Electrocatalytic reduction of nitrate to ammonia has been considered a promising and sustainable pathway for pollutant treatment and ammonia has significant potential as a clean energy.Therefore,the method has receive...Electrocatalytic reduction of nitrate to ammonia has been considered a promising and sustainable pathway for pollutant treatment and ammonia has significant potential as a clean energy.Therefore,the method has received much attention.In this work,Cu/Fe 2D bimetallic metal-organic frameworks were synthesized by a facile method applied as cathode materials without high-temperature carbonization.Bimetallic centers(Cu,Fe)with enhanced intrinsic activity demonstrated higher removal efficiency.Meanwhile,the 2D nanosheet reduced themass transfer barrier between the catalyst and nitrate and increased the reaction kinetics.Therefore,the catalysts with a 2D structure showed much better removal efficiency than other structures(3D MOFs and BulkMOFs).Under optimal conditions,Cu/Fe-2D MOF exhibited high nitrate removal efficiency(87.8%)and ammonium selectivity(89.3%)simultaneously.The ammonium yielded up to significantly 907.2μg/(hr·mg_(cat))(7793.8μg/(hr·mg_(metal)))with Faradaic efficiency of 62.8%at an initial 100 mg N/L.The catalyst was proved to have good stability and was recycled 15 times with excellent effect.DFT simulations confirm the reduced Gibbs free energy of Cu/Fe-2D MOF.This study demonstrates the promising application of Cu/Fe-2D MOF in nitrate reduction to ammonia and provides new insights for the design of efficient electrode materials.展开更多
Lithium-ion batteries(LIBs)with high energy and power densities are extensively applied in various fields,such as portable electronic devices and electric vehicles.Compared with traditional inorganic electrode materia...Lithium-ion batteries(LIBs)with high energy and power densities are extensively applied in various fields,such as portable electronic devices and electric vehicles.Compared with traditional inorganic electrode materials,which confront the challenges of resource scarcity and restrained energy density,covalent organic frameworks(COFs)are attractive candidates as electrode materials for the next-generation LIBs.Herein,rational Schiff-base condensation of tetraphenyl-pphenylenediamine(TPPDA)and 5,12-bis(4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione(QA-PCHO)yields a two-dimensional(2D)QT-COF as the cathode.2D QT-COF features a high crystalline nature with kgm topology and hierarchically micro-/meso-porous structure,which can strengthen the stability of the chemical structure and promote the fast Li^(+)diffusion under large current densities.These merits make the QT-COF cathode exhibit 110,000 ultralong cycling stability with~100%retention at 10,000 mA g^(-1)upon running for 150 days,exceeding all the thus far reported COF-based electrodes.Additionally,the combination of ex situ X-ray photoelectron spectroscopy,in-situ Raman investigation,and theoretical calculation exhaustively unveils the ion storage mechanism and the rationale underlying the exceptional property of QT-COF.The present result offers an advanced COF with enormous potential as organic electrodes for LIBs,hopefully solving the challenges of ultrahigh cycling stability with superb capacity preservation at high current densities.展开更多
The hydrogen-bonded organic frameworks(HOFs)as a new type of porous framework materials have been widely studied in various areas.However,the lack of appropriate active sites,low intrinsic conductivity,and poor stabil...The hydrogen-bonded organic frameworks(HOFs)as a new type of porous framework materials have been widely studied in various areas.However,the lack of appropriate active sites,low intrinsic conductivity,and poor stability limited their performance in the field of electrocatalysis.Herein,we designed two 2D metal hydrogen-bonded organic frameworks(2D–M–HOF,M=Cu^(2+)or Ni^(2+))with coordination compounds based on 2,3,6,7,14,15-hexahydroxyl cyclotricatechylene and transition metal ions(Cu^(2+)and Ni^(2+)),respectively.The crystal structure of 2D–Cu–HOF is determined by continuous rotation electron diffraction,indicating an undulated 2D hydrogen-bond network with interlayeredπ-πstacking.The flexible structure of 2D–M–HOF leads to the formation of self-adaption interlayered sites,resulting in superior activity and selectivity in the electrocatalytic conversion of CO_(2) to C_(2) products,achieving a total Faradaic efficiency exceeding 80%due to the high-efficiency C–C coupling.The experimental results and density functional calculations verify that the undulated 2D–M–HOF enables the energetically favorable formation of*OCCHO intermediate.This work provides a promising strategy for designing HOF catalysts in electrocatalysis and related processes.展开更多
