The architectural design of electrodes offers new opportunities for next-generation electrochemical energy storage devices(EESDs)by increasing surface area,thickness,and active materials mass loading while maintaining...The architectural design of electrodes offers new opportunities for next-generation electrochemical energy storage devices(EESDs)by increasing surface area,thickness,and active materials mass loading while maintaining good ion diffusion through optimized electrode tortuosity.However,conventional thick electrodes increase ion diffusion length and cause larger ion concentration gradients,limiting reaction kinetics.We demonstrate a strategy for building interpenetrated structures that shortens ion diffusion length and reduces ion concentration inhomogeneity.This free-standing device structure also avoids short-circuiting without needing a separator.The feature size and number of interpenetrated units can be adjusted during printing to balance surface area and ion diffusion.Starting with a 3D-printed interpenetrated polymer substrate,we metallize it to make it conductive.This substrate has two individually addressable electrodes,allowing selective electrodeposition of energy storage materials.Using a Zn//MnO_(2) battery as a model system,the interpenetrated device outperforms conventional separate electrode configurations,improving volumetric energy density by 221%and exhibiting a higher capacity retention rate of 49%compared to 35%at temperatures from 20 to 0℃.Our study introduces a new EESD architecture applicable to Li-ion,Na-ion batteries,supercapacitors,etc.展开更多
One novel cobalt coordination polymer, {[Co（HTCB）（4,4＇btb）]＇HzO}n （1, H3TCB = 1,3,5-tris（4-carboxyphenyl）benzene, 4,4＇-btb = 4,4＇-bis（1,2,4-triazol-3-yl）biphenyl）, has been synthesized and characterized ...One novel cobalt coordination polymer, {[Co（HTCB）（4,4＇btb）]＇HzO}n （1, H3TCB = 1,3,5-tris（4-carboxyphenyl）benzene, 4,4＇-btb = 4,4＇-bis（1,2,4-triazol-3-yl）biphenyl）, has been synthesized and characterized by elemental analysis, IR, powder X-ray diffraction （PXRD）, and thermogravimetric （TG） analyses. X-ray diffraction analysis reveals that complex 1 is a 2D 2-fold interpenetrated {44,62}-sql [Co（HTCB）（4,4＇-btb）] sheet based on the 1D [Co（HTCB）]n chains and 1D [Co（4,4＇-btb）]n chains. The crystal of 1 crystallizes in triclinic, space group P1 with a = 9.529（12）, b = 13.914（16）, c = 14.906（17） A, V= 1903（4） A3, Z = 2, C45H34N6CoO71 Mr= 829.71, Dc = 1.448 g/cm3, F（000） = 858 andμ（MoKa） = 0.514 mm-1. The final R = 0.0655 and wR = 0.1136 for 6603 observed reflections with 1 〉 2a（/） and R = 0.1136 and wR = 0.1747 for all data.展开更多
A novel,porous and doubly interpenetrated MOF（FJU-29） was synthesized and characterized by FT-IR,TGA and X-ray single-crystal/powder diffraction.FJU-29 crystallizes in monoclinic,space group C2/c with a = 22.2890（7...A novel,porous and doubly interpenetrated MOF（FJU-29） was synthesized and characterized by FT-IR,TGA and X-ray single-crystal/powder diffraction.FJU-29 crystallizes in monoclinic,space group C2/c with a = 22.2890（7）,b = 10.9175（2）,c = 21.5601（7） ？,β = 112.908（4）o,V = 4832.7（3） ？~3,Z = 8,Mr = 450.26,D_c = 1.238 g/cm^3,F（000） = 1832,μ（CuKα） = 5.885 mm^（-1）,R = 0.0585 and wR = 0.1544 for 4789 observed reflections（I 〉 2s（I））,and R = 0.0726 and wR = 0.1627 for all data.FJU-29 possesses paddle-wheel {Co_2（COO）_4} clusters bridged by bi-pyrazolate naphthalene diimide ligands（H_2NDI） and H_2BDC to from a 3D framework with a pcu-topology.The desolvated FJU-29a shows the BET surface area of 560.44 m^2·g^（-1） accompanies with discriminating uptakes in CO_2 and N_2.The adsorption selectivity determined by ideal adsorbed solution theory（IAST） indicated that FJU-29 a has high CO_2/N_2（18/85） selectivity（75.5） at 296 K and 100 kPa.The relatively high selectivity further implies that FJU-29 a is a potential material for practical flue gas purification.展开更多
