Graphene Oxide–(Ferrocenylmethyl) Dimethylammonium Nitrate Composites as Catalysts for Ammonium Perchlorate Thermolysis

Abstract

Graphene oxide has attracted attention due to its excellent catalytic properties, and it is expected to be used in the field of burning rate catalysis. To investigate the synergistic effect of graphene oxide and ferrocene derivatives, graphene oxide–(ferrocenylmethyl) dimethylammonium nitrate composites (GO–FcMANO3) were prepared and characterized by X-ray photoelectron spectroscopy (XPS), Raman analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM), and their thermal stability and catalytic effect on ammonium perchlorate (AP) were studied by thermogravimetry–differential scanning calorimetry (TG–DSC) techniques. Based on interaction region indicator (IRI) analysis, electrostatic potential (ESP) and energy decomposition analysis on the basis of forcefield (EDA-FF), the dispersion effect is the dominant component of interaction energy, and the contribution of electrostatic attraction is small. The frontier molecular orbitals illustrate that a higher highest occupied molecular orbital (HOMO) energy makes GO–FcMANO3 more susceptible to oxidization and is more conducive to catalyzing AP decomposition. The TG data illustrated that the presence of GO in the composites increased the thermal stability of FcMANO3 during AP decomposition. The catalytic effect of GO–FcMANO3 for AP decomposition manifested in two ways: it advanced the peak temperature in the second stage of AP decomposition and reduced the exothermic temperature width between two stages; it also increased the heat released during AP decomposition. Combined kinetic analysis and the Friedman method provided more detailed information about the catalytic behavior of composites for AP thermolysis, and GO–FcMANO3 composites decreased the E a of the second stage of AP decomposition. The introduction of GO influenced the decomposition physical model of FcMANO3 for AP catalysis. The first stage of AP decomposition transformed from random nucleation and two-dimensional growth of nuclei model (A2) to random nucleation and three-dimensional growth of nuclei model (A3), and the second stage changed from the phase boundary-controlled reaction (R2) to random nucleation and two-dimensional growth of nuclei model (A2).

Triazine-Augmented Catalytic Activity of Cyclobutadiene Tricarbonyl Fe(0) Complexes for Thermal Decomposition of Ammonium Perchlorate

“…Accordingly, expanding the π-systems of Cb ligands might enhance the integration of the half-sandwich structures of CbFe(CO) 3 . Moreover, our group identified [1,3,5]-triazine as conjugated wing tips accelerated the rate-determining transmetalation of an NHC-Pd-catalyzed carbonylative C−C coupling reaction. 24 Herein, we hypothesize that the conjugation of cyclobutadiene with triazine might augment the thermal stability of iron carbonyl units and enhance their catalytic performance for AP thermal decomposition.…”

“…14 Our group prepared the thermally stable diiron carbonyl complex Cp 2 Fe 2 (CO) 4 , which significantly improved the burning behavior of the HTPB/AP/Al propellant. 15 Recently, Morales-Verdejo reported four heterometallic catalysts of Mn(CO) 3 number of electrons generated in the HTD process of AP decomposition. 7 These primitive attempts shed light on the potential of transition-metal carbonyls as molecular combustion catalysts.…”

“…Ammonium perchlorate (AP) is the most utilized solid oxidant for the combustion of various composite energetic materials in civilian rockets and military ammunition. , The combustion catalysts of iron boost the thermal decomposition of AP with more heat in a shorter period and, consequenty, provide a powerful impetus for composite energetic systems. , The extensive use of the empirical materials of an iron complex and oxides with trial and error developed many Fe combustion catalysts of iron oxides and complexes such as nano-Fe 2 O 3 , catoncene, butacene, and other ferrocene derivatives for industrial application and scientific research . Investigation of the catalytic events in the condensed phase showed the redox interaction of AP with Fe combustion catalysts forms Fe 2 O 3 at 140–200 °C .…”

Polymeric Carbon Nitride/Iron Oxide Composites: A Novel Class of Catalysts with Reduced Metal Content for Ammonium Perchlorate Thermal Decomposition

“…These supports serve as a perfect platform for (1) the uniform dispersion of nanoparticles without any agglomeration and (2) their efficient stabilization. The heterogeneous catalysts thus formed possess enhanced properties compared to homogeneous metallic catalysts like facile synthesis, easy handling, and recyclability. , gCN is regarded as an emerging material among the above due to its fascinating merits such as easy synthesis from low-cost materials, moderate band gap (2.7 eV), good stability, nontoxicity, and unique layered structure . Due to the above properties, gCN has been proven as a potential burn rate modifier for the thermal decomposition of AP .…”

Interaction Between Prussian Blue Ultrathin Nanosheet and Ammonium Perchlorate for Highly Efficient Thermal Decomposition

“…At present, the most effective catalyst is still transition metal oxide, whose surface has good adsorbability and acid-base properties, which is considered to be able to adsorb and catalyze the decomposition products of AP, thus accelerating the combustion of propellant. [19][20][21][22][23] Sherif Elbasuney prepared CuO nanoparticles with a particle size of 15 nm by hydrothermal method, which can reduce the hightemperature decomposition peak of AP to 350 °C and increase the heat release by 53%. [24] Zhou used ZnCo-ZIF as the precursor to testing the catalytic effect of its decomposition products, ZnO and Co 3 O 4 , on the thermal decomposition of AP.…”