Synergy of Single Atoms and Lewis Acid Sites for Efficient and Selective Lignin Disassembly into Monolignol Derivatives

Ge Meng; Wu Lan; Lilong Zhang; Shibin Wang; Tanhao Zhang; Shuo Zhang; Ming Xu; Yu Wang; Jian Zhang; Fengxia Yue; Yulong Wu; Dingsheng Wang

doi:10.1021/jacs.3c04028

Synergy of Single Atoms and Lewis Acid Sites for Efficient and Selective Lignin Disassembly into Monolignol Derivatives

J Am Chem Soc. 2023 Jun 14;145(23):12884-12893. doi: 10.1021/jacs.3c04028. Epub 2023 May 30.

Authors

Ge Meng¹, Wu Lan², Lilong Zhang³, Shibin Wang⁴, Tanhao Zhang², Shuo Zhang², Ming Xu⁵, Yu Wang⁶, Jian Zhang¹, Fengxia Yue², Yulong Wu⁷, Dingsheng Wang⁸

Affiliations

¹ Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou 325035, China.
² State Key Laboratory of Pulp and Paper Engineering, School of Light Industry and Engineering, South China University of Technology, Guangzhou 510640, China.
³ College of Chemical Engineering, Nanjing Tech University, Nanjing, Jiangsu 211816, China.
⁴ Institute of Industrial Catalysis, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China.
⁵ State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
⁶ Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, 239 Zhangheng Road, Pudong New District, Shanghai 201204, China.
⁷ Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China.
⁸ Department of Chemistry, Tsinghua University, Beijing 100084, China.

PMID: 37249907
DOI: 10.1021/jacs.3c04028

Abstract

Lignin is the most abundant aromatic polymer from the natural and renewable lignocellulosic biomass resource. Developing highly efficient catalysts for lignin depolymerization to produce valuable monophenols with high yield and selectivity remains a desirable but challenging target in this field. Here, we design a synergistic catalyst combining atomically dispersed Mo centers and Al Lewis acid sites on a MgO substrate (Mo₁Al/MgO) for the depolymerization of Eucalyptus lignin via the β-aryl ether bond cleavage. A near-theoretical monophenol yield of 46% with an ultrahigh selectivity of 92% for coniferyl and sinapyl methyl ether, as well as good cycling durability, was achieved simultaneously by Mo₁Al/MgO in an inert N₂ atmosphere. First-principles calculations and control catalytic experiments confirmed the synergistic catalysis mechanism between Mo₁-O₅ single-atom centers and the neighboring Al Lewis acid sites with the participation of a methanol solvent. This study validates the feasibility of designing better-performing catalysts with synergistic multiactive sites for the efficient and selective disassembly of complex renewable biopolymers into highly value-added products with lower cost and greater security.