Metal-organic frameworks(MOFs),assembled periodically by coordinating inorganic metal ions and organic motifs,have arisen widespread curiosity and intensive investigation owing to their tailorable electronic propertie...Metal-organic frameworks(MOFs),assembled periodically by coordinating inorganic metal ions and organic motifs,have arisen widespread curiosity and intensive investigation owing to their tailorable electronic properties and well-defined topological structure.However,the majority of MOFs are intrinsically dielectric or insulative[1]and typically form as 3D bulk or powder crystals,making them incompatible with complementary metal-oxide semiconductor(CMOS)techniques.In recent years,layer-stacked two-dimensional conjugated MOFs(2D c-MOFs),composed of planar conjugated ligands and linkages[2],have demonstrated high in-plane π conjugation and weak out-of-plane van der Waals interactions,due to their long-range electron delocalization over metal ions and ligands[3].As a result,highly tunable band gaps from semiconductor to conductor,modulable porosity from micropore to macropore and versatile processability into conductive 2D thin films with controllable lateral thickness and domain size are presented,rendering charming potential for applications in(opto-)electronics compared with classic 2D metal oxide,chalcogenide and crystalline polymer materials.To improve interfacial charge-transport and precisely tune the charge extraction and band alignment of 2D c-MOFs in(opto-)electronic devices[4],developing highly efficient synthetic methods of 2D c-MOFs is of utmost importance.展开更多
The introduction of two-dimensional(2D)perovskite layers on top of three-dimensional(3D)perovskite films enhances the performance and stability of perovskite solar cells(PSCs).However,the electronic effect of the spac...The introduction of two-dimensional(2D)perovskite layers on top of three-dimensional(3D)perovskite films enhances the performance and stability of perovskite solar cells(PSCs).However,the electronic effect of the spacer cation and the quality of the 2D capping layer are critical factors in achieving the required results.In this study,we compared two fluorinated salts:4-(trifluoromethyl)benzamidine hydrochloride(4TF-BA·HCl)and 4-fluorobenzamidine hydrochloride(4F-BA·HCl)to engineer the 3D/2D perovskite films.Surprisingly,4F-BA formed a high-performance 3D/2D heterojunction,while4TF-BA produced an amorphous layer on the perovskite films.Our findings indicate that the balanced intramolecular charge polarization,which leads to effective hydrogen bonding,is more favorable in 4F-BA than in 4TF-BA,promoting the formation of a crystalline 2D perovskite.Nevertheless,4TF-BA managed to improve efficiency to 24%,surpassing the control device,primarily due to the natural passivation capabilities of benzamidine.Interestingly,the devices based on 4F-BA demonstrated an efficiency exceeding 25%with greater longevity under various storage conditions compared to 4TF-BA-based and the control devices.展开更多
Photocatalytic carbon dioxide(CO_(2))reduction offers an alternative strategy for converting CO_(2)into high-value added gaseous fuels,thereby paving the way for the development of clean and renewable energy.Metal-org...Photocatalytic carbon dioxide(CO_(2))reduction offers an alternative strategy for converting CO_(2)into high-value added gaseous fuels,thereby paving the way for the development of clean and renewable energy.Metal-organic frameworks(MOFs),characterized by their highly porous structure,exceptional CO_(2)adsorption capacity,and tunable architecture,have emerged as promising candidates for photocatalytic CO_(2)reduction.This review systematically examines the