Bi 2 S 3 -Cu 3 BiS 3 Mixed Phase Interlayer for High-Performance Cu 3 BiS 3 -Photocathode for 2.33% Unassisted Solar Water Splitting Efficiency.

To realize practical solar hydrogen production, a low-cost photocathode with high photocurrent density and onset potential should be developed. Herein, an efficient and stable overall photoelectrochemical tandem cell is developed with a Cu 3 BiS 3 -based photocathode. By exploiting the crystallographic similarities between Bi 2 S 3 and Cu 3 BiS 3 , a one-step solution process with two sulfur sources is used to prepare the Bi 2 S 3 -Cu 3 BiS 3 blended interlayer. The elongated Bi 2 S 3 -Cu 3 BiS 3 mixed-phase 1D nanorods atop a planar Cu 3 BiS 3 film enable a high photocurrent density of 7.8 mA cm -2 at 0 V versus the reversible hydrogen electrode, with an onset potential of 0.9 V RHE . The increased performance over the single-phase Cu 3 BiS 3 thin-film photocathode is attributed to the enhanced light scattering and charge collection through the unique 1D nanostructure, improved electrical conductivity, and better band alignment with the n-type CdS layer. A solar-to-hydrogen efficiency of 2.33% is achieved under unassisted conditions with a state-of-the-art Mo:BiVO 4 photoanode, with excellent stability exceeding 21 h.