Tunable hydrogen coverage on electron-deficient platinum nanoparticles for efficient hydrogenation reactions

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 H₂ 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 °C and 10 bar H₂ for phenol hydrogenation on the Pt/BC, outperforming the bench-marked catalysts by a factor of 9.