GUO Hangrui1 ，ZHOU Xing1 ，ZHOU Wei1 ，LIU Yaohua1 ，ZHAO Yan1，2
1. College of Aerospace Science and Engineering， National University of Defense Technology， Changsha 413200，China；
2. Inner Mongolia Power Machinery Research Institute， Hohhot 010010， China
Abstract
Objective Enhancing the thermal decomposition of ultrafine ammonium perchlorate （AP） is a primary method to increase the burning rate of solid propellants. Current catalytic approaches typically employ transition metals， transition metal oxides， ferrocene， and ferrocene derivatives， yet these conventional catalysts present significant limitations. The addition of transition metals and oxides may compromise processing performance， and the incorporation of ferrocene derivatives into ultrafine AP exhibits high mechanical sensitivity， posing safety risks during propellant manufacturing. These challenges have driven the need for safer， more efficient combustion catalysts with reduced sensitivity. In recent years， metal-organic framework （MOF）-based catalysts have shown significant progress. By combining different metal centers with organic ligands， it offers precise control over material characteristics， showing great application potential. Moreover， bimetallic cobalt-iron （Co-Fe） MOFs have attracted wide attention for their superior catalytic activity and stability compared to single metal MOFs， achieved through Co-Fe synergistic effects. In this study， to improve the burning rate of solid propellants， the zeolitic imidazolate framework-67 （ZIF-67） is modified by introducing ferrocene carboxylic acid （FcA） as an Fe-containing organic ligand， partially replacing the low-activity organic ligand 2-methylimidazole. Through the Co-Fe bimetallic synergy， this study investigates the catalytic effects of ZIF-67 on AP thermal decomposition， providing foundational data and support for developing high-performance solid propellants with optimized burning rates.
Methods To address the demand for high-burning-rate propellants， FcA-modified ZIF-67 with varying Fe contents （ZIF-67@25%FcA， ZIF-67@50%FcA， and ZIF-67@100%FcA） was synthesized through stirring and ultrasonication. The microstructure and crystal structure of the modified ZIF-67 were characterized using scanning electron microscopy （SEM）， X-ray diffraction （XRD）， and Fourier transform infrared spectroscopy （FTIR）. The catalytic effects on AP thermal decomposition were investigated via thermogravimetry analysis-differential scanning calorimetry （TGA-DSC）， while the impact on the burning rate of AP-based solid propellants was assessed using a laser ignition setup.
Results and Discussion The modified ZIF-67 particles exhibited a uniform dodecahedral morphology with a particle size of approximately 2 μm. Among all the modified products， ZIF-67@100%FcA demonstrated superior catalytic performance. It reduced the high-temperature decomposition peak temperature of AP to 312 ℃， increased the apparent decomposition heat by about 1.5 times， and enhanced the burning rate of AP-based solid propellants by 13.3% at 7 MPa in an argon atmosphere.
Conclusion The introduction of FcA significantly enhances the catalytic performance of ZIF-67 without notably impacting the mechanical sensitivity of solid propellants. Compared to the baseline formulation， the incorporation of ZIF-67 resulted in a 4.8% increase in burning rate， while ZIF-67@100%FcA achieved a more substantial 13.3% enhancement， demonstrating the effectiveness of this modification. Previous studies have shown that MOFs exhibit better catalytic performance when metal oxides form in situ during heating compared to direct addition. As a Co-based MOF with self-assembled 2-methylimidazole as the organic ligand， ZIF-67 benefits from the unique advantages of MOF materials， including unique microporous structures， high chemical tunability， and excellent catalytic properties， which are particularly effective for promoting AP decomposition.
Keywords： burning rate； zinc imidazolate framework； solid propellant； catalytic performance
Get Citation: GUO Hangrui， ZHOU Xing， ZHOU Wei， et al. Catalytic performance of modified ZIF-67 in thermal decomposition of ammonium perchlorate［J］. China Powder Science and Technology， 2026， 32（1）： 1-9.
Received: 2025-06-09 .Revised: 2025-06-12, Online: 2025-06-26
Funding Project: 国防基础性JG科研院所稳定支持项目，编号：WDZC20230202；国防科技大学自主创新科学基金项目，编号：23-ZZCX-ZZGC-01-10。
First Author: 郭航瑞（2001—），男，硕士生，研究方向为特种能源技术。E-mail：2243977558@qq.com。
Corresponding Author: 周星（1981—），男，副教授，博士，硕士生导师，研究方向为特种能源技术。E-mail：xingzhou_nudt@nudt.edu.cn。
DOI：10.13732/j.issn.1008-5548.2026.01.016
CLC No: TB34； TB4 Type Code: A
Serial No: 1008-5548（2026）01-0001-09
