化工进展 ›› 2022, Vol. 41 ›› Issue (8): 4181-4191.DOI: 10.16085/j.issn.1000-6613.2021-2161

• 工业催化 • 上一篇    下一篇

水热法制备3D花球状Bi2SiO5及其光催化油酸酯化反应

常耀萍(), 官修帅, 郑谦, 靳山彪, 张长明, 张小超()   

  1. 太原理工大学化学化工学院,山西 太原 030024
  • 收稿日期:2021-10-21 修回日期:2022-02-26 出版日期:2022-08-25 发布日期:2022-08-22
  • 通讯作者: 张小超
  • 作者简介:常耀萍(1996—),女,硕士研究生,研究方向为太阳能光催化材料及其应用。E-mail:1351150871@qq.com
  • 基金资助:
    国家自然科学基金(21978196);中国博士后基金(2020M672825)

Hydrothermal preparation of 3D flower-spherical Bi2SiO5 for photocatalytic esterification of oleic acid

CHANG Yaoping(), GUAN Xiushuai, ZHENG Qian, JIN Shanbiao, ZHANG Changming, ZHANG Xiaochao()   

  1. College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
  • Received:2021-10-21 Revised:2022-02-26 Online:2022-08-25 Published:2022-08-22
  • Contact: ZHANG Xiaochao

摘要:

化石燃料资源的枯竭和环境污染等问题,使寻找生物燃料等可持续、可再生能源成为世界关注的焦点。本文通过简单水热法制备3D花球状Bi2SiO5,并用于在模拟太阳光照射下油酸与甲醇的光催化酯化反应。为了解Bi2SiO5催化剂的物理、化学和光学性质,采用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、高分辨率透射电子显微镜(HRTEM)、氨-程序升温脱附(NH3-TPD)和紫外-可见漫反射光谱(UV-vis DRS)对其进行表征,且通过傅里叶变换红外光谱(FTIR)分析反应产物成分组成。酯化反应产物油酸甲酯的产率通过1H NMR进行定量分析,计算过程简单、结果精确可靠。在模拟太阳光照射下,最优反应条件为:醇油比为12∶1、催化剂用量为5%(质量分数)、反应温度为70℃、光照反应时间为6h,油酸甲酯产率为28.8%。核磁共振氢谱(1H NMR)分析结果显示油酸甲酯选择性高达100%,且催化剂循环3次后油酸甲酯产率仍可达26.8%,稳定性强。电子自旋共振(ESR)测试表明,Bi2SiO5光催化酯化反应过程中存在羟基自由基(·OH)和超氧基自由基(·O2-)。基于Bi2SiO5首次用于光催化酯化反应,为解释其具有催化活性的原因,提出了其光催化酯化反应机理。

关键词: 油酸, 油酸甲酯, 光催化酯化反应, 反应机理, 氢核磁共振

Abstract:

The fossil fuel depletion and environmental pollution have made the search for sustainable and renewable energy sources (e.g. biofuels) become a world focus. In this paper, 3D flower-spherical Bi2SiO5 was prepared via a simple hydrothermal method and used for the photocatalytic esterification of oleic acid with methanol under simulated sunlight irradiation. To understand the physical, chemical and optical properties of Bi2SiO5 catalyst, the as-prepared samples were characterized by XRD, XPS, SEM, HRTEM, NH3-TPD and UV-vis DRS, and the compositions of reaction products were analyzed by FTIR. The yield of methyl oleate as the esterification product was quantified by 1H NMR, due to the simple calculation and accurate and reliable results. Under simulated sunlight irradiation, the optimum reaction conditions were 12:1 alcohol to oil ratio, 5% catalyst, 70℃ and 6h, under which the yield of methyl oleate was 28.8%. The 1H NMR analysis showed that the selectivity of methyl oleate was as high as 100% and the yield of methyl oleate was still 26.8% after three recycles of catalyst. ESR tests confirmed the existence of hydroxyl radical (·OH) and superoxide radical (·O2-) in the reaction. As the first application of Bi2SiO5 in photocatalytic esterification, a possible reaction mechanism was proposed to explain the relative catalytic activity.

Key words: oleic acid, methyl oleate, photocatalytic esterification reaction, reaction mechanism, 1H nuclear magnetic resonance spectra (1H NMR)

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