Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme hetero...Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.展开更多
Constructing a step-scheme heterojunction at the interface between two semiconductors is an efficient way to optimize the redox ability and accelerate the charge carrier separation of a photocatalytic system for achie...Constructing a step-scheme heterojunction at the interface between two semiconductors is an efficient way to optimize the redox ability and accelerate the charge carrier separation of a photocatalytic system for achieving high photocatalytic performance.In this study,we prepared a hierarchical ZnO@ZnS step-scheme photocatalyst by incorporating ZnS into the outer shell of hollow ZnO microspheres via a simple in situ sulfidation strategy.The ZnO@ZnS step-scheme photocatalysts had a large surface area,high light utilization capacity,and superior separation efficiency for photogenerated charge carriers.In addition,the material simulation revealed that the formation of the step-scheme heterojunction between ZnO and ZnS was due to the presence of the built-in electric field.Our study paves the way for design of high-performance photocatalysts for H_(2) production.展开更多
Ce-doped ZnO microspheres were solvothermally prepared, and their microstructure, morphology, photoluminescence, and gas sensing were investigated by X-ray diffractometer, field emission scanning electron microscopy, ...Ce-doped ZnO microspheres were solvothermally prepared, and their microstructure, morphology, photoluminescence, and gas sensing were investigated by X-ray diffractometer, field emission scanning electron microscopy, transmission electron microscopy, fluorescence spectrometer and gas sensing analysis system. The results showed that the Ce-doped ZnO microspheres were composed of numerous nanorods with a diameter of 70 nm and a wurtzite structure. Ce-doping could cause a morphological transition from loose nanorods assembly to a tightly assembly in the microspheres. Compared with pure ZnO, the photoluminescence of the Ce-doped microspheres showed red-shifted UV emission and an enhanced blue emission. Particularly, the Ce-doped ZnO sensors exhibited much higher sensitivity and selectivity to ethanol than that of pure ZnO sensor at 320 °C. The ZnO microspheres doped with 6% Ce (mole fraction) exhibited the highest sensitivity (about 30) with rapid response (2 s) and recovery time (16 s) to 50×10?6 ethanol gas.展开更多
In this study,ZnO formation during the dissolution-passivation process of Zn anodes is observed via in situ Raman and optical characterization.The Zn passivation during galvanostatic anodization merely follows the dis...In this study,ZnO formation during the dissolution-passivation process of Zn anodes is observed via in situ Raman and optical characterization.The Zn passivation during galvanostatic anodization merely follows the dissolution-precipitation model,whereas that of potentiodynamic polarization exhibits different behaviors in different potential ranges.Initially,the Zn electrode is gradually covered by a ZnO precipitation film and then undergoes solid-state oxidation at~255 mV.The starting point of solid-state oxidation is well indicated by the abrupt current drop and yellow coloration of the electrode surface.During the pseudo passivation,an intense current oscillation is observed.Further,blink-like color changes between yellow and dark blue are revealed for the first time,implying that the oscillation is caused by the dynamic adsorption and desorption of OH groups.The as-formed ZnOs then experience a dissolution-reformation evolution,during which the crystallinity of the primary ZnO film is improved but the solid-state-formed ZnO layer becomes rich in oxygen vacancies.Eventually,oxide densification is realized,contributing to the Zn passivation.This study provides new insights into the Zn dissolution-passivation behavior,which is critical for the future optimization of Zn batteries.展开更多
Microspheres covered with ZnO nanowires were fabricated by oxidative evaporation of pure zinc powder without catalyst at 450℃. X-my diffraction （XRD） demonstrates that the as-obtained sample can be indexed to high ...Microspheres covered with ZnO nanowires were fabricated by oxidative evaporation of pure zinc powder without catalyst at 450℃. X-my diffraction （XRD） demonstrates that the as-obtained sample can be indexed to high crystaUinity with wurtzite structure. The structural features associated with different growth stages were monitored using scanning elec- tron microscope （SEM）, which described the direct observation nucleation and growth process. Meanwhile, room temperature photoluminescence （PL） spectrum showed a UV emission at -388 nm and a broad green emission at -505 nm. The ZnO nanowires with the self-catalyzed growth mechanism were discussed in detail.展开更多