recent advancement in MOFs-based photocatalysts for CO_(2)reduction to CO.It begins with the overview of the fundamental mechanisms and processes of MOFs towards photocatalytic CO_(2)reduction.Subsequently,common strategies for the modulation of MOFs-based photocatalysts are summarized,including metallic site modification,functionalized ligand incorporation,morphological control,defect engineering,and heterostructure construction.Notably,the review analyzes the critical factors contributing to the high selectivity of CO_(2)photoreduction to CO from both thermodynamic and kinetic perspectives.The conclusion addresses current challenges and future perspectives in designing highly efficient photocatalysts with abundant active sites,providing valuable insights for their continued development.展开更多
The growing global energy demand and worsening climate change highlight the urgent need for clean,efficient and sustainable energy solutions.Among emerging technologies,atomically thin two-dimensional(2D)materials off...The growing global energy demand and worsening climate change highlight the urgent need for clean,efficient and sustainable energy solutions.Among emerging technologies,atomically thin two-dimensional(2D)materials offer unique advantages in photovoltaics due to their tunable optoelectronic properties,high surface area and efficient charge transport capabilities.This review explores recent progress in photovoltaics incorporating 2D materials,focusing on their application as hole and electron transport layers to optimize bandgap alignment,enhance carrier mobility and improve chemical stability.A comprehensive analysis is presented on perovskite solar cells utilizing 2D materials,with a particular focus on strategies to enhance crystallization,passivate defects and improve overall cell efficiency.Additionally,the application of 2D materials in organic solar cells is examined,particularly for reducing recombination losses and enhancing charge extraction through work function modification.Their impact on dye-sensitized solar cells,including catalytic activity and counter electrode performance,is also explored.Finally,the review outlines key challenges,material limitations and performance metrics,offering insight into the future development of nextgeneration photovoltaic devices encouraged by 2D materials.展开更多
Two-dimensional(2D)materials show great potential as novel membrane materials due to their atomic thickness and periodic pore structure.Currently,free-standing membranes based on 2D materials open up new avenues for u...Two-dimensional(2D)materials show great potential as novel membrane materials due to their atomic thickness and periodic pore structure.Currently,free-standing membranes based on 2D materials open up new avenues for ultra-fast and highly selective separation.With the absence of porous substrates,free-standing membranes offer shortened transport paths for efficient mass transfer.The interfacial defects between the substrate and selective layer are eliminated to alleviate the internal membrane fouling,enabling the intact structure for precise separation.Hence,this review aims to outline the superiority of 2D material-based free-standing membranes for selective separation applications.Free-standing 2D material membranes composed of the most representative graphenebased materials,MXene,covalent organic framework(COF),metal organic framework(MOF),and hydrogen-bonded organic framework(HOF)are summarized with the discussion on the influence of substrate on their structural properties.The separation performance enhancement strategies in regard to the 2D material,membrane structure,and mechanical properties are examined.Finally,we propose several critical challenges and perspectives in terms of pore size control,mechanical strength improvement,understanding the underlying mass transfer mechanism,issues related to membrane fabrication optimization,scale production,and separation application versatility.This review will provide researchers with practical guidelines for advancing free-standing 2D material membranes for future selective separation applications.展开更多
