The design and construction of heterojunction photocatalysts,which possess a staggered energy band structure and appropriate interfacial contact,is an effective way to achieve outstanding photocatalytic performance.In...The design and construction of heterojunction photocatalysts,which possess a staggered energy band structure and appropriate interfacial contact,is an effective way to achieve outstanding photocatalytic performance.In this study,2D/2D BiOBr/g‐C_(3)N_(4)heterojunctions were successfully obtained by a convenient in situ self‐assembly route.Under simulated sunlight irradiation,99%of RhB(10 mg·L–1,100 mL)was efficiently degraded by 1.5‐BiOBr/g‐C_(3)N_(4)within 30 min,which is better than the performance of both BiOBr and g‐C_(3)N_(4),and it has superior stability.In addition,the composite also exhibits enhanced photocatalytic activity for H2 production.The enhanced activity can be attributed to the intimate interface contact,the larger surface area,and the highly efficient separation of photoinduced electron–hole pairs.Based on the experimental results,a novel S‐scheme model was proposed to illuminate the transfer process of charge carriers.This study presents a simple way to develop novel step‐scheme photocatalysts for environmental and related applications.展开更多
A novel 2D/2D Bi_(2)MoO_(6)/g-C_(3)N_(4) step-scheme(S-scheme)composite by loading Au as cocatalyst was successfully fabricated using a photoreduction and hydrothermal route.The obtained Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au ...A novel 2D/2D Bi_(2)MoO_(6)/g-C_(3)N_(4) step-scheme(S-scheme)composite by loading Au as cocatalyst was successfully fabricated using a photoreduction and hydrothermal route.The obtained Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au photocatalysts were characterized by X-ray diffraction(XRD),transmission electron microscope(TEM),X-ray photo-electron spectroscopy(XPS),UV–vis diffuse reflectance spectra(UV–vis),Fourier transform infrared spectroscopy(FTIR),photoluminescence(PL),photocurrent response(I-t),and electrochemical impedance spectroscopy(EIS).The HRTEM images revealed that an intimate interface in composites were formed.The optimum photocatalytic activity of Rhodamine B degradation over Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au was about 9.7 times and 13.1 times as high as those of Bi_(2)MoO_(6) and g-C_(3)N_(4),respectively.The notably improved photocatalytic activity of Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au could be mainly ascribed to the abundant active sites and the enhanced separation efficiency of photogenerated carriers in Bi_(2)MoO_(6)/g-C_(3)N_(4) S-scheme system.Notably,Au nanoparticles could act as a co-catalyst to further promote electron transfer and separation from the conduction band of g-C_(3)N_(4).Additionally,a possible step-scheme photocatalytic reaction mechanism of Rh B degradation over Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au was tentatively proposed.PL and transient photocurrent analysis implied that Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au photocatalysts possessed the lower recombination rate of photogenerated carriers compared with pure Bi_(2) MoO_(6) and g-C_(3)N_(4),respectively.The present work is expected to provide useful information in designing 2D/2D S-scheme heterojunction photocatalysts.展开更多
Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination ra...Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate.Herein,a novel metal-free 2D/2D van der Waals heterojunction,composed of a two-dimensional(2D)COF with ketoenamine linkage(TpPa-1-COF)and 2D defective hexagonal boron nitride(h-BN),is successfully constructed through in situ solvothermal method.Benefitting from the presence of VDW heterojunction,larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN,which make contributions to promoting charge car-riers separation.The introduced defects can also endow the h-BN with porous structure,thus providing more reactive sites.Moreover,the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN,which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF,and suppress electron backflow,corroborated by experimental and density functional theory calculations results.Accordingly,the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays out-standing solar energy catalytic activity for water splitting without co-catalysts,and the H_(2) evolution rate can reach up to 3.15 mmol g^(−1) h^(−1),which is about 67 times greater than that of pristine TpPa-1-COF,also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date.In particular,it is the first work for constructing COFs-based heterojunctions with the help of h-BN,which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H_(2) evolution.展开更多
Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high...Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic performance.Herein,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction efficiency.Charge transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area interface.Work function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance spectroscopy.Moreover,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform spectra.Density functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and CO.Introducing Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 eV.This study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.展开更多
Constructing 2D/2D face-to-face heterojunctions is believed to be an effective strategy to enhance photocatalytic performance due to the enlarged contact interface and increased surface active sites.Herein,2D porous N...Constructing 2D/2D face-to-face heterojunctions is believed to be an effective strategy to enhance photocatalytic performance due to the enlarged contact interface and increased surface active sites.Herein,2D porous NiCo oxyphosphide(NiCoOP)was synthesized for the first time and coupled with graphitic carbon nitride(g-C_(3)N_(4))nanosheets to form 2D/2D heterojunctions via an in-situ phosphating method.The optimal 4 wt.%2D/2D NiCoOP/g-C_(3)N_(4)(OPCN)photocatalyst achieves a hydrogen evolution rate of 1.4 mmol·h^(−1)·g^(−1),which is 33 times higher than that of pure g-C_(3)N_(4).The greatly improved photocatalytic performance of the composite photocatalysts could be attributed to the formation of interfacial surface bonding states and sufficient charge transfer channels for accelerating carrier separation and transfer and the porous structure of NiCoOP nanosheets with abundant surface active sites for promoting surface reactions.Amazingly,the 2D/2D OPCN composite photocatalysts also exhibit superior stability during photocatalytic reactions.This study not only designs new noble-metal-free NiCoOP/g-C_(3)N_(4)composite photocatalysts but also provides a new sight in fabricating face-to-face 2D/2D heterojunctions for their application in energy conversion areas.展开更多
Photocatalytic H_(2) evolution from seawater splitting presents a promising approach to tackle the fossil energy crisis and mitigate carbon emission due to the abundant source of seawater and sunlight on the earth.How...Photocatalytic H_(2) evolution from seawater splitting presents a promising approach to tackle the fossil energy crisis and mitigate carbon emission due to the abundant source of seawater and sunlight on the earth.However,the development of efficient photocatalysts for seawater splitting remains a formidable challenge.Herein,a 2D/2D ZnIn_(2)S_(4)/WO_(3)(ZIS/WO_(3))heterojunction nanostructure is fabricated to efficiently separate the photoinduced carriers by steering electron transfer from the conduction band minimum of WO_(3) to the valence band maximum of ZIS via constructing internal electric field.Subsequently,plasmonic Au nanoparticles(NPs)as a novel photosensitizer and a reduction cocatalyst are anchored on ZIS/WO_(3) surface to further enhance the optical absorption of ZIS/WO_(3) heterojunction and accelerate the catalytic conversion.The obtained Au/ZIS/WO_(3) photocatalyst exhibits an outstanding H_(2) evolution rate of 2610.6 or 3566.3μmol g^(-1)h~(-1)from seawater splitting under visible or full-spectrum light irradiation,respectively.These rates represent an impressive increase of approximately 7.3-and 6,6-fold compared to those of ZIS under the illumination of the same light source.The unique 2D/2D structure,internal electric field,and plasmonic metal modification together boost the photocatalytic H_(2) evolution rate of Au/ZIS/WO_(3),making it even comparable to H_(2) evolution from pure water splitting.The present work sheds light on the development of efficient photocatalysts for seawater splitting.展开更多
