Design, Preparation and Performance of Cyanoborohydride Based Coordination Compounds for Hypergolic Fuels

doi:10.6023/A25070259

Abstract

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 2~57 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-dimethylhydrazine (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

Cite this article

Lei Dai, Mingcheng Ge, Ye Zhong, Linna Liang, Haiyan Jiang, Jianguo Zhang, Zhimin Li. Design, Preparation and Performance of Cyanoborohydride Based Coordination Compounds for Hypergolic Fuels[J]. Acta Chimica Sinica, 2025, 83(12): 1538-1550.

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Item No.	MCCHF-1	MCCHF-2	MCCHF-3	MCCHF-4
compounds	Co(1-MTZ)₄(CBH)₂	Co(MIM)₄(CBH)₂	Ni(MIM)₄(CBH)₂	Ni(1-MTZ)₄(CBH)₂
formula	C₁₀H₂₂B₂N₁₈Co	C₁₈H₃₀B₂N₁₀Co	C₁₈H₃₀B₂N₁₀Ni	C₁₀H₂₂B₂N₁₈Ni
form. mass	475.01	467.07	466.85	474.79
T/K	296.15	293(2)	293(2)	296(2)
crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic
space group	P2₁/c	P2₁/n	P2₁/c	P2₁/c
a/nm	0.74388(4)	0.78597(7)	0.78521(7)	0.7377
b/nm	1.69365(10)	1.10832(11)	1.10513(11)	1.6947
c/nm	0.94913(5)	1.41131(13)	1.56381(14)	0.9412
α/(°)	90.00	90	90	90.00
β/(°)	108.7460(10)	94.484(2)	115.738(5)	108.58
γ/(°)	90.00	90	90	90.00
V/nm³	1.13235(11)	1.2256(2)	1.2224(2)	1.1154
Z	2	2	2	2
ρ_calcd/(g•cm⁻³)	1.393	1.266	1.268	1.414
μ/mm⁻¹	0.796	0.725	0.819	0.908
F(000)	490	490	492	492
Goodness-of-fit on F²	1.050	1.034	1.042	1.165
Final R indexes [I≥2σ(I)]	R₁=0.0413, wR₂=0.0842	R₁=0.0954, wR₂=0.1554	R₁=0.0895, wR₂=0.1861	R₁=0.0732, wR₂=0.1662
Final R indexes [all data]	R₁=0.0640, wR₂=0.0952	R₁=0.2156, wR₂=0.1814	R₁=0.1928, wR₂=0.2109	R₁=0.1196, wR₂=0.1828
CCDC	2240151	2451525	2451527	2240152

Item No.	MCCHF-1	MCCHF-2	MCCHF-3	MCCHF-4
compounds	Co(1-MTZ)₄(CBH)₂	Co(MIM)₄(CBH)₂	Ni(MIM)₄(CBH)₂	Ni(1-MTZ)₄(CBH)₂
formula	C₁₀H₂₂B₂N₁₈Co	C₁₈H₃₀B₂N₁₀Co	C₁₈H₃₀B₂N₁₀Ni	C₁₀H₂₂B₂N₁₈Ni
form. mass	475.01	467.07	466.85	474.79
T/K	296.15	293(2)	293(2)	296(2)
crystal system	Monoclinic	Monoclinic	Monoclinic	Monoclinic
space group	P2₁/c	P2₁/n	P2₁/c	P2₁/c
a/nm	0.74388(4)	0.78597(7)	0.78521(7)	0.7377
b/nm	1.69365(10)	1.10832(11)	1.10513(11)	1.6947
c/nm	0.94913(5)	1.41131(13)	1.56381(14)	0.9412
α/(°)	90.00	90	90	90.00
β/(°)	108.7460(10)	94.484(2)	115.738(5)	108.58
γ/(°)	90.00	90	90	90.00
V/nm³	1.13235(11)	1.2256(2)	1.2224(2)	1.1154
Z	2	2	2	2
ρ_calcd/(g•cm⁻³)	1.393	1.266	1.268	1.414
μ/mm⁻¹	0.796	0.725	0.819	0.908
F(000)	490	490	492	492
Goodness-of-fit on F²	1.050	1.034	1.042	1.165
Final R indexes [I≥2σ(I)]	R₁=0.0413, wR₂=0.0842	R₁=0.0954, wR₂=0.1554	R₁=0.0895, wR₂=0.1861	R₁=0.0732, wR₂=0.1662
Final R indexes [all data]	R₁=0.0640, wR₂=0.0952	R₁=0.2156, wR₂=0.1814	R₁=0.1928, wR₂=0.2109	R₁=0.1196, wR₂=0.1828
CCDC	2240151	2451525	2451527	2240152

