The development of urbanization and industrialization leads to rapid depletion of fossil fuels.Therefore,the production of fuel from renewable resources is highly desired.Electrotechnical energy conversion and storage...The development of urbanization and industrialization leads to rapid depletion of fossil fuels.Therefore,the production of fuel from renewable resources is highly desired.Electrotechnical energy conversion and storage is a benign technique with reliable output and is eco-friendly.Developing an exceptional electrochemical catalyst with tunable properties like a huge specific surface area,porous channels,and abundant active sites is critical points.Recently,Metal-organic frameworks(MOFs)and two-dimensional(2D)transition-metal carbides/nitrides(MXenes)have been extensively investigated in the field of electrochemical energy conversion and storage.However,advances in the research on MOFs are hampered by their limited structural stability and conventionally low electrical conductivity,whereas the practical electrochemical performance of MXenes is impeded by their low porosity,inadequate redox sites,and agglomeration.Consequently,researchers have been designing MOF/MXene nanoarchitectures to overcome the limitations in electrochemical energy conversion and storage.This review explores the recent advances in MOF/MXene nanoarchitectures design strategies,tailoring their properties based on the morphologies(0D,1D,2D,and 3D),and broadening their future opportunities in electrochemical energy storage(batteries,supercapacitors)and catalytic energy conversion(HER,OER,and ORR).The intercalation of MOF in between the MXene layers in the nanoarchitectures functions synergistically to address the issues associated with bare MXene and MOF in the electrochemical energy storage and conversion.This review gives a clear emphasis on the general aspects of MOF/MXene nanoarchitectures,and the future research perspectives,challenges of MOF/MXene design strategies and electrochemical applications are highlighted.展开更多
溶剂热的条件下合成的金属有机框架[Cd(ABTC)(H2O)2(DMA)]·4DMA(JLNU-4,JLNU=Jilin Normal University)具有三维孔道结构,对该化合物的碘吸附性能研究发现其吸附效率可以达到92.9%,且吸附和释放后,晶型并未发生改变,具有较高稳定性...溶剂热的条件下合成的金属有机框架[Cd(ABTC)(H2O)2(DMA)]·4DMA(JLNU-4,JLNU=Jilin Normal University)具有三维孔道结构,对该化合物的碘吸附性能研究发现其吸附效率可以达到92.9%,且吸附和释放后,晶型并未发生改变,具有较高稳定性,可以作为一种方便、经济以及环境友好型材料开发其在I2吸附领域的应用。展开更多
以MIL-53(Al)、MIL-96(Al)和MIL-120(Al)(MIL:Material Institute of Lavorisier)三种金属有机骨架材料为载体,采用浸渍法制备了负载廉价金属镍纳米颗粒的催化剂.将其用于催化硝基苯加氢合成苯胺反应,发现以MIL-53(Al)为载体制得的催化...以MIL-53(Al)、MIL-96(Al)和MIL-120(Al)(MIL:Material Institute of Lavorisier)三种金属有机骨架材料为载体,采用浸渍法制备了负载廉价金属镍纳米颗粒的催化剂.将其用于催化硝基苯加氢合成苯胺反应,发现以MIL-53(Al)为载体制得的催化剂表现出优异的催化性能.采用不同的镍前驱体,如硝酸镍、醋酸镍、乙二胺合镍,制备了一系列Ni/MIL-53(Al)催化剂.通过X射线衍射、傅里叶变换红外光谱、电感耦合等离子体、N2物理吸附、H2程序升温还原、透射电镜等技术对其进行了表征,研究了镍前驱体对金属-载体相互作用、镍颗粒尺寸以及分散程度的影响.结果表明:以乙二胺合镍为镍前驱体制得的催化剂具有金属-载体相互作用适中、镍纳米颗粒更小(4-5 nm)和分布更均匀的特点,在硝基苯加氢反应中表现出优异的催化性能,硝基苯转化率达到100%.回收重复使用5次后,此催化剂仍保持催化活性,硝基苯转化率达92%.展开更多
Stimuli-responsive coordination polymers(CPs)are among one of the most prolific research areas in developing the next-generation functional materials.Their capability of being accurately excited by particular external...Stimuli-responsive coordination polymers(CPs)are among one of the most prolific research areas in developing the next-generation functional materials.Their capability of being accurately excited by particular external changes with pre-determined and observable/characterizable behaviors correspond,are the so called“stimuli”and“responsive”.Abundant types of CP compounds,especially metal-organic frameworks(MOFs),are of rocketing interest owing to their compositional diversity,structural tunability,and in essence their highly engineerable functionality.This present review is aimed to sketch several common types of stimulation and the corresponding responses for CPs,accompanied with the broad logic and mechanisms underneath.And further from the aspect of material revolution,some representative progresses together with the latest advances of CP-based materials in various fields are covered in attempt to display a broader picture towards the possible prospects of this topic.展开更多
