One novel metal-organic framework [Cu2（L）（μ3-OH）]n（1, H3L = [1,1＇：3＇,1＇＇-terphenyl]-4,4＇＇,5＇-tricarboxylic acid） has been synthesized and characterized by single-crystal powder X-ray diffraction, IR and...One novel metal-organic framework [Cu2（L）（μ3-OH）]n（1, H3L = [1,1＇：3＇,1＇＇-terphenyl]-4,4＇＇,5＇-tricarboxylic acid） has been synthesized and characterized by single-crystal powder X-ray diffraction, IR and thermogravimetric analyses. Complex 1 crystallizes in orthorhombic crystal system, space group Pbca with a = 21.573（19）, b = 5.404（5）, c = 33.78（3） ？, C21H（12）O7Cu2, Mr = 503.39, V = 3938（6） A^3, Z = 8, Dc = 1.698 g·cm^-3, μ = 2.202 mm^-1, F（000） = 2016, 1.531〈θ〈25.009°, λ（Mo Kα） = 0.71073 A, T = 293（2） K, the final R = 0.0448 and wR = 0.1002. The structure of complex 1 is a three-dimensional（3D） framework based on infinite rod-shaped secondary building units and can be simplified as kgd topology. The gas adsorption measurements for N2, CO2, H2O, CH3OH and CH3CH2OH have been done. Fortunately, the selective sorption of CO2 over N2 was found at 195 K.展开更多
A new metal-organic framework（MOF） based on metal clusters as secondary building units（SBU）,has been synthesized and structurally characterized.The reported MOF presents an interesting 8-connected self-penetrating...A new metal-organic framework（MOF） based on metal clusters as secondary building units（SBU）,has been synthesized and structurally characterized.The reported MOF presents an interesting 8-connected self-penetrating coordination network based on dinuclear cadmium cluster with a 4^（24）·5·6~3 topology. Moreover,the thermal stability and luminescence property of this compound have been investigated.展开更多
Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure.The aluminosilicate precursors comprising zeolite seconda...Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure.The aluminosilicate precursors comprising zeolite secondary building units were first synthesized by carefully controlling reaction conditions and then were assembled using co-templates of gemini surfactant[C18H37N(CH3)2(CH2)3-N(CH3)2C18H37]2+(18-3-18)and triethanolamine(TEA).X-ray Diffraction(XRD)patterns of the as-made samples indicated that highly ordered mesostructured MCM-48 was formed.Transmission Electron Microscopy(TEM)images further verified the formation of MCM-48 with uniform cubic pore channel system having the pore opening diameter of about 25Å.Compared with the conventionally synthesized MCM-48,the as-synthesized MCM-48 sample showed an adsorption band at 520–600 cm-1 in its FT-IR spectrum,which was assigned to five-membered ring vibration from zeolite structure.This suggested the presence of zeolite building units in the pore wall.N2 adsorption data showed that the material had a much higher specific surface area(1200 m2/g)than the conventional MCM-48(1100 m2/g).Finally,the cat-alytic performance of the as-made MCM-48 was evaluated by hydrogenation dealkylation reaction of heavy aromatic hydrocarbons.Catalytic results showed that the as-made MCM-48 catalyst exhibited higher conversion than the con-ventional MCM-48 catalyst.The as-made mesostructured MCM-48 may have a potential catalytic application in the conversion of bulky molecules.展开更多
In the development of metal-organic frameworks(MOFs),secondary building units(SBUs)have been utilized as molecular modules for the construction of nanoporous materials with robust structures.Under solvothermal synthet...In the development of metal-organic frameworks(MOFs),secondary building units(SBUs)have been utilized as molecular modules for the construction of nanoporous materials with robust structures.Under solvothermal synthetic conditions,dynamic changes in the metal coordination environments and ligand coordination modes of SBUs determine the resultant product structures.Alternatively,MOF phases with new topologies can also be achieved by post-synthetic treatment of as-synthesized MOFs via the introduction of acidic or basic moieties that cause the simultaneous cleavage/reformation of coordination bonds in the solid state.In this sense,we studied the solid-state transformation of two ndc-based Zn-MOFs(ndc=1,4-naphthalene