氰基硼氢金属配合物自燃燃料设计制备与性能研究

doi:10.6023/A25070259

摘要/Abstract

固液混合自燃推进剂在空间动力系统中有良好的应用前景,为探索新型自燃固体燃料,以Co(II)、Ni(II)为中心金属离子,1-甲基咪唑、1-甲基四唑为配体,氰基硼氢根为阴离子合成了4种金属配合物自燃燃料MCCHFs 1-4,准确测定出其晶体结构,并对它们的热行为、机械感度、自燃点火燃烧和能量性能进行了详细研究。结果表明：4种配合物的热分解峰温在152.4-176.3 ℃之间,MCCHF-1和MCCHF-4表现出一定的机械刺激敏感性（IS：8 J,17 J;FS：288 N,216 N）,MCCHF-2和MCCHF-3对机械刺激钝感（IS>40 J,FS>360 N）;4种配合物均能与白烟硝酸发生自燃点火反应,点火延迟时间处于2 ms-57 ms范围,其中MCCHF-1表现最佳,仅为2 ms;燃烧热值以MCCHF-2最高,质量能量密度为25.41 kJ·g^-1,体积能量密度为32.17 kJ·cm^-3,MCCHF-1、MCCHF-4与HNO₃、N₂O₄、H₂O₂三种液体氧化剂组合,表现出良好的比冲性能,其中与H₂O₂组合的推进剂性能最佳,真空比冲高达268.37 s,高于偏二甲肼（258 s）等传统自燃燃料。氰基硼氢阴离子的高活性金属配合物自燃燃料作为一种新型自燃固体燃料,有望推动固液推进剂技术发展。

关键词: 推进剂, 含能配合物, 自燃燃料, 点火延迟时间, 氰基硼氢根

Solid-liquid hybrid hypergolic propellants have potential application in space power systems, in order to explore novel hypergolic fuels, four metal complex hypergolic fuels MCCHFs 1-4 were designed and synthesized by using Co(II) and Ni(II) as the central metal ions, 1-methylimidazole and 1-methyltetrazolium as ligands, and cyano-borohydride as the anion. The crystal structures of these complexes were accurately determined, and their thermal behavior, mechanical sensitivities, hypergolic and energetic performances were studied in detail. The results show that the peak temperatures of the thermal decomposition of the four complexes were in the range of 152.4-176.3 ℃, MCCHF-1 and MCCHF-4 exhibit mechanical stimulation sensitivity (IS: 8 J, 17 J; FS: 288 N, 216 N), MCCHF-2 and MCCHF-3 are insensitive to mechanical stimulation (IS>40 J, FS>360 N). The four compounds are all able to react with white fuming nitric acid by spontaneous ignition, and the ignition delay time are in the range of 2 ms-57 ms, with MCCHF-1 performing the best of 2 ms. The heat of combustion of MCCHF-2 is the highest, with a mass energy density of 25.41 kJ·g^-1 and a volumetric energy density of 32.17 kJ·cm^-3. MCCHF-1, MCCHF-4 with HNO₃, N₂O₄, and H₂O₂ three liquid oxidizers, show good specific impulse performance, in which the propellant combined with H₂O₂ has the best performance, with a vacuum specific impulse as high as 268.37 s, which was higher than that of the traditional spontaneous combustion fuels, such as meta-di-methylhydrazine (258 s). As a new type of hypergolic solid fuel, the active metal complexes based on cyanoborohydride anion are expected to promote the development of solid-liquid propellant technology.

Key words: Propellants, Energy Complexes, Hypergolic Fuels, Ignition Delay Time, Cyanoborohydride

引用此文

戴磊, 葛明成, 钟野, 梁琳娜, 蒋海燕, 张建国, 李志敏. 氰基硼氢金属配合物自燃燃料设计制备与性能研究[J]. 化学学报, doi: 10.6023/A25070259.

Dai Lei, Ge Mingcheng, Zhong Ye, Liang Linna, Jiang Haiyan, Zhang Jianguo, Li Zhimin. Design, Preparation and Performance of Cyanoborohydride Based Coordination Compounds for Hypergolic Fuels[J]. Acta Chimica Sinica, doi: 10.6023/A25070259.

