Cargando…
Selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts
Selective hydrogenolysis of the C(aryl)–O bonds in lignin is a key strategy for the generation of fuels and chemical feedstocks from biomass. Currently, hydrogenolysis has been mainly conducted using hydrogen, which is flammable and not sustainable or economical. Herein, an external hydrogen-free pr...
Autores principales: | , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2019
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6482439/ https://www.ncbi.nlm.nih.gov/pubmed/31057773 http://dx.doi.org/10.1039/c9sc00691e |
_version_ | 1783413885141778432 |
---|---|
author | Jiang, Liang Guo, Haiwei Li, Changzhi Zhou, Peng Zhang, Zehui |
author_facet | Jiang, Liang Guo, Haiwei Li, Changzhi Zhou, Peng Zhang, Zehui |
author_sort | Jiang, Liang |
collection | PubMed |
description | Selective hydrogenolysis of the C(aryl)–O bonds in lignin is a key strategy for the generation of fuels and chemical feedstocks from biomass. Currently, hydrogenolysis has been mainly conducted using hydrogen, which is flammable and not sustainable or economical. Herein, an external hydrogen-free process for aryl ethers hydrogenolysis in lignin models and dioxasolv lignin over nickel nanoparticles supported on Al(2)O(3), is reported. Kinetic studies reveal that the transfer hydrogenolysis activity of the three model compounds decreased in the following order: benzyl phenyl ether (α-O-4), 2-phenylethyl phenyl ether (β-O-4) and diphenyl ether (4-O-5), which linearly corresponds to their binding energies and the activation energies. The main reaction route for the three model compounds was the cleavage of the ether bonds to produce aromatic alkanes and phenol, and the latter was further reduced to cyclohexanol. Dioxasolv lignin depolymerization results exhibit a significant C(aryl)–O decrease over the Ni nanoparticles supported on Al(2)O(3) with iso-propanol as the hydrogen source through 2D-HSQC-NMR analysis, which confirmed the transfer hydrogenolysis conclusion in the model study. This work provides an economical and environmentally-friendly method for the selective cleavage of lignin and lignin model compounds into value-added chemicals. |
format | Online Article Text |
id | pubmed-6482439 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-64824392019-05-03 Selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts Jiang, Liang Guo, Haiwei Li, Changzhi Zhou, Peng Zhang, Zehui Chem Sci Chemistry Selective hydrogenolysis of the C(aryl)–O bonds in lignin is a key strategy for the generation of fuels and chemical feedstocks from biomass. Currently, hydrogenolysis has been mainly conducted using hydrogen, which is flammable and not sustainable or economical. Herein, an external hydrogen-free process for aryl ethers hydrogenolysis in lignin models and dioxasolv lignin over nickel nanoparticles supported on Al(2)O(3), is reported. Kinetic studies reveal that the transfer hydrogenolysis activity of the three model compounds decreased in the following order: benzyl phenyl ether (α-O-4), 2-phenylethyl phenyl ether (β-O-4) and diphenyl ether (4-O-5), which linearly corresponds to their binding energies and the activation energies. The main reaction route for the three model compounds was the cleavage of the ether bonds to produce aromatic alkanes and phenol, and the latter was further reduced to cyclohexanol. Dioxasolv lignin depolymerization results exhibit a significant C(aryl)–O decrease over the Ni nanoparticles supported on Al(2)O(3) with iso-propanol as the hydrogen source through 2D-HSQC-NMR analysis, which confirmed the transfer hydrogenolysis conclusion in the model study. This work provides an economical and environmentally-friendly method for the selective cleavage of lignin and lignin model compounds into value-added chemicals. Royal Society of Chemistry 2019-03-21 /pmc/articles/PMC6482439/ /pubmed/31057773 http://dx.doi.org/10.1039/c9sc00691e Text en This journal is © The Royal Society of Chemistry 2019 http://creativecommons.org/licenses/by-nc/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported Licence (CC BY-NC 3.0) |
spellingShingle | Chemistry Jiang, Liang Guo, Haiwei Li, Changzhi Zhou, Peng Zhang, Zehui Selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts |
title | Selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts
|
title_full | Selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts
|
title_fullStr | Selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts
|
title_full_unstemmed | Selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts
|
title_short | Selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts
|
title_sort | selective cleavage of lignin and lignin model compounds without external hydrogen, catalyzed by heterogeneous nickel catalysts |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6482439/ https://www.ncbi.nlm.nih.gov/pubmed/31057773 http://dx.doi.org/10.1039/c9sc00691e |
work_keys_str_mv | AT jiangliang selectivecleavageofligninandligninmodelcompoundswithoutexternalhydrogencatalyzedbyheterogeneousnickelcatalysts AT guohaiwei selectivecleavageofligninandligninmodelcompoundswithoutexternalhydrogencatalyzedbyheterogeneousnickelcatalysts AT lichangzhi selectivecleavageofligninandligninmodelcompoundswithoutexternalhydrogencatalyzedbyheterogeneousnickelcatalysts AT zhoupeng selectivecleavageofligninandligninmodelcompoundswithoutexternalhydrogencatalyzedbyheterogeneousnickelcatalysts AT zhangzehui selectivecleavageofligninandligninmodelcompoundswithoutexternalhydrogencatalyzedbyheterogeneousnickelcatalysts |