The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(...The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.展开更多
Defect and charge transfer efficiency of nano-photocatalysts are important factors which influence their photocatalytic performance.In this work,oxygen vacancies are successfully introduced in the synthesis process of...Defect and charge transfer efficiency of nano-photocatalysts are important factors which influence their photocatalytic performance.In this work,oxygen vacancies are successfully introduced in the synthesis process of Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterojunctions through one-step in situ selfcombustion method.High-resolution transmission electron microscopy (HRTEM),UV-Vis diffuse reflectance spectra (UV-Vis DRS),and electron spin resonance (ESR) measurements confirm the existence of oxygen vacancies.In addition,by controlling the ratio of reactants of Bi(NO_(3))_(3)to Al(NO_(3))_(3),the ratio of Bi_(2)Al_(4)O_(9)and β-Bi_(2)O_(3)in the heterojunction can be easily adjusted.Photocurrent responses and surface photovoltage spectroscopy (SPV) indicate that the construction of the Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterostructure improves the separation efficiency of the photo-generated electrons and holes.CO_(2)-TPD results imply that the amounts and stability of heterojunctions are enhanced compared with their counterparts.The Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterojunction with 14 mol%Bi_(2)Al_(4)O_(9)shows the highest photocatalytic ability for reduction of CO_(2)into CO.The enhanced photoreduction of CO_(2)performance can be ascribed to the synergistic effects of the heterojunction for electron separation and oxygen vacancies for CO_(2)activation.展开更多
Semiconductor photocatalysis has been considered as a potential technology for the removal of organic dyes from wastewater.The development of photocatalysts with high stability and strong catalytic activity is the mos...Semiconductor photocatalysis has been considered as a potential technology for the removal of organic dyes from wastewater.The development of photocatalysts with high stability and strong catalytic activity is the most important in application.Visible-light-induced NiCo_(2)O_(4)@Co_(3)O_(4) core/shell heterojunctions were synthesized via a sol-gel method in this paper.Compared to bare NiCo_(2)O_(4) and Co_(3)O_(4),NiCo_(2)O_(4)@Co_(3)O_(4) showed a remarkably enhanced removal rate towards congo red(CR)degradation with 98.4%of the removal rate to CR at 120 min under irradiation.The excellent performance of NiCo_(2)O_(4)@Co_(3)O_(4) benefits from the effective separation of photogenerated electron-holes by forming a heterojunction,and the rapid transfer efficiency of photo-generated charge carriers results from the core/shell architectures.A mechanism that NiCo_(2)O_(4)@Co_(3)O_(4) degrades CR to harmless inorganic substances by h^(+),•O-2 and•OH during the photocatalytic process was proposed.展开更多
Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions...Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions were synthesized by a facile solvothermal route.The resultant materials were examined by X-ray photoelectron spectrometer(XPS),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),photoluminescence spectroscopy(PL),Fourier transform infrared spectroscopy(FT-IR),UV-Vis diffuse reflection spectroscopy(UV-vis DRS),photocurrent density,electrochemical impedance spectroscopy(EIS),and Brunauer–Emmett–Teller(BET)analyses.After the integration of Fe-MOF with GCN-NSh/Bi_(5)O_(7)Br,the removal constant of tetracycline over the optimal GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite was promoted 33 times compared with that of the pristine GCN.The GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite showed superior photoactivity to azithromycin,metronidazole,and cephalexin removal that was 36.4,20.2,and 14.6 times higher than that of pure GCN,respectively.Radical quenching tests showed that·O_(2)-and h+mainly contributed to the elimination reaction.In addition,the nanocomposite maintained excellent activity after 4 successive cycles.Based on the developed n–n heterojunctions among n-GCN-NSh,n-Bi_(5)O_(7)Br,and n-Fe-MOF semiconductors,the double S-scheme charge transfer mechanism was proposed for the destruction of the selected antibiotics.展开更多
