The AgOCH3- and Ag-(CH3OH)x(x=l, 2) anions are studied by photoelectron imaging as well as ab initio calculations. The adiabatic and vertical detachment energies (ADE and VDE) of AgOCH3- are determined as 1.29(...The AgOCH3- and Ag-(CH3OH)x(x=l, 2) anions are studied by photoelectron imaging as well as ab initio calculations. The adiabatic and vertical detachment energies (ADE and VDE) of AgOCH3- are determined as 1.29(2) and 1.34(2) eV, respectively, from the vibrational resolved photoelectron spectrum. The Ag-(CH3OH)l,2 anionic complexes are characterized as metal atomic anion solvated by the CH3OH molecules with the electron mainly localized on the metal. The photoelectron spectra of Ag-(CH3OH)x (x=O, 1, 2) show a gradual increase in VDE with increasing x, due to the solvent stabilization. Evidence for the methanol-methanol hydrogen bonding interactions appears when the Ag- is solvated by two methanol molecules.展开更多
The solvent‐free oxidation of benzyl alcohol was studied using supported Pd‐Ni bimetallic nanoparticles.Compared with monometallic Pd,the addition of Ni to Pd was found to be effective in suppressing the nondesired ...The solvent‐free oxidation of benzyl alcohol was studied using supported Pd‐Ni bimetallic nanoparticles.Compared with monometallic Pd,the addition of Ni to Pd was found to be effective in suppressing the nondesired product toluene,thereby enhancing the selectivity towards benzaldehyde.This result was attributed to a dual effect of Ni addition:the weakening of dissociative adsorption of benzyl alcohol and the promotion of oxygen species involved in the oxidation pathway.展开更多
Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their m...Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their morphologies to expose more active sites is a fundamental objective for the practical application of fuel cells.Herein,we report a new class of hierarchically skeletal Pt-Ni nanocrystals(HSNs)with a multi-layered structure,prepared by an inorganic acid-induced solvothermal method.The addition of H_(2)SO_(4)to the synthetic protocol provides a critical trigger for the successful growth of Pt-Ni nanocrystals with the desired structure.The Pt-Ni HSNs synthesized by this method exhibit enhanced mass activity of 1.25 A mgpt−1 at 0.9 V(versus the reversible hydrogen electrode)towards ORR in 0.1-M HClO_(4),which is superior to that of Pt-Ni multi-branched nanocrystals obtained by the same method in the absence of inorganic acid;it is additionally 8.9-fold higher than that of the commercial Pt/C catalyst.Meanwhile,it displays enhanced stability,with only 21.6%mass activity loss after 10,000 cycles(0.6–1.0 V)for ORR.Furthermore,the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for MOR.The superb activity of the Pt-Ni HSNs for ORR and MOR is fully attributed to an extensively exposed electrochemical surface area and high intrinsic activity,induced by strain effects,provided by the unique hierarchically skeletal alloy structure.The novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.展开更多
Rifapentine, an important antibiotic, was crystallized from methanol solvent in the form of its methanol solvate. The crystal structure of rifapentine methanol solvate belongs to monoclinic, space group P21, with the ...Rifapentine, an important antibiotic, was crystallized from methanol solvent in the form of its methanol solvate. The crystal structure of rifapentine methanol solvate belongs to monoclinic, space group P21, with the unit cell parameters of a = 1.2278(3) nm, b = 1.9768(4) rim, c = 1.2473(3) nm, Z= 2, and β = 112.35(3). The parallelepiped.morphology was also predicted by Materials Studio simulation program.. The influence of intermolecular in-teraction was taken into account in the attachment energy model. The crystal shape fits the calculated morphology well, which was performed on the potential energy minimized model using a generic DREIDING 2.21 force fieldand developed minimization protocol with derived'partial charges.展开更多
This paper describes the effect of the prepara- tion method of binary oxide supports (TiO2-Al2O3) on catalytic performance of V2O5/TiO2-Al2O3 catalysts for methanol selective oxidation to dimethoxymethane (DMM). T...This paper describes the effect of the prepara- tion method of binary oxide supports (TiO2-Al2O3) on catalytic performance of V2O5/TiO2-Al2O3 catalysts for methanol selective oxidation to dimethoxymethane (DMM). The TiO2-A1203 supports are synthesized by a number of methods including mechanical mixing, ball milling, precipitation, co-precipitation, and sol-gel method, which is followed by incipient wetness impregnation to produce V2O5/TiO2-Al2O3 catalysts. Among these samples, the V2O5/TiO2-Al2O3 catalyst prepared by the sol-gel method has the best catalytic performance with a maximum methanol conversion of 48.9 % and a high DMM selectivity of 89.9 % at 393 K, showing superior performance than V2O5/TiO2 and V2O5/Al2O3. The excellent catalytic performance of V2O5/TiO2-Al2O3 is attributed to the effective interaction between the active component and the mixed support. Such interaction changes the chemical states of supported active V components, produces an increased amount of V^4+ species, and facilitates the electron transfer between support and active component. Additionally, the incorporation of titanium cation into the alumina structure could also help produce an appropriate amount of acidic sites, which increases the DMM selectivity. The coordinated environment of the dispersed vanadia on TiO2-Al2O3 mixed support improves the catalytic efficiency on methanol oxidation to DMM.展开更多
基金This work was supported by the National Natural Science Foundation of China (No.20933003 and No.21073186) and the National Basic Research Program of China (No.2007CBSI5203, No.2010CB732306, and No.2007CBSI5201).
