物理化学学报 >> 2015, Vol. 31 >> Issue (12): 2366-2374.doi: 10.3866/PKU.WHXB201510141

催化和表面科学 上一篇    下一篇

电化学合成Cu3(BTC)2-MOF及用于NH3选择性催化还原NO

刘震震,石勇*(),李春艳,肇启东,李新勇   

  • 收稿日期:2015-07-14 发布日期:2015-12-04
  • 通讯作者: 石勇 E-mail:sys-99@163.com
  • 基金资助:
    国家重点基础研究发展规划项目(973)(2011CB936002);国家自然科学基金(51178076);中央高校基本科研业务费专项基金(DUT14LK17)

Electrochemical Synthesis of Cu3(BTC)2-MOF for Selective Catalytic Reduction of NO with NH3

Zhen-Zhen. LIU,Yong. SHI*(),Chun-Yan. LI,Qi-Dong. ZHAO,Xin-Yong. LI   

  • Received:2015-07-14 Published:2015-12-04
  • Contact: Yong. SHI E-mail:sys-99@163.com
  • Supported by:
    the National Key Basic Research Program of China (973)(2011CB936002);National Natural Science Foundation ofChina(51178076);Fundamental Research Funds for the Central Universities, China(DUT14LK17)

摘要:

采用电化学方法合成Cu3(BTC)2-MOF (Cu3(BTC)2:均苯三甲酸合铜; MOF:金属有机框架化合物)催化剂并首次用于去除氮氧化物(NOx)的氨法选择催化还原(SCR)反应,通过优化溶剂、电解液浓度、电压、电解时间等反应条件,制备出纯净、晶型结构良好的Cu3(BTC)2材料,产率高达97.2%.应用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、热重分析(TGA)、Raman光谱、原位傅里叶变换红外(in-situ FTIR)光谱、程序升温脱附(TPD)、X射线光电子能谱(XPS)等手段对催化剂的物理化学性能进行了表征,热重测试表明催化剂在310℃下可以保持良好的热稳定.应用于NH3-SCR反应,发现活化温度对Cu3(BTC)2的催化性能有很大影响,经240℃活化的Cu3(BTC)2的催化性能最佳,其220-280℃温度窗口下的NO转化率为90%,并用in-situ FTIR技术对NH3-SCR的反应机理进行了探究.

关键词: 电化学合成, Cu3(BTC)2, 金属有机框架化合物, 一氧化氮, 氨法选择性催化还原

Abstract:

A Cu3(BTC)2 (copper(Ⅱ) benzene 1, 3, 5-tricarboxylate) metal organic framework (MOF) catalyst was successfully prepared through an electrochemical route and used for selective catalytic reduction of nitrogen oxide (NOx) with NH3 for the first time. After systematically optimizing the reaction conditions such as solvents, voltage, electrolyte concentration, and reaction time, pure Cu3(BTC)2 with high crystallinity was obtained in 97.2% yield. The physicochemical properties of the catalyst were determined using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Raman spectroscopy, in situ Fourier transform infrared (FTIR) spectroscopy, temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). TGA results indicated that the framework was stable up to 310℃. The catalytic activity of Cu3(BTC)2 was evaluated using NO conversion as a model reaction. The Cu3(BTC)2 activation temperature significantly affected the catalytic activity. The Cu3(BTC)2 sample activated at 240℃ had the best catalytic activity and gave NO conversion of 90% at 220-280℃. A reaction mechanism was proposed based on the in situ FTIR spectroscopy results.

Key words: Electrochemical synthesis, Cu3(BTC)2, Metal-organic framework, NO, NH3-selective catalytic reduction

MSC2000: 

  • O643