Non-layered two-dimensional materials(NL2DMs)have emerged as a promising complement to layered 2D materials,offering unique properties derived from their isotropic bonding and structural diversity.However,their synthe...Non-layered two-dimensional materials(NL2DMs)have emerged as a promising complement to layered 2D materials,offering unique properties derived from their isotropic bonding and structural diversity.However,their synthesis is still facing significant challenges due to the lack of intrinsic anisotropic growth driving force.This review comprehensively outlines strategies for chemical vapor deposition(CVD)-based synthesis of NL2DMs,demonstrating how integrated thermodynamic and kinetic control enables precise thickness and morphology modulation.We also analyze the existing challenges and propose future research directions.This systematic framework paves the way for engineering NL2DMs growth with customized functionalities for next-generation optoelectronics,energy storage,and catalysis.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
传统的功率分配算法由于复杂的矩阵运算与迭代所造成的高时延,在实际通信中实时获取信道信息十分困难,当前重要的研究方向是在系统性能和计算复杂度之间找到有效平衡。针对终端直通(Device-to-Device,D2D)用户与蜂窝用户的联合功率分配...传统的功率分配算法由于复杂的矩阵运算与迭代所造成的高时延,在实际通信中实时获取信道信息十分困难,当前重要的研究方向是在系统性能和计算复杂度之间找到有效平衡。针对终端直通(Device-to-Device,D2D)用户与蜂窝用户的联合功率分配问题,提出一种异构功率控制图神经网络(Heterogeneous Power Control Graph Neural Network,HPCGNN)算法,旨在最大化所有用户的加权和速率。首先通过构建干扰的异构图,将信道和噪声等信息嵌入到图的节点和边;再由HPCGNN完成消息传递和更新,采用无监督学习方式优化深度神经网络(Deep Neural Network,DNN)参数,最终得到最佳的功率分配。仿真结果表明,相较于其他深度学习算法,所提算法能够有效提高系统性能,且在损失5%性能下相较分式规划(Fractional Programming,FP)能降低82%~98%的时间复杂度。展开更多
The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growt...The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growth strategy to construct the ultrathin carboxylated carbon nanotubes(C-CNTs)interpenetrated nickel MOF(Ni-MOF/C-CNTs)nanosheets.The deliberate thickness and specific surface area of novel 2D hybrid nanosheets can be effectively tuned via finely controlling C-CNTs involvement.Due to the unique microstructure,the integrated 2D hybrid nanosheets are endowed with plentiful electroactive sites to promote the electrochemical performances greatly.The prepared Ni-MOF/C-CNTs nanosheets exhibit superior specific capacity of 680 C g^−1 at 1 A g^−1 and good capacity retention.The assembled hybrid device demonstrated the maximum energy density of 44.4 Wh kg^−1 at a power density of 440 W kg^−1.Our novel strategy to construct ultrathin 2D MOF with unique properties can be extended to synthesize various MOF-based functional materials for diverse applications.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
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.52370044 and 21976134)the State Key Laboratory of Pollution Control and Resource Reuse Foundation(Nos.PCRRK21003 and PCRRK21001)+1 种基金Shanghai Scientific Research Plan Project(No.23ZR1467000)the State Key Laboratory of Treatments and Recycling for Organic Effluents by Adsorption in Petroleum and Chemical Industry(No.SDHY2206).
文摘Electrocatalytic reduction of nitrate to ammonia has been considered a promising and sustainable pathway for pollutant treatment and ammonia has significant potential as a clean energy.Therefore,the method has received much attention.In this work,Cu/Fe 2D bimetallic metal-organic frameworks were synthesized by a facile method applied as cathode materials without high-temperature carbonization.Bimetallic centers(Cu,Fe)with enhanced intrinsic activity demonstrated higher removal efficiency.Meanwhile,the 2D nanosheet reduced themass transfer barrier between the catalyst and nitrate and increased the reaction kinetics.Therefore,the catalysts with a 2D structure showed much better removal efficiency than other structures(3D MOFs and BulkMOFs).Under optimal conditions,Cu/Fe-2D MOF exhibited high nitrate removal efficiency(87.8%)and ammonium selectivity(89.3%)simultaneously.The ammonium yielded up to significantly 907.2μg/(hr·mg_(cat))(7793.8μg/(hr·mg_(metal)))with Faradaic efficiency of 62.8%at an initial 100 mg N/L.The catalyst was proved to have good stability and was recycled 15 times with excellent effect.DFT simulations confirm the reduced Gibbs free energy of Cu/Fe-2D MOF.This study demonstrates the promising application of Cu/Fe-2D MOF in nitrate reduction to ammonia and provides new insights for the design of efficient electrode materials.
