A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal st...A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.展开更多
Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as...Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms,the obtained Pt-on-Co/C400 catalysts exhib-ited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency(TOF)value of 3022 min^(-1)at 303 K.Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability,and there were no changes in the catalyst structures and catalytic activities after 10 cycles.展开更多
A new cobalt(Ⅱ)-radical complex:[Co(im4-py)_(2)(PNB)_(2)](im4-py=2-(4'-pyridyl)-4,4,5,5-tetramethylimidazole-1-oxyl,HPNB=p-nitrobenzoic acid)has been synthesized and characterized by X-ray diffraction analysis,el...A new cobalt(Ⅱ)-radical complex:[Co(im4-py)_(2)(PNB)_(2)](im4-py=2-(4'-pyridyl)-4,4,5,5-tetramethylimidazole-1-oxyl,HPNB=p-nitrobenzoic acid)has been synthesized and characterized by X-ray diffraction analysis,elemental analysis,IR,and magnetic properties.X-ray diffraction analysis shows that the complex exists as mononuclear molecules and Co(Ⅱ)ion is four-coordinated with two radicals and two PNB-ligands.The magnetic susceptibility study indicates the complex exhibits weak ferromagnetic interactions between cobalt(Ⅱ)and im4-py radical.The magnetic property is explained by the magnetic and structure exchange mechanism.CCDC:976028.展开更多
A cobalt-based metal-organic framework[Co_(3)(L)_(2)(1,4-bib)_(4)]·4H_(2)O(Co-MOF)was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid(H_(3)L)and 1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib)as ligands.The...A cobalt-based metal-organic framework[Co_(3)(L)_(2)(1,4-bib)_(4)]·4H_(2)O(Co-MOF)was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid(H_(3)L)and 1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib)as ligands.Then,an electrochemical sensor modified with Co-MOF on a glassy carbon electrode(Co-MOF@GCE)was constructed for detecting Cd^(2+)and Pb^(2+)in aqueous solutions.The sensor exhibited a linear range of 1.0-16.0µmol·L^(-1)with a detection limit(LOD)of 4.609 nmol·L^(-1)for Cd^(2+),and 0.5-10.0µmol·L^(-1)with an LOD of 1.307 nmol·L^(-1)for Pb^(2+).Simultaneous detection of both ions within 0.5-7.0µmol·L^(-1)achieved LOD values of 0.47 nmol·L^(-1)(Cd^(2+))and 0.008 nmol·L^(-1)(Pb^(2+)),respectively.Analysis of real water samples(tap water,mineral water,and river water)yielded recoveries of 95%-105%,validating practical applicability.Density functional theory(DFT)calculations reveal that synergistic interactions between cobalt centers and N/O atoms enhance adsorption and electron-transfer efficiency.CCDC:2160744.展开更多
(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under...(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.展开更多
Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1....Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.展开更多
Two metal-organic frameworks(MOFs),trans-[Co(L)(μ_(2)-H_(2)O)(H_(2)O)2]·2H_(2)O(1)and cis-[Mn(L)(Bipy)](2)(H_(2)L=2,2'-dimethyl-4,4'-biphenyldicarboxylic acid,Bipy=4,4'-bipyridine),have been synthesi...Two metal-organic frameworks(MOFs),trans-[Co(L)(μ_(2)-H_(2)O)(H_(2)O)2]·2H_(2)O(1)and cis-[Mn(L)(Bipy)](2)(H_(2)L=2,2'-dimethyl-4,4'-biphenyldicarboxylic acid,Bipy=4,4'-bipyridine),have been synthesized and character-ized by FTIR,thermogravimetric analysis(TGA),powder and single crystal X-ray diffraction.MOF 1 crystallizes in the triclinic system with a P1 space group and contains two crystallographically different Coions.Each trans-[CoO_(6)]octahedron is connected byμ_(2)-H_(2)O and L^(2-)ligand with a bis(unidentate)coordination mode to produce a 2D sql topological network.MOF 2 crystallizes in the monoclinic system with a C2/c space group.The Mncation adopts a cis-[MnO_(4)N_(2)]octahedron as a 6-connected node and is linked by L^(2-)ligand as a 4-connected node to gener-ate a binodal(4,6)-connected 3D fsc framework.The intermolecular interactions in 1 and 2 have been investigated by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main interactions are H…H and O…H/H…O contacts in 1,and H…H and C…H/H…C contacts in 2.The TGA indicated that 1 and 2 were stable below 390 and 370℃,respectively.展开更多