Visible-light-initiated organic transformations have received much attention because of low cost, relative safety, and environmental friendliness. In this work, we report on a novel type of visible-light-driven photoc...Visible-light-initiated organic transformations have received much attention because of low cost, relative safety, and environmental friendliness. In this work, we report on a novel type of visible-light-driven photocatalysts, namely, porous nanocomposites of CdS-nanoparticle-decorated metal-organic frameworks （MOF）, prepared by a simple solvothermal method in which porous MIL-100（Fe） served as the support and cadmium acetate （Cd（Ac）2） as the CdS precursor. When the selective oxidation of benzyl alcohol to benzaldehyde is used as the probe reaction, the results show that the combination of MIL-100（Fe） and CdS semiconductor can remarkably enhance the photocatalytic efficiency at room temperature, as compared to that of pure CdS. The enhanced photocatalytic performance can be attributed to the combined effects of enhanced light absorption, more efficient separation of photogenerated electron-hole pairs, and increased surface area of CdS due to the presence of MIL-100（Fe）. This work demonstrates that MOF-based composite materials hold great promise for applications in the field of solar-energy conversion into chemical energy.展开更多
Understanding the origin of the catalytic activity for the development of efficient catalysts is critical yet challenging.Herein,we report a simple strategy for the synthesis of chromium nitride nanoparticles(CrNNPs)e...Understanding the origin of the catalytic activity for the development of efficient catalysts is critical yet challenging.Herein,we report a simple strategy for the synthesis of chromium nitride nanoparticles(CrNNPs)encapsulated into hollow chromium-nitrogen-carbon capsules(CrN@H-Cr-N_(x)-C).The CrN@H-Cr-N_(x)-C demonstrated excellent electrocatalytic activity for the oxygen reduction reaction(ORR)in acidic solutions.When applied as a cathode material in a proton-exchange membrane fuel cell(PEMFC),the CrN@H-Cr-N_(x)-C achieved outstanding initial performance,which is better than that of the PEMFC with H-Cr-N_(x)-C cathode material.The CrN@H-Cr-N_(x)-C cathode also showed good stability over 110 h of operation.These results demonstrated that the coexistence of atomically dispersed CrN_(x) sites and sufficient CrNNPs is essential for excellent PEMFC performances.Density functional theory(DFT)studies further corroborated that CrNNPs can boost the ORR activity of H-Cr-N_(x)-C.This finding opens a new avenue for the fabrication of low-cost,highly active,and durable ORR catalysts for PEMFC and other applications.展开更多
