物理化学学报 >> 2016, Vol. 32 >> Issue (8): 2093-2100.doi: 10.3866/PKU.WHXB201605121

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多孔纳米CoFe2O4的制备及其对高氯酸铵的热分解催化性能

熊文慧,张文超*(),俞春培,沈瑞琪,程佳,叶家海,秦志春   

  • 收稿日期:2016-02-01 发布日期:2016-07-29
  • 通讯作者: 张文超 E-mail:zhangwenchao303@aliyun.com
  • 基金资助:
    国家自然科学基金(51576101);江苏省自然科学基金(BK20141399);中央高校基本科研业务费专项资金(30915012101)

Preparation of Nanoporous CoFe2O4 and Its Catalytic Performance during the Thermal Decomposition of Ammonium Perchlorate

Wen-Hui XIONG,Wen-Chao ZHANG*(),Chun-Pei YU,Rui-Qi SHEN,Jia CHENG,Jia-Hai YE,Zhi-Chun QIN   

  • Received:2016-02-01 Published:2016-07-29
  • Contact: Wen-Chao ZHANG E-mail:zhangwenchao303@aliyun.com
  • Supported by:
    the National Natural Science Foundation of China(51576101);Natural Science Foundation of Jiangsu Province, China(BK20141399);Fundamental Research Funds for the Central Universities, China(30915012101)

摘要:

采用胶晶模板法制备出具有三维多孔结构的纳米CoFe2O4。利用X射线衍射仪(XRD)、傅里叶变换红外(FT-IR)光谱仪、扫描电镜(SEM)、透射电镜(TEM)和N2吸附-脱附对样品的晶型和形貌结构等进行表征,采用差示扫描量热法(DSC)对比研究多孔纳米CoFe2O4和球形纳米CoFe2O4对高氯酸铵(AP)的热分解性能的影响,并考察这两种催化剂对AP催化热分解的动力学参数。结果显示,制备出的多孔纳米CoFe2O4样品具有典型的尖晶石结构,孔径约200 nm;比表面积明显高于40 nm球形CoFe2O4,达到55.646 m2·g-1。DSC测试结果表明:多孔纳米CoFe2O4的加入促进了AP的热分解,最高使AP的高温分解峰温降低91.46℃,能量释放最高达1120.88 J·g-1,是纯AP分解放热量的2.3倍;多孔纳米CoFe2O4具有较高的比表面积,能提高催化反应的接触面积,使AP的高温分解峰温度更低,反应活化能较小,从而表现出比球形纳米CoFe2O4更高的催化活性。此外,对多孔纳米CoFe2O4催化AP的热分解机理进行初步探索,纳米多孔催化剂对气态中间产物的作用促进了AP的热分解。

关键词: 胶晶模板, 多孔纳米CoFe2O4, 高氯酸铵, 热分解, 催化

Abstract:

Three-dimensional, nanoporous CoFe2O4 catalysts were synthesized, employing a colloidal crystal template method. X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and N2 adsorption-desorption were subsequently used to characterize the crystal structures and morphologies of the samples. The catalytic activities of nanoporous CoFe2O4 and CoFe2O4 nanospheres during the thermal decomposition of ammonium perchlorate (AP) were also investigated by differential scanning calorimetry (DSC). The results show that the spinel framework of these materials has an ordered open network of pores averaging 200 nm in diameter. The specific surface area of the nanoporous CoFe2O4 was 55.646 m2·g-1, a value that was higher than that of the nanosphere material. DSC analysis indicates that the catalytic activity of the nanoporous CoFe2O4 is superior to that of the spherical material during the thermal decomposition of AP, and that the nanoporous catalyst makes the peak temperature of high temperature decomposition decrease by 91.46℃. The heat release from the AP in the presence of nanoporous CoFe2O4 (1120.88 J·g-1) is 2.3 times that obtained frompureAP. Both the higher specific surface area and greater quantity of active reduction sites on the nanoporous CoFe2O4 relative to the nanosphere material act to reduce the activation energy during the AP decomposition process. Based on the results of this work, a possible catalytic mechanismfor the thermal decomposition of AP over nanoporous CoFe2O4 is proposed, in which gaseous intermediates play an important role.

Key words: Colloidal crystal template, Nanoporous CoFe2O4, Ammonium perchlorate, Thermal decomposition, Catalysis

MSC2000: 

  • O643