dicarboxylate)with different SBUs but the same pcu topology to another MOF with sev topology.One of the chosen MOFs with pcu nets is[Zn_(2)(ndc)_(2)(bpy)]_(n)(bpy=4,4,-bipyridine),(6C_(bpy)-MOF)consisting of a 6-connected pillared-paddlewheel SBU,and the other is IRMOF-7 composed of 6-connected Zn40(C 00)6 SBUs and ndc.Upon post-structural modification,these pcu MOFs were converted into the same MOF with sev topology constructed from the uncommon 7-connected Zri_(4)O(COO)_(7)SBU(7C-MOF).The appropriate post-synthetic conditions for the transformation of each SBUs were systematically examined.In addition,the effect of the pillar molecules in the pillared-paddlewheel MOFs on the topology conversion was studied in terms of the linker basicity,which determines the inertness during the solid-state phase transformation.This post-synthetic modification approach is expected to expand the available methods for designing and synthesizing MOFs with controlled topologies.展开更多
A new metal-organic framework (MOF),{[Zn_7 (BPS)_4 (OH)_6 (H_2O)_2]·5 H_2O]_n}(1), (H_2 BPS=4,4′-bibenzoic acid-2,2′-sulfone), based on a wavy and infinite chain-shaped secondary building units, has been synthe...A new metal-organic framework (MOF),{[Zn_7 (BPS)_4 (OH)_6 (H_2O)_2]·5 H_2O]_n}(1), (H_2 BPS=4,4′-bibenzoic acid-2,2′-sulfone), based on a wavy and infinite chain-shaped secondary building units, has been synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction and further confirmed by PXRD, TGA and IR spectrum. The solid-state emission spectra reveal that compound 1 presents strong luminescence emission bands at room temperature. The fluorescent properties of compound 1 in diverse organic solvents indicated that 1 has palpable luminescent sense effects for DMF and DMAC.展开更多
为探究不同反应条件对MOFs微观结构和宏观性能的影响,在不同反应条件下,以硫酸铜(CuSO_(4)·5H_(2)O)和6-(吡啶-3′-基)间苯二甲酸(H_(2)L)为材料,制备了2种金属有机框架材料(MOFs){[Cu_(2)(L)_(2)·C _(2) H _(3) N]}n(1)和{[C...为探究不同反应条件对MOFs微观结构和宏观性能的影响,在不同反应条件下,以硫酸铜(CuSO_(4)·5H_(2)O)和6-(吡啶-3′-基)间苯二甲酸(H_(2)L)为材料,制备了2种金属有机框架材料(MOFs){[Cu_(2)(L)_(2)·C _(2) H _(3) N]}n(1)和{[Cu(HL)_(2)]}n(2),并对合成的金属有机框架材料1和2进行了结构分析、TGA和FTIR表征以及对染料的吸附性能研究。单晶衍射数据分析表明:配合物1和2都属单斜晶系,P 21/c空间群。配合物1是一种基于双核轮桨次级构筑单元[Cu_(2)(COO)_(4)]构筑的三维紧密堆积化合物,配合物2由于配体部分质子化,结构中存在氢键[O_(3)—H…O_(4)],将二维层状网络结构连接成三维结构。配合物1是rtl拓扑类型的网络结构,拓扑符号为(42.610.83);配合物2是sql拓扑类型的网络结构,拓扑符号为(4^(4).6^(2))。2种配合物在相同时间间隔下对不同染料降解性能表明配合物2对水溶液中的孔雀石绿具有一定的化学吸附降解能力。展开更多
A metal-organic framework,Ce-FDM-50,was constructed by employing gallic acid featuring both carboxylate and pyrogallate as the coordinating sites and Ce(Ⅲ).The co-assembly of the carboxylates and pyrogallates with tw...A metal-organic framework,Ce-FDM-50,was constructed by employing gallic acid featuring both carboxylate and pyrogallate as the coordinating sites and Ce(Ⅲ).The co-assembly of the carboxylates and pyrogallates with two metal ions have achieved a new type of paddle wheel secondary building unit.These building units were further joined by organic struts to obtain frameworks in sql topology.This synthetic approach could be expanded to five different lanthanide metals(Nd,Eu,Gd,Tb,Yb)for the construction of a series of isoreticular MOFs based on FDM-50,and even MTV-MOFs in which mixed lanthanide metals with specific ratios were distributed.In addition,featuring the lanthanide metals as the inorganic nodes in the network,Tb-FDM-50 showed distinct luminescence properties that could be furtherly tuned for variable applications.展开更多
Construction of sophisticated metal-organic frameworks(MOFs)with multiple kinds of metals is essential for further advancement of porous materials toward various applications.Order and arrangement of the metals in the...Construction of sophisticated metal-organic frameworks(MOFs)with multiple kinds of metals is essential for further advancement of porous materials toward various applications.Order and arrangement of the metals in the secondary building units(SBUs)greatly influence the MOF structures outcome.While most of the previous heterometallic MOFs either have multiple kinds of discrete SBUs with different metals,or single kind of SBU with mixed metals inside,other forms of metal distribution still