基金financially supported by the Natural Science Foundation of China(22235001,22175020 and 22001015)the Fundamental Research Funds for the Central Universities(No.2050205)+2 种基金the Guizhou Provincial Key Laboratory Platform Project(ZSYS[2025]008)the Talent Program of Guizhou University(No.[2024]11)the Science and Technology Project of Jiangsu Province(BZ2022056)。
文摘Lithium-ion batteries(LIBs)with high energy and power densities are extensively applied in various fields,such as portable electronic devices and electric vehicles.Compared with traditional inorganic electrode materials,which confront the challenges of resource scarcity and restrained energy density,covalent organic frameworks(COFs)are attractive candidates as electrode materials for the next-generation LIBs.Herein,rational Schiff-base condensation of tetraphenyl-pphenylenediamine(TPPDA)and 5,12-bis(4-(5,5-dimethyl-1,3-dioxan-2-yl)phenyl)-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione(QA-PCHO)yields a two-dimensional(2D)QT-COF as the cathode.2D QT-COF features a high crystalline nature with kgm topology and hierarchically micro-/meso-porous structure,which can strengthen the stability of the chemical structure and promote the fast Li^(+)diffusion under large current densities.These merits make the QT-COF cathode exhibit 110,000 ultralong cycling stability with~100%retention at 10,000 mA g^(-1)upon running for 150 days,exceeding all the thus far reported COF-based electrodes.Additionally,the combination of ex situ X-ray photoelectron spectroscopy,in-situ Raman investigation,and theoretical calculation exhaustively unveils the ion storage mechanism and the rationale underlying the exceptional property of QT-COF.The present result offers an advanced COF with enormous potential as organic electrodes for LIBs,hopefully solving the challenges of ultrahigh cycling stability with superb capacity preservation at high current densities.
基金financially supported by the National Natural Science Foundation of China(nos.21971012,61933002,21601015,21625102,21674012,and 81601549)the National Key Research and Development Program of China(2020YFB1506300)Beijing Institute of Technology Research Fund Program for Young Scholars。
文摘The hydrogen-bonded organic frameworks(HOFs)as a new type of porous framework materials have been widely studied in various areas.However,the lack of appropriate active sites,low intrinsic conductivity,and poor stability limited their performance in the field of electrocatalysis.Herein,we designed two 2D metal hydrogen-bonded organic frameworks(2D–M–HOF,M=Cu^(2+)or Ni^(2+))with coordination compounds based on 2,3,6,7,14,15-hexahydroxyl cyclotricatechylene and transition metal ions(Cu^(2+)and Ni^(2+)),respectively.The crystal structure of 2D–Cu–HOF is determined by continuous rotation electron diffraction,indicating an undulated 2D hydrogen-bond network with interlayeredπ-πstacking.The flexible structure of 2D–M–HOF leads to the formation of self-adaption interlayered sites,resulting in superior activity and selectivity in the electrocatalytic conversion of CO_(2) to C_(2) products,achieving a total Faradaic efficiency exceeding 80%due to the high-efficiency C–C coupling.The experimental results and density functional calculations verify that the undulated 2D–M–HOF enables the energetically favorable formation of*OCCHO intermediate.This work provides a promising strategy for designing HOF catalysts in electrocatalysis and related processes.
基金supported by the National Natural Science Foundation of China(Nos.22201086,22471084,92261204,21925104,and 22431005).
文摘Metal-organic frameworks(MOFs),assembled periodically by coordinating inorganic metal ions and organic motifs,have arisen widespread curiosity and intensive investigation owing to their tailorable electronic properties and well-defined topological structure.However,the majority of MOFs are intrinsically dielectric or insulative[1]and typically form as 3D bulk or powder crystals,making them incompatible with complementary metal-oxide semiconductor(CMOS)techniques.In recent years,layer-stacked two-dimensional conjugated MOFs(2D c-MOFs),composed of planar conjugated ligands and linkages[2],have demonstrated high in-plane π conjugation and weak out-of-plane van der Waals interactions,due to their long-range electron delocalization over metal ions and ligands[3].As a result,highly tunable band gaps from semiconductor to conductor,modulable porosity from micropore to macropore and versatile processability into conductive 2D thin films with controllable lateral thickness and domain size are presented,rendering charming potential for applications in(opto-)electronics compared with classic 2D metal oxide,chalcogenide and crystalline polymer materials.To improve interfacial charge-transport and precisely tune the charge extraction and band alignment of 2D c-MOFs in(opto-)electronic devices[4],developing highly efficient synthetic methods of 2D c-MOFs is of utmost importance.
