Magneli phase titanium sub-oxide conductive ceramic Tin O2n-1 was used as the support for Pt due to its excellent resistance to electrochemical oxidation, and Pt/Tin O2n-1 composites were prepared by the impregnation-...Magneli phase titanium sub-oxide conductive ceramic Tin O2n-1 was used as the support for Pt due to its excellent resistance to electrochemical oxidation, and Pt/Tin O2n-1 composites were prepared by the impregnation-reduction method. The electrochemical stability of Tin O2n-1 was investigated and the results show almost no change in the redox region after oxidation for 20 h at 1.2 V(vs NHE) in 0.5 mol/L H2SO4 aqueous solution. The catalytic activity and stability of the Pt/Tin O2n-1 toward the oxygen reduction reaction(ORR) in 0.5 mol/L H2SO4 solution were investigated through the accelerated aging tests(AAT), and the morphology of the catalysts before and after the AAT was observed by transmission electron microscopy. At the potential of 0.55 V(vs SCE), the specific kinetic current density of the ORR on the Pt/Tin O2n-1 is about 1.5 times that of the Pt/C. The LSV curves for the Pt/C shift negatively obviously with the half-wave potential shifting about 0.02 V after 8000 cycles AAT, while no obvious change takes place for the LSV curves for the Pt/Tin O2n-1. The Pt particles supported on the carbon aggregate obviously, while the morphology of the Pt supported on Tin O2n-1 remains almost unchanged, which contributes to the electrochemical surface area loss of Pt/C being about 2times that of the Pt/Tin O2n-1. The superior catalytic stability of Pt/Tin O2n-1 toward the ORR could be attributed to the excellent stability of the Tin O2n-1 and the electronic interaction between the metals and the support.展开更多
Phenylurea reacted with dichlorophenylphosphine and aldehydes or ketones by Mannich-type reaction in anhydrous benzene to give five-mem- bered phosphorous heterocyclic compounds.However.derivatives of α-ureidoalkylph...Phenylurea reacted with dichlorophenylphosphine and aldehydes or ketones by Mannich-type reaction in anhydrous benzene to give five-mem- bered phosphorous heterocyclic compounds.However.derivatives of α-ureidoalkylphosphonic acids were obtained as the reaction performed in glacial acetic acid.展开更多
The reaction mechanisms of intermolecular cleavage reaction of N-（2-hydroxyphenyl）-phthalamic acid were studied via the density functional theory（DFT）. All geometries of the reactant, transition states, and produc...The reaction mechanisms of intermolecular cleavage reaction of N-（2-hydroxyphenyl）-phthalamic acid were studied via the density functional theory（DFT）. All geometries of the reactant, transition states, and products were optimized at the B3LYP/6-31G（d, p） level. Vibration analysis was carried out to confirm its identity as transitions＇ structure, and the intrinsic reaction coordinate method（IRC） was used to search the minimum energy path. Two possible reaction channels are reported in this article. The calculated results indicate that O-cyclization reaction channel has the lower activation barrier, and therefore, it occurs more easier than the other.展开更多
The electronic structure of catalytic active sites can be influenced by modulating the coordination bonding of the central single metal atom,but it is difficult to achieve.Herein,we reported the single Zn-atom incorpo...The electronic structure of catalytic active sites can be influenced by modulating the coordination bonding of the central single metal atom,but it is difficult to achieve.Herein,we reported the single Zn-atom incorporated dual doped P,N carbon framework(Zn-N_(4)P/C)for ORR via engineering the surrounding coordination environment of active centers.The Zn-N_(4)P/C catalyst exhibited comparable ORR activity(E_(1/2)=0.86 V)and significantly better ORR stability than that of Pt/C catalyst.It also shows respectable performance in terms of maximum peak power density(249.6 mW cm^(-2)),specific capacitance(779 mAh g^(-1)),and charge-discharge cycling stability for 150 hours in Zn-air battery.The high catalytic activity is attributed to the uniform active sites,tunable electronic/geometric configuration,optimized intrinsic activity,and faster mass transfer during ORR-pathway.Further,theoretical results exposed that the Zn-N_(4)P configuration is more electrochemically active as compared to Zn-N_(4) structure for the oxygen reduction reaction.展开更多
