Breaking the Limit of Lignin Monomer Production via Cleavage of Interunit Carbon-Carbon Linkages
Breaking the Limit of Lignin Monomer Production via Cleavage of Interunit Carbon-Carbon Linkages
复制标题
通过单元间碳-碳键的断裂突破木质素单体生产的极限
DOI：
10.1016/j.chempr.2019.03.007
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发表时间：
2019-06-13
期刊：
影响因子：
23.5
通讯作者：
Wang, Yanqin
中科院分区：
文献类型：
--
作者：
Dong, Lin;Lin, Longfei;Wang, Yanqin
将木质素转化为单环烃作为商品化学品和替代燃料是生物炼油厂非常理想的目标。然而，天然木质素中稳定的单元间碳-碳键的存在以及木质素提取过程中形成的碳-碳键严重阻碍了这一点。在这里，我们报道了一种新型多功能催化剂Ru/NbOPO4，它实现了一锅木质素转化中单元间C-C和C-O键的催化裂解，获得了124%-153%的单环烃，是现有的硝基苯氧化法的1.2-1.5倍。该催化剂在重复循环中对单环芳烃表现出高的稳定性和选择性(高达68%)。通过原位非弹性中子散射与模拟相结合的方法，揭示了联苯中5-5C-C键的活化和断裂机理，作为采用最强C-C键的木质素模型。本研究突破了木质素单体生产的常规理论极限。
Conversion of lignin into monocyclic hydrocarbons as commodity chemicals and drop-in fuels is a highly desirable target for biorefineries. However, this is severely hindered by the presence of stable interunit carbon-carbon linkages in native lignin and those formed during lignin extraction. Herein, we report a newmultifunctional catalyst, Ru/NbOPO4, that achieves the first example of catalytic cleavage of both interunit C-C and C-O bonds in one-pot lignin conversions to yield 124%-153% of monocyclic hydrocarbons, which is 1.2-1.5 times the yields obtained from the established nitrobenzene oxidation method. This catalyst also exhibits high stability and selectivity (up to 68%) to monocyclic arenes over repeated cycles. The mechanism of the activation and cleavage of 5-5 C-C bonds in biphenyl, as a lignin model adopting the most robust C-C linkages, has been revealed via in situ inelastic neutron scattering coupled with modeling. This study breaks the conventional theoretical limit on lignin monomer production.