Heterojunction design in a two-dimensional(2D)fashion has been deemed beneficial for improving the photocatalytic activity of g-C_(3)N_(4)because of the promoted interfacial charge transfer,yet still facing challenges...Heterojunction design in a two-dimensional(2D)fashion has been deemed beneficial for improving the photocatalytic activity of g-C_(3)N_(4)because of the promoted interfacial charge transfer,yet still facing challenges.Herein,we construct a novel 2D/2D Cu_(3)P nanosheet/P-doped g-C_(3)N_(4)(PCN)nanosheet heterojunction photocatalyst(PCN/Cu_(3)P)through a simple in-situ phosphorization treatment of 2D/2D CuS/g-C_(3)N_(4)composite for photocatalytic H2 evolution.We demonstrate that the 2D lamellar structure of both CuS and g-C_(3)N_(4)could be well reserved in the phosphorization process,while CuS and g-C_(3)N_(4)in-situ transformed into Cu_(3)P and PCN,respectively,leading to the formation of PCN/Cu_(3)P tight 2D/2D heterojunction.Owing to the large contact area provided by intimate face-to-face 2D/2D structure,the PCN/Cu_(3)P photocatalyst exhibits significantly enhanced charge separation efficiency,thus achieving a boosted visible-light-driven photocatalytic behavior.The highest rate for H2 evolution reaches 5.12 umol·h^(-1),nearly 24 times and 368 times higher than that of pristine PCN and g-C_(3)N_(4),respectively.This work represents an excellent example in elaborately con-structing g-C_(3)N_(4)-based 2D/2D heterostructure and could be extended to other photocatalyst/co-catalyst system.展开更多
文摘The design and construction of heterojunction photocatalysts,which possess a staggered energy band structure and appropriate interfacial contact,is an effective way to achieve outstanding photocatalytic performance.In this study,2D/2D BiOBr/g‐C_(3)N_(4)heterojunctions were successfully obtained by a convenient in situ self‐assembly route.Under simulated sunlight irradiation,99%of RhB(10 mg·L–1,100 mL)was efficiently degraded by 1.5‐BiOBr/g‐C_(3)N_(4)within 30 min,which is better than the performance of both BiOBr and g‐C_(3)N_(4),and it has superior stability.In addition,the composite also exhibits enhanced photocatalytic activity for H2 production.The enhanced activity can be attributed to the intimate interface contact,the larger surface area,and the highly efficient separation of photoinduced electron–hole pairs.Based on the experimental results,a novel S‐scheme model was proposed to illuminate the transfer process of charge carriers.This study presents a simple way to develop novel step‐scheme photocatalysts for environmental and related applications.
基金financially supported by the Fundamental Research Funds for the Central Universities(No.JUSRP51716A)the National Natural Science Foundation of China(Nos.21203077 and 21773099)the financially support from the Qing Lan Project of Jiangsu Province。
文摘A novel 2D/2D Bi_(2)MoO_(6)/g-C_(3)N_(4) step-scheme(S-scheme)composite by loading Au as cocatalyst was successfully fabricated using a photoreduction and hydrothermal route.The obtained Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au photocatalysts were characterized by X-ray diffraction(XRD),transmission electron microscope(TEM),X-ray photo-electron spectroscopy(XPS),UV–vis diffuse reflectance spectra(UV–vis),Fourier transform infrared spectroscopy(FTIR),photoluminescence(PL),photocurrent response(I-t),and electrochemical impedance spectroscopy(EIS).The HRTEM images revealed that an intimate interface in composites were formed.The optimum photocatalytic activity of Rhodamine B degradation over Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au was about 9.7 times and 13.1 times as high as those of Bi_(2)MoO_(6) and g-C_(3)N_(4),respectively.The notably improved photocatalytic activity of Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au could be mainly ascribed to the abundant active sites and the enhanced separation efficiency of photogenerated carriers in Bi_(2)MoO_(6)/g-C_(3)N_(4) S-scheme system.Notably,Au nanoparticles could act as a co-catalyst to further promote electron transfer and separation from the conduction band of g-C_(3)N_(4).Additionally,a possible step-scheme photocatalytic reaction mechanism of Rh B degradation over Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au was tentatively proposed.PL and transient photocurrent analysis implied that Bi_(2)MoO_(6)/g-C_(3)N_(4)/Au photocatalysts possessed the lower recombination rate of photogenerated carriers compared with pure Bi_(2) MoO_(6) and g-C_(3)N_(4),respectively.The present work is expected to provide useful information in designing 2D/2D S-scheme heterojunction photocatalysts.
