波谱学杂志 ›› 2022, Vol. 39 ›› Issue (2): 133-143.doi: 10.11938/cjmr20212952

• 研究论文 • 上一篇    下一篇

Pd-Sn双金属催化剂催化1, 3-丁二烯加氢反应的仲氢诱导极化研究

胡涵1,2,王伟宇1,徐君1,*(),邓风1   

  1. 1. 中国科学院精密测量科学与技术创新研究院, 波谱与原子分子物理国家重点实验室, 武汉磁共振中心, 湖北 武汉 430071
    2. 中国科学院大学, 北京 100049
  • 收稿日期:2021-10-29 出版日期:2022-06-05 发布日期:2022-05-28
  • 通讯作者: 徐君 E-mail:xujun@wipm.ac.cn
  • 基金资助:
    国家自然科学基金(21902181);国家自然科学基金(U1932218);国家自然科学基金(21733013);国家自然科学基金(22061130202);国家自然科学基金(21872170);湖北省自然科学基金(2021CFA021)

1, 3-Butadienen Hydrogenation on Supported Pd-Sn Bimetallic Catalysts Investigated by Parahydrogen-induced Polarization

Han HU1,2,Wei-yu WANG1,Jun XU1,*(),Feng DENG1   

  1. 1. State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China
    2. University of Chinese Academy of Sciences, Beijing 100049, China
  • Received:2021-10-29 Online:2022-06-05 Published:2022-05-28
  • Contact: Jun XU E-mail:xujun@wipm.ac.cn

摘要:

本文首先利用等体积共浸渍法合成了一系列Pd/Sn比(原子比)不同的Pd1-Snx/Al2O3双金属催化剂,然后通过多相催化仲氢诱导极化(PHIP)技术研究了Pd-Sn/Al2O3双金属催化剂上1, 3-丁二烯选择性加氢反应.结果发现催化剂的Pd/Sn比会影响1, 3-丁二烯反应活性和丁烯选择性:随着Pd/Sn比的下降,反应中1, 3-丁二烯转化率降低,丁烯选择性提高.利用PASADENA(parahydrogen and synthesis allow for dramatically enhanced nuclear alignment)技术,发现Pd/Sn比的变化影响了1-丁烯与2-丁烯之间的异构化过程:随着Pd/Sn比的下降,1-丁烯异构化率降低,这是由于Sn组分含量的提高减少了表面暴露的Pd组分,使得催化剂反应活性降低;Sn组分含量的提高同时导致了Pd电子密度的上升,使得选择性还原产物丁烯更易脱附,阻止其进一步加氢生成丁烷,并抑制了1-丁烯异构化反应过程.

关键词: 1,3-丁二烯加氢反应, 双金属催化剂, 核磁共振(NMR), 异构化过程, 仲氢诱导极化(PHIP)

Abstract:

The selective hydrogenation of 1, 3-butadiene over Pd-Sn/Al2O3 bimetallic catalysts was investigated by heterogeneous parahydrogen-induced polarization (PHIP). A series of Pd1-Snx/Al2O3 bimetallic catalysts with different Pd/Sn ratios were synthesized by incipient wetness co-impregnation method. It was observed that the Pd/Sn ratios of the catalysts had a significant effect on the reaction activity of 1, 3-butadiene and the selectivity to butene. A monotonic decrease of reaction conversion was observed as the Pd/Sn ratio decreased, while the selectivity to butene showed an opposite trend. This can be attributed to the ensemble effect and the ligand effect caused by the increasing tin component content: as the Pd/Sn ratio decreases, less palladium component was exposed on the surface, leading to low activity. The electronic properties of the Pd atoms were altered, which led to a weaker adsorption strength of the semi-hydrogenation product butene and an increased selectivity. Smaller Pd ensembles were exposed on Sn-rich catalysts surface, which favored a higher ratio of pairwise addition process, leading to a stronger PHIP effect. The isomerization measurements by PASADENA (parahydrogen and synthesis allow for dramatically enhanced nuclear alignment) showed that the isomerization process between 1-butene and 2-butene decreased with the increase of Sn content. This can be accounted for by the easier desorption of 1-butene on Sn-rich catalysts.

Key words: 1,3-butadiene hydrogenation, bimetallic catalyst, nuclear magnetic resonance (NMR), isomerization process, parahydrogen-induced polarization (PHIP)

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