Construction of Three-Dimensional Hematite/Graphene with Effective Catalytic Activity for the Thermal Decomposition of CL-20

Citation: Zhang Ting, Li Cuicui, Wang Wei, Guo Zhaoqi, Pang Aimin, Ma Haixia. Construction of Three-Dimensional Hematite/Graphene with Effective Catalytic Activity for the Thermal Decomposition of CL-20[J]. Acta Physico-Chimica Sinica, 2020, 36(6): 1905048-0. doi: 10.3866/PKU.WHXB201905048 shu

三维氧化铁/石墨烯的构建及其对CL-20的热分解性能的影响

张婷 ^1,2, ,
李翠翠 ^1, ,
王伟 ^2, ,
郭兆琦 ^1, ,
庞爱民 ^{2,
,} ,
马海霞 ^{1,
,}

1.
西北大学化工学院，西安 710069
2.
湖北航天化学技术研究所，航天化学动力技术重点实验室，湖北襄阳 441003

通讯作者: 庞爱民, ppam@tom.com
马海霞, mahx@nwu.edu.cn

基金项目:
国家自然科学基金 21673179

航天化学动力技术重点实验室基金 STACPL320181B03-2

国家自然科学基金(21673179, 21373161), 航天化学动力技术重点实验室基金(STACPL320181B03-2)项目资助

国家自然科学基金 21373161

摘要: 首先采用水热法合成了两种不同形貌的氧化铁(棒状rFe₂O₃和颗粒状pFe₂O₃)，然后采用界面自组装法制备了两种具备高比表面积和三维网状结构的氧化铁与石墨烯的复合物(rFe₂O₃/G和pFe₂O₃/G)。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电镜(TEM)和X射线光电子能谱(XPS)对样品的相态、组成及结构性质进行确证。根据热重-红外联用分析(TGA-IR)和差式扫描量热法(DSC)测试对所制备的催化剂对CL-20的催化热分解活性进行评估。通过逻辑选择法对Cl-20、Fe₂O₃/Cl-20和Fe₂O₃/G/CL-20的非等温热分解动力学进行系统研究发现，其均遵循相同的机理函数模型。对比分析表明，棒状氧化铁/石墨烯复合物(rFe₂O₃/G)对CL-20的热分解表现出最佳的催化活性。以rFe₂O₃及rFe₂O₃/G为样本，研究其对CL-20撞击感度的影响。测试结果表明，rFe₂O₃/G比rFe₂O₃更能有效降低Cl-20的撞击感度。综合分析可知，rFe₂O₃与石墨烯的结合不仅能够促进Cl-20的热分解，且能同时提高Cl-20的安全性能。

关键词:

English

Construction of Three-Dimensional Hematite/Graphene with Effective Catalytic Activity for the Thermal Decomposition of CL-20

Zhang Ting ^1,2, ,
Li Cuicui ^1, ,
Wang Wei ^2, ,
Guo Zhaoqi ^1, ,
Pang Aimin ^{2,
,} ,
Ma Haixia ^{1,
,}

1.
School of Chemical Engineering, Northwest University, Xi'an 710069, P. R. China
2.
Science and Technology on Aerospace Chemical Power Laboratory, Hubei Institute of Aerospace Chemotechnology, Xiangyang 441003, Hubei Province, P. R. China

Corresponding author: Pang Aimin, ppam@tom.com Ma Haixia, mahx@nwu.edu.cn

Received Date: 13 May 2019
Accepted Date: 11 June 2019
Revised Date: 10 June 2019
Available Online: 15 June 2020
Fund Project:
the National Natural Science Foundation of China 21673179

Open Research Fund Program of Science and Technology on Aerospace Chemical Power Laboratory STACPL320181B03-2

