SnOx-modulated Ni nanoparticles with tailored electronic microenvironment for efficient hydrogenative rearrangement of furfural to cyclopentanone

SnO x clusters anchor and disperse Ni nanoparticles on Y zeolite. • Electronic transfer creates Ni δ+ sites, switching FOL adsorption flat to vertical. • Rearrangement Ea drops 52.9 to 38.8kJ·mol −1 ; over-hydrogenation Ea rises 59.9 to 88.3 kJ· mol −1 . • 10Ni/Sn-Y-30 affords 95.3% cyclopentanone yield at full conversion. The highly efficient and directionally selective hydrogenation-rearrangement of the biomass platform molecule furfural (FF) to high-value-added cyclopentanone (CPO) represents a core pathway for biomass upgrading and utilization. However, constructing highly active and selective non-noble metal catalysts that precisely suppress over-hydrogenation remains elusive. In this work, we report a SnO x cluster-modified Ni-based catalyst (10Ni/Sn-Y-30) supported on Y-type zeolite. According to the characterization and density functional theory (DFT) calculations, surface SnO x clusters act as robust anchoring sites for metallic Ni, thereby significantly boosting the dispersion of Ni nanoclusters. Furthermore, the directional electron transfer from Ni to SnO x creates electron-deficient Ni δ+ centers, which lowers the reduction energy barrier and optimizes the substrate adsorption configuration. The superiority of this regulation strategy is further corroborated by kinetic tests, attesting to its effective modulation of the rates of the primary and competing reactions. In an aqueous reaction system at 150 °C, the optimized   10Ni/Sn-Y-30 catalyst delivers exceptional catalytic activity, yielding a peak CPO yield of 95.3%. This study provides a novel design strategy for the precise structural modulation of low-cost, non-noble metal catalysts and the directional upgrading of biomass resources. Download: Download high-res image (125KB) Download: Download full-size image