Zhang Guangpu, Gou Bingwang, Yang Yanpeng, Liu Meng, Li Xiaojiang, Xiao Lei, Hao Gazi, Zhao Fengqi, Jiang Wei
National Special Superfine Powder Engineering Research Center of China, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China.
Science and Technology on Combustion and Explosion Laboratory, Xi'an Modern Chemistry Research Institute, Xi'an 710065, China.
ACS Omega. 2020 Dec 11;5(50):32667-32676. doi: 10.1021/acsomega.0c05050. eCollection 2020 Dec 22.
In this present article, we reported a facile and efficient milling method to prepare a series of CuO/PbO nanocomposite metal oxides (CuO/PbO NMOs), with CuO/PbO molar ratios of 1:2, 1:1, 1:0.5, and 1:0.25 as a potential catalyst to catalyze the thermal decomposition of ammonium perchlorate (AP). The obtained CuO/PbO NMOs were systematically characterized. X-ray diffraction (XRD), X-ray energy-dispersive spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS) analyses showed that the characteristic peaks of CuO/PbO NMOs were almost the superposition of nano CuO and nano PbO, while few new weak peaks were observed resulting from the lattice defects and new structural arrangements and chemical bonds between nano CuO and nano PbO during a high-energy grinding process. Scanning electron microscopy (SEM) and transition electron microscopy (TEM) observations exhibited that the particle sizes of the CuO/PbO NMOs were distributed in the range of 10-20 nm. Thermogravimetric (TG) analysis coupled with differential scanning calorimetric (DSC) techniques verified that CuO/PbO NMOs with a CuO/PbO molar ratio of 1:1 presented the best catalytic effect for AP thermal decomposition among the other CuO/PbO NMOs, as well as the single nano CuO and nano PbO. The outstanding catalytic performance is mainly reflected as follows: shifting the peak temperature of AP in high-temperature decomposition stages from 441.3 to 347.6 °C, increasing the decomposition heat of AP from 941 to 1711 J/g, and decreasing the Gibbs free energy of AP from 199.8 to 172.1 kJ/mol, supporting the existence of a synergistic catalytic effect between nano CuO and nano PbO.
在本文中，我们报道了一种简便高效的球磨方法来制备一系列氧化铜/氧化铅纳米复合金属氧化物（CuO/PbO NMOs），其氧化铜/氧化铅摩尔比分别为1:2、1:1、1:0.5和1:0.25，作为催化高氯酸铵（AP）热分解的潜在催化剂。对所制备的CuO/PbO NMOs进行了系统表征。X射线衍射（XRD）、X射线能谱（EDS）和X射线光电子能谱（XPS）分析表明，CuO/PbO NMOs的特征峰几乎是纳米CuO和纳米PbO的叠加，而在高能研磨过程中，由于纳米CuO与纳米PbO之间的晶格缺陷、新的结构排列和化学键，观察到了一些新的弱峰。扫描电子显微镜（SEM）和透射电子显微镜（TEM）观察表明，CuO/PbO NMOs的粒径分布在10-20nm范围内。热重（TG）分析结合差示扫描量热（DSC）技术证实，在其他CuO/PbO NMOs以及单一纳米CuO和纳米PbO中，氧化铜/氧化铅摩尔比为1:1的CuO/PbO NMOs对AP热分解具有最佳催化效果。其优异的催化性能主要体现在以下方面：将AP高温分解阶段的峰值温度从441.3℃降至347.6℃，将AP的分解热从941J/g提高到1711J/g，并将AP的吉布斯自由能从199.8kJ/mol降低到172.1kJ/mol，这支持了纳米CuO和纳米PbO之间存在协同催化作用。