Transition-metal oxides （TMOs） have gradually attracted attention from resear- chers as anode materials for lithium-ion batteries （LIBs） and sodium-ion batteries （SIBs） because of their high theoretical capacity...Transition-metal oxides （TMOs） have gradually attracted attention from resear- chers as anode materials for lithium-ion batteries （LIBs） and sodium-ion batteries （SIBs） because of their high theoretical capacity. However, their poor cycling stability and inferior rate capability resulting from the large volume variation during the lithiation/sodiation process and their low intrinsic electronic con- ductivity limit their applications. To solve the problems of TMOs, carbon-based metal-oxide composites with complex structures derived from metal-organic frameworks （MOFs） have emerged as promising electrode materials for LIBs and SIBs. In this study, we adopted a facile interface-modulated method to synthesize yolk-shell carbon-based Co3O4 dodecahedrons derived from ZIF-67 zeolitic imida- zolate frameworks. This strategy is based on the interface separation between the ZIF-67 core and the carbon-based shell during the pyrolysis process. The unique yolk-shell structure effectively accommodates the volume expansion during lithiation or sodiation, and the carbon matrix improves the electrical conductivity of the electrode. As an anode for LIBs, the yolk-shell Co3O4/C dodecahedrons exhibit a high specific capacity and excellent cycling stability （1,100 mAh.g-1 after 120 cycles at 200 mA-g-1）. As an anode for S1Bs, the composites exhibit an outstand- ing rate capability （307 mAh-g-1 at 1,000 mA-g-1 and 269 mAh.g-1 at 2,000 mA-g-1）. Detailed electrochemical kinetic analysis indicates that the energy storage for Li＋ and Na＋ in yolk-sheU Co3O4/C dodecahedrons shows a dominant capacitive behavior. This work introduces an effective approach for fabricating carbon- based metal-oxide composites by using MOFs as ideal precursors and as electrode materials to enhance the electrochemical performance of LIBs and SIBs.展开更多
基金supported by the National Research Foundation(NRF-2020R1C1C1012655 NRF-2020K1A3A7A09078095,and NRF2021R1A4A5030513,M.Y.)also supported by grants from the National Research Foundation of Korea(2020R1A2C1101561 and 2021M3F6A1085886,M.J.K.)。
文摘The development of urbanization and industrialization leads to rapid depletion of fossil fuels.Therefore,the production of fuel from renewable resources is highly desired.Electrotechnical energy conversion and storage is a benign technique with reliable output and is eco-friendly.Developing an exceptional electrochemical catalyst with tunable properties like a huge specific surface area,porous channels,and abundant active sites is critical points.Recently,Metal-organic frameworks(MOFs)and two-dimensional(2D)transition-metal carbides/nitrides(MXenes)have been extensively investigated in the field of electrochemical energy conversion and storage.However,advances in the research on MOFs are hampered by their limited structural stability and conventionally low electrical conductivity,whereas the practical electrochemical performance of MXenes is impeded by their low porosity,inadequate redox sites,and agglomeration.Consequently,researchers have been designing MOF/MXene nanoarchitectures to overcome the limitations in electrochemical energy conversion and storage.This review explores the recent advances in MOF/MXene nanoarchitectures design strategies,tailoring their properties based on the morphologies(0D,1D,2D,and 3D),and broadening their future opportunities in electrochemical energy storage(batteries,supercapacitors)and catalytic energy conversion(HER,OER,and ORR).The intercalation of MOF in between the MXene layers in the nanoarchitectures functions synergistically to address the issues associated with bare MXene and MOF in the electrochemical energy storage and conversion.This review gives a clear emphasis on the general aspects of MOF/MXene nanoarchitectures,and the future research perspectives,challenges of MOF/MXene design strategies and electrochemical applications are highlighted.