Porous spherical MnCo_(2)S_(4) was synthesized by a simple solvothermal method.Thanks to the well-designedbimetallic composition and the unique porous spherical structure,the MnCo_(2)S_(4) electrode exhibited an excep...Porous spherical MnCo_(2)S_(4) was synthesized by a simple solvothermal method.Thanks to the well-designedbimetallic composition and the unique porous spherical structure,the MnCo_(2)S_(4) electrode exhibited an exceptionalspecific capacitance of 190.8 mAh·g^(-1)at 1 A·g^(-1),greatly higher than the corresponding monometallic sulfides MnS(31.7 mAh·g^(-1))and Co_(3)S_(4)(86.7 mAh·g^(-1)).Impressively,the as-assembled MnCo_(2)S_(4)||porous carbon(PC)hybridsupercapacitor(HSC),showed an outstanding energy density of 76.88 Wh·kg^(-1)at a power density of 374.5 W·kg^(-1),remarkable cyclic performance with a capacity retention of 86.8% after 10000 charge-discharge cycles at 5 A·g^(-1),and excellent Coulombic efficiency of 99.7%.展开更多
文摘A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.
文摘Ultrafine,highly dispersed Pt clusters were immobilized onto the Co nanoparticle surfaces by one-step pyrolysis of the precursor Pt(Ⅱ)-encapsulating Co-MOF-74.Owing to the small size effects of Pt clusters as well as the strongly enhanced synergistic interactions between Pt and Co atoms,the obtained Pt-on-Co/C400 catalysts exhib-ited excellent catalytic activity toward the hydrolysis of ammonia borane with an extremely high turnover frequency(TOF)value of 3022 min^(-1)at 303 K.Durability test indicated that the obtained Pt-on-Co/C400 catalysts possessed high catalytic stability,and there were no changes in the catalyst structures and catalytic activities after 10 cycles.
文摘A new cobalt(Ⅱ)-radical complex:[Co(im4-py)_(2)(PNB)_(2)](im4-py=2-(4'-pyridyl)-4,4,5,5-tetramethylimidazole-1-oxyl,HPNB=p-nitrobenzoic acid)has been synthesized and characterized by X-ray diffraction analysis,elemental analysis,IR,and magnetic properties.X-ray diffraction analysis shows that the complex exists as mononuclear molecules and Co(Ⅱ)ion is four-coordinated with two radicals and two PNB-ligands.The magnetic susceptibility study indicates the complex exhibits weak ferromagnetic interactions between cobalt(Ⅱ)and im4-py radical.The magnetic property is explained by the magnetic and structure exchange mechanism.CCDC:976028.
文摘A cobalt-based metal-organic framework[Co_(3)(L)_(2)(1,4-bib)_(4)]·4H_(2)O(Co-MOF)was prepared using 5-[(4-carboxyphenoxy)methyl]isophthalic acid(H_(3)L)and 1,4-bis(1H-imidazol-1-yl)benzene(1,4-bib)as ligands.Then,an electrochemical sensor modified with Co-MOF on a glassy carbon electrode(Co-MOF@GCE)was constructed for detecting Cd^(2+)and Pb^(2+)in aqueous solutions.The sensor exhibited a linear range of 1.0-16.0µmol·L^(-1)with a detection limit(LOD)of 4.609 nmol·L^(-1)for Cd^(2+),and 0.5-10.0µmol·L^(-1)with an LOD of 1.307 nmol·L^(-1)for Pb^(2+).Simultaneous detection of both ions within 0.5-7.0µmol·L^(-1)achieved LOD values of 0.47 nmol·L^(-1)(Cd^(2+))and 0.008 nmol·L^(-1)(Pb^(2+)),respectively.Analysis of real water samples(tap water,mineral water,and river water)yielded recoveries of 95%-105%,validating practical applicability.Density functional theory(DFT)calculations reveal that synergistic interactions between cobalt centers and N/O atoms enhance adsorption and electron-transfer efficiency.CCDC:2160744.
