化学学报 ›› 2023, Vol. 81 ›› Issue (3): 239-245.DOI: 10.6023/A22120481 上一篇    下一篇

研究论文

原位合成氮掺杂石墨烯负载钯纳米颗粒用于催化香兰素高选择性加氢反应

徐斌a,b, 韦秀芝b,d, 孙江敏a,b, 刘建国c,*(), 马隆龙c,d,*()   

  1. a 中国科学技术大学 能源科学与技术学院 合肥 230026
    b 中国科学院广州能源研究所 可再生能源重点实验室 广州 510640
    c 东南大学 能源与环境学院 南京 210096
    d 中国科学技术大学 工程科学学院 合肥 230026
  • 投稿日期:2022-12-01 发布日期:2023-02-24
  • 基金资助:
    国家自然科学基金(51976225); 国家自然科学基金(52236010)

In-situ Synthesis of Nitrogen-doped Graphene Layer Encapsulated Palladium Nanoparticles for Highly Selective Hydrogenation of Vanillin

Bin Xua,b, Xiuzhi Weib,d, Jiangmin Suna,b, Jianguo Liuc(), Longlong Mac,d()   

  1. a School of Energy Science and Engineering, University of Science and Technology of China, Hefei 230026
    b CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Guangzhou 510640
    c School of Energy and Environment, Southeast University, Nanjing 210096
    d School of Engineering Science, University of Science and Technology of China, Hefei 230026
  • Received:2022-12-01 Published:2023-02-24
  • Contact: E-mail: liujg@seu.edu.cn; mall@seu.edu.cn; Tel.: 13172092043
  • Supported by:
    National Natural Science Foundation of China(51976225); National Natural Science Foundation of China(52236010)

通过原位合成法制备了氮掺杂石墨烯负载钯纳米颗粒催化剂Pd@N/C-2, 用于催化香兰素选择性加氢反应. 采用X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)等方法对Pd@N/C-2催化剂进行结构与性能的表征, 分析表明石墨烯层在活性钯纳米颗粒表面起到了保护作用, 提高了催化剂在反应条件下的稳定性, 在五次循环回收实验后催化剂仍保持很高的反应活性. 通过对石墨烯掺杂氮原子引入了催化反应的化学活性中心和金属纳米颗粒沉积的锚定中心, 从而使石墨烯在加氢催化反应中的性能得到进一步提高. 并且通过对溶剂的调控实现了香兰素分别高选择性生成香草醇和对甲基愈创木酚, 在优化的反应条件下, 香草醇和对甲基愈创木酚的产率分别为89%和99%.

关键词: 香兰素, 香草醇, 对甲基愈创木酚, 均相催化剂, 选择性加氢

As the only natural and sustainable carbon source, biomass shows great potential in solving current environmental and energy problems and creating a carbon-neutral society. Selective hydrogenation is a kind of important reaction. Various unsaturated functional groups in biomass are typical targets of selective hydrogenation. Therefore, selectivity is the key index to measure the efficiency of the hydrogenation reaction. Vanillin is an important platform compound in biomass conversion. In recent years, selective hydrogenation of vanillin to biofuels and other high-value-added chemicals has received widespread attention. Because vanillin has different reducible functional groups (aldehyde group, methoxy group, and hydroxyl group), it is very important to control the selectivity of vanillin hydrogenation. Vanillyl alcohol has long-lasting sweetness and nutty aromas and is used in the food and perfume industries. 2-Methoxy-4-methylphenol (MMP) is also an important biofuel. Therefore, selective hydrogenation of vanillin to vanillyl alcohol or MMP is an important synthesis route. Here, we propose a strategy to introduce the chemical active center of catalytic reaction and the anchoring center of metal nanoparticle deposition by doping nitrogen atoms of graphene, which makes the application of graphene in hydrogenation catalysis obtain better performance. In this work, we report a simple method for in-situ synthesis of nitrogen-doped graphene-supported palladium nanoparticles Pd@N/C-2 catalyst and its application in selective hydrogenation of the C=O bond. The prepared catalyst has good catalytic activity and product selectivity for the hydrogenation of vanillin and has the advantages of simple preparation, high activity and stable performance. It is easy to be separated from organic reaction conditions and can be reused many times. Under relatively mild reaction conditions, Pd@N/C-2 catalyzed the complete conversion of vanillin to vanillyl alcohol and MMP, and the yields were 89% and 99%, respectively. It is worth noting that through the regulation of solvents, we achieved highly selective hydrogenation of vanillin to vanillyl alcohol and MMP, respectively.

Key words: vanillin, vanillyl alcohol, 2-methoxy-4-methylphenol, homogeneous catalyst, selective hydrogenation