锆基金属有机骨架(Zr-based metal organic frameworks,Zr-MOFs)材料是由金属锆离子或金属锆簇与多齿有机配体自组装而形成的多孔晶体材料,其优异的稳定性及简单丰富的制备方法使其在有毒气体吸附领域具有广阔的应用前景。本文简述了Zr-...锆基金属有机骨架(Zr-based metal organic frameworks,Zr-MOFs)材料是由金属锆离子或金属锆簇与多齿有机配体自组装而形成的多孔晶体材料,其优异的稳定性及简单丰富的制备方法使其在有毒气体吸附领域具有广阔的应用前景。本文简述了Zr-MOFs材料的组成及优点,综述了Zr-MOFs作为防毒面具吸附材料对酸性、碱性及中性有毒气体的吸附性能的研究进展,同时展望了其发展前景,指出高效、广谱Zr-MOFs是防毒面具吸附材料研究的重点方向。展开更多
Different materials,such as metal sulphides,are often combined with metal‐organic frameworks(MOFs)to develop multi‐functional composites and improve their photocatalytic properties.However,the high interfacial energ...Different materials,such as metal sulphides,are often combined with metal‐organic frameworks(MOFs)to develop multi‐functional composites and improve their photocatalytic properties.However,the high interfacial energy barrier limits the formation and nano‐assembly of the heterogeneous junctions between MOFs and metal sulphides.Herein,the heterostructured Zr‐MOF‐S@CdS are successfully constructed through a sequential synthesis method,in which the mesoporous Zr‐MOF are firstly decorated with thioglycolic acid through pore functionalization,and followed by the S^(2-)anion exchange process resulting in the surface close attached growth of CdS onto Zr‐MOF‐S materials.Due to the presence of molecules linkers,the CdS can be precisely decorated onto Zr‐MOF‐S without aggregation,which can provide more active sites.Moreover,the intimate connections and the suitable band structures between two materials can also facilitate the photogenerated electron‐hole pairs separation.Therefore,the resulting Zr‐MOF‐S@CdS with appropriate ratio exhibits high photocatalytic activity for water reduction,in which the H_(2) evolution rate can reach up to 1861.7μmol·g^(‒1)·h^(‒1),4.5 times higher than pure CdS and 2.3 times higher than of Zr‐MOF/CdS,respectively.Considering the promising future of MOF‐based photocatalysts,this work may provide an avenue for the further design and synthesis MOF‐based composite photocatalysts for efficient H_(2) evolution.展开更多
PTA/UiO-66 composites were successfully synthesized by the hydrothermal method.The results showed that the synergistic effect between phosphotungstic acid(PTA)and UiO-66 could enhance the oxidative desulfurization(ODS...PTA/UiO-66 composites were successfully synthesized by the hydrothermal method.The results showed that the synergistic effect between phosphotungstic acid(PTA)and UiO-66 could enhance the oxidative desulfurization(ODS)activity.The XRD results proved that UiO-66 retained its structure in the PTA/UiO-66 composites.The SEM results showed that the PTA/UiO-66 catalysts exhibited regular octahedral shape.The Raman spectra revealed that PTA in the composites retained the Keggin structure.The XPS results showed that the electron transfer occurred from Zr-MOF to PTA.The ODS reaction mechanism was discussed.Electrons transfer from Zr-MOF to PTA can promote the generation of active species(·OH)and thus enhance the ODS activity.This explanation can be confirmed by the formation of oxygen vacancy and W0 as revealed by the XPS analysis.展开更多
As an important type of metal-organic framework(MOF),Zr-MOF shows excellent CO2 adsorption performance.In this work,a Zr-MOF was synthesized by a solvothennal method and adopted to support Ru through simple incipient-...As an important type of metal-organic framework(MOF),Zr-MOF shows excellent CO2 adsorption performance.In this work,a Zr-MOF was synthesized by a solvothennal method and adopted to support Ru through simple incipient-wetness impreg nation.Then the Ru/Zr-MOF was applied for CO2 hydrogenation(Vh2:VCO2=4:1)with the assistance of dielectric banner dischai'ge(DBD)plasma.The hydrogenation of Cd2 results showed that methane was produced selectively under the synergistic effect between plasma and the Ru/Zr-MOF catalyst,and the selectivity and yield of methane reached 94.6%and 39.1%,respectively.The XRD and SEM analyses indicate that the basic crystalline phase structure and morphology of the Zr-MOF and Ru/Zr-MOF remained the same after DBD plasma treatment,suggesting that the catalysts are stable in plasma.The guest molecules in the pores of the Zr-MOF are removed and the Ru"ions are reduced to metallic Ru()in the reduction atmosphere according to the BET and XPS results,which are responsible for the high performance of plasma with the Ru/Zr-MOF catalyst.In situ optical emission spectra of pure plasma,plasma with Zr-MOF,and plasma with Ru/Zr-MOF were measured,and the active species of C,H and CH for CO2 hydrogenation were detected.The plasma-assisted Ru/Zr-MOF exhibited high catalytic activity and stability in CO2 hydrogenation to methane,and it has great guiding significance for CO2 hydrogenation by using plasma and MOF materials.展开更多
