Abstract
Bare Pd metal nanoparticles invariably suffer from poor selectivity in furfural hydrogenation by forming flat configurations,with the aromatic ring of the substrate molecules parallel to the metal surface.Herein,we put forward a promising solution by using CeO2 as promoters to modify Pd nanoparticles for modu-lating the adsorption behaviors of furfural molecules.To achieve the highly-desired ultra-small Pd@CeO2 core@shell nanostructure,a"constrained auto-redox"synthesis is developed,in which silicalite-1 sup-ports play the key role of providing their surface as the landing place of PdOx precursors for inhibiting the overgrowth and the deformation.To the best of our knowledge,this is one of the smallest core@shell materials obtained from aqueous synthesis.When evaluated as catalysts,Pd@CeO2/S-1 gives 98.9％con-version of furfural with 94.3％selectivity for furfural alcohol in 15 h,which is much better than that of Pd/S-1(88.6％conversion with 44.3％selectively).The DFT simulation reveals a strong interaction between the defects of CeO2 and the oxygen atom of the-CHO group in furfural molecules,which benefits the selective hydrogenation occurred in the-CHO group rather than the furan ring.
基金项目
financial aid from National science and Technology Major Project of China(2022YFB3504000)
国家自然科学基金(22020102003)
国家自然科学基金(22025506)
国家自然科学基金(22271274)
NETL
NSTL
万方数据