Attempts to immobilize molecular catalysts to the surface of electrode materials, showed in recent years that immobilized electrocatalysts often behave quite differently from their solution counterparts. The implication of this is that surface-confined catalysts are subject to different local environmental influences compared to their counterparts in homogenous solution. Foremost among these are the electric fields at the interface between the electrode surface and the double layer. We have recently measured the magnitudes of the electric fields on molecular catalysts confined to electrode surfaces. This has been accomplished by Stark tuning of the n(CO) vibrational modes of complexes of the type MCl(CO)3(4-SH-bpy) (M = Mn, Re) and M(CO)5(CN-C6H4-NC) (M = Cr, Mo, W) covalently attached to Au electrode surfaces by thiol linkages as a function of electrode potential. Here we report how chemical reactivity of transition metal complexes changes under the influence of interfacial electric fields. We also will report our findings of how the rates of molecular catalysts for transfer hydrogenation can be tuned by an electric field.

Exploring the implications of interfacial electric fields on molecular catalysts

ACS Spring Meeting 2021

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.