Rely on the density functional theory(DFT)calculation,the catalytic performance of Pd_(x)Cu_(y)/GDY(x=1,2,3,4;x+y≤4)for CO oxidative coupling reaction was obtained.The Pdx/GDY(x=1,2,3,4)are not ideal catalyst for dim...Rely on the density functional theory(DFT)calculation,the catalytic performance of Pd_(x)Cu_(y)/GDY(x=1,2,3,4;x+y≤4)for CO oxidative coupling reaction was obtained.The Pdx/GDY(x=1,2,3,4)are not ideal catalyst for dimethyl oxalate(DMO)formation because byproduct dimethyl carbonate(DMC)is easily formed on Pd_(1)/GDY and Pd_(2)/GDY,and high activation energies are needed on Pd_(3)/GDY and Pd_(4)/GDY.Therefore the second metal Cu is doped to regulate the performance of Pdx/GDY(x=1,2,3,4).Doping Cu not only improve the activity of DMO formation,but more importantly,controlling the ratio of Cu:Pd can effectively regulate the selectivity of DMO.Thus taking into account the activity and selectivity of the reaction for the preparation of DMO by CO oxidative coupling,the Pd_(1)Cu_(1)/GDY and Pd_(1)Cu_(2)/GDY with the activation energies of 105.2 and 99.2 kJ mol^(-1)to generate DMO show excellent catalytic activity and high DMO selectivity,which are considered as good catalysts for CO oxidative coupling.The differential charge density analysis shows the decrease in the charge density of metal clusters is an important reason for improving the selectivity of the catalyst.展开更多
基金financially supported by the Key projects of National Natural Science Foundation of China(No.21736007)the National Natural Science Foundation of China(Grant Nos.21576178 and 21476155)Research Project Supported by Shanxi Scholarship Council of China(No.2016-030)。
文摘Rely on the density functional theory(DFT)calculation,the catalytic performance of Pd_(x)Cu_(y)/GDY(x=1,2,3,4;x+y≤4)for CO oxidative coupling reaction was obtained.The Pdx/GDY(x=1,2,3,4)are not ideal catalyst for dimethyl oxalate(DMO)formation because byproduct dimethyl carbonate(DMC)is easily formed on Pd_(1)/GDY and Pd_(2)/GDY,and high activation energies are needed on Pd_(3)/GDY and Pd_(4)/GDY.Therefore the second metal Cu is doped to regulate the performance of Pdx/GDY(x=1,2,3,4).Doping Cu not only improve the activity of DMO formation,but more importantly,controlling the ratio of Cu:Pd can effectively regulate the selectivity of DMO.Thus taking into account the activity and selectivity of the reaction for the preparation of DMO by CO oxidative coupling,the Pd_(1)Cu_(1)/GDY and Pd_(1)Cu_(2)/GDY with the activation energies of 105.2 and 99.2 kJ mol^(-1)to generate DMO show excellent catalytic activity and high DMO selectivity,which are considered as good catalysts for CO oxidative coupling.The differential charge density analysis shows the decrease in the charge density of metal clusters is an important reason for improving the selectivity of the catalyst.
