Unveiling Intrinsic Charge Transfer Dynamics in Bone-Joint S-Scheme Heterostructures for Promoting Photocatalytic Hydrogen Peroxide Generation

Abstract Constructing compact direct Z- and S-scheme heterostructures is an efficient strategy for realizing highly efficient charge separation and photocatalytic performance. However, the driving charge source of the built-in electric field (BEF) for internal electron-hole complexation sites remains unknown, which is a barrier to rationally design heterojunctions. Here, experimental results and theoretical research unveiled that complicated internal charges can be directly transferred to an intermediate co-crystal plane for electron–hole complexation in compact S-scheme heterostructures, called “bone-joint” heterostructures. It acted as an inner source of BEF that compels charge directed migration and exciton dissociation. Moreover, those bone joint structures adjust the inherent chemical and energetic interactions that manipulate the reactant adsorption mode and surface reaction energy. As a result, a synthesized catalyst displayed remarkable hydrogen peroxide production performance and stability. This offers a new paradigm for intrinsic charge transfer dynamics in heterostructures and a guiding philosophy for designing efficient heterostructures.