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Chlorine-Modified Ru/TiO2 Catalyst for Selective Guaiacol Hydrodeoxygenation

  • Xinchao Wang
    Xinchao Wang
    State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, PR China
    Jilin Province Key Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
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  • Peixuan Wu
    Peixuan Wu
    State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, PR China
    Jilin Province Key Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    More by Peixuan Wu
  • Zhuangqing Wang
    Zhuangqing Wang
    State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, PR China
    Jilin Province Key Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
  • Leilei Zhou
    Leilei Zhou
    State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, PR China
    Jilin Province Key Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    More by Leilei Zhou
  • Yanchun Liu
    Yanchun Liu
    State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    Jilin Province Key Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    Department of Chemistry, Northeast Normal University, Changchun 130024, PR China
    More by Yanchun Liu
  • Haiyang Cheng
    Haiyang Cheng
    State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    Jilin Province Key Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
  • Masahiko Arai
    Masahiko Arai
    State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    Jilin Province Key Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
  • Chao Zhang*
    Chao Zhang
    State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    Jilin Province Key Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    *Email: [email protected]. Phone: +86-431-85262410. Fax: +86-431-85262410.
    More by Chao Zhang
  • , and 
  • Fengyu Zhao*
    Fengyu Zhao
    State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, PR China
    Jilin Province Key Laboratory of Green Chemistry and Process, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
    *Email: [email protected]
    More by Fengyu Zhao
Cite this: ACS Sustainable Chem. Eng. 2021, 9, 8, 3083–3094
Publication Date (Web):February 15, 2021
https://doi.org/10.1021/acssuschemeng.0c07292
Copyright © 2021 American Chemical Society
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Abstract

The selective hydrodeoxygenation of lignin-derived guaiacol to value-added products, especially phenol, under relatively mild reaction conditions remains an important challenge. A Cl-modified Ru/TiO2 catalyst exhibited higher phenol selectivity compared with an unmodified one in the conversion of guaiacol in 1,4-dioxane at 240 °C and 1 MPa H2. Unlike Ru/TiO2, the modified catalyst exhibited a modest activity of demethoxylation producing phenol but an inferior ability of hydrogenation of its aromatic ring, resulting in much slower consumption of phenol. The Cl species were likely localized at the metal–support interface and on the surface of metal particles, and these modified both Ru and Ti species electronically. It is presumed that electron-enriched Ru inhibits the ring hydrogenation reaction, and the defects on the TiO2 surface promote the deoxygenation reaction.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.0c07292.

  • XRD patterns of catalysts, amount of H2 consumption derived from H2-TPR results, surface atomic ratios of catalysts, Cl 2p XPS profiles, EDS elemental mapping, amount of H2 desorption derived from H2-TPD results, results of guaiacol conversion over Ru/TiO2 and Ru/Cl/TiO2 [using Ru(acac)3 as a Ru precursor], Ru 3d XPS profiles and TEM images of Ru/TiO2 and Ru/Cl(x)/TiO2 catalysts prepared from the Ru(acac)3 precursor, reuse experiments of the catalyst, TEM images of the Rucoll/TiO2 catalyst and Rucoll/Cl/TiO2 catalyst, and the relationship between conversion and the reciprocal of particle size in guaiacol HDO (PDF)

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Cited By


This article is cited by 3 publications.

  1. Yaowen Zhang, Guoli Fan, Lan Yang, Lirong Zheng, Feng Li. Cooperative Effects between Ni-Mo Alloy Sites and Defective Structures over Hierarchical Ni-Mo Bimetallic Catalysts Enable the Enhanced Hydrodeoxygenation Activity. ACS Sustainable Chemistry & Engineering 2021, 9 (34) , 11604-11615. https://doi.org/10.1021/acssuschemeng.1c04762
  2. Z. Moravvej, F. Farshchi Tabrizi, M. R. Rahimpour. Vapor Phase Conversion of Furfural to Valuable Biofuel and Chemicals Over Alumina-Supported Catalysts: Screening Catalysts. Topics in Catalysis 2021, 15 https://doi.org/10.1007/s11244-021-01470-9
  3. Binbin Jin, Xin Ye, Heng Zhong, Fangming Jin, Yun Hang Hu. Enhanced photocatalytic CO2 hydrogenation with wide-spectrum utilization over black TiO2 supported catalyst. Chinese Chemical Letters 2021, 10 https://doi.org/10.1016/j.cclet.2021.07.046