The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,q...The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.展开更多
One novel organically templated zincophophate （CsN2HI4）.[Zn3（OH2）（POn）2（HPO4）] has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction together with elemental a...One novel organically templated zincophophate （CsN2HI4）.[Zn3（OH2）（POn）2（HPO4）] has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction together with elemental analysis, infrared spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. The title compound crystallizes in the monoclinic space group P21/n, with a = 9.7904（11）, b = 14.0287（14）, c = 11.8651（13） A, β= 104.690（3）°, V= 1576.4（3） A^3, Z= 4, T= 296（2） K, Mr = 601.31 and Dc = 2.533 g/cm^3. The compound consists of a macroanionic [Zn3（OH2）（PO4）2（HPO4）]^2- framework and （C5N2H14）^2＋ cations, and its structure is built up from ZnO3（OH2）, ZnO4, HPO4 and PO4 tetrahedral units that result in 4, 8 and 10-ring channels.展开更多
The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is prop...The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs(NH-MOFs)with high crystallinity and excellent stability.This approach allows the morphology and porosity of MOFs to be fine tuned,thereby enabling the nanoscale crystal generation and a well-defined hierarchical system.The aqueous solution facilitates rapid nucleation kinetics,and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent(SDA)to guide the formation of hierarchical networks.The assynthesized NH-MOFs(NH-ZIF-67)were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules,outperforming the parent microZIF-67.This study focuses on understanding the NH-MOF growth rules,which could allow tailor-designing NH-MOFs for various functions.展开更多
A new Cd（Ⅱ） coordination polymer, namely {Cd_2（L）（biimpy）（H_2O）}_n（1, H4 L = 3-（3？,5？-dicarboxylphenoxy）phthalic acid, biimpy = 2,6-bis（1-imdazoly）pyridine）, has been successfully synthesized via the ...A new Cd（Ⅱ） coordination polymer, namely {Cd_2（L）（biimpy）（H_2O）}_n（1, H4 L = 3-（3？,5？-dicarboxylphenoxy）phthalic acid, biimpy = 2,6-bis（1-imdazoly）pyridine）, has been successfully synthesized via the hydrothermal reactions of Cd（Ⅱ） ions, H_4L and biimpy. The crystal structure is of triclinic, space group P1 with a = 7.7874（5）, b = 9.9716（5）, c = 18.5278（6） ？, α = 91.327（4）, β = 96.689（4）, γ = 111.896（5）o, V = 1322.39（12） ？~3, C_（27）H_（17）Cd_2N_5O_（10）, M_r = 796.26, Z = 2,D_c = 2.000 g/cm^3, F（000） = 780, μ = 1.679 mm^（-1）, R = 0.0345 and wR = 0.0767 for 3890 observed reflections（I 〉 2s（I））. Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional（3D） framework based on two different dinuclear [Cd_2（COO）_2] building subunits, and topological analysis shows that it can be simplified into a binodal（4,6）-connected topological network with the point symbol of {3.4~2.5~2.6}{3~2.4~2.5~2.6~4.7~4.8}. Moreover, the thermal stability and luminescent property of compound 1 were also studied.展开更多
基金supported by the Program for New Century Excellent Talents in University (NCET-04-0270)National Basic Research Program of China (2011CB201301)
文摘The adsorptive denitrogenation from fuels over three metal-organic frameworks(MIL-96(Al),MIL-53(Al)and MIL-101(Cr))was studied by batch adsorption experiments.Four nitrogen-containing compounds(NCCs)pyridine,pyrrole,quinoline and indole were used as model NCCs in fuels to study the adsorption mechanism.The physicochemical properties of the adsorbents were characterized by XRD,N2physical adsorption,FT-IR spectrum and Hammett indicator method.The metal-organic frameworks(MOFs),especially the MIL-101(Cr)containing Lewis acid sites as well as high specific surface area,can adsorb large quantities of NCCs from fuels.In addition,the adsorptive capacity over MIL-101(Cr)will be different for NCCs with different basicity.The stronger basicity of the NCC is,the more it can be absorbed over MIL-101(Cr).Furthermore,pore size and shape also affect the adsorption capacity for a given adsorbate,which can be proved by the adsorption over MIL-53(Al)and MIL-96(Al).The pseudo-second-order kinetic model and Langmuir equation can be used to describe kinetics and thermodynamics of the adsorption process,respectively.Finally,the regeneration of the used adsorbent has been conducted successfully by just washing it with ethanol.
