Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catal...Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER.Herein,combining density functional theory calculations and experiment results assisted with operando analysis,we found that the Co_(Oh) site acts as the main active site for CER in spinel Co_(3)O_(4),which shows better Cl^(-)adsorption and more moderate intermediate adsorption toward CER than CoTd site,and does not undergo redox transition under CER condition at applied potentials.Guided by above findings,the oxygen vacancies were further introduced into the Co_(3)O_(4) to precisely manipulate the electronic configuration of Co_(Oh) to boost Cl^(-)adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly.Our work figures out the importance of geometric configuration dependent CER activity,shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level.展开更多
An efficient and reliable approach based on solvent extraction to selectively recover copper from leaching solution of Jinchuan copper smelting ash has been developed in this work.And the extraction isotherm of 50%((?...An efficient and reliable approach based on solvent extraction to selectively recover copper from leaching solution of Jinchuan copper smelting ash has been developed in this work.And the extraction isotherm of 50%((?)) N902 with initial aqueous acidity of 19.6 g/L was determined at 25℃.The results show that the extractant,N902,has good selectivity to copper, and its saturated capacity of copper under the given conditions is over 23 g/L.The recovery rate of copper in the extraction is over 99%.And copper extraction equilibrium is reached in 90 s using 50% N902 with kerosene as the diluenting agent at an organic and aqueous volume phase ratio(O/A)of 1.Furthermore,over 99.5% of the loaded copper in the organic phase could be stripped by applying 196 g/L H_2SO_4 as the stripping agent.展开更多
The complex [Tm（TBTA）1.5（bipy）（H2O）2]n （H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, bipy = 2,2-bipyridyl） has been synthesized in water-methanol solution at ambient temperature and characterized by single-cr...The complex [Tm（TBTA）1.5（bipy）（H2O）2]n （H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, bipy = 2,2-bipyridyl） has been synthesized in water-methanol solution at ambient temperature and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum and thermogravimetric analysis. The crystal belongs to triclinic, space group P1 with a = 11.1429（2）, b = 11.485（2）, c = 12.872（2）, V = 1498.1（5）3 , Z = 2, C22H14Br6N2O9Tm, Mr = 1098.74, Dc = 2.436 g/cm3 , μ（MoKα） = 11.013 mm-1 , F（000） = 1022, T = 296.15 K, the final R （I 〉2σ（I）） = 0.0494 and wR （all data） = 0.1246. The asymmetric unit of the complex is composed of one Tm ion, one and a half of coordinated TBTA 2-anions, one bipy, two coordinated and one lattice water molecules. The adjacent metal ions are bridged by TBTA 2- anions to form a 2D wave-like layer.展开更多
Homology models of the ligand binding domain of the wild-type and Y151S mutant brown planthopper {Nilaparvata lugens)α1 and rat(Rattus norvegicus)β2 nicotinic acetylcholine receptor(nAChR) subunits were generated ba...Homology models of the ligand binding domain of the wild-type and Y151S mutant brown planthopper {Nilaparvata lugens)α1 and rat(Rattus norvegicus)β2 nicotinic acetylcholine receptor(nAChR) subunits were generated based on the crystal structure of acetylcholine binding protein of Lymnaea stagnalis.Neonicotinoid insecticide imidacloprid was docked into the putative binding site of wild-type and mutantα1β2 dimeric receptors by Surflex-docking,and the calculated docking energies were in agreement with experimen...展开更多
