Structural origins of selectivity in guaiacol hydrodeoxygenation on copper

doi:10.1016/S1872-2067(26)65098-X

Abstract

Abstract:

Efficient upgrading of lignin-derived bio-oils requires selective hydrodeoxygenation (HDO) of oxygen-containing groups without hydrogenating the aromatic ring, a central challenge in biomass valorization. Here we combine density functional theory and microkinetic simulations to elucidate the HDO mechanism of guaiacol on copper catalysts. Across Cu(100), Cu(111), and Cu(211) surfaces, two competing routes dominate product distribution: (1) hydrogen-assisted deoxygenation (H-DO) via methoxy dissociation, producing phenol, and (2) partial hydrogenation (PHDO) of the aromatic ring, leading to cyclohexanone-type products. We show that H-DO activity is largely insensitive to surface orientation due to weak Cu-C₂ interactions, whereas PHDO activity depends strongly on surface structure through Cu-C₃/C₆ bonding. This difference establishes the d-band center as a reliable electronic descriptor for selectivity. Cu(111), with its more negative d-band center and weaker adsorption, exhibits the highest aromatic selectivity. Guided by this insight, we propose and validate grain boundary (GB) engineering as a design strategy: Cu(111)/(111) GB selectively suppresses PHDO by destabilizing hydrogenation transition states, while retaining H-DO activity. These results establish a clear structure-activity-selectivity relationship for guaiacol HDO and demonstrate that electronic tuning through facet and GB control provides a general framework for designing metal catalysts for selective biomass upgrading.

Key words: Hydrodeoxygenation, First-principles calculations, Biomass upgradation, Grain boundary, Selectivity

Tianchun Li, Tianyang Liu, Yu Jing. Structural origins of selectivity in guaiacol hydrodeoxygenation on copper[J]. Chinese Journal of Catalysis, 2026, 87: 376-385.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65098-X

https://www.cjcatal.com/EN/Y2026/V87/I8/376

Figures/Tables 6

Scheme 1. Simplified reaction routes of guaiacol HDO on Cu surfaces, including the DDO, H-DO, EO and PHDO pathways.

Fig. 1. Structural diagram of vertical (a) and parallel (b) adsorption configurations of guaiacol on Cu surfaces. (c) Side and top views of adsorbed guaiacol and H2 on the Cu(111). (d) Adsorption energy of guaiacol and H2 on the Cu(100), Cu(111) and Cu(211).

Fig. 2. (a?c) IS, TS and FS for methyl, hydroxyl and methoxy dissociation. (d?f) Energy profiles of the first elementary step along the DDO and H-DO pathways on Cu(111). (g) The general reaction scheme of H-DO pathway on different Cu facets.

Fig. 3. Reaction scheme and kinetic Ea for the initial hydrogenation of guaiacol (a) and the final hydrogenation of C6H9(OH)(OCH3)* species (b) along the PHDO pathway on the Cu(111) surface. The yellow balls represent an additional H*. (c) Reaction scheme for the overall PHDO pathway on Cu surfaces.

Fig. 4. (a) Schematics for the competition between the H-DO and PHDO pathways on Cu surfaces that determined by the first elementary step. (b) Energy profiles along the H-DO and PHDO pathways, respectively, on Cu surfaces. The correlation of adsorption energy of guaiacol (Eguaiacol) with d-band center on Cu surfaces (c) and the variation of kinetic Ea with Eguaiacol for the first elementary step (d) along the H-DO and PHDO pathways, respectively, on Cu surfaces.

Fig. 5. (a) Top and side views of the Cu(111)/(111) GB. The light-yellow balls represent the Cu atoms at the boundaries. (b) Schematics for the first elementary step along H-DO and PHDO pathways on Cu GBs. The simulated kinetic Ea of the first elementary step along the H-DO (c) and PHDO (d) pathways on Cu GBs. (e) The variation of Ea for the first PHDO step (Ea(PHDO)). (f) The Ea difference between the first elementary step of H-DO and PHDO (ΔEa = Ea(H-DO) ? Ea(PHDO)) as a function of d-band center of different Cu catalysts. (g) The TOF values for phenol formation as a function of temperature variation at a guaiacol partial pressure of 1/10 atm via the H-DO pathway on different Cu catalysts.

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