基金Supported by the Science and Technology Development Foundation of Fuzhou University(No.2004-xq-05)
文摘One novel organically templated zincophophate （CsN2HI4）.[Zn3（OH2）（POn）2（HPO4）] has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction together with elemental analysis, infrared spectroscopy, thermogravimetric analysis, and powder X-ray diffraction. The title compound crystallizes in the monoclinic space group P21/n, with a = 9.7904（11）, b = 14.0287（14）, c = 11.8651（13） A, β= 104.690（3）°, V= 1576.4（3） A^3, Z= 4, T= 296（2） K, Mr = 601.31 and Dc = 2.533 g/cm^3. The compound consists of a macroanionic [Zn3（OH2）（PO4）2（HPO4）]^2- framework and （C5N2H14）^2＋ cations, and its structure is built up from ZnO3（OH2）, ZnO4, HPO4 and PO4 tetrahedral units that result in 4, 8 and 10-ring channels.
基金the National Key Research and Development Program(2019YFC1805804)the National Natural Science Foundation of China(22008032)+3 种基金the Guangdong Natural Science Foundation(2022A1515011192)the Guangdong Basic and Applied Basic Research Foundation(2019A1515110706)the Guangdong Provincial Key Lab of Green Chemical Product Technology(GC202111)the China Postdoctoral Science Foundation(2021M691059).
文摘The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs(NH-MOFs)with high crystallinity and excellent stability.This approach allows the morphology and porosity of MOFs to be fine tuned,thereby enabling the nanoscale crystal generation and a well-defined hierarchical system.The aqueous solution facilitates rapid nucleation kinetics,and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent(SDA)to guide the formation of hierarchical networks.The assynthesized NH-MOFs(NH-ZIF-67)were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules,outperforming the parent microZIF-67.This study focuses on understanding the NH-MOF growth rules,which could allow tailor-designing NH-MOFs for various functions.
基金Supported by the 973 Program of China(2011CBA00505)the"Strategic Priority Research Program"of the Chinese Academy of Sciences(XDA07070200,XDA09030102)the Science Foundation of Fujian Province(2006L2005)
文摘A new Cd（Ⅱ） coordination polymer, namely {Cd_2（L）（biimpy）（H_2O）}_n（1, H4 L = 3-（3？,5？-dicarboxylphenoxy）phthalic acid, biimpy = 2,6-bis（1-imdazoly）pyridine）, has been successfully synthesized via the hydrothermal reactions of Cd（Ⅱ） ions, H_4L and biimpy. The crystal structure is of triclinic, space group P1 with a = 7.7874（5）, b = 9.9716（5）, c = 18.5278（6） ？, α = 91.327（4）, β = 96.689（4）, γ = 111.896（5）o, V = 1322.39（12） ？~3, C_（27）H_（17）Cd_2N_5O_（10）, M_r = 796.26, Z = 2,D_c = 2.000 g/cm^3, F（000） = 780, μ = 1.679 mm^（-1）, R = 0.0345 and wR = 0.0767 for 3890 observed reflections（I 〉 2s（I））. Single-crystal X-ray structural analysis reveals that compound 1 features a three-dimensional（3D） framework based on two different dinuclear [Cd_2（COO）_2] building subunits, and topological analysis shows that it can be simplified into a binodal（4,6）-connected topological network with the point symbol of {3.4~2.5~2.6}{3~2.4~2.5~2.6~4.7~4.8}. Moreover, the thermal stability and luminescent property of compound 1 were also studied.
