To attain the objectives of carbon peaking and carbon neutrality,the development of stable and highperformance ion-conducting materials holds enormous relevance in various energy storage and conversion devices.Particu...To attain the objectives of carbon peaking and carbon neutrality,the development of stable and highperformance ion-conducting materials holds enormous relevance in various energy storage and conversion devices.Particularly,crystalline porous materials possessing built-in ordered nanochannels exhibit remarkable superiority in comprehending the ion transfer mechanisms with precision.In this regard,covalent organic frameworks(COFs)are highly regarded as a promising alternative due to their preeminent structural tunability,accessible well-defined pores,and excellent thermal/chemical stability under hydrous/anhydrous conditions.By the availability of organic units and the diversity of topologies and connections,advances in COFs have been increasing rapidly over the last decade and they have emerged as a new field of proton-conducting materials.Therefore,a comprehensive summary and discussion are urgently needed to provide an"at a glance"understanding of the prospects and challenges in the development of proton-conducting COFs.In this review,we target a comprehensive review of COFs in the field of proton conductivity from the aspects of design strategies,the proton conducting mechanism/features,the relationships of structure-function,and the application of research.The relevant content of theoretical simulation,advanced structural characterizations,prospects,and challenges are also presented elaborately and critically.More importantly,we sincerely hope that this progress report will form a consistent view of this field and provide inspiration for future research.展开更多
Metal-organic frameworks(MOFs)are among the most promising materials for lithium-ion batteries(LIBs)owing to their high surface area,periodic porosity,adjustable pore size,and controllable chemical composition.For ins...Metal-organic frameworks(MOFs)are among the most promising materials for lithium-ion batteries(LIBs)owing to their high surface area,periodic porosity,adjustable pore size,and controllable chemical composition.For instance,their unique porous structures promote electrolyte penetration,ions transport,and make them ideal for battery separators.Regulating the chemical composition of MOF can introduce more active sites for electrochemical reactions.Therefore,MOFs and their related composites have been extensively and thoroughly explored for LIBs.However,the reported reviews solely include the applications of MOFs in the electrode materials of LIBs and rarely involve other aspects.A systematic review of the application of MOFs in LIBs is essential for understanding the mechanism of MOFs and better designing related MOFs battery materials.This review systematically evaluates the latest developments in pristine MOFs and MOF composites for LIB applications,including MOFs as the main materials(anode,cathode,separators,and electrolytes)to auxiliary materials(coating layers and additives for electrodes).Furthermore,the synthesis,modification methods,challenges,and prospects for the application of MOFs in LIBs are discussed.展开更多
Covalent organic frameworks(COFs),a rapidly developing category of crystalline conjugated organic polymers,possess highly ordered structures,large specific surface areas,stable chemical properties,and tunable pore mic...Covalent organic frameworks(COFs),a rapidly developing category of crystalline conjugated organic polymers,possess highly ordered structures,large specific surface areas,stable chemical properties,and tunable pore microenvironments.Since the first report of boroxine/boronate ester-linked COFs in 2005,COFs have rapidly gained popularity,showing important application prospects in various fields,such as sensing,catalysis,separation,and energy storage.Among them,COFs-based electrochemical(EC)sensors with upgraded analytical performance are arousing extensive interest.In this review,therefore,we summarize the basic properties and the general synthesis methods of COFs used in the field of electroanalytical chemistry,with special emphasis on their usages in the fabrication of chemical sensors,ions sensors,immunosensors,and aptasensors.Notably,the emerged COFs in the electrochemiluminescence(ECL)realm are thoroughly covered along with their preliminary applications.Additionally,final conclusions on state-of-the-art COFs are provided in terms of EC and ECL sensors,as well as challenges and prospects for extending and improving the research and applications of COFs in electroanalytical chemistry.展开更多
Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic fram...Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.展开更多
