Two-dimensional(2D)materials have come to light due to their unique thickness that owns abundant exposed edges with enhanced electrocatalytic properties.2D molybdenum disulfide(MoS_(2))nanosheet has aroused considerab...Two-dimensional(2D)materials have come to light due to their unique thickness that owns abundant exposed edges with enhanced electrocatalytic properties.2D molybdenum disulfide(MoS_(2))nanosheet has aroused considerable attention due to its tunable surface chemistry and high electrochemical sur-face area.Nonetheless,several shortcomings associated with MoS_(2),such as its naturally existing semi-conducting 2H phase,which has limited active sites due to the inert basal plane,restrict its application in water electrocatalysis.Taking into account the benefits of the 1T/2H phase of MoS_(2),as well as the importance of engineering 2D/2D heterojunction interface for boosted electrocatalysis,metallic Ti_(3)C_(2)Tx was integrated with 1T/2H MoS_(2) to develop 2D/2D 1T/2H MoS_(2)/Ti_(3)C_(2)Tx heterostructured nanocompos-ites.Herein,with only 25%of the intercalating agent,1T/2H MoS_(2) with the highest 1T phase content of~82%was successfully synthesized.It was further incorporated with 1 wt%of Ti_(3)C_(2)Tx through a com-bination of ultrasonication and mechanical stirring process.The 1T/2H MoS_(2)(25D)/Ti_(3)C_(2)Tx-1(MTC-1)manifested outstanding electrocatalytic performance with an overpotential and Tafel slope of 280 mV(83.80 mV dec^(-1))and 300 mV(117.2 mV dec^(-1)),for catalyzing acidic and alkaline medium HER,respec-tively.Pivotally,the as-prepared catalysts also illustrated long-term stability for more than 40 h.The coupling method for the 2D nanosheets is crucial to suppress the oxidation of Ti_(3)C_(2)Tx and the restack-ing issue of 2D nanosheets.The superior HER activity is ascribed to the synergistic effect between the heterostructure,enhancing the electronic structure and charge separation capability.The intrinsic prop-erty of the catalyst further confirms by turnover frequency(TOF)calculation.As such,this research paves the way for designing high-efficiency 2D electrocatalysts and sheds light on the further advancement of tunable 2D electrocatalysts for robust water splitting and beyond.展开更多
The 2D/3D heterojunction perovskites have garnered increasing attention due to their exceptional moisture and thermal stability.However,few works have paid attention to the influence of the subsequent change process o...The 2D/3D heterojunction perovskites have garnered increasing attention due to their exceptional moisture and thermal stability.However,few works have paid attention to the influence of the subsequent change process of 2D/3D heterojunction PSC on the stability of PSCs.Moreover,the evolution of the interface and carrier dynamic behavior of the 2D/3D perovskite films with long-term operation has not been systematically developed befo re.In this work,the effects of 2D/3 D heterojunction evolution on the interface of perovskite films and different carrier dynamics during 2D/3D evolution are systematically analyzed for the first time.The decomposition of 2D/3D heterojunction in the perovskite film will have a certain impact on the surface and carrier dynamics behavior of perovskite.During the evolution of 2D/3D heterojunction,PbI_(2)crystals will appear,which will improve the interfacial energy level matching between the electron transport layer and perovskite film.With a long evolution time,some holes will appear on the surface of perovskite film.The open circuit voltage(V_(OC))of PSCs increased from 1.14 to1.18 V and the PCE increased to 23.21%after 300 h storage in the nitrogen atmosphere,and maintained 89%initial performance for with 3000 h stability test in N_(2)box.This discovery has a significant role in promoting the development of inverted heterojunction PSCs and constructing the revolution mechanism of charge carrier dynamic.展开更多
