The influence of Li intercalation on the electronic structures of oxygen and vanadium ions in α-V205 was investigated using first-principles calculations based on the density functional theory with local density appr...The influence of Li intercalation on the electronic structures of oxygen and vanadium ions in α-V205 was investigated using first-principles calculations based on the density functional theory with local density approximation. Two different intercalation sites for Li in the V205 lattices were considered. The calculation results demonstrate that intercalated Li ions at different sites show different effects on the electronic structures of O2p and V3d orbitals. But in both cases Li intercalation will weaken the V---O1 bonding and cause the split-off in V3d valence band to narrow or even disappear and simultaneously broaden the O2p conduction band. Further, the average electron transfer number from per intercalated Li2s to V3d orbitals is determined to total be about 0.52.展开更多
The magnetic structure of the spin-chain antiferromagnet SrCo2 V208 is determined by single-crystal neutron diffraction experiment. The system undergoes a long-range magnetic order below the critical temperature TN=4....The magnetic structure of the spin-chain antiferromagnet SrCo2 V208 is determined by single-crystal neutron diffraction experiment. The system undergoes a long-range magnetic order below the critical temperature TN=4.96 K. The moment of 2.16#B per Co at 1.6K in the screw chain running along the c axis Mternates in the c axis. The moments of neighboring screw chains are arranged antiferromagnetically along one in-plane axis and ferromagnetieally Monk the other in-plane axis. This magnetic configuration breaks the four-fold symmetry of the tetragonM crystal structure and leads to two equally populated magnetic twins with the antiferromagnetic vector in the a or b axis. The very similar magnetic state to the isostructural BaCo2 V~ 08 warrants SrCo2 V2 08 as another interesting half-integer spin-chain antiferromagnet for investigation on quantum antiferromagnetism.展开更多
The complex K_3H_4GeW_9V_3O_(40)·8H_2O crystallized in a monocliinie system with space group P2, Mr=2784.67, a=11.099(3), b=16.452(4), c=13.534(4) , β=108.14(2)°, Z=2,V=2348.49 ~3, F(000):2456, μ=239.7cm^(...The complex K_3H_4GeW_9V_3O_(40)·8H_2O crystallized in a monocliinie system with space group P2, Mr=2784.67, a=11.099(3), b=16.452(4), c=13.534(4) , β=108.14(2)°, Z=2,V=2348.49 ~3, F(000):2456, μ=239.7cm^(-1), De=3.932 g/cm^3. The final R=0.083 for 4528 non-zero reflexions. The structure of anions GeW_9V_3O_(40)~and GeW_9O_(34)~belongs to A-type.展开更多
[Zr（phen）4（H2O）4O2（V4O12）]（phen）2 1 （phen = 1,10-phenanthroline） was synthesized under hydrothermal condition. The crystal of 1 belongs to triclinic, space group P1^- with a = 10.6334（8）, b = 11.9201（8）,...[Zr（phen）4（H2O）4O2（V4O12）]（phen）2 1 （phen = 1,10-phenanthroline） was synthesized under hydrothermal condition. The crystal of 1 belongs to triclinic, space group P1^- with a = 10.6334（8）, b = 11.9201（8）, c = 14.6505（10） A, α = 69.9980（10）, β = 84.9240（10）, γ = 84-1300（10）°, V = 1733.0（2） A^3, Z = 1, Mr = 1672.27, Dc = 1.602 g/cm^3, C72H56N12O18V4Zr, F（000） = 848, μ（MoKa） = 0.747 mm^-1, S = 0.957, R = 0.0504 and wR = 0.1173 for 4011 observed reflections （1 〉 20（I））. The crystal structure of 1 could be discussed in terms of {Zr（phen）2（H2O）2O2}, un-coordinated 1,10-phenanthroline molecules and { V4O12 } unit. In { Zr（phen）2（H2O）2O2 }, the coordination geometry of zirconium is a dodecahedron, but {V4O12} unit is constructed from four apex-sharing {VO4} tetrahedra. Furthermore, {V4O12} links with two {Zr（phen）2（H2O）2O2} units via two bridging oxygen atoms. Interestingly, the two {Zr（phen）2（H2O）2O2} units display D- and L-enantiomers, respectively, upon which the whole molecule represents a racemoid configuration.展开更多
By allowing H_(2)SeO_(4),Cy_(2)NH,CyNH_(2) or Bz2NH to react respectively with SnPh_(3)Cl(in methanol),SnPh_(2)Cl_(2)(in water+methanol)and MgCl_(2)·6H_(2)O(in methanol)in specific ratios,the studied complexes ar...By allowing H_(2)SeO_(4),Cy_(2)NH,CyNH_(2) or Bz2NH to react respectively with SnPh_(3)Cl(in methanol),SnPh_(2)Cl_(2)(in water+methanol)and MgCl_(2)·6H_(2)O(in methanol)in specific ratios,the studied complexes are obtained.The suggested structures are discrete and polymer,the environment of the tin center being trans trigonal bipyramidal(compound 1),tetrahedral(compound 2)and octahedral(compound 3),the anions behaving as a bidentate selenate.展开更多
