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.

In recent times, selective hydrogenation of biomass-derived 5-hydroxymethylfurfural(5-HMF) to produce novel difuranic polyol scaffold 2,5-dihydroxymethylfuran (DHMF) has attracted the interests of the many researchers due to its peculiar symmetrical structure as well as its wide application as a monomer for the preparation of cross-linked polyesters and polyurethane. Copper-based catalysts have been explored accountable for the selective catalytic hydrogenation however the hurdles are still associated with the strongly reducing H2 atmosphere and oxidizing C-O bond that makes the Cu 0 and Cu x+ surface active species unstable, limiting the rational design of highly efficient integrated catalyst systems. To address this, herein, we built catalytic systems for 5-HMF hydrogenation with stable and balanced Cu 0 and Cu x+ active surface species inside the nanocage of catechol based Porous-Organic-Polymer (POP) endowed with large surface areas, impressive stabilities, and spatial restriction inhibiting NPs aggregation.Batch reactor screening indentified that superior catalytic performance (DHMF selectivity of 98%) has been achieved with our newly designed Cu@C-POP at 150ºC temperature and 20 bar H2 pressure, which was also higher than that of other reported copper catalysts. Comprehensive characterizations understanding with H2-TPR and XPS study revealed that substantially boosted activity is induced by the presence of bulk CuOx phase and atomically dispersed Cu species incorporating isolated Cu ions, which are further confirmed through the positive binding energy shift of Cu-2p3/2 XPS spectra (~0.4eV). The Cu environment in our catalytic systems comprises predominantly square planar (well probably Jahn-Teller distorted Oh) which we gleaned from the EXAFS analysis featuring two adjacent copper atoms with the valence state in between of 0 and +2 as validated by XANES absorption edge positions. EXAFS studies further revealed a

A novel Pd-based catalyst hosted over a nitrogen enriched fibrous porous-organic-polymer with a high density of step sites and exhibits versatile catalytic performance over different types of vegetable oils to furnish long chain diesel-range alkanes.