Interpenetrated polymer networks of chitosan (CHI), polyacrylic acid (PAA) and polyacrylamide (PAM) were prepared by free radical polymerization. These hydrogels were either washed with double distilled water (CHI/PAA...Interpenetrated polymer networks of chitosan (CHI), polyacrylic acid (PAA) and polyacrylamide (PAM) were prepared by free radical polymerization. These hydrogels were either washed with double distilled water (CHI/PAA/PAM) A or hydrolyzed with 1M sodium hydroxide (NaOH), (CHI/PAA/PAM) S. Both types of hydrogels were characterized by infrared spectroscopy, microstructural techniques and compressive mechanical testing. Finally, hydrogels were loaded with bovine serum albumin (BSA) and release followed at different pHs. Infrared spectra analysis showed correspondence between hydrogels and monomer feed compositions. Hydrolyzed hydrogels, had increased water content and pH swelling dependence. Compression modulus of swelled hydrolyzed hydrogels decreased with increasing equilibrium water content. Higher BSA loadings were achieved on hydrolyzed hydrogels due to their high water content and porosity. Protein release from hydrogels was low (≤ 20% after 10 hours) at pH 1.2, but sustained release was observed at pH 6.8 and 7.4. The integrity of the protein released at 6.8 and 7.4 by hydrolyzed hydrogels was unaffected. The hydrogles showed no cytotoxic effects on human skin dermal fibroblasts as determined by MTT assay except for two compositions of (CHI/PAA/PAM) A samples, which after seven days presented a viability lower than 80% respect to the control.展开更多
A coordination polymer [Ni（pbc）2（H2O）]n（Hpbc = 3-pyrid-4-ylbenzoic acid） has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction,IR and elemental analysis.The crystal is...A coordination polymer [Ni（pbc）2（H2O）]n（Hpbc = 3-pyrid-4-ylbenzoic acid） has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction,IR and elemental analysis.The crystal is of monoclinic,space group C2/c with a=19.624（5）,b=12.029（5）,c=19.452（5）A,β=104.45（5）°,C24H18NiN2O5,Mr=473.11,V=4447（2）A^3,Dc=1.413 g/cm^3,F（000）=1952,μ = 0.91 cm^-1,Z = 8,the final R=0.0424 and wR=0.0871 for 3757 reflections with I〉2σ（I）.X-ray diffraction analysis reveals that the pbc-ligands act as diconnectors to link two Ni（Ⅱ） centers and adopt two coordination modes of μ2-N,O and μ2-N,O,O to form infinite wavy nickel-carboxylate chains along the bc plane.The topological analysis of compound [Ni（pbc）2（H2O）]n reveals that it is a typical CdS framework.展开更多
A new three-dimensional（3D） coordination polymer, [Cd（L）2H2O]n·5nH2O 1 with 4-[（3-pyridyl）methylamino]benzoate acid（HL）, has been synthesized by slow evaporation solvent at room temperature, and structura...A new three-dimensional（3D） coordination polymer, [Cd（L）2H2O]n·5nH2O 1 with 4-[（3-pyridyl）methylamino]benzoate acid（HL）, has been synthesized by slow evaporation solvent at room temperature, and structurally characterized by elemental analysis, IR spectrum, thermal analysis, fluorescence spectrum and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system, space group I-4, with a = 20.7937（16）, c = 13.515（2）, V = 5843.5（11） 3, C26H34CdN4O10, Mr = 674.97, Dc = 1.534 g/cm3, μ（MoKα） = 0.808 mm-1, F（000） = 2768, Z = 8, the final R = 0.0276 and wR = 0.0691 for 5323 observed reflections（I 〉 2σ（I））. The result of thermal analysis shows that 1 is stable under 290 ℃. Moreover, it exhibits blue photoluminescence at room temperature.展开更多
