High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we...High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.展开更多
A kind of inorganic-organic hybrid semiconductor composite nanoparticles： Dawson-type phosphomolybdate- doped polypyrrole （P2Mo18-PPy） was designed and prepared using microemulsion oxidation-polymerization at room ...A kind of inorganic-organic hybrid semiconductor composite nanoparticles： Dawson-type phosphomolybdate- doped polypyrrole （P2Mo18-PPy） was designed and prepared using microemulsion oxidation-polymerization at room temperature and characterized by TEM and IR. The P2Mo18-PPy was used as a bulk-modifier to fabricate a chemically modified carbon paste electrode（CPE） by direct mixing, which represents the example of polyoxometalates（ POMs）- doped semiconductor polymer nanoparticles modified electrode. Both the advantage of POMs-doped polymer and the surface-renewal property of the CPE were fully utilized. The electrochemical behavior of the P2Mo18-PPY bulk-modified CPE（P2Mo18-PPy-CPE） was investigated with cyclic voltammetry. Three couples of reversible redox peaks were observed in the range from ＋ 800 to 0 mV, which corresponded to the reduction and oxidation through two-, four- and six-electron processes, respectively. The P2 Mo18-PPY-CPE showed a high electrocatalytic activity for the reduction of nitrite, which expanded the application of POMs-doped semiconductor polymer nanoparticles.展开更多
Five novel vanadium substituted series of Dawson-type heteropoly acid H7 [As2Mo17VO62 ]·10H2O （1）, H8 [ As2Mo16 V2O62 ]· 7H2O（2）, Ha [ As2MO15 V3O62 ]·8H2O（3）, H8 [ As2Mo14 V4O62 H2 ]·7H2O（...Five novel vanadium substituted series of Dawson-type heteropoly acid H7 [As2Mo17VO62 ]·10H2O （1）, H8 [ As2Mo16 V2O62 ]· 7H2O（2）, Ha [ As2MO15 V3O62 ]·8H2O（3）, H8 [ As2Mo14 V4O62 H2 ]·7H2O（ 4 ）, H9[As2Mo13V5O62H2] ·10H2O（5） were prepared respectively in aqueous solution. When magnetic stirring and pH meter monitoring, all reactants mixed and controled different pH, then the mixture was refluxed for 10 h, later extracted by aether when it cooled, finally, it could be recrystaled by 0.5 % sulphuic acid solution, then yielded productions that we need. Compounds （ 1 ） - （5） were characterized by elemental analysis, thermogravimetic analysis （TGA）, infrared spectroscopy （IR）, ultraviolet and visible spectroscopy（UV-Vis）, X-ray powder diffraction analysis, ^51V nuclear magnetic resonance （SIV NMR） structure analysis. The study indicates that these compounds possess Dawson structures, ^51V NMR spectra reveals that V atom is polar-site substituted indeed.展开更多
A new 3D extended structural compound, （dpdo）2H2{[Cu（2,2＇-bipy）212（P2W18O62）}.SH2O 1 （dpdo = 4,4＇-bipyridine-N,N＇- dioxide; 2,2＇-bipy = 2,2＇-bipyridine）, has been hydrothermally synthesized and characteri...A new 3D extended structural compound, （dpdo）2H2{[Cu（2,2＇-bipy）212（P2W18O62）}.SH2O 1 （dpdo = 4,4＇-bipyridine-N,N＇- dioxide; 2,2＇-bipy = 2,2＇-bipyridine）, has been hydrothermally synthesized and characterized by elemental analyses, IR, TG analyses, cyclic voltammetry, and single-crystal X-my diffraction. Compound 1 is built up of [P2WlsO62]6- cluster as the structural motif covalently linked by [Cu（2,2＇-bipy）2]^2＋ coordination complexes to yield the 1D chains, which axe further in close contact forming a 3D supramolecular framework via aromatic π-π stacking interactions and extensive hydrogen-bonding interactions among polyoxoanions, coordinated 2,2＇-bipy organic ligands, free dpdo organic molecules and lattice water molecules.展开更多
