TiO2/FePS3 S‐Scheme Heterojunction for Greatly Raised Photocatalytic Hydrogen Evolution

Abstract The aggravating extreme climate changes and natural disasters stimulate the exploration of low‐carbon/zero‐carbon alternatives to traditional carbon‐based fossil fuels. Solar‐to‐hydrogen (STH) transformation is considered as appealing route to convert renewable solar energy into carbon‐free hydrogen. Restricted by the low efficiency and high cost of noble metal cocatalysts, high‐performance and cost‐effective photocatalysts are required to realize the realistic STH transformation. Herein, the 2D FePS 3 (FPS) nanosheets anchored with TiO 2 nanoparticles (TiO 2 /FePS 3 ) are synthesized and tested for the photocatalytic hydrogen evolution reaction. With the integration of FPS, the photocatalytic H 2 ‐evolution rate on TiO 2 /FePS 3 is radically increased by ≈1686%, much faster than that of TiO 2 alone. The origin of the greatly raised activity is revealed by theoretical calculations and various advanced characterizations, such as transient‐state photoluminescence spectroscopy/surface photovoltage spectroscopy, in situ atomic force microscopy combined with Kelvin probe force microscopy (AFM‐KPFM), in situ X‐ray photoelectron spectroscopy (XPS), and synchrotron‐based X‐ray absorption near edge structure. Especially, the in situ AFM‐KPFM and in situ XPS together confirm the electron transport pathway in TiO 2 /FePS 3 with light illumination, unveiling the efficient separation/transfer of charge carrier in TiO 2 /FePS 3 step‐scheme heterojunction. This work sheds light on designing and fabricating novel 2D material‐based S‐scheme heterojunctions in photocatalysis.