Catalytic C−H bond activation is one of the backbones of the chemical industry.Supported metal subnanoclusters consisting of a few atoms have shown attractive properties for heterogeneous catalysis.However,the creatio...Catalytic C−H bond activation is one of the backbones of the chemical industry.Supported metal subnanoclusters consisting of a few atoms have shown attractive properties for heterogeneous catalysis.However,the creation of such catalyst systems with high activity and excellent anti-sintering ability remains a grand challenge.Here,we report on alkali ion-promoted Pd subnanoclusters supported over defectiveγ-Al_(2)O_(3) nanosheets,which display exceptional catalytic activity for C−H bond activation in the benzene oxidation reaction.The presence of Pd subnanoclusters is verified by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy,X-ray absorption spectroscopy,and X-ray photoelectron spectroscopy.This catalyst shows excellent catalytic activity,with a turnover frequency of 280 h^(−1) and yield of 98%,in benzene oxidation reaction to give phenol under mild conditions.Moreover,the introduction of alkali ion greatly retards the diffusion and migration of metal atoms when tested under high-temperature sintering conditions.Density functional theory(DFT)calculations reveal that the addition of alkali ion to Pd nanoclusters can significantly impact the catalyst’s structure and electronic properties,and eventually promote its activity and stability.This work sheds light on the facile and scalable synthesis of highly active and stable catalyst systems with alkali additives for industrially important reactions.展开更多
基金support of this work by the China Postdoctoral Science Foundation(Nos.2019M661247 and 2020T130091)Postdoctoral Science Foundation of Heilongjiang Province(No.LBH-Z19047)+2 种基金Scientific Research Foundation for Returned Scholars of Heilongjiang Province of China(No.719900091)Heilongjiang Touyan Innovation Team Program,the National Key Technology Research and Development Program of China(No.2017YFA0403403)the National Natural Science Foundation of China(No.21872131)。
文摘Catalytic C−H bond activation is one of the backbones of the chemical industry.Supported metal subnanoclusters consisting of a few atoms have shown attractive properties for heterogeneous catalysis.However,the creation of such catalyst systems with high activity and excellent anti-sintering ability remains a grand challenge.Here,we report on alkali ion-promoted Pd subnanoclusters supported over defectiveγ-Al_(2)O_(3) nanosheets,which display exceptional catalytic activity for C−H bond activation in the benzene oxidation reaction.The presence of Pd subnanoclusters is verified by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy,X-ray absorption spectroscopy,and X-ray photoelectron spectroscopy.This catalyst shows excellent catalytic activity,with a turnover frequency of 280 h^(−1) and yield of 98%,in benzene oxidation reaction to give phenol under mild conditions.Moreover,the introduction of alkali ion greatly retards the diffusion and migration of metal atoms when tested under high-temperature sintering conditions.Density functional theory(DFT)calculations reveal that the addition of alkali ion to Pd nanoclusters can significantly impact the catalyst’s structure and electronic properties,and eventually promote its activity and stability.This work sheds light on the facile and scalable synthesis of highly active and stable catalyst systems with alkali additives for industrially important reactions.