Two 2D layer complexes {[La（TBTA）1.5（phen）2H2O].3H2O}n （1） and {[Ce（TBTA）l.5（phen）2H2O]-3H2O}n （2） （H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, phen = 1.10-phenanthroline） have been synthesized and cha...Two 2D layer complexes {[La（TBTA）1.5（phen）2H2O].3H2O}n （1） and {[Ce（TBTA）l.5（phen）2H2O]-3H2O}n （2） （H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, phen = 1.10-phenanthroline） have been synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and thermogravimetric analyses. Both crystals belong to monoclinic, space group P21/n. Crystal data for 1： a = 8.7097（11）, b = 34.276（4）, c = 13.7281（17） A, β = 95.397（2）°, V= 4080.1（9） A3, Z = 4, LaC36H24Br6N4O10, Mr= 1290.96, Dc = 2.102 g/cm3,μ（MoKa） = 6.983 mm-1, F（000） = 2460.0, T = 296（2） K, the final R （I 〉 2σ（I）） = 0.0478 and wR （all data） = 0.0985 for 10127 independent （Rint = 0.0775） and 7137 observed reflections with I 〉 2σ（I）. Crystal data for 2： a = 8.709（2）, b = 34.202（9）, c = 13.685（4） A, β = 95.714（4）, V= 4055.9（19） A3, Z = 4, CeBr6C36H24O10N4, Mr = 1292.17, Dc = 2.116 g/cm3, μ（MoKa） = 7.094 mm-1, F（000） = 2464.0, T= 296（2） K, the final R（I 〉 2σ（I）） = 0.0590 and wR（all data） = 0.1453 for 10014 independent （Rint = 0.1253） and 6081 observed reflections with I 〉 2σ（I）. Both complexes are allomerism with the general molecular formula of {[M（TBTA）1.5（phen）2H2O].3H2O}n. In the structures, the H2TBTA ligands adopt a monodentate coordination mode. Both the 2D layer frameworks are further extended to be 3D layers via H-bonding interactions.展开更多
We investigated the effects of a standardized extract of Caralluma fimbriata Wall (CFE) on learning and memory in mice using various behavioural models. Unusually, CFE exerts both nootropic and anxiolytic effects.
It is important and challenging to analyze nanocluster structure with atomic precision.Herein,α-hemolysin nanopore was used to identify nanoclusters at the single molecule level by providing two-dimensional(2D)dwell ...It is important and challenging to analyze nanocluster structure with atomic precision.Herein,α-hemolysin nanopore was used to identify nanoclusters at the single molecule level by providing two-dimensional(2D)dwell time–current blockage spectra and translocation event frequency which sensitively depended on their structures.Nanoclusters such as Anderson,Keggin,Dawson,and a few lacunary Dawson polyoxometalates with very similar structures,even with only a two-atom difference,could be discriminated.This nanopore device could simultaneously measure multiple nanoclusters in a mixture qualitatively and quantitatively.Furthermore,molecular dynamics(MD)simulations provided microscopic understandings of the nanocluster translocation dynamics and yielded 2D dwell time–current blockage spectra in close agreement with experiments.The nanopore platform provides a novel powerful tool for nanocluster characterization.展开更多
MgAPO-5 molecular sieves have been synthesized using diethylaminoethanol as the templating agent in a wide range of the MgO/Al2O3 ratio.The samples were characterized by XRD,SEM,solid state NMR,FT-IR and NH3-TPD.Using...MgAPO-5 molecular sieves have been synthesized using diethylaminoethanol as the templating agent in a wide range of the MgO/Al2O3 ratio.The samples were characterized by XRD,SEM,solid state NMR,FT-IR and NH3-TPD.Using MgAPO-5 as acidic supports,bifunctional Pt/MgAPO-5 catalysts were prepared for hydrogenation of nitrobenzene to p-aminophenol (PAP).The results showed that the MgO/Al2O3 ratios influenced the Mg content and the acidity of MgAPO-5 samples,thereby greatly affecting the catalytic performance of Pt/MgAPO-5 catalysts.The selectivity to PAP over Pt/MgAPO-5 was dependent on the amount of strong acid sites of MgAPO-5.When the MgO/Al2O3 molar ratio was 0.5,the synthesized MgAPO-5 sample exhibited the largest amount of strong acid and a highest PAP yield of 41.1% was achieved over Pt/MgAPO-5 catalyst.展开更多
Two novel tetra-armed conjugated microporous polymers with different geometries have been designed and synthesized via Suzuki-Miyaura cross coupling polycondensation. Both polymers are stable in various organic solven...Two novel tetra-armed conjugated microporous polymers with different geometries have been designed and synthesized via Suzuki-Miyaura cross coupling polycondensation. Both polymers are stable in various organic solvents tested and are thermally stable. The pyrene-containing polymer of PrPy with the rigid pyrene unit shows a higher Brunauer-Emmet-Teller specific surface area of 1219m2g-1 than the tetraphenylethylene-containing polymer of PrTPE （770m2g 1）, which leads to a high CO2 uptake ability of 3.89mmolg I at 1.13bar/273K and a H2 uptake ability of 1.69wt% at 1.13bar/77K. The photocatalytic hydrogen production experiments revealed that PrPy also shows a better photocatalytic performance than PrTPE due to the higher conjugation degree and planar structure, the broader UV-visible （UV-Vis） absorption, the lower photoluminescence lifetime, and the higher specific surface area.展开更多