Metal-organic frameworks(MOFs),which are self-assembled porous coordination materials,have garnered considerable attention in the fields of optoelectronics,photovoltaic,photochemistry,and photocatalysis due to their d...Metal-organic frameworks(MOFs),which are self-assembled porous coordination materials,have garnered considerable attention in the fields of optoelectronics,photovoltaic,photochemistry,and photocatalysis due to their diverse structures and excellent tunability.However,the performance of MOF-based optoelectronic applications currently falls short of the industry benchmark.To enhance the performance of MOF materials,it is imperative to undertake comprehensive investigations aimed at gaining a deeper understanding of photophysics and sequentially optimizing properties related to photocarrier transport,recombination,interaction,and transfer.By utilizing femtosecond laser pulses to excite MOFs,time-resolved optical spectroscopy offers a means to observe and characterize these ultrafast microscopic processes.This approach adds the time coordinate as a novel dimension for comprehending the interaction between light and MOFs.Accordingly,this review provides a comprehensive overview of the recent advancements in the photophysics of MOFs and additionally outlines potential avenues for exploring the time domain in the investigation of MOFs.展开更多
This study investigated the integration of geospatial technologies within smart city frameworks to achieve the European Union’s climate neutrality goals by 2050. Focusing on rapid urbanization and escalating climate ...This study investigated the integration of geospatial technologies within smart city frameworks to achieve the European Union’s climate neutrality goals by 2050. Focusing on rapid urbanization and escalating climate challenges, the research analyzed how smart city frameworks, aligned with climate neutrality objectives, leverage geospatial technologies for urban planning and climate action. The study included case studies from three leading European cities, extracting lessons and best practices in implementing Climate City Contracts across sectors like energy, transport, and waste management. These insights highlighted the essential role of EU and national authorities in providing technical, regulatory, and financial support. Additionally, the paper presented the application of a WEBGIS platform in Limassol Municipality, Cyprus, demonstrating citizen engagement and acceptance of the proposed geospatial framework. Concluding with recommendations for future research, the study contributed significant insights into the advancement of urban sustainability and the effectiveness of geospatial technologies in smart city initiatives for combating climate change.展开更多
When data privacy is imposed as a necessity,Federated learning(FL)emerges as a relevant artificial intelligence field for developing machine learning(ML)models in a distributed and decentralized environment.FL allows ...When data privacy is imposed as a necessity,Federated learning(FL)emerges as a relevant artificial intelligence field for developing machine learning(ML)models in a distributed and decentralized environment.FL allows ML models to be trained on local devices without any need for centralized data transfer,thereby reducing both the exposure of sensitive data and the possibility of data interception by malicious third parties.This paradigm has gained momentum in the last few years,spurred by the plethora of real-world applications that have leveraged its ability to improve the efficiency of distributed learning and to accommodate numerous participants with their data sources.By virtue of FL,models can be learned from all such distributed data sources while preserving data privacy.The aim of this paper is to provide a practical tutorial on FL,including a short methodology and a systematic analysis of existing software frameworks.Furthermore,our tutorial provides exemplary cases of study from three complementary perspectives:i)Foundations of FL,describing the main components of FL,from key elements to FL categories;ii)Implementation guidelines and exemplary cases of study,by systematically examining the functionalities provided by existing software frameworks for FL deployment,devising a methodology to design a FL scenario,and providing exemplary cases of study with source code for different ML approaches;and iii)Trends,shortly reviewing a non-exhaustive list of research directions that are under active investigation in the current FL landscape.The ultimate purpose of this work is to establish itself as a referential work for researchers,developers,and data scientists willing to explore the capabilities of FL in practical applications.展开更多
Metal-organic frameworks recently have been burgeoning and used as precursors to obtain various metal-nitrogen-carbon catalysts for oxygen reduction reaction(ORR).Although rarely studied,Mn-N-C is a promising catalyst...Metal-organic frameworks recently have been burgeoning and used as precursors to obtain various metal-nitrogen-carbon catalysts for oxygen reduction reaction(ORR).Although rarely studied,Mn-N-C is a promising catalyst for ORR due to its weak Fenton reaction activity and strong graphitization catalysis.Here,we developed a facile strategy for anchoring the atomically dispersed nitrogen-coordinated single Mn sites on carbon nanosheets(MnNCS)from an Mn-hexamine coordination framework.The atomically dispersed Mn-N4 sites were dispersed on ultrathin carbon nanosheets with a hierarchically porous structure.The optimized MnNCS displayed an excellent ORR performance in half-cells(0.89 V vs.reversible hydrogen electrode(RHE)in base and 0.76 V vs.RHE in acid in half-wave potential)and Zn-air batteries(233 mW cm^(−2)in peak power density),along with significantly enhanced stability.Density functional theory calculations further corroborated that the Mn-N4-C1_(2)site has favorable adsorption of*OH as the rate-determining step.These findings demonstrate that the metal-hexamine coordination framework can be used as a model system for the rational design of highly active atomic metal catalysts for energy applications.展开更多
Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD...Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD)2/COD/bpy system,suffering from great instability and high cost.Herein,we developed an in situ reduction of the Ni(II)catalytic system to synthesize PAF-1 in low cost and high yield.The active Ni(0)species produced from the NiCl_(2)/bpy/NaI/Mg catalyst system can effectively catalyze homocoupling of tetrakis(4-bromophenyl)methane at the room temperature to form PAF-1 with high Brunauer-Emmett-Teller(BET)-specific surface area up to 4948 m^(2) g^(−1)(Langmuir surface area,6785 m2 g−1).The possible halogen exchange and dehalogenation coupling mechanisms for this new catalytic process in PAF's synthesis are discussed in detail.The efficiency and universality of this innovative catalyst system have also been demonstrated in other PAFs'synthesis.This work provides a cheap,facile,and efficient method for scalable synthesis of PAFs and explores their application for high-pressure storage of Xe and Kr.展开更多
This review offers an overview of the latest developments in metal-covalent organic framework(MCOF)and covalent metal-organic framework(CMOF)materials,whose construction entails a combination of reversible coordinatio...This review offers an overview of the latest developments in metal-covalent organic framework(MCOF)and covalent metal-organic framework(CMOF)materials,whose construction entails a combination of reversible coordination and covalent bonding adapted from metal-organic frameworks(MOFs)and covalent organic frameworks(COFs),respectively.With an emphasis on the MCOF and CMOF structures,this review surveys their building blocks and topologies.Specifically,the frameworks are classified based on the dimensions of their components(building blocks),namely,discrete building blocks and one-dimensional infinite building blocks.For the first category,the materials are further divided into collections of two-and three-dimensional networks based on their topologies.For the second category,the recently emerging MCOFs with woven structures are covered.Finally,the state-of-the-art in MCOF and CMOF chemistry has been laid out for promising avenues in future developments.展开更多
Electrochemically reducing CO_(2)to more reduced chemical species is a promising way that not only enables the conversion of intermittent energy resources to stable fuels,but also helps to build a closed-loop anthropo...Electrochemically reducing CO_(2)to more reduced chemical species is a promising way that not only enables the conversion of intermittent energy resources to stable fuels,but also helps to build a closed-loop anthropogenic carbon cycle.Among various electrocatalysts for electrochemical CO_(2)reduction,multifunctional metal–organic frameworks(MOFs)have been employed as highly efficient and selective heterogeneous electrocatalysts due to their ultrahigh porosity and topologically diverse structures.Up to now,great progress has been achieved in the design and synthesis of highly active and selective MOF-related catalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR),and their corresponding reaction mechanisms have been thoroughly studied.In this review,we summarize the recent progress of applying MOFs and their derivatives in CO_(2)RR,with a focus on the design strategies for electrocatalysts and electrolyzers.We first discussed the reaction mechanisms for different CO_(2)RR products and introduced the commonly applied electrolyzer configurations in the current CO_(2)RR system.Then,an overview of several categories of products(CO,HCOOH,CH_(4),CH_(3)OH,and multi-carbon chemicals)generated from MOFs or their derivatives via CO_(2)RR was discussed.Finally,we offer some insights and perspectives for the future development of MOFs and their derivatives in electrochemical CO_(2)reduction.We aim to provide new insights into this field and further guide future research for large-scale 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