The discovery of novel electrode materials promises to unleash a number of technological advances in lithium-ion batteries.V2O5 is recognized as a high-performance cathode that capitalizes on the rich redox chemistry ...The discovery of novel electrode materials promises to unleash a number of technological advances in lithium-ion batteries.V2O5 is recognized as a high-performance cathode that capitalizes on the rich redox chemistry of vanadium to store lithium.To unlock the full potential of V2O5,nanotechnology solution and rational electrode design are used to imbue V2O5 with high energy and power density by addressing some of their intrinsic disadvantages in macroscopic crystal form.Here,we demonstrate a facile and environmental-friendly method to prepare nanorods-constructed 3D porous V2O5 architectures(3 D-V2O5)in large-scale.The 3D porous architecture is found to be responsible for the enhanced charge transfer kinetics and Li-ion diffusion rate of the 3D-V2O5 electrode.As the result,the 3D-V2O5 surpasses the conventional bulk V2O5 by showing enhanced discharge capacity and rate capability(delivering 154 and 127 m Ah g^-1 at 15 and 20 C,respectively).展开更多
Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_（24）Cl_（13）（1） and MgCsV_2O_6Cl（2）,were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm（No. 123）,with a = 14.801（2）,c = 12....Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_（24）Cl_（13）（1） and MgCsV_2O_6Cl（2）,were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm（No. 123）,with a = 14.801（2）,c = 12.341（3） ？,V = 2703.5（8） ？~3,Z = 2,Mr = 3015.56,F（000） = 2640,μ = 11.044 mm-1,Dc = 3.704 g/cm3,the final R = 0.0380 and wR = 0.0937 for 1654 observed reflections with I 〉 2σ（I）. 2 crystallizes in a monoclinic space group C2/c（No. 15） with a = 11.128（2）,b = 10.540（2）,c = 6.9892（14） ？,β = 118.38（3）°,V = 721.2（2） ？~3,Z = 4,M_r = 390.55,F（000） = 712,μ = 7.997 mm-1,D_c = 3.597 g/cm^3,the final R = 0.0537 and w R = 0.1363 for 740 observed reflections with I 〉 2σ（I）. 1 exhibits a novel 8-membered-ring [V_8O_（24）] consisting of 8 corner-shared VO_4 tetrahetra,but in 2,an infinite ladder-like [VO_3]_∞ chain is formed by VO_5 square pyramids through sharing the edges.展开更多
The interaction of water(H2O) with metal oxide surfaces is of fundamental importance to various fields of science, ranging from batteries to catalysis. In particular, vanadium pentoxide(V2O5) has been widely used as e...The interaction of water(H2O) with metal oxide surfaces is of fundamental importance to various fields of science, ranging from batteries to catalysis. In particular, vanadium pentoxide(V2O5) has been widely used as electrode materials for aqueous-battery and catalysts. Herein, theoretical(density functional theory) study gives atomic-scale insights into water monolayers in V2O5 and single-molecule adsorption and dissociation at three low-index surfaces and oxygen-vacancy V2O5(001) surface. The H2O/V2O5 interface structure was identified. The results show that H2O is adsorbed on the stoichiometric V2O5(001) surface with physisorption mechanism, and the dissociation hardly occurs. Water adsorbs as an intact monomer with a computed binding energy of 0.75 eV. The formation of ordered water overlayers has been observed on V2O5(001) surface, suggesting a locally ordered superstructure of molecular water. The molecular H2O adsorption on oxygen-vacancy V2O5(001) surface is stronger than that on the stoichiometric V2O5(001) surface, and H2O can undergo dissociative chemisorption to form a surface hydroxyl group and a H adatom. V2O5 can take the oxygen from H2O, which is consistent with the experimental results.展开更多
V2O5 flower-like structures assembled by thin nanosheets were in-situ growth on ceramic tubes by hydrothermal process.The structural characterization indicates that V2O5 flower-like structures is orthogonal diamond ph...V2O5 flower-like structures assembled by thin nanosheets were in-situ growth on ceramic tubes by hydrothermal process.The structural characterization indicates that V2O5 flower-like structures is orthogonal diamond phase,which entirely covered on the surface of ceramic tubes.TMA sensing measured results revealed that the sensor based on V2O5 flower-like structures exhibited fast reversible and response,good selectivity to TMA and good stability at 200℃.The good sensing performance may be ascribed to flower-like structure s and directly growth sensing film on the ceramic tube without structure damage.Our works give a simple in-situ growth flower-like structures route on sensing device,which exhibits potential application for detecting trace amounts of TMA gas.展开更多
基金This work was supported of by the National Natural Science Foundation of China （No.20603028）, the Project of Young Talents Innovation of Fujian Province （No.2005J005）, and the Project of New Century Excel- lent Talent of Fujian Province.
