Atomically Dispersed Pt and NiO Clusters Synergistically Enhanced C–O Bond Hydrogenolysis

C–Obond activation is a highly efficient,fundamental strategy in the depolymerization and hydrodeoxygenation of chemicals with oxygen-containing functional groups such as oil,coal,and biomass.Developing efficient catalysts for C–Oactivation with ultralow-loading noble and non-noble metals is highly desirable for the improvement of metal atomic utilization.Herein,bimetallic catalysts with atomically dispersed Pt and NiO clusters on different supports were fabricated,and the prepared Pt^(δ+)-NiO/Nb_(2)O_(5)and Pt^(δ+)-NiO/TiO_(2)showed outstanding activity for the hydrogenolysis of benzyl phenyl ether with>99%yield of phenol and toluene due to the excellent cooperation of atomically dispersed Pt and NiO clusters.The synergy mechanism between Pt and Ni and their respective roles in the bimetallic catalyst for C–O hydrogenolysis were clearly clarified.These findings deepen our understanding of the synergy of the two active components and are expected to provide new design concepts for the development of multicomponents catalysts.

Crystal-phase engineering of PdCu nanoalloys facilitates selective hydrodeoxygenation at room temperature

Selective hydrodeoxygenation of biomass-derived aromatic alcohols to value-added chemical or fuel is of great importance for sustainable biomass upgrading,and hydrodeoxygenation of 5-hydroxymethylfurfural(HMF)to 2,5-dimethylfuran(DMF)is one of the most attractive reactions.Achieving the conversion of HMF to DMF using H_(2)at ambient temperature is challenging.In this work,we used PdCu nanoalloys to catalyze the selective hydrodeoxygenation reaction of HMF to DMF using H_(2)as the reducing agent.The reaction path and the product selectivity are governed by the crystallographic phase of the PdCu nanoalloys.It was discovered that body-centered cubic(BCC)PdCu nanoalloys supported on activated carbon(AC)exhibited outstanding performance with 93.6%yield of DMF at room temperature(PdCu/AC-BCC).A combination of experimental and density functional theory(DFT)studies showed that the tilted adsorption modes of furanic intermediates on PdCu-BCC nanoalloy surfaces accounted for the high selectivity of DMF;however,furan ring was activated on PdCu face-centered cubic(FCC)nanoalloy surfaces.Furthermore,PdCu/AC-BCC could also catalyze the hydrodeoxygenation of other aromatic alcohols at room temperature while maintaining the aromatic structures.This work opens the way for selective hydrodeoxygenation of the aromatic alcohols at room temperature with the aromatic ring intact.