The hydrogenation of SiCl_4 to SiHCl_3 was studied in a stirred bed reactor with CuCl catalyst.The properties of the CuCl catalysts and silicon particles before and after the reaction were characterized by SEM,XRD and...The hydrogenation of SiCl_4 to SiHCl_3 was studied in a stirred bed reactor with CuCl catalyst.The properties of the CuCl catalysts and silicon particles before and after the reaction were characterized by SEM,XRD and XPS.The XRD showed that the active component of Cu3Si was formed during the reaction,and the EDX proved the molar ratio of Cu and Si on the region of apertures.The valent of Cu was discussed by XPS before and after the hydrogen reaction.Then the effects of the reaction temperature,pressure,molar ratio of H2 to SiC l4,weight hourly space velocity(WHSV),and catalyst loading were studied.The results showed that the conversion rate of Si Cl4 was about 38%at WHSV of 190 Nm3/(t·h),temperature of 540℃,pressure of 1.8 MPa,catalyst loading of 0.9%(ω),and molar ratio of H2 to Si Cl4 1.7:1.Based on the experemental results,a reaction mechanism was proposed,which involved the continuous consumption of silicon(many apertures was showed on SEM image)and formation of new Cu3Si active component during the hydrogenation reaction.展开更多
基金the National Natural Science Foundation of China(U21A20286,22206054 and 21805069)Natural Science Foundation of Hubei(2021CFB094)the Fundamental Research Funds for the Central China Normal University(CCNU)for financial support。
文摘Spinel cobalt oxide(Co_(3)O_(4)),consisting of tetrahedral Co^(2+)(CoTd)and octahedral Co^(3+)(CoOh),is considered as promising earth-abundant electrocatalyst for chlorine evolution reaction(CER).Identifying the catalytic contribution of geometric Co site in the electrocatalytic CER plays a pivotal role to precisely modulate electronic configuration of active Co sites to boost CER.Herein,combining density functional theory calculations and experiment results assisted with operando analysis,we found that the Co_(Oh) site acts as the main active site for CER in spinel Co_(3)O_(4),which shows better Cl^(-)adsorption and more moderate intermediate adsorption toward CER than CoTd site,and does not undergo redox transition under CER condition at applied potentials.Guided by above findings,the oxygen vacancies were further introduced into the Co_(3)O_(4) to precisely manipulate the electronic configuration of Co_(Oh) to boost Cl^(-)adsorption and optimize the reaction path of CER and thus to enhance the intrinsic CER activity significantly.Our work figures out the importance of geometric configuration dependent CER activity,shedding light on the rational design of advanced electrocatalysts from geometric configuration optimization at the atomic level.
文摘An efficient and reliable approach based on solvent extraction to selectively recover copper from leaching solution of Jinchuan copper smelting ash has been developed in this work.And the extraction isotherm of 50%((?)) N902 with initial aqueous acidity of 19.6 g/L was determined at 25℃.The results show that the extractant,N902,has good selectivity to copper, and its saturated capacity of copper under the given conditions is over 23 g/L.The recovery rate of copper in the extraction is over 99%.And copper extraction equilibrium is reached in 90 s using 50% N902 with kerosene as the diluenting agent at an organic and aqueous volume phase ratio(O/A)of 1.Furthermore,over 99.5% of the loaded copper in the organic phase could be stripped by applying 196 g/L H_2SO_4 as the stripping agent.
