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. 2022 Dec 2;66(4):1641–1648. doi: 10.1007/s40843-022-2257-6

Periodate-based molecular perovskites as promising energetic biocidal agents

高碘酸根分子钙钛矿作为新型含能杀菌剂

Zhi-Hong Yu 1, De-Xuan Liu 1, Yu-Yi Ling 1, Xiao-Xian Chen 1, Yu Shang 1, Shao-Li Chen 1, Zi-Ming Ye 1, Wei-Xiong Zhang 1,✉, Xiao-Ming Chen 1
PMCID: PMC9734302  PMID: 36532126

Abstract

Epidemics caused by pathogens in recent years have created an urgent need for energetic biocidal agents with the capacity of detonation and releasing bactericides. Herein we present a new type of energetic biocidal agents based on a series of iodine-rich molecular perovskites, (H2dabco)M(IO4)3 (dabco = 1,4-diazabicyclo[2.2.2]octane, M = Na+/K+/Rb+/NH4+ for DAI-1/2/3/4) and (H2dabco)Na(H4IO6)3 (DAI-X1). These compounds possess a cubic perovskite structure, and notably have not only high iodine contents (49–54 wt%), but also high performance in detonation velocity (6.331–6.558 km s−1) and detonation pressure (30.69–30.88 GPa). In particular, DAI-4 has a very high iodine content of 54.0 wt% and simultaneously an exceptional detonation velocity up to 6.558 km s−1. As disclosed by laser scanning confocal microscopy observation and a standard micro-broth dilution method, the detonation products of DAI-4 exhibit a broad-spectrum bactericidal effect against bacteria (E. coli, S. aureus, and P. aeruginosa). The advantages of easy scale-up synthesis, low cost, high detonation performance, and high iodine contents enable these periodate-based molecular perovskites to be highly promising candidates for energetic biocidal agents.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at 10.1007/s40843-022-2257-6.

Keywords: energetic material, single explosive, energetic biocidal agent, periodate-based molecular perovskite

Acknowledgements

This work was supported by the National Natural Science Foundation of China (22071273 and 21821003), the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01C161), and the Fundamental Innovation Team Fund (CXTD-202001). The authors thank Prof. Cai-Ping Tan at Sun Yat-Sen University for her assistance in biocidal experiments.

Supporting Information

40843_2022_2257_MOESM1_ESM.pdf (1.2MB, pdf)

Periodate-based molecular perovskites as promising energetic biocidal agents

Author contributions

Zhang WX and Chen XM designed the research. Yu ZH conducted the synthetic experiments and most measurements. Liu DX, Chen XX, and Ye ZM provided assistance in the single-crystal XRD analysis. Shang Y, Chen SL offered help in the detonation parameter calculation. Ling YY conducted biocidal experiments. Yu ZH, Zhang WX, and Chen XM wrote the manuscript. All the authors contributed to the discussion.

Footnotes

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Zhi-Hong Yu was born in 1996. He is an MSc candidate in inorganic chemistry at Sun Yat-Sen University (SYSU). His research focuses on energetic salts.

Wei-Xiong Zhang obtained his BSc in 2004 and PhD in 2009 at SYSU, and was a JSPS postdoc at Tohoku University from 2010 to 2012. He joined SYSU in 2012, and became a professor in 2018. His current research interest is in crystal engineering of multi-component dense crystals, especially the structural-phase-transition functional crystals and energetic crystals.