文摘(2E,6E)-4-methyl-2,6-bis(pyridin-3-ylmethylene)cyclohexan-1-one(L_(1))and 4-methyl-2,6-bis[(E)-4-(pyridin-4-yl)benzylidene]cyclohexan-1-one(L_(2))were synthesized and combined with isophthalic acid(H_(2)IP),then under solvothermal conditions,to react with transition metals achieving four novel metal-organic frameworks(MOFs):[Zn(IP)(L_(1))]_(n)(1),{[Cd(IP)(L_(1))]·H_(2)O}_(n)(2),{[Co(IP)(L_(1))]·H_(2)O}_(n)(3),and[Zn(IP)(L_(2))(H_(2)O)]_(n)(4).MOFs 1-4 have been characterized by single-crystal X-ray diffraction,powder X-ray diffraction,thermogravimetry,and elemental analysis.Single-crystal X-ray diffraction shows that MOF 1 crystallizes in the monoclinic crystal system with space group P2_(1)/n,and MOFs 2-4 belong to the triclinic system with the P1 space group.1-3 are 2D sheet structures,2 and 3 have similar structural characters,whereas 4 is a 1D chain structure.Furthermore,1-3 exhibited certain photocatalytic capability in the degradation of rhodamine B(Rh B)and pararosaniline hydrochloride(PH).4could be used as a heterogeneous catalyst for the Knoevenagel reaction starting with benzaldehyde derivative and malononitrile.4 could promote the reaction to achieve corresponding products in moderate yields within 3 h.Moreover,the catalyst exhibited recyclability for up to three cycles without significantly dropping its activity.A mechanism for MOF 4 catalyzed Knoevenagel condensation reaction of aromatic aldehyde and malononitrile has been initially proposed.CCDC:2356488,1;2356497,2;2356499,3;2356498,4.
文摘Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.
文摘Two metal-organic frameworks(MOFs),trans-[Co(L)(μ_(2)-H_(2)O)(H_(2)O)2]·2H_(2)O(1)and cis-[Mn(L)(Bipy)](2)(H_(2)L=2,2'-dimethyl-4,4'-biphenyldicarboxylic acid,Bipy=4,4'-bipyridine),have been synthesized and character-ized by FTIR,thermogravimetric analysis(TGA),powder and single crystal X-ray diffraction.MOF 1 crystallizes in the triclinic system with a P1 space group and contains two crystallographically different Coions.Each trans-[CoO_(6)]octahedron is connected byμ_(2)-H_(2)O and L^(2-)ligand with a bis(unidentate)coordination mode to produce a 2D sql topological network.MOF 2 crystallizes in the monoclinic system with a C2/c space group.The Mncation adopts a cis-[MnO_(4)N_(2)]octahedron as a 6-connected node and is linked by L^(2-)ligand as a 4-connected node to gener-ate a binodal(4,6)-connected 3D fsc framework.The intermolecular interactions in 1 and 2 have been investigated by 3D Hirshfeld surface analyses and 2D fingerprint plots to reveal that the main interactions are H…H and O…H/H…O contacts in 1,and H…H and C…H/H…C contacts in 2.The TGA indicated that 1 and 2 were stable below 390 and 370℃,respectively.
文摘Porous spherical MnCo_(2)S_(4) was synthesized by a simple solvothermal method.Thanks to the well-designedbimetallic composition and the unique porous spherical structure,the MnCo_(2)S_(4) electrode exhibited an exceptionalspecific capacitance of 190.8 mAh·g^(-1)at 1 A·g^(-1),greatly higher than the corresponding monometallic sulfides MnS(31.7 mAh·g^(-1))and Co_(3)S_(4)(86.7 mAh·g^(-1)).Impressively,the as-assembled MnCo_(2)S_(4)||porous carbon(PC)hybridsupercapacitor(HSC),showed an outstanding energy density of 76.88 Wh·kg^(-1)at a power density of 374.5 W·kg^(-1),remarkable cyclic performance with a capacity retention of 86.8% after 10000 charge-discharge cycles at 5 A·g^(-1),and excellent Coulombic efficiency of 99.7%.