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由多相镍催化剂催化，在无外部氢气的情况下对木质素和木质素模型化合物进行选择性裂解。

Selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts.

作者信息

Jiang Liang, Guo Haiwei, Li Changzhi, Zhou Peng, Zhang Zehui

机构信息

Key Laboratory of Catalysis and Materials Sciences of the Ministry of Education , South-Central University for Nationalities , Wuhan , 430074 , China . Email:

State Key Laboratory of Catalysis , Dalian Institute of Chemical Physics , Chinese Academy of Sciences , Dalian 116023 , China . Email:

出版信息

Chem Sci. 2019 Mar 21;10(16):4458-4468. doi: 10.1039/c9sc00691e. eCollection 2019 Apr 28.

DOI:10.1039/c9sc00691e
PMID:31057773
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6482439/
Abstract

Selective hydrogenolysis of the C-O bonds in lignin is a key strategy for the generation of fuels and chemical feedstocks from biomass. Currently, hydrogenolysis has been mainly conducted using hydrogen, which is flammable and not sustainable or economical. Herein, an external hydrogen-free process for aryl ethers hydrogenolysis in lignin models and dioxasolv lignin over nickel nanoparticles supported on AlO, is reported. Kinetic studies reveal that the transfer hydrogenolysis activity of the three model compounds decreased in the following order: benzyl phenyl ether (α-O-4), 2-phenylethyl phenyl ether (β-O-4) and diphenyl ether (4-O-5), which linearly corresponds to their binding energies and the activation energies. The main reaction route for the three model compounds was the cleavage of the ether bonds to produce aromatic alkanes and phenol, and the latter was further reduced to cyclohexanol. Dioxasolv lignin depolymerization results exhibit a significant C-O decrease over the Ni nanoparticles supported on AlO with iso-propanol as the hydrogen source through 2D-HSQC-NMR analysis, which confirmed the transfer hydrogenolysis conclusion in the model study. This work provides an economical and environmentally-friendly method for the selective cleavage of lignin and lignin model compounds into value-added chemicals.

摘要

木质素中碳氧键的选择性氢解是从生物质中生成燃料和化学原料的关键策略。目前，氢解主要使用氢气进行，而氢气易燃且不具有可持续性或经济性。在此，报道了一种在负载于AlO上的镍纳米颗粒上对木质素模型和二氧六环溶剂木质素进行芳基醚氢解的无外部氢气工艺。动力学研究表明，三种模型化合物的转移氢解活性按以下顺序降低：苄基苯基醚（α-O-4）、2-苯乙基苯基醚（β-O-4）和二苯醚（4-O-5），这与它们的结合能和活化能呈线性对应关系。三种模型化合物的主要反应途径是醚键断裂生成芳烃烷烃和苯酚，后者进一步还原为环己醇。通过二维异核单量子相干核磁共振（2D-HSQC-NMR）分析，以异丙醇为氢源，二氧六环溶剂木质素在负载于AlO上的镍纳米颗粒上的解聚结果显示出显著的碳氧键减少，这证实了模型研究中的转移氢解结论。这项工作为将木质素和木质素模型化合物选择性裂解为增值化学品提供了一种经济且环保的方法。

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