Optimizing the oxygen balance by changing the A-site cations in molecular perovskite high-energetic materials
- 12 October 2018
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in CrystEngComm
- Vol. 20 (46), 7458-7463
- https://doi.org/10.1039/c8ce01350k
Abstract
We presented two new members of molecular perovskite high-energetic materials, (H2pz)[Na(ClO4)3] (PAP-1) and (H2dabco-O)[K(ClO4)3] (DAP-O2), in which H2pz2+ (piperazine-1,4-diium) and H2dabco-O2+ (1-hydroxy-1,4-diazabicyclo[2.2.2]octane-1,4-diium) act as A-site fuel cations, respectively. Compared with their H2dabco2+ analogues, (H2dabco)[M(ClO4)3] (H2dabco2+ = 1,4-diazabicyclo[2.2.2]octane-1,4-diium, M = Na+ for DAP-1 and K+ for DAP-2, respectively), PAP-1 and DAP-O2 exhibit optimized oxygen balance by employing two strategies to change the A-site cations, i.e., “trimming the C and H atoms” of H2dabco2+ by using H2pz2+ to form PAP-1 and adding an O atom into H2dabco2+ by using H2dabco-O2+ to form DAP-O2, respectively. As suggested by DFT calculations and the K–J equation, the smaller H2pz2+ cation in PAP-1 gives a significantly-optimized oxygen balance from −22.0% to −3.9% and an increased crystal density from 2.02 to 2.07 g cm−3, resulting in a better detonation performance for PAP-1. Meanwhile the larger H2dabco-O2+ cation gives a slightly-optimized oxygen balance from −21.3% to −17.1% but a decreased crystal density from 2.04 to 1.98 g cm−3, leading to a decreased detonation performance from DAP-2 to DAP-O2. This study demonstrated how to rationally choose the A-site cations in a perovskite structure for modulating the properties of molecular perovskite high-energetic materials, providing important clues for designing more advanced energetic materials for practical use.Keywords
Funding Information
- National Natural Science Foundation of China (21290173, 21722107)
This publication has 51 references indexed in Scilit:
- Environmentally friendly high-energy MOFs: crystal structures, thermostability, insensitivity and remarkable detonation performancesGreen Chemistry, 2014
- Metal–Organic Frameworks as High Explosives: A New Concept for Energetic MaterialsAngewandte Chemie, 2014
- 3D Energetic Metal–Organic Frameworks: Synthesis and Properties of High Energy MaterialsAngewandte Chemie, 2013
- Crystal structure and explosive performance of a new CL-20/caprolactam cocrystalJournal of Molecular Structure, 2013
- New Roles for 1,1-Diamino-2,2-dinitroethene (FOX-7): Halogenated FOX-7 and Azo-bis(diahaloFOX) as Energetic Materials and OxidizersJournal of the American Chemical Society, 2013
- Metal–Organic Frameworks (MOFs) as Safer, Structurally Reinforced EnergeticsChemistry – A European Journal, 2012
- Pushing the limits of energetic materials – the synthesis and characterization of dihydroxylammonium 5,5′-bistetrazole-1,1′-diolateJournal of Materials Chemistry, 2012
- Cocrystals of 1,3,5,7-Tetranitro-1,3,5,7-tetrazacyclooctane (HMX)Crystal Growth & Design, 2012
- Ionic Polymers as a New Structural Motif for High-Energy-Density MaterialsJournal of the American Chemical Society, 2012
- There's Room in the MiddleScience, 2007