ZnS nanophases were synthesized through a low-temperature route using a mixed solvent, diethylenetriamine （DETA） and deionized water （DIW）, as the reaction medium. The assynthesized products were characterized by ...ZnS nanophases were synthesized through a low-temperature route using a mixed solvent, diethylenetriamine （DETA） and deionized water （DIW）, as the reaction medium. The assynthesized products were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM） and high-resolution transmission electron microscopy （HRTEM）. The experimental results indicate that ZnS nanophase is formed through a phase evolution of ZnS·（DETA）1/2→ ZnS.DETA→ZnS. The ZnS flower-like microspheres sized around 2μm consist of many nanobelts whose structure could be regarded as an alternative admixture of hexagonal wurtzite （WZ） and cubic zinc blende （ZB）. The optical absorption measurements demonstrate that the spectral feature of the sample changes with the evolution of the phase structure.展开更多
ZnO/ZnGa_2O_4 composite microspheres with heterojunction were successfully synthesized by one-pot hydrothermal method.These samples were characterized by TG/DTA,XRD,TEM,HRTEM,UV-vis DRS,FL and BET techniques.The resul...ZnO/ZnGa_2O_4 composite microspheres with heterojunction were successfully synthesized by one-pot hydrothermal method.These samples were characterized by TG/DTA,XRD,TEM,HRTEM,UV-vis DRS,FL and BET techniques.The results indicated the as-prepared samples showed better degree of crystalline and large specific surface area.The photocatalytic activity was evaluated by degradation of methyl orange with the concentration of 50 mg/L under the irradiation of simulated sunlight.The effects of molar ratio of Zn to Ga and calcination temperature on the photocatalytic activity were investigated in detail.The results showed that the highest photocatalytic degradation efficiency was observed at the molar ratio of Zn to Ga of 1:0.5 in the starting materials and the calcination temperature of 400 °C.The maximum photocatalytic degradation rate of MO was 97.1% within 60 min under the simulated sunlight irradiation,which is greatly higher than that of ZnO and ZnGa_2O_4.展开更多
This paper introduces the method of porous ZnO microspheres by sodium citrate assisted hydrothermal synthesis with a mild, economy： first, basic synthesis globose precursor of Zinc Carbonate Hydroxide, then followed ...This paper introduces the method of porous ZnO microspheres by sodium citrate assisted hydrothermal synthesis with a mild, economy： first, basic synthesis globose precursor of Zinc Carbonate Hydroxide, then followed by thermal decompose the precursor to obtain porous Zinc Oxide microspheres. The morphology and structure of the precursor and synthesized porous microspheres were characterize by a series of methods, and did a series of experiments by changing dosage and reaction time of the sodium citrate and urea, finally the paper discussed the formation mechanism of porous ZnO microspheres.展开更多
文摘Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.
文摘Constructing a step-scheme heterojunction at the interface between two semiconductors is an efficient way to optimize the redox ability and accelerate the charge carrier separation of a photocatalytic system for achieving high photocatalytic performance.In this study,we prepared a hierarchical ZnO@ZnS step-scheme photocatalyst by incorporating ZnS into the outer shell of hollow ZnO microspheres via a simple in situ sulfidation strategy.The ZnO@ZnS step-scheme photocatalysts had a large surface area,high light utilization capacity,and superior separation efficiency for photogenerated charge carriers.In addition,the material simulation revealed that the formation of the step-scheme heterojunction between ZnO and ZnS was due to the presence of the built-in electric field.Our study paves the way for design of high-performance photocatalysts for H_(2) production.
基金Project(61079010)supported by the National Natural Science Foundation of China and the Civil Aviation Administration of ChinaProject(3122013P001)supported by the Significant Pre-research Funds of Civil Aviation University of ChinaProject(MHRD20140209)supported by the Science and Technology Innovation Guide Funds of Civil Aviation Administration of China
文摘Ce-doped ZnO microspheres were solvothermally prepared, and their microstructure, morphology, photoluminescence, and gas sensing were investigated by X-ray diffractometer, field emission scanning electron microscopy, transmission electron microscopy, fluorescence spectrometer and gas sensing analysis system. The results showed that the Ce-doped ZnO microspheres were composed of numerous nanorods with a diameter of 70 nm and a wurtzite structure. Ce-doping could cause a morphological transition from loose nanorods assembly to a tightly assembly in the microspheres. Compared with pure ZnO, the photoluminescence of the Ce-doped microspheres showed red-shifted UV emission and an enhanced blue emission. Particularly, the Ce-doped ZnO sensors exhibited much higher sensitivity and selectivity to ethanol than that of pure ZnO sensor at 320 °C. The ZnO microspheres doped with 6% Ce (mole fraction) exhibited the highest sensitivity (about 30) with rapid response (2 s) and recovery time (16 s) to 50×10?6 ethanol gas.