References

  • 1.Chang J, Zhao G, Zhao X, et al. New promises from an old friend: Iodine-rich compounds as prospective energetic biocidal agents. Acc Chem Res. 2021;54:332–343. doi: 10.1021/acs.accounts.0c00623. [DOI] [PubMed] [Google Scholar]
  • 2.Kaiho T. Iodine Chemistry and Applications. New York: John Wiley & Sons; 2015. [Google Scholar]
  • 3.He C, Parrish DA, Shreeve JM. Alkyl ammonium cation stabilized biocidal polyiodides with adaptable high density and low pressure. Chem Eur J. 2014;20:6699–6706. doi: 10.1002/chem.201402176. [DOI] [PubMed] [Google Scholar]
  • 4.He C, Zhao G, Hooper JP, et al. Energy and biocides storage compounds: Synthesis and characterization of energetic bridged bis(triiodoazoles) Inorg Chem. 2017;56:13547–13552. doi: 10.1021/acs.inorgchem.7b02277. [DOI] [PubMed] [Google Scholar]
  • 5.Zhao G, He C, Kumar D, et al. Functional energetic biocides by coupling of energetic and biocidal polyiodo building blocks. Chem Eng J. 2019;368:244–251. doi: 10.1016/j.cej.2019.02.192. [DOI] [Google Scholar]
  • 6.Zhao G, Kumar D, He C, et al. New generation agent defeat weapons: Energetic N, N’-ethylene-bridged polyiodoazoles. Chem Eur J. 2017;23:16753–16757. doi: 10.1002/chem.201704798. [DOI] [PubMed] [Google Scholar]
  • 7.Zhao G, He C, Zhou W, et al. Control of biohazards: A high performance energetic polycyclized iodine-containing biocide. Inorg Chem. 2018;57:8673–8680. doi: 10.1021/acs.inorgchem.8b01600. [DOI] [PubMed] [Google Scholar]
  • 8.Zhao G, He C, Kumar D, et al. 1,3,5-Triiodo-2,4,6-trinitrobenzene (TITNB) from benzene: Balancing performance and high thermal stability of functional energetic materials. Chem Eng J. 2019;378:122119. doi: 10.1016/j.cej.2019.122119. [DOI] [Google Scholar]
  • 9.Chang J, He C, Pang S, et al. N, N’-methylene-bridged nitroiodoazoles: Biocidal compounds with enhanced thermal stability. Chem Eng J. 2022;450:137841. doi: 10.1016/j.cej.2022.137841. [DOI] [Google Scholar]
  • 10.He C, Zhang J, Shreeve JM. Dense iodine-rich compounds with low detonation pressures as biocidal agents. Chem Eur J. 2013;19:7503–7509. doi: 10.1002/chem.201300565. [DOI] [PubMed] [Google Scholar]
  • 11.He C, Hooper JP, Shreeve JM. Iodine-rich imidazolium iodate and periodate salts: Enroute to single-based biocidal agents. Inorg Chem. 2016;55:12844–12850. doi: 10.1021/acs.inorgchem.6b02195. [DOI] [PubMed] [Google Scholar]
  • 12.Li Y, Cao Y, Song S, et al. Self-assembly of iodine-containing oxidants with nitrogen-rich heterocyclic compounds for novel energetic biocidal agents. Chem Eng J. 2022;442:136326. doi: 10.1016/j.cej.2022.136326. [DOI] [Google Scholar]
  • 13.Zhang J, Zhu Z, Zhou M, et al. Superior high-energy-density biocidal agent achieved with a 3D metal-organic framework. ACS Appl Mater Interfaces. 2020;12:40541–40547. doi: 10.1021/acsami.0c12251. [DOI] [PubMed] [Google Scholar]
  • 14.Zhang J, Hooper JP, Zhang J, et al. Well-balanced energetic cocrystals of H5IO6/HIO3 achieved by a small acid-base gap. Chem Eng J. 2021;405:126623. doi: 10.1016/j.cej.2020.126623. [DOI] [Google Scholar]
  • 15.Kumar CA, Shlomovich A, Shamis O, et al. Combustion of energetic iodine-rich coordination polymer—Engineering of new biocidal materials. Chem Eng J. 2018;350:1084–1091. doi: 10.1016/j.cej.2018.06.056. [DOI] [Google Scholar]
  • 16.Deng P, Ren H, Jiao Q. Enhanced the combustion performances of ammonium perchlorate-based energetic molecular perovskite using functionalized graphene. Vacuum. 2019;169:108882. doi: 10.1016/j.vacuum.2019.108882. [DOI] [Google Scholar]
  • 17.Deng P, Wang H, Yang X, et al. Thermal decomposition and combustion performance of high-energy ammonium perchlorate-based molecular perovskite. J Alloys Compd. 2020;827:154257. doi: 10.1016/j.jallcom.2020.154257. [DOI] [Google Scholar]
  • 18.Han K, Zhang X, Deng P, et al. Study of the thermal catalysis decomposition of ammonium perchlorate-based molecular perovskite with titanium carbide MXene. Vacuum. 2020;180:109572. doi: 10.1016/j.vacuum.2020.109572. [DOI] [Google Scholar]
  • 19.Jia Q, Bai X, Zhu S, et al. Fabrication and characterization of nano (H2dabco)[K(ClO4)3] molecular perovskite by ball milling. J Energ Mater. 2020;38:377–385. doi: 10.1080/07370652.2019.1698675. [DOI] [Google Scholar]
