Accelerated Decomposition Kinetics of Ammonium Perchlorate via Conformal Graphene Coating

Abstract

Ammonium perchlorate (AP) is an oxidizer material that is widely employed in applications ranging from rocketry to airbags. Previous research has suggested that efficient electron transfer plays a critical role in determining the kinetics of catalyzed AP decomposition reactions. Consequently, intimate contact between AP crystals and electron acceptors has the potential to accelerate decomposition kinetics, which motivates the development of conformal coatings with suitably tailored electronic structures. Here, we demonstrate a scalable method for conformally coating AP crystals with two atomically well-defined 2D materials with orthogonal electronic propertiesnamely, pristine graphene, which is a zero-band gap semiconductor that has been shown to be an effective electron acceptor in diverse heterojunctions and hexagonal boron nitride (hBN), which is a wide-band gap electrical insulator. Consistent with an electron transfer mechanism, graphene-coated AP undergoes accelerated decomposition kinetics compared to uncoated (neat) or hBN-coated AP. Through extensive structural characterization including electron microscopy and X-ray diffraction, the effects of AP crystal size and crystallinity are examined. In addition, the accelerated decomposition kinetics of graphene-coated AP are quantified through thermogravimetric analysis, gas chromatography mass spectrometry, and kinetic modeling. Overall, this work establishes pristine graphene as an effective coating for promoting accelerated decomposition of AP, which enhances its utility in various applications.

Enhanced Decomposition of Ammonium Perchlorate–Ethyl Cellulose–Molybdenum Disulfide Nanocomposites

“…This event had a consistent endotherm enthalpy (ΔH endo ) for all AP composites ranging from 100 to 112 J/g and was comparable to the value reported previously with nitrocellulose-wrapped AP (94−99 J/g). 28 Thus, the result implies that the EC or the wrapping agent (i.e., 2D nanomaterial) does not affect the crystalline structure or phase transitions of AP. A detailed analysis of the powder XRD (PXRD) (Figure S3 Following the orthorhombic to cubic phase transition, the exothermic decomposition of AP was observed.…”

“…Gr−EC−AP had a small, broad peak centered at 300 °C representing LTD, but the peak was much smaller than the LTD peak observed in previous studies with NC used as the wrapping agent. 28 This result implies that the nanomaterial formed from EC and Gr does not have a strong catalytic effect on AP decomposition like that of NC and Gr. 28 In previous work by Secor et al, printed graphene with NC showed enhanced conductivity compared to EC, which is likely the reason for the differences in reactivity for Gr−EC−AP compared to Gr−NC−AP.…”

Understanding the synergistically enhanced thermocatalytic decomposition of ammonium perchlorate using cobalt nanoparticle-embedded nitrogen-doped graphitized carbon

“…For the LTD process, AP mainly undergoes a gas-solid phase reaction, where generating the intermediate products HClO 4 and NH 3 based on the electron transfer from ClO 4to NH 4 + , which is generally considered to be one of the controlling step 62 . The NC and Co-NPs in Co-NPs@NC-T respectively with high electrical conductivity and partially filled 3d orbital can accelerate the electron transfer process to crack the controlling step 24,48,[63][64][65][66] . In addition, the generated HClO 4 and NH 3 are both adsorbed on the AP surface, which has a chance to undergo a redox reaction with each other.…”

Effects of Barium‐Copper‐Cobalt oxide composites supported on reduced graphene oxide in the thermolysis of ammonium perchlorate and 3‐nitro‐1,2,4‐triazol‐5‐one

“…For example, literatures have reported that graphene oxide (GO) or reduced graphene oxide (rGO) based composites impart better results than pure PTOs because of the large surface of GO or rGO available during the thermal decomposition of HEMs. [21][22][23][24] The current study employs the citric acid sol-gel method to synthesize BCC, with a focus on producing particles with a narrow particle size. The BCC was then combined with thermally reduced (rGO) to produce BCC/rGO composite.…”

“…Moreover, when combined with metal oxides, the high surface area and reactivity of GO can enhance the catalytic activity of the metal oxides, leading to improved thermal performance. For example, literatures have reported that graphene oxide (GO) or reduced graphene oxide (rGO) based composites impart better results than pure PTOs because of the large surface of GO or rGO available during the thermal decomposition of HEMs [21–24] …”