Earth-Abundant Transition Metal Oxide-based Catalysts for Composite Solid Propellants
Gladiya Mani, Suresh Mathew
Earth-abundant transition metal oxides are well known for their catalytic potency for ammonium perchlorate (AP) thermal decomposition, the widely used oxidiser in composite solid propellants. AP constitutes approximately 60–75% of propellant mass. The extreme sensitivity of AP to additives influences its thermal decomposition pattern, hence the propellant’s performance. Earth-abundant transition metal oxides are garnering great attention as ideal catalyst candidates owing to their cost-effectiveness, abundance, low toxicity, and sustainability. Additionally, the structural flexibility and tunability of transition metal oxides make them ideal for mixed metal oxide and composite formation, which helps in exploring new combinations with superior catalytic efficacy for harsh conditions as well as future applications.
Keywords
Earth-Abundant Transition Metal Oxides, Ammonium Perchlorate, Composite Solid Propellants, Iron Oxide, Copper Oxide, Nickel Oxide
Published online 9/10/2025, 17 pages
Citation: Gladiya Mani, Suresh Mathew, Earth-Abundant Transition Metal Oxide-based Catalysts for Composite Solid Propellants, Materials Research Foundations, Vol. 179, pp 20-36, 2025
DOI: https://doi.org/10.21741/9781644903711-2
Part of the book on Applications for Earth-Abundant Transition Metals
References
[1] P.N. Dave, R. Sirach, Investigating the catalytic effect of nanoferrites additives on the thermal decomposition of ammonium perchlorate and burning rate modification of the composite solid propellants, Mater. Sci. Eng. B 301 (2024) 117136. https://doi.org/10.1016/j.mseb.2023.117136
[2] F.-M. Dîrloman, A.-N. Rotariu, T. Rotariu, G.-F. Noja, R.-E. Ginghină, N.-D. Zvîncu, Ballistic and thermal characterisation of greener composite solid propellants based on phase-stabilized ammonium nitrate, Case Stud. Therm. Eng. 54 (2024) 103987. https://doi.org/10.1016/j.csite.2024.103987
[3] F.Y. Chen, C.L. Xuan, Q.Q. Lu, L. Xiao, J.Q. Yang, Y.B. Hu, G.P. Zhang, Y.L. Wang, F.Q. Zhao, G.Z. Hao, W. Jiang, A review on the high energy oxidizer ammonium dinitramide: Its synthesis, thermal decomposition, hygroscopicity, and application in energetic materials, Def. Technol. 19 (2023) 163-195. https://doi.org/10.1016/j.dt.2022.04.006
[4] J. Jos, S. Mathew, Ammonium nitrate as an eco-friendly oxidizer for composite solid propellants: promises and challenges, Crit. Rev. Solid State Mater. Sci. 42(6) (2017) 470-498. https://doi.org/10.1080/10408436.2016.1244642
[5] V.V. Boldyrev, Thermal decomposition of ammonium perchlorate, Thermochimica Acta 443(1) (2006) 1-36. https://doi.org/10.1016/j.tca.2005.11.038
[6] G. Mani, J. Jos, P.R. Nair, S. Mathew, Investigation of kinetic parameters for ammonium perchlorate thermal decomposition in presence of gCN/CuO by TG-MS analysis and kinetic compensation correction, J. Solid State Chem. 301 (2021) 122301. https://doi.org/10.1016/j.jssc.2021.122301
[7] S.-b. Cao, X.-g. Han, L.-l. Zhang, J.-x. Wang, Y. Luo, H.-k. Zou, J.-f. Chen, Facile and scalable preparation of α-Fe2O3 nanoparticle by high-gravity reactive precipitation method for catalysis of solid propellants combustion, Powder Technol. 353 (2019) 444-449. https://doi.org/10.1016/j.powtec.2019.05.062
[8] N. Yadav, P.K. Srivastava, M. Varma, Recent advances in catalytic combustion of AP-based composite solid propellants, Def. Technol. 17(3) (2021) 1013-1031. https://doi.org/10.1016/j.dt.2020.06.007
[9] R.M. Paul Chirik, Getting Down to Earth: The Renaissance of Catalysis with Abundant Metals, Accounts of Chemical Research 48(9) (2015) 2495-2495. https://doi.org/10.1021/acs.accounts.5b00385
[10] K.M.P. Wheelhouse, R.L. Webster, G.L. Beutner, Advances and Applications in Catalysis with Earth-Abundant Metals, Organometallics 42(14) (2023) 1677-1679. https://doi.org/10.1021/acs.organomet.3c00292
[11] P.A. Cox, Transition Metal Oxides: An Introduction to their Electronic Structure and Properties, Clarendon Press2010.
