ZrO2/生物炭纳米复合物催化转移氢化制备γ-戊内酯

doi:10.19894/j.issn.1000-0518.210106

摘要/Abstract

摘要： γ-戊内酯(GVL)是重要的生物质基平台化合物。通过催化转移氢化反应将乙酰丙酸转化为GVL是生物质转化领域的重要反应。本实验利用具有多级孔道结构的生物炭(BC)作为载体、氯氧化锆为前驱体,通过溶胶水热反应,制备了一种ZrO₂/生物炭纳米复合物,利用红外光谱(FT-IR)、拉曼光谱(Raman)、比表面分析(BET)、粉末X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和光电子能谱(XPS)等技术手段对其结构进行了表征,并研究了该复合物催化转移氢化乙酰丙酸制备GVL的能力。结果表明,生物炭载体自身所具有的高比表面积和多级孔道结构,能够促进纳米ZrO₂颗粒稳定分散。在Zr⁴⁺物种和生物炭载体协同作用下,ZrO₂/BC纳米复合物表现出优异的催化转移氢化活性,能够在温和条件下,快速、高效地将乙酰丙酸转化为GVL。在最优化反应条件下,乙酰丙酸的转化率最高达94.8%,GVL选择性最高达87.5%。此外,该复合物可通过过滤回收,循环使用5次后仍然能够保持较好的催化活性。

关键词: 催化转移氢化, 乙酰丙酸, γ-戊内酯, ZrO₂/生物炭纳米复合物

Abstract: Catalytic transfer hydrogenation (CTH) of biomass-derived levulinic acid (LA) to γ-valerolactone (GVL) has attracted much interest in the field of biomass transformation. Herein, a novel ZrO₂-biochar composite was developed and served as an available catalyst for LA conversion into GVL via a Meerwein-Ponndorf-Verley (MPV) reaction, known as the typical CTH process. The catalyst was prepared by a sol-hydrothermal method, and its structure was characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption-desorption, energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FT-IR) spectroscopy. It is found that the high surface area and hierarchical structure of biochar matrix facilitates the dispersion of the zirconium oxide active species on it, and the catalytic activity for LA conversion is further promoted in the presence of isopropanol as hydrogen donors. The effects of catalyst loading, reaction temperature and time are examined, and the highest LA conversion reaches 94.8% with 87.5% GVL selectivity at 150 ℃ for 16 h with the catalyst loading of 19.8%. Afterwards, the catalysts are collected by centrifugation and reused for five times without the obvious loss of activity. Therefore, this eco-friendly catalyst is favorable for efficient transformation from LA to GVL due to its merits of cost-effectiveness and easy availability.

Key words: Catalyst transfer hydrogenation, Levulinic acid, γ-Valerolactone, Zirconium oxide, Biochar support

中图分类号:

O643.3

张奇峰, 张振杰, 刘梦影, 潘剑, 禹兴海. ZrO₂/生物炭纳米复合物催化转移氢化制备γ-戊内酯[J]. 应用化学, 2021, 38(12): 1621-1631.

ZHANG Qi-Feng, ZHANG Zheng-Jie, LIU Meng-Ying, PAN Jian, YU Xing-Hai. Facile and Efficient Conversion of Levulinic Acid to γ-Valerolactone over ZrO₂-Biochar Nanocomposite Through Catalytic Transfer Hydrogenation[J]. Chinese Journal of Applied Chemistry, 2021, 38(12): 1621-1631.

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ZrO₂/生物炭纳米复合物催化转移氢化制备γ-戊内酯

Facile and Efficient Conversion of Levulinic Acid to γ-Valerolactone over ZrO₂-Biochar Nanocomposite Through Catalytic Transfer Hydrogenation

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