Efficient photocatalytic water splitting can be significantly enhanced through the careful design of S-scheme heterostructures,which play a pivotal role in optimizing performance.Herein,we report the construction of Z...Efficient photocatalytic water splitting can be significantly enhanced through the careful design of S-scheme heterostructures,which play a pivotal role in optimizing performance.Herein,we report the construction of ZnIn_(2)S_(4)/CdS S-scheme heterojunctions under ambient conditions,based on a sonochemical strategy.This structure is facilitated by the well-matched interface between the(007)plane of layered ZnIn_(2)S_(4)and the(101)plane of CdS,leading to a threshold optical response of 2.12 eV,which optimally aligns with visible light absorption.As a proof of concept,the resulting ZnIn_(2)S_(4)/CdS catalysts demonstrate a remarkable improvement in photocatalytic H_(2) evolution,achieving a rate of 5678.2μmol h^(-1)g^(-1)under visible light irradiation(λ>400 nm).This rate is approximately 10 times higher than that of pristine ZnIn_(2)S_(4)nanosheets(NSs)and about 4.6 times higher than that of CdS nanoparticles(NPs),surpassing the performance of most ZnIn_(2)S_(4)-based photocatalysts reported to date.Moreover,they deliver a robust photocatalytic performance during long-term operation of up to 60 h,showing their potential for use in practical applications.Based on the theoretical calculation and experimental results,it is verified that the movements of electrons and holes in the opposite direction could be induced by the disparity in the work function and the internal electric field within the interfaces,thus facilitating the construction of S-scheme heterojunctions,which fundamentally suppresses carrier recombination while minimizing photocorrosion of ZnIn_(2)S_(4)toward enhanced photocatalytic behaviors.展开更多
Metal organic framework(MOF) shows great potential in the research field of photocatalysis,and it is a big challenge to achieve efficient photocatalytic activity.In this work,we have successfully grown two-dimensional...Metal organic framework(MOF) shows great potential in the research field of photocatalysis,and it is a big challenge to achieve efficient photocatalytic activity.In this work,we have successfully grown two-dimensional MOF(2D-MOF) nanosheets on 2D-MOF nanosheets for the first time using a homometallic nodal strategy,and successfully prepared ultrathin nanosheets with tightly bound 2D/2D heterojunctions.2D Ni-BDC nanosheets were used as carriers to grow 2D Ni-TCPP nanosheets on top of them.Ni-TCPP has a high light absorption capacity,thus extending the light absorption range of 2D/2D heterojunctions.The tight coupling of the heterojunction effectively shortens the electron transfer distance,promotes the separation of interracial charges,and improves the photocatalytic activity.Particularly,Ni-BDC/Ni-TCPP-3can achieve to a hydrogen production rate of428.0 μmol·g^(-1),approximately 5.75 times higher than NiBDC and 5.24 times higher than Ni-TCPP,respectively.Thus,2D-MOF/2D-MOF heterojunctions provide a promising strategy for enhancing photocatalytic performance through rational heterostructure design with homometallic node strategy.展开更多
Herein,a new type of two-dimensional(2D)/2D Ti_(3)C_(2)/TiO_(2) heterojunction was developed for efficient photocatalytic nitrogen reduction reaction(NRR),in which TiO_(2) nanosheets(TiO_(2) Ns)were designed as the ma...Herein,a new type of two-dimensional(2D)/2D Ti_(3)C_(2)/TiO_(2) heterojunction was developed for efficient photocatalytic nitrogen reduction reaction(NRR),in which TiO_(2) nanosheets(TiO_(2) Ns)were designed as the main catalyst,while Ti_(3)C_(2) MXene served as the co-catalyst.Experimental and theoretical results revealed that Ti_(3)C_(2) MXene introduced electron-rich unsaturated Ti sites,serving as highly active sites for both the adsorption and activation of N_(2) on the Ti_(3)C_(2)/TiO_(2) heterojunction.Furthermore,the 2D/2D Ti_(3)C_(2)/TiO_(2) heterostructure greatly promoted the directional separation and transfer of charge carriers,facilitated by the internal electric field.This structural feature enabled the spatial separation of the N_(2) reduction and H2 O oxidation half-reactions on the distinct surfaces of Ti_(3)C_(2)(001)and TiO_(2)(001),con-sequently reducing the reaction energy barrier for each respective process.The synergistic effects arising from the interface and surface interactions within the heterojunction conspicuously improved the photo-catalytic NRR activity.As a result,the optimized Ti_(3)C_(2)/TiO_(2) heterojunction exhibited a high NH_(3) produc-tion rate of 24.4μmol g−1 h−1 in the absence of sacrificial agents,representing a remarkable 12.8-fold increase compared to individual TiO_(2) Ns.This work provides new insights into rational design of high-performance heterogeneous photocatalysts and offers a deeper understanding of the mechanism under-lying surface active sites in the photocatalytic NRR process.展开更多