文摘溶剂热的条件下合成的金属有机框架[Cd(ABTC)(H2O)2(DMA)]·4DMA(JLNU-4,JLNU=Jilin Normal University)具有三维孔道结构,对该化合物的碘吸附性能研究发现其吸附效率可以达到92.9%,且吸附和释放后,晶型并未发生改变,具有较高稳定性,可以作为一种方便、经济以及环境友好型材料开发其在I2吸附领域的应用。
基金supported by the National Key Basic Research Program of China(973)(2011CB201301)~~
文摘以MIL-53(Al)、MIL-96(Al)和MIL-120(Al)(MIL:Material Institute of Lavorisier)三种金属有机骨架材料为载体,采用浸渍法制备了负载廉价金属镍纳米颗粒的催化剂.将其用于催化硝基苯加氢合成苯胺反应,发现以MIL-53(Al)为载体制得的催化剂表现出优异的催化性能.采用不同的镍前驱体,如硝酸镍、醋酸镍、乙二胺合镍,制备了一系列Ni/MIL-53(Al)催化剂.通过X射线衍射、傅里叶变换红外光谱、电感耦合等离子体、N2物理吸附、H2程序升温还原、透射电镜等技术对其进行了表征,研究了镍前驱体对金属-载体相互作用、镍颗粒尺寸以及分散程度的影响.结果表明:以乙二胺合镍为镍前驱体制得的催化剂具有金属-载体相互作用适中、镍纳米颗粒更小(4-5 nm)和分布更均匀的特点,在硝基苯加氢反应中表现出优异的催化性能,硝基苯转化率达到100%.回收重复使用5次后,此催化剂仍保持催化活性,硝基苯转化率达92%.
基金This work was supported by the National Key Research and Development Program of China(2022YFA1502901)the National Natural Science Foundation of China[22035003,22371137 and 22201137]+3 种基金the Nature Science Fund of Tianjin,China[19JCZDJC37200]the Fundamental Research Funds for the Central Universities[63233040]the Haihe Laboratory of Sustainable Chemical Transformations[YYJC202101]the Science Foundation of State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter[20230029].
文摘Stimuli-responsive coordination polymers(CPs)are among one of the most prolific research areas in developing the next-generation functional materials.Their capability of being accurately excited by particular external changes with pre-determined and observable/characterizable behaviors correspond,are the so called“stimuli”and“responsive”.Abundant types of CP compounds,especially metal-organic frameworks(MOFs),are of rocketing interest owing to their compositional diversity,structural tunability,and in essence their highly engineerable functionality.This present review is aimed to sketch several common types of stimulation and the corresponding responses for CPs,accompanied with the broad logic and mechanisms underneath.And further from the aspect of material revolution,some representative progresses together with the latest advances of CP-based materials in various fields are covered in attempt to display a broader picture towards the possible prospects of this topic.
基金This work is supported by the National Natural Science Foundation of China （Grant No. U1232102）, National Basic Research Program of China （Nos. 2010CB923302 and 2013CB834605）, and the Specialized Research Fund for the Doctoral Program of Higher Education （SRFDP） of Ministry of Education （Grant No. 20113402110029）.
文摘Visible-light-initiated organic transformations have received much attention because of low cost, relative safety, and environmental friendliness. In this work, we report on a novel type of visible-light-driven photocatalysts, namely, porous nanocomposites of CdS-nanoparticle-decorated metal-organic frameworks （MOF）, prepared by a simple solvothermal method in which porous MIL-100（Fe） served as the support and cadmium acetate （Cd（Ac）2） as the CdS precursor. When the selective oxidation of benzyl alcohol to benzaldehyde is used as the probe reaction, the results show that the combination of MIL-100（Fe） and CdS semiconductor can remarkably enhance the photocatalytic efficiency at room temperature, as compared to that of pure CdS. The enhanced photocatalytic performance can be attributed to the combined effects of enhanced light absorption, more efficient separation of photogenerated electron-hole pairs, and increased surface area of CdS due to the presence of MIL-100（Fe）. This work demonstrates that MOF-based composite materials hold great promise for applications in the field of solar-energy conversion into chemical energy.
