采用溶剂热法在不同反应体系和温度下,制备了一系列Cu In S2(CIS)粉体。CIS粉体的物相、形貌、光吸收性能分别用X射线衍射(XRD)仪、场发射扫描电镜(FESEM)、透射电镜(TEM)、紫外-可见光谱仪(UV-Vis)等手段进行了表征。结果表明,180℃时...采用溶剂热法在不同反应体系和温度下,制备了一系列Cu In S2(CIS)粉体。CIS粉体的物相、形貌、光吸收性能分别用X射线衍射(XRD)仪、场发射扫描电镜(FESEM)、透射电镜(TEM)、紫外-可见光谱仪(UV-Vis)等手段进行了表征。结果表明,180℃时乙醇-硫脲体系所得"绣球"状CIS粉体为黄铜矿结构,而乙二胺-硫化钠体系则为"花簇"状纤锌矿结构,升高溶剂热温度,两者形貌均往"球体"演变;结合XRD,差热(DSC)分析表明纤锌矿CIS具有往黄铜矿CIS转变的趋势,物相转变温度约为453℃;受物相转变影响,纤锌矿CIS的带隙值由黄铜矿的1.43 e V减小至1.35 e V,其可见光吸收能力增强。同时探讨了CIS物相的转变机理。展开更多
Photocatalytic hydrogen production technology is an ideal approach to addressing energy and environmental issues,with efficient charge transfer being the key to achieving high-performance hydrogen production.Ultra-thi...Photocatalytic hydrogen production technology is an ideal approach to addressing energy and environmental issues,with efficient charge transfer being the key to achieving high-performance hydrogen production.Ultra-thin CuInS_(2)nanosheets were prepared through a solvothermal method.Subsequently,metallic Ni was surface-modified onto CuInS_(2)through photo-deposition to serve as a co-catalyst.The optimized photocatalyst exhibited a hydrogen production rate of 15.5 mmol·g^(-1)·h^(-1)in water when used an ascorbic acid as hole scavenger,which is 9 times that of the original CuInS_(2).Transient absorption spectra(TAS)analysis demonstrates that the hole transfer from CuInS_(2)nanosheets to ascorbic acid,yielding a long-lived electron with a lifetime of 45.6μs.The electrons in CuInS_(2)are efficiently captured by Ni as active sites for driving hydrogen evolution.In situ TAS further indicates that ascorbic acid and Ni sites synergistically promote the electron transfer dynamics of CuInS_(2),achieving an electron transfer efficiency of 48.4%.This work provides a viable strategy for designing highly efficient photocatalysts with enhanced charge transfer.展开更多
Rational design of composite catalysts with efficient charge separation and transfer is of great significance to achieve efficient degradation of pollutants.Herein,CuInS_(2)nanoparticles are skillfully deposited on Ti...Rational design of composite catalysts with efficient charge separation and transfer is of great significance to achieve efficient degradation of pollutants.Herein,CuInS_(2)nanoparticles are skillfully deposited on TiO_(2)nanofibers through a hydrothermal method.The formation of S-scheme heterojunction is confirmed through free radical trapping experiments,in‐situ irradiated X-ray photoelectron spectroscopy(ISI-XPS)measurements,density functional theory(DFT)calculations and femtosecond transient absorption spectroscopy(fs-TAS)results.These results reveal that the built-in electric field within the S-scheme heterojunction significantly enhances charge separation and transfer,boosting the catalyst's redox capabilities.The TiO_(2)/CuInS_(2)photocatalyst exhibits superior photocatalytic performance,achieving a degradation rate of 89%within 21 min of light irradiation,which is almost 2.2 times higher than that of TiO_(2).Additionally,the degradation products of TCH are investigated using in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and liquid chromatography–mass spectrometry(LC-MS),offering insights into the degradation pathway.This study highlights the potential advantage of ultrafast charge carrier transfer in S-scheme heterojunction,providing a promising strategy for designing high-efficiency photocatalytic systems for environmental remediation.The findings offer new directions for improving the degradation of persistent pollutants like tetracyclines.展开更多