The project was supported by the National Natural Science Foundation of China (21673179, 21373161), Open Research Fund Program of Science and Technology on Aerospace Chemical Power Laboratory (STACPL320181B03-2)

the National Natural Science Foundation of China 21373161

Abstract: High-performance solid propellants are very important for the development of modern weapons. Aside from their high energy and high burning rate, safety performance is regarded as the most important factor that should be considered whenever a new solid propellant recipe is formulated. Therefore, exploring a new type of combustion catalyst that can improve both catalytic activity and reduce the sensitivity of the energetic component is significant. Traditionally, transition metals or metal oxides are used as a combustion catalyst for accelerating the thermal decomposition of energetic components. However, the existing problem of these catalysts is the aggregation of particles accompanied by poor surface area. Coupling metal oxides with graphene is a promising approach to obtain a binary composite with stable structure and large specific surface area. In this work, rod-like and granular Fe₂O₃ nanoparticles were synthesized using a hydrothermal method. Then, the two as-prepared Fe₂O₃ nanoparticles were coupled with graphene sheets using an interfacial self-assembly method, which can effectively prevent the aggregation of Fe₂O₃ particles and simultaneously increase the active sites that participate in the reaction. X-ray diffraction and X-ray photoelectron spectroscopy were used to identify the phase states and chemical compositions of the prepared samples. The morphology and internal structures were further demonstrated through scanning electron microscopy, transmission electron microscopy and nitrogen adsorption-desorption tests. Both phase analysis and structure identification indicate that the prepared Fe₂O₃/G has high purity and high surface area. The catalytic performance of the prepared Fe₂O₃ and Fe₂O₃/G in the thermal decomposition of hexanitrohexaazaisowurtzitane (CL-20) was evaluated based on thermal gravimetric analysis-infrared spectroscopy (TGA-IR) and differential scanning calorimetry (DSC) tests. The non-isothermal decomposition kinetics of CL-20, Fe₂O₃/CL-20, and Fe₂O₃/G/CL-20 were further studied by DSC. The results reveal the excellent catalytic activity of Fe₂O₃/G in the thermal decomposition of CL-20, which is attributed to the presence of abundant pore structure and large surface area. The reaction mechanisms of the exothermic decomposition process of CL-20, Fe₂O₃/CL-20, and Fe₂O₃/G/CL-20 were obtained by the logical choice method, and the composites all followed same mechanism function model as CL-20. Through comparison, the rod-like Fe₂O₃ coupled with graphene was found to have the best catalytic activity in the thermal decomposition of CL-20. Thus, the rod-like Fe₂O₃ and its Fe₂O₃/G composite were used to investigate their influence on the impact sensitivity of CL-20 by fall hammer apparatus. The results show that rFe₂O₃/G can effectively decrease the impact sensitivity of CL-20 compared with pure CL-20 and rFe₂O₃/CL-20. Therefore, rFe₂O₃ coupled with graphene not only promotes the thermal decomposition but also improves the safety performance of CL-20.

Key words:

