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Cleavage of the lignin beta-O-4 ether bond via a dehydroxylation-hydrogenation strategy over a NiMo sulfide catalyst
Zhang, Chaofeng1,2; Lu, Jianmin1; Zhang, Xiaochen1; MacArthur, Katherine3,4; Heggen, Marc3,4; Li, Hongji1,2; Wang, Feng1
刊名GREEN CHEMISTRY
2016
DOI10.1039/c6gc01456a
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
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
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.
语种英语
WOS记录号WOS:000389341800015
引用统计
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/150425
专题中国科学院大连化学物理研究所
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
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GB/T 7714
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.
APA Zhang, Chaofeng.,Lu, Jianmin.,Zhang, Xiaochen.,MacArthur, Katherine.,Heggen, Marc.,...&Wang, Feng.(2016).Cleavage of the lignin beta-O-4 ether bond via a dehydroxylation-hydrogenation strategy over a NiMo sulfide catalyst.GREEN CHEMISTRY,18(24),6545-6555.
MLA Zhang, Chaofeng,et al."Cleavage of the lignin beta-O-4 ether bond via a dehydroxylation-hydrogenation strategy over a NiMo sulfide catalyst".GREEN CHEMISTRY 18.24(2016):6545-6555.
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