Transition metal tetrapentafluorophenyl porphyrin catalyzed hydrogen evolution from acetic acid and water

The performance of Cu (1), Co (2) and Zn (3) complexes of meso-tetrakis(pentafluorophenyl)porphyrin in the electrocatalyzed evolution of hydrogen has been investigated. In acetic acid media, hydrogen evolution turnover frequency (TOF) values for complexes 1, 2 and 3 were 22.1, 19.8 and 18.1 h^?1, respectively, at an overpotential of 942 mV versus Ag/AgNO₃. In buffer solution at pH 7.0, the corresponding hydrogen evolution TOF values increased dramatically, to 266, 234, 218 h^?1 at a similar overpotential of 878 mV versus SHE. The Faradaic yields of 1, 2, and 3 for sustained proton reduction in catalytic experiments at a glassy carbon electrode over 72 h were 89.7, 90.4 and 91.0%, respectively, with no observable catalyst decomposition.