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
Electrocatalytic conversion of carbon dioxide(CO_(2))into formate offers a sustainable pathway to mitigate environmental degradation and the energy crisis.Tin(Sn)-based materials are promising electrocatalysts for CO_...Electrocatalytic conversion of carbon dioxide(CO_(2))into formate offers a sustainable pathway to mitigate environmental degradation and the energy crisis.Tin(Sn)-based materials are promising electrocatalysts for CO_(2)reduction to formate;however,their efficiency is limited by weak CO_(2)adsorption and activation,as well as sluggish reaction kinetics.In this work,we designed an intercrossing nanoporous Cu_(6)Sn_(5)/Sn intermetallic heterojunction via a scalable alloying-etching protocol.The resulting Cu_(6)Sn_(5)/Sn catalyst with abundant interfacial sites exhibited enhanced formate selectivity(60.79%)at−0.93 V versus the reversible hydrogen electrode(RHE),together with a high partial current density of 12.56 mA/cm^(2)and stable operation for 16 h.The modulated electronic structure of Cu_(6)Sn_(5)coupled with the robust interfacial interaction between Sn and Cu_(6)Sn_(5)synergistically promoted CO_(2)adsorption and activation,thereby improving CO_(2)reduction reaction(CO_(2)RR)performance.Electrochemical measurements and in situ infrared spectroscopy confirmed that the dual-phase interfaces facilitate H_(2)O decomposition and the generation of abundant*H intermediates,which in turn accelerate the protonation of CO_(2)to formate.This work highlights a scalable strategy for constructing intermetallic heterojunction catalysts that combine facile synthesis,reproducibility,and superior catalytic activity for CO_(2)RR.展开更多
Organic-inorganic hybrid perovskite solar cells achieve remarkable efficiencies(>26%)yet face stability challenges.Quasi-2D alternating-cation-interlayer perovskites offer enhanced stability through hydrophobic spa...Organic-inorganic hybrid perovskite solar cells achieve remarkable efficiencies(>26%)yet face stability challenges.Quasi-2D alternating-cation-interlayer perovskites offer enhanced stability through hydrophobic spacer cations but suffer from vertical phase segregation and buried interface defects.Herein,we introduce dicyanodiamide(DCD)to simultaneously address these dual limitations in GA(MA)_(n)Pb_(n)I_(3n+1)perovskites.The guanidine group in DCD passivates undercoordinated Pb^(2+)and MA^(+)vacancies at the perovskite/TiO_(2)interface,while cyano groups eliminate oxygen vacancies in TiO_(2)via Ti^(4+)-CN coordination,reducing interfacial trap density by 73%with respect to the control sample.In addition,DCD regulates crystallization kinetics,suppressing low-n-phase aggregation and promoting vertical alignment of high-n phases,which benefit for carrier transport.This dual-functional modification enhances charge transport and stabilizes energy-level alignment.The optimized devices achieve a record power conversion efficiency of 21.54%(vs.19.05%control)and retain 94%initial efficiency after 1200 h,outperforming unmodified counterparts(84%retention).Combining defect passivation with phase homogenization,this work establishes a molecular bridge strategy to decouple stability-efficiency trade-offs in low-dimensional perovskites,providing a universal framework for interface engineering in high-performance optoelectronics.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
