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TEMPO-Functionalized Silica as an Efficient and Recyclable Oxidation Catalyst for Conversion of a Lignin Model Compound to Value-Added Products

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Abstract

Catalytic oxidation of a lignin model compound, vanillyl alcohol (VAL), to vanillin (VN), is a promising process for valorizing lignin-based biomass. As research interests in oxidation of alcohols are concentrated on direct usage of O2, 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) has been developed as an oxidation catalyst which can be mediated by O2 to cyclically oxidize alcohols. However, as recover of homogeneous TEMPO from reaction media could be an issue, it is necessary to develop a recyclable heterogeneous TEMPO for VAL oxidation. In the present study, a particular heterogeneous TEMPO is fabricated via a simple condensation of OH-TEMPO and tetraethyl orthosilicate to insert TEMPO functional groups into SiO2 matrices. The resulting composite of TEMPO@SiO2 is then employed for the first time for oxidation of VAL to VN. By incorporation with a co-catalyst, Cu+, TEMPO@SiO2/Cu+ successfully and selectively converts VAL to VN, and the corresponding conversion efficiency reaches CVAL = 96% with SVN = 96.5 and YVN = 92.6%. Such a superior conversion efficiency is achieved conveniently at ambient temperature within 30 min, demonstrating that TEMPO@SiO2 is not only a highly active catalyst but also a sustainable oxidation catalyst. The optimum condition of TEMPO@SiO2/Cu+ is 7.5 g/L of TEMPO@SiO2 and 5 g/L of Cu salt. TEMPO@SiO2 can be also reused over multiple cycles for VAL conversion to VN with a stably high selectivity for VN. These features validate that TEMPO@SiO2 is indeed a promising, highly-selective and efficient heterogeneous catalyst for valorization of VAL, the lignin model compound, to the target product, VN.

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Authors and Affiliations

  1. Department of Environmental Engineering & Innovation and Development Center of Sustainable Agriculture & Research Center of Sustainable Energy and Nanotechnology, National Chung Hsing University, 250 Kuo-Kuang Road, Taichung, Taiwan

    Meng-Wei Zheng & Kun-Yi Andrew Lin

  2. Department of Biotechnology, National Formosa University, Yunlin, 63208, Taiwan

    Chia-Hua Lin

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Zheng, MW., Lin, KY.A. & Lin, CH. TEMPO-Functionalized Silica as an Efficient and Recyclable Oxidation Catalyst for Conversion of a Lignin Model Compound to Value-Added Products. Waste Biomass Valor 11, 6917–6928 (2020). https://doi.org/10.1007/s12649-019-00910-8

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