基金Project(21406273)supported by the National Natural Science Foundation of China
文摘Magneli phase titanium sub-oxide conductive ceramic Tin O2n-1 was used as the support for Pt due to its excellent resistance to electrochemical oxidation, and Pt/Tin O2n-1 composites were prepared by the impregnation-reduction method. The electrochemical stability of Tin O2n-1 was investigated and the results show almost no change in the redox region after oxidation for 20 h at 1.2 V(vs NHE) in 0.5 mol/L H2SO4 aqueous solution. The catalytic activity and stability of the Pt/Tin O2n-1 toward the oxygen reduction reaction(ORR) in 0.5 mol/L H2SO4 solution were investigated through the accelerated aging tests(AAT), and the morphology of the catalysts before and after the AAT was observed by transmission electron microscopy. At the potential of 0.55 V(vs SCE), the specific kinetic current density of the ORR on the Pt/Tin O2n-1 is about 1.5 times that of the Pt/C. The LSV curves for the Pt/C shift negatively obviously with the half-wave potential shifting about 0.02 V after 8000 cycles AAT, while no obvious change takes place for the LSV curves for the Pt/Tin O2n-1. The Pt particles supported on the carbon aggregate obviously, while the morphology of the Pt supported on Tin O2n-1 remains almost unchanged, which contributes to the electrochemical surface area loss of Pt/C being about 2times that of the Pt/Tin O2n-1. The superior catalytic stability of Pt/Tin O2n-1 toward the ORR could be attributed to the excellent stability of the Tin O2n-1 and the electronic interaction between the metals and the support.
基金the National Natural Science Foundation of People's Republic of China:
文摘Phenylurea reacted with dichlorophenylphosphine and aldehydes or ketones by Mannich-type reaction in anhydrous benzene to give five-mem- bered phosphorous heterocyclic compounds.However.derivatives of α-ureidoalkylphosphonic acids were obtained as the reaction performed in glacial acetic acid.
基金Supported by the National Natural Science Foundation of China(No.20672104)
文摘The reaction mechanisms of intermolecular cleavage reaction of N-（2-hydroxyphenyl）-phthalamic acid were studied via the density functional theory（DFT）. All geometries of the reactant, transition states, and products were optimized at the B3LYP/6-31G（d, p） level. Vibration analysis was carried out to confirm its identity as transitions＇ structure, and the intrinsic reaction coordinate method（IRC） was used to search the minimum energy path. Two possible reaction channels are reported in this article. The calculated results indicate that O-cyclization reaction channel has the lower activation barrier, and therefore, it occurs more easier than the other.
文摘The electronic structure of catalytic active sites can be influenced by modulating the coordination bonding of the central single metal atom,but it is difficult to achieve.Herein,we reported the single Zn-atom incorporated dual doped P,N carbon framework(Zn-N_(4)P/C)for ORR via engineering the surrounding coordination environment of active centers.The Zn-N_(4)P/C catalyst exhibited comparable ORR activity(E_(1/2)=0.86 V)and significantly better ORR stability than that of Pt/C catalyst.It also shows respectable performance in terms of maximum peak power density(249.6 mW cm^(-2)),specific capacitance(779 mAh g^(-1)),and charge-discharge cycling stability for 150 hours in Zn-air battery.The high catalytic activity is attributed to the uniform active sites,tunable electronic/geometric configuration,optimized intrinsic activity,and faster mass transfer during ORR-pathway.Further,theoretical results exposed that the Zn-N_(4)P configuration is more electrochemically active as compared to Zn-N_(4) structure for the oxygen reduction reaction.
