物理化学学报 >> 2015, Vol. 31 >> Issue (1): 137-144.doi: 10.3866/PKU.WHXB201411171

催化和表面科学 上一篇    下一篇

金属有机骨架材料负载镍纳米颗粒催化硝基苯加氢

姜俊, 李钢, 孔令浩   

  1. 大连理工大学化工学院, 精细化工国家重点实验室, 辽宁 大连 116024
  • 收稿日期:2014-09-17 修回日期:2014-11-14 发布日期:2014-12-25
  • 通讯作者: 李钢 E-mail:liganghg@dlut.edu.cn
  • 基金资助:

    国家重点基础研究发展规划项目(973) (2011CB201301)资助

Hydrogenation of Nitrobenzene Catalyzed by Metal-Organic Framework-Supported Ni Nanoparticles

JIANG Jun, LI Gang, KONG Ling-Hao   

  1. State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning Province, P. R. China
  • Received:2014-09-17 Revised:2014-11-14 Published:2014-12-25
  • Contact: LI Gang E-mail:liganghg@dlut.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Programof China (973) (2011CB201301).

摘要:

以MIL-53(Al)、MIL-96(Al)和MIL-120(Al) (MIL: Material Institute of Lavorisier)三种金属有机骨架材料为载体, 采用浸渍法制备了负载廉价金属镍纳米颗粒的催化剂. 将其用于催化硝基苯加氢合成苯胺反应, 发现以MIL-53(Al)为载体制得的催化剂表现出优异的催化性能. 采用不同的镍前驱体, 如硝酸镍、醋酸镍、乙二胺合镍, 制备了一系列Ni/MIL-53(Al)催化剂. 通过X射线衍射、傅里叶变换红外光谱、电感耦合等离子体、N2物理吸附、H2程序升温还原、透射电镜等技术对其进行了表征, 研究了镍前驱体对金属-载体相互作用、镍颗粒尺寸以及分散程度的影响.结果表明:以乙二胺合镍为镍前驱体制得的催化剂具有金属-载体相互作用适中、镍纳米颗粒更小(4-5 nm)和分布更均匀的特点, 在硝基苯加氢反应中表现出优异的催化性能, 硝基苯转化率达到100%.回收重复使用5次后, 此催化剂仍保持催化活性,硝基苯转化率达92%.

关键词: 金属有机骨架材料, 镍, 载体, 前驱体, 硝基苯加氢

Abstract:

The metal-organic frameworks (MOFs), MIL-53(Al), MIL-96(Al), and MIL-120(Al) (MIL: Material Institute of Lavorisier) were synthesized and used as supports, to incorporate low-cost Ni nanoparticles (NPs) by wet impregnation. The samples were used as catalysts in the hydrogenation of nitrobenzene to aniline. The catalyst prepared with MIL- 53(Al) as a support exhibited excellent catalytic performance. Ni/MIL- 53(Al) heterogeneous catalysts were prepared using nickel nitrate, nickel acetate, and nickel ethanediamine as precursors. Characterization by powder X-ray diffraction, Fourier-transforminfrared spectroscopy, inductively coupled plasma spectroscopy, N2 sorption measurements, H2-temperature programmed reduction, and transmission electron microscopy showed that the Ni precursor affected the metal-support interaction, Ni particle size and particle distribution. The catalyst prepared using nickel ethanediamine possessed moderate metalsupport interactions, smaller Ni nanoparticles (4-5 nm), and a high Ni distribution. This resulted in its superior catalytic activity, with 100% conversion of nitrobenzene in the hydrogenation. The Ni/MIL-53(Al) catalyst retained its catalytic activity after five cycles, and exhibited a nitrobenzene conversion of ~92%.

Key words: Metal-organic framework, Nickel, Support, Precursor, Nitrobenzene hydrogenation

MSC2000: 

  • O643