Cleavage of the lignin beta-O-4 ether bond via a dehydroxylation-hydrogenation strategy over a NiMo sulfide catalyst
文献类型：期刊论文
| 作者 | MacArthur, Katherine3,4; Heggen, Marc3,4; Zhang, Chaofeng1,2; Lu, Jianmin1; Zhang, Xiaochen1; Li, Hongji1,2; Wang, Feng1 |
| 刊名 | GREEN CHEMISTRY
 |
| 出版日期 | 2016 |
| 卷号 | 18期号:24页码:6545-6555 |
| 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. |
| 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 |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000389341800015 |
| 源URL | [http://cas-ir.dicp.ac.cn/handle/321008/150425]  |
| 专题 | 大连化学物理研究所_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 |
| 推荐引用方式 GB/T 7714 | MacArthur, Katherine,Heggen, Marc,Zhang, Chaofeng,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 | MacArthur, Katherine.,Heggen, Marc.,Zhang, Chaofeng.,Lu, Jianmin.,Zhang, Xiaochen.,...&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 | MacArthur, Katherine,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. |
入库方式： OAI收割
来源：大连化学物理研究所
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