Synergy of Single Atoms and Lewis Acid Sites for Efficient and Selective Lignin Disassembly into Monolignol Derivatives
Synergy of Single Atoms and Lewis Acid Sites for Efficient and Selective Lignin Disassembly into Monolignol Derivatives
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DOI：
10.1021/jacs.3c04028
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发表时间：
2023-05-30
影响因子：
15
通讯作者：
Wang, Dingsheng
中科院分区：
文献类型：
--
作者：
Meng, Ge;Lan, Wu;Wang, Dingsheng
木质素是天然可再生木质纤维素生物质资源中含量最丰富的芳香族聚合物。开发高效的木质素解聚催化剂，以高产率和高选择性地生产有价值的单酚，仍然是该领域的一个理想但具有挑战性的目标。在此，我们设计了一种以MgO为载体的Mo中心和Al刘易斯酸中心的协同催化剂（Mo 1 Al/MgO），用于桉树木质素的β-芳醚键裂解解聚。在惰性N2气氛下，Mo_1Al/MgO催化剂可同时获得46%的单酚收率和92%的松柏类芥子基甲醚的选择性，以及良好的循环稳定性。第一性原理计算和控制催化实验证实了Mo（1）-O-5单原子中心和相邻Al刘易斯酸中心在甲醇溶剂参与下的协同催化机理，验证了设计具有协同多活性中心的催化剂的可行性，以更低的成本和更高的安全性有效和选择性地将复杂的可再生生物聚合物分解成高附加值的产品。
Lignin is the most abundant aromatic polymer from thenatural andrenewable lignocellulosic biomass resource. Developing highly efficientcatalysts for lignin depolymerization to produce valuable monophenolswith high yield and selectivity remains a desirable but challengingtarget in this field. Here, we design a synergistic catalyst combiningatomically dispersed Mo centers and Al Lewis acid sites on a MgO substrate(Mo1Al/MgO) for the depolymerization of Eucalyptus lignin via the beta-aryl ether bond cleavage. A near-theoreticalmonophenol yield of 46% with an ultrahigh selectivity of 92% for coniferyland sinapyl methyl ether, as well as good cycling durability, wasachieved simultaneously by Mo1Al/MgO in an inert N-2 atmosphere. First-principles calculations and control catalyticexperiments confirmed the synergistic catalysis mechanism betweenMo(1)-O-5 single-atom centers and the neighboringAl Lewis acid sites with the participation of a methanol solvent.This study validates the feasibility of designing better-performingcatalysts with synergistic multiactive sites for the efficient andselective disassembly of complex renewable biopolymers into highlyvalue-added products with lower cost and greater security.