基金supported by the National Natural Science Foundation of China(Nos.22101105,52071171,52202248)the Research Fund for the Doctoral Program of Liaoning Province(2021-BS-086)+6 种基金Liaoning BaiQianWan Talents Program(LNBQW2018B0048)Shenyang Science and Technology Project(21-108-9-04)Australian Research Council(ARC)through Future Fellowship(FT210100298,FT210100806)Discovery Project(DP220100603)Linkage Project(LP210100467,LP210200504,LP210200345,LP220100088)Industrial Transformation Training Centre(IC180100005)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077).
文摘Covalent organic frameworks(COFs)have emerged as a kind of rising star materials in photocatalysis.However,their photocatalytic activities are restricted by the high photogenerated electron-hole pairs recombination rate.Herein,a novel metal-free 2D/2D van der Waals heterojunction,composed of a two-dimensional(2D)COF with ketoenamine linkage(TpPa-1-COF)and 2D defective hexagonal boron nitride(h-BN),is successfully constructed through in situ solvothermal method.Benefitting from the presence of VDW heterojunction,larger contact area and intimate electronic coupling can be formed between the interface of TpPa-1-COF and defective h-BN,which make contributions to promoting charge car-riers separation.The introduced defects can also endow the h-BN with porous structure,thus providing more reactive sites.Moreover,the TpPa-1-COF will undergo a structural transformation after being integrated with defective h-BN,which can enlarge the gap between the conduction band position of the h-BN and TpPa-1-COF,and suppress electron backflow,corroborated by experimental and density functional theory calculations results.Accordingly,the resulting porous h-BN/TpPa-1-COF metal-free VDW heterojunction displays out-standing solar energy catalytic activity for water splitting without co-catalysts,and the H_(2) evolution rate can reach up to 3.15 mmol g^(−1) h^(−1),which is about 67 times greater than that of pristine TpPa-1-COF,also surpassing that of state-of-the-art metal-free-based photocatalysts reported to date.In particular,it is the first work for constructing COFs-based heterojunctions with the help of h-BN,which may provide new avenue for designing highly efficient metal-free-based photocatalysts for H_(2) evolution.
文摘Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic performance.Herein,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction efficiency.Charge transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area interface.Work function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance spectroscopy.Moreover,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform spectra.Density functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and CO.Introducing Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 eV.This study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.
基金the National Natural Science Foundation of China(Nos.52072197 and 52102272)Taishan Scholar Young Talent Program(No.tsqn201909114)+5 种基金the Natural Science Foundation of Shandong Province(No.ZR2021QE063)Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(No.2019KJC004)Major Scientific and Technological Innovation Project(No.2019JZZY020405)Outstanding Youth Foundation of Shandong Province,China(No.ZR2019JQ14)Major Basic Research Program of the Natural Science Foundation of Shandong Province(No.ZR2020ZD09)Talent Foundation funded by Province and Ministry Co-construction Collaborative Innovation Center of Eco-chemical Engineering(No.STHGYX2213).
文摘Constructing 2D/2D face-to-face heterojunctions is believed to be an effective strategy to enhance photocatalytic performance due to the enlarged contact interface and increased surface active sites.Herein,2D porous NiCo oxyphosphide(NiCoOP)was synthesized for the first time and coupled with graphitic carbon nitride(g-C_(3)N_(4))nanosheets to form 2D/2D heterojunctions via an in-situ phosphating method.The optimal 4 wt.%2D/2D NiCoOP/g-C_(3)N_(4)(OPCN)photocatalyst achieves a hydrogen evolution rate of 1.4 mmol·h^(−1)·g^(−1),which is 33 times higher than that of pure g-C_(3)N_(4).The greatly improved photocatalytic performance of the composite photocatalysts could be attributed to the formation of interfacial surface bonding states and sufficient charge transfer channels for accelerating carrier separation and transfer and the porous structure of NiCoOP nanosheets with abundant surface active sites for promoting surface reactions.Amazingly,the 2D/2D OPCN composite photocatalysts also exhibit superior stability during photocatalytic reactions.This study not only designs new noble-metal-free NiCoOP/g-C_(3)N_(4)composite photocatalysts but also provides a new sight in fabricating face-to-face 2D/2D heterojunctions for their application in energy conversion areas.
