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Thermal stability and decomposition mechanism of synthetic covellite samples

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Abstract

Recrystallization of the copper sulfide occurs during the thermal treatment of the samples and directly affects the size of the nanoparticles. Since particle size is one of the most important characteristics of copper sulfides, in determining the electrochemical and optical properties of nanostructured sulfides, the investigation of the thermal stability of copper sulfides is relevant. In this work, the mechanism of the thermal decomposition of synthetic covellite was investigated and proposed. According to the literature, thermal decomposition and oxidation presumably occur up to 600 °C, and therefore, the experiments were carried out in a temperature range of 25–600 °C. The thermal behavior and decomposition were investigated and characterized by XRD, DSC, and SEM–EDX analysis methods. It was determined that the duration of synthesis had an influence on the temperature of decomposition of synthetic covellite, because by prolonging the duration of synthesis from 0.5 to 4 h, the temperature range of the stability of covellite increased by 100 °C (from 300 to 400 °C). Furthermore, the application of different sulfurizing agents for hydrothermal synthesis insignificantly affected the mineral changes of the annealing products in the temperature range of 250–400 °C. It was established that minor reactions of covellite decomposition started in 300 °C, by forming Cu7S4 and Cu9S5. The majority of digenite formed at a temperature higher than 400 °C. It was determined that at a temperature higher than 450 °C, Cu1.81S and Cu2S formed and copper sulfide oxidation to copper sulfate occurred.

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References

  1. Majumdar D. Recent progress in copper sulfide based nanomaterials for high energy supercapacitor applications. J Electroanal Chem. 2020. https://doi.org/10.1016/j.jelechem.2020.114825.

    Article  Google Scholar 

  2. Sun S, Li P, Liang S, Yang Z. Diversified copper sulfide (Cu2–xS) micro-/nanostructures: a comprehensive review on synthesis, modifications and applications. Nanoscale Royal Soc Chem. 2017;9:11357–404.

    CAS  Google Scholar 

  3. Chen Y, Li J, Lei Z, Huo Y, Yang L, Zeng S, et al. Hollow CuS nanoboxes as Li-free cathode for high-rate and long-life lithium metal batteries. Adv Energy Mater. 2020. https://doi.org/10.1002/aenm.201903401.

    Article  Google Scholar 

  4. Liu M, Liu Y, Gu B, Wei X, Xu G, Wang X, et al. Recent advances in copper sulphide-based nanoheterostructures. Chem Soc Rev Royal Soc Chem. 2019;48:4950–65.

    Article  CAS  Google Scholar 

  5. Shaikh S, Rabinal MK. Rapid ambient growth of copper sulfide microstructures: binder free electrodes for supercapacitor. J Energy Storage. 2020;28:101288.

    Article  Google Scholar 

  6. Zhao T, Yang W, Zhao X, Peng X, Hu J, Tang C, et al. Facile preparation of reduced graphene oxide/copper sulfide composite as electrode materials for supercapacitors with high energy density. Compos Part B Eng. 2018;150:60–7.

    Article  CAS  Google Scholar 

  7. Zhou S, Gong L, Zhao X, Liang Q, Zhang W, Wang L, et al. Synthesis and photocatalytic performance of copper sulfide by a simple solvothermal method. Chem Phys Lett. 2020;759:138034.

    Article  CAS  Google Scholar 

  8. Nabi G, Tanveer M, Bilal Tahir M, Kiran M, Rafique M, Khalid NR, et al. Mixed solvent based surface modification of CuS nanostructures for an excellent photocatalytic application. Inorg Chem Commun. 2020. https://doi.org/10.1016/j.inoche.2020.108205.

    Article  Google Scholar 

  9. Iqbal S, Bahadur A, Anwer S, Ali S, Saeed A, Muhammad Irfan R, et al. Shape and phase-controlled synthesis of specially designed 2D morphologies of l-cysteine surface capped covellite (CuS) and chalcocite (Cu2S) with excellent photocatalytic properties in the visible spectrum. Appl Surf Sci. 2020. https://doi.org/10.1016/j.apsusc.2020.146691.

    Article  Google Scholar 

  10. Tsiba Matondo J, Malouangou Maurice D, Chen Q, Bai L, Guli M. Inorganic copper-based hole transport materials for perovskite photovoltaics: challenges in normally structured cells, advances in photovoltaic performance and device stability. Sol Energy Mater Sol Cells. 2021. https://doi.org/10.1016/j.solmat.2021.111011.

    Article  Google Scholar 

  11. Tirado J, Roldán-Carmona C, Muñoz-Guerrero FA, Bonilla-Arboleda G, Ralaiarisoa M, Grancini G, et al. Copper sulfide nanoparticles as hole-transporting-material in a fully-inorganic blocking layers n-i-p perovskite solar cells: Application and working insights. Appl Surf Sci. 2019. https://doi.org/10.1016/j.apsusc.2019.01.289.