基金supported by the Research and Development Initiative for Scientific Innovation of New Generation Batteries(RISING)Projects,RISING2[JPNP16001]and RISING3[JPNP21006],commissioned by of the New Energy and Industrial Technology Development Organization(NEDO),Japanthe State Scholarship Fund of the China Scholarship Council[No.201906230294]for their support
文摘In this study,ZnO formation during the dissolution-passivation process of Zn anodes is observed via in situ Raman and optical characterization.The Zn passivation during galvanostatic anodization merely follows the dissolution-precipitation model,whereas that of potentiodynamic polarization exhibits different behaviors in different potential ranges.Initially,the Zn electrode is gradually covered by a ZnO precipitation film and then undergoes solid-state oxidation at~255 mV.The starting point of solid-state oxidation is well indicated by the abrupt current drop and yellow coloration of the electrode surface.During the pseudo passivation,an intense current oscillation is observed.Further,blink-like color changes between yellow and dark blue are revealed for the first time,implying that the oscillation is caused by the dynamic adsorption and desorption of OH groups.The as-formed ZnOs then experience a dissolution-reformation evolution,during which the crystallinity of the primary ZnO film is improved but the solid-state-formed ZnO layer becomes rich in oxygen vacancies.Eventually,oxide densification is realized,contributing to the Zn passivation.This study provides new insights into the Zn dissolution-passivation behavior,which is critical for the future optimization of Zn batteries.
文摘Microspheres covered with ZnO nanowires were fabricated by oxidative evaporation of pure zinc powder without catalyst at 450℃. X-my diffraction （XRD） demonstrates that the as-obtained sample can be indexed to high crystaUinity with wurtzite structure. The structural features associated with different growth stages were monitored using scanning elec- tron microscope （SEM）, which described the direct observation nucleation and growth process. Meanwhile, room temperature photoluminescence （PL） spectrum showed a UV emission at -388 nm and a broad green emission at -505 nm. The ZnO nanowires with the self-catalyzed growth mechanism were discussed in detail.
基金Supported by the project of Nano-molecular Functional Materials of Fujian Province (2005HZ01-1)
文摘ZnS nanophases were synthesized through a low-temperature route using a mixed solvent, diethylenetriamine （DETA） and deionized water （DIW）, as the reaction medium. The assynthesized products were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM） and high-resolution transmission electron microscopy （HRTEM）. The experimental results indicate that ZnS nanophase is formed through a phase evolution of ZnS·（DETA）1/2→ ZnS.DETA→ZnS. The ZnS flower-like microspheres sized around 2μm consist of many nanobelts whose structure could be regarded as an alternative admixture of hexagonal wurtzite （WZ） and cubic zinc blende （ZB）. The optical absorption measurements demonstrate that the spectral feature of the sample changes with the evolution of the phase structure.
基金Projects(21306041,21271071)supported by the National Natural Science Foundation of ChinaProject(15A076)supported by the Scientific Research Foundation of Hunan Provincial Education Department of China
文摘ZnO/ZnGa_2O_4 composite microspheres with heterojunction were successfully synthesized by one-pot hydrothermal method.These samples were characterized by TG/DTA,XRD,TEM,HRTEM,UV-vis DRS,FL and BET techniques.The results indicated the as-prepared samples showed better degree of crystalline and large specific surface area.The photocatalytic activity was evaluated by degradation of methyl orange with the concentration of 50 mg/L under the irradiation of simulated sunlight.The effects of molar ratio of Zn to Ga and calcination temperature on the photocatalytic activity were investigated in detail.The results showed that the highest photocatalytic degradation efficiency was observed at the molar ratio of Zn to Ga of 1:0.5 in the starting materials and the calcination temperature of 400 °C.The maximum photocatalytic degradation rate of MO was 97.1% within 60 min under the simulated sunlight irradiation,which is greatly higher than that of ZnO and ZnGa_2O_4.
文摘This paper introduces the method of porous ZnO microspheres by sodium citrate assisted hydrothermal synthesis with a mild, economy： first, basic synthesis globose precursor of Zinc Carbonate Hydroxide, then followed by thermal decompose the precursor to obtain porous Zinc Oxide microspheres. The morphology and structure of the precursor and synthesized porous microspheres were characterize by a series of methods, and did a series of experiments by changing dosage and reaction time of the sodium citrate and urea, finally the paper discussed the formation mechanism of porous ZnO microspheres.