Large-area two-dimensional(2D)materials,such as graphene,MoS_(2),WS_(2),h-BN,black phosphorus,and MXenes,are a class of advanced materials with many possible applications.Different applications need different substrat...Large-area two-dimensional(2D)materials,such as graphene,MoS_(2),WS_(2),h-BN,black phosphorus,and MXenes,are a class of advanced materials with many possible applications.Different applications need different substrates,and each substrate may need a different way of transferring the 2D material onto it.Problems such as local stress concentrations,an uneven surface tension,inconsistent adhesion,mechanical damage and contamination during the transfer can adversely affect the quality and properties of the transferred material.Therefore,how to improve the integrity,flatness and cleanness of large area 2D materials is a challenge.In order to achieve high-quality transfer,the main concern is to control the interface adhesion between the substrate,the 2D material and the transfer medium.This review focuses on this topic,and finally,in order to promote the industrial use of large area 2D materials,provides a recipe for this transfer process based on the requirements of the application,and points out the current problems and directions for future development.展开更多
Photocatalytic CO_(2)reduction into value-added chemicals holds significant promise for carbon-neutral recycling and solar-to-fuel conversion.Enhancing reaction efficiency by manipulating charge transfer is a key appr...Photocatalytic CO_(2)reduction into value-added chemicals holds significant promise for carbon-neutral recycling and solar-to-fuel conversion.Enhancing reaction efficiency by manipulating charge transfer is a key approach to unlocking this potential.In this work,we construct a two-dimensional/twodimensional(2D/2D)FeSe_(2)/protonated carbon nitride(FeSe_(2)/PCN)heterostructure to promote the interfacial charge transfer dynamics,leading to a four-fold improved conversion efficiency of photocatalytic CO_(2)reduction with near 100%CO selectivity.Combining in situ X-ray photoelectron spectroscopy,in situ soft X-ray absorption spectroscopy,and femtosecond transient absorption spectroscopy,it is revealed that FeSe_(2)acts as an electron acceptor upon photoexcitation,introducing an additional electron transfer pathway from PCN to FeSe_(2)that suppresses radiative recombination and promotes charge transfer.In situ X-ray absorption fine structure spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy,and density functional theory calculation further unravel that the electron-enriched FeSe_(2)functions as the active sites for CO_(2)activation and significantly reduces the energy barrier of key intermediate COOH*formation,which is the rate-determined step for CO generation.This work underscores the importance of regulating photocarrier relaxation pathways to achieve effective spatial charge separation for promoted photocatalytic CO_(2)reduction and demonstrates the powerful functions of in situ spectroscopies in in-depth understanding of the photocatalytic mechanism.展开更多
为研发同时预防和控制猪圆环病毒2d基因型(PCV2d)和猪伪狂犬病病毒(PRV)的疫苗,将PCV2dORF2基因克隆到含有绿色荧光蛋白(EGFP)基因的PRV转移质粒pG中BamHⅠ位点,获得重组质粒pG-PCV2d-EGFP。运用转染试剂ZLip2000将其与PRV变异株3基因...为研发同时预防和控制猪圆环病毒2d基因型(PCV2d)和猪伪狂犬病病毒(PRV)的疫苗,将PCV2dORF2基因克隆到含有绿色荧光蛋白(EGFP)基因的PRV转移质粒pG中BamHⅠ位点,获得重组质粒pG-PCV2d-EGFP。运用转染试剂ZLip2000将其与PRV变异株3基因缺失毒株gE^(-)/g^(-)/TK^(-)PRV NY DNA转入ST细胞中,经绿色荧光蚀斑纯化,得到表达EGFP的重组病毒rPRV-PCV2d-EGFP。采用CRISPR/Cas9基因双敲除质粒敲除重组病毒中EGFP基因,经蚀斑纯化,拯救出不表达EGFP的重组病毒rPRV-PCV2d。重组病毒rPRV-PCV2d与亲本株gE^(-)/g^(-)/TK^(-)PRV NY具有相近的遗传稳定性,且能够表达PCV2d衣壳(Cap)蛋白。在6周龄小鼠免疫试验中,与商品化PCV2灭活疫苗相比,rPRV-PCV2d刺激小鼠机体诱导了更高的PCV2特异性抗体,且用PCV2d强毒株攻毒后,rPRV-PCV2d显著降低了小鼠心脏、肝脏、脾脏等组织中PCV2d载量。此外,rPRV-PCV2d在小鼠体内激发PRV特异性免疫应答,并能阻止PRV强毒对小鼠的侵袭。表明rPRV-PCV2d具有良好的免疫原性。展开更多