CuInS_(2)quantum-dot(CIS QD)-modified g-C_(3)N_(4)(CN)catalysts(CIS/CN)were prepared with the aid of an in-situ growth process.The as-obtained photocatalysts were explored by measuring their crystallinity,surface morp...CuInS_(2)quantum-dot(CIS QD)-modified g-C_(3)N_(4)(CN)catalysts(CIS/CN)were prepared with the aid of an in-situ growth process.The as-obtained photocatalysts were explored by measuring their crystallinity,surface morphology,binding energy and light absorption activity.The photocatalytic efficiency of the pho-tocatalysts was evaluated through photocatalytic water splitting for hydrogen production and tetracycline(TC)antibiotic degradation under the simulated solar light and visible light respectively.The optimized sample(10CIS/CN)showed the best photocatalytic activity:producing 102.4μmol g^(-1)h^(-1)of hydrogen in 1 h,or degrading 52.16%of TC in 120 min,which were respectively 48 or 3.4 times higher than the photocatalytic activity of CN itself.The enhancement in the efficiency of the composite system was prin-cipally accredited to the enlargement of light absorption,the more effective in charge transfer and the dropping of the charge carrier pair recombination through a formed S-scheme heterojunctional interface.This work is an effort to adjust CN-based polysulfide QD for speedy photocatalysis.The enriched photo-catalytic activity grants a new sense for adjusting the optical properties of CN.展开更多
Herein,a dual near-infrared(NIR)-response AgInS_(2)and CuInS_(2)co-sensitized ZnO photoelectrode array consisting of two spatial-resolved paper working electrodes(PWE1and PWE2)was established to enable paper-based rat...Herein,a dual near-infrared(NIR)-response AgInS_(2)and CuInS_(2)co-sensitized ZnO photoelectrode array consisting of two spatial-resolved paper working electrodes(PWE1and PWE2)was established to enable paper-based ratiometric photoelec trochemical(PEC)aptasensing of Di(2-ethylhexyl)phthalate(DEHP)based on triple-helix molecular switch(THMS)-mediated"on-off"switching of co-sensitization effect.Profiting from the cosensitization of AgInS_(2)and CuInS_(2)on paper-based ZnO,the dual NIR-response cascade sensitization structure of AgInS_(2)/CuInS_(2)/ZnO exhibited a wide light response range and high charge separation efficiency,giving a"switch on"state of co-sensitization effect with markedly high photocurrent response.The"switch off"state of the co-sensitization effect was made by RecJf exonuclease-assisted target recycling-induced conformation change of THMS,which caused the detachment of AgInS_(2)quantum dots from the aptasensing interface,leading to a significantly decreased photocurrent signal.Accordingly,the constant I_(1)of PWE_(1)and varying I_(2)of PWE_(2)were collected based on the incubation of constant concentration of DEHP on PWE1and various concentrations of DEHP on PWE_(2).The ultrasensitive detection of DEHP was realized by calculating the ratio of I_(2)/I_(1).This work brought new insights into the establishment of a high-performance paper-based ratiometric PEC aptasensing platform for highly sensitive quantification of DEHP.展开更多
Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-mat...Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-matched S-scheme heterostructure and establishing a robust built-in electric field emerge as pivotal strategies.In pursuit of this goal,a core-shell structured CuInS_(2)@CoS_(2)S-scheme heterojunction was meticulously engineered through a two-step molten salt method.This approach over the CuInS_(2)-based composites produced an internal electric field owing to the disparity be-tween the Fermi levels of CoS_(2) and CuInS_(2) at their interface.Consequently,the electric field facili-tated the directed migration of charges and the proficient separation of photoinduced carriers.The resulting CuInS_(2)@CoS_(2) heterostructure exhibited remarkable CO_(2) photoreduction performance,which was 21.7 and 26.5 times that of pure CuInS_(2) and CoS_(2),respectively.The S-scheme heterojunc-tion photogenerated charge transfer mechanism was validated through a series of rigorous anal-yses,including in situ irradiation X-ray photoelectron spectroscopy,work function calculations,and differential charge density examinations.Furthermore,in situ infrared spectroscopy and density functional theory calculations corroborated the fact that the CuInS_(2)@CoS_(2) heterojunction substan-tially lowered the formation energy of *COOH and *CO.This study demonstrates the application potential of S-scheme heterojunctions fabricated via the molten salt method in the realm of ad-dressing carbon-related environmental issues.展开更多