  • 20.Jia Q, Deng P, Li X, et al. Insight into the thermal decomposition properties of potassium perchlorate (KClO4)-based molecular perovskite. Vacuum. 2020;175:109257. doi: 10.1016/j.vacuum.2020.109257. [DOI] [Google Scholar]
  • 21.Li X, Hu S, Cao X, et al. Ammonium perchlorate-based molecular perovskite energetic materials: Preparation, characterization, and thermal catalysis performance with MoS2. J Energ Mater. 2020;38:162–169. doi: 10.1080/07370652.2019.1679281. [DOI] [Google Scholar]
  • 22.Li ZY, Cao X, Li XX, et al. Synthesis, characterization and hygroscopicity testing of molecular perovskite energetic materials. J Energ Mater. 2020;28:539–543. [Google Scholar]
  • 23.Zhang WX, Chen SL, Shang Y, et al. Molecular perovskites as a new platform for designing advanced multi-component energetic crystals. Energ Mater Front. 2020;1:123–135. doi: 10.1016/j.enmf.2020.12.003. [DOI] [Google Scholar]
  • 24.Hu L, Du Z, Liu Y, et al. Green fabrication of nanoscale energetic molecular perovskite (H2dabco)[Na(ClO4)3] with reduced mechanical sensitivity. Cent Eur J Energ Mater. 2021;18:369–384. doi: 10.22211/cejem/142572. [DOI] [Google Scholar]
  • 25.Zhai P, Shi C, Zhao S, et al. Thermal decomposition of ammonium perchlorate-based molecular perovskite from TG-DSC-FTIR-MS and ab initio molecular dynamics. RSC Adv. 2021;11:16388–16395. doi: 10.1039/D0RA10559G. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 26.Shang Y, Sun L, Ye Z, et al. Phase transition and thermal expansion of molecular perovskite energetic crystal (C6N2H14)(NH4)(ClO4)3 (DAP-4) FirePhysChem. 2022;2:221–225. doi: 10.1016/j.fpc.2022.01.002. [DOI] [Google Scholar]
  • 27.Chen SL, Yang ZR, Wang BJ, et al. Molecular perovskite high-energetic materials. Sci China Mater. 2018;61:1123–1128. doi: 10.1007/s40843-017-9219-9. [DOI] [Google Scholar]
  • 28.Yao LN, Wang H, Dai ZX, et al. A kind of low-cost high temperature explosive, preparation method and application. China Patent, CN114292151A. 2022-04-08
  • 29.Chen SL, Shang Y, He CT, et al. Optimizing the oxygen balance by changing the A-site cations in molecular perovskite high-energetic materials. CrystEngComm. 2018;20:7458–7463. doi: 10.1039/C8CE01350K. [DOI] [Google Scholar]
  • 30.Shang Y, Huang RK, Chen SL, et al. Metal-free molecular perovskite high-energetic materials. Cryst Growth Des. 2020;20:1891–1897. doi: 10.1021/acs.cgd.9b01592. [DOI] [Google Scholar]
  • 31.Shang Y, Chen SL, Yu ZH, et al. Silver(I)-based molecular perovskite energetic compounds with exceptional thermal stability and energetic performance. Inorg Chem. 2022;61:4143–4149. doi: 10.1021/acs.inorgchem.1c03958. [DOI] [PubMed] [Google Scholar]
  • 32.Shang Y, Yu ZH, Huang RK, et al. Metal-free hexagonal perovskite high-energetic materials with NH3OH+/NH2NH3+ as B-site cations. Engineering. 2020;6:1013–1018. doi: 10.1016/j.eng.2020.05.018. [DOI] [Google Scholar]
  • 33.Chen S, Shang Y, Jiang J, et al. A new nitrate-based energetic molecular perovskite as a modern edition of black powder. Energetic Mater Front. 2022;3:122–127. doi: 10.1016/j.enmf.2022.07.003. [DOI] [Google Scholar]
  • 34.Dolomanov OV, Bourhis LJ, Gildea RJ, et al. OLEX2: A complete structure solution, refinement and analysis program. J Appl Crystlogr. 2010;42:339–341. doi: 10.1107/S0021889808042726. [DOI] [Google Scholar]
  • 35.Sheldrick GM. SHELXT—Integrated space-group and crystal-structure determination. Acta Crystlogr Found Adv. 2015;71:3–8. doi: 10.1107/S2053273314026370. [DOI] [PMC free article] [PubMed] [Google Scholar]
  • 36.Xu JG, Li XZ, Wu HF, et al. Substitution of nitrogen-rich linkers with insensitive linkers in azide-based energetic coordination polymers toward safe energetic materials. Cryst Growth Des. 2019;19:3934–3944. doi: 10.1021/acs.cgd.9b00351. [DOI] [Google Scholar]
  • 37.Meyer R, Köhler J, Homburg A. Explosives. Weinheim: Wiley; 2016. [Google Scholar]
  • 38.Mallick S, Sharma S, Banerjee M, et al. Iodine-stabilized Cu nanoparticle chitosan composite for antibacterial applications. ACS Appl Mater Interfaces. 2012;4:1313–1323. doi: 10.1021/am201586w. [DOI] [PubMed] [Google Scholar]

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