调控合成生物质芳香胺Elucidating Functional Group Governance for Catalytic Synthesis of Bio-based Aromatic Amines
星期五, 6 3 月, 2026Elucidating Functional Group Governance for Catalytic Synthesis of Bio-based Aromatic Amines
Recently, PhD student Ge-liang Xie supervised by Dr. Lu-jiang Xu and Prof. Zhen Fang published a research paper on the functional group regulation mechanism for catalytic synthesis of bio-based aromatic amines from lignin-derived phenols in the international academic journal Biomass and Bioenergy (Q1; Impact factor: 5.7)
The study investigated the effects of alkyl and methoxy substituents on the HZSM-5-catalyzed amination of lignin-derived phenolic model compounds, revealing a “promotion-inhibition dichotomy”: alkyl groups enhanced amination reactivity (4-propylphenol yield: 44.3 mol%, 34.7% higher than phenol), while methoxy groups strongly inhibited the reaction (4-propylguaiacol yield: only 11.0 mol%). Mechanistic analysis showed alkyl groups reduce protonation energy barriers and generate promoting hydrogen radicals, while methoxy groups cause intermediate coking and block active site interactions.
To overcome methoxy inhibition, a Mo-Ga/HZSM-5 catalyst with NH₃-H₂ atmosphere was developed, doubling 4-propylguaiacol yield to 25.9 mol%. A sequential hydrodeoxygenation-amination strategy was further proposed, increasing the yield to 34.1 mol%. Combining this strategy with lignin-first biorefining, birch wood was directly converted to aromatic amines with a yield of 16.6 mol% (lignin basis), higher than previous reports. This work clarifies functional group reactivity rules in lignin valorization and provides a new integrated process for sustainable aromatic amine production from biomass.
It elucidates the effects of different functional groups on the amination efficiency of lignin model compounds, providing a new integrated tandem process route for the sustainable production of aromatic amines from biomass. Publication:
GL Xie, Y Luo, KC Xia, SR Li, LJ Xu, Zhen Fang. Elucidating Functional Group Governance for Catalytic Synthesis of Bio-based Aromatic Amines. Biomass and Bioenergy, 2026, 8 (211), 109198. https://doi.org/10.1016/j.biombioe.2026.109198.
博士生谢葛亮阐明催化合成生物基芳香胺的官能团调控
最近，博士生谢葛亮在徐禄江副教授和方真教授的指导下，在国际学术期刊《生物质与生物能源》Biomass and Bioenergy (Q1; Impact factor: 5.7)上发表一篇研究论文，揭示了木质素衍生酚催化合成生物基芳香胺过程中的官能团调控机制。
不同官能团对木质素衍生酚氨化合成芳香氨的影响Catalytic animation pyrolysis of birch and lignin-derived phenols to Aromatic amines
文章阐明了烷基、甲氧基取代基对HZSM-5催化木质素衍生酚胺化存在显著影响，具有明显的“促进-抑制二分效应”：烷基可提升胺化反应活性（4-丙基苯酚的芳香胺产率达44.3 mol%，较苯酚高出34.7%）；而甲氧基对反应有强抑制作用（4-丙基愈创木酚的芳香胺产率仅为11.0 mol%）。机理分析表明，烷基可降低质子化能垒，且断裂产生的氢自由基可促进反应进程；甲氧基则会引发中间体结焦，同时阻碍反应物与催化剂活性位点的相互作用。
为破解甲氧基的抑制效应，研究开发了Mo-Ga/HZSM-5双金属催化剂并采用NH3-H2反应气氛，使4-丙基愈创木酚的芳香胺产率提升一倍至25.9 mol%。团队进一步提出加氢脱氧-胺化顺序策略，将该产物的产率提升至34.1 mol%。将该策略与“木质素优先”生物炼制方法结合后，成功实现桦木直接转化制备芳香胺，产率达16.6 mol%（以木质素为基准），优于此前已报道的研究结果。
本研究阐明了不同官能团对木质素模型化合物氨化效率的影响，为从生物质可持续生产芳香胺提供了全新的集成串联工艺路径。
详情可见：
GL Xie, Y Luo, KC Xia, SR Li, LJ Xu, Zhen Fang. Elucidating Functional Group Governance for Catalytic Synthesis of Bio-based Aromatic Amines. Biomass and Bioenergy, 2026, 8 (211), 109198. https://doi.org/10.1016/j.biombioe.2026.109198.