水热法合成了一个无机-有机杂化的NH_(4)[Cu_(3)^(I)(C_(10)H_(8)N_(2))_(3)Mo_(8)O_(26)]化合物,通过元素分析和单晶X-射线衍射进行了表征。化合物为三斜晶系,P1空间群,晶胞参数a=1.08763(9)nm,b=1.12674(10)nm,c=1.13067(10)nm,α=68....水热法合成了一个无机-有机杂化的NH_(4)[Cu_(3)^(I)(C_(10)H_(8)N_(2))_(3)Mo_(8)O_(26)]化合物,通过元素分析和单晶X-射线衍射进行了表征。化合物为三斜晶系,P1空间群,晶胞参数a=1.08763(9)nm,b=1.12674(10)nm,c=1.13067(10)nm,α=68.4820(10)°,β=83.523(2)°,γ=64.4180(10)°,V=1.16095(2)nm^(3),Z=1,Dc=2.661 g/cm^(3),Mr=1860.73,μ(MoKα)=35.22 cm^(-1),F(000)=888,R=0.0478,wR=0.099。化合物的结构包含2个结晶学上独立的铜原子、不连续的多氧阴离子β-[Mo_(8)O_(2)6]4-和无限扩展的[Cu I(C_(10)H_(8)N_(2))]链。每一个铜原子为类似的{CuN_(2)}配位模式,被4,4’-联吡啶连接成一维沿a轴方向的[Cu(C 10 H 8 N 2)]+链。分子结构中存在氢键和π…π作用。对化合物的热稳定性、荧光性质也进行了研究。展开更多
A hydrothermal reaction of zinc acetate with molybdenum trioxide, vanadium pentoxide, phosphorus pentoxide and 2,2?-bpy (2,2?-bipyridine) led to the title compound [Zn(2,2?- bpy)2(H2O)]2[HPMo12O40(VO)2] 1. Single-cr...A hydrothermal reaction of zinc acetate with molybdenum trioxide, vanadium pentoxide, phosphorus pentoxide and 2,2?-bpy (2,2?-bipyridine) led to the title compound [Zn(2,2?- bpy)2(H2O)]2[HPMo12O40(VO)2] 1. Single-crystal X-ray diffraction revealed that 1 (C40H36- N8O44PV2Zn2Mo12) crystallizes in the triclinic system, space group P1 with a = 11.881(2), b = 12.468(2), c = 12.622(2) ?, α = 71.333(8), β = 74.485(4), γ = 86.896(5)o, V = 1705.8(4) ?3, Mr = 2747.64, Z = 1, Dc = 2.675 g/cm3, μ = 3.201 mm-1, F(000) = 1309, S = 1.070, the final R = 0.0697 and wR = 0.1905 for 5368 observed reflections with I > 2σ(I). Compound 1 is built on a mixed-metal bicapped [HPMo12V2O42] subunit covalently bonded to two [Zn(2,2?-bpy)2(H2O)]2+ clusters via terminal oxygen atoms of the capping V atoms. Each Zn atom is six-coordinated by four nitrogen atoms from two 2,2?-bpy ligands, one terminal oxygen atom from coordinated water mole- cule and another one from the capped {VO} unit.展开更多
Two novel uranium-containing selenotungstates Na_(3)[H_(19)(UO_(2))_(2)(μ_(2)-O)(Se_(2)W_(14)O_(52))_(2)]·41 H_(2)O(U_(2))and(NH_(4))_(10)[H_(4)(SeO)_(2)(UO_(2))_(2)(H_(2)O)_(2)(H_(2)Se_(2)W_(14)O_(52))(Se_(2)W_...Two novel uranium-containing selenotungstates Na_(3)[H_(19)(UO_(2))_(2)(μ_(2)-O)(Se_(2)W_(14)O_(52))_(2)]·41 H_(2)O(U_(2))and(NH_(4))_(10)[H_(4)(SeO)_(2)(UO_(2))_(2)(H_(2)O)_(2)(H_(2)Se_(2)W_(14)O_(52))(Se_(2)W_(14)O_(52))]·66 H_(2)O(Se_(2)U_(2))based on the{Se_(2)W_(14)O_(52)}unit were successfully prepared and fully characterized.To our knowledge,the uranium is firstly introduced into the selenotungstates.Moreover,it is notable that U_(2)exhibits excellent Lewis acid-base catalytic activities in the condensation cyclization of sulfonyl hydrazides with diketones to synthesize polysubstituted pyrazoles.All the desired products were obtained in moderate to good yields(up to 99%).展开更多
基金This work was financially supported by the National Natural Science Foundation of China(No.21722604)the Postdoctoral Foundation of China(Nos.2019M651743 and 2020M671365)+1 种基金the Natural Science Foundation of Jiangsu Province(No.BK20190852)the National Youth Natural Science Foundation(No.8111310009).