A new coordination polymer,[Co_(2)(L)_(2)(4,4'-bipy)]_(n)·3nH_(2)O(1)based on 5-(3-methyl-5-phenyl-4H-1,2,4-tri-azol-4-yl)isophthalic acid(H_(2)L)and 4,4'-bipyridine(4,4'-bipy)has been hydrothermally ...A new coordination polymer,[Co_(2)(L)_(2)(4,4'-bipy)]_(n)·3nH_(2)O(1)based on 5-(3-methyl-5-phenyl-4H-1,2,4-tri-azol-4-yl)isophthalic acid(H_(2)L)and 4,4'-bipyridine(4,4'-bipy)has been hydrothermally synthesized and character-ized by single-crystal X-ray diffraction,XRPD,IR,and elemental analysis.Temperature-dependent magnetic sus-ceptibility and thermal degradation for 1 were also studied.The asymmetric unit of compound 1 consists of two crystallographically independent Co(II)ion,two L^(2−)ligand,one 4,4'-bipy ligand,and three lattice water molecules.The 2D triangle networks were linked by the bridging 4,4'-bipy ligand to give rise to a 2-fold interpenetrated 3D architecture.The simplest cyclic motif of the 2D networks is a triangle ring consisting of three Co(II)cations and three L^(2−)ligands.So we can define Co(II)ions as 4-connected nodes and the L^(2−)ligands as 3-connected nodes.Thus,the 3D structure can be described as a 2-fold parallel interpenetrated ins InS 3,4-conn topology.展开更多
Metal-organic frameworks are a sort of rapid development crystal solids,which have greatly attracted a large amount of attention in recent decades.The construction of 3D[Ni(bcp)(bpp)]n(namely complex 1)displays a rare...Metal-organic frameworks are a sort of rapid development crystal solids,which have greatly attracted a large amount of attention in recent decades.The construction of 3D[Ni(bcp)(bpp)]n(namely complex 1)displays a rare[3+3+3]nine-fold interpenetrated diamond topology,which can be successfully synthesized by a mixed strategy of 1,3-bis(4-carboxyphenoxy)propane(H2bcp)and 1,4-bis(4-pyridylmethyl)piperazine(bpp).The interpenetrated network may be ascribed to these flexible bridging linkers to facilitate the penetration degree.In addition,the resultant sample was adequately characterized by elemental analysis,single-crystal X-ray diffraction,powder X-ray diffraction,and thermal gravimetric analysis.Furthermore,the as-synthesized sample can be used as catalysis for chemical fixation of CO2 and epoxide to carbonate.展开更多
基金financial support from the Center for Coastal Climate Resilience of the University of California,Santa Cruz(UCSC)This work was performed under the auspices of the US Department of Energy by Lawrence Livermore National Laboratory under Contract No.DE-AC52-07NA27344 and supported by Laboratory Directed Research and Development award 23-SI-002.IM release number:LLNL-JRNL-862347。
文摘The architectural design of electrodes offers new opportunities for next-generation electrochemical energy storage devices(EESDs)by increasing surface area,thickness,and active materials mass loading while maintaining good ion diffusion through optimized electrode tortuosity.However,conventional thick electrodes increase ion diffusion length and cause larger ion concentration gradients,limiting reaction kinetics.We demonstrate a strategy for building interpenetrated structures that shortens ion diffusion length and reduces ion concentration inhomogeneity.This free-standing device structure also avoids short-circuiting without needing a separator.The feature size and number of interpenetrated units can be adjusted during printing to balance surface area and ion diffusion.Starting with a 3D-printed interpenetrated polymer substrate,we metallize it to make it conductive.This substrate has two individually addressable electrodes,allowing selective electrodeposition of energy storage materials.Using a Zn//MnO_(2) battery as a model system,the interpenetrated device outperforms conventional separate electrode configurations,improving volumetric energy density by 221%and exhibiting a higher capacity retention rate of 49%compared to 35%at temperatures from 20 to 0℃.Our study introduces a new EESD architecture applicable to Li-ion,Na-ion batteries,supercapacitors,etc.
