Light‐Assisted Semi‐Hydrogenation of 1,3‐Butadiene with Water

Wei, Qi-Chen; Chen, Ya; Wang, Zhao; Yu, Da-Zhuang; Wang, Wei-Hao; Qu, Yi; Chen, Lihua; Liu, Yu; Su, Bao‐Lian

doi:10.1002/ange.202210573

Cited by 4 publications

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References 42 publications

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“…The semihydrogenation of alkynes to alkenes is widely used in the industrial production of polymers and pharmaceutical intermediates. − Transition metal oxide (e.g., TiO 2 , CeO 2 , and ZrO 2 )-supported noble metals (e.g., Pd and Pt) are conventional catalysts applied in the semihydrogenation of alkynes, in which both noble metal sites and oxide support have been identified as active sites. Specifically, Pd and Pt species can efficiently activate hydrogen, but undesired overhydrogenation products are commonly attained because alkenes are not easily desorbed on the noble metal ensembles.…”

Section: Introductionmentioning

confidence: 99%

Unraveling Hydrogenation Kinetic Behavior of Transition Metal Oxides via Decoupling Dihydrogen Dissociation and Substrate Activation

Gao,

Wang,

et al. 2024

ACS Catal.

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Both noble metals and transition metal oxides are recognized as active centers for alkyne hydrogenation. However, it is still a "black box" how the catalytic behavior of oxides evolves upon the catalytic intervention of noble metals. Herein, we report a modularized strategy to track the hydrogenation mechanism of oxides (e.g., TiO 2 , CeO 2 , and ZrO 2 ) using a core−shell micromesoporous zeolite as a structure model, in which the oxide and noble metal (Pt) are functionally separated within a mesopore shell and a micropore core (TS-1 zeolite), respectively. The Pt species are atomically distributed and stabilized by the oxygen atoms of fivemembered rings in TS-1 zeolite, which facilitates the heterolytic activation of dihydrogen over Pt δ+ •••O 2− units. The active hydrogen species, i.e., H + and H δ− , migrate to the oxide surface, where the adsorbed reactants are activated for hydrogenation. Mechanistic studies reveal that TiO 2 , CeO 2 , and ZrO 2 possess efficient hydrogenation properties at near-room temperature with the assistance of spillover hydrogen species, demonstrating dihydrogen dissociation as the main rate-limiting step for pure oxide. Impressively, the adsorbed H 2 O molecule on TiO 2 , ZrO 2 , and CeO 2 not only acts as a bridge of hydrogen spillover in reducing the proton diffusion barrier but also forms H 3 O + species on the TiO 2 (100) surface and endows TiO 2 with extraordinary hydrogenation properties. This work opens the "black box" for the hydrogenation behavior of transition metal oxides and develops a molecule-assisted strategy for the rational design of hydrogenation catalysts.

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