Abstract

Several copper corrole complexes were synthesized, and their catalytic activities for hydrogen (H2) evolution were examined. Our results showed that substituents at the meso positions of corrole macrocycles played significant roles in regulating the redox and thus the catalytic properties of copper corrole complexes: strong electron-withdrawing substituents can improve the catalysis for hydrogen evolution, while electron-donating substituents are not favored in this system. The copper complex of 5,15-pentafluorophenyl-10-(4-nitrophenyl)corrole (1) was shown to have the best electrocatalytic performance among copper corroles examined. Complex 1 can electrocatalyze H2 evolution using trifluoroacetic acid (TFA) as the proton source in acetonitrile. In cyclic voltammetry, the value of icat/ip = 303 (icat is the catalytic current, ip is the one-electron peak current of 1 in the absence of acid) at a scan rate of 100 mV s–1 and 20 °C is remarkable. Electrochemical and spectroscopic measurements revealed that 1 ...

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