Enormous efforts have been initiated in the production of biobased fuels and value-added chemicals via biorefinery owing to the scarcity of fossil resources and huge environmental synchronization. Herein, non-noble metal-based metal/mixed metal oxide supported on carbon employing a metal–organic framework as a sacrificial template is demonstrated for the first time in the selective hydrodeoxygenation (HDO) of biomass-derived furfural (FFR) to 2-methyl furan (MF). The aforementioned catalyst (referred to as Cu/CuFe2O4@C-A) exhibited extraordinary catalytic proficiency (100% selectivity toward MF) compared with the conventional Cu/CuFe2O4@C-B catalyst which was prepared by the wet impregnation method. High-resolution transmission electron microscopy and synchrotron X-ray diffraction studies evidenced the existence of both metal (Cu) and mixed metal oxide (CuFe2O4) phases, in which the metal could help in hydrogenation to alcohol and metal oxide could assist in the hydroxyl group removal step during HDO reaction. The stabilization of encapsulated metal/metal oxide nanoparticles in the carbon matrix, modulation of the electronic structure, and regulation of geometric effects in the Cu/CuFe2O4@C-A are thought to play an important role in its excellent catalytic performance, confirmed by X-ray photoelectron spectroscopy and X-ray absorption spectroscopy investigations. Furthermore, the structure and activity interconnection was confirmed by in situ attenuated total reflection–IR studies, which manifested the strong interfacial interaction between FFR and the Cu/CuFe2O4@C-A catalyst. This finding was further supported by NH3 temperature-programmed desorption analysis, which suggested that the presence of more Lewis/weak acidic sites in this catalyst was beneficial for the hydrogenolysis step in HDO reaction. Additionally, H2 temperature-programmed reduction studies revealed that the adsorption of H2 was stronger on the Cu/CuFe2O4@C-A than that over the conventional Cu/CuFe2O4@C-B catalyst; thus, the former catalyst promoted activation of H2. A detailed kinetic analysis which demonstrated the lower activation energy barrier along with dual active sites attributed for the activation of the two separate reactions in the HDO process on the Cu/CuFe2O4@C-A catalyst. This work has great implication in developing a highly stable catalyst for the selective upgradation of biomass without deactivation of metal sites in extended catalytic cycles and opens the door of opportunity for developing a sustainably viable catalyst in biomass refinery industries.
Defect aggregates in doped ceria play a crucial role in blocking the movement of oxygen vacancies and hence in reducing ionic conductivity. Nevertheless, evaluation of their amount and the correlation between domain size and transport properties is still an open issue. Data derived from a high-pressure X-ray diffraction investigation performed on the Ce 1– x (Nd 0.74 Tm 0.26 ) x O 2– x /2 system are employed to develop a novel approach aimed at evaluating the defect aggregate content; the results are critically discussed in comparison to the ones previously obtained from Sm- and Lu-doped ceria. Defect clusters are present even at the lowest considered x value, and their content increases with increasing x and decreasing rare earth ion (RE 3+ ) size; their amount, distribution, and spatial correlation can be interpreted as a complex interplay between the defects’ binding energy, nucleation rate, and growth rate. The synoptic analysis of data derived from all of the considered systems also suggests that the detection limit of the defects by X-ray diffraction is correlated to the defect size rather than to their amount, and that the vacancies’ flow through the lattice is hindered by defects irrespective of their size and association degree.
COF‐1 has a structure with rigid 2D layers composed of benzene and B3O3 rings and weak van der Waals bonding between the layers. The as‐synthesized COF‐1 structure contains pores occupied by solvent molecules. A high surface area empty‐pore structure is obtained after vacuum annealing. High‐pressure XRD and Raman experiments with mesitylene‐filled (COF‐1‐M) and empty‐pore COF‐1 demonstrate partial amorphization and collapse of the framework structure above 12–15 GPa. The ambient pressure structure of COF‐1‐M can be reversibly recovered after compression up to 10–15 GPa. Remarkable stability of highly porous COF‐1 structure at pressures at least up to 10 GPa is found even for the empty‐pore structure. The bulk modulus of the COF‐1 structure (11.2(5) GPa) and linear incompressibilities (k[100]=111(5) GPa, k[001]=15.0(5) GPa) were evaluated from the analysis of XRD data and cross‐checked against first‐principles calculations.
Some authors have found a time dependence of dielectric breakdown in MOSstructures when studying breakdown behaviour of thin dielectric films (1). Breakdown does not immediately occur after the stress voltage has been applied. This
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