Effects of TiO2 Anatase Polymorph on Ammonium Perchlorate Decomposition

被引:2
作者
de Rezende, Armando [1 ]
Zamora, Jeremiah [1 ]
Braga, Leticia S. [2 ]
Pantoya, Michelle L. [1 ]
Tunega, Daniel [4 ]
Demko, Andrew R. [3 ]
Aquino, Adelia J. A. [1 ]
机构
[1] Texas Tech Univ, Dept Mech Engn, Lubbock, TX 79409 USA
[2] Univ Fed Lavras, Dept Chem, Campus Univ, BR-37200000 Lavras, MG, Brazil
[3] Naval Air Warfare Ctr, Weap Div, China Lake, CA 93555 USA
[4] Univ Nat Resources & Life Sci, Inst Soil Res, A-1190 Vienna, Austria
关键词
TOTAL-ENERGY CALCULATIONS; OXYGEN VACANCIES; THERMAL-DECOMPOSITION; OPTICAL-PROPERTIES; SURFACE; ADSORPTION; RUTILE; DFT; O-2; NANOPARTICLES;
D O I
10.1021/acs.jpcc.4c04361
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Ammonium perchlorate (AP) is a common oxidizer for solid propellants. It undergoes decomposition characterized by initial endothermic dissociation and gasification followed by an exothermic reaction of gaseous products. The acceleration of the initial gasification process contributes to an overall increase in the AP decomposition rate, thereby increasing the oxidizer's potential for power generation. In this study, we use density functional theory to examine the mechanism for the acceleration at two common surfaces of the titanium dioxide (TiO2) mineral anatase (001) and (101) on AP decomposition, as well as the impact of surface oxygen vacancies (O-vac) on anatase reactivity with AP. The adsorption of immediate AP gasification products, NH3 and HClO4, on the anatase surfaces was evaluated in terms of adsorption energies and calculated atomic Bader charges to elucidate the interactions between anatase surfaces and AP. The calculated enthalpy of adsorption (Delta H ads) revealed strongly exothermic adsorption reactions. At the experimentally observed highest decomposition temperature of (similar to 700 K), Delta H ads was -159 kJ/mol for the (001) surface and -172 kJ/mol for the (101) surface, respectively. The presence of an O-vac significantly altered these values, resulting in -243 kJ/mol for the (001) surface and -387 kJ/mol for the (101) surface at 700 K. These findings underscore the crucial role of oxygen vacancy defects in increasing adsorption, which in turn promotes the subsequent AP decomposition rate.
引用
收藏
页码:19337 / 19347
页数:11
相关论文
共 66 条
  • [1] Toward reliable density functional methods without adjustable parameters: The PBE0 model
    Adamo, C
    Barone, V
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1999, 110 (13) : 6158 - 6170
  • [2] TiO2 anatase's bulk and (001) surface, structural and electronic properties: A DFT study on the importance of Hubbard and van der Waals contributions
    Araujo-Lopez, Eduard
    Alcala Varilla, Luis
    Seriani, Nicola
    Montoya, Javier A.
    [J]. SURFACE SCIENCE, 2016, 653 : 187 - 196
  • [3] Effects of morphology on surface hydroxyl concentration:: a DFT comparison of anatase-TiO2 and γ-alumina catalytic supports
    Arrouvel, C
    Digne, M
    Breysse, M
    Toulhoat, H
    Raybaud, P
    [J]. JOURNAL OF CATALYSIS, 2004, 222 (01) : 152 - 166
  • [4] Peroxide and superoxide states of adsorbed O2 on anatase TiO2 (101) with subsurface defects
    Aschauer, Ulrich
    Chen, Jia
    Selloni, Annabella
    [J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2010, 12 (40) : 12956 - 12960
  • [5] A QUANTUM-THEORY OF MOLECULAR-STRUCTURE AND ITS APPLICATIONS
    BADER, RFW
    [J]. CHEMICAL REVIEWS, 1991, 91 (05) : 893 - 928
  • [6] IMPROVED TETRAHEDRON METHOD FOR BRILLOUIN-ZONE INTEGRATIONS
    BLOCHL, PE
    JEPSEN, O
    ANDERSEN, OK
    [J]. PHYSICAL REVIEW B, 1994, 49 (23): : 16223 - 16233
  • [7] Boldyrev VV, 2006, USP KHIM+, V75, P203
  • [8] Titanium Dioxide (Anatase and Rutile): Surface Chemistry, Liquid Solid Interface Chemistry, and Scientific Synthesis of Supported Catalysts
    Bourikas, Kyriakos
    Kordulis, Christos
    Lycourghiotis, Alexis
    [J]. CHEMICAL REVIEWS, 2014, 114 (19) : 9754 - 9823
  • [9] Solid propellants: AP/HTPBcomposite propellants
    Chaturvedi, Shalini
    Dave, Pragnesh N.
    [J]. ARABIAN JOURNAL OF CHEMISTRY, 2019, 12 (08) : 2061 - 2068
  • [10] Dispersion of Defects in TiO2 Semiconductor: Oxygen Vacancies in the Bulk and Surface of Rutile and Anatase
    Elahifard, Mohammadreza
    Sadrian, Mohammad Reza
    Mirzanejad, Amir
    Behjatmanesh-Ardakani, Reza
    Ahmadvand, Seyedsaeid
    [J]. CATALYSTS, 2020, 10 (04)