Heterometal Incorporation in Ordered Mesoporous SnO ₂ Single Crystals Enables Electron‐Density‐Tunable Pt Nanocatalysts for Efficient Biomass Valorization

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.