Mechanistic exploration of furfural hydrogenation on copper surface in aqueous phase by DFT and AIMD simulations

Yao, Zhen; Xia, Guang-Jie; Cao, Wei; Zeng, Ke-Han; Wang, Yang -Gang

2023-02-01

10.1016/j.jcat.2022.12.024

JOURNAL OF CATALYSIS   Impact Factor & Quartile

0021-9517

1090-2694

The catalytic hydrogenation of biomass-derived compounds in the aqueous phase is crucial to upgrading renewable biochemicals and biofuels. Herein, by combining density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations, we have explored the selective hydrogenation mechanism of furfural on the copper surface with a fully explicit solvation model. The presence of water solvent could significantly affect the reaction mechanism, in adjunct with the charge interactions between the reaction intermediates and the Cu surface. It demonstrates a proton-shuttling mechanism for furfural hydrogenation where the initial hydrogen source for reducing the carbonyl group is from the dissociation of the adjacent water. Furthermore, the water solvation effect results in the dynamic charge separation between the copper surface and the reaction intermediates, significantly reducing the energy barrier. These results deepen our mechanistic understanding of selective hydrogenation of furfural over Cu-catalysts, paving the way for upgrading renewable biomass derivatives in applications. (c) 2023 Elsevier Inc. All rights reserved.

Biomass conversion Furfural Furfuryl alcohol Density functional theory (DFT) Ab initio molecular dynamics Explicit solvation

SCI

English

First ; Corresponding

NSFC of China["22003022","22203041"] ; Natural Science Foundation of Guangdong Province of China[2021A1515010213] ; Guangdong "Pearl River" Talent Plan[2019QN01L353] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Guangdong Basic and Applied Basic Research Foundation, China[2021A1515110406]

Chemistry ; Engineering

Chemistry, Physical ; Engineering, Chemical

WOS:000923775100001

ACADEMIC PRESS INC ELSEVIER SCIENCE

CHEMISTRY

Web of Science

Southern Univ Sci & Technol, Dept Chem, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China

Yao, Zhen,Xia, Guang-Jie,Cao, Wei,et al. Mechanistic exploration of furfural hydrogenation on copper surface in aqueous phase by DFT and AIMD simulations[J]. JOURNAL OF CATALYSIS,2023,418.

Yao, Zhen,Xia, Guang-Jie,Cao, Wei,Zeng, Ke-Han,&Wang, Yang -Gang.(2023).Mechanistic exploration of furfural hydrogenation on copper surface in aqueous phase by DFT and AIMD simulations.JOURNAL OF CATALYSIS,418.

Yao, Zhen,et al."Mechanistic exploration of furfural hydrogenation on copper surface in aqueous phase by DFT and AIMD simulations".JOURNAL OF CATALYSIS 418(2023).