Leveraging Cu/CuFe2O4-Catalyzed Bio-Mass Derived Furfural Hydrodeoxygenation: Nanoscale Metal-Organic-Framework Template Is the Prime Key.

Enormous efforts have been initiated in the production of bio-based fuels and value-added chemicals via bio-refinery owing to the scarcity of fossil resources and huge environmental synchronization. Herein, first time non-noble metal-based metal/mixed metal oxide supported on carbon employing metal organic framework (MOF) as sacrificial template for the selective hydrodeoxygenation of biomass derived furfural to 2-methyl furan (MF). The aforementioned catalyst (named as Cu/CuFe2O4@C-A) exhibited extraordinary catalytic proficiency (100% selectivity towards MF) compared with conventional Cu/CuFe2O4@C-B catalyst which was prepared by the wet impregnation method. HR-TEM and synchrotron X-ray diffraction studies evidenced the existence of both metal (Cu) and mixed metal oxide (CuFe2O4) phase in which metal could help in hydrogenation to alcohol and metal oxide assist in hydroxyl group removal step during hydrodeoxygenation (HDO) reaction. The stabilization of encapsulated metal/metal oxide nanoparticles in carbon matrix, modulation of electronic structure and regulation of geometric effects in the Cu/CuFe2O4@C-A which could play an important role in its excellent catalyst performance, confirmed by XPS and XAS investigations. Also this structure and activity interconnection were strengthened by in-situ ATR-IR studies which manifested the strong interfacial interaction between furfural and Cu/CuFe2O4@C-A catalyst and it was in good agreement with NH3-TPD analysis which suggested the presence of more Lewis/weak acidic sites in this catalyst was beneficial for the hydrogenolysis step in HDO reaction. Furthermore, the adsorption of H2 was stronger in Cu/CuFe2O4@C-A than that over the corresponding conventional one; thus, the activation of H2 was obviously promoted as proposed by H2-TPR study. We also detailed kinetic analysis which clearly proposed the lower activation energy barrier along with dual active site in Cu/CuFe2O4@C-A catalyst, that could be attributed for the activation of the two separate reactions in HDO process. This work has great implication in developing highly stable catalyst for the selective upgradation of biomass without deactivation of metal sites in long run of catalytic cycles as well as open the door of opportunity of sustainably viable catalyst in biomass refinery industries.