Plasmonic nonmetal semiconductors with localized surface plasmon resonance(LSPR)effects possess extended light-response ranges and can act as highly efficient H2 generation photocatalysts.Herein,an LSPR-enhanced 0D/2D...Plasmonic nonmetal semiconductors with localized surface plasmon resonance(LSPR)effects possess extended light-response ranges and can act as highly efficient H2 generation photocatalysts.Herein,an LSPR-enhanced 0D/2D CdS/MoO3‒x heterojunction has been synthesized by the growth of 0D CdS nanoparticles on 2D plasmonic MoO3‒x elliptical nanosheets via a simple coprecipitation method.Taking advantage of the LSPR effect of the MoO3‒x elliptical nanosheets,the light absorption of the CdS/MoO3‒x heterojunction was extended from 600 nm to the near-infrared region(1400 nm).Furthermore,the introduction of 2D plasmonic MoO3‒x elliptical nanosheets not only provided a platform for the growth of CdS nanoparticles,but also contributed to the construction of an LSPR-enhanced S-scheme structure due to the interface between the MoO3‒x and CdS,accelerating the separation of light-induced electrons and holes.Therefore,the CdS/MoO3‒x heterojunction exhibited higher photocatalytic H2 generation activity than pristine CdS under visible light irradiation,including under 420,450,550,and 650 nm monochromic light,as well as improved photo-corrosion performance.展开更多
Sub-stoichiometric MoO_(3−x)nanostructures with plasmonic absorption via creating oxygen vacancies have attracted extensive attentions for many intriguing applications.However,the synthesis of one-dimensional(1D)plasm...Sub-stoichiometric MoO_(3−x)nanostructures with plasmonic absorption via creating oxygen vacancies have attracted extensive attentions for many intriguing applications.However,the synthesis of one-dimensional(1D)plasmonic MoO_(3−x)nanostructures with widely tunable plasmonic absorption has remained a significant challenge because of their serious morphological destruction and phase change with increasing the concentration of oxygen vacancies.Here we demonstrate a surface-ligand protected reduction strategy for the synthesis of 1D MoO_(3−x)nanobelts with tunable plasmonic absorption in a wide wavelength range from 200 to 2,500 nm.Polyethylene glycol(PEG-400)is used as both the reductant to produce oxygen vacancies and the surface protected ligands to maintain 1D morphology during the formation process of MoO_(3−x)nanobelts,enabling the widely tunable plasmonic absorption.Owing to their broad plasmonic absorption and unique 1D nanostructure,we further demonstrate the application of 1D MoO_(3−x)nanobelts as photothermal film for interfacial solar evaporator.The surface-ligand protected reduction strategy provides a new avenue for the developing plasmonic semiconductor oxides with maintained particle morphology and thus enriching their wide applications.展开更多
Molybdenum trioxide(MoO_(3))has recently attracted wide attention as a typical conversion-type anode of Li-ion batteries(LIBs).Nevertheless,the inferior intrinsic conductivity and rapid capacity fading during charge/d...Molybdenum trioxide(MoO_(3))has recently attracted wide attention as a typical conversion-type anode of Li-ion batteries(LIBs).Nevertheless,the inferior intrinsic conductivity and rapid capacity fading during charge/discharge process seriously limit large-scale commercial application of MoO_(3).Herein,the density function theory(DFT)calculations show that electron-proton co-doping preferentially bonds symmetric oxygen to form unstable HxMoO_(3).When the-OH-group in HxMoO_(3) is released into the solution in the form of H_(2)O,it is going to form MoO_(3-x)with lower binding energy.By the means of both electron-proton co-doping and high-energy nanosizing,oxygen vacancies and nanoflower structure are introduced into MoO_(3) to accelerate the ion and electronic diffusion/transport kinetics.Benefitting from the promotion of ion diffusion kinetics related to nanostructures,as well as both the augmentation of active sites and the improvement of electrical conductivity induced by oxygen vacancies,the MoO_(3-x)/nanoflower structures show excellent lithium-ion storage performance.The prepared specimen has a high lithium-ion storage capacity of 1261 mA h g^(-1)at 0.1 A g^(-1)and cyclic stability(450 cycle),remarkably higher than those of previously reported MoO_(3)-based anode materials.展开更多