基金Supported by the International Scientific and Technological Cooperation Projects of Shanxi Province (2011081022)International S&T Cooperation Program of China (2011DFA51980)
文摘The complex [Tm（TBTA）1.5（bipy）（H2O）2]n （H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, bipy = 2,2-bipyridyl） has been synthesized in water-methanol solution at ambient temperature and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum and thermogravimetric analysis. The crystal belongs to triclinic, space group P1 with a = 11.1429（2）, b = 11.485（2）, c = 12.872（2）, V = 1498.1（5）3 , Z = 2, C22H14Br6N2O9Tm, Mr = 1098.74, Dc = 2.436 g/cm3 , μ（MoKα） = 11.013 mm-1 , F（000） = 1022, T = 296.15 K, the final R （I 〉2σ（I）） = 0.0494 and wR （all data） = 0.1246. The asymmetric unit of the complex is composed of one Tm ion, one and a half of coordinated TBTA 2-anions, one bipy, two coordinated and one lattice water molecules. The adjacent metal ions are bridged by TBTA 2- anions to form a 2D wave-like layer.
文摘Homology models of the ligand binding domain of the wild-type and Y151S mutant brown planthopper {Nilaparvata lugens)α1 and rat(Rattus norvegicus)β2 nicotinic acetylcholine receptor(nAChR) subunits were generated based on the crystal structure of acetylcholine binding protein of Lymnaea stagnalis.Neonicotinoid insecticide imidacloprid was docked into the putative binding site of wild-type and mutantα1β2 dimeric receptors by Surflex-docking,and the calculated docking energies were in agreement with experimen...
基金Supported by the International Scientific and Technological Cooperation Projects of Shanxi Province (2011081022)International S&T Cooperation Program of China (No. 2011DFA51980)the Natural Science Foundation of Shanxi Province (No. 2009021024)
文摘Two 2D layer complexes {[La（TBTA）1.5（phen）2H2O].3H2O}n （1） and {[Ce（TBTA）l.5（phen）2H2O]-3H2O}n （2） （H2TBTA = 2,3,5,6-tetrabromoterephthalic acid, phen = 1.10-phenanthroline） have been synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and thermogravimetric analyses. Both crystals belong to monoclinic, space group P21/n. Crystal data for 1： a = 8.7097（11）, b = 34.276（4）, c = 13.7281（17） A, β = 95.397（2）°, V= 4080.1（9） A3, Z = 4, LaC36H24Br6N4O10, Mr= 1290.96, Dc = 2.102 g/cm3,μ（MoKa） = 6.983 mm-1, F（000） = 2460.0, T = 296（2） K, the final R （I 〉 2σ（I）） = 0.0478 and wR （all data） = 0.0985 for 10127 independent （Rint = 0.0775） and 7137 observed reflections with I 〉 2σ（I）. Crystal data for 2： a = 8.709（2）, b = 34.202（9）, c = 13.685（4） A, β = 95.714（4）, V= 4055.9（19） A3, Z = 4, CeBr6C36H24O10N4, Mr = 1292.17, Dc = 2.116 g/cm3, μ（MoKa） = 7.094 mm-1, F（000） = 2464.0, T= 296（2） K, the final R（I 〉 2σ（I）） = 0.0590 and wR（all data） = 0.1453 for 10014 independent （Rint = 0.1253） and 6081 observed reflections with I 〉 2σ（I）. Both complexes are allomerism with the general molecular formula of {[M（TBTA）1.5（phen）2H2O].3H2O}n. In the structures, the H2TBTA ligands adopt a monodentate coordination mode. Both the 2D layer frameworks are further extended to be 3D layers via H-bonding interactions.
文摘We investigated the effects of a standardized extract of Caralluma fimbriata Wall (CFE) on learning and memory in mice using various behavioural models. Unusually, CFE exerts both nootropic and anxiolytic effects.
基金supported by the National Key Research and Development Program of China(No.2021YFA1200104)New Cornerstone Science Foundation,the National Natural Science Foundation of China(Nos.22027807,22034004,and 22078104)+1 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000)Tsinghua-Vanke Special Fund for Public Health and Health Discipline Development(No.2022Z82WKJ003).