Heterojunction photocatalysts have shown considerable activities for organic pollutants degradation.However,the faint connection interface and inferior charge shift efficiency critically block the property of heteroju...Heterojunction photocatalysts have shown considerable activities for organic pollutants degradation.However,the faint connection interface and inferior charge shift efficiency critically block the property of heterojunction photocatalysis.Herein,Bi_(2)O_(2)S/NiFe_(2)O_(4) nanosheets heterojunction with ultrastrong inter-face interaction and high internal electric field are designed by an in-situ growth method.Tentative and theoretical consequences prove that the interfacial interaction and internal electric field not only act as the electron flow bridge but also decrease the electrons shift energy obstacle,thus speeding up electrons transfer and achieving effective spatial electron-hole separation.Therefore,a large amount of·O_(2)^(-)and holes as active species were generated.Remarkably,Bi_(2)O_(2) S/NiFe_(2)O_(4) establishes a considerably boosted photocatalytic performance for tetracycline degradation(0.032 min^(-1)),which is about 14.2-fold and 7.8-fold of the pristine BOS and NFO,respectively.This work provides a promising motivation for modulating charge transfer by interface control and internal electric field to boost photocatalytic performance.展开更多
基金Ministry of Higher Education(MOHE)Malaysia under the Fundamental Research Grant Scheme(FRGS)(Ref No:FRGS/1/2020/TK0/XMU/02/1)We would also like to thank the Ministry of Science,Technology and Innovation(MOSTI)Malaysia under the Strategic Research Fund(SRF-APP)(S.22015)+5 种基金The authors would also like to acknowledge the financial support provided by the National Natural Science Foundation of China(Ref No.22202168)Guangdong Basic and Applied Basic Re-search Foundation(Ref No.2021A1515111019)We would also like to acknowledge the financial support from the State Key Labo-ratory of Physical Chemistry of Solid Surfaces,Xiamen University(No.2023X11)This work is also funded by Xiamen University Malaysia Investigatorship Grant(Grant No.IENG/0038)Xiamen University Malaysia Research Fund(ICOE/0001,XMUMRF/2021-C8/IENG/0041 and XMUMRF/2019-C3/IENG/0013)Hengyuan International Sdn.Bhd.(Grant No.EENG/0003).
文摘Two-dimensional(2D)materials have come to light due to their unique thickness that owns abundant exposed edges with enhanced electrocatalytic properties.2D molybdenum disulfide(MoS_(2))nanosheet has aroused considerable attention due to its tunable surface chemistry and high electrochemical sur-face area.Nonetheless,several shortcomings associated with MoS_(2),such as its naturally existing semi-conducting 2H phase,which has limited active sites due to the inert basal plane,restrict its application in water electrocatalysis.Taking into account the benefits of the 1T/2H phase of MoS_(2),as well as the importance of engineering 2D/2D heterojunction interface for boosted electrocatalysis,metallic Ti_(3)C_(2)Tx was integrated with 1T/2H MoS_(2) to develop 2D/2D 1T/2H MoS_(2)/Ti_(3)C_(2)Tx heterostructured nanocompos-ites.Herein,with only 25%of the intercalating agent,1T/2H MoS_(2) with the highest 1T phase content of~82%was successfully synthesized.It was further incorporated with 1 wt%of Ti_(3)C_(2)Tx through a com-bination of ultrasonication and mechanical stirring process.The 1T/2H MoS_(2)(25D)/Ti_(3)C_(2)Tx-1(MTC-1)manifested outstanding electrocatalytic performance with an overpotential and Tafel slope of 280 mV(83.80 mV dec^(-1))and 300 mV(117.2 mV dec^(-1)),for catalyzing acidic and alkaline medium HER,respec-tively.Pivotally,the as-prepared catalysts also illustrated long-term stability for more than 40 h.The coupling method for the 2D nanosheets is crucial to suppress the oxidation of Ti_(3)C_(2)Tx and the restack-ing issue of 2D nanosheets.The superior HER activity is ascribed to the synergistic effect between the heterostructure,enhancing the electronic structure and charge separation capability.The intrinsic prop-erty of the catalyst further confirms by turnover frequency(TOF)calculation.As such,this research paves the way for designing high-efficiency 2D electrocatalysts and sheds light on the further advancement of tunable 2D electrocatalysts for robust water splitting and beyond.