文摘The influence of Li intercalation on the electronic structures of oxygen and vanadium ions in α-V205 was investigated using first-principles calculations based on the density functional theory with local density approximation. Two different intercalation sites for Li in the V205 lattices were considered. The calculation results demonstrate that intercalated Li ions at different sites show different effects on the electronic structures of O2p and V3d orbitals. But in both cases Li intercalation will weaken the V---O1 bonding and cause the split-off in V3d valence band to narrow or even disappear and simultaneously broaden the O2p conduction band. Further, the average electron transfer number from per intercalated Li2s to V3d orbitals is determined to total be about 0.52.
基金Supported by the National Basic Research Program of China under Grant Nos 2012CB921700 and 2011CBA00112the National Natural Science Foundation of China under Grant Nos 11034012 and 11190024
文摘The magnetic structure of the spin-chain antiferromagnet SrCo2 V208 is determined by single-crystal neutron diffraction experiment. The system undergoes a long-range magnetic order below the critical temperature TN=4.96 K. The moment of 2.16#B per Co at 1.6K in the screw chain running along the c axis Mternates in the c axis. The moments of neighboring screw chains are arranged antiferromagnetically along one in-plane axis and ferromagnetieally Monk the other in-plane axis. This magnetic configuration breaks the four-fold symmetry of the tetragonM crystal structure and leads to two equally populated magnetic twins with the antiferromagnetic vector in the a or b axis. The very similar magnetic state to the isostructural BaCo2 V~ 08 warrants SrCo2 V2 08 as another interesting half-integer spin-chain antiferromagnet for investigation on quantum antiferromagnetism.
文摘The complex K_3H_4GeW_9V_3O_(40)·8H_2O crystallized in a monocliinie system with space group P2, Mr=2784.67, a=11.099(3), b=16.452(4), c=13.534(4) , β=108.14(2)°, Z=2,V=2348.49 ~3, F(000):2456, μ=239.7cm^(-1), De=3.932 g/cm^3. The final R=0.083 for 4528 non-zero reflexions. The structure of anions GeW_9V_3O_(40)~and GeW_9O_(34)~belongs to A-type.
基金This work was supported by the Project of Science and Technology of Jilin Province (20040803)
文摘[Zr（phen）4（H2O）4O2（V4O12）]（phen）2 1 （phen = 1,10-phenanthroline） was synthesized under hydrothermal condition. The crystal of 1 belongs to triclinic, space group P1^- with a = 10.6334（8）, b = 11.9201（8）, c = 14.6505（10） A, α = 69.9980（10）, β = 84.9240（10）, γ = 84-1300（10）°, V = 1733.0（2） A^3, Z = 1, Mr = 1672.27, Dc = 1.602 g/cm^3, C72H56N12O18V4Zr, F（000） = 848, μ（MoKa） = 0.747 mm^-1, S = 0.957, R = 0.0504 and wR = 0.1173 for 4011 observed reflections （1 〉 20（I））. The crystal structure of 1 could be discussed in terms of {Zr（phen）2（H2O）2O2}, un-coordinated 1,10-phenanthroline molecules and { V4O12 } unit. In { Zr（phen）2（H2O）2O2 }, the coordination geometry of zirconium is a dodecahedron, but {V4O12} unit is constructed from four apex-sharing {VO4} tetrahedra. Furthermore, {V4O12} links with two {Zr（phen）2（H2O）2O2} units via two bridging oxygen atoms. Interestingly, the two {Zr（phen）2（H2O）2O2} units display D- and L-enantiomers, respectively, upon which the whole molecule represents a racemoid configuration.
文摘By allowing H_(2)SeO_(4),Cy_(2)NH,CyNH_(2) or Bz2NH to react respectively with SnPh_(3)Cl(in methanol),SnPh_(2)Cl_(2)(in water+methanol)and MgCl_(2)·6H_(2)O(in methanol)in specific ratios,the studied complexes are obtained.The suggested structures are discrete and polymer,the environment of the tin center being trans trigonal bipyramidal(compound 1),tetrahedral(compound 2)and octahedral(compound 3),the anions behaving as a bidentate selenate.