SnO_(2)/Co_(3)O_(4)nanofibers(NFs)are synthesized by using a homopolar electrospinning system with double jets of positive polarity electric fields.The morphology and structure of SnO_(2)/Co_(3)O_(4)hetero-nanofibers ...SnO_(2)/Co_(3)O_(4)nanofibers(NFs)are synthesized by using a homopolar electrospinning system with double jets of positive polarity electric fields.The morphology and structure of SnO_(2)/Co_(3)O_(4)hetero-nanofibers are characterized by using field emission scanning electron microscope(FE-SEM),transmission electron microscope(TEM),x-ray diffraction(XRD),and x-ray photoelectron spectrometer(XPS).The analyses of SnO_(2)/Co_(3)O_(4)NFs by EDS and HRTEM show that the cobalt and tin exist on one nanofiber,which is related to the homopolar electrospinning and the crystallization during sintering.As a typical n-type semiconductor,Sn O_(2)has the disadvantages of high optimal operating temperature and poor reproducibility.Comparing with Sn O_(2),the optimal operating temperature of SnO_(2)/Co_(3)O_(4)NFs is reduced from 350℃to 250℃,which may be related to the catalysis of Co_(2)O_(2).The response of SnO_(2)/Co_(3)O_(4)to 100-ppm ethanol at 250℃is 50.9,9 times higher than that of pure Sn O_(2),which may be attributed to the p–n heterojunction between the n-type Sn O_(2)crystalline grain and the p-type Co_(2)O_(2)crystalline grain.The nanoscale p–n heterojunction promotes the electron migration and forms an interface barrier.The synergy effects between Sn O_(2)and Co_(2)O_(2),the crystalline grain p–n heterojunction,the existence of nanofibers and the large specific surface area all jointly contribute to the improved gas sensing performance.展开更多
g-C_(3)N_(4)emerges as a promising metal-free semiconductor photocatalyst due to its cost-effectiveness,facile synthesis,suitable visible light response,and robust thermal stability.However,its practical application i...g-C_(3)N_(4)emerges as a promising metal-free semiconductor photocatalyst due to its cost-effectiveness,facile synthesis,suitable visible light response,and robust thermal stability.However,its practical application in photocatalytic hydrogen evolution reaction(HER)is impeded by rapid carrier recombination and limited light absorption capacity.In this study,we successfully develop a novel g-C_(3)N_(4)-based step-scheme(S-scheme)heterojunction comprising two-dimensional(2D)sulfur-doped g-C_(3)N_(4)nanosheets(SCN)and one-dimensional(1D)FeCo_(2)O_(4)nanorods(FeCo_(2)O_(4)),demonstrating enhanced photocatalytic HER activity.The engineered SCN/FeCo_(2)O_(4)S-scheme heterojunction features a well-defined 2D/1D heterogeneous interface facilitating directed interfacial electron transfer from FeCo_(2)O_(4)to SCN,driven by the lower Fermi level of SCN compared to FeCo_(2)O_(4).This establishment of electron-interacting 2D/1D S-scheme heterojunction not only facilitates the separation and migration of photogenerated carriers,but also enhances visible-light absorption and mitigates electron-hole pair recombination.Band structure analysis and density functional theory calculations corroborate that the carrier migration in the SCN/FeCo_(2)O_(4)photocatalyst adheres to a typical S-scheme heterojunction mechanism,effectively retaining highly reactive photogenerated electrons.Consequently,the optimized SCN/FeCo_(2)O_(4)heterojunction exhibits a substantially high hydrogen production rate of 6303.5μmol·g^(-1)·h^(-1)under visible light excitation,which is 2.4 times higher than that of the SCN.Furthermore,the conjecture of the S-scheme mechanism is confirmed by in situ XPS measurement.The 2D/1D S-scheme heterojunction established in this study provides valuable insights into the development of high-efficiency carbon-based catalysts for diverse energy conversion and storage applications.展开更多
The fabrication of heterojunction catalysts is an effective strategy to enhance charge separation efficiency,thus boosting the performance of photocatalysts.This work presents the synthesis and investigation of a nove...The fabrication of heterojunction catalysts is an effective strategy to enhance charge separation efficiency,thus boosting the performance of photocatalysts.This work presents the synthesis and investigation of a novel KNbO_(3)/Bi_(4)O_(5)Br_(2) heterostructure catalyst for photocatalytic N_(2)-to-NH_(3) conversion under light illumination.While morphology analysis revealed KNbO_(3) microcubes embedded within Bi_(4)O_(5)Br_(2) nanosheets,the composite exhibited no significant improvement in specific surface area or optical property compared to Bi_(4)O_(5)Br_(2) due to the relatively wide band gap and low surface area of KNbO_(3).The main contribution lies in the enhanced separation efficiency of photogenerated electrons and holes.Besides,the band structure analysis suggests that KNbO_(3) and Bi_(4)O_(5)Br_(2) exhibit suitable band potentials to form a type II heterojunction.Benefiting from the higher Fermi level of KNbO_(3) than Bi_(4)O_(5)Br_(2),the electron drift at the contact region thus occurs and leads to the formation of a built-in electric field with the direction from KNbO_(3) to Bi_(4)O_(5)Br_(2),accelerating electron migration and improving the operational efficiency of the photocatalysts.Consequently,the KNbO_(3)/Bi_(4)O_(5)Br_(2) catalyst shows an increased photoactivity,achieving an NH_(3) generation rate 1.78 and 1.58 times those of KNbO_(3) and Bi_(4)O_(5)Br_(2),respectively.This work may offer valuable insights for the design and synthesis of heterojunction composite photocatalysts.展开更多
文摘The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.