Lithium metal batteries(LMBs)have attracted wide attentions because of their high theoretical specific capacity and low electrochemical potential.However,the growth of lithium dendrites seriously affects the practical...Lithium metal batteries(LMBs)have attracted wide attentions because of their high theoretical specific capacity and low electrochemical potential.However,the growth of lithium dendrites seriously affects the practical application of LMBs.Thus,the lithium-philic carbonyl and carboxy dualgroup-modified covalent organic framework(COF-COOH)is designed to coat the polypropylene(PP)separator(COF-COOH@PP separator),realizing the regulation of ion transport and uniform lithium deposition.The plentiful and negative charge sites in the COF-COOH can suppress the diffusion of the freely movable lithium salt anion by the electrostatic interaction.Density functional theory(DFT)calculations demonstrate that the COF-COOH possesses the function of anchoring anion and desolvation.Consequently,the Li^(+)transference number(0.7),ion conductivity(0.64 mS cm^(-1)),and desolvating of Li^(+)are obviously improved by using the COF-COOH@PP separator.The modified Li-Li symmetric battery delivers stable cycle for more than 1000 h and lower voltage hysteresis(0.02 V).This dendrite-free deposition strategy holds great promise for practical application of Li metal anodes.展开更多
The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity...The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.展开更多
To solve low efficiency,environmental pollution,and toxicity for synthesizing zeolitic imidazolate frameworks(ZIFs)in organic solvents,a KOH-assisted aqueous strategy is proposed to synthesize bimetallic ZIFs polyhedr...To solve low efficiency,environmental pollution,and toxicity for synthesizing zeolitic imidazolate frameworks(ZIFs)in organic solvents,a KOH-assisted aqueous strategy is proposed to synthesize bimetallic ZIFs polyhedrons,which are used as precursors to prepare bimetallic selenide and N-doped carbon(NC)composites.Among them,Fe–Co–Se/NC retains the three-dimensional(3D)polyhedrons with mesoporous structure,and Fe–Co–Se nanoparticles are uniform in size and evenly distributed.When assessed as anode material for lithium-ion batteries,Fe–Co–Se/NC achieves an excellent initial specific capacity of 1165.9 m Ah·g^(-1)at 1.0 A·g^(-1),and the reversible capacity of Fe–Co–Se/NC anode is 1247.4 m Ah·g^(-1)after 550 cycles.It is attributed to that the uniform composite of bimetallic selenides and N-doped carbon can effectively tune redox active sites,the stable 3D structure of Fe–Co–Se/NCs guarantees the structural stability and wettability of the electrolyte,and the uniform distribution of Fe–Co–S nanoparticles in size esuppresses the volume expansion and accelerates the electrochemical reaction kinetics.展开更多
基金financial support from the National Natural Science Foundation of China(21978024)the Beijing Natural Science Foundation(2202034)。
文摘To attain the objectives of carbon peaking and carbon neutrality,the development of stable and highperformance ion-conducting materials holds enormous relevance in various energy storage and conversion devices.Particularly,crystalline porous materials possessing built-in ordered nanochannels exhibit remarkable superiority in comprehending the ion transfer mechanisms with precision.In this regard,covalent organic frameworks(COFs)are highly regarded as a promising alternative due to their preeminent structural tunability,accessible well-defined pores,and excellent thermal/chemical stability under hydrous/anhydrous conditions.By the availability of organic units and the diversity of topologies and connections,advances in COFs have been increasing rapidly over the last decade and they have emerged as a new field of proton-conducting materials.Therefore,a comprehensive summary and discussion are urgently needed to provide an"at a glance"understanding of the prospects and challenges in the development of proton-conducting COFs.In this review,we target a comprehensive review of COFs in the field of proton conductivity from the aspects of design strategies,the proton conducting mechanism/features,the relationships of structure-function,and the application of research.The relevant content of theoretical simulation,advanced structural characterizations,prospects,and challenges are also presented elaborately and critically.More importantly,we sincerely hope that this progress report will form a consistent view of this field and provide inspiration for future research.
基金supported by the National Natural Science Foundation of China(22179006)。
文摘Metal-organic frameworks(MOFs)are among the most promising materials for lithium-ion batteries(LIBs)owing to their high surface area,periodic porosity,adjustable pore size,and controllable chemical composition.For instance,their unique porous structures promote electrolyte penetration,ions transport,and make them ideal for battery separators.Regulating the chemical composition of MOF can introduce more active sites for electrochemical reactions.Therefore,MOFs and their related composites have been extensively and thoroughly explored for LIBs.However,the reported reviews solely include the applications of MOFs in the electrode materials of LIBs and rarely involve other aspects.A systematic review of the application of MOFs in LIBs is essential for understanding the mechanism of MOFs and better designing related MOFs battery materials.This review systematically evaluates the latest developments in pristine MOFs and MOF composites for LIB applications,including MOFs as the main materials(anode,cathode,separators,and electrolytes)to auxiliary materials(coating layers and additives for electrodes).Furthermore,the synthesis,modification methods,challenges,and prospects for the application of MOFs in LIBs are discussed.