文摘The AgOCH3- and Ag-(CH3OH)x(x=l, 2) anions are studied by photoelectron imaging as well as ab initio calculations. The adiabatic and vertical detachment energies (ADE and VDE) of AgOCH3- are determined as 1.29(2) and 1.34(2) eV, respectively, from the vibrational resolved photoelectron spectrum. The Ag-(CH3OH)l,2 anionic complexes are characterized as metal atomic anion solvated by the CH3OH molecules with the electron mainly localized on the metal. The photoelectron spectra of Ag-(CH3OH)x (x=O, 1, 2) show a gradual increase in VDE with increasing x, due to the solvent stabilization. Evidence for the methanol-methanol hydrogen bonding interactions appears when the Ag- is solvated by two methanol molecules.
基金supported by National Natural Science Foundation of China(21271153,21373181,21222307,U1402233)Major Research Plan of National Natural Science Foundation of China(91545113)the Fundamental Research Funds for the Central Universities(2014XZZX003-02)~~
文摘The solvent‐free oxidation of benzyl alcohol was studied using supported Pd‐Ni bimetallic nanoparticles.Compared with monometallic Pd,the addition of Ni to Pd was found to be effective in suppressing the nondesired product toluene,thereby enhancing the selectivity towards benzaldehyde.This result was attributed to a dual effect of Ni addition:the weakening of dissociative adsorption of benzyl alcohol and the promotion of oxygen species involved in the oxidation pathway.
文摘Pt based materials are the most efficient electrocatalysts for the oxygen reduction reaction(ORR)and methanol oxidation reaction(MOR)in fuel cells.Maximizing the utilization of Pt based materials by modulating their morphologies to expose more active sites is a fundamental objective for the practical application of fuel cells.Herein,we report a new class of hierarchically skeletal Pt-Ni nanocrystals(HSNs)with a multi-layered structure,prepared by an inorganic acid-induced solvothermal method.The addition of H_(2)SO_(4)to the synthetic protocol provides a critical trigger for the successful growth of Pt-Ni nanocrystals with the desired structure.The Pt-Ni HSNs synthesized by this method exhibit enhanced mass activity of 1.25 A mgpt−1 at 0.9 V(versus the reversible hydrogen electrode)towards ORR in 0.1-M HClO_(4),which is superior to that of Pt-Ni multi-branched nanocrystals obtained by the same method in the absence of inorganic acid;it is additionally 8.9-fold higher than that of the commercial Pt/C catalyst.Meanwhile,it displays enhanced stability,with only 21.6%mass activity loss after 10,000 cycles(0.6–1.0 V)for ORR.Furthermore,the Pt-Ni HSNs show enhanced activity and anti-toxic ability in CO for MOR.The superb activity of the Pt-Ni HSNs for ORR and MOR is fully attributed to an extensively exposed electrochemical surface area and high intrinsic activity,induced by strain effects,provided by the unique hierarchically skeletal alloy structure.The novel open and hierarchical structure of Pt-Ni alloy provides a promising approach for significant improvements of the activity of Pt based alloy electrocatalysts.
基金Supported by Open Fund of Mineral Resources Chemistry Key Laboratory of Scihuan Higher Education Institutions
文摘Rifapentine, an important antibiotic, was crystallized from methanol solvent in the form of its methanol solvate. The crystal structure of rifapentine methanol solvate belongs to monoclinic, space group P21, with the unit cell parameters of a = 1.2278(3) nm, b = 1.9768(4) rim, c = 1.2473(3) nm, Z= 2, and β = 112.35(3). The parallelepiped.morphology was also predicted by Materials Studio simulation program.. The influence of intermolecular in-teraction was taken into account in the attachment energy model. The crystal shape fits the calculated morphology well, which was performed on the potential energy minimized model using a generic DREIDING 2.21 force fieldand developed minimization protocol with derived'partial charges.
基金supported by the National Natural Science Foundation of China(21006068,21222604)the Program for New Century Excellent Talents in University(NCET-10-0611)+2 种基金Specialized Research Fund for the Doctoral Program of Higher Education(20120032110024)the Scientific Research Foundation for the Returned Overseas Chinese Scholars(MOE)the Program of Introducing Talents of Discipline to Universities(B06006)
文摘This paper describes the effect of the prepara- tion method of binary oxide supports (TiO2-Al2O3) on catalytic performance of V2O5/TiO2-Al2O3 catalysts for methanol selective oxidation to dimethoxymethane (DMM). The TiO2-A1203 supports are synthesized by a number of methods including mechanical mixing, ball milling, precipitation, co-precipitation, and sol-gel method, which is followed by incipient wetness impregnation to produce V2O5/TiO2-Al2O3 catalysts. Among these samples, the V2O5/TiO2-Al2O3 catalyst prepared by the sol-gel method has the best catalytic performance with a maximum methanol conversion of 48.9 % and a high DMM selectivity of 89.9 % at 393 K, showing superior performance than V2O5/TiO2 and V2O5/Al2O3. The excellent catalytic performance of V2O5/TiO2-Al2O3 is attributed to the effective interaction between the active component and the mixed support. Such interaction changes the chemical states of supported active V components, produces an increased amount of V^4+ species, and facilitates the electron transfer between support and active component. Additionally, the incorporation of titanium cation into the alumina structure could also help produce an appropriate amount of acidic sites, which increases the DMM selectivity. The coordinated environment of the dispersed vanadia on TiO2-Al2O3 mixed support improves the catalytic efficiency on methanol oxidation to DMM.