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参考文献

[1] Hongjae K.; Jonghan W.; Wook B. S.; Sejin K.Combust. Flame 2017, 181, 149.
[2] Bhosale V. K.;Jeong. J.; Kwon. S. FUEL .2019, 255, 16.
[3] Cui,Y,K.;Cheng,S,F.;Ling,L.;Li,Y,X.;Lu L.Acta Chim.Sinica,2024,82,377 (in Chinese).
(崔勇康,成守飞,凌琳,李玉学,吕龙,化学学报,2024,82,377)
[4] Bablee A.; Amarasekara A.; Gabitto J.; Bhuiyan A.; Shamim N. ENERGIES2025 , 18, 267.
[5] Yu Y.; Jiang J.; Zeng X.-L.; Ju, X.-H. Int. J. Hydrogen Energy2025, 105, 959.
[6] Bao, L. R.; Zhang, W.; Zhang, X.J.; Chen, Y.Y.; Chen, S.H.; Wu, L. Z.; Shen, R. Q.; Ye, Y. H.; Combust. Flame 2020, 218, 10.
[7] Bao L. R.; Wang, H; Zheng T.T.; Chen S.H.; Zhang W.; Zhang X.J.; Huang Y.Y.; Shen R. Q.; Ye Y. H.PROPELL EXPLOS PYROT 2020, 45, 1790.
[8] Lim D. H.; Gnanaprakash K.; Rajak R.; Yoh, J. J. Thermochim. Acta2023, 727, 179562.
[9] Cai, G, B. Journal of Propulsion Technology2012, 6, 831(in Chinese).
(蔡国飙. 推进技术, 2012, 6, 831.)
[10] Davydenko N.A.; Gollender R.G.; Gubertov A.M.; Mironov V.V.; Volkov, N.N. Aerosp. Sci. Technol.2007, 11, 55.
[11] Wei,T,F.; Cai,G,B.; Tian,H.; Zhu,H.; Zhang,Y,J.; Li,X,T. FirePhys Chem, 2021 , 1,212.
[12] Chen,Q,H.;Fu,X,D.;Yu,H,J.;Meng,S,Q.J.Ordn.Equip.Eng.,2025,46,279. (in Chinese)
(陈启航,付小龙,蔚红建,.兵器装备工程学报,2025,46,279.)
[13] Bhosale V. K.; Jeong J.; Kwon S.FUEL 2019, 255, 115729.
[14] John J.; Nandagopalan P.; Baek S. W.; June, C. S. Combust. Flame2020, 212, 205.
[15] Wang,Y.;Hu,S,Q.;Liu,L,L.;Liu,X,L,;Li,L,Q. Journal of Propulsion Technology2020, 48, 1807 (in Chinese).
(王印,胡松启,刘林林,李连强. 推进技术, 2020, 48, 1807)
[16] Zhang,Z,L.;Lin,X.;Wang,R,Y.;Luo,J.X.;Wang,Z,Z.;Zhang,C,Y.;Li,F.;Yu,X,L. Journal of Propulsion Technology2023, 44, 2211059
(in Chinese).
(张泽林,林鑫,王若岩,罗家枭,王泽众,张春元,李飞,余西龙. 推进技术, 2023, 44, 2211059)
[17] Yang,Y,X.; Hu,C,B.; He,G,Q.; Cai,T,M. Journal of Astronautics, 2008, 5,1616. (in Chinese)
(杨玉新,胡春波,何国强, 蔡体敏.宇航学报, 2008, 5,1616)
[18] Ju,Y,J.; Song,C,J.; Lee,B,J. J PROPUL POWER,2024,4,42
[19] Radhika K. S.; Saraswathi R.; Thomas D.; Periya K. V.; Kuttan P. CHEMISTRYSELECT2025, 10, e202405705.
[20] Zheng,D.;Xiong,P F .;Zhong,B,J. Acta Phys. Chim. Sin.2019, 35,1241 (in Chinese)