基金This research was supported by Natural Science Foundation of Jiangsu Province(BK20220405)National Natural Science Foundation of China(21834004,22276100,22304086)+5 种基金Key Laboratory for Organic Electronics&Information Displays,NJUPT(GZR2022010010,GZR2023010045)Nanjing Science and Technology Innovation Project for Chinese Scholars Studying Abroad(NJKCZYZZ2022-01)Research Fund for Jiangsu Distinguished Professor(RK030STP22001)Natural Science Research Start-up Foundation of Recruiting Talents of NJUPT(NY221006,NY223051)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(23KJB150025)State Key Laboratory of Analytical Chemistry for Life Science,Nanjing University(SKLACLS2311).
文摘Covalent organic frameworks(COFs),a rapidly developing category of crystalline conjugated organic polymers,possess highly ordered structures,large specific surface areas,stable chemical properties,and tunable pore microenvironments.Since the first report of boroxine/boronate ester-linked COFs in 2005,COFs have rapidly gained popularity,showing important application prospects in various fields,such as sensing,catalysis,separation,and energy storage.Among them,COFs-based electrochemical(EC)sensors with upgraded analytical performance are arousing extensive interest.In this review,therefore,we summarize the basic properties and the general synthesis methods of COFs used in the field of electroanalytical chemistry,with special emphasis on their usages in the fabrication of chemical sensors,ions sensors,immunosensors,and aptasensors.Notably,the emerged COFs in the electrochemiluminescence(ECL)realm are thoroughly covered along with their preliminary applications.Additionally,final conclusions on state-of-the-art COFs are provided in terms of EC and ECL sensors,as well as challenges and prospects for extending and improving the research and applications of COFs in electroanalytical chemistry.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21978119,22202088)Key Research and Development Plan of Hainan Province(ZDYF2022SHFZ285)Jiangsu Funding Program for Excellent Postdoctoral Talent(2022ZB636)。
文摘Synergic catalytic effect between active sites and supports greatly determines the catalytic activity for the aerobic oxidative desulfurization of fuel oils.In this work,Ni-doped Co-based bimetallic metal-organic framework(CoNi-MOF)is fabricated to disperse N-hydroxyphthalimide(NHPI),in which the whole catalyst provides plentiful synergic catalytic effect to improve the performance of oxidative desulfurization(ODS).As a bimetallic MOF,the second metal Ni doping results in the flower-like morphology and the modification of electronic properties,which ensure the exposure of NHPI and strengthen the synergistic effect of the overall catalyst.Compared with the monometallic Co-MOF and naked NHPI,the NHPI@CoNi-MOF triggers the efficient activation of molecular oxygen and improves the ODS performance without an initiator.The sulfur removal of dibenzothiophene-based model oil reaches 96.4%over the NHPI@CoNi-MOF catalyst in 8 h of reaction.Furthermore,the catalytic product of this aerobic ODS reaction is sulfone,which is adsorbed on the catalyst surface due to the difference in polarity.This work provides new insight and strategy for the design of a strong synergic catalytic effect between NHPI and bimetallic supports toward high-activity aerobic ODS materials.
基金Project supported by the Science Challenge Project(Grant No.TZ2018001)the National Natural Science Foundation of China(Grant Nos.11872058 and 21802036)the Project of State Key Laboratory of Environment-friendly Energy Materials,and Southwest University of Science and Technology(Grant No.21fksy07)。
文摘Metal-organic frameworks(MOFs),which are self-assembled porous coordination materials,have garnered considerable attention in the fields of optoelectronics,photovoltaic,photochemistry,and photocatalysis due to their diverse structures and excellent tunability.However,the performance of MOF-based optoelectronic applications currently falls short of the industry benchmark.To enhance the performance of MOF materials,it is imperative to undertake comprehensive investigations aimed at gaining a deeper understanding of photophysics and sequentially optimizing properties related to photocarrier transport,recombination,interaction,and transfer.By utilizing femtosecond laser pulses to excite MOFs,time-resolved optical spectroscopy offers a means to observe and characterize these ultrafast microscopic processes.This approach adds the time coordinate as a novel dimension for comprehending the interaction between light and MOFs.Accordingly,this review provides a comprehensive overview of the recent advancements in the photophysics of MOFs and additionally outlines potential avenues for exploring the time domain in the investigation of MOFs.