[12] Y. Xia, C.T. Campbell, B. Roldan Cuenya, M. Mavrikakis, Introduction: Advanced Materials and Methods for Catalysis and Electrocatalysis by Transition Metals, Chem. Rev. 121(2) (2021) 563-566. https://doi.org/10.1021/acs.chemrev.0c01269
[13] E. Khare, N. Holten-Andersen, M.J. Buehler, Transition-metal coordinate bonds for bioinspired macromolecules with tunable mechanical properties, Nature Reviews Materials 6(5) (2021) 421-436. https://doi.org/10.1038/s41578-020-00270-z
[14] A.T. Howe, P.J. Fensham, Electronic properties of binary compounds of the first-row transition metals, Quarterly Reviews, Chemical Society 21(4) (1967) 507-524. https://doi.org/10.1039/qr9672100507
[15] D. Wang, D. Astruc, The recent development of efficient Earth-abundant transition-metal nanocatalysts, Chem. Soc. Rev. 46(3) (2017) 816-854. https://doi.org/10.1039/C6CS00629A
[16] P. Du, R. Eisenberg, Catalysts made of earth-abundant elements (Co, Ni, Fe) for water splitting: recent progress and future challenges, Energy & Environmental Science 5(3) (2012) 6012-6021. https://doi.org/10.1039/c2ee03250c
[17] I. Roger, M.A. Shipman, M.D. Symes, Earth-abundant catalysts for electrochemical and photoelectrochemical water splitting, Nature Reviews Chemistry 1(1) (2017) 1-13. https://doi.org/10.1038/s41570-016-0003
[18] F. Ma, Z.-M. Luo, J.-W. Wang, B.M. Aramburu-Trošelj, G. Ouyang, Earth-abundant-metal complexes as photosensitizers in molecular systems for light-driven CO2 reduction, Coord. Chem. Rev. 500 (2024) 215529. https://doi.org/10.1016/j.ccr.2023.215529
[19] L. Rotundo, R. Gobetto, C. Nervi, Electrochemical CO2 reduction with earth-abundant metal catalysts, Current Opinion in Green and Sustainable Chemistry 31 (2021) 100509. https://doi.org/10.1016/j.cogsc.2021.100509
[20] A. Budhwar, A. Gautam, P.V. More, C.S. Pant, S. Banerjee, P.K. Khanna, Modified iron oxide nanoparticles as burn rate enhancer in composite solid propellants, Vacuum 156 (2018) 483-491. https://doi.org/10.1016/j.vacuum.2018.08.013
[21] R. Arun Chandru, R.P. Patel, C. Oommen, B. Raghunandan, Initial studies on development of high-performance nano-structured Fe2O3 catalysts for solid rocket propellants, J. Mater. Eng. Perform. 28 (2019) 810-816. https://doi.org/10.1007/s11665-018-3812-x
[22] S.S. Joshi, P.R. Patil, V. Krishnamurthy, Thermal decomposition of ammonium perchlorate in the presence of nanosized ferric oxide, Defence Science Journal 58(6) (2008) 721-727. https://doi.org/10.14429/dsj.58.1699
[23] M. Kohga, S. Togo, Catalytic effect of added Fe2O3 amount on thermal decomposition behaviors and burning characteristics of ammonium nitrate/ammonium perchlorate propellants, Combust. Sci. Technol. 192(9) (2020) 1668-1681. https://doi.org/10.1080/00102202.2019.1620736
[24] M. Kohga, S. Togo, Influence of iron oxide on thermal decomposition behavior and burning characteristics of ammonium nitrate/ammonium perchlorate-based composite propellants, Combust. Flame 192 (2018) 10-24. https://doi.org/10.1016/j.combustflame.2018.01.040
[25] J. Pei, H. Zhao, F. Yang, D. Yan, Graphene Oxide/Fe2O3 Nanocomposite as an Efficient Catalyst for Thermal Decomposition of Ammonium Perchlorate via the Vacuum-Freeze-Drying Method, Langmuir 37(20) (2021) 6132-6138. https://doi.org/10.1021/acs.langmuir.1c00108
