Enriched Localized Electron Confined Ultrafine Pt NPs Sites for Selective Catalytic Hydrogenation in Sulfur‐Containing Feedstocks

ABSTRACT Ultrafine metal nanoparticles (NPs) have attracted exhaustive research attention due to their large surface‐to‐volume ratio, especially in heterogeneous catalysis. However, the intrinsic agglomeration propensity originating from the high chemical potential of metal NPs has emerged as a major bottleneck to their catalytic stability. Herein, we report an electronic confinement strategy to maintain ultrafine Pt NPs under exceedingly harsh conditions. Specifically, the localized electron‐richness on the multi‐layered graphene is ideally suited for stabilizing Pt NPs, illuminating strong adsorption to decrease the chemical potential and disjoining the agglomeration path of metal NPs for efficient catalytic hydrogenation reaction. The reaction rate of p ‐CNB to p ‐CAN is estimated at 1.0 MPa H ₂ and 40°C, obtaining an impressive of 33.1 mol _{p ‐CAN} ∙g _Pt ⁻¹ ∙h ⁻¹ for Pt/Co@NC catalyst, which corresponds to a turnover frequency (TOF) value of up to 6448.9 h ⁻¹ with excellent durability of 20 catalytic cycles. Analogously, the catalyst demonstrated excellent activity and stability in the hydrogenation of industrial feedstocks containing 4.0 wt.% inorganic/organic sulfur‐containing poisons. Comprehensive investigations testify that the Co‐graphene 3 d ‐2 p and C‐Pt 2 p ‐5 d orbital overlapping, coupled with the electron transfer from Co to carbon, disturbs the conjugation effect of graphene π‐electrons, causing strengthened Pt‐graphene and electron‐rich Pt NPs, which simultaneously intensifies catalytic performance and stability.