催化学报 ›› 2015, Vol. 36 ›› Issue (8): 1358-1364.DOI: 10.1016/S1872-2067(15)60854-3

• 论文 • 上一篇    下一篇

氧化铜修饰羟基磷灰石负载金对醇类需氧氧化的双金属协同催化

田涛, 刘英, 张勋高   

  1. 武汉大学化学与分子科学学院, 湖北武汉430072
  • 收稿日期:2015-02-10 修回日期:2015-03-27 出版日期:2015-07-29 发布日期:2015-07-30
  • 通讯作者: 张勋高
  • 基金资助:

    湖北省自然科学基金(2013CFB291).

Bimetallic synergistic Au/CuO-hydroxyapatite catalyst for aerobic oxidation of alcohols

Tao Tian, Ying Liu, Xungao Zhang   

  1. College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, Hubei, China
  • Received:2015-02-10 Revised:2015-03-27 Online:2015-07-29 Published:2015-07-30
  • Supported by:

    This work was supported by Natural Science Foundation of Hebei Province of China (2013CFB291).

摘要:

采用均匀沉积-沉淀法制备了氧化铜修饰羟基磷灰石负载金催化剂(Au/CuO-HAP), 并用原子吸收光谱、N2吸附脱附、X射线粉末衍射、透射电镜和X射线光电子能谱等方法对催化剂结构和形貌进行了表征. 考察了催化剂对醇类液相需氧氧化的催化性能. 与单金属Au/HAP或CuO-HAP相比较, 双金属Au/CuO-HAP对苯甲醇氧化的催化活性和苯甲醛的选择性有显著提高, 120 ℃反应1.5 h, 苯甲醇的转化率和苯甲醛的选择性分别达到99.7%和98.4%. 在Au/CuO-HAP的催化下, 其它类型的芳香醇均可高选择性转化为相应的醛或酮. Au/CuO-HAP催化剂有很好的稳定性和可回收性, 4次回收后, 其催化活性没有明显变化.

关键词: 多相催化, 金-铜双金属催化剂, 醇类的需氧氧化, 羟基磷灰石, 重复使用性

Abstract:

A catalyst consisting of Au supported on copper oxide-modified hydroxyapatite (Au/CuO-HAP) was prepared using a homogeneous deposition-precipitation method. The catalyst was characterized using atomic absorption spectrometry, N2 adsorption-desorption, powder X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The catalytic performance in liquid-phase aerobic oxidation of alcohols was investigated. The catalytic activity and benzaldehyde selectivity in benzyl alcohol oxidation with the bimetallic Au/CuO-HAP catalyst were significantly better than those with monometallic Au/HAP and CuO-HAP catalysts. The conversion of benzyl alcohol and selectivity for benzaldehyde at 120 ℃ for 1.5 h under aerobic oxidation conditions were 99.7% and 98.4%, respectively. Various aromatic alcohols were selectively converted to their corresponding aldehydes or ketones over Au/CuO-HAP. The Au/CuO-HAP catalyst could be reused at least four times without loss of activity.

Key words: Heterogeneous catalysis, Gold-copper bimetallic catalyst, Aerobic oxidation of alcohols, Hydroxyapatite, Reusability