1. [1]
  Lan, Y. F.; Li, X. Y.; Li, G. P.; Luo, Y. J. J. Nanopart. Res. 2015, 17, 395. doi: 10.1007/s11051-015-3200-5 doi: 10.1007/s11051-015-3200-5
2. [2]
  Zou, Y. Q.; Kan, J.; Wang, Y. J. Phys. Chem. C 2011, 115, 20747. doi: 10.1021/jp206876t doi: 10.1021/jp206876t
3. [3]
  Han, S. C.; Hu, L. F.; Liang, Z. P.; Wageh, S.; Al-Ghamdi, A. A.; Chen, Y. S.; Fang, X. S. Adv. Funct. Mater. 2015, 24, 5719. doi: 10.1002/adfm.201401279 doi: 10.1002/adfm.201401279
4. [4]
  Yan, N.; Qin, L. J.; Hao, H. X.; Hui, L. F.; Zhao, F. Q.; Feng, H. Appl. Surf. Sci. 2017, 408, 51. doi: 10.1016/j.apsusc.2017.02.169 doi: 10.1016/j.apsusc.2017.02.169
5. [5]
  Chen, Y.; Ma, K. F.; Wang, J. X.; Gao, Y.; Zhu, X. F.; Zhang, W. C. Mater. Res. Bull. 2018, 101, 56. doi: 10.1016/j.materresbull.2018.01.013 doi: 10.1016/j.materresbull.2018.01.013
6. [6]
  Wei, Z. X.; Xu, Y. Q.; Liu, H. Y.; Hu, C. W. J. Hazard. Mater. 2009, 165, 1056. doi: 10.1016/j.jhazmat.2008.10.086 doi: 10.1016/j.jhazmat.2008.10.086
7. [7]
  Yan, Q. L.; Zhao, F. Q.; Kuo, K. K.; Zhang, X. H.; Zeman, S.; DeLuca. L. T. Prog. Energ. Combust. 2016, 57, 75. doi: 10.1016/j.pecs.2016.08.002 doi: 10.1016/j.pecs.2016.08.002
8. [8]
  胡耀娟, 金娟, 张卉, 吴萍, 蔡称心.物理化学学报, 2010, 26, 2073.doi: 10.3866/PKU.WHXB20100812Hu, Y. J.; Jin, J.; Zhang, H.; Wu, P.; Cai, C. X. Acta Phys. -Chim. Sin. 2010, 26, 2073. doi: 10.3866/PKU.WHXB20100812
9. [9]
  Yan, N.; Qin, L. J.; Li, J. G.; Zhao, F. Q.; Feng, H. Appl. Surf. Sci. 2018, 451, 155. doi: 10.1016/j.apsusc.2018.04.247 doi: 10.1016/j.apsusc.2018.04.247
10. [10]
  Li, Z. M.; Wang, Y.; Zhang, Y. Q.; Liu, L.; Zhang, S. RSC Adv. 2015, 5, 98925. doi: 10.1039/c5ra16228a doi: 10.1039/c5ra16228a
11. [11]
  Smeu, M.; Zahid, F.; Ji, W.; Guo, H.; Jaidann, M.; Abou-Rachid, H. J. Phys. Chem. C 2011, 115, 10985. doi: 10.1021/jp201756p doi: 10.1021/jp201756p
12. [12]
  Turcotte, R.; Vachon, M.; Kwok, Q. S. M.; Wang, R. P.; Jones, D. E. G. Thermochim. Acta 2005, 433, 105. doi: 10.1016/j.tca.2005.02.021 doi: 10.1016/j.tca.2005.02.021
13. [13]
  Sivabalan, R.; Gore, G. M.; Nair, U. R.; Saikia, A.; Venugopalan, S.; Gandhe, B. R. J. Hazard. Mater. 2007, 139, 199. doi: 10.1016/j.jhazmat.2006.06.027 doi: 10.1016/j.jhazmat.2006.06.027
14. [14]
  Ayoman, E.; Hosseini, S. G. J. Therm. Anal. Calorim. 2016, 123, 1213. doi: 10.1007/s10973-015-5059-1 doi: 10.1007/s10973-015-5059-1
15. [15]
  Liu, B.; Wang, W. M.; Wang, J. J.; Zhang, Y.; Xu, K. Z.; Zhao, F. Q. J. Nanopart. Res. 2019, 21, 48. doi:10.1007/s11051-019-4493-6 doi: 10.1007/s11051-019-4493-6
16. [16]
  Hu, X. L.; Liao, X.; Xiao, L. Q.; Jian, X. X.; Zhou, W. L. Propell. Explos. Pyrot. 2016, 40, 867. doi: 10.1002/prep.201500046 doi: 10.1002/prep.201500046
17. [17]
  Wei, Z. X.; Xu, Y. Q.; Liu, H. Y.; Hu, C. W. J. Hazard. Mater. 2009, 165, 1056. doi: 10.1016/j.jhazmat.2008.10.086 doi: 10.1016/j.jhazmat.2008.10.086
18. [18]
  Zhang, T.; Zhao, N. N.; Li, J. C.; Gong, H. J.; An, T.; Zhao, F. Q.; Ma, H. X. RSC Adv. 2017, 7, 23583. doi: 10.1039/c6ra28502c doi: 10.1039/c6ra28502c