基金financial support from the National Natural Science Foundation of China(21776059,21376061)the Natural Science Foundation for Distinguished Young Scholars of Hebei Province(B2015208010)the Research Foundation of Hebei Province Education Department(No.ZC2016007)。
文摘Defect and charge transfer efficiency of nano-photocatalysts are important factors which influence their photocatalytic performance.In this work,oxygen vacancies are successfully introduced in the synthesis process of Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterojunctions through one-step in situ selfcombustion method.High-resolution transmission electron microscopy (HRTEM),UV-Vis diffuse reflectance spectra (UV-Vis DRS),and electron spin resonance (ESR) measurements confirm the existence of oxygen vacancies.In addition,by controlling the ratio of reactants of Bi(NO_(3))_(3)to Al(NO_(3))_(3),the ratio of Bi_(2)Al_(4)O_(9)and β-Bi_(2)O_(3)in the heterojunction can be easily adjusted.Photocurrent responses and surface photovoltage spectroscopy (SPV) indicate that the construction of the Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterostructure improves the separation efficiency of the photo-generated electrons and holes.CO_(2)-TPD results imply that the amounts and stability of heterojunctions are enhanced compared with their counterparts.The Bi_(2)Al_(4)O_(9)/β-Bi_(2)O_(3)heterojunction with 14 mol%Bi_(2)Al_(4)O_(9)shows the highest photocatalytic ability for reduction of CO_(2)into CO.The enhanced photoreduction of CO_(2)performance can be ascribed to the synergistic effects of the heterojunction for electron separation and oxygen vacancies for CO_(2)activation.
基金Project(2017TP1031)supported by the Hunan Key Laboratory for Rare Earth Functional Materials,ChinaProject(2020JJ4735)supported by the Natural Science Foundation of Hunan Province,China+1 种基金Project(2018GK4001)supported by Science and Technology Department of Hunan Province Tackling Key Scientific and Technological Problems and Transformation of Major Scientific and Technological Achievements,ChinaProject(CSUZC202126)supported by the Open Sharing Fund for the Large-scale Instruments and Equipments of Central South University,China。
文摘Semiconductor photocatalysis has been considered as a potential technology for the removal of organic dyes from wastewater.The development of photocatalysts with high stability and strong catalytic activity is the most important in application.Visible-light-induced NiCo_(2)O_(4)@Co_(3)O_(4) core/shell heterojunctions were synthesized via a sol-gel method in this paper.Compared to bare NiCo_(2)O_(4) and Co_(3)O_(4),NiCo_(2)O_(4)@Co_(3)O_(4) showed a remarkably enhanced removal rate towards congo red(CR)degradation with 98.4%of the removal rate to CR at 120 min under irradiation.The excellent performance of NiCo_(2)O_(4)@Co_(3)O_(4) benefits from the effective separation of photogenerated electron-holes by forming a heterojunction,and the rapid transfer efficiency of photo-generated charge carriers results from the core/shell architectures.A mechanism that NiCo_(2)O_(4)@Co_(3)O_(4) degrades CR to harmless inorganic substances by h^(+),•O-2 and•OH during the photocatalytic process was proposed.
文摘Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions were synthesized by a facile solvothermal route.The resultant materials were examined by X-ray photoelectron spectrometer(XPS),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),photoluminescence spectroscopy(PL),Fourier transform infrared spectroscopy(FT-IR),UV-Vis diffuse reflection spectroscopy(UV-vis DRS),photocurrent density,electrochemical impedance spectroscopy(EIS),and Brunauer–Emmett–Teller(BET)analyses.After the integration of Fe-MOF with GCN-NSh/Bi_(5)O_(7)Br,the removal constant of tetracycline over the optimal GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite was promoted 33 times compared with that of the pristine GCN.The GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite showed superior photoactivity to azithromycin,metronidazole,and cephalexin removal that was 36.4,20.2,and 14.6 times higher than that of pure GCN,respectively.Radical quenching tests showed that·O_(2)-and h+mainly contributed to the elimination reaction.In addition,the nanocomposite maintained excellent activity after 4 successive cycles.Based on the developed n–n heterojunctions among n-GCN-NSh,n-Bi_(5)O_(7)Br,and n-Fe-MOF semiconductors,the double S-scheme charge transfer mechanism was proposed for the destruction of the selected antibiotics.
