Selective production of arenes via direct lignin upgrading over a niobium-based catalyst

Yi Shao; Qineng Xia; Lin Dong; Xiaohui Liu; Xue Han; Stewart F. Parker; Yongqiang Cheng; Luke L. Daemen; Anibal J. Ramirez-Cuesta; Sihai Yang; Yanqin Wang

doi:10.1038/ncomms16104

Selective production of arenes via direct lignin upgrading over a niobium-based catalyst

Yi Shao, Qineng Xia, Lin Dong, Xiaohui Liu, Xue Han, Stewart F. Parker, Yongqiang Cheng, Luke L. Daemen, Anibal J. Ramirez-Cuesta, Sihai Yang, Yanqin Wang

Research output: Contribution to journal › Article › peer-review

388 Scopus citations

Abstract

Lignin is the only large-volume renewable source of aromatic chemicals. Efficient depolymerization and deoxygenation of lignin while retaining the aromatic functionality are attractive but extremely challenging. Here we report the selective production of arenes via direct hydrodeoxygenation of organosolv lignin over a porous Ru/Nb₂O₅ catalyst that enabled the complete removal of the oxygen content from lignin. The conversion of birch lignin to monomer C₇-C₉ hydrocarbons is nearly quantitative based on its monomer content, with a total mass yield of 35.5 wt% and an exceptional arene selectivity of 71 wt%. Inelastic neutron scattering and DFT calculations confirm that the Nb₂O₅ support is catalytically unique compared with other traditional oxide supports, and the disassociation energy of C_aromatic-OH bonds in phenolics is significantly reduced upon adsorption on Nb₂O₅, resulting in its distinct selectivity to arenes. This one-pot process provides a promising approach for improved lignin valorization with general applicability.

Original language	English
Article number	16104
Journal	Nature Communications
Volume	8
DOIs	https://doi.org/10.1038/ncomms16104
State	Published - Jul 24 2017

Funding

This project was financially supported by the National Natural Science Foundation of China (No. 91545103 21603072 and 21403065), the Science and Technology Commission of Shanghai Municipality (10dz2220500), the Fundamental Research Funds for the Central Universities (No. 222201718003), University of Manchester and the EPSRC (EP/P011632/1) in the United Kingdom. We are especially grateful to the Oak Ridge National Laboratory for access to Beamline VISION (supported by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy) and to Science and Technology Facilities Council (STFC) and the ISIS Neutron Facility for access to the Beamlines TOSCA. We thank Drs Pedro Duarte-Vaz and Svemir Rudić for help at TOSCA. Computing resources were provided by STFC e-Science facility (time on the SCARF cluster for the CASTEP calculations) and by the VirtuES (Virtual Experiments in Spectroscopy) and ICE-MAN (Integrated Computational Environment-Modeling & Analysis for Neutrons) projects, funded by Laboratory Directed Research and Development program at the Oak Ridge National Laboratory.

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title = "Selective production of arenes via direct lignin upgrading over a niobium-based catalyst",

abstract = "Lignin is the only large-volume renewable source of aromatic chemicals. Efficient depolymerization and deoxygenation of lignin while retaining the aromatic functionality are attractive but extremely challenging. Here we report the selective production of arenes via direct hydrodeoxygenation of organosolv lignin over a porous Ru/Nb2O5 catalyst that enabled the complete removal of the oxygen content from lignin. The conversion of birch lignin to monomer C7-C9 hydrocarbons is nearly quantitative based on its monomer content, with a total mass yield of 35.5 wt% and an exceptional arene selectivity of 71 wt%. Inelastic neutron scattering and DFT calculations confirm that the Nb2O5 support is catalytically unique compared with other traditional oxide supports, and the disassociation energy of Caromatic-OH bonds in phenolics is significantly reduced upon adsorption on Nb2O5, resulting in its distinct selectivity to arenes. This one-pot process provides a promising approach for improved lignin valorization with general applicability.",

author = "Yi Shao and Qineng Xia and Lin Dong and Xiaohui Liu and Xue Han and Parker, {Stewart F.} and Yongqiang Cheng and Daemen, {Luke L.} and Ramirez-Cuesta, {Anibal J.} and Sihai Yang and Yanqin Wang",

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AU - Shao, Yi

AU - Xia, Qineng

AU - Dong, Lin

AU - Liu, Xiaohui

AU - Han, Xue

AU - Parker, Stewart F.

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Ramirez-Cuesta, Anibal J.

AU - Yang, Sihai

AU - Wang, Yanqin

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N2 - Lignin is the only large-volume renewable source of aromatic chemicals. Efficient depolymerization and deoxygenation of lignin while retaining the aromatic functionality are attractive but extremely challenging. Here we report the selective production of arenes via direct hydrodeoxygenation of organosolv lignin over a porous Ru/Nb2O5 catalyst that enabled the complete removal of the oxygen content from lignin. The conversion of birch lignin to monomer C7-C9 hydrocarbons is nearly quantitative based on its monomer content, with a total mass yield of 35.5 wt% and an exceptional arene selectivity of 71 wt%. Inelastic neutron scattering and DFT calculations confirm that the Nb2O5 support is catalytically unique compared with other traditional oxide supports, and the disassociation energy of Caromatic-OH bonds in phenolics is significantly reduced upon adsorption on Nb2O5, resulting in its distinct selectivity to arenes. This one-pot process provides a promising approach for improved lignin valorization with general applicability.

AB - Lignin is the only large-volume renewable source of aromatic chemicals. Efficient depolymerization and deoxygenation of lignin while retaining the aromatic functionality are attractive but extremely challenging. Here we report the selective production of arenes via direct hydrodeoxygenation of organosolv lignin over a porous Ru/Nb2O5 catalyst that enabled the complete removal of the oxygen content from lignin. The conversion of birch lignin to monomer C7-C9 hydrocarbons is nearly quantitative based on its monomer content, with a total mass yield of 35.5 wt% and an exceptional arene selectivity of 71 wt%. Inelastic neutron scattering and DFT calculations confirm that the Nb2O5 support is catalytically unique compared with other traditional oxide supports, and the disassociation energy of Caromatic-OH bonds in phenolics is significantly reduced upon adsorption on Nb2O5, resulting in its distinct selectivity to arenes. This one-pot process provides a promising approach for improved lignin valorization with general applicability.

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Selective production of arenes via direct lignin upgrading over a niobium-based catalyst

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