Integration of Interfacial and Alloy Effects to Modulate Catalytic Performance of Metal–Organic-Framework-Derived Cu–Pd Nanocrystals toward Hydrogenolysis of 5-Hydroxymethylfurfural
2019
Sarkar, Chitra | Koley, Paramita | Shown, Indrajit | Lee, Jihyeon | Liao, Yen-Fa | An, Kwangjin | Tardio, James | Nakka, Lingaiah | Chen, Kuei-Hsien | Mondal, John
Selective formation of 2,5-dimethylfuran (DMF) by hydrogenolysis of lignocellulosic biomass-derived 5-hydroxymethylfurfural (HMF) is highly desirable for renewable liquid biofuel production. Here we have synthesized Cu–Pd bimetallic nanoparticles embedded in carbon matrix (Cu–Pd@C) by simple pyrolysis of Pd-impregnated Cu-based metal–organic frameworks (MOFs) followed by conventional hydrogenation route. It was found that Cu–Pd@C-B (solid–gas-phase hydrogenation route) with Cu–Pd bimetallic alloying exhibited brilliant catalytic performance at 120 °C under 15 bar H₂ pressure to produce liquid DMF biofuel with 96.5% yield from HMF as compared with the Cu–Pd@C-A catalyst (liquid phase hydrogenation route), which gave 46.4% yield under the same conditions. X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) studies reveal that Pd in Cu–Pd@C-B catalyst is electronically promoted by Cu with the unique intrinsic synergy of increased Pd–Pd bond distance and decreased Cu–Cu bond length, which eventually modulate the local atomic structural environment and result in enhanced catalytic activity. Moreover, the entrapped bimetallic nanoparticles with carbon shells in Cu–Pd@C-B catalyst further protect the active catalytic site from migration, aggregation, and leaching during hydrogenolysis reaction and improve the stability of the catalyst.
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