开发了一种使用直写成型(DIW)3D打印方法制备多孔TiO_(2)光催化降解筛的成型技术,厘清了打印浆料中P25粉末、TiO_(2)前驱体溶胶和聚乙烯醇(PVA)含量对其成型性能的影响规律;进一步研究了降解筛的物相组成、微观形貌、能带结构和载流子寿...开发了一种使用直写成型(DIW)3D打印方法制备多孔TiO_(2)光催化降解筛的成型技术,厘清了打印浆料中P25粉末、TiO_(2)前驱体溶胶和聚乙烯醇(PVA)含量对其成型性能的影响规律;进一步研究了降解筛的物相组成、微观形貌、能带结构和载流子寿命,并在模拟自然光下测定了其对盐酸四环素(TC)的光催化降解性能和循环稳定性.结果表明:TiO_(2)前驱体溶胶起到了分散P25颗粒和稳定浆料的作用,而PVA的加入则进一步改善了浆料的流变性能.当使用9 g P25粉末与10 mL TiO_(2)前驱体溶胶和1 mL质量分数为7%的PVA溶液混合时,得到了具有最佳成型性能的打印浆料,制备的降解筛结构完整,无塌陷和开裂.热处理后TiO_(2)前驱体溶胶转化而来的小粒径TiO_(2)填充在P25颗粒之间,起到了增强机械强度的作用,而PVA作为造孔剂极大地丰富了降解筛的孔隙结构.TiO_(2)光催化降解筛对TC表现出优异的光催化性能和循环稳定性,140 min内的降解率为98.4%,并在5次循环之后保持96.0%的降解率.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supported by Natural Science Foundation of Shandong Province(No.ZR2023ME155)the project of“20 Items of University”of Jinan(No.202228046)the Tais-han Scholar Project of Shandong Province(Nos.tsqn202306226 and tsqn202211171).
文摘Electrocatalytic conversion of carbon dioxide(CO_(2))into formate offers a sustainable pathway to mitigate environmental degradation and the energy crisis.Tin(Sn)-based materials are promising electrocatalysts for CO_(2)reduction to formate;however,their efficiency is limited by weak CO_(2)adsorption and activation,as well as sluggish reaction kinetics.In this work,we designed an intercrossing nanoporous Cu_(6)Sn_(5)/Sn intermetallic heterojunction via a scalable alloying-etching protocol.The resulting Cu_(6)Sn_(5)/Sn catalyst with abundant interfacial sites exhibited enhanced formate selectivity(60.79%)at−0.93 V versus the reversible hydrogen electrode(RHE),together with a high partial current density of 12.56 mA/cm^(2)and stable operation for 16 h.The modulated electronic structure of Cu_(6)Sn_(5)coupled with the robust interfacial interaction between Sn and Cu_(6)Sn_(5)synergistically promoted CO_(2)adsorption and activation,thereby improving CO_(2)reduction reaction(CO_(2)RR)performance.Electrochemical measurements and in situ infrared spectroscopy confirmed that the dual-phase interfaces facilitate H_(2)O decomposition and the generation of abundant*H intermediates,which in turn accelerate the protonation of CO_(2)to formate.This work highlights a scalable strategy for constructing intermetallic heterojunction catalysts that combine facile synthesis,reproducibility,and superior catalytic activity for CO_(2)RR.
基金support from the National Key R&D Program of China(Grant No.2023YFE0111500)the National Natural Science Foundation of China(Grant No.52321006,T2394480,T2394484,22109143,22479131)+8 种基金Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-202005)the China Postdoctoral Innovative Talent Support Program(Grant No.BX2021271)the China Postdoctoral Science Foundation(2022M712851)the Opening Project of State Key Laboratory of Advanced Technology for Float Glass(Grant No.2022KF04)Graduate Education Reform Project of Henan Province(Grant No.2023SJGLX136Y)Key R&D Special Program of Henan Province(Grant No.241111242000)Program for Science and Technology Innovation Talents in Universities of Henan Province(Grant No.25HASTIT005)Training Plan for Young Backbone Teachers of Zhengzhou University(Grant No.2023ZDGGJS017)the Joint Research Project of Puyang Shengtong Juyuan New Materials Co.,Ltd.(Grant No.20230128A).