基金financial support provided by the Sichuan Science and Technology Program(No.2022NSFSC0226)Sichuan Science and Technology Program(No.2023ZYD0163)+6 种基金the Production-Education Integration Demonstration Project of Sichuan Provincethe Photovoltaic Industry Production-Education Integration Comprehensive Demonstration Base of Sichuan Province(Sichuan Financial Education[2022]No.106)China Tianfu Yongxing Laboratory Science and Technology Key Project(2023KJGG15)National Key Research and Development Program of China(2022YFB3803300)Beijing Natural Science Foundation(IS23037)the Department for Energy Security and Net Zero(project ID:NEXTCCUS)the ACT program(Accelerating CCS Technologies,Horizon2020 project NO.691712)。
文摘The 2D/3D heterojunction perovskites have garnered increasing attention due to their exceptional moisture and thermal stability.However,few works have paid attention to the influence of the subsequent change process of 2D/3D heterojunction PSC on the stability of PSCs.Moreover,the evolution of the interface and carrier dynamic behavior of the 2D/3D perovskite films with long-term operation has not been systematically developed befo re.In this work,the effects of 2D/3 D heterojunction evolution on the interface of perovskite films and different carrier dynamics during 2D/3D evolution are systematically analyzed for the first time.The decomposition of 2D/3D heterojunction in the perovskite film will have a certain impact on the surface and carrier dynamics behavior of perovskite.During the evolution of 2D/3D heterojunction,PbI_(2)crystals will appear,which will improve the interfacial energy level matching between the electron transport layer and perovskite film.With a long evolution time,some holes will appear on the surface of perovskite film.The open circuit voltage(V_(OC))of PSCs increased from 1.14 to1.18 V and the PCE increased to 23.21%after 300 h storage in the nitrogen atmosphere,and maintained 89%initial performance for with 3000 h stability test in N_(2)box.This discovery has a significant role in promoting the development of inverted heterojunction PSCs and constructing the revolution mechanism of charge carrier dynamic.
基金supported by the National Natural Science Foundation of China(NSFC,Grant No.52372063,62204246 and 52401244)the Young Elite Scientists Sponsorship Program by CAST(Grant No.2023QNRC001)+1 种基金the Postdoctoral Fellowship Program of CPSF(Grant No.GZC20233001,GZC20233006)the China Postdoctoral Science Foundation(Grant No.2024M753526)。
文摘Efficient photocatalytic water splitting can be significantly enhanced through the careful design of S-scheme heterostructures,which play a pivotal role in optimizing performance.Herein,we report the construction of ZnIn_(2)S_(4)/CdS S-scheme heterojunctions under ambient conditions,based on a sonochemical strategy.This structure is facilitated by the well-matched interface between the(007)plane of layered ZnIn_(2)S_(4)and the(101)plane of CdS,leading to a threshold optical response of 2.12 eV,which optimally aligns with visible light absorption.As a proof of concept,the resulting ZnIn_(2)S_(4)/CdS catalysts demonstrate a remarkable improvement in photocatalytic H_(2) evolution,achieving a rate of 5678.2μmol h^(-1)g^(-1)under visible light irradiation(λ>400 nm).This rate is approximately 10 times higher than that of pristine ZnIn_(2)S_(4)nanosheets(NSs)and about 4.6 times higher than that of CdS nanoparticles(NPs),surpassing the performance of most ZnIn_(2)S_(4)-based photocatalysts reported to date.Moreover,they deliver a robust photocatalytic performance during long-term operation of up to 60 h,showing their potential for use in practical applications.Based on the theoretical calculation and experimental results,it is verified that the movements of electrons and holes in the opposite direction could be induced by the disparity in the work function and the internal electric field within the interfaces,thus facilitating the construction of S-scheme heterojunctions,which fundamentally suppresses carrier recombination while minimizing photocorrosion of ZnIn_(2)S_(4)toward enhanced photocatalytic behaviors.
