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 (F₁₀C−Si, F₁₀C−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, F₁₀C−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 F₁₀C−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.