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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.

Authors:
 [1];  [1];  [1];  [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [4]; ORCiD logo [4];  [2]; ORCiD logo [1]
  1. East China University of Science and Technology, Shanghai (China). Shanghai Key Laboratory of Functional Materials Chemistry, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering
  2. Univ. of Manchester (United Kingdom). School of Chemistry
  3. Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab., ISIS Facility
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). The Chemical and Engineering Materials Division (CEMD), Neutron Sciences Directorate
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1422566
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Shao, Yi, Xia, Qineng, Dong, Lin, Liu, Xiaohui, Han, Xue, Parker, Stewart F., Cheng, Yongqiang, Daemen, Luke L., Ramirez-Cuesta, Anibal J., Yang, Sihai, and Wang, Yanqin. Selective production of arenes via direct lignin upgrading over a niobium-based catalyst. United States: N. p., 2017. Web. doi:10.1038/ncomms16104.
Shao, Yi, Xia, Qineng, Dong, Lin, Liu, Xiaohui, Han, Xue, Parker, Stewart F., Cheng, Yongqiang, Daemen, Luke L., Ramirez-Cuesta, Anibal J., Yang, Sihai, & Wang, Yanqin. Selective production of arenes via direct lignin upgrading over a niobium-based catalyst. United States. doi:10.1038/ncomms16104.
Shao, Yi, Xia, Qineng, Dong, Lin, Liu, Xiaohui, Han, Xue, Parker, Stewart F., Cheng, Yongqiang, Daemen, Luke L., Ramirez-Cuesta, Anibal J., Yang, Sihai, and Wang, Yanqin. Mon . "Selective production of arenes via direct lignin upgrading over a niobium-based catalyst". United States. doi:10.1038/ncomms16104. https://www.osti.gov/servlets/purl/1422566.
@article{osti_1422566,
title = {Selective production of arenes via direct lignin upgrading over a niobium-based catalyst},
author = {Shao, Yi and Xia, Qineng and Dong, Lin and Liu, Xiaohui and Han, Xue and Parker, Stewart F. and Cheng, Yongqiang and Daemen, Luke L. and Ramirez-Cuesta, Anibal J. and Yang, Sihai and Wang, Yanqin},
abstractNote = {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.},
doi = {10.1038/ncomms16104},
journal = {Nature Communications},
number = ,
volume = 8,
place = {United States},
year = {2017},
month = {7}
}

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    Works referencing / citing this record:

    Economic feasibility of gasoline production from lignocellulosic wastes in Hong Kong
    journal, December 2019


    Lignin Valorizations with Ni Catalysts for Renewable Chemicals and Fuels Productions
    journal, May 2019


    Selective production of indane and its derivatives from lignin over a modified niobium-based catalyst
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