基金supported by the National Natural Science Foundation of China(20873150)the Natural Science Foundation of Shandong Province(ZR2010BQ023)
文摘One novel cobalt coordination polymer, {[Co（HTCB）（4,4＇btb）]＇HzO}n （1, H3TCB = 1,3,5-tris（4-carboxyphenyl）benzene, 4,4＇-btb = 4,4＇-bis（1,2,4-triazol-3-yl）biphenyl）, has been synthesized and characterized by elemental analysis, IR, powder X-ray diffraction （PXRD）, and thermogravimetric （TG） analyses. X-ray diffraction analysis reveals that complex 1 is a 2D 2-fold interpenetrated {44,62}-sql [Co（HTCB）（4,4＇-btb）] sheet based on the 1D [Co（HTCB）]n chains and 1D [Co（4,4＇-btb）]n chains. The crystal of 1 crystallizes in triclinic, space group P1 with a = 9.529（12）, b = 13.914（16）, c = 14.906（17） A, V= 1903（4） A3, Z = 2, C45H34N6CoO71 Mr= 829.71, Dc = 1.448 g/cm3, F（000） = 858 andμ（MoKa） = 0.514 mm-1. The final R = 0.0655 and wR = 0.1136 for 6603 observed reflections with 1 〉 2a（/） and R = 0.1136 and wR = 0.1747 for all data.
基金Financially supported by the National Natural Science Foundation of China(21273033,21673039 and 21573042)
文摘A novel,porous and doubly interpenetrated MOF（FJU-29） was synthesized and characterized by FT-IR,TGA and X-ray single-crystal/powder diffraction.FJU-29 crystallizes in monoclinic,space group C2/c with a = 22.2890（7）,b = 10.9175（2）,c = 21.5601（7） ？,β = 112.908（4）o,V = 4832.7（3） ？~3,Z = 8,Mr = 450.26,D_c = 1.238 g/cm^3,F（000） = 1832,μ（CuKα） = 5.885 mm^（-1）,R = 0.0585 and wR = 0.1544 for 4789 observed reflections（I 〉 2s（I））,and R = 0.0726 and wR = 0.1627 for all data.FJU-29 possesses paddle-wheel {Co_2（COO）_4} clusters bridged by bi-pyrazolate naphthalene diimide ligands（H_2NDI） and H_2BDC to from a 3D framework with a pcu-topology.The desolvated FJU-29a shows the BET surface area of 560.44 m^2·g^（-1） accompanies with discriminating uptakes in CO_2 and N_2.The adsorption selectivity determined by ideal adsorbed solution theory（IAST） indicated that FJU-29 a has high CO_2/N_2（18/85） selectivity（75.5） at 296 K and 100 kPa.The relatively high selectivity further implies that FJU-29 a is a potential material for practical flue gas purification.
文摘Interpenetrated polymer networks of chitosan (CHI), polyacrylic acid (PAA) and polyacrylamide (PAM) were prepared by free radical polymerization. These hydrogels were either washed with double distilled water (CHI/PAA/PAM) A or hydrolyzed with 1M sodium hydroxide (NaOH), (CHI/PAA/PAM) S. Both types of hydrogels were characterized by infrared spectroscopy, microstructural techniques and compressive mechanical testing. Finally, hydrogels were loaded with bovine serum albumin (BSA) and release followed at different pHs. Infrared spectra analysis showed correspondence between hydrogels and monomer feed compositions. Hydrolyzed hydrogels, had increased water content and pH swelling dependence. Compression modulus of swelled hydrolyzed hydrogels decreased with increasing equilibrium water content. Higher BSA loadings were achieved on hydrolyzed hydrogels due to their high water content and porosity. Protein release from hydrogels was low (≤ 20% after 10 hours) at pH 1.2, but sustained release was observed at pH 6.8 and 7.4. The integrity of the protein released at 6.8 and 7.4 by hydrolyzed hydrogels was unaffected. The hydrogles showed no cytotoxic effects on human skin dermal fibroblasts as determined by MTT assay except for two compositions of (CHI/PAA/PAM) A samples, which after seven days presented a viability lower than 80% respect to the control.
