铜基催化剂上愈创木酚加氢脱氧反应选择性的结构起源

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

摘要/Abstract

摘要：

木质素衍生生物油的提质转化是生物质资源化利用的关键环节, 其核心挑战在于如何在不破坏芳香环的前提下, 选择性脱除含氧官能团, 即实现选择性加氢脱氧. 该过程对于生产高附加值芳烃化学品及液体燃料至关重要. 愈创木酚作为典型的木质素酚类单体模型化合物, 其甲氧基和酚羟基共存的结构使得C-O键断裂与芳香环加氢之间存在强烈的竞争. 当前, 开发兼具高活性和高芳烃选择性的非贵金属催化剂仍是生物质催化领域的核心挑战. 铜基催化剂因其优异的氢解活性和结构稳定性, 且能够有效抑制芳香环过度加氢, 但其构效关系及选择性调控机制尚不明确.

本工作基于密度泛函理论与微观动力学模拟, 系统建立了愈创木酚在Cu(100), Cu(111)及Cu(211)三个特征晶面及Cu晶界模型上的加氢脱氧反应网络, 从原子尺度揭示了反应路径竞争的本质及其对表面电子结构的依赖性. 研究首先发现, 愈创木酚在铜表面的转化遵循两条竞争路径: 一是通过甲氧基解离进行的氢助脱氧路径(H-DO), 生成芳香产物苯酚; 二是通过芳香环邻位和间位碳原子(C3/C6)部分加氢进行的芳环饱和路径(PHDO), 生成环己酮类产物. 计算结果表明, 铜与甲氧基碳原子(C₂)的相互作用普遍较弱, 导致H-DO路径的活性对铜表面取向不敏感, 受表面配位环境影响有限. 相比之下, 芳环C3/C6位点与铜表面之间的成键强度具有明显差异, 不同晶面通过d带中心位置调控金属和关键中间体之间的作用强度, 从而影响芳香环的加氢能垒, 导致PHDO路径的反应活性具有显著的结构敏感性. 由于d带中心位置较深, Cu(111)表面和吸附质相互作用显著减弱, 能够在保证良好脱氧活性的同时抑制芳香环的进一步饱和, 在三种低指数晶面中表现出最高的芳烃选择性. 基于此认识, 本研究进一步提出并验证了晶界工程是一种有效的选择性调控策略. 其中, Cu(111)/(111)晶界, 具有更深的d带中心, 能够在保持良好脱氧活性的同时, 进一步抑制副反应路径, 实现更高的芳烃选择性.

综上, 本文完整建立了愈创木酚在铜催化剂上加氢脱氧的结构-活性-选择性关联, 不仅从机理上阐明了铜表面具备芳环保留特性的物理根源, 更提出了“晶界工程”这一兼具理论深度与实用潜力的催化剂设计新策略, 通过该策略调节表面电子结构, 实现产物选择性的有效调控. 未来, 该策略有望拓展至其他贵金属替代体系及更复杂的生物质衍生含氧化合物转化过程, 为非石油路线的绿色化学品生产提供理论基础与材料平台.

关键词: 加氢脱氧, 第一性原理计算, 生物质高值化, 晶界, 选择性

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

李天春, 刘天阳, 荆宇. 铜基催化剂上愈创木酚加氢脱氧反应选择性的结构起源[J]. 催化学报, 2026, 87: 376-385.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65098-X

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

图/表 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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