文摘Organic-inorganic hybrid perovskite solar cells achieve remarkable efficiencies(>26%)yet face stability challenges.Quasi-2D alternating-cation-interlayer perovskites offer enhanced stability through hydrophobic spacer cations but suffer from vertical phase segregation and buried interface defects.Herein,we introduce dicyanodiamide(DCD)to simultaneously address these dual limitations in GA(MA)_(n)Pb_(n)I_(3n+1)perovskites.The guanidine group in DCD passivates undercoordinated Pb^(2+)and MA^(+)vacancies at the perovskite/TiO_(2)interface,while cyano groups eliminate oxygen vacancies in TiO_(2)via Ti^(4+)-CN coordination,reducing interfacial trap density by 73%with respect to the control sample.In addition,DCD regulates crystallization kinetics,suppressing low-n-phase aggregation and promoting vertical alignment of high-n phases,which benefit for carrier transport.This dual-functional modification enhances charge transport and stabilizes energy-level alignment.The optimized devices achieve a record power conversion efficiency of 21.54%(vs.19.05%control)and retain 94%initial efficiency after 1200 h,outperforming unmodified counterparts(84%retention).Combining defect passivation with phase homogenization,this work establishes a molecular bridge strategy to decouple stability-efficiency trade-offs in low-dimensional perovskites,providing a universal framework for interface engineering in high-performance optoelectronics.
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 National Key R&D Program of China(2022YFA1505200)the National Natural Science Foundation of China(22472140,22021001)the Fundamental Research Funds for the Central Universities(20720210017 and 20720210009)。
文摘Large-area two-dimensional(2D)materials,such as graphene,MoS_(2),WS_(2),h-BN,black phosphorus,and MXenes,are a class of advanced materials with many possible applications.Different applications need different substrates,and each substrate may need a different way of transferring the 2D material onto it.Problems such as local stress concentrations,an uneven surface tension,inconsistent adhesion,mechanical damage and contamination during the transfer can adversely affect the quality and properties of the transferred material.Therefore,how to improve the integrity,flatness and cleanness of large area 2D materials is a challenge.In order to achieve high-quality transfer,the main concern is to control the interface adhesion between the substrate,the 2D material and the transfer medium.This review focuses on this topic,and finally,in order to promote the industrial use of large area 2D materials,provides a recipe for this transfer process based on the requirements of the application,and points out the current problems and directions for future development.
基金supported by the National Natural Science Foundation of China(12241502,92045301)Fundamental Research Funds for the Central Universities(20720220010)+7 种基金USTC Research Funds of the Double First-Class Initiative(YD2310002012)the Launching Special Funds of Scientific Research for Introduced Talents from University of Science and Technology of China(KY2310000060)National Key Research and Development Program of China(2019YFA0405602)Anhui Provincial Natural Science Foundation(2408085QB049)the Instruments Center for Physical Science and USTC Center for Micro and Nanoscale Research and Fabrication,University of Science and Technology of Chinathe solid supports from the BL03U,BL10B,and BL12B beamlines of the National Synchrotron Radiation Laboratory(NSRL,Hefei)the Shanghai Synchrotron Radiation Facility(SSRF,Shanghai)of BL11B(https://cstr.cn/31124.02.SSRF.BL11B)and BL14W1(https://cstr.cn/31124.02.SSRF.BL14W1)beamlines for the assistance on XAFS measurementsAnhui Chuangpu Instruments Co.,Ltd.for the assistance in the test of Table XAFS。
文摘Photocatalytic CO_(2)reduction into value-added chemicals holds significant promise for carbon-neutral recycling and solar-to-fuel conversion.Enhancing reaction efficiency by manipulating charge transfer is a key approach to unlocking this potential.In this work,we construct a two-dimensional/twodimensional(2D/2D)FeSe_(2)/protonated carbon nitride(FeSe_(2)/PCN)heterostructure to promote the interfacial charge transfer dynamics,leading to a four-fold improved conversion efficiency of photocatalytic CO_(2)reduction with near 100%CO selectivity.Combining in situ X-ray photoelectron spectroscopy,in situ soft X-ray absorption spectroscopy,and femtosecond transient absorption spectroscopy,it is revealed that FeSe_(2)acts as an electron acceptor upon photoexcitation,introducing an additional electron transfer pathway from PCN to FeSe_(2)that suppresses radiative recombination and promotes charge transfer.In situ X-ray absorption fine structure spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy,and density functional theory calculation further unravel that the electron-enriched FeSe_(2)functions as the active sites for CO_(2)activation and significantly reduces the energy barrier of key intermediate COOH*formation,which is the rate-determined step for CO generation.This work underscores the importance of regulating photocarrier relaxation pathways to achieve effective spatial charge separation for promoted photocatalytic CO_(2)reduction and demonstrates the powerful functions of in situ spectroscopies in in-depth understanding of the photocatalytic mechanism.
