Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully construct...Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.展开更多
The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecul...The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.展开更多
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
A novel coordination polymer of [Co( p-CPOA)(2,2′-bipy)(H2O)]n ( p-CPOA2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single cr...A novel coordination polymer of [Co( p-CPOA)(2,2′-bipy)(H2O)]n ( p-CPOA2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction. The title complex crystallizes in monoclinic space group C2/c, with a=1.424 4(3) nm, b=1.316 6(3) nm, c=1.947 7(4) nm, β=104.56(3)°. V=3.535 3(14) nm3, Z=8, R=0.028 5, wR=0.089 1. The cobalt(Ⅱ) ion displays a distorted octahedral coordination geometry, defined by three carboxyl oxygen atoms from different p-CPOA2- groups, two nitrogen atoms from 2,2′-bipyridine ligand and one water molecule. The cobalt atoms are bridged by p-CPOA2- groups, forming a one-dimensional chain structure along a axis. The adjacent Co...Co atoms distance is 0.996 8 nm. A layer supramolecular network is contrsucted by the hydrogen bonds and π-π stacking interactions. CCDC: 220039.展开更多
By using the combination of solvothermal and microemulsion methods, hierarchical cobalt nanorods with 70 nm width and 39 mm length have been prepared under mild conditions. The nanorods are composed of a bundle of 20 ...By using the combination of solvothermal and microemulsion methods, hierarchical cobalt nanorods with 70 nm width and 39 mm length have been prepared under mild conditions. The nanorods are composed of a bundle of 20 nm wide whiskers, which are composed of spherical nanoparticles（\{5 nm\}）. It is suggested that the co-operation of the reduction of Co 2+ and the transition from spherical \{micelles\} into hexagonal rod-like micelles lead to the formation of the nanostructured cobalt filaments.展开更多
Cobaltous hydroxide nanorods were synthesized by solid-state chemical reactions of Co(Ac)2·4H2O, and NaOH at room temperature in the presence of polyethylene glycol 400 (PEG-400). The compositions and morphologie...Cobaltous hydroxide nanorods were synthesized by solid-state chemical reactions of Co(Ac)2·4H2O, and NaOH at room temperature in the presence of polyethylene glycol 400 (PEG-400). The compositions and morphologies of the products were characterized by XRD, TEM, IR and TG-DTA. The results show that Co(OH)2 nanorods can be obtained only in one-step by means of surfactant-assisted soft-template solid-state chemical reaction method. The surfactant (PEG-400) plays a soft-template like role in the process of Co(OH)2 nanorods formation and leads nanocrystallines to grow along certain direction into nanorods.展开更多
文摘Under hydrothermal and solvothermal conditions,two novel cobalt-based complexes,{[Co_(2)(CIA)(OH)(1,4-dtb)]·3.2H_(2)O}n(HU23)and{[Co_(2)(CIA)(OH)(1,4-dib)]·3.5H2O·DMF}n(HU24),were successfully constructed by coordinatively assembling the semi-rigid multidentate ligand 5-(1-carboxyethoxy)isophthalic acid(H₃CIA)with the Nheterocyclic ligands 1,4-di(4H-1,2,4-triazol-4-yl)benzene(1,4-dtb)and 1,4-di(1H-imidazol-1-yl)benzene(1,4-dib),respectively,around Co^(2+)ions.Single-crystal X-ray diffraction analysis revealed that in both complexes HU23 and HU24,the CIA^(3-)anions adopt aκ^(7)-coordination mode,bridging six Co^(2+)ions via their five carboxylate oxygen atoms and one ether oxygen atom.This linkage forms tetranuclear[Co4(μ3-OH)2]^(6+)units.These Co-oxo cluster units were interconnected by CIA^(3-)anions to assemble into 2D kgd-type structures featuring a 3,6-connected topology.The 2D layers were further connected by 1,4-dtb and 1,4-dib,resulting in 3D pillar-layered frameworks for HU23 and HU24.Notably,despite the similar configurations of 1,4-dtb and 1,4-dib,differences in their coordination spatial orientations lead to topological divergence in the 3D frameworks of HU23 and HU24.Topological analysis indicates that the frameworks of HU23 and HU24 can be simplified into a 3,10-connected net(point symbol:(4^(10).6^(3).8^(2))(4^(3))_(2))and a 3,8-connected tfz-d net(point symbol:(4^(3))_(2)((4^(6).6^(18).8^(4)))),respectively.This structural differentiation confirms the precise regulatory role of ligands on the topology of metal-organic frameworks.Moreover,the ultraviolet-visible absorption spectra confirmed that HU23 and HU24 have strong absorption capabilities for ultraviolet and visible light.According to the Kubelka-Munk method,their bandwidths were 2.15 and 2.08 eV,respectively,which are consistent with those of typical semiconductor materials.Variable-temperature magnetic susceptibility measurements(2-300 K)revealed significant antiferromagnetic coupling in both complexes,with their effective magnetic moments decreasing markedly as the temperature lowered.CCDC:2457554,HU23;2457553,HU24.
文摘The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.
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A novel coordination polymer of [Co( p-CPOA)(2,2′-bipy)(H2O)]n ( p-CPOA2-=4-carboxylphenoxyacetate dianion, 2,2′-bipy=2,2′-bipyridine) was synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction. The title complex crystallizes in monoclinic space group C2/c, with a=1.424 4(3) nm, b=1.316 6(3) nm, c=1.947 7(4) nm, β=104.56(3)°. V=3.535 3(14) nm3, Z=8, R=0.028 5, wR=0.089 1. The cobalt(Ⅱ) ion displays a distorted octahedral coordination geometry, defined by three carboxyl oxygen atoms from different p-CPOA2- groups, two nitrogen atoms from 2,2′-bipyridine ligand and one water molecule. The cobalt atoms are bridged by p-CPOA2- groups, forming a one-dimensional chain structure along a axis. The adjacent Co...Co atoms distance is 0.996 8 nm. A layer supramolecular network is contrsucted by the hydrogen bonds and π-π stacking interactions. CCDC: 220039.
文摘By using the combination of solvothermal and microemulsion methods, hierarchical cobalt nanorods with 70 nm width and 39 mm length have been prepared under mild conditions. The nanorods are composed of a bundle of 20 nm wide whiskers, which are composed of spherical nanoparticles（\{5 nm\}）. It is suggested that the co-operation of the reduction of Co 2+ and the transition from spherical \{micelles\} into hexagonal rod-like micelles lead to the formation of the nanostructured cobalt filaments.
文摘Cobaltous hydroxide nanorods were synthesized by solid-state chemical reactions of Co(Ac)2·4H2O, and NaOH at room temperature in the presence of polyethylene glycol 400 (PEG-400). The compositions and morphologies of the products were characterized by XRD, TEM, IR and TG-DTA. The results show that Co(OH)2 nanorods can be obtained only in one-step by means of surfactant-assisted soft-template solid-state chemical reaction method. The surfactant (PEG-400) plays a soft-template like role in the process of Co(OH)2 nanorods formation and leads nanocrystallines to grow along certain direction into nanorods.