基金supported by the National Key Research and Development Programs-Intergovernmental International Cooperation in Science and Technology Innovation Project(Grant No.2022YFE0118400)the Natural Science Foundation of Hunan Province(2023JJ50132)+1 种基金Shenzhen Science and Technology Innovation Committee(Grants Nos.JCYJ20220818100211025,and KCXST20221021111616039)Shenzhen Science and Technology Program(No.20231128110928003)。
文摘The introduction of two-dimensional(2D)perovskite layers on top of three-dimensional(3D)perovskite films enhances the performance and stability of perovskite solar cells(PSCs).However,the electronic effect of the spacer cation and the quality of the 2D capping layer are critical factors in achieving the required results.In this study,we compared two fluorinated salts:4-(trifluoromethyl)benzamidine hydrochloride(4TF-BA·HCl)and 4-fluorobenzamidine hydrochloride(4F-BA·HCl)to engineer the 3D/2D perovskite films.Surprisingly,4F-BA formed a high-performance 3D/2D heterojunction,while4TF-BA produced an amorphous layer on the perovskite films.Our findings indicate that the balanced intramolecular charge polarization,which leads to effective hydrogen bonding,is more favorable in 4F-BA than in 4TF-BA,promoting the formation of a crystalline 2D perovskite.Nevertheless,4TF-BA managed to improve efficiency to 24%,surpassing the control device,primarily due to the natural passivation capabilities of benzamidine.Interestingly,the devices based on 4F-BA demonstrated an efficiency exceeding 25%with greater longevity under various storage conditions compared to 4TF-BA-based and the control devices.
基金supported by the National Key Research and Development Program of China(No.2021YFC2901100)the National Natural Science Foundation of China(No.22478425).
文摘Photocatalytic carbon dioxide(CO_(2))reduction offers an alternative strategy for converting CO_(2)into high-value added gaseous fuels,thereby paving the way for the development of clean and renewable energy.Metal-organic frameworks(MOFs),characterized by their highly porous structure,exceptional CO_(2)adsorption capacity,and tunable architecture,have emerged as promising candidates for photocatalytic CO_(2)reduction.This review systematically examines the recent advancement in MOFs-based photocatalysts for CO_(2)reduction to CO.It begins with the overview of the fundamental mechanisms and processes of MOFs towards photocatalytic CO_(2)reduction.Subsequently,common strategies for the modulation of MOFs-based photocatalysts are summarized,including metallic site modification,functionalized ligand incorporation,morphological control,defect engineering,and heterostructure construction.Notably,the review analyzes the critical factors contributing to the high selectivity of CO_(2)photoreduction to CO from both thermodynamic and kinetic perspectives.The conclusion addresses current challenges and future perspectives in designing highly efficient photocatalysts with abundant active sites,providing valuable insights for their continued development.
基金supported by the IITP(Institute of Information & Communications Technology Planning & Evaluation)-ITRC(Information Technology Research Center) grant funded by the Korea government(Ministry of Science and ICT) (IITP-2025-RS-2024-00437191, and RS-2025-02303505)partly supported by the Korea Basic Science Institute (National Research Facilities and Equipment Center) grant funded by the Ministry of Education. (No. 2022R1A6C101A774)the Deanship of Research and Graduate Studies at King Khalid University, Saudi Arabia, through Large Research Project under grant number RGP-2/527/46
文摘The growing global energy demand and worsening climate change highlight the urgent need for clean,efficient and sustainable energy solutions.Among emerging technologies,atomically thin two-dimensional(2D)materials offer unique advantages in photovoltaics due to their tunable optoelectronic properties,high surface area and efficient charge transport capabilities.This review explores recent progress in photovoltaics incorporating 2D materials,focusing on their application as hole and electron transport layers to optimize bandgap alignment,enhance carrier mobility and improve chemical stability.A comprehensive analysis is presented on perovskite solar cells utilizing 2D materials,with a particular focus on strategies to enhance crystallization,passivate defects and improve overall cell efficiency.Additionally,the application of 2D materials in organic solar cells is examined,particularly for reducing recombination losses and enhancing charge extraction through work function modification.Their impact on dye-sensitized solar cells,including catalytic activity and counter electrode performance,is also explored.Finally,the review outlines key challenges,material limitations and performance metrics,offering insight into the future development of nextgeneration photovoltaic devices encouraged by 2D materials.
