CO2 Reduction Catalysts on Gold Electrode Surfaces Influenced by Large Electric Fields

• DOI: 10.1021/jacs.8b09852
• Publication Date: 2018-11-23T16:35:54Z
• Authors: Melissa L. Clark; Aimin Ge; Pablo E. Videla; Benjamin Rudshteyn; Christopher J. Mi...; Jia Song; Victor S. Batista; Tianquan Lian; Clifford P. Kubiak
• Keywords: Bipyridine

Attaching molecular catalysts to metal and semiconductor electrodes is a promising approach developing new catalytic with combined advantages of heterogeneous catalysts. However, the effect interfacial electric field on stability, activity, selectivity often poorly understood due complexity interfaces. In this work, we examine strength at binding site CO2 reduction including Re(S-2,2′-bipyridine)(CO)3Cl Mn(S-2,2′-bipyridine)(CO)3Br immobilized Au electrodes. The vibrational spectra are probed by sum frequency generation spectroscopy (SFG), showing pronounced potential-dependent shifts carbonyl stretching modes. Calculations SFG Stark tuning rates based density functional theory allow for direct interpretation configurations bound surfaces influence field. We find that electrocatalysts supported have tilt angles about 65–75° relative surface normal one ligands in contact surface. Large fields 108–109 V/m determined through analysis experimental theoretical symmetric CO mode. These large thus significantly site.