基金supported by the Scientific Research Foundation of Fujian Education Depart ment(JB08002)the Science Technology Development Foundation of Fuzhou University(2008-XQ-14)
基金the National Key R&D Research Program of China (No. 2018YFB0905400)the National Natural Science Foundation of China (Grant Nos. 51622210, 51872277, 21606003 and 51802044)+2 种基金the DNL cooperation Fund, CAS (DNL180310)the Fundamental Research Funds for the Central Universities (WK3430000004)Opening Projects of CAS Key Laboratory of Materials for Energy Conversion and State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization
文摘The discovery of novel electrode materials promises to unleash a number of technological advances in lithium-ion batteries.V2O5 is recognized as a high-performance cathode that capitalizes on the rich redox chemistry of vanadium to store lithium.To unlock the full potential of V2O5,nanotechnology solution and rational electrode design are used to imbue V2O5 with high energy and power density by addressing some of their intrinsic disadvantages in macroscopic crystal form.Here,we demonstrate a facile and environmental-friendly method to prepare nanorods-constructed 3D porous V2O5 architectures(3 D-V2O5)in large-scale.The 3D porous architecture is found to be responsible for the enhanced charge transfer kinetics and Li-ion diffusion rate of the 3D-V2O5 electrode.As the result,the 3D-V2O5 surpasses the conventional bulk V2O5 by showing enhanced discharge capacity and rate capability(delivering 154 and 127 m Ah g^-1 at 15 and 20 C,respectively).
基金supported by the National Natural Science Foundation of China(No.21541009)
文摘Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_（24）Cl_（13）（1） and MgCsV_2O_6Cl（2）,were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm（No. 123）,with a = 14.801（2）,c = 12.341（3） ？,V = 2703.5（8） ？~3,Z = 2,Mr = 3015.56,F（000） = 2640,μ = 11.044 mm-1,Dc = 3.704 g/cm3,the final R = 0.0380 and wR = 0.0937 for 1654 observed reflections with I 〉 2σ（I）. 2 crystallizes in a monoclinic space group C2/c（No. 15） with a = 11.128（2）,b = 10.540（2）,c = 6.9892（14） ？,β = 118.38（3）°,V = 721.2（2） ？~3,Z = 4,M_r = 390.55,F（000） = 712,μ = 7.997 mm-1,D_c = 3.597 g/cm^3,the final R = 0.0537 and w R = 0.1363 for 740 observed reflections with I 〉 2σ（I）. 1 exhibits a novel 8-membered-ring [V_8O_（24）] consisting of 8 corner-shared VO_4 tetrahetra,but in 2,an infinite ladder-like [VO_3]_∞ chain is formed by VO_5 square pyramids through sharing the edges.
基金financially supported by startup R&D funding from the One-Hundred Young Talents Program of Guangdong University of Technology(No.22041331901)National Key R&D Program of China(2016YFB0700600)+1 种基金Soft Science Research Project of Guangdong Province(No.2017B030301013)Shenzhen Science and Technology Research Grant(ZDSYS201707281026184)。
文摘The interaction of water(H2O) with metal oxide surfaces is of fundamental importance to various fields of science, ranging from batteries to catalysis. In particular, vanadium pentoxide(V2O5) has been widely used as electrode materials for aqueous-battery and catalysts. Herein, theoretical(density functional theory) study gives atomic-scale insights into water monolayers in V2O5 and single-molecule adsorption and dissociation at three low-index surfaces and oxygen-vacancy V2O5(001) surface. The H2O/V2O5 interface structure was identified. The results show that H2O is adsorbed on the stoichiometric V2O5(001) surface with physisorption mechanism, and the dissociation hardly occurs. Water adsorbs as an intact monomer with a computed binding energy of 0.75 eV. The formation of ordered water overlayers has been observed on V2O5(001) surface, suggesting a locally ordered superstructure of molecular water. The molecular H2O adsorption on oxygen-vacancy V2O5(001) surface is stronger than that on the stoichiometric V2O5(001) surface, and H2O can undergo dissociative chemisorption to form a surface hydroxyl group and a H adatom. V2O5 can take the oxygen from H2O, which is consistent with the experimental results.
基金financially supported by the National Natural Science Foundation of China(Nos.61973223,61673367 and 51674067)Liao Ning Revitalization Talents Program(No.XLYC1807198)。
文摘V2O5 flower-like structures assembled by thin nanosheets were in-situ growth on ceramic tubes by hydrothermal process.The structural characterization indicates that V2O5 flower-like structures is orthogonal diamond phase,which entirely covered on the surface of ceramic tubes.TMA sensing measured results revealed that the sensor based on V2O5 flower-like structures exhibited fast reversible and response,good selectivity to TMA and good stability at 200℃.The good sensing performance may be ascribed to flower-like structure s and directly growth sensing film on the ceramic tube without structure damage.Our works give a simple in-situ growth flower-like structures route on sensing device,which exhibits potential application for detecting trace amounts of TMA gas.