基金supported by the National Natural Science Foundation of China(21872104,21501131,21978216 and 22272082)the Natural Science Foundation of Tianjin for Distinguished Young Scholar(20JCJQJC00150)the Analytical&Testing Center of Tiangong University for PL work。
文摘Photocatalytic H_(2) evolution from seawater splitting presents a promising approach to tackle the fossil energy crisis and mitigate carbon emission due to the abundant source of seawater and sunlight on the earth.However,the development of efficient photocatalysts for seawater splitting remains a formidable challenge.Herein,a 2D/2D ZnIn_(2)S_(4)/WO_(3)(ZIS/WO_(3))heterojunction nanostructure is fabricated to efficiently separate the photoinduced carriers by steering electron transfer from the conduction band minimum of WO_(3) to the valence band maximum of ZIS via constructing internal electric field.Subsequently,plasmonic Au nanoparticles(NPs)as a novel photosensitizer and a reduction cocatalyst are anchored on ZIS/WO_(3) surface to further enhance the optical absorption of ZIS/WO_(3) heterojunction and accelerate the catalytic conversion.The obtained Au/ZIS/WO_(3) photocatalyst exhibits an outstanding H_(2) evolution rate of 2610.6 or 3566.3μmol g^(-1)h~(-1)from seawater splitting under visible or full-spectrum light irradiation,respectively.These rates represent an impressive increase of approximately 7.3-and 6,6-fold compared to those of ZIS under the illumination of the same light source.The unique 2D/2D structure,internal electric field,and plasmonic metal modification together boost the photocatalytic H_(2) evolution rate of Au/ZIS/WO_(3),making it even comparable to H_(2) evolution from pure water splitting.The present work sheds light on the development of efficient photocatalysts for seawater splitting.
基金We acknowledge the support from the National Natural Science Foundation of China(Nos.51876173 and 52142604)the Natural Science Foundation of Jiangsu Province(No.BK20190054)+2 种基金the Suzhou Science and Technology Program(SYG202101)Fok Ying-Tung Education Foundation(No.171048)the China Fundamental Research Funds for the Central Universities.
文摘Heterojunction design in a two-dimensional(2D)fashion has been deemed beneficial for improving the photocatalytic activity of g-C_(3)N_(4)because of the promoted interfacial charge transfer,yet still facing challenges.Herein,we construct a novel 2D/2D Cu_(3)P nanosheet/P-doped g-C_(3)N_(4)(PCN)nanosheet heterojunction photocatalyst(PCN/Cu_(3)P)through a simple in-situ phosphorization treatment of 2D/2D CuS/g-C_(3)N_(4)composite for photocatalytic H2 evolution.We demonstrate that the 2D lamellar structure of both CuS and g-C_(3)N_(4)could be well reserved in the phosphorization process,while CuS and g-C_(3)N_(4)in-situ transformed into Cu_(3)P and PCN,respectively,leading to the formation of PCN/Cu_(3)P tight 2D/2D heterojunction.Owing to the large contact area provided by intimate face-to-face 2D/2D structure,the PCN/Cu_(3)P photocatalyst exhibits significantly enhanced charge separation efficiency,thus achieving a boosted visible-light-driven photocatalytic behavior.The highest rate for H2 evolution reaches 5.12 umol·h^(-1),nearly 24 times and 368 times higher than that of pristine PCN and g-C_(3)N_(4),respectively.This work represents an excellent example in elaborately con-structing g-C_(3)N_(4)-based 2D/2D heterostructure and could be extended to other photocatalyst/co-catalyst system.
