Exploring the Reaction Mechanisms of Furfural Hydrodeoxygenation on a CuNiCu(111) Bimetallic Catalyst Surface from Computation

Abstract

In this study, the selectively catalytic hydrodeoxygenation of furfural (F–CHO) to 2-methylfuran (F–CH 3 ) on the CuNiCu(111) bimetallic catalyst surface was systematically investigated based on the periodic density functional theory, including dispersion correction. The formation of furfuryl alcohol (F–CH 2 OH) involved two steps: the preferred first step was the hydrogenation of the branched C atom, forming the alkoxyl intermediate (F–CHO + H = F–CH 2 O), and the second step was H addition to the alkoxyl group, resulting in furfuryl alcohol (F–CH 2 O + H = F–CH 2 OH), which was the rate-controlling step. In contrast, in the formation of 2-methylfuran, the first step was the dehydroxylation of furfuryl alcohol, resulting in alkyl (F–CH 2 ) and OH (F–CH 2 OH = F–CH 2 + OH) groups, the second step was the hydrogenation of F–CH 2 (F–CH 2 + OH + H = F–CH 3 + OH), and the rate-controlling step was the hydrogenation of OH to H 2 O (OH + H = H 2 O). Based on the comparison results of the NiCuCu(111), Cu(111), and CuNiCu(111) surfaces, it was concluded that the catalytic performance of the catalyst was closely related to the adsorption structure of furfural. These results provide a basis for studying the intrinsic activity of NiCu catalysts during the hydrodeoxygenation of refined oxygenated compounds involving biomass-derived oils.

Mechanistic insights into the catalytic transfer hydrogenation of furfural to furfuryl alcohol over a N-doped carbon-supported Ni single atom catalyst from first principles

“…14 Over the past few decades, liquid phase hydrogenation of FF to FA with various metal-based heterogeneous catalysts has been extensively studied experimentally and theoretically. [14][15][16][17][18][19][20][21][22][23][24][25][26] In this liquid-phase process, in which molecular hydrogen (H 2 ) was used as the hydrogen source, solvent and high H 2 pressures are required. Compared to the H 2 -hydrogenation reaction, catalytic transfer hydrogenation (CTH) using renewable and liquid-phase hydrogen sources, such as alcohols, formic acid, formate and hydrosilane, represents an attractive, safer and more convenient alternative for the hydrogenation of aldehydes and ketones into alcohols.…”

Theoretical Insights into Facet-Dependent Activity and Selectivity of Cu Catalysts in Electrochemical Furfural Reduction

“…Although the electrochemical hydrogenation of furfural (ECHFF) has been experimentally studied to improve the selectivity of target products and energy conversion efficiency, the theoretical research on the ECHFF process needs to be clarified. − There are very few studies about theoretical research on ECHFF. Shan et al reported the mechanistic study of the electrocatalytic hydrogenation of FF on Ag, Pb, and Ni.…”

Comparative DFT study of methanol decomposition on Mo2C(001) and Mo2C(101) surfaces

“…adsorption of methanol as compared to that of other small molecules such as H 2 O, CO 2 , CH 4 , C 2 H 2 , C 2 H 4 , C 2 H 6 , etc. 52 This very strong dissociative adsorption of CH 3 OH indicates the rather low stability of the (001) surface. It is expected that the metallic Mo 2 C(001) surface can be easily oxidized or carburized.…”

“…It is expected that the metallic Mo 2 C(001) surface can be easily oxidized or carburized. 52 Nevertheless, the CO formation was computed for comparison, and it was found that the energy barrier is 2.81 eV. To complete the reaction, the desorption of CO and H 2 was computed.…”

“…On Mo 2 C(101), the preferred reaction path is CH eV, 52 it is inferred that the dissociated O atoms will be accumulated on the surface instead of forming O 2 to be desorbed. Therefore, the steps of O 2 formation and desorption are not included in Fig.…”