文摘采用溶剂热法在不同反应体系和温度下,制备了一系列Cu In S2(CIS)粉体。CIS粉体的物相、形貌、光吸收性能分别用X射线衍射(XRD)仪、场发射扫描电镜(FESEM)、透射电镜(TEM)、紫外-可见光谱仪(UV-Vis)等手段进行了表征。结果表明,180℃时乙醇-硫脲体系所得"绣球"状CIS粉体为黄铜矿结构,而乙二胺-硫化钠体系则为"花簇"状纤锌矿结构,升高溶剂热温度,两者形貌均往"球体"演变;结合XRD,差热(DSC)分析表明纤锌矿CIS具有往黄铜矿CIS转变的趋势,物相转变温度约为453℃;受物相转变影响,纤锌矿CIS的带隙值由黄铜矿的1.43 e V减小至1.35 e V,其可见光吸收能力增强。同时探讨了CIS物相的转变机理。
文摘Photocatalytic hydrogen production technology is an ideal approach to addressing energy and environmental issues,with efficient charge transfer being the key to achieving high-performance hydrogen production.Ultra-thin CuInS_(2)nanosheets were prepared through a solvothermal method.Subsequently,metallic Ni was surface-modified onto CuInS_(2)through photo-deposition to serve as a co-catalyst.The optimized photocatalyst exhibited a hydrogen production rate of 15.5 mmol·g^(-1)·h^(-1)in water when used an ascorbic acid as hole scavenger,which is 9 times that of the original CuInS_(2).Transient absorption spectra(TAS)analysis demonstrates that the hole transfer from CuInS_(2)nanosheets to ascorbic acid,yielding a long-lived electron with a lifetime of 45.6μs.The electrons in CuInS_(2)are efficiently captured by Ni as active sites for driving hydrogen evolution.In situ TAS further indicates that ascorbic acid and Ni sites synergistically promote the electron transfer dynamics of CuInS_(2),achieving an electron transfer efficiency of 48.4%.This work provides a viable strategy for designing highly efficient photocatalysts with enhanced charge transfer.
基金financially supported by the National Natural Science Foundation of China(Nos.42207386,22378103,52372294,and 22262025)the Middle-aged and Young Teachers’Basic Ability Promotion Project of Guangxi(No.2021KY0390).
文摘Rational design of composite catalysts with efficient charge separation and transfer is of great significance to achieve efficient degradation of pollutants.Herein,CuInS_(2)nanoparticles are skillfully deposited on TiO_(2)nanofibers through a hydrothermal method.The formation of S-scheme heterojunction is confirmed through free radical trapping experiments,in‐situ irradiated X-ray photoelectron spectroscopy(ISI-XPS)measurements,density functional theory(DFT)calculations and femtosecond transient absorption spectroscopy(fs-TAS)results.These results reveal that the built-in electric field within the S-scheme heterojunction significantly enhances charge separation and transfer,boosting the catalyst's redox capabilities.The TiO_(2)/CuInS_(2)photocatalyst exhibits superior photocatalytic performance,achieving a degradation rate of 89%within 21 min of light irradiation,which is almost 2.2 times higher than that of TiO_(2).Additionally,the degradation products of TCH are investigated using in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and liquid chromatography–mass spectrometry(LC-MS),offering insights into the degradation pathway.This study highlights the potential advantage of ultrafast charge carrier transfer in S-scheme heterojunction,providing a promising strategy for designing high-efficiency photocatalytic systems for environmental remediation.The findings offer new directions for improving the degradation of persistent pollutants like tetracyclines.
基金supported by National Natural Science Foundation of China(Nos.52272287,22268003 and 22202138)Project from Yunnan Province(Nos.202301AT070027,202305AF150116)Development Fund from Dali University(No.KY2296129740).