The photocatalytic reduction of CO2 with H2O to fuels and chemicals using solar energy is one of the most attractive but highly difficult routes.Thus far,only a very limited number of photocatalysts has been reported ...The photocatalytic reduction of CO2 with H2O to fuels and chemicals using solar energy is one of the most attractive but highly difficult routes.Thus far,only a very limited number of photocatalysts has been reported to be capable of catalyzing the photocatalytic reduction of CO2 under visible light.The utilization of the localized surface plasmon resonance(LSPR)phenomenon is an attractive strategy for developing visible-light photocatalysts.Herein,we have succeeded in synthesizing plasmonic MoO3?x-TiO2 nanocomposites with tunable LSPR by a simple solvothermal method.The well-structured nanocomposite containing two-dimensional(2D)molybdenum oxide(MoO3?x)nanosheets and one-dimensional(1D)titanium oxide nanotubes(TiO2-NT)showed LSPR absorption band in the visible-light region,and the incorporation of TiO2-NT significantly enhanced the LSPR absorption band.The MoO3?x-TiO2-NT nanocomposite is promising for application in the photocatalytic reduction of CO2 with H2O under visible light irradiation.展开更多
Design of a robust catalyst with high activity but the low cost for the hydrodeoxygenation(HDO) of biooils is of great importance to bring the biorefinery concept into reality.In this study,density functional theory(D...Design of a robust catalyst with high activity but the low cost for the hydrodeoxygenation(HDO) of biooils is of great importance to bring the biorefinery concept into reality.In this study,density functional theory(DFT) calculation was adopted to analyze the optimal location of Ni on MoO_(3-x) containing oxygen vacancy,and the corresponding result demonstrated that metallic Ni cluster located at the neighborhood of oxygen vacancies would significantly evoke HDO activity.Enlightened by DFT results,NiMoO_(4) was first hydrothermally synthesized and then employed to fabricate Ni-MoO_(3-x) catalyst via a low-temperature reduction,where Ni escaped from NiMoO_(4) and was reduced to its metallic state.Such an evolution of Ni species also induced the formation of oxygen vacancies around metallic Ni cluster.In the HDO of p-cresol,Ni-MoO_(3-x) exhibited high activity with a complete conversion and a methylcyclohexane selectivity of 99.4% at 150℃.Moreover,the catalyst showed good versatility in catalyzing HDO of diverse lignin-derived oxygenates and lignin oil.2D HSQC NMR,gas chromatograph and elemental analysis of the lignin oil demonstrated the high deoxygenation efficiency and saturation of the benzene ring over Ni-MoO_(3-x).In the upgrading of crude lignin oil,the deoxygenation degree was up to 99%,and the overall carbon yield of the naphthenes was as high as 69.4%.Importantly,the structures and carbon numbers of the naphthene products are similar to jet fuel-range cycloalka nes,which are expected to have a high density that can be blended into jet fuel to raise the range(or payload) of airplanes.This work demonstrates the feasibility for improving the targeted catalytic reactivity by rational tailoring the catalyst structure under the guidance of theoretical analysis,and provides an energy-efficient route for the upgrading of lignin crude oil into valuable naphthenes.展开更多
Simultaneous generation of H_(2) fuel and value-added chemicals has attracted increasing attention since the photogenerated electrons and holes can be both employed to convert solar light into chemical energy.Herein,f...Simultaneous generation of H_(2) fuel and value-added chemicals has attracted increasing attention since the photogenerated electrons and holes can be both employed to convert solar light into chemical energy.Herein,for realizing UV-visible-NIR light driven dehydrogenation of benzyl alcohol(BA)into benzaldehydes(BAD)and H_(2),a novel localized surface plasmon resonance(LSPR)enhanced S-scheme heterojunction was designed by combining noble-metal-free plasmon MoO_(3-x) as oxidation semiconductor and Zn_(0.1)Cd_(0.9)S as reduction semiconductor.The photoredox system of Zn_(0.1)Cd_(0.9)S/MoO_(3-x) displayed an unconventional reaction model,in which the BA served as both electron donor and acceptor.The S-scheme charge transfer mechanism induced by the formed internal electric field enhanced the redox ability of charge carriers thermodynamically and boosted charge separation kinetically.Moreover,due to the LSPR effect of MoO_(3-x) nanosheets,Zn_(0.1)Cd_(0.9)S/MoO_(3-x) photocatalysts exhibited strong absorption in the region of full solar spectrum.Therefore,the Zn_(0.1)Cd_(0.9)S/MoO_(3-x) composite generated H_(2) and BAD simultaneously via selective oxidation of BA with high production(34.38 and 33.83 mmol×g^(–1) for H_(2) and BAD,respectively)upon full solar illumination.Even under NIR light irradiation,the H_(2) production rate could up to 94.5 mmol×g^(–1)×h^(–1).In addition,the Zn_(0.1)Cd_(0.9)S/MoO_(3-x) composite displayed effective photocatalytic H_(2) evolution rate up to 149.2 mmol×g^(–1)×h^(–1) from water,which was approximate 6 times that of pure Zn_(0.1)Cd_(0.9)S.This work provides a reference for rational design of plasmonic S-scheme heterojunction photocatalysts for coproduction of high-value chemicals and solar fuel production.展开更多
