Electrocatalytic Reduction of Carbon Dioxide to Carbon Monoxide by a Polymerized Film of an Alkynyl-Substituted Rhenium(I) Complex

The alkynyl-substituted Re(I) complex [Re(5,5′-bisphenylethynyl-2,2′-bipyridyl)(CO)(3)Cl] was immobilized by electropolymerization onto a Pt-plate electrode. The polymerized film exhibited electrocatalytic activity for the reduction of CO(2) to CO. Cyclic voltammetry studies and bulk controlled-potential electrolysis experiments were performed by using a CO(2)-saturated acetonitrile solution. The CO(2) reduction, determined by cyclic voltammetry, occurs at approximately −1150 mV versus the normal hydrogen electrode (NHE). Quantitative analysis by GC and IR spectroscopy was used to determine a Faradaic efficiency of approximately 33 % for the formation of CO. Both values of the modified electrode were compared to the performance of the homogenous monomer [Re(5,5′-bisphenylethynyl-2,2′-bipyridyl)(CO)(3)Cl] in acetonitrile. The polymer formation and its properties were studied by using SEM, AFM, and attenuated total reflectance (ATR) FTIR and UV/Vis spectroscopy.