基金The authors gratefully acknowledge the support from the Robert A.Welch Foundation(B-0027)(S.M.).Support from North China Electric Power University(no.XM2009903)the National Science Foundation of China(grant no.22006036)are also acknowledged(H.Y.and X.W.).R.W.M.and J.T.W.acknowledge support from the U.S.National Science Foundation(no.DMR-1708617)Materials Research Collaborative Access Team(MRCAT)operations are supported by the Department of Energy(DOE)and the MRCAT member institutions.This research used resources of the Advanced Photon Source,a U.S.DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract no.DE-AC02-06CH11357.
文摘Understanding the origin of the catalytic activity for the development of efficient catalysts is critical yet challenging.Herein,we report a simple strategy for the synthesis of chromium nitride nanoparticles(CrNNPs)encapsulated into hollow chromium-nitrogen-carbon capsules(CrN@H-Cr-N_(x)-C).The CrN@H-Cr-N_(x)-C demonstrated excellent electrocatalytic activity for the oxygen reduction reaction(ORR)in acidic solutions.When applied as a cathode material in a proton-exchange membrane fuel cell(PEMFC),the CrN@H-Cr-N_(x)-C achieved outstanding initial performance,which is better than that of the PEMFC with H-Cr-N_(x)-C cathode material.The CrN@H-Cr-N_(x)-C cathode also showed good stability over 110 h of operation.These results demonstrated that the coexistence of atomically dispersed CrN_(x) sites and sufficient CrNNPs is essential for excellent PEMFC performances.Density functional theory(DFT)studies further corroborated that CrNNPs can boost the ORR activity of H-Cr-N_(x)-C.This finding opens a new avenue for the fabrication of low-cost,highly active,and durable ORR catalysts for PEMFC and other applications.
基金This work was supported by the National Key Research and Development Program of China （No. 2016YFA0202603）, the National Basic Research Program of China （No. 2013CB934103）, the National Natural Science Foundation of China （Nos. 51521001 and 51272197）, the National Natural Science Fund for Distinguished Young Scholars （No. 51425204）, the Fundamental Research Funds for the Central Universities （WUT： 22016III001, 2017IVA096） and the Foundation of National Excellent Doctoral Dissertation of PR China （No. 2016-YB-004） Prof. Liqiang Mai gratefully acknowledges the financial support from China Scholarship Council （No. 201606955096）.
文摘Transition-metal oxides （TMOs） have gradually attracted attention from resear- chers as anode materials for lithium-ion batteries （LIBs） and sodium-ion batteries （SIBs） because of their high theoretical capacity. However, their poor cycling stability and inferior rate capability resulting from the large volume variation during the lithiation/sodiation process and their low intrinsic electronic con- ductivity limit their applications. To solve the problems of TMOs, carbon-based metal-oxide composites with complex structures derived from metal-organic frameworks （MOFs） have emerged as promising electrode materials for LIBs and SIBs. In this study, we adopted a facile interface-modulated method to synthesize yolk-shell carbon-based Co3O4 dodecahedrons derived from ZIF-67 zeolitic imida- zolate frameworks. This strategy is based on the interface separation between the ZIF-67 core and the carbon-based shell during the pyrolysis process. The unique yolk-shell structure effectively accommodates the volume expansion during lithiation or sodiation, and the carbon matrix improves the electrical conductivity of the electrode. As an anode for LIBs, the yolk-shell Co3O4/C dodecahedrons exhibit a high specific capacity and excellent cycling stability （1,100 mAh.g-1 after 120 cycles at 200 mA-g-1）. As an anode for S1Bs, the composites exhibit an outstand- ing rate capability （307 mAh-g-1 at 1,000 mA-g-1 and 269 mAh.g-1 at 2,000 mA-g-1）. Detailed electrochemical kinetic analysis indicates that the energy storage for Li＋ and Na＋ in yolk-sheU Co3O4/C dodecahedrons shows a dominant capacitive behavior. This work introduces an effective approach for fabricating carbon- based metal-oxide composites by using MOFs as ideal precursors and as electrode materials to enhance the electrochemical performance of LIBs and SIBs.