基金supported by the Natural Science Foundation of Shandong Province (No Y2007F68)
文摘A coordination polymer [Ni（pbc）2（H2O）]n（Hpbc = 3-pyrid-4-ylbenzoic acid） has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction,IR and elemental analysis.The crystal is of monoclinic,space group C2/c with a=19.624（5）,b=12.029（5）,c=19.452（5）A,β=104.45（5）°,C24H18NiN2O5,Mr=473.11,V=4447（2）A^3,Dc=1.413 g/cm^3,F（000）=1952,μ = 0.91 cm^-1,Z = 8,the final R=0.0424 and wR=0.0871 for 3757 reflections with I〉2σ（I）.X-ray diffraction analysis reveals that the pbc-ligands act as diconnectors to link two Ni（Ⅱ） centers and adopt two coordination modes of μ2-N,O and μ2-N,O,O to form infinite wavy nickel-carboxylate chains along the bc plane.The topological analysis of compound [Ni（pbc）2（H2O）]n reveals that it is a typical CdS framework.
基金supported by the Science and Technology Development Project of Jilin Provincial Science & Technology Department(201205080)the Science and Technology Research Projects of the Education Office of Jilin Province(No.2013.384)
文摘A new three-dimensional（3D） coordination polymer, [Cd（L）2H2O]n·5nH2O 1 with 4-[（3-pyridyl）methylamino]benzoate acid（HL）, has been synthesized by slow evaporation solvent at room temperature, and structurally characterized by elemental analysis, IR spectrum, thermal analysis, fluorescence spectrum and single-crystal X-ray diffraction. Compound 1 crystallizes in the tetragonal system, space group I-4, with a = 20.7937（16）, c = 13.515（2）, V = 5843.5（11） 3, C26H34CdN4O10, Mr = 674.97, Dc = 1.534 g/cm3, μ（MoKα） = 0.808 mm-1, F（000） = 2768, Z = 8, the final R = 0.0276 and wR = 0.0691 for 5323 observed reflections（I 〉 2σ（I））. The result of thermal analysis shows that 1 is stable under 290 ℃. Moreover, it exhibits blue photoluminescence at room temperature.
基金This work was supported by the National Natural Science Foundation of China(Nos.21071083 and 20771062).
文摘A new coordination polymer,[Co_(2)(L)_(2)(4,4'-bipy)]_(n)·3nH_(2)O(1)based on 5-(3-methyl-5-phenyl-4H-1,2,4-tri-azol-4-yl)isophthalic acid(H_(2)L)and 4,4'-bipyridine(4,4'-bipy)has been hydrothermally synthesized and character-ized by single-crystal X-ray diffraction,XRPD,IR,and elemental analysis.Temperature-dependent magnetic sus-ceptibility and thermal degradation for 1 were also studied.The asymmetric unit of compound 1 consists of two crystallographically independent Co(II)ion,two L^(2−)ligand,one 4,4'-bipy ligand,and three lattice water molecules.The 2D triangle networks were linked by the bridging 4,4'-bipy ligand to give rise to a 2-fold interpenetrated 3D architecture.The simplest cyclic motif of the 2D networks is a triangle ring consisting of three Co(II)cations and three L^(2−)ligands.So we can define Co(II)ions as 4-connected nodes and the L^(2−)ligands as 3-connected nodes.Thus,the 3D structure can be described as a 2-fold parallel interpenetrated ins InS 3,4-conn topology.
文摘Metal-organic frameworks are a sort of rapid development crystal solids,which have greatly attracted a large amount of attention in recent decades.The construction of 3D[Ni(bcp)(bpp)]n(namely complex 1)displays a rare[3+3+3]nine-fold interpenetrated diamond topology,which can be successfully synthesized by a mixed strategy of 1,3-bis(4-carboxyphenoxy)propane(H2bcp)and 1,4-bis(4-pyridylmethyl)piperazine(bpp).The interpenetrated network may be ascribed to these flexible bridging linkers to facilitate the penetration degree.In addition,the resultant sample was adequately characterized by elemental analysis,single-crystal X-ray diffraction,powder X-ray diffraction,and thermal gravimetric analysis.Furthermore,the as-synthesized sample can be used as catalysis for chemical fixation of CO2 and epoxide to carbonate.
