-P (P=porphyrin) bearing four meso-C6F5 groups to improve solubility and activity was used to explore different hydrogen-evolution-reaction (HER) mechanisms. Doubly reduced Ni-P ([Ni-P](2-)) was involved in H-2 production from acetic acid, whereas a singly reduced species ([Ni-P](-)) initiated HER with stronger trifluoroacetic acid (TFA). High activity and stability of Ni-P were observed in catalysis, with a remarkable i(c)/i(p) value of 77 with TFA at a scan rate of 100 mVs(-1) and 20 degrees C. Electrochemical, stopped-flow, and theoretical studies indicated that a hydride species [H-Ni-P] is formed by oxidative protonation of [Ni-P](-). Subsequent rapid bimetallic homolysis to give H-2 and Ni-P is probably involved in the catalytic cycle. HER cycling through this one-electron-reduction and homolysis mechanism has been proposed previously but rarely validated. The present results could thus have broad implications for the design of new exquisite cycles for H-2 generation.
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