(郑东,熊鹏飞,钟北京,.物理化学学报,2019, 35,1241)
[21] He W.; Ao W.; Yang G. C.; Yang Z. J.; Guo Z. Q.; Liu P. J.; Yan, Q. L. Chem. Eng. J.2020, 381, 122623.
[22] Lin,C,X.;Guo,L.;Li,Q,S.;Zhang,Z,Z.;Yuan,Y,F.;Xu,F,B.;Chin.J.OrgChem. 2014,34,239 (in Chinese).
(林彩霞,郭琳,李庆山,张正之,袁耀锋,徐凤波. 有机化学, 2014,34,239)
[23] Wang Q. Y.; Feng X.; Wang S.; Song N. M.; Chen Y. F.; Tong W. C.; Han Y. Z.; Yang L.; Wang B.Adv. Mater.2016, 28, 5837.
[24] Yang,J.;Ling,L.;Li,Y,X.; Lu L. Acta Chim. Sinica,2023, 81, 328 (in Chinese).
(杨洁,凌琳,李玉学,吕龙,化学学报,2023,81,328)
[25] Wu,Y.;Pang,A,M.;Hu,L.;He,G,S.;Zhang,Y,Y.; Zhang,L,X.; Li,M,H.; Ma,Z Y. Acta Chim. Sinica,2020, 78,337 (in Chinese).
(武艳,庞爱民,胡磊,何根升,张莹莹,张利雄,李明海,马振叶.化学学报,2020,78,337)
[26] Yao,Y.;Li X,Q.; Liu,J,X.;Gu,J.;Tu,Tao.; Yang,[J].Acta Chim. Sinica, 2025, 1(in Chinese).
(喻尧,李晓强,刘佳鑫,顾军,涂涛,杨军,化学学报,2025,1)
[27] Ma,X,L.;Li,M.;Lei M.Acta Chim. Sinica,2023,81,84(in Chinese).
(马雪璐,李蒙,雷鸣,化学学报, 2023, 81,84)
[28] Mikula A.; Kusior A. MATERIALS2022, 16, 67.
[29] Yang L.; Zhang, G Y.; Liu Y.; Zhang,T. L. Acta Phys. Chim. Sin.2017, 33,2463 (in Chinese)
(杨利,张国英,刘影,张同来.物理化学学报,2017, 33, 2463).
[30] Bhosale. V. K.; Jeong. J.; Kwon. S. FUEL.2019, 255,115729.
[31] Titi H.M.; Marrett J.M.; Dayaker G.; Arhangelskis M.; Mottillo C.; Morris A.J.; Rachiero G.P.; Friščić T.; Rogers R.D. Sci. Adv.2019, 5, eaav9044.
[32] Chen B. Q.; Zhang C. L.; Pang Z. G.; Rong X. G.; Guo Y. L.; He W.Chem. Eng. J. 2024, 501, 157616.
[33] Chang J. Y.; Ding N.; Sun Q.; Wei Z. H.; Zhan Z. H.; Ren X. T.; He J. X.; Li S. H.; Pang, S. P. ACS Mater. Lett.2025, 7, 1112.
[34] Shi Y. H.; Cao X. F.; Ren Q. N.; Song T. Y.; Wu Y. H.; Wei Z. X.; Cao X. FUEL2024, 375, 132615.
[35] Wu C. Y.; Chen Y. C.; Wang T. H.; Lin C. I.; Huang C. W.; Zhou, S. R. Combust. Flame2021, 232, 111556.
[36] Liu Y. F.; Jin S. H.; Yang H. T.; Li S. H.; Xie W. X.; Zhao Y.; Zhang W.; Chen Y.; Fan, X. D. Combust. Flame2021, 225, 57.
[37] Liang, L. N; Zhong, Y.; Chen, J. M; Zhang, J. G; Zhang, T. L ; Li, Z. M. Inorg. Chem.2022, 61, 14864.
[38] Ge, M. C; Xu, X.; Su Z.; Zhong Y.; Yuan B. F.; Huang, H. S; Zhang, J. G; Li, Z. M.DEF TECHNOL 2025.
