愈创木酚在Ni-Fe团簇/Al₂O₃界面上加氢脱氧的密度泛函理论研究

Density Functional Theory Studies of Guaiacol Hydrodeoxygenation on Ni-Fe Cluster/Al₂O₃ Surface

摘要

为阐明双金属负载型催化剂在愈创木酚加氢脱氧反应中的协同机理， 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.

Abstract

To elucidate the synergistic mechanism of bimetallic supported catalysts in the hydrodeoxygenation (HDO) 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.

关键词

愈创木酚 / Ni-Fe团簇 / Al₂O₃载体 / 加氢脱氧 / 密度泛函理论

Key words

Guaiacol / Ni-Fe cluster / Al₂O₃ support / Hydrodeoxygenation / Density functional theory

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基金资助

国家自然科学基金(52406251)

国家自然科学基金(52376172)

江苏省高校自然科学研究项目(21KJB480004)

江苏省高校自然科学研究项目(22KJA480001)