need further exploration.Herein,a bifunctional linker is applied to achieving differential coordination toward different metals.With Ce and Cu serving as the carboxylate-philic and pyrazole-philic metal ions,three heterometallic MOFs(FDM-121—FDM-123)are synthesized.In addition to the common metal arrangement modes,the new MOFs provide a joint reticulation of a discrete SBU and an infinite chain-like SBU featuring different metals in FDM-121,and an assembly from heterometallic infinite chain-like SBU in FDM-122.This study demonstrates the potential of bifunctional linkers for the design and synthesis of heterometallic MOFs and opens up the possibilities to create MOFs with tailored properties for specific applications.展开更多
基金Supported by the Natural Science Foundation of Shandong Province(No.ZR2016BL01)the Talent Introduction Project of Dezhou University(No.320116)
文摘One novel metal-organic framework [Cu2（L）（μ3-OH）]n（1, H3L = [1,1＇：3＇,1＇＇-terphenyl]-4,4＇＇,5＇-tricarboxylic acid） has been synthesized and characterized by single-crystal powder X-ray diffraction, IR and thermogravimetric analyses. Complex 1 crystallizes in orthorhombic crystal system, space group Pbca with a = 21.573（19）, b = 5.404（5）, c = 33.78（3） ？, C21H（12）O7Cu2, Mr = 503.39, V = 3938（6） A^3, Z = 8, Dc = 1.698 g·cm^-3, μ = 2.202 mm^-1, F（000） = 2016, 1.531〈θ〈25.009°, λ（Mo Kα） = 0.71073 A, T = 293（2） K, the final R = 0.0448 and wR = 0.1002. The structure of complex 1 is a three-dimensional（3D） framework based on infinite rod-shaped secondary building units and can be simplified as kgd topology. The gas adsorption measurements for N2, CO2, H2O, CH3OH and CH3CH2OH have been done. Fortunately, the selective sorption of CO2 over N2 was found at 195 K.
基金supported by the National Science Foundation of China(No.51073079)the Natural Science Fund of Tianjin,China (No.10JCZDJC22100)the Fundamental Research Funds for the Central Universities
文摘A new metal-organic framework（MOF） based on metal clusters as secondary building units（SBU）,has been synthesized and structurally characterized.The reported MOF presents an interesting 8-connected self-penetrating coordination network based on dinuclear cadmium cluster with a 4^（24）·5·6~3 topology. Moreover,the thermal stability and luminescence property of this compound have been investigated.
基金supported by National Basic Research Program of China(Grant No.2004CB217806)National Natural Science Foundation of China(Grant No.20476060)。
文摘Mesoporous aluminosilicate MCM-48 containing zeolite secondary building units in the pore wall has been synthesized in alkaline media with a two-step procedure.The aluminosilicate precursors comprising zeolite secondary building units were first synthesized by carefully controlling reaction conditions and then were assembled using co-templates of gemini surfactant[C18H37N(CH3)2(CH2)3-N(CH3)2C18H37]2+(18-3-18)and triethanolamine(TEA).X-ray Diffraction(XRD)patterns of the as-made samples indicated that highly ordered mesostructured MCM-48 was formed.Transmission Electron Microscopy(TEM)images further verified the formation of MCM-48 with uniform cubic pore channel system having the pore opening diameter of about 25Å.Compared with the conventionally synthesized MCM-48,the as-synthesized MCM-48 sample showed an adsorption band at 520–600 cm-1 in its FT-IR spectrum,which was assigned to five-membered ring vibration from zeolite structure.This suggested the presence of zeolite building units in the pore wall.N2 adsorption data showed that the material had a much higher specific surface area(1200 m2/g)than the conventional MCM-48(1100 m2/g).Finally,the cat-alytic performance of the as-made MCM-48 was evaluated by hydrogenation dealkylation reaction of heavy aromatic hydrocarbons.Catalytic results showed that the as-made MCM-48 catalyst exhibited higher conversion than the con-ventional MCM-48 catalyst.The as-made mesostructured MCM-48 may have a potential catalytic application in the conversion of bulky molecules.
基金the National Research Foundation of Korea(NRF)Grant funded by the Ministry of Science and ICT(Nos.NRF-2016R1A5A1009405,NRF-2019M3E6A1103980,NRF-2019R1A6A3A01096867).