Amino-functionalized Zr-MOF(amino-Zr-MOF)was synthesized using 2-aminoterephthalic acid as an organic linker.The physicochemical properties of the material were characterized by X-ray diffraction(XRD),scanning electro...Amino-functionalized Zr-MOF(amino-Zr-MOF)was synthesized using 2-aminoterephthalic acid as an organic linker.The physicochemical properties of the material were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),thermogravimetric analysis(TGA),Fourier transform infrared spectroscopy(FTIR),and N_(2) adsorption to understand its crystalline structure,morphology,thermal stability,and porous structure.CO_(2) adsorption isotherms on amino-Zr-MOF were obtained at 1 atm and at different temperatures.In addition,CO_(2) and CH_(4) adsorption at high pressure(up to 10 atm)was also measured.CO_(2) adsorption capacity on amino-Zr-MOF was 9 mmol/g at 988 kPa,0℃,while CH_(4) adsorption capacity was 3.7 mmol/g at 900 kPa,0℃.The heat of CO_(2) adsorption on amino-Zr-MOF was estimated to be 29.4 kJ/mol.Continuous column tests of CO_(2) adsorption were performed at different concentrations of CO_(2) in nitrogen at 20 mL/min and 0.7 g adsorbent and total adsorbed amounts of CO_(2) within the column during the breakthrough time were calculated to be 4.55,5.26 and 4.37 mmol/g at 10%,15%and 20%CO_(2),respectively.展开更多
Zirconium-based metal-organic frameworks(Zr-MOFs)have been explored for applications including but not limited to water adsorption,gas storage and separation,heterogeneous catalysis,and chemical sensing.Zr-MOFs serve ...Zirconium-based metal-organic frameworks(Zr-MOFs)have been explored for applications including but not limited to water adsorption,gas storage and separation,heterogeneous catalysis,and chemical sensing.Zr-MOFs serve as a major class of functional MOFs thanks to their high thermal,chemical and hydrolytic stability,large surface area,and tunable structures with the versatile connectivity.In this work,we highlight the design and synthesis of zirconium-based MOFs as well as their applications.Specifically,we demonstrate how reticular chemistry can direct the rational design and synthesis of functional ZrMOFs and describe their structure–property relationship.In addition,we feature synthetic strategies,including isoreticular expansion,linker functionalization,node functionalization,and defect engineering,as toolkits to construct tailored material for specific applications.展开更多
基金the National Natural Science Foundation of China(52102111)the Natural Science Foundation of Hubei Province(No.2021CFB218)the Unveils List System Science and Technology Project of Hubei Provincial Science and Technology Department(No.2021BEC016)。
文摘锆基金属有机骨架(Zr-based metal organic frameworks,Zr-MOFs)材料是由金属锆离子或金属锆簇与多齿有机配体自组装而形成的多孔晶体材料,其优异的稳定性及简单丰富的制备方法使其在有毒气体吸附领域具有广阔的应用前景。本文简述了Zr-MOFs材料的组成及优点,综述了Zr-MOFs作为防毒面具吸附材料对酸性、碱性及中性有毒气体的吸附性能的研究进展,同时展望了其发展前景,指出高效、广谱Zr-MOFs是防毒面具吸附材料研究的重点方向。
文摘Different materials,such as metal sulphides,are often combined with metal‐organic frameworks(MOFs)to develop multi‐functional composites and improve their photocatalytic properties.However,the high interfacial energy barrier limits the formation and nano‐assembly of the heterogeneous junctions between MOFs and metal sulphides.Herein,the heterostructured Zr‐MOF‐S@CdS are successfully constructed through a sequential synthesis method,in which the mesoporous Zr‐MOF are firstly decorated with thioglycolic acid through pore functionalization,and followed by the S^(2-)anion exchange process resulting in the surface close attached growth of CdS onto Zr‐MOF‐S materials.Due to the presence of molecules linkers,the CdS can be precisely decorated onto Zr‐MOF‐S without aggregation,which can provide more active sites.Moreover,the intimate connections and the suitable band structures between two materials can also facilitate the photogenerated electron‐hole pairs separation.Therefore,the resulting Zr‐MOF‐S@CdS with appropriate ratio exhibits high photocatalytic activity for water reduction,in which the H_(2) evolution rate can reach up to 1861.7μmol·g^(‒1)·h^(‒1),4.5 times higher than pure CdS and 2.3 times higher than of Zr‐MOF/CdS,respectively.Considering the promising future of MOF‐based photocatalysts,this work may provide an avenue for the further design and synthesis MOF‐based composite photocatalysts for efficient H_(2) evolution.