文摘This study investigated the integration of geospatial technologies within smart city frameworks to achieve the European Union’s climate neutrality goals by 2050. Focusing on rapid urbanization and escalating climate challenges, the research analyzed how smart city frameworks, aligned with climate neutrality objectives, leverage geospatial technologies for urban planning and climate action. The study included case studies from three leading European cities, extracting lessons and best practices in implementing Climate City Contracts across sectors like energy, transport, and waste management. These insights highlighted the essential role of EU and national authorities in providing technical, regulatory, and financial support. Additionally, the paper presented the application of a WEBGIS platform in Limassol Municipality, Cyprus, demonstrating citizen engagement and acceptance of the proposed geospatial framework. Concluding with recommendations for future research, the study contributed significant insights into the advancement of urban sustainability and the effectiveness of geospatial technologies in smart city initiatives for combating climate change.
基金the R&D&I,Spain grants PID2020-119478GB-I00 and,PID2020-115832GB-I00 funded by MCIN/AEI/10.13039/501100011033.N.Rodríguez-Barroso was supported by the grant FPU18/04475 funded by MCIN/AEI/10.13039/501100011033 and by“ESF Investing in your future”Spain.J.Moyano was supported by a postdoctoral Juan de la Cierva Formación grant FJC2020-043823-I funded by MCIN/AEI/10.13039/501100011033 and by European Union NextGenerationEU/PRTR.J.Del Ser acknowledges funding support from the Spanish Centro para el Desarrollo Tecnológico Industrial(CDTI)through the AI4ES projectthe Department of Education of the Basque Government(consolidated research group MATHMODE,IT1456-22)。
文摘When data privacy is imposed as a necessity,Federated learning(FL)emerges as a relevant artificial intelligence field for developing machine learning(ML)models in a distributed and decentralized environment.FL allows ML models to be trained on local devices without any need for centralized data transfer,thereby reducing both the exposure of sensitive data and the possibility of data interception by malicious third parties.This paradigm has gained momentum in the last few years,spurred by the plethora of real-world applications that have leveraged its ability to improve the efficiency of distributed learning and to accommodate numerous participants with their data sources.By virtue of FL,models can be learned from all such distributed data sources while preserving data privacy.The aim of this paper is to provide a practical tutorial on FL,including a short methodology and a systematic analysis of existing software frameworks.Furthermore,our tutorial provides exemplary cases of study from three complementary perspectives:i)Foundations of FL,describing the main components of FL,from key elements to FL categories;ii)Implementation guidelines and exemplary cases of study,by systematically examining the functionalities provided by existing software frameworks for FL deployment,devising a methodology to design a FL scenario,and providing exemplary cases of study with source code for different ML approaches;and iii)Trends,shortly reviewing a non-exhaustive list of research directions that are under active investigation in the current FL landscape.The ultimate purpose of this work is to establish itself as a referential work for researchers,developers,and data scientists willing to explore the capabilities of FL in practical applications.
基金Basic and Applied Basic Research Foundation of Guangdong Province,Grant/Award Numbers:2021A1515110245,2022A1515140108,2023B1515040013National Youth Top-notch Talent Support Program,Grant/Award Number:x2qsA4210090+5 种基金Guangzhou Key Research and Development Program,Grant/Award Number:SL2022B03J01256Guangdong Provincial Key Laboratory of Distributed Energy Systems,Grant/Award Number:2020B1212060075Engineering Research Center of None-food Biomass Efficient Pyrolysis and Utilization Technology of Guangdong Higher Education Institutes,Grant/Award Number:2016GCZX009State Key Laboratory of Pulp and Paper Engineering,Grant/Award Numbers:202215,2022PY02Key projects of social science and technology development in Dongguan,Grant/Award Number:20231800936352National Natural Science Foundation of China,Grant/Award Numbers:21736003,21905044,31971614,32071714。
文摘Metal-organic frameworks recently have been burgeoning and used as precursors to obtain various metal-nitrogen-carbon catalysts for oxygen reduction reaction(ORR).Although rarely studied,Mn-N-C is a promising catalyst for ORR due to its weak Fenton reaction activity and strong graphitization catalysis.Here,we developed a facile strategy for anchoring the atomically dispersed nitrogen-coordinated single Mn sites on carbon nanosheets(MnNCS)from an Mn-hexamine coordination framework.The atomically dispersed Mn-N4 sites were dispersed on ultrathin carbon nanosheets with a hierarchically porous structure.The optimized MnNCS displayed an excellent ORR performance in half-cells(0.89 V vs.reversible hydrogen electrode(RHE)in base and 0.76 V vs.RHE in acid in half-wave potential)and Zn-air batteries(233 mW cm^(−2)in peak power density),along with significantly enhanced stability.Density functional theory calculations further corroborated that the Mn-N4-C1_(2)site has favorable adsorption of*OH as the rate-determining step.These findings demonstrate that the metal-hexamine coordination framework can be used as a model system for the rational design of highly active atomic metal catalysts for energy applications.
