Mild selective oxidative cleavage of lignin C-C bonds over a copper catalyst in water

doi:10.1039/d1gc02102h

	Mild selective oxidative cleavage of lignin C-C bonds over a copper catalyst in water
	Hu, Yuzhen 2,3; Yan, Long 2; Zhao, Xuelai 4; Wang, Chenguang 2,4; Li, Song 2,3; Zhang, Xinghua 1,2; Ma, Longlong 1,2; Zhang, Qi 1,2
刊名	GREEN CHEMISTRY
	2021-08-04
页码	11
ISSN号	1463-9262
DOI	10.1039/d1gc02102h
通讯作者	Wang, Chenguang(wangcg@ms.giec.ac.cn) ; Zhang, Qi(zhangqi@ms.giec.ac.cn)
英文摘要	The conversion of lignin into aromatics as commodity chemicals and high-quality fuels is a highly desirable goal for biorefineries. However, the presence of robust inter-unit carbon-carbon (C-C) bonds in natural lignin seriously impedes this process. Herein, for the first time, we report the selective cleavage of C-C bonds in beta-O-4 and beta-1 linkages catalyzed by cheap copper and a base to yield aromatic acids and phenols in excellent yields in water at 30 degrees C under air without the need for additional complex ligands. Isotope-labeling experiments show that a base-mediated C-beta-H bond cleavage is the rate-determining step for C-alpha-C-beta bond cleavage. Density functional theory (DFT) calculations suggest that the oxidation of beta-O-4 ketone to a key intermediate, i.e., a peroxide, by copper and O-2 lowers the C-alpha-C-beta bond dissociation energy and facilitates its subsequent cleavage. In addition, the catalytic system could be successfully applied to the depolymerization of various authentic lignin feedstocks, affording excellent yields of aromatic compounds and high selectivity of a single monomer. This study offers the potential to economically produce aromatic chemicals from biomass.
资助项目	National Natural Science Foundation of China[51876209] ; National Key Research and Development Program of China[2018YFB1501504] ; Transformational Technologies for Clean Energy and Demonstration ; Strategic Priority Research Program of the Chinese Academy of Sciences[XDA21060102] ; Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program[2017BT01N092] ; Guangdong Special Support Plan Science and Technology Innovation Leader Project[2019TX05L362]
WOS关键词	MODEL COMPOUNDS ; VALUABLE CHEMICALS ; ALCOHOL OXIDATION ; MOLECULAR-OXYGEN ; DEPOLYMERIZATION ; ACID ; WOOD ; PYROLYSIS ; CELLULOSE ; HYDROGENOLYSIS
WOS研究方向	Chemistry ; Science & Technology - Other Topics
语种	英语
出版者	ROYAL SOC CHEMISTRY
WOS记录号	WOS:000686294100001
资助机构	National Natural Science Foundation of China ; National Key Research and Development Program of China ; Transformational Technologies for Clean Energy and Demonstration ; Strategic Priority Research Program of the Chinese Academy of Sciences ; Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program ; Guangdong Special Support Plan Science and Technology Innovation Leader Project
内容类型	期刊论文
源URL	[http://ir.giec.ac.cn/handle/344007/33642]
专题	中国科学院广州能源研究所
通讯作者	Wang, Chenguang; Zhang, Qi
作者单位	1.Southeast Univ, Sch Energy & Environm, Minist Educ, Key Lab Energy Thermal Convers & Control, Nanjing 210096, Jiangsu, Peoples R China 2.Chinese Acad Sci, Guangzhou Inst Energy Convers, CAS Key Lab Renewable Energy, Guangdong Prov Key Lab New & Renewable Energy Res, Guangzhou 510640, Guangdong, Peoples R China 3.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 4.Univ Sci & Technol China, Dept Thermal Sci & Energy Engn, Hefei 233022, Anhui, Peoples R China
推荐引用方式 GB/T 7714	Hu, Yuzhen,Yan, Long,Zhao, Xuelai,et al. Mild selective oxidative cleavage of lignin C-C bonds over a copper catalyst in water[J]. GREEN CHEMISTRY,2021:11.
APA	Hu, Yuzhen.,Yan, Long.,Zhao, Xuelai.,Wang, Chenguang.,Li, Song.,...&Zhang, Qi.(2021).Mild selective oxidative cleavage of lignin C-C bonds over a copper catalyst in water.GREEN CHEMISTRY,11.
MLA	Hu, Yuzhen,et al."Mild selective oxidative cleavage of lignin C-C bonds over a copper catalyst in water".GREEN CHEMISTRY (2021):11.