First Application of Non‐Metallic A₂B Type Silicon Corrole Complexes in Electrocatalytic Hydrogen Evolution

In this study, we have successfully synthesized two non‐metallic‐based silicon corrole complexes (F 10 C−Si, F 10 C−CN−Si) and used them as HER electrocatalysts for the first time. Electrochemical studies indicate the electrocatalytic HER may go via EE‐CEEC (E: electron transfer step, C: chemical step) pathway. Notably, it can be seen that the introduction of electron‐withdrawing cyano group on the meso ‐phenyl of the corrole macrocycle may enhance the catalytic activity of silicon corrole complexes. In DMF with TsOH as the proton source, F 10 C−CN−Si exhibits a turnover frequency (TOF) of 331.48 s −1 and a high catalytic efficiency (C.E) of 1.29. Furthermore, the catalytic prowess of the silicon corrole complexes extends to neutral aqueous solution, with F 10 C−CN−Si achieving a TOF of 52.72 h −1 at an overpotential of 1188 mV. This study extends the application of non‐metallic‐based silicon corrole molecular catalysts in the electrocatalytic HER field.