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 ...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.展开更多
Au@Cu2O core-shell nanorods with tunable thickness of Cu2O shell were synthesized and their linear and nonlinear optical responses were investigated. Two transverse plasmon resonance peaks were observed when the Au na...Au@Cu2O core-shell nanorods with tunable thickness of Cu2O shell were synthesized and their linear and nonlinear optical responses were investigated. Two transverse plasmon resonance peaks were observed when the Au nanorods were coated with Cu2O shells, which were adjusted by the Cu2O shell thickness. The nonlinear absorption of the Au@Cu2O nanorods is enhanced by 5 times at the longitudinal plasmon resonance wavelength compared with that of bare Au nanorods. More intriguingly, largely enhanced nonlinear refraction and suppressed nonlinear absorption at the transverse plasmon resonance wavelength were observed in the Au@Cu2O nanorods. Our findings indicate the existence of strong local field enhancement at the interface between the Au core and the Cu2O shell, which would provide a promising strategy in designing plasmonic nonlinear nanodevices with good nonlinear figures of merit.展开更多
基金supported by the National Natural Science Foundation of China(22162007)the Science and Technology Supporting Project of Guizhou Province([2021]480)+1 种基金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)。
文摘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(91750113,11674254)
文摘Au@Cu2O core-shell nanorods with tunable thickness of Cu2O shell were synthesized and their linear and nonlinear optical responses were investigated. Two transverse plasmon resonance peaks were observed when the Au nanorods were coated with Cu2O shells, which were adjusted by the Cu2O shell thickness. The nonlinear absorption of the Au@Cu2O nanorods is enhanced by 5 times at the longitudinal plasmon resonance wavelength compared with that of bare Au nanorods. More intriguingly, largely enhanced nonlinear refraction and suppressed nonlinear absorption at the transverse plasmon resonance wavelength were observed in the Au@Cu2O nanorods. Our findings indicate the existence of strong local field enhancement at the interface between the Au core and the Cu2O shell, which would provide a promising strategy in designing plasmonic nonlinear nanodevices with good nonlinear figures of merit.
