First-row transition metal porphyrins for electrocatalytic hydrogen evolution - a SPP/JPP Young Investigator Award paper

A series of first-row transition metal complexes of tetrakis(pen uorophenyl) porphyrin (1), denoted as 1-M (M = Mn, Fe, Co, Ni, Cu, and Zn), were synthesized and examined as electrocatalysts for the hydrogen evolution reaction (HER). All these transition metal porphyrins were shown to be active for HER in acetonitrile using trifluoroacetic acid (TFA) as the proton source. The molecular nature and the stability of these metal porphyrins when functioning as HER catalysts were confirmed, and all catalysts gave Faradaic efficiency of >97% for H-2 generation during bulk electrolysis. Importantly, by using 1-Cu, a remarkably high turnover frequency (TOF) of 48500 s' can be obtained, making 1-Cu the most efficient among this series of metal porphyrin catalysts. This TOF value also represents one of the highest values reported in the literature. In addition, electrochemical analysis demonstrated that catalytic HER mechanisms with these 1-M complexes are different. These results show that with the same porphyrin ligand, the change of metal ions will have significant impact on both catalytic efficiency and mechanism. This work for the first time provides direct comparison of electrocatalytic HER features of transition metal complexes of tetrakis(pentafluorophenyl)porphyrin under identical conditions, and will be valuable for future design and development of more efficient HER electrocatalysts of this series.