文摘CuInS_(2)quantum-dot(CIS QD)-modified g-C_(3)N_(4)(CN)catalysts(CIS/CN)were prepared with the aid of an in-situ growth process.The as-obtained photocatalysts were explored by measuring their crystallinity,surface morphology,binding energy and light absorption activity.The photocatalytic efficiency of the pho-tocatalysts was evaluated through photocatalytic water splitting for hydrogen production and tetracycline(TC)antibiotic degradation under the simulated solar light and visible light respectively.The optimized sample(10CIS/CN)showed the best photocatalytic activity:producing 102.4μmol g^(-1)h^(-1)of hydrogen in 1 h,or degrading 52.16%of TC in 120 min,which were respectively 48 or 3.4 times higher than the photocatalytic activity of CN itself.The enhancement in the efficiency of the composite system was prin-cipally accredited to the enlargement of light absorption,the more effective in charge transfer and the dropping of the charge carrier pair recombination through a formed S-scheme heterojunctional interface.This work is an effort to adjust CN-based polysulfide QD for speedy photocatalysis.The enriched photo-catalytic activity grants a new sense for adjusting the optical properties of CN.
基金financially supported by the National Natural Science Foundation of China(No.22306070)Shandong Provincial Natural Science Foundation(No.ZR2023QB002)+5 种基金the Science and Technology Program of University of Jinan(No.XKY2203)the National Undergraduate Innovation and Entrepreneurship Training Program(Nos.202210427008 and 202210427005)the Postdoctoral Science Foundation of University of Jinan(No.XBH2208)Taishan Scholars Program(No.tsqn202103082)the Excellent Youth Innovation Team in Universities of Shandong(No.2021KJ021)China Postdoctoral Science Foundation(No.2023M731302)。
文摘Herein,a dual near-infrared(NIR)-response AgInS_(2)and CuInS_(2)co-sensitized ZnO photoelectrode array consisting of two spatial-resolved paper working electrodes(PWE1and PWE2)was established to enable paper-based ratiometric photoelec trochemical(PEC)aptasensing of Di(2-ethylhexyl)phthalate(DEHP)based on triple-helix molecular switch(THMS)-mediated"on-off"switching of co-sensitization effect.Profiting from the cosensitization of AgInS_(2)and CuInS_(2)on paper-based ZnO,the dual NIR-response cascade sensitization structure of AgInS_(2)/CuInS_(2)/ZnO exhibited a wide light response range and high charge separation efficiency,giving a"switch on"state of co-sensitization effect with markedly high photocurrent response.The"switch off"state of the co-sensitization effect was made by RecJf exonuclease-assisted target recycling-induced conformation change of THMS,which caused the detachment of AgInS_(2)quantum dots from the aptasensing interface,leading to a significantly decreased photocurrent signal.Accordingly,the constant I_(1)of PWE_(1)and varying I_(2)of PWE_(2)were collected based on the incubation of constant concentration of DEHP on PWE1and various concentrations of DEHP on PWE_(2).The ultrasensitive detection of DEHP was realized by calculating the ratio of I_(2)/I_(1).This work brought new insights into the establishment of a high-performance paper-based ratiometric PEC aptasensing platform for highly sensitive quantification of DEHP.
文摘Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-matched S-scheme heterostructure and establishing a robust built-in electric field emerge as pivotal strategies.In pursuit of this goal,a core-shell structured CuInS_(2)@CoS_(2)S-scheme heterojunction was meticulously engineered through a two-step molten salt method.This approach over the CuInS_(2)-based composites produced an internal electric field owing to the disparity be-tween the Fermi levels of CoS_(2) and CuInS_(2) at their interface.Consequently,the electric field facili-tated the directed migration of charges and the proficient separation of photoinduced carriers.The resulting CuInS_(2)@CoS_(2) heterostructure exhibited remarkable CO_(2) photoreduction performance,which was 21.7 and 26.5 times that of pure CuInS_(2) and CoS_(2),respectively.The S-scheme heterojunc-tion photogenerated charge transfer mechanism was validated through a series of rigorous anal-yses,including in situ irradiation X-ray photoelectron spectroscopy,work function calculations,and differential charge density examinations.Furthermore,in situ infrared spectroscopy and density functional theory calculations corroborated the fact that the CuInS_(2)@CoS_(2) heterojunction substan-tially lowered the formation energy of *COOH and *CO.This study demonstrates the application potential of S-scheme heterojunctions fabricated via the molten salt method in the realm of ad-dressing carbon-related environmental issues.
基金Foundation items:National Nature Science Foundation of China(50972107,51172165)Zhejinag Province Key Scientific and Technological Innovations Team of China(2009R50010)+1 种基金Key Foundation of Zhejiang Province Natural Science Foundation of China(Z4110347)Wenzhou Municipal Science and Technology Bureau Key Program(G20090082)
