高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

愈创木酚在Ni-Fe团簇/Al2O3界面上加氢脱氧的DFT研究

赵豪1, 代博文1, 程崇博1, 卞凤杰1, 沈德魁2, 姜小祥1   

  1. 1. 南京师范大学能源与机械工程学院 2. 东南大学能源与环境学院

  • 收稿日期:2025-12-30 修回日期:2026-02-09 网络首发:2026-02-10 发布日期:2026-02-10
  • 通讯作者: 程崇博 E-mail:62125@njnu.edu.cn
  • 基金资助:
    国家自然科学基金(批准号: 52406251, 52376172)和江苏省高校自然科学研究项目(批准号: 21KJB480004, 22KJA480001)资助

DFT study of guaiacol hydrodeoxygenation on Ni-Fe cluster/Al2O3 surface

ZHAO Hao1, DAI Bowen1, CHENG Chongbo1*, BIAN Fengjie1, SHEN Dekui2, JIANG Xiaoxiang1   

  1. 1. School of Energy and Mechanical Engineering, Nanjing Normal University 2. School of Energy and Environment, Southeast University

  • Received:2025-12-30 Revised:2026-02-09 Online First:2026-02-10 Published:2026-02-10
  • Contact: Chong-Bo CHENG E-mail:62125@njnu.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China(Nos. 52406251, 52376172) and the Natural Science Research Project in Colleges and Universities of Jiangsu Province, China(Nos. 21KJB480004, 22KJA480001)

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摘要： 为阐明双金属负载型催化剂在愈创木酚加氢脱氧中的协同机理，本文基于密度泛函理论，构建了Ni/Al2O3和Ni-Fe/Al2O3模型，系统探究了愈创木酚的吸附活化及反应路径。结果表明，Fe的掺杂显著增强了金属-载体相互作用，从而提升了催化剂的结构稳定性。愈创木酚在两种催化剂上均优先发生脱甲基反应，Fe的引入特异性地活化了甲氧基C-O键，使其断裂能垒从1.20 eV降至0.84 eV，导致加氢脱氧反应的速率控制步骤由脱甲基反应转变为中间产物的加氢反应。对于中间体邻苯二酚的后续转化，Fe掺杂虽未改变优先脱羟基的主路径，但普遍升高了各基元步骤的能垒。电子结构分析揭示，Fe的高亲氧性驱动电子从金属团簇向载体迁移，导致金属团簇电子密度降低。这种电子重构效应在促进C-O键活化（脱氧）的同时，抑制了苯环加氢活性，为理解非贵金属催化剂的高选择性脱氧机理提供了理论依据。

关键词: 愈创木酚, Ni-Fe团簇, Al2O3载体, 加氢脱氧, 密度泛函理论

Abstract: To elucidate the synergistic mechanism of bimetallic supported catalysts in the hydrodeoxygenation of guaiacol, this study constructed Ni/Al2O3 and Ni-Fe/Al2O3 models based on density functional theory to systematically investigate the adsorption activation and reaction pathways of guaiacol. The results indicate that Fe doping significantly enhances the metal-support interaction, thereby improving the structural stability of the catalyst. Guaiacol preferentially undergoes demethylation on both catalysts; however, the introduction of Fe specifically activates the methoxy C-O bond, reducing its cleavage energy barrier from 1.20 eV to 0.84 eV. This shifts the rate-determining step of the HDO reaction from demethylation to the hydrogenation of intermediate products. Regarding the subsequent transformation of the catechol intermediate, while Fe doping does not alter the primary pathway of preferential dehydroxylation, it generally increases the energy barriers for the elementary steps. Electronic structure analysis reveals that the high oxophilicity of Fe drives electron migration from the metal cluster to the support, resulting in reduced electron density within the metal cluster. This electronic reconstruction effect promotes C-O bond activation (deoxygenation) while inhibiting benzene ring hydrogenation activity, providing a theoretical basis for understanding the high selectivity deoxygenation mechanism of non-noble metal catalysts.

Key words: Guaiacol, Ni-Fe cluster, Al2O3, Hydrodeoxygenation, Density functional theory

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