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 pu...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 CeO_(2)as promoters to modify Pd nanoparticles for modulating the adsorption behaviors of furfural molecules.To achieve the highly-desired ultra-small Pd@CeO_(2)core@shell nanostructure,a“constrained auto-redox”synthesis is developed,in which silicalite-1 supports play the key role of providing their surface as the landing place of PdO_(x)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@CeO_(2)/S-1 gives 98.9%conversion 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 CeO_(2)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.展开更多
基金supported by the financial aid from National Science and Technology Major Project of China(No.2022YFB3504000)National Natural Science Foundation of China(Nos.22020102003,22025506 and 22271274)。
文摘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 CeO_(2)as promoters to modify Pd nanoparticles for modulating the adsorption behaviors of furfural molecules.To achieve the highly-desired ultra-small Pd@CeO_(2)core@shell nanostructure,a“constrained auto-redox”synthesis is developed,in which silicalite-1 supports play the key role of providing their surface as the landing place of PdO_(x)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@CeO_(2)/S-1 gives 98.9%conversion 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 CeO_(2)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.
