Embedding Tandem Built-in Electric Fields within Hollow Architectures for Enhanced Photothermal Effect in Alcohol Oxidation Coupled with H2 Production

Abstract

Rationally designing nanostructures based on a comprehensive understanding of structure-property relationships is instrumental in enhancing the photothermal effect. Here, a general two-stage morphology-structure-control strategy is presented to construct tandem built-in electric fields (BIEFs) embedded hollow bifunctional photocatalysts (Sv-chalcogenide hollow nanocage/NiCo₂S₄ heterojunctions, Sv represents sulfur vacancies, chalcogenides include ZnIn₂S₄, CdS, CdIn₂S₄). This strategy involves fabricating polyhedral cages via constraint epitaxy and embedding tandem BIEFs (consisting of intra-component and inter-component BIEF) within hollow nanocages through defect-mediated heterocomponent anchorage. The resulting hollow nanoreactors synergize multilight scattering/reflection with directional charge-transfer to boost photocarrier dynamics by stimulating plentiful carrier generation and driving continuous carrier localization and delocalized-electron transportation. Subsequently, the localized surface plasmon resonance (LSPR)-induced photogenerated electron excitation continuously collaborates with the intrinsic excitation for hot electron generation, thus improving the photothermal effect. Heterojunctions with efficient photothermal regulation optimize the pivotal intermediate adsorption/activation in selective alcohol oxidation coupled with H₂ evolution, delivering unprecedented reactivity and broad alcohol substrate compatibility. This study provides a programmable framework for structurally designing BIEFs within hollow architectures, elucidating the substantial impact of morphology-structure control on photogenerated carrier dynamics and molecular catalytic behavior.