基金National Natural Science Foundation of China,Grant/Award Numbers:21975096,22178280Key Laboratory of Nuclear Data Foundation,Grant/Award Number:JCKY2021201C151Young Talent Support Plan,Grant/Award Number:HG6J001。
文摘Porous aromatic framework 1(PAF-1)is an extremely representative nanoporous organic framework owing to its high stability and exceptionally high surface area.Currently,the synthesis of PAF-1 is catalyzed by the Ni(COD)2/COD/bpy system,suffering from great instability and high cost.Herein,we developed an in situ reduction of the Ni(II)catalytic system to synthesize PAF-1 in low cost and high yield.The active Ni(0)species produced from the NiCl_(2)/bpy/NaI/Mg catalyst system can effectively catalyze homocoupling of tetrakis(4-bromophenyl)methane at the room temperature to form PAF-1 with high Brunauer-Emmett-Teller(BET)-specific surface area up to 4948 m^(2) g^(−1)(Langmuir surface area,6785 m2 g−1).The possible halogen exchange and dehalogenation coupling mechanisms for this new catalytic process in PAF's synthesis are discussed in detail.The efficiency and universality of this innovative catalyst system have also been demonstrated in other PAFs'synthesis.This work provides a cheap,facile,and efficient method for scalable synthesis of PAFs and explores their application for high-pressure storage of Xe and Kr.
基金financially supported by the National Natural Science Foundation of China(No.22176135)the Fundamental Research Funds for the Central Universities in China(No.YJ201976)。
文摘This review offers an overview of the latest developments in metal-covalent organic framework(MCOF)and covalent metal-organic framework(CMOF)materials,whose construction entails a combination of reversible coordination and covalent bonding adapted from metal-organic frameworks(MOFs)and covalent organic frameworks(COFs),respectively.With an emphasis on the MCOF and CMOF structures,this review surveys their building blocks and topologies.Specifically,the frameworks are classified based on the dimensions of their components(building blocks),namely,discrete building blocks and one-dimensional infinite building blocks.For the first category,the materials are further divided into collections of two-and three-dimensional networks based on their topologies.For the second category,the recently emerging MCOFs with woven structures are covered.Finally,the state-of-the-art in MCOF and CMOF chemistry has been laid out for promising avenues in future developments.
基金the National Key Research and Development Program of China(2022YFB4102000)NSFC(22102018 and 52171201)+5 种基金the Natural Science Foundation of Sichuan Province(2022NSFSC0194)the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2023C03017)the Hefei National Research Center for Physical Sciences at the Microscale(KF2021005)the University of Electronic Science and Technology of China for startup funding(A1098531023601264)Q.J.acknowledges the China Postdoctoral Science Foundation funded project(2022M710601)the University of Electronic Science and Technology of China for startup funding(Y030212059003039).