[39] Chen C.; Li, H. J; Yi, J. H; Zhang, Y.; Sun, Z. H; Xu, Y.; Wang Y.; Chen, X. L; Xu, S. Y; Zhao, F. Q. FUEL2025, 390, 134683.
[40] Zhou P.; Zhang S. W.; Ren Z. Q.; Wang, Y. Z; Zhang, Y. F.; Huang C. Inorg. Chem. Front. 2022, 9, 5195.
[41] Xu Y. Q.; Wang Y. N.; Zhong Y.; Lei, G. R; Li, Z. M; Zhang, J. G; Zhang, T. L. Inorg. Chem.2021, 60, 5100.
[42] Zhong Y.; Li, Z. M; Xu, Y. Q; Lei, G. R; Zhang, J. G; Zhang, T. L.J. Energetic Mater. 2021, 39, 215.
[43] Titli,H.M.;Marrett J. M.; Dayaker G.; Arhangelskis M.; Mottillo A.; Morris A. J.; Rachiero G. P.; Friščić T.; Rogers, R. D. Sci Adv.2019, 5, eaav9044.)
[44] Xu,Y,Q; Wang, Y N; Zhong Y; Lei, G R; Li, Z M; Zhang, J G; Zhang, T L. Inorg. Chem.2021, 60, 5100.
[45] Weng, J L; Li, L C; Wang, J X; Yang Y; Jiang, P H; Zhang, N N; Cui M; Xu, J G; Guo, G,C. Cryst. Growth Des.2025, 25, 1247.
[46] Fei,T; Xu,R; Zhao,P,Y; Xu,T; Du,Z G. J. Rocket Propulsion.2024, 50,33 (in Chinese)
(费腾,徐冉,赵鹏宇,徐涛,杜宗罡.火箭推进,2024,50,33)
[47] Wu,Y,T.;Fei,L,H.;Kong,X,D.;Wang,Z.;Tang,C,L.;Huang,Z,H.CIESC Journal. 2024, 75, 2017(in Chinese).
(武颖韬,费立涵,孔祥东,王帜,汤成龙,黄佐华.化工学报,2024,75, 2017)
[48] Liang, L N; Zhong Y; Xu, Y,Q. Chem. Eng. J.2021, 426, 131866.
[49] Biswas,S; McAnally,M; Chambreau,SD; Schneider,S; Sun,R; Kaiser RI. CHEM-EUR J.2025, 31, e202500593.
[50] El Seoud O. A.; Pires P. A. R.; Abdel - Moghny T.; Bastos, E. L. J. Colloid Interface Sci.2007, 313, 296.
[51] Bhosale,V,K.; Jeong, J,Y; Choi, J,H; Churchill, D,G.; Lee, Y,H; Kwon, S,J. Combust. Flame 2020, 214, 426.
[52] Kissinger H.E.Anal. Chem. 1957, 29, 1702.
[53] Ozawa, T. Bull. Chem. Soc. Jpn.1965, 38, 1881.
[54] Spackman P.R.; Turner M.J.; McKinnon J.J.; Wolff S.K.; Grimwood D.J.; Jayatilaka D.; Spackman, M.A. J. Appl. Crystallogr.2021, 54, 1006.
[55] Sengupta D.; Vaghjiani, G. L. PROPELL EXPLOS PYROT2015, 40, 144.
[56] Li S. Q.; Gao H. X.; Shreeve, J. M. ANGEW CHEM INT EDIT2014, 53, 2969.
[57] Yuan W. L.; Zhang L.; Tao G. H.; Wang S. L.; Wang Y.; Zhu Q. H.; Zhang G. H.; Zhang Z.; Xue Y.; Qin S.; He L.; Shreeve J. M.Sci. Adv.2020, 6, eabb1899.
[58] Bhosale,V,K.; Jeong, J,Y; Choi, J,H; Churchill, D,G.; Lee, Y,H; Kwon, S,J. Combust. Flame 2020, 214, 426.