文摘In the development of metal-organic frameworks(MOFs),secondary building units(SBUs)have been utilized as molecular modules for the construction of nanoporous materials with robust structures.Under solvothermal synthetic conditions,dynamic changes in the metal coordination environments and ligand coordination modes of SBUs determine the resultant product structures.Alternatively,MOF phases with new topologies can also be achieved by post-synthetic treatment of as-synthesized MOFs via the introduction of acidic or basic moieties that cause the simultaneous cleavage/reformation of coordination bonds in the solid state.In this sense,we studied the solid-state transformation of two ndc-based Zn-MOFs(ndc=1,4-naphthalene dicarboxylate)with different SBUs but the same pcu topology to another MOF with sev topology.One of the chosen MOFs with pcu nets is[Zn_(2)(ndc)_(2)(bpy)]_(n)(bpy=4,4,-bipyridine),(6C_(bpy)-MOF)consisting of a 6-connected pillared-paddlewheel SBU,and the other is IRMOF-7 composed of 6-connected Zn40(C 00)6 SBUs and ndc.Upon post-structural modification,these pcu MOFs were converted into the same MOF with sev topology constructed from the uncommon 7-connected Zri_(4)O(COO)_(7)SBU(7C-MOF).The appropriate post-synthetic conditions for the transformation of each SBUs were systematically examined.In addition,the effect of the pillar molecules in the pillared-paddlewheel MOFs on the topology conversion was studied in terms of the linker basicity,which determines the inertness during the solid-state phase transformation.This post-synthetic modification approach is expected to expand the available methods for designing and synthesizing MOFs with controlled topologies.
基金supported by the National Natural Science Foundation of China(Nos. 21771111, 21601092 and 21371104)the Tianjin Natural Science Foundation(Nos. 15JCZDJC38800 and 16JCZDJC36900)
文摘A new metal-organic framework (MOF),{[Zn_7 (BPS)_4 (OH)_6 (H_2O)_2]·5 H_2O]_n}(1), (H_2 BPS=4,4′-bibenzoic acid-2,2′-sulfone), based on a wavy and infinite chain-shaped secondary building units, has been synthesized under solvothermal conditions and characterized by single crystal X-ray diffraction and further confirmed by PXRD, TGA and IR spectrum. The solid-state emission spectra reveal that compound 1 presents strong luminescence emission bands at room temperature. The fluorescent properties of compound 1 in diverse organic solvents indicated that 1 has palpable luminescent sense effects for DMF and DMAC.
基金supported by the National Natural Science Foundation of China(Nos.21571037,21733003,21961132003)the National Key Research and Development Project of China(No.2018YFA0209400)National Top-Notch Talent Program,and the Science&Technology Commission of Shanghai Municipality(Nos.16520710100,17JC1400100)。
文摘A metal-organic framework,Ce-FDM-50,was constructed by employing gallic acid featuring both carboxylate and pyrogallate as the coordinating sites and Ce(Ⅲ).The co-assembly of the carboxylates and pyrogallates with two metal ions have achieved a new type of paddle wheel secondary building unit.These building units were further joined by organic struts to obtain frameworks in sql topology.This synthetic approach could be expanded to five different lanthanide metals(Nd,Eu,Gd,Tb,Yb)for the construction of a series of isoreticular MOFs based on FDM-50,and even MTV-MOFs in which mixed lanthanide metals with specific ratios were distributed.In addition,featuring the lanthanide metals as the inorganic nodes in the network,Tb-FDM-50 showed distinct luminescence properties that could be furtherly tuned for variable applications.
基金supported by the National Key Research and Development Program of China(No.2018YFA0209402)the National Natural Science Foundation of China(Nos.21922103,21961132003,22088101).
文摘Construction of sophisticated metal-organic frameworks(MOFs)with multiple kinds of metals is essential for further advancement of porous materials toward various applications.Order and arrangement of the metals in the secondary building units(SBUs)greatly influence the MOF structures outcome.While most of the previous heterometallic MOFs either have multiple kinds of discrete SBUs with different metals,or single kind of SBU with mixed metals inside,other forms of metal distribution still need further exploration.Herein,a bifunctional linker is applied to achieving differential coordination toward different metals.With Ce and Cu serving as the carboxylate-philic and pyrazole-philic metal ions,three heterometallic MOFs(FDM-121—FDM-123)are synthesized.In addition to the common metal arrangement modes,the new MOFs provide a joint reticulation of a discrete SBU and an infinite chain-like SBU featuring different metals in FDM-121,and an assembly from heterometallic infinite chain-like SBU in FDM-122.This study demonstrates the potential of bifunctional linkers for the design and synthesis of heterometallic MOFs and opens up the possibilities to create MOFs with tailored properties for specific applications.