19. [19]
  Li, S. Z.; Zhang, H.; Wu, J. B.; Ma, X. Y.; Yang, D. Cryst. Growth Des. 2006, 6, 351. doi: 10.1021/cg0495835 doi: 10.1021/cg0495835
20. [20]
  Guo, L. L.; Kou, X. Y.; Ding, M. D.; Wang, C.; Dong, L. L.; Zhang, H.; Feng, C. H.; Sun, Y. F.; Gao, Y.; Sun, P.; et al. Sensor Actuat. B-Chem. 2017, 244, 233. doi: 10.1016/j.snb.2016.12.137 doi: 10.1016/j.snb.2016.12.137
21. [21]
  Pang, M. J.; Long, G. H.; Jiang, S.; Ji, Y.; Han, W.; Wang, B.; Liu, X. L.; Xi, Y. L.; Wang, D. X.; Xu, F. Z. Chem. Eng. J. 2015, 280, 377. doi: 10.1016/j.cej.2015.06.053 doi: 10.1016/j.cej.2015.06.053
22. [22]
  Xue, L.; Zhao, F. Q.; Hu, R. Z.; Gao, H. X. J. Energ. Mater. 2010, 28, 17. doi: 10.1080/07370650903124518 doi: 10.1080/07370650903124518
23. [23]
  Zhao, N. N.; Li, J. C.; Gong, H. J.; An, T.; Zhao, F. Q.; Yang, A. W.; Hu, R. Z.; Ma, H. X. J. Anal. Appl. Pyrol. 2016, 120, 165. doi: 10.1016/j.jaap.2016.05.002 doi: 10.1016/j.jaap.2016.05.002
24. [24]
  Vyazovkin, S.; Dollimore, D. J. Chem. Inf. Comput. Sci. 1996, 36, 42. doi: 10.1021/ci950062m doi: 10.1021/ci950062m
25. [25]
  Ma, H. X.; Yan, B.; Ren, Y. H.; Guan, Y. L.; Zhao, F. Q.; Song, J. R.; Hu, R. Z. J. Therm. Anal. Calorim. 2011, 103, 569. doi: 10.1007/s10973-010-0950-2 doi: 10.1007/s10973-010-0950-2
26. [26]
  Zhang, T.; Guo, Y.; Li, J. C.; Guan, Y. L.; Guo, G. Q.; Ma, H. X. Propell. Explos. Pyrot. 2018, 43, 1263. doi: 10.1002/prep.201800014 doi: 10.1002/prep.201800014
27. [27]
  Yi, J. H.; Zhao, F. Q.; Xu, S. Y.; Zhang, L. Y.; Gao, H. X.; Hu, R. Z. J. Hazard. Mater. 2009, 165, 853. doi: 10.1016/j.jhazmat.2008.10.107 doi: 10.1016/j.jhazmat.2008.10.107
28. [28]
  Jiang, Z.; Li, S. F.; Zhao, F. Q.; Chen, P.; Yin, C. M.; Li, S. W. J. Propul. Technol. 2002, 23, 258. doi: 10.1002/mop.10502 doi: 10.1002/mop.10502
29. [29]
  Karpowicz, R. J.; Brill, T. B. Combust. Flame 1984, 56, 317. doi: 10.1016/0010-2180(84)90065-8 doi: 10.1016/0010-2180(84)90065-8
30. [30]
  Xiang, M.; Jiao, Q. J.; Zhu, Y. L.; Yu, J. Y.; Chen, L. P. J. Therm. Anal. Calorim. 2014, 116, 1159. doi: 10.1007/s10973-013-3625-y doi: 10.1007/s10973-013-3625-y
31. [31]
  王晓红, 衡淑云, 张皋, 刘子如, 施震灏, 谭惠民.火炸药学报, 2007, 30, 20. doi: 10.3969/j.issn.1007-7812.2007.04.006Wang, X. H.; Heng, S. Y.; Zhang, G.; Liu, Z. R.; Shi, Z. H.; Tan, H. M. Chin. J. Explos. Propell. 2007, 30, 20. doi: 10.3969/j.issn.1007-7812.2007.04.006
32. [32]
  Zhang, T. L.; Hu, R. Z.; Xie, Y.; Li, F. P. Thermochim. Acta 1994, 244, 171. doi: 10.1016/0040-6031(94)80216-5 doi: 10.1016/0040-6031(94)80216-5

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

三维氧化铁/石墨烯的构建及其对CL-20的热分解性能的影响

通讯作者: 庞爱民, ppam@tom.com 马海霞, mahx@nwu.edu.cn

English

Construction of Three-Dimensional Hematite/Graphene with Effective Catalytic Activity for the Thermal Decomposition of CL-20

Corresponding author: Pang Aimin, ppam@tom.com Ma Haixia, mahx@nwu.edu.cn

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通讯作者: 庞爱民, ppam@tom.com
马海霞, mahx@nwu.edu.cn