Particulate photoelectrodes are promising for the development of innovative unbiased water-splitting devices by combining a photoanode and a photocathode. This configuration relaxes the requirements for band edge potentials of oxygen- and hydrogen-evolution systems while enhancing the solar-to-hydrogen conversion efficiency. However, particulate photocathodes often exhibit lower performance than thin-film-based photocathodes because of the difficulty of implementing functional structures. In this study, a novel CdTe-based particulate photocathode prepared via the modified particle transfer method, along with a ZnTe contact layer introduced via the close-spaced sublimation method, is presented. A ZnxCd1−xTe (0 ≤ x ≤ 1) solid solution with a composition gradient is produced under the appropriate preparation conditions, and the conduction-band minimum gradient introduced by the composition gradient suppresses charge recombination and shifts the onset potential of the cathodic photocurrent to +0.7 VRHE. The introduction of a Cu layer to the back contact and post-deposition rapid thermal annealing further enhances the photocurrent, which reaches −7mA cm−2 at 0 VRHE and a half-cell solar-to-hydrogen efficiency of 1.1% at 0.28 VRHE. The photocathode also exhibits an incident photon-to-current conversion efficiency (IPCE) of 36% at 520 nm and greater than 10% IPCE across the wavelength range 440–800 nm, which is the highest IPCE reported thus far for a particulate photocathode. These findings demonstrate the potential of the method of introducing a composition gradient for enhancing photoelectrochemical and photocatalytic hydrogen evolution.