文摘SnO_(2)/Co_(3)O_(4)nanofibers(NFs)are synthesized by using a homopolar electrospinning system with double jets of positive polarity electric fields.The morphology and structure of SnO_(2)/Co_(3)O_(4)hetero-nanofibers are characterized by using field emission scanning electron microscope(FE-SEM),transmission electron microscope(TEM),x-ray diffraction(XRD),and x-ray photoelectron spectrometer(XPS).The analyses of SnO_(2)/Co_(3)O_(4)NFs by EDS and HRTEM show that the cobalt and tin exist on one nanofiber,which is related to the homopolar electrospinning and the crystallization during sintering.As a typical n-type semiconductor,Sn O_(2)has the disadvantages of high optimal operating temperature and poor reproducibility.Comparing with Sn O_(2),the optimal operating temperature of SnO_(2)/Co_(3)O_(4)NFs is reduced from 350℃to 250℃,which may be related to the catalysis of Co_(2)O_(2).The response of SnO_(2)/Co_(3)O_(4)to 100-ppm ethanol at 250℃is 50.9,9 times higher than that of pure Sn O_(2),which may be attributed to the p–n heterojunction between the n-type Sn O_(2)crystalline grain and the p-type Co_(2)O_(2)crystalline grain.The nanoscale p–n heterojunction promotes the electron migration and forms an interface barrier.The synergy effects between Sn O_(2)and Co_(2)O_(2),the crystalline grain p–n heterojunction,the existence of nanofibers and the large specific surface area all jointly contribute to the improved gas sensing performance.
基金supported by the National Natural Science Foundation of China(No.62004143)the Key R&D Program of Hubei Province(No.2022BAA084)the Natural Science Foundation of Hubei Province(Nos.2021CFB133 and 2024AFB890).
文摘g-C_(3)N_(4)emerges as a promising metal-free semiconductor photocatalyst due to its cost-effectiveness,facile synthesis,suitable visible light response,and robust thermal stability.However,its practical application in photocatalytic hydrogen evolution reaction(HER)is impeded by rapid carrier recombination and limited light absorption capacity.In this study,we successfully develop a novel g-C_(3)N_(4)-based step-scheme(S-scheme)heterojunction comprising two-dimensional(2D)sulfur-doped g-C_(3)N_(4)nanosheets(SCN)and one-dimensional(1D)FeCo_(2)O_(4)nanorods(FeCo_(2)O_(4)),demonstrating enhanced photocatalytic HER activity.The engineered SCN/FeCo_(2)O_(4)S-scheme heterojunction features a well-defined 2D/1D heterogeneous interface facilitating directed interfacial electron transfer from FeCo_(2)O_(4)to SCN,driven by the lower Fermi level of SCN compared to FeCo_(2)O_(4).This establishment of electron-interacting 2D/1D S-scheme heterojunction not only facilitates the separation and migration of photogenerated carriers,but also enhances visible-light absorption and mitigates electron-hole pair recombination.Band structure analysis and density functional theory calculations corroborate that the carrier migration in the SCN/FeCo_(2)O_(4)photocatalyst adheres to a typical S-scheme heterojunction mechanism,effectively retaining highly reactive photogenerated electrons.Consequently,the optimized SCN/FeCo_(2)O_(4)heterojunction exhibits a substantially high hydrogen production rate of 6303.5μmol·g^(-1)·h^(-1)under visible light excitation,which is 2.4 times higher than that of the SCN.Furthermore,the conjecture of the S-scheme mechanism is confirmed by in situ XPS measurement.The 2D/1D S-scheme heterojunction established in this study provides valuable insights into the development of high-efficiency carbon-based catalysts for diverse energy conversion and storage applications.
基金supported by the National Natural Science Foundation of China (Grant No.22172144)the Key Research and Development Program of Zhejiang Province (Grant No.2023C03148).
文摘The fabrication of heterojunction catalysts is an effective strategy to enhance charge separation efficiency,thus boosting the performance of photocatalysts.This work presents the synthesis and investigation of a novel KNbO_(3)/Bi_(4)O_(5)Br_(2) heterostructure catalyst for photocatalytic N_(2)-to-NH_(3) conversion under light illumination.While morphology analysis revealed KNbO_(3) microcubes embedded within Bi_(4)O_(5)Br_(2) nanosheets,the composite exhibited no significant improvement in specific surface area or optical property compared to Bi_(4)O_(5)Br_(2) due to the relatively wide band gap and low surface area of KNbO_(3).The main contribution lies in the enhanced separation efficiency of photogenerated electrons and holes.Besides,the band structure analysis suggests that KNbO_(3) and Bi_(4)O_(5)Br_(2) exhibit suitable band potentials to form a type II heterojunction.Benefiting from the higher Fermi level of KNbO_(3) than Bi_(4)O_(5)Br_(2),the electron drift at the contact region thus occurs and leads to the formation of a built-in electric field with the direction from KNbO_(3) to Bi_(4)O_(5)Br_(2),accelerating electron migration and improving the operational efficiency of the photocatalysts.Consequently,the KNbO_(3)/Bi_(4)O_(5)Br_(2) catalyst shows an increased photoactivity,achieving an NH_(3) generation rate 1.78 and 1.58 times those of KNbO_(3) and Bi_(4)O_(5)Br_(2),respectively.This work may offer valuable insights for the design and synthesis of heterojunction composite photocatalysts.
