Selective oxidation of propane to acetone(AC)with H_(2) and O_(2) provides a direct route to convert low-cost propane into valueadded products.Unfortunately,the catalytic activity of conventional Au/Ti-based catalysts...Selective oxidation of propane to acetone(AC)with H_(2) and O_(2) provides a direct route to convert low-cost propane into valueadded products.Unfortunately,the catalytic activity of conventional Au/Ti-based catalysts is constrained by the high energy barrier for H_(2) dissociation.Herein,uncalcined TS-1 supported Au-Pd bimetallic catalysts were prepared,and the relationship between the active-site structure and corresponding performance in the selective oxidation of propane with H_(2) and O_(2) in the gas phase was systematically investigated.In contrast to the liquid-phase reaction,trace Pd alloyed with Au triggered an increase in both catalytic activity and selectivity,in which Au_(20)-Pd_(1)/TS-1-B catalyst exhibited excellent activity(170 gAC·h^(−1)·kgcat^(−1))and AC selectivity(90.6%),much higher than those of the Au/TS-1-B catalyst(AC formation rate of 100 gAC·h^(−1)·kgcat^(−1)and AC selectivity of 86.3%).It was found that Pd was gradually isolated into monomers with the increase of Au/Pd molar ratio,and the synergy between Pd single atoms and Au improved the catalytic performance via enhancing hydrogen dissociation and modulating the electronic structure of Au.Furthermore,the reaction conditions were optimized based on the kinetics studies and the Au_(20)-Pd_(1)/TS-1-B catalyst exhibited enhanced H_(2) selectivity(45%)and long-term stability(over 130 h).The insights gained here can offer valuable guidance for the design of Au-Pd catalysts applicable to other gas-phase oxidation reactions.展开更多
基金supported by the Ministry of Science and Technology of the People’s Republic of China under the Research Fund for National Key Research and Development Program of China(No.2021YFA1501403)the National Natural Science Foundation of China(Nos.22208093,22038003,and 22178100)+2 种基金the Shanghai Science and Technology Innovation Action Plan(No.22JC1403800)the Innovation Program of the Shanghai Municipal Education Commission,the Program of Shanghai Academic/Technology Research Leader(No.21XD1421000)the Fundamental Research Funds for the Central Universities.
文摘Selective oxidation of propane to acetone(AC)with H_(2) and O_(2) provides a direct route to convert low-cost propane into valueadded products.Unfortunately,the catalytic activity of conventional Au/Ti-based catalysts is constrained by the high energy barrier for H_(2) dissociation.Herein,uncalcined TS-1 supported Au-Pd bimetallic catalysts were prepared,and the relationship between the active-site structure and corresponding performance in the selective oxidation of propane with H_(2) and O_(2) in the gas phase was systematically investigated.In contrast to the liquid-phase reaction,trace Pd alloyed with Au triggered an increase in both catalytic activity and selectivity,in which Au_(20)-Pd_(1)/TS-1-B catalyst exhibited excellent activity(170 gAC·h^(−1)·kgcat^(−1))and AC selectivity(90.6%),much higher than those of the Au/TS-1-B catalyst(AC formation rate of 100 gAC·h^(−1)·kgcat^(−1)and AC selectivity of 86.3%).It was found that Pd was gradually isolated into monomers with the increase of Au/Pd molar ratio,and the synergy between Pd single atoms and Au improved the catalytic performance via enhancing hydrogen dissociation and modulating the electronic structure of Au.Furthermore,the reaction conditions were optimized based on the kinetics studies and the Au_(20)-Pd_(1)/TS-1-B catalyst exhibited enhanced H_(2) selectivity(45%)and long-term stability(over 130 h).The insights gained here can offer valuable guidance for the design of Au-Pd catalysts applicable to other gas-phase oxidation reactions.