文摘High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.
基金Supported by Natural Science Foundation of Liaoning Province(No. 20032138) and Education Committee Foundation of Liaon-ing Province(No. 2004F023).
文摘A kind of inorganic-organic hybrid semiconductor composite nanoparticles： Dawson-type phosphomolybdate- doped polypyrrole （P2Mo18-PPy） was designed and prepared using microemulsion oxidation-polymerization at room temperature and characterized by TEM and IR. The P2Mo18-PPy was used as a bulk-modifier to fabricate a chemically modified carbon paste electrode（CPE） by direct mixing, which represents the example of polyoxometalates（ POMs）- doped semiconductor polymer nanoparticles modified electrode. Both the advantage of POMs-doped polymer and the surface-renewal property of the CPE were fully utilized. The electrochemical behavior of the P2Mo18-PPY bulk-modified CPE（P2Mo18-PPy-CPE） was investigated with cyclic voltammetry. Three couples of reversible redox peaks were observed in the range from ＋ 800 to 0 mV, which corresponded to the reduction and oxidation through two-, four- and six-electron processes, respectively. The P2 Mo18-PPY-CPE showed a high electrocatalytic activity for the reduction of nitrite, which expanded the application of POMs-doped semiconductor polymer nanoparticles.
文摘Five novel vanadium substituted series of Dawson-type heteropoly acid H7 [As2Mo17VO62 ]·10H2O （1）, H8 [ As2Mo16 V2O62 ]· 7H2O（2）, Ha [ As2MO15 V3O62 ]·8H2O（3）, H8 [ As2Mo14 V4O62 H2 ]·7H2O（ 4 ）, H9[As2Mo13V5O62H2] ·10H2O（5） were prepared respectively in aqueous solution. When magnetic stirring and pH meter monitoring, all reactants mixed and controled different pH, then the mixture was refluxed for 10 h, later extracted by aether when it cooled, finally, it could be recrystaled by 0.5 % sulphuic acid solution, then yielded productions that we need. Compounds （ 1 ） - （5） were characterized by elemental analysis, thermogravimetic analysis （TGA）, infrared spectroscopy （IR）, ultraviolet and visible spectroscopy（UV-Vis）, X-ray powder diffraction analysis, ^51V nuclear magnetic resonance （SIV NMR） structure analysis. The study indicates that these compounds possess Dawson structures, ^51V NMR spectra reveals that V atom is polar-site substituted indeed.
基金supported by the Postdoctoral station Foundation of Ministry of Education(No.20060200002)the Testing Foundation of Northeast Normal University
文摘A new 3D extended structural compound, （dpdo）2H2{[Cu（2,2＇-bipy）212（P2W18O62）}.SH2O 1 （dpdo = 4,4＇-bipyridine-N,N＇- dioxide; 2,2＇-bipy = 2,2＇-bipyridine）, has been hydrothermally synthesized and characterized by elemental analyses, IR, TG analyses, cyclic voltammetry, and single-crystal X-my diffraction. Compound 1 is built up of [P2WlsO62]6- cluster as the structural motif covalently linked by [Cu（2,2＇-bipy）2]^2＋ coordination complexes to yield the 1D chains, which axe further in close contact forming a 3D supramolecular framework via aromatic π-π stacking interactions and extensive hydrogen-bonding interactions among polyoxoanions, coordinated 2,2＇-bipy organic ligands, free dpdo organic molecules and lattice water molecules.
