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题名: Cleavage of the lignin beta-O-4 ether bond via a dehydroxylation-hydrogenation strategy over a NiMo sulfide catalyst
作者: Zhang, Chaofeng1, 2;  Lu, Jianmin1;  Zhang, Xiaochen1;  MacArthur, Katherine3, 4;  Heggen, Marc3, 4;  Li, Hongji1, 2;  Wang, Feng1
刊名: GREEN CHEMISTRY
发表日期: 2016
DOI: 10.1039/c6gc01456a
卷: 18, 期:24, 页:6545-6555
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Multidisciplinary
英文摘要: The efficient cleavage of lignin beta-O-4 ether bonds to produce aromatics is a challenging and attractive topic. Recently a growing number of studies have revealed that the initial oxidation of C alpha HOH to C alpha=O can decrease the beta-O-4 bond dissociation energy (BDE) from 274.0 kJ mol(-1) to 227.8 kJ mol(-1), and thus the beta-O-4 bond is more readily cleaved in the subsequent transfer hydrogenation, or acidolysis. Here we show that the first reaction step, except in the above-mentioned pre-oxidation methods, can be a C-alpha-OH bond dehydroxylation to form a radical intermediate on the acid-redox site of a NiMo sulfide catalyst. The formation of a C-alpha radical greatly decreases the C-beta-OPh BDE from 274.0 kJ mol(-1) to 66.9 kJ mol(-1) thereby facilitating its cleavage to styrene, phenols and ethers with H-2 and an alcohol solvent. This is supported by control experiments using several reaction intermediates as reactants, analysis of product generation and by radical trap with TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) as well as by density functional theory (DFT) calculations. The dehydroxylation-hydrogenation reaction is conducted under non-oxidative conditions, which are beneficial for stabilizing phenol products.
关键词[WOS]: C-O BONDS ;  HETEROGENEOUS NICKEL-CATALYSTS ;  MOLYBDENUM CARBIDE CATALYST ;  MODEL COMPOUNDS ;  ARYL ETHERS ;  KRAFT LIGNIN ;  SELECTIVE OXIDATION ;  VALUABLE CHEMICALS ;  ORGANOSOLV LIGNIN ;  PHENOLIC MONOMERS
语种: 英语
WOS记录号: WOS:000389341800015
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/150425
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian Natl Lab Clean Energy, State Key Lab Catalysis, Dalian 116023, Peoples R China
2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
3.Forschungszentrum Juelich, Ernst Ruska Ctr Microscopy & Spect Electrons, D-52425 Julich, Germany
4.Forschungszentrum Juelich, Peter Grunberg Inst, D-52425 Julich, Germany

Recommended Citation:
Zhang, Chaofeng,Lu, Jianmin,Zhang, Xiaochen,et al. Cleavage of the lignin beta-O-4 ether bond via a dehydroxylation-hydrogenation strategy over a NiMo sulfide catalyst[J]. GREEN CHEMISTRY,2016,18(24):6545-6555.
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