基金This work was supported by the Natural Science Foundation of Tianjin(19JCTPJC46300).
文摘PTA/UiO-66 composites were successfully synthesized by the hydrothermal method.The results showed that the synergistic effect between phosphotungstic acid(PTA)and UiO-66 could enhance the oxidative desulfurization(ODS)activity.The XRD results proved that UiO-66 retained its structure in the PTA/UiO-66 composites.The SEM results showed that the PTA/UiO-66 catalysts exhibited regular octahedral shape.The Raman spectra revealed that PTA in the composites retained the Keggin structure.The XPS results showed that the electron transfer occurred from Zr-MOF to PTA.The ODS reaction mechanism was discussed.Electrons transfer from Zr-MOF to PTA can promote the generation of active species(·OH)and thus enhance the ODS activity.This explanation can be confirmed by the formation of oxygen vacancy and W0 as revealed by the XPS analysis.
文摘As an important type of metal-organic framework(MOF),Zr-MOF shows excellent CO2 adsorption performance.In this work,a Zr-MOF was synthesized by a solvothennal method and adopted to support Ru through simple incipient-wetness impreg nation.Then the Ru/Zr-MOF was applied for CO2 hydrogenation(Vh2:VCO2=4:1)with the assistance of dielectric banner dischai'ge(DBD)plasma.The hydrogenation of Cd2 results showed that methane was produced selectively under the synergistic effect between plasma and the Ru/Zr-MOF catalyst,and the selectivity and yield of methane reached 94.6%and 39.1%,respectively.The XRD and SEM analyses indicate that the basic crystalline phase structure and morphology of the Zr-MOF and Ru/Zr-MOF remained the same after DBD plasma treatment,suggesting that the catalysts are stable in plasma.The guest molecules in the pores of the Zr-MOF are removed and the Ru"ions are reduced to metallic Ru()in the reduction atmosphere according to the BET and XPS results,which are responsible for the high performance of plasma with the Ru/Zr-MOF catalyst.In situ optical emission spectra of pure plasma,plasma with Zr-MOF,and plasma with Ru/Zr-MOF were measured,and the active species of C,H and CH for CO2 hydrogenation were detected.The plasma-assisted Ru/Zr-MOF exhibited high catalytic activity and stability in CO2 hydrogenation to methane,and it has great guiding significance for CO2 hydrogenation by using plasma and MOF materials.
基金supported by the National Natural Science Foundation of China(82172041 and 81801808)Harbin Medical University Cancer Hospital Haiyan Foundation(JJZD202101,JJQN2019-02,and JJZD2018-02)+2 种基金Heilongjiang Postdoctoral Fund(LBH-Z18160 and LBHTZ2018)the Natural Science Foundation of Heilongjiang(YQ2023H023 and LH_(2)020H127)Heilongjiang Province Youth Innovative Talents Training Program(UNPYSCT-2020162)。
文摘Amino-functionalized Zr-MOF(amino-Zr-MOF)was synthesized using 2-aminoterephthalic acid as an organic linker.The physicochemical properties of the material were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),thermogravimetric analysis(TGA),Fourier transform infrared spectroscopy(FTIR),and N_(2) adsorption to understand its crystalline structure,morphology,thermal stability,and porous structure.CO_(2) adsorption isotherms on amino-Zr-MOF were obtained at 1 atm and at different temperatures.In addition,CO_(2) and CH_(4) adsorption at high pressure(up to 10 atm)was also measured.CO_(2) adsorption capacity on amino-Zr-MOF was 9 mmol/g at 988 kPa,0℃,while CH_(4) adsorption capacity was 3.7 mmol/g at 900 kPa,0℃.The heat of CO_(2) adsorption on amino-Zr-MOF was estimated to be 29.4 kJ/mol.Continuous column tests of CO_(2) adsorption were performed at different concentrations of CO_(2) in nitrogen at 20 mL/min and 0.7 g adsorbent and total adsorbed amounts of CO_(2) within the column during the breakthrough time were calculated to be 4.55,5.26 and 4.37 mmol/g at 10%,15%and 20%CO_(2),respectively.
基金support by the National Natural Science Foundation of China (22201247)the startup funding from Zhejiang University。
文摘Zirconium-based metal-organic frameworks(Zr-MOFs)have been explored for applications including but not limited to water adsorption,gas storage and separation,heterogeneous catalysis,and chemical sensing.Zr-MOFs serve as a major class of functional MOFs thanks to their high thermal,chemical and hydrolytic stability,large surface area,and tunable structures with the versatile connectivity.In this work,we highlight the design and synthesis of zirconium-based MOFs as well as their applications.Specifically,we demonstrate how reticular chemistry can direct the rational design and synthesis of functional ZrMOFs and describe their structure–property relationship.In addition,we feature synthetic strategies,including isoreticular expansion,linker functionalization,node functionalization,and defect engineering,as toolkits to construct tailored material for specific applications.
