ABSTRACT Engineering the electronic microenvironments of supported metal catalysts is significant but remains a pivotal challenge for efficient catalysis. Herein, we develop a facile heterometal‐incorporating strategy to modulate the surface electron density of Pt nanoparticles anchored in ordered‐mesoporous SnO 2 single crystals (OM‐SnO 2 ) for efficient biomass valorization. We demonstrate that Mn, Ti, Ce, or Zr elements with different electronegativities can be successfully incorporated into the OM‐SnO 2 lattices to motivate controllable lattice distortion and charge redistribution, thereby synergistically optimizing the surface electron density of its anchored Pt nanoparticles. Impressively, the resultant Pt/OM‐Mn‐SnO 2, featuring the lowest Pt surface electron density, exhibits the highest turnover frequency of 6587.8 h −1 for the hydrogenation of biomass‐derived levulinic acid (LA) to γ‐valerolactone (GVL), which is ∼10.6 times that of the Pt/OM‐Zr‐SnO 2 counterpart featuring the highest Pt surface electron density. Furthermore, this electronic structure tuning strategy also endows Pt/OM‐Mn‐SnO 2 with remarkably enhanced activities for the selective hydrogenation of biomass‐derived benzaldehyde and furfural. Mechanistic studies demonstrate that the lowest Pt surface electron density of Pt/OM‐Mn‐SnO 2 can not only reduce the energy barriers for LA hydrogenation and H 2 dissociation, but also facilitate the desorption of GVL via weakening the electronic interaction between GVL and Pt, which jointly account for its remarkably‐enhanced catalytic performance.
Xiao et al. (Thu,) studied this question.