基金granted by Shandong Provincial Natural Science Foundation,China(No.ZR2023QB170)Guangxi First class Disciplines(Agricultural Resources and Environment),Open Project of State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.ES202428)+3 种基金Shandong Excellent Young Scientists Fund Program(Overseas)(No.2024HWYQ-051)the National Natural Science Fund of China(No.22506033)Young Elite Scientists Sponsorship Program by CASTYoung Taishan Scholars Program of Shandong Province.
文摘Two-dimensional(2D)materials show great potential as novel membrane materials due to their atomic thickness and periodic pore structure.Currently,free-standing membranes based on 2D materials open up new avenues for ultra-fast and highly selective separation.With the absence of porous substrates,free-standing membranes offer shortened transport paths for efficient mass transfer.The interfacial defects between the substrate and selective layer are eliminated to alleviate the internal membrane fouling,enabling the intact structure for precise separation.Hence,this review aims to outline the superiority of 2D material-based free-standing membranes for selective separation applications.Free-standing 2D material membranes composed of the most representative graphenebased materials,MXene,covalent organic framework(COF),metal organic framework(MOF),and hydrogen-bonded organic framework(HOF)are summarized with the discussion on the influence of substrate on their structural properties.The separation performance enhancement strategies in regard to the 2D material,membrane structure,and mechanical properties are examined.Finally,we propose several critical challenges and perspectives in terms of pore size control,mechanical strength improvement,understanding the underlying mass transfer mechanism,issues related to membrane fabrication optimization,scale production,and separation application versatility.This review will provide researchers with practical guidelines for advancing free-standing 2D material membranes for future selective separation applications.
基金supported by the National Natural Science Foundation of China(Nos.12474163,52202161 and 12034002)State Key Laboratory for Advanced Metals and Materials(No.2025-S02).
文摘Non-layered two-dimensional materials(NL2DMs)have emerged as a promising complement to layered 2D materials,offering unique properties derived from their isotropic bonding and structural diversity.However,their synthesis is still facing significant challenges due to the lack of intrinsic anisotropic growth driving force.This review comprehensively outlines strategies for chemical vapor deposition(CVD)-based synthesis of NL2DMs,demonstrating how integrated thermodynamic and kinetic control enables precise thickness and morphology modulation.We also analyze the existing challenges and propose future research directions.This systematic framework paves the way for engineering NL2DMs growth with customized functionalities for next-generation optoelectronics,energy storage,and catalysis.
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。
文摘传统的功率分配算法由于复杂的矩阵运算与迭代所造成的高时延,在实际通信中实时获取信道信息十分困难,当前重要的研究方向是在系统性能和计算复杂度之间找到有效平衡。针对终端直通(Device-to-Device,D2D)用户与蜂窝用户的联合功率分配问题,提出一种异构功率控制图神经网络(Heterogeneous Power Control Graph Neural Network,HPCGNN)算法,旨在最大化所有用户的加权和速率。首先通过构建干扰的异构图,将信道和噪声等信息嵌入到图的节点和边;再由HPCGNN完成消息传递和更新,采用无监督学习方式优化深度神经网络(Deep Neural Network,DNN)参数,最终得到最佳的功率分配。仿真结果表明,相较于其他深度学习算法,所提算法能够有效提高系统性能,且在损失5%性能下相较分式规划(Fractional Programming,FP)能降低82%~98%的时间复杂度。
基金supported by National Natural Science Foundation of China(21878062)
文摘The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growth strategy to construct the ultrathin carboxylated carbon nanotubes(C-CNTs)interpenetrated nickel MOF(Ni-MOF/C-CNTs)nanosheets.The deliberate thickness and specific surface area of novel 2D hybrid nanosheets can be effectively tuned via finely controlling C-CNTs involvement.Due to the unique microstructure,the integrated 2D hybrid nanosheets are endowed with plentiful electroactive sites to promote the electrochemical performances greatly.The prepared Ni-MOF/C-CNTs nanosheets exhibit superior specific capacity of 680 C g^−1 at 1 A g^−1 and good capacity retention.The assembled hybrid device demonstrated the maximum energy density of 44.4 Wh kg^−1 at a power density of 440 W kg^−1.Our novel strategy to construct ultrathin 2D MOF with unique properties can be extended to synthesize various MOF-based functional materials for diverse applications.
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.