文摘It is important and challenging to analyze nanocluster structure with atomic precision.Herein,α-hemolysin nanopore was used to identify nanoclusters at the single molecule level by providing two-dimensional(2D)dwell time–current blockage spectra and translocation event frequency which sensitively depended on their structures.Nanoclusters such as Anderson,Keggin,Dawson,and a few lacunary Dawson polyoxometalates with very similar structures,even with only a two-atom difference,could be discriminated.This nanopore device could simultaneously measure multiple nanoclusters in a mixture qualitatively and quantitatively.Furthermore,molecular dynamics(MD)simulations provided microscopic understandings of the nanocluster translocation dynamics and yielded 2D dwell time–current blockage spectra in close agreement with experiments.The nanopore platform provides a novel powerful tool for nanocluster characterization.
基金supported by the National Basic Research Program of China (2010CB234602)the National Natural Science Foundation of China (20636030,20706011 & 20876033)+1 种基金the Basic Research Program of Tianjin (07JCZDJC00100)the Education Bureau of Hebei Province (2005005D)
文摘MgAPO-5 molecular sieves have been synthesized using diethylaminoethanol as the templating agent in a wide range of the MgO/Al2O3 ratio.The samples were characterized by XRD,SEM,solid state NMR,FT-IR and NH3-TPD.Using MgAPO-5 as acidic supports,bifunctional Pt/MgAPO-5 catalysts were prepared for hydrogenation of nitrobenzene to p-aminophenol (PAP).The results showed that the MgO/Al2O3 ratios influenced the Mg content and the acidity of MgAPO-5 samples,thereby greatly affecting the catalytic performance of Pt/MgAPO-5 catalysts.The selectivity to PAP over Pt/MgAPO-5 was dependent on the amount of strong acid sites of MgAPO-5.When the MgO/Al2O3 molar ratio was 0.5,the synthesized MgAPO-5 sample exhibited the largest amount of strong acid and a highest PAP yield of 41.1% was achieved over Pt/MgAPO-5 catalyst.
基金supported by the National Natural Science Foundation of China(21574077,21304055)the Fundamental Research Funds for the Central Universities(GK201501002,2016CBZ001)the Opening Project of State Key Laboratory of Polymer Materials Engineering from Sichuan University(sklpme2016-4-22)
文摘Two novel tetra-armed conjugated microporous polymers with different geometries have been designed and synthesized via Suzuki-Miyaura cross coupling polycondensation. Both polymers are stable in various organic solvents tested and are thermally stable. The pyrene-containing polymer of PrPy with the rigid pyrene unit shows a higher Brunauer-Emmet-Teller specific surface area of 1219m2g-1 than the tetraphenylethylene-containing polymer of PrTPE （770m2g 1）, which leads to a high CO2 uptake ability of 3.89mmolg I at 1.13bar/273K and a H2 uptake ability of 1.69wt% at 1.13bar/77K. The photocatalytic hydrogen production experiments revealed that PrPy also shows a better photocatalytic performance than PrTPE due to the higher conjugation degree and planar structure, the broader UV-visible （UV-Vis） absorption, the lower photoluminescence lifetime, and the higher specific surface area.
文摘The hydrogenation of SiCl_4 to SiHCl_3 was studied in a stirred bed reactor with CuCl catalyst.The properties of the CuCl catalysts and silicon particles before and after the reaction were characterized by SEM,XRD and XPS.The XRD showed that the active component of Cu3Si was formed during the reaction,and the EDX proved the molar ratio of Cu and Si on the region of apertures.The valent of Cu was discussed by XPS before and after the hydrogen reaction.Then the effects of the reaction temperature,pressure,molar ratio of H2 to SiC l4,weight hourly space velocity(WHSV),and catalyst loading were studied.The results showed that the conversion rate of Si Cl4 was about 38%at WHSV of 190 Nm3/(t·h),temperature of 540℃,pressure of 1.8 MPa,catalyst loading of 0.9%(ω),and molar ratio of H2 to Si Cl4 1.7:1.Based on the experemental results,a reaction mechanism was proposed,which involved the continuous consumption of silicon(many apertures was showed on SEM image)and formation of new Cu3Si active component during the hydrogenation reaction.
