Optimized immobilization of ZnO:Co electrocatalysts realizes 5% efficiency in photo-assisted splitting of water

Abstract

Organic solvents with varied electrophoretic mobility have been employed for deposition of nanocrystalline ZnO:Co particles onto fluorinated tin oxide supports. Evaluation of the electrochemical activity for the oxygen evolution reaction proves a clear solvent-dependence with highest activity upon deposition from acetonitrile and lowest activity upon deposition from ethanol. Analysis of the resulting layer thickness and density attributes the improved electrochemical activity of acetonitrile-prepared samples to larger film thicknesses with lower film densities, i.e. to films with higher porosity. The findings suggest that the ZnO:Co films represent an initially nanocrystalline system where the catalytic activity is predominantly confined to a thin surface region rather than to comprise the entire volume. Closer inspection of this surface region proves successive in operando transformation of the nanocrystalline to an amorphous phase during evolution of oxygen. Furthermore, less active but highly transparent ZnO:Co phases, prepared from ethanol-containing suspensions, can be successfully employed in a stacking configuration with a low-cost triple-junction solar cell. Thereby, a solar-to-hydrogen efficiency of 5.0% in splitting of water at pH 14 could be realized. In contrast, highly light-absorbing acetonitrile/acetone-prepared samples limit the efficiency to about 1%, demonstrating thus the decisive influence of the used organic solvent upon electrophoretic deposition. Stability investigations over several days finally prove that the modular architecture, applied here, represents an attractive approach for coupling of highly active electrocatalysts with efficient photovoltaic devices.