[26] G. Mani, P.R. Nair, S. Mathew, Polymeric Carbon Nitride/Iron Oxide Composites: A Novel Class of Catalysts with Reduced Metal Content for Ammonium Perchlorate Thermal Decomposition, ACS omega 7(43) (2022) 38512-38524. https://doi.org/10.1021/acsomega.2c03761
[27] L. Yang, Z. Mi, H. Fang, R. Xu, B. Lv, J. Li, G. Zhang, Fabrication of highly catalytic active α-Fe2O3-carbon nanotube composites for thermal decomposition of ammonium perchlorate by light and temperature control strategy, Surfaces and Interfaces 44 (2024) 103642. https://doi.org/10.1016/j.surfin.2023.103642
[28] S. Paulose, R. Raghavan, B.K. George, Graphite oxide-iron oxide nanocomposites as a new class of catalyst for the thermal decomposition of ammonium perchlorate, RSC Advances 6(51) (2016) 45977-45985. https://doi.org/10.1039/C6RA06860J
[29] P. Majumder, R. Gangopadhyay, Evolution of graphene oxide (GO)-based nanohybrid materials with diverse compositions: an overview, RSC advances 12(9) (2022) 5686-5719. https://doi.org/10.1039/D1RA06731A
[30] A. Dey, J. Athar, P. Varma, H. Prasant, A.K. Sikder, S. Chattopadhyay, Graphene-iron oxide nanocomposite (GINC): an efficient catalyst for ammonium perchlorate (AP) decomposition and burn rate enhancer for AP based composite propellant, RSC Advances 5(3) (2015) 1950-1960. https://doi.org/10.1039/C4RA10812D
[31] M. Zhang, F. Zhao, Y. Yang, J. Zhang, N. Li, H. Gao, Effect of rGO-Fe2O3 nanocomposites fabricated in different solvents on the thermal decomposition properties of ammonium perchlorate, CrystEngComm 20(43) (2018) 7010-7019. https://doi.org/10.1039/C8CE01434E
[32] N.M. Juibari, A. Eslami, Green synthesis of ZnCo2O4 nanoparticles by Aloe albiflora extract and its application as catalyst on the thermal decomposition of ammonium perchlorate, J. Therm. Anal. Calorim. 130 (2017) 1327-1333. https://doi.org/10.1007/s10973-017-6613-9
[33] M. Zhang, F. Zhao, Y. Yang, T. An, W. Qu, H. Li, J. Zhang, N. Li, Catalytic activity of ferrates (NiFe2O4, ZnFe2O4 and CoFe2O4) on the thermal decomposition of ammonium perchlorate, Propellants, Explosives, Pyrotechnics 45(3) (2020) 463-471. https://doi.org/10.1002/prep.201900211
[34] W. Wang, S. Guo, D. Zhang, Z. Yang, One-pot hydrothermal synthesis of reduced graphene oxide/zinc ferrite nanohybrids and its catalytic activity on the thermal decomposition of ammonium perchlorate, Journal of Saudi Chemical Society 23(2) (2019) 133-140. https://doi.org/10.1016/j.jscs.2018.05.001
[35] Y. Zu, Y. Zhao, K. Xu, Y. Tong, F. Zhao, Preparation and comparison of catalytic performance for nano MgFe2O4, GO-loaded MgFe2O4 and GO-coated MgFe2O4 nanocomposites, Ceram. Int. 42(16) (2016) 18844-18850. https://doi.org/10.1016/j.ceramint.2016.09.030
[36] S. Elbasuney, M. Yehia, Thermal decomposition of ammonium perchlorate catalyzed with CuO nanoparticles, Def. Technol. 15(6) (2019) 868-874. https://doi.org/10.1016/j.dt.2019.03.004
[37] M. Nourine, M.K. Boulkadid, S. Touidjine, H. Akbi, S. Belkhiri, Exploring the potential of nitrocellulose for improving the catalytic efficiency of nano copper oxide in the thermal degradation of ammonium perchlorate, Reaction Kinetics, Mechanisms and Catalysis 136(5) (2023) 2769-2783. https://doi.org/10.1007/s11144-023-02469-x
