Dissociation of active H species over the catalytic sites with the carbon-supported Pt metals as the mainstream catalysts is crucial to facilitate hydrogen donation and accelerate the hydrogen addition process in cata...Dissociation of active H species over the catalytic sites with the carbon-supported Pt metals as the mainstream catalysts is crucial to facilitate hydrogen donation and accelerate the hydrogen addition process in catalytic hydrogenation systems to produce polymers,pharmaceuticals,agrochemicals,fragrances,and biofuels at million-ton scale.Much attention has been paid to the design of the more active catalytic site to effectively adsorb and activate reactants and H_(2) molecules.At the same time,there is still a huge room to develop powerful strategies to accelerate the donation of acted H species to the reactants from the Pt surface further to boost the final catalytic efficiencies of Pt catalysts and depress the total Pt consumption.Herein,we present a new strategy for promoting the Pt-H bond dissociation by increasing surface hydrogen coverage on designed electron-deficient Pt nanoparticles.The electron deficiency of Pt nanoparticles has been successfully tuned by constructing a rectifying contact with an even“noble”boron-rich carbon support(Pt/BC).Theoretical and experimental results confirm the dominant role of the pronounced electron deficiencies of Pt nanoparticles in enhancing the H coverage for 2.3 times higher than that of neutral Pt nanoparticles,significantly boosting the Pt-H bond dissociation and thus the whole hydrogenation process as reflected by the extremely high turnover frequency(TOF)value of 388 h^(-1)at 30℃ and 10 bar H_(2) for phenol hydrogenation on the Pt/BC,outperforming the bench-marked catalysts by a factor of 9.展开更多
基金This work was supported by the Shanghai Science and Technology Committee(No.20520711600)the National Natural Science Foundation of China(Nos.22071146 and 21931005)the SJTU-MPI partner group,and the Open Research Fund of the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(Jilin University,China,No.2021-1).
文摘Dissociation of active H species over the catalytic sites with the carbon-supported Pt metals as the mainstream catalysts is crucial to facilitate hydrogen donation and accelerate the hydrogen addition process in catalytic hydrogenation systems to produce polymers,pharmaceuticals,agrochemicals,fragrances,and biofuels at million-ton scale.Much attention has been paid to the design of the more active catalytic site to effectively adsorb and activate reactants and H_(2) molecules.At the same time,there is still a huge room to develop powerful strategies to accelerate the donation of acted H species to the reactants from the Pt surface further to boost the final catalytic efficiencies of Pt catalysts and depress the total Pt consumption.Herein,we present a new strategy for promoting the Pt-H bond dissociation by increasing surface hydrogen coverage on designed electron-deficient Pt nanoparticles.The electron deficiency of Pt nanoparticles has been successfully tuned by constructing a rectifying contact with an even“noble”boron-rich carbon support(Pt/BC).Theoretical and experimental results confirm the dominant role of the pronounced electron deficiencies of Pt nanoparticles in enhancing the H coverage for 2.3 times higher than that of neutral Pt nanoparticles,significantly boosting the Pt-H bond dissociation and thus the whole hydrogenation process as reflected by the extremely high turnover frequency(TOF)value of 388 h^(-1)at 30℃ and 10 bar H_(2) for phenol hydrogenation on the Pt/BC,outperforming the bench-marked catalysts by a factor of 9.