文摘Electrochemically reducing CO_(2)to more reduced chemical species is a promising way that not only enables the conversion of intermittent energy resources to stable fuels,but also helps to build a closed-loop anthropogenic carbon cycle.Among various electrocatalysts for electrochemical CO_(2)reduction,multifunctional metal–organic frameworks(MOFs)have been employed as highly efficient and selective heterogeneous electrocatalysts due to their ultrahigh porosity and topologically diverse structures.Up to now,great progress has been achieved in the design and synthesis of highly active and selective MOF-related catalysts for electrochemical CO_(2)reduction reaction(CO_(2)RR),and their corresponding reaction mechanisms have been thoroughly studied.In this review,we summarize the recent progress of applying MOFs and their derivatives in CO_(2)RR,with a focus on the design strategies for electrocatalysts and electrolyzers.We first discussed the reaction mechanisms for different CO_(2)RR products and introduced the commonly applied electrolyzer configurations in the current CO_(2)RR system.Then,an overview of several categories of products(CO,HCOOH,CH_(4),CH_(3)OH,and multi-carbon chemicals)generated from MOFs or their derivatives via CO_(2)RR was discussed.Finally,we offer some insights and perspectives for the future development of MOFs and their derivatives in electrochemical CO_(2)reduction.We aim to provide new insights into this field and further guide future research for large-scale 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.
基金financial support provided by the National Natural Science Foundation of China(52064049)the Key National Natural Science Foundation of Yunnan Province(2018FA028 and 2019FY003023)+2 种基金International Joint Research Center for Advanced Energy Materials of Yunnan Province(202003AE140001)Key Laboratory of Solid State Ions for Green Energy of Yunnan University(2019)the Analysis and Measurements Center of Yunnan University for the sample testing service.
文摘Lithium metal batteries(LMBs)have attracted wide attentions because of their high theoretical specific capacity and low electrochemical potential.However,the growth of lithium dendrites seriously affects the practical application of LMBs.Thus,the lithium-philic carbonyl and carboxy dualgroup-modified covalent organic framework(COF-COOH)is designed to coat the polypropylene(PP)separator(COF-COOH@PP separator),realizing the regulation of ion transport and uniform lithium deposition.The plentiful and negative charge sites in the COF-COOH can suppress the diffusion of the freely movable lithium salt anion by the electrostatic interaction.Density functional theory(DFT)calculations demonstrate that the COF-COOH possesses the function of anchoring anion and desolvation.Consequently,the Li^(+)transference number(0.7),ion conductivity(0.64 mS cm^(-1)),and desolvating of Li^(+)are obviously improved by using the COF-COOH@PP separator.The modified Li-Li symmetric battery delivers stable cycle for more than 1000 h and lower voltage hysteresis(0.02 V).This dendrite-free deposition strategy holds great promise for practical application of Li metal anodes.
基金Changjiang Scholars Program of the Ministry of Education,Grant/Award Number:Q2018270Outstanding Youth Funding of Anhui Province,Grant/Award Number:OUFAH 1908085J10+2 种基金Jiangsu Students'Innovation and Entrepreneurship Training Program,Grant/Award Number:202111117079YNatural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200044National Natural Science Foundation of China,Grant/Award Numbers:NSFC 21671004,NSFC 21975001,NSFC U1904215。
文摘The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.
基金financially supported by the National Natural Science Foundation of China(No.52102100)the Natural Science Foundation of Jiangsu Province(No.BK20181469)the Guangdong Basic and Applied Basic Research Foundation,China(No.2020A1515110035)。
文摘To solve low efficiency,environmental pollution,and toxicity for synthesizing zeolitic imidazolate frameworks(ZIFs)in organic solvents,a KOH-assisted aqueous strategy is proposed to synthesize bimetallic ZIFs polyhedrons,which are used as precursors to prepare bimetallic selenide and N-doped carbon(NC)composites.Among them,Fe–Co–Se/NC retains the three-dimensional(3D)polyhedrons with mesoporous structure,and Fe–Co–Se nanoparticles are uniform in size and evenly distributed.When assessed as anode material for lithium-ion batteries,Fe–Co–Se/NC achieves an excellent initial specific capacity of 1165.9 m Ah·g^(-1)at 1.0 A·g^(-1),and the reversible capacity of Fe–Co–Se/NC anode is 1247.4 m Ah·g^(-1)after 550 cycles.It is attributed to that the uniform composite of bimetallic selenides and N-doped carbon can effectively tune redox active sites,the stable 3D structure of Fe–Co–Se/NCs guarantees the structural stability and wettability of the electrolyte,and the uniform distribution of Fe–Co–S nanoparticles in size esuppresses the volume expansion and accelerates the electrochemical reaction kinetics.