[38] D.L. Sivadas, D. Thomas, M.S. Haseena, T. Jayalatha, G. Rekha Krishnan, S. Jacob, R. Rajeev, Insight into the catalytic thermal decomposition mechanism of ammonium perchlorate, J. Therm. Anal. Calorim. 138(1) (2019) 1-10. https://doi.org/10.1007/s10973-019-08209-5
[39] L. Tan, J. Xu, S. Li, D. Li, Y. Dai, B. Kou, Y. Chen, Direct Growth of CuO Nanorods on Graphitic Carbon Nitride with Synergistic Effect on Thermal Decomposition of Ammonium Perchlorate, Materials 10(5) (2017) 484. https://doi.org/10.3390/ma10050484
[40] J. Xu, S. Li, L. Tan, B. Kou, Enhanced catalytic activity of mesoporous graphitic carbon nitride on thermal decomposition of ammonium perchlorate via copper oxide modification, Mater. Res. Bull. 93 (2017) 352-360. https://doi.org/10.1016/j.materresbull.2017.05.038
[41] S. Saha, A. Chowdhury, N. Kumbhakarna, Effect of copper chromite on ammonium perchlorate decomposition-A TGA-FTIR-MS and FE-SEM study, J. Therm. Anal. Calorim. 149(17) (2024) 9401-9412. https://doi.org/10.1007/s10973-024-13395-y
[42] A.P. Sanoop, R. Rajeev, B.K. George, Synthesis and characterization of a novel copper chromite catalyst for the thermal decomposition of ammonium perchlorate, Thermochimica Acta 606 (2015) 34-40. https://doi.org/10.1016/j.tca.2015.03.006
[43] D. Zhang, Q. Li, R. Li, H. Li, H. Gao, F. Zhao, L. Xiao, G. Zhang, G. Hao, W. Jiang, Significantly Enhanced Thermal Decomposition of Mechanically Activated Ammonium Perchlorate Coupling with Nano Copper Chromite, ACS Omega 6(24) (2021) 16110-16118. https://doi.org/10.1021/acsomega.1c02002
[44] Y. Zhao, X. Zhang, X. Xu, Y. Zhao, H. Zhou, J. Li, H. Jin, Synthesis of NiO nanostructures and their catalytic activity in the thermal decomposition of ammonium perchlorate, CrystEngComm 18(25) (2016) 4836-4843. https://doi.org/10.1039/C6CE00627B
[45] C. Bai, D. Yang, C. Liu, F. Zhu, C. Tu, G. Li, Y. Luo, In situ synthesis NiO@ TiO2/MXene as a promoter for ammonium perchlorate based solid propellants, Appl. Surf. Sci. 652 (2024) 159228. https://doi.org/10.1016/j.apsusc.2023.159228
[46] Y. Lan, B. Jin, J. Deng, Y. Luo, Graphene/nickel aerogel: an effective catalyst for the thermal decomposition of ammonium perchlorate, RSC advances 6(85) (2016) 82112-82117. https://doi.org/10.1039/C6RA15661D
[47] Y. Zhang, Z. Li, M. Ma, Synthesis of Ni nanopowders with cauliflower-like shapes and their catalytic property on the thermal decomposition of ammonium perchlorate, Reaction Kinetics, Mechanisms and Catalysis 136(4) (2023) 2327-2341. https://doi.org/10.1007/s11144-023-02473-1
[48] S. Bao, T. Li, C. Guo, Y. Zhao, H. Zhang, R. Wu, H. Shi, One-Pot Preparation of HTPB/nNi and Its Catalyst for AP, Nanomaterials 12(15) (2022) 2669. https://doi.org/10.3390/nano12152669
[49] L. Bircumshaw, B. Newman, The thermal decomposition of ammonium perchlorate, II. The kinetics of the decomposition, the effect of particle size, and discussion of results, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences 227(1169) (1955) 228-241. https://doi.org/10.1098/rspa.1955.0006
[50] V. Boldyrev, Thermal decomposition of ammonium perchlorate, Thermochimica Acta 443(1) (2006) 1-36. https://doi.org/10.1016/j.tca.2005.11.038