文摘为研发同时预防和控制猪圆环病毒2d基因型(PCV2d)和猪伪狂犬病病毒(PRV)的疫苗,将PCV2dORF2基因克隆到含有绿色荧光蛋白(EGFP)基因的PRV转移质粒pG中BamHⅠ位点,获得重组质粒pG-PCV2d-EGFP。运用转染试剂ZLip2000将其与PRV变异株3基因缺失毒株gE^(-)/g^(-)/TK^(-)PRV NY DNA转入ST细胞中,经绿色荧光蚀斑纯化,得到表达EGFP的重组病毒rPRV-PCV2d-EGFP。采用CRISPR/Cas9基因双敲除质粒敲除重组病毒中EGFP基因,经蚀斑纯化,拯救出不表达EGFP的重组病毒rPRV-PCV2d。重组病毒rPRV-PCV2d与亲本株gE^(-)/g^(-)/TK^(-)PRV NY具有相近的遗传稳定性,且能够表达PCV2d衣壳(Cap)蛋白。在6周龄小鼠免疫试验中,与商品化PCV2灭活疫苗相比,rPRV-PCV2d刺激小鼠机体诱导了更高的PCV2特异性抗体,且用PCV2d强毒株攻毒后,rPRV-PCV2d显著降低了小鼠心脏、肝脏、脾脏等组织中PCV2d载量。此外,rPRV-PCV2d在小鼠体内激发PRV特异性免疫应答,并能阻止PRV强毒对小鼠的侵袭。表明rPRV-PCV2d具有良好的免疫原性。
文摘开发了一种使用直写成型(DIW)3D打印方法制备多孔TiO_(2)光催化降解筛的成型技术,厘清了打印浆料中P25粉末、TiO_(2)前驱体溶胶和聚乙烯醇(PVA)含量对其成型性能的影响规律;进一步研究了降解筛的物相组成、微观形貌、能带结构和载流子寿命,并在模拟自然光下测定了其对盐酸四环素(TC)的光催化降解性能和循环稳定性.结果表明:TiO_(2)前驱体溶胶起到了分散P25颗粒和稳定浆料的作用,而PVA的加入则进一步改善了浆料的流变性能.当使用9 g P25粉末与10 mL TiO_(2)前驱体溶胶和1 mL质量分数为7%的PVA溶液混合时,得到了具有最佳成型性能的打印浆料,制备的降解筛结构完整,无塌陷和开裂.热处理后TiO_(2)前驱体溶胶转化而来的小粒径TiO_(2)填充在P25颗粒之间,起到了增强机械强度的作用,而PVA作为造孔剂极大地丰富了降解筛的孔隙结构.TiO_(2)光催化降解筛对TC表现出优异的光催化性能和循环稳定性,140 min内的降解率为98.4%,并在5次循环之后保持96.0%的降解率.