文摘Plasmonic nonmetal semiconductors with localized surface plasmon resonance(LSPR)effects possess extended light-response ranges and can act as highly efficient H2 generation photocatalysts.Herein,an LSPR-enhanced 0D/2D CdS/MoO3‒x heterojunction has been synthesized by the growth of 0D CdS nanoparticles on 2D plasmonic MoO3‒x elliptical nanosheets via a simple coprecipitation method.Taking advantage of the LSPR effect of the MoO3‒x elliptical nanosheets,the light absorption of the CdS/MoO3‒x heterojunction was extended from 600 nm to the near-infrared region(1400 nm).Furthermore,the introduction of 2D plasmonic MoO3‒x elliptical nanosheets not only provided a platform for the growth of CdS nanoparticles,but also contributed to the construction of an LSPR-enhanced S-scheme structure due to the interface between the MoO3‒x and CdS,accelerating the separation of light-induced electrons and holes.Therefore,the CdS/MoO3‒x heterojunction exhibited higher photocatalytic H2 generation activity than pristine CdS under visible light irradiation,including under 420,450,550,and 650 nm monochromic light,as well as improved photo-corrosion performance.
基金supported by the Natural Science Foundation of Shandong Province(No.ZR2019JQ15)the National Natural Science Foundation of China(Nos.21671120 and 51972199).
文摘Sub-stoichiometric MoO_(3−x)nanostructures with plasmonic absorption via creating oxygen vacancies have attracted extensive attentions for many intriguing applications.However,the synthesis of one-dimensional(1D)plasmonic MoO_(3−x)nanostructures with widely tunable plasmonic absorption has remained a significant challenge because of their serious morphological destruction and phase change with increasing the concentration of oxygen vacancies.Here we demonstrate a surface-ligand protected reduction strategy for the synthesis of 1D MoO_(3−x)nanobelts with tunable plasmonic absorption in a wide wavelength range from 200 to 2,500 nm.Polyethylene glycol(PEG-400)is used as both the reductant to produce oxygen vacancies and the surface protected ligands to maintain 1D morphology during the formation process of MoO_(3−x)nanobelts,enabling the widely tunable plasmonic absorption.Owing to their broad plasmonic absorption and unique 1D nanostructure,we further demonstrate the application of 1D MoO_(3−x)nanobelts as photothermal film for interfacial solar evaporator.The surface-ligand protected reduction strategy provides a new avenue for the developing plasmonic semiconductor oxides with maintained particle morphology and thus enriching their wide applications.
基金financially supported by the National Natural Science Foundation of China(Key Program: 52034011,51974219General Program: 51974219)。
文摘Molybdenum trioxide(MoO_(3))has recently attracted wide attention as a typical conversion-type anode of Li-ion batteries(LIBs).Nevertheless,the inferior intrinsic conductivity and rapid capacity fading during charge/discharge process seriously limit large-scale commercial application of MoO_(3).Herein,the density function theory(DFT)calculations show that electron-proton co-doping preferentially bonds symmetric oxygen to form unstable HxMoO_(3).When the-OH-group in HxMoO_(3) is released into the solution in the form of H_(2)O,it is going to form MoO_(3-x)with lower binding energy.By the means of both electron-proton co-doping and high-energy nanosizing,oxygen vacancies and nanoflower structure are introduced into MoO_(3) to accelerate the ion and electronic diffusion/transport kinetics.Benefitting from the promotion of ion diffusion kinetics related to nanostructures,as well as both the augmentation of active sites and the improvement of electrical conductivity induced by oxygen vacancies,the MoO_(3-x)/nanoflower structures show excellent lithium-ion storage performance.The prepared specimen has a high lithium-ion storage capacity of 1261 mA h g^(-1)at 0.1 A g^(-1)and cyclic stability(450 cycle),remarkably higher than those of previously reported MoO_(3)-based anode materials.
