物理化学学报 >> 2014, Vol. 30 >> Issue (8): 1527-1534.doi: 10.3866/PKU.WHXB201406121

催化和表面科学 上一篇    下一篇

不同载体对负载型氧化钨催化剂在己二酸合成反应中的结构及性能影响

张召艳1, 祝全敬1, 丁靖1, 戴维林1, 宗保宁2   

  1. 1. 复旦大学化学系, 上海市分子催化和功能材料重点实验室, 上海 200433;
    2. 中国石化石油化工科学研究院, 催化材料与反应工程国家重点实验室, 北京 100083
  • 收稿日期:2014-04-14 修回日期:2014-06-12 发布日期:2014-07-18
  • 通讯作者: 戴维林 E-mail:wldai@fudan.edu.cn
  • 基金资助:

    国家重点基础研究发展规划项目（973）（2012CB224804），国家自然科学基金（21173052，21373054），石油化工催化材料与反应工程国家重点实验室（中国石油化工股份有限公司石油化工科学研究院）开放基金课题及上海市科委科技基金（08DZ2270500）资助

Effect of Support on the Structural Evolution and Catalytic Performance of WO3-Supported Catalysts in the Synthesis of Adipic Acid

ZHANG Zhao-Yan1, ZHU Quan-Jing1, DING Jing1, DAI Wei-Lin1, ZONG Bao-Ning2   

  1. 1. Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, P. R. China;
    2. State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, China Petroleum & Chemical Corporation, Beijing 100083, P. R. China
  • Received:2014-04-14 Revised:2014-06-12 Published:2014-07-18
  • Contact: DAI Wei-Lin E-mail:wldai@fudan.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (973) (2012CB224804), National Natural Science Foundation of China (21173052, 21373054), State Key Laboratory of Catalytic Materials and Reaction Engineering, China (RIPP, SINOPEC), and Science and Technology Commission of Shanghai Municipality, China (08DZ2270500).

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摘要：

以SBA-15、六角介孔二氧化硅（HMS）和SnO2为载体，通过浸渍法合成了含钨负载型催化剂，并考察了三种催化剂在环氧环己烷选择氧化制备己二酸反应中的催化性能. 通过X射线衍射（XRD），透射电镜/场发射透射电镜（TEM/FETEM），紫外-可见漫反射光谱（UV-Vis DRS），拉曼（Raman）光谱，X射线光电子能谱（XPS）以及傅里叶变换红外（FTIR）光谱等手段对各种催化剂的结构进行表征. 结果表明，载体与催化剂的性能有密切的关系. 以SnO2为载体的WO3/SnO2催化剂活性最高，其次是WO3/HMS催化剂，WO3/SBA-15 催化剂的活性最差.XRD 分析显示WO3/SnO2催化剂中氧化钨物种的晶化程度最低，TEM 和XPS 结果表明氧化钨物种在WO3/SnO2催化剂表面高度分散并且粒径尺寸很小（约2 nm），UV-Vis DRS结果表明在WO3/SnO2催化剂中存在孤立[WO4]四面体和低聚态的钨物种，这些物种的存在可能是WO3/SnO2催化剂具有高活性的主要原因. 此外，WO3/SnO2催化剂可以重复使用多次，6 次反应后己二酸（AA）得率仍然保持在80%以上，说明氧化钨物种与SnO2载体间存在强烈的相互作用，从而提高了催化剂的稳定性.

关键词: 三氧化钨, SBA-15, HMS, 二氧化锡, 己二酸, 高分散性

Abstract:

A series of tungsten-based catalysts were synthesized via a traditional impregnation method using SBA-15, hexagonal mesoporous silica (HMS), and SnO2 as the support. The supported catalysts were characterized by X-ray powder diffraction (XRD), transmission electron microscopy/field-emission transmission electron microscopy (TEM/FETEM), UV-Vis diffuse reflection spectroscopy (UV-Vis DRS), Raman spectrometry, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared (FTIR) spectroscopy. It was found that the support was crucial to the dispersion and nature of the tungsten species on the catalyst. In this study, the catalytic performances of catalysts with different supports were investigated for the synthesis of adipic acid (AA) from the selective oxidation of cyclohexene oxide. The excellent catalytic performance of the catalyst was obtained over WO3/SnO2, followed by WO3/HMS and WO3/SBA-15. The XRD results indicate that the degree of crystallinity of the tungsten species of WO3/SnO2 catalyst was low and the particle size of WO3 was small (~2 nm). TEM and XPS results imply a high dispersion of tungsten species on the SnO2 support. The UV-Vis DRS spectra demonstrate the existence of [WO4] and low-polymeric tungsten species. In addition, the W-based catalyst with SnO2 as the support could retain high activity, even after being reused six times, suggesting that there is strong interaction between tungsten species and the SnO2-support that enhanced the stability of the catalyst. This shows the potential of the WO3/SnO2 as a catalyst for the synthesis of adipic acid.

Key words: Tungsten oxide, SBA-15, HMS, Tin oxide, Adipic acid, High dispersion