	MCCHF-1	MCCHF-2	MCCHF-3	MCCHF-4
M^a/(g•mol⁻¹)	475.01	467.07	466.85	474.79
ρ^b/(g•cm⁻³)	1.393	1.266	1.268	1.414
t_id^c/ms	2	20	57	37
T_p^d/℃	152.4	176.3	171.8	168.8
E_g ^e/(kJ•g⁻¹)	20.44	25.41	23.77	18.36
E_v ^f/(kJ•cm⁻³)	28.47	32.17	30.14	25.97
IS^g/J	8	>40	>40	17
FS^h/N	288	>360	>360	216
ΔU_c ⁱ/(J•g⁻¹)	－20433.05	－25434.78	－23746.10	－18367.83
ΔH_c ^j/(kJ•mol⁻¹)	－9709.2	－11868.24	－11097.02	－8717.14
ΔH_f ^k/(kJ•mol⁻¹)	1051.95	－1080.41	－1786.25	125.27

	MCCHF-1	MCCHF-2	MCCHF-3	MCCHF-4
M^a/(g•mol⁻¹)	475.01	467.07	466.85	474.79
ρ^b/(g•cm⁻³)	1.393	1.266	1.268	1.414
t_id^c/ms	2	20	57	37
T_p^d/℃	152.4	176.3	171.8	168.8
E_g ^e/(kJ•g⁻¹)	20.44	25.41	23.77	18.36
E_v ^f/(kJ•cm⁻³)	28.47	32.17	30.14	25.97
IS^g/J	8	>40	>40	17
FS^h/N	288	>360	>360	216
ΔU_c ⁱ/(J•g⁻¹)	－20433.05	－25434.78	－23746.10	－18367.83
ΔH_c ^j/(kJ•mol⁻¹)	－9709.2	－11868.24	－11097.02	－8717.14
ΔH_f ^k/(kJ•mol⁻¹)	1051.95	－1080.41	－1786.25	125.27

参数		MCCHF-1	MCCHF-2	MCCHF-3	MCCHF-4
β/(℃•min⁻¹)	5	173.5	200.2	209.6	172.8
	10	177.7	203.5	213.3	177.6
	15	180.5	206.4	216.2	179.8
	20	182.4	209.5	218.5	181.7
Kissinger法	E_K/(kJ•mol⁻¹)	255.3	274.7	299.3	256.3
	lg A_K	27.97	28.44	30.51	28.21
	R_K	－0.9996	－0.9836	－0.9957	－0.9986
Ozawa法	E_O/(kJ•mol⁻¹)	249.9	268.8	292.3	250.8
Ozawa法	R_O	－0.9997	－0.9845	－0.9959	－0.9986
E_a/(kJ•mol⁻¹)		256.2	271.7	295.8	253.5
T_po^a/℃		167.40	195.90	204.90	163.10
T_b^b/℃		173.91	202.75	211.42	169.45
ΔS^≠ ^c/(J•K⁻¹•mol⁻¹)		287.29	295.77	335.24	291.97
ΔH^≠^d/(kJ•mol⁻¹)		251.64	270.80	295.33	252.67
ΔG^{≠ e}/(kJ•mol⁻¹)		126.07	132.07	135.06	125.30

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