摘要
Structural engineering enhances plasmonic stability and amplifies localized electric fields,yet the limited intrinsic activity of plasmonic materials necessitates integrating catalytic active sites.Herein,we design a yolk@shell nanoreactor featuring dual-plasmonic Au@CuS core-shell structures encapsulated by sulfur vacancy-rich ZnIn2S4(Sv-ZIS).The electromagnetic“hotspots”from Au and CuS near-field coupling concentrate incident light to boost hot-carrier generation and migration while sulfur vacancies in Sv-ZIS promote hydrogen evolution.This dual mechanism synergistically achieves 86.3 mmol g^(-1)h-1of H2production(65.6%quantum efficiency at 420 nm),maintaining 48.3 mmol g^(-1)h-1at 6℃.Density functional theory(DFT)simulations demonstrate that sulfur vacancies not only reduce the H*adsorption energy barrier from 0.87 to 0.11 eV but also amplify the interfacial electric field strength by 9%.Vacancy-redirected fields favor proton reduction pathways,accelerating charge transfer kinetics.Comparative studies confirm the universal superiority of dual-plasmonic architecture,while Sv-ZIS shells exhibit optimized activity through defect-mediated electronic interactions.This work provides a blueprint for bridging plasmonic field enhancement and defect engineering in multi-component photocatalysts.
基金
supported by the National Natural Science Foundation of China(22162007)
the Science and Technology Supporting Project of Guizhou Province([2021]480)
the Science and Technology Supporting Project of Guizhou Province([2023)379)
the Project from Guizhou Institute of Innovation and development of dual-carbon and new energy technologies(DCRE-2023-05)。