文摘水热法合成了一个无机-有机杂化的NH_(4)[Cu_(3)^(I)(C_(10)H_(8)N_(2))_(3)Mo_(8)O_(26)]化合物,通过元素分析和单晶X-射线衍射进行了表征。化合物为三斜晶系,P1空间群,晶胞参数a=1.08763(9)nm,b=1.12674(10)nm,c=1.13067(10)nm,α=68.4820(10)°,β=83.523(2)°,γ=64.4180(10)°,V=1.16095(2)nm^(3),Z=1,Dc=2.661 g/cm^(3),Mr=1860.73,μ(MoKα)=35.22 cm^(-1),F(000)=888,R=0.0478,wR=0.099。化合物的结构包含2个结晶学上独立的铜原子、不连续的多氧阴离子β-[Mo_(8)O_(2)6]4-和无限扩展的[Cu I(C_(10)H_(8)N_(2))]链。每一个铜原子为类似的{CuN_(2)}配位模式,被4,4’-联吡啶连接成一维沿a轴方向的[Cu(C 10 H 8 N 2)]+链。分子结构中存在氢键和π…π作用。对化合物的热稳定性、荧光性质也进行了研究。
基金Supported by the Natural Science Foundation of China(21101055,21301049,U1304208)the Natural Science Foundation of Henan Province(122300410106)+1 种基金the Foundation of Education Department of Henan Province(2010B150006)the Students Innovative Pilot Plan of Henan University(2012,2013)
基金Project supported by the Natural Science Foundation of Fujian Province (E0310016) the Education Committee Foundation of Fujian Province (JA02176)
文摘A hydrothermal reaction of zinc acetate with molybdenum trioxide, vanadium pentoxide, phosphorus pentoxide and 2,2?-bpy (2,2?-bipyridine) led to the title compound [Zn(2,2?- bpy)2(H2O)]2[HPMo12O40(VO)2] 1. Single-crystal X-ray diffraction revealed that 1 (C40H36- N8O44PV2Zn2Mo12) crystallizes in the triclinic system, space group P1 with a = 11.881(2), b = 12.468(2), c = 12.622(2) ?, α = 71.333(8), β = 74.485(4), γ = 86.896(5)o, V = 1705.8(4) ?3, Mr = 2747.64, Z = 1, Dc = 2.675 g/cm3, μ = 3.201 mm-1, F(000) = 1309, S = 1.070, the final R = 0.0697 and wR = 0.1905 for 5368 observed reflections with I > 2σ(I). Compound 1 is built on a mixed-metal bicapped [HPMo12V2O42] subunit covalently bonded to two [Zn(2,2?-bpy)2(H2O)]2+ clusters via terminal oxygen atoms of the capping V atoms. Each Zn atom is six-coordinated by four nitrogen atoms from two 2,2?-bpy ligands, one terminal oxygen atom from coordinated water mole- cule and another one from the capped {VO} unit.
基金supported by the National Natural Science Foundation of China(Nos.22071045,22001034)Excellent Youth Science Fund Project of Henan Province(No.202300410042)+1 种基金the Open Fund of the Jiangxi Province Key Laboratory of Synthetic Chemistry(No.JXSC202008)the start-up fund of Henan University。
文摘Two novel uranium-containing selenotungstates Na_(3)[H_(19)(UO_(2))_(2)(μ_(2)-O)(Se_(2)W_(14)O_(52))_(2)]·41 H_(2)O(U_(2))and(NH_(4))_(10)[H_(4)(SeO)_(2)(UO_(2))_(2)(H_(2)O)_(2)(H_(2)Se_(2)W_(14)O_(52))(Se_(2)W_(14)O_(52))]·66 H_(2)O(Se_(2)U_(2))based on the{Se_(2)W_(14)O_(52)}unit were successfully prepared and fully characterized.To our knowledge,the uranium is firstly introduced into the selenotungstates.Moreover,it is notable that U_(2)exhibits excellent Lewis acid-base catalytic activities in the condensation cyclization of sulfonyl hydrazides with diketones to synthesize polysubstituted pyrazoles.All the desired products were obtained in moderate to good yields(up to 99%).
