Modulation of Electrocatalytic Overall Water Splitting Performance by β,β'-Functionalization of Ni(II) Porphyrins

In this work, we present a methodology for modulating the HER and OER catalytic activities of nickel porphyrins by β,β'-modification. The syntheses of Ni2 with fused butano ring porphyrin and Ni3 with fused benzo porphyrin were achieved. The catalytic performance of Ni2 was found to be excellent for HER, while Ni3 exhibited superior performance for the OER. The present study demonstrates that the β,β-modification of porphyrins has a significant impact on the reactivity of the metal active site. The results provide new insights into the modulation of the HER and the OER properties by fine-tuning the electronic structure of porphyrins.