文摘The photocatalytic reduction of CO2 with H2O to fuels and chemicals using solar energy is one of the most attractive but highly difficult routes.Thus far,only a very limited number of photocatalysts has been reported to be capable of catalyzing the photocatalytic reduction of CO2 under visible light.The utilization of the localized surface plasmon resonance(LSPR)phenomenon is an attractive strategy for developing visible-light photocatalysts.Herein,we have succeeded in synthesizing plasmonic MoO3?x-TiO2 nanocomposites with tunable LSPR by a simple solvothermal method.The well-structured nanocomposite containing two-dimensional(2D)molybdenum oxide(MoO3?x)nanosheets and one-dimensional(1D)titanium oxide nanotubes(TiO2-NT)showed LSPR absorption band in the visible-light region,and the incorporation of TiO2-NT significantly enhanced the LSPR absorption band.The MoO3?x-TiO2-NT nanocomposite is promising for application in the photocatalytic reduction of CO2 with H2O under visible light irradiation.
基金supported by the National Key R&D Program of China (2022YFB3805401, 2019YFC1905300)the National Natural Science Foundation of China (22178297)+1 种基金the Hunan Provincial Natural Science Foundation (2022JJ40425, 2022JJ40432)the Process Intensification and Green Chemical Engineering Innovation Team of Hunan Province。
文摘Design of a robust catalyst with high activity but the low cost for the hydrodeoxygenation(HDO) of biooils is of great importance to bring the biorefinery concept into reality.In this study,density functional theory(DFT) calculation was adopted to analyze the optimal location of Ni on MoO_(3-x) containing oxygen vacancy,and the corresponding result demonstrated that metallic Ni cluster located at the neighborhood of oxygen vacancies would significantly evoke HDO activity.Enlightened by DFT results,NiMoO_(4) was first hydrothermally synthesized and then employed to fabricate Ni-MoO_(3-x) catalyst via a low-temperature reduction,where Ni escaped from NiMoO_(4) and was reduced to its metallic state.Such an evolution of Ni species also induced the formation of oxygen vacancies around metallic Ni cluster.In the HDO of p-cresol,Ni-MoO_(3-x) exhibited high activity with a complete conversion and a methylcyclohexane selectivity of 99.4% at 150℃.Moreover,the catalyst showed good versatility in catalyzing HDO of diverse lignin-derived oxygenates and lignin oil.2D HSQC NMR,gas chromatograph and elemental analysis of the lignin oil demonstrated the high deoxygenation efficiency and saturation of the benzene ring over Ni-MoO_(3-x).In the upgrading of crude lignin oil,the deoxygenation degree was up to 99%,and the overall carbon yield of the naphthenes was as high as 69.4%.Importantly,the structures and carbon numbers of the naphthene products are similar to jet fuel-range cycloalka nes,which are expected to have a high density that can be blended into jet fuel to raise the range(or payload) of airplanes.This work demonstrates the feasibility for improving the targeted catalytic reactivity by rational tailoring the catalyst structure under the guidance of theoretical analysis,and provides an energy-efficient route for the upgrading of lignin crude oil into valuable naphthenes.
文摘Simultaneous generation of H_(2) fuel and value-added chemicals has attracted increasing attention since the photogenerated electrons and holes can be both employed to convert solar light into chemical energy.Herein,for realizing UV-visible-NIR light driven dehydrogenation of benzyl alcohol(BA)into benzaldehydes(BAD)and H_(2),a novel localized surface plasmon resonance(LSPR)enhanced S-scheme heterojunction was designed by combining noble-metal-free plasmon MoO_(3-x) as oxidation semiconductor and Zn_(0.1)Cd_(0.9)S as reduction semiconductor.The photoredox system of Zn_(0.1)Cd_(0.9)S/MoO_(3-x) displayed an unconventional reaction model,in which the BA served as both electron donor and acceptor.The S-scheme charge transfer mechanism induced by the formed internal electric field enhanced the redox ability of charge carriers thermodynamically and boosted charge separation kinetically.Moreover,due to the LSPR effect of MoO_(3-x) nanosheets,Zn_(0.1)Cd_(0.9)S/MoO_(3-x) photocatalysts exhibited strong absorption in the region of full solar spectrum.Therefore,the Zn_(0.1)Cd_(0.9)S/MoO_(3-x) composite generated H_(2) and BAD simultaneously via selective oxidation of BA with high production(34.38 and 33.83 mmol×g^(–1) for H_(2) and BAD,respectively)upon full solar illumination.Even under NIR light irradiation,the H_(2) production rate could up to 94.5 mmol×g^(–1)×h^(–1).In addition,the Zn_(0.1)Cd_(0.9)S/MoO_(3-x) composite displayed effective photocatalytic H_(2) evolution rate up to 149.2 mmol×g^(–1)×h^(–1) from water,which was approximate 6 times that of pure Zn_(0.1)Cd_(0.9)S.This work provides a reference for rational design of plasmonic S-scheme heterojunction photocatalysts for coproduction of high-value chemicals and solar fuel production.