    Article  Google Scholar 

  12. Hu R, Zhang R, Ma Y, Liu W, Chu L, Mao W, et al. Enhanced hole transfer in hole-conductor-free perovskite solar cells via incorporating CuS into carbon electrodes. Appl Surf Sci. 2018;462:840–6.

    Article  CAS  Google Scholar 

  13. Li M, Liu Y, Zhang Y, Han X, Zhang T, Zuo Y, et al. Effect of the annealing atmosphere on crystal phase and thermoelectric properties of copper sulfide. ACS Nano Am Chem Soc. 2021;15:4967–78.

    Article  CAS  Google Scholar 

  14. Sadovnikov SI. Thermal stability and recrystallization of semiconductor nanostructured sulfides and sulfide solid solutions. J Alloys Compd. 2019;788:586–99.

    Article  CAS  Google Scholar 

  15. Tang H, Sun F-H, Dong J-F, Zhuang H-L, Pan Y, et al. Graphene network in copper sulfide leading to enhanced thermoelectric properties and thermal stability. Nano Energy. 2018;49:267–73.

    Article  CAS  Google Scholar 

  16. Mikhlin Y, Nasluzov V, Ivaneeva A, Vorobyev S, Likhatski M, Romanchenko A, Krylov A, Zharkov S, Meira DM. Formation, evolution and characteristics of copper sulfide nanoparticles in the reactions of aqueous cupric and sulfide ions. Mater Chem Phys. 2020;255:123600.

    Article  CAS  Google Scholar 

  17. Dexter M, Gao Z, Bansal S, Chang C-H, Malhotra R. Temperature, crystalline phase and influence of substrate properties in intense pulsed light sintering of copper sulfide nanoparticle thin films. Sci Rep. 2018;8:1–14.

    Article  CAS  Google Scholar 

  18. Nafees M, Ikram M, Ali S. Thermal behavior and decomposition of copper sulfide nanomaterial synthesized by aqueous sol method. Dig J Nanomater Biostruct. 2015;10:635–41.

    Google Scholar 

  19. Dunn J, Muzenda C. Thermal oxidation of covellite (CuS). Thermochim Acta. 2001. https://doi.org/10.1016/S0040-6031(00)00748-6.

    Article  Google Scholar 

  20. Simonescu CM, Teodorescu VS, Carp O, Patron L, Capatina C. Thermal behaviour of CuS (covellite) obtained from copper–thiosulfate system. J Therm Anal Calorim. 2007. https://doi.org/10.1007/s10973-006-8079-z.

    Article  Google Scholar 

  21. Botha NL, Ajibade PA. Effect of temperature on crystallite sizes of copper sulfide nanocrystals prepared from copper(II) dithiocarbamate single source precursor. Mater Sci Semicond Process. 2016. https://doi.org/10.1016/j.mssp.2015.12.006.

    Article  Google Scholar 

  22. Mousavi-Kamazani M, Zarghami Z, Salavati-Niasari M. Facile and novel chemical synthesis, characterization, and formation mechanism of copper sulfide (Cu2S, Cu2S/CuS, CuS) nanostructures for increasing the efficiency of solar cells. J Phys Chem C. 2016. https://doi.org/10.1021/acs.jpcc.5b11566.

    Article  Google Scholar 

  23. Abouserie A, El-Nagar GA, Heyne B, Günter C, Schilde U, Mayer MT, et al. Facile synthesis of hierarchical CuS and CuCo2S4 structures from an ionic liquid precursor for electrocatalysis applications. ACS Appl Mater Interfaces. 2020. https://doi.org/10.1021/acsami.0c13927.

    Article  PubMed  Google Scholar 

  24. Sarapajevaite G, Baltakys K. Purification of sulfur waste under hydrothermal conditions. Waste Biomass Valoriz. 2021. https://doi.org/10.1007/s12649-020-01206-y.

    Article  Google Scholar 

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Authors and Affiliations

  1. Department of Silicate Technology, Kaunas University of Technology, Radvilenu road 19, LT – 50254, Kaunas, Lithuania

    Gabriele Sarapajevaite & Kestutis Baltakys

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  1. Gabriele Sarapajevaite
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  2. Kestutis Baltakys
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GS and KB contributed to conceptualization; KB was involved in methodology, writing—review and editing, and supervision; and GS contributed to formal analysis and investigation and writing.

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Correspondence to Gabriele Sarapajevaite.

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Sarapajevaite, G., Baltakys, K. Thermal stability and decomposition mechanism of synthetic covellite samples. J Therm Anal Calorim 147, 10951–10963 (2022). https://doi.org/10.1007/s10973-022-11313-8

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  • DOI: https://doi.org/10.1007/s10973-022-11313-8

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