Semi Transparent Three-Dimensional Macroporous Quaternary Oxynitride Photoanodes for Photoelectrochemical Water Oxidation

Semi transparent three-dimensional macroporous (3DM) photoanodes based on quaternary oxynitrides have the potential to simultaneously realize superior light harvesting and efficient charge transfer in a tandem photoelectrochemical (PEC) cell. A 3DM CaTaO2N photoanode was prepared for the first time on a GaN/Al2O3 substrate via a chemical route, and it exhibits a high transmittance of >60% in the wide solar spectrum and a photoresponse onset at −0.3 V versus the reversible hydrogen electrode (VRHE) under simulated solar illumination. In particular, a plateau photocurrent density of 0.21 mA cm–2 was achieved at a low potential of 0.4 VRHE, which was 1.6-fold and more than 50-fold higher than a two-dimensional macroporous (2DM) CaTaO2N/GaN/Al2O3 photoanode and a conventional particle-based CaTaO2N/GaN/Al2O3 photoanode, respectively. The bicontinuous, interconnected pore structure within this 3DM film can improve charge carrier separation and collection by reducing the average diffusion distance for minority carriers toward the electrolyte. Optical measurements and simulations verified the enhanced sunlight harvesting in the 3DM photoanode, which was ascribed to the concentrated distribution of the electric field and multiple scattering. This study provides guidance for future synthesis of highly efficient semitransparent 3DM quaternary oxynitride-based photoanodes for a tandem PEC device.