Crystal Facet‐Controlled Efficient SnS Photocathodes for High Performance Bias‐Free Solar Water Splitting

To achieve a high solar‐to‐hydrogen (STH) conversion efficiency, delicate strategies toward high photocurrent together with sufficient onset potential should be developed. Herein, an SnS semiconductor is reported as a high‐performance photocathode. Use of proper sulfur precursor having weak dipole moment allows to obtain high‐quality dense SnS nanoplates with enlarged favorable crystallographic facet, while suppressing inevitable anisotropic growth. Furthermore, the introducing Ga(2)O(3) layer between SnS and TiO(2) in SnS photocathodes efficiently improves the charge transport kinetics without charge trapping. The SnS photocathode reveals the highest photocurrent density of 28 mA cm(−2) at 0 V versus the reversible hydrogen electrode. Overall solar water splitting is demonstrated for the first time by combining the optimized SnS photocathode with a Mo:BiVO(4) photoanode, achieving a STH efficiency of 1.7% and long‐term stability of 24 h. High performance and low‐cost SnS photocathode represent a promising new material in the field of photoelectrochemical solar water splitting.