Interface-induced charge transfer pathway switching of a Cu2O-TiO2 photocatalyst from p-n to S-scheme heterojunction for effective photocatalytic H2 evolution

Photocatalytic hydrogen evolution from water splitting is an appealing method for producing clean chemical fuels. Cu2O, with a suitable bandgap, holds promise as a semiconductor for this process. However, the photocatalytic decomposition of Cu2O strongly limits its application in the photocatalytic field. Herein, an S-scheme heterojunction photocatalyst composed of TiO2 and Cu2O was rationally designed to effectively avoid the photo-corrosion of Cu2O. The introduction of an interfacial nitrogen-doped carbon (NC) layer switches the heterojunction interfacial charge transfer pathway from the p-n to S-scheme heterojunction, which avoids excessive accumulation of photogenerated holes on the surface of Cu2O. Meanwhile, the hybrid structure shows a broad spectral response (300–800 nm) and efficient charge separation and transfer efficiency. Interestingly, the highest photocatalytic hydrogen evolution rate of TiO2-NC-3%Cu2O-3%Ni is 13521.9 μmol g−1 h−1, which is approximately 664 times higher than that of pure Cu2O. In-situ X-ray photoelectron spectroscopy and Kelvin probe confirm the charge transfer mechanism of the S-scheme heterojunction. The formation of S-scheme heterojunctions effectively accelerates the separation of photogenerated electron-hole pairs and enhances redox capacity, thereby improving the photocatalytic performance and stability of Cu2O. This study provides valuable insights into the rational design of highly efficient Cu2O-based heterojunction photocatalysts for hydrogen production.