Exploring Furfural Catalytic Conversion on Cu(111) from Computation

Abstract

The full potential energy surface of the catalytic conversion of furfural to 2-methylfuran on the Cu(111) surface has been systematically computed on the basis of density functional theory, including dispersion and zero-point energy corrections. For furfuryl alcohol formation, the more favorable step is the first H addition to the carbon atom of the CO group, forming an alkoxyl intermediate (F-CHO +H → F-CH2O); the second H atom addition, leading to furfuryl alcohol formation (F-CH2O + H → F-CH2OH), is the rate-determining step. For 2-methylfuran formation from furfuryl alcohol dissociation into surface alkyl (F-CH2) and OH groups, H2O formation is the rate-determining step (OH + H → H2O). Our results explain perfectly the experimentally observed selective formation of furfuryl alcohol and the equilibrium of furfural/furfuryl alcohol conversion under hydrogen-rich conditions as well as the effect of H2O suppressing furfural conversion. In addition, it is found that dispersion correction (PBE-D3) overestimates the adsorption energies of furfural, furfuryl alcohol, and 2-methylfuran considerably, whereas those of H2 and H2O can be reproduced nearly quantitatively. Our results provide insights into Cu-catalyzed furfural selective conversion and broaden our fundamental understanding into deoxygenation reactions of oxygenates involved in the refining of biomass-derived oils.

Kinetics of Furfural Hydrogenation over Bimetallic Overlayer Catalysts and the Effect of Oxygen Vacancy Concentration on Product Selectivity

“…The product selectivity of furfural conversion is believed to be closely related with the furfural adsorption geometry on metal surface . A tilted adsorption configuration with aldehydic oxygen interacting with the metal surface will lead to the formation of furfuryl alcohol and the subsequent 2‐methylfuran, while furfural decarbonylation product (furan) and ring hydrogenation products (tetrahydrofurfuryl alcohol and tetrahydrofuran) require the adsorption of furfural through flat adsorption conformation with the furan ring parallel to the catalyst surface . Resasco et al.…”

High coverage adsorption and co-adsorption of CO and H2 on Ru(0001) from DFT and thermodynamics

“…In our calculations, all adsorption structures are obtained from PBE optimization, while all energies are obtained from RPBE single-point energy calculations on the PBE structures. 49 In our computations, an energy cut-off of 400 eV and a second-order Methfessel-Paxton 50 electron smearing with s = 0.2 eV were used to ensure accurate energies with errors due to smearing of less than 1 meV per unit cell. In our calculations we used the Grimme GGA-type functional (PBE-D3).…”

Selective Hydrogenation of Furfural in a Proton Exchange Membrane Reactor Using Hybrid Pd/Pd Black on Alumina

“…Under H 2 ‐rich conditions, Cu/SiO 2 yields higher selectivity for furfuryl alcohol at lower temperatures and for 2‐methylfuran at higher temperatures due to the proposed Eley‐Rideal mechanism. This mechanism exhibits a rate‐determining step of water removal from the surface, which inhibits the intermediate from dissociating into 2‐methylfuran . With these distinctions in reaction pathways for furfural, the catalyst performance could be understood by correlating the hydrogen coverage on the surface to selectivity and hydrogenation rate.…”