基金financially supported by the National Natural Science Foundation of China (Nos.62104003,21972065 and 21803002)the Natural Science Foundation of Anhui Province (No.1908085QB75)+3 种基金Anhui Provincial Natural Science Foundation for Distinguished Young Scholars (No.2008085J11)the Natural Science Foundation of Jiangsu Province (No.BK20220006)the Key projects of Anhui Provincial Department of Education,China (Nos.KJ2021ZD0044 and KJ2020A0228)Hefei National Laboratory for Physical Sciences at the Microscale (No.KF2020006)。
文摘Metal organic framework(MOF) shows great potential in the research field of photocatalysis,and it is a big challenge to achieve efficient photocatalytic activity.In this work,we have successfully grown two-dimensional MOF(2D-MOF) nanosheets on 2D-MOF nanosheets for the first time using a homometallic nodal strategy,and successfully prepared ultrathin nanosheets with tightly bound 2D/2D heterojunctions.2D Ni-BDC nanosheets were used as carriers to grow 2D Ni-TCPP nanosheets on top of them.Ni-TCPP has a high light absorption capacity,thus extending the light absorption range of 2D/2D heterojunctions.The tight coupling of the heterojunction effectively shortens the electron transfer distance,promotes the separation of interracial charges,and improves the photocatalytic activity.Particularly,Ni-BDC/Ni-TCPP-3can achieve to a hydrogen production rate of428.0 μmol·g^(-1),approximately 5.75 times higher than NiBDC and 5.24 times higher than Ni-TCPP,respectively.Thus,2D-MOF/2D-MOF heterojunctions provide a promising strategy for enhancing photocatalytic performance through rational heterostructure design with homometallic node strategy.
基金supported by the National Natural Science Foundation of China(No.21773089)the Henan Center for Outstanding Overseas Scientist(No.GZS2024004).
文摘Herein,a new type of two-dimensional(2D)/2D Ti_(3)C_(2)/TiO_(2) heterojunction was developed for efficient photocatalytic nitrogen reduction reaction(NRR),in which TiO_(2) nanosheets(TiO_(2) Ns)were designed as the main catalyst,while Ti_(3)C_(2) MXene served as the co-catalyst.Experimental and theoretical results revealed that Ti_(3)C_(2) MXene introduced electron-rich unsaturated Ti sites,serving as highly active sites for both the adsorption and activation of N_(2) on the Ti_(3)C_(2)/TiO_(2) heterojunction.Furthermore,the 2D/2D Ti_(3)C_(2)/TiO_(2) heterostructure greatly promoted the directional separation and transfer of charge carriers,facilitated by the internal electric field.This structural feature enabled the spatial separation of the N_(2) reduction and H2 O oxidation half-reactions on the distinct surfaces of Ti_(3)C_(2)(001)and TiO_(2)(001),con-sequently reducing the reaction energy barrier for each respective process.The synergistic effects arising from the interface and surface interactions within the heterojunction conspicuously improved the photo-catalytic NRR activity.As a result,the optimized Ti_(3)C_(2)/TiO_(2) heterojunction exhibited a high NH_(3) produc-tion rate of 24.4μmol g−1 h−1 in the absence of sacrificial agents,representing a remarkable 12.8-fold increase compared to individual TiO_(2) Ns.This work provides new insights into rational design of high-performance heterogeneous photocatalysts and offers a deeper understanding of the mechanism under-lying surface active sites in the photocatalytic NRR process.
基金the financial support by the National Natural Science Foundation of China as general projects(Grant Nos.51779068,52070066,52211530084,42277059,and 22006029)Tianjin Commission of Science and Technology as key technologies R&D projects(No.21YFSNSN00250)+1 种基金Doctoral Inno-vation Project of Hebei Province(CXZZBS2023031)the Royal Society/International Exchanges 2021 Cost Share/NSFC(Grant No.IEC\NSFC\211142).
文摘Heterojunction photocatalysts have shown considerable activities for organic pollutants degradation.However,the faint connection interface and inferior charge shift efficiency critically block the property of heterojunction photocatalysis.Herein,Bi_(2)O_(2)S/NiFe_(2)O_(4) nanosheets heterojunction with ultrastrong inter-face interaction and high internal electric field are designed by an in-situ growth method.Tentative and theoretical consequences prove that the interfacial interaction and internal electric field not only act as the electron flow bridge but also decrease the electrons shift energy obstacle,thus speeding up electrons transfer and achieving effective spatial electron-hole separation.Therefore,a large amount of·O_(2)^(-)and holes as active species were generated.Remarkably,Bi_(2)O_(2) S/NiFe_(2)O_(4) establishes a considerably boosted photocatalytic performance for tetracycline degradation(0.032 min^(-1)),which is about 14.2-fold and 7.8-fold of the pristine BOS and NFO,respectively.This work provides a promising motivation for modulating charge transfer by interface control and internal electric field to boost photocatalytic performance.
