Selective Catalytic Electroreduction of CO2 at Silicon Nanowires (SiNWs) Photocathodes Using Non-Noble Metal-Based Manganese Carbonyl Bipyridyl Molecular Catalysts in Solution and Grafted onto SiNWs

The electrocatalytic reduction of CO2 to CO in hydroorganic medium has been investigated at illuminated (lambda > 600 nm; 20 mW cm(-2)) hydrogen-terminated silicon nanowires (SiNWs-H) photocathodes using three Mn-based carbonyl bipyridyl complexes as homogeneous molecular catalysts ([Mn(L) (CO)(3)(CH3CN)](PF6) and [Mn(bpy) (CO)(3)Br) with L = bpy = 2,2'-bipyridine and dmbpy = 4,4'-dimethyl-2,2'-bipyridine). Systematic comparison of their cyclic voltammetry characteristics with those obtained at flat hydrogen-terminated silicon and traditional glassy carbon electrodes (GCE) enabled us to demonstrate the superior catalytic efficiency of SiNWs-H in terms of cathodic photocurrent densities and overpotentials. For example, the photocurrent densities measured at -1.0 V vs SCE for [Mn(bpy) (CO)(3)(CH3CN)](PF6) at SiNWs-H exceeded 1.0 mA cm(-2) in CO2-saturated CH3CN + 5% v/v H2O, whereas almost zero current was measured at this potential at GCE. Such characteristics have been supported by the energetic diagrams built for the different SiNWs vertical bar Mn-based catalyst interfaces. The fill factor FF and energy conversion efficiency eta calculated under catalytic conditions were higher for [Mn(bpy or dmbpy) (CO)(3)(CH3CN)](PF6) (FF = 0.35 and 0.34; eta = 3.0 and 2.0%, respectively). Further preparative-scale electrolysis at SiNWs-H photocathode with Mn-based complex catalysts in electrolytic solution evidenced the quantitative conversion of CO2 to CO with a higher stability of the [Mn(dmbpy) (CO)(3)(CH3CN)](PF6) complex. Finally, in order to develop technologically viable electrocatalytic devices, the elaboration of SiNWs-H photoelectrodes modified with a Mn-based complex has been successfully achieved from an electropolymerizable catalyst, and it was shown that the electrocatalytic activity of the complex was retained after immobilization.