4.6 Article

CoZn/N-Doped porous carbon derived from bimetallic zeolite imidazolate framework/g-C3N4 for efficient hydrodeoxygenation of vanillin

Journal

CATALYSIS SCIENCE & TECHNOLOGY
Volume 12, Issue 16, Pages 5178-5188

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cy00642a

Keywords

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Funding

  1. National Natural Science Foundation of China [21878243, 22002120, 21908176]
  2. Key Research and Development Program of Shaanxi [2022GY-153]
  3. Natural Science Foundation of Chongqing, China [cstc2020jcyj-msxmX0750]
  4. Natural Science Foundation of Shanxi Province [2022JQ-115]
  5. Shaanxi Key Laboratory of Special Energy Chemistry and Materials [SPCF-SKL-2021-0013]
  6. Innovation and practice ability training project for postgraduates of Xi'an Shiyou University [YCS21111008]

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In this study, a promising non-noble Co-Zn/NPC catalyst for the hydrodeoxygenation (HDO) of vanillin was prepared by pyrolysis of Co-Zn zeolite imidazolate framework/graphitic carbon nitride composites. The catalyst showed full vanillin conversion with 99% MMP selectivity, with the presence of g-C3N4 promoting the formation of mesopores benefiting fast mass transfer. The introduction of Zn downsizes the size of Co nanoparticles, lowers the electron density around the Co atoms, and may function as a basic site to enhance the MMP selectivity.
The development of non-noble metal catalysts with high efficiency for the hydrodeoxygenation (HDO) of bio-oil is of great importance for the utilization of lignin biomass resources. As a crucial lignin-based platform chemical, vanillin is a promising candidate for the production of fine chemicals and polymers. Here, a promising non-noble Co-Zn/NPC catalyst (NPC: nitrogen-doped porous carbon materials) for the HDO of vanillin was prepared by pyrolysis of Co-Zn zeolite imidazolate framework/graphitic carbon nitride (Co-Zn-ZIF/g-C3N4) composites. Full vanillin conversion with 99% MMP (2-methoxy-4-methylphenol) selectivity could be achieved at 100 degrees C and 1 MPa H-2 over 4Co-1Zn/NPC. Characterization results indicate that the presence of g-C3N4 promotes the formation of mesopores, which is beneficial for fast mass transfer. Additionally, the introduction of Zn downsizes the size of Co nanoparticles, and lowers the electron density around the Co atoms in Co-Zn/NPC catalysts, which can accelerate the hydrogenation of vanillin. More importantly, the Zn introduced in the catalyst may function as a basic site to facilitate the conversion of the intermediate HMP (4-hydroxy-3-methoxybenzyl alcohol) into MMP, thus enhancing the MMP selectivity. Moreover, Co-Zn/NPC presents excellent stability in the HDO reaction of vanillin. This work provides some useful insights into the design of novel non-noble metal catalysts with high efficiency for HDO of bio-oil.

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