Assessing the Novel Mixed Tutton Salts K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.18</sub>Cu<sub>0.82</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study
In this paper, novel mixed Tutton salts with the chemical formulas K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.1...
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| Format: | Article |
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MDPI AG
2023-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/24/8058 |
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| author | João G. de Oliveira Neto Jailton R. Viana Antonio D. da S. G. Lima Jardel B. O. Lopes Alejandro P. Ayala Mateus R. Lage Stanislav R. Stoyanov Adenilson O. dos Santos Rossano Lang |
| author_facet | João G. de Oliveira Neto Jailton R. Viana Antonio D. da S. G. Lima Jardel B. O. Lopes Alejandro P. Ayala Mateus R. Lage Stanislav R. Stoyanov Adenilson O. dos Santos Rossano Lang |
| author_sort | João G. de Oliveira Neto |
| collection | DOAJ |
| description | In this paper, novel mixed Tutton salts with the chemical formulas K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.18</sub>Cu<sub>0.82</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> were synthesized and studied as compounds for thermochemical heat storage potential. The crystallographic structures of single crystals were determined by X-ray diffraction. Additionally, a comprehensive computational study, based on density functional theory (DFT) calculations and Hirshfeld surface analysis, was performed to calculate structural, electronic, and thermodynamic properties of the coordination complexes [M<sup>II</sup>(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup> (M<sup>II</sup> = Mn, Ni, and Cu), as well as to investigate intermolecular interactions and voids in the framework. The axial compressions relative to octahedral coordination geometry observed in the crystal structures were correlated and elucidated using DFT investigations regarding Jahn–Teller effects arising from complexes with different spin multiplicities. The spatial distributions of the frontier molecular orbital and spin densities, as well as energy gaps, provided further insights into the stability of these complexes. Thermogravimetry, differential thermal analysis, and differential scanning calorimetry techniques were also applied to identify the thermal stability and physicochemical properties of the mixed crystals. Values of dehydration enthalpy and storage energy density per volume were also estimated. The two mixed sulfate hydrates reported here have low dehydration temperatures and high energy densities. Both have promising thermal properties for residential heat storage systems, superior to the Tutton salts previously reported. |
| first_indexed | 2024-03-08T20:29:43Z |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-08T20:29:43Z |
| publishDate | 2023-12-01 |
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| series | Molecules |
| spelling | doaj.art-2e19aa4310174ad7a61ef0bd98831f592023-12-22T14:27:35ZengMDPI AGMolecules1420-30492023-12-012824805810.3390/molecules28248058Assessing the Novel Mixed Tutton Salts K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.18</sub>Cu<sub>0.82</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> for Thermochemical Heat Storage Applications: An Experimental–Theoretical StudyJoão G. de Oliveira Neto0Jailton R. Viana1Antonio D. da S. G. Lima2Jardel B. O. Lopes3Alejandro P. Ayala4Mateus R. Lage5Stanislav R. Stoyanov6Adenilson O. dos Santos7Rossano Lang8Center for Social Sciences, Health and Technology, Federal University of Maranhão—UFMA, Imperatriz 65900-410, MA, BrazilCenter for Social Sciences, Health and Technology, Federal University of Maranhão—UFMA, Imperatriz 65900-410, MA, BrazilCenter for Social Sciences, Health and Technology, Federal University of Maranhão—UFMA, Imperatriz 65900-410, MA, BrazilCenter for Social Sciences, Health and Technology, Federal University of Maranhão—UFMA, Imperatriz 65900-410, MA, BrazilDepartment of Physics, Federal University of Ceará—UFC, Fortaleza 65455-900, CE, BrazilCenter for Social Sciences, Health and Technology, Federal University of Maranhão—UFMA, Imperatriz 65900-410, MA, BrazilNatural Resources Canada, CanmetENERGY Devon, 1 Oil Patch Drive, Devon, AB T9G 1A8, CanadaCenter for Social Sciences, Health and Technology, Federal University of Maranhão—UFMA, Imperatriz 65900-410, MA, BrazilInstitute of Science and Technology, Federal University of São Paulo—UNIFESP, São José dos Campos 12231-280, SP, BrazilIn this paper, novel mixed Tutton salts with the chemical formulas K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.18</sub>Cu<sub>0.82</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> were synthesized and studied as compounds for thermochemical heat storage potential. The crystallographic structures of single crystals were determined by X-ray diffraction. Additionally, a comprehensive computational study, based on density functional theory (DFT) calculations and Hirshfeld surface analysis, was performed to calculate structural, electronic, and thermodynamic properties of the coordination complexes [M<sup>II</sup>(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup> (M<sup>II</sup> = Mn, Ni, and Cu), as well as to investigate intermolecular interactions and voids in the framework. The axial compressions relative to octahedral coordination geometry observed in the crystal structures were correlated and elucidated using DFT investigations regarding Jahn–Teller effects arising from complexes with different spin multiplicities. The spatial distributions of the frontier molecular orbital and spin densities, as well as energy gaps, provided further insights into the stability of these complexes. Thermogravimetry, differential thermal analysis, and differential scanning calorimetry techniques were also applied to identify the thermal stability and physicochemical properties of the mixed crystals. Values of dehydration enthalpy and storage energy density per volume were also estimated. The two mixed sulfate hydrates reported here have low dehydration temperatures and high energy densities. Both have promising thermal properties for residential heat storage systems, superior to the Tutton salts previously reported.https://www.mdpi.com/1420-3049/28/24/8058single-crystal growthmixed Tutton saltsHirshfeld fingerprint plotsDFT calculationsthermochemical compounds |
| spellingShingle | João G. de Oliveira Neto Jailton R. Viana Antonio D. da S. G. Lima Jardel B. O. Lopes Alejandro P. Ayala Mateus R. Lage Stanislav R. Stoyanov Adenilson O. dos Santos Rossano Lang Assessing the Novel Mixed Tutton Salts K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.18</sub>Cu<sub>0.82</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study Molecules single-crystal growth mixed Tutton salts Hirshfeld fingerprint plots DFT calculations thermochemical compounds |
| title | Assessing the Novel Mixed Tutton Salts K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.18</sub>Cu<sub>0.82</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study |
| title_full | Assessing the Novel Mixed Tutton Salts K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.18</sub>Cu<sub>0.82</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study |
| title_fullStr | Assessing the Novel Mixed Tutton Salts K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.18</sub>Cu<sub>0.82</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study |
| title_full_unstemmed | Assessing the Novel Mixed Tutton Salts K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.18</sub>Cu<sub>0.82</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study |
| title_short | Assessing the Novel Mixed Tutton Salts K<sub>2</sub>Mn<sub>0.03</sub>Ni<sub>0.97</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> and K<sub>2</sub>Mn<sub>0.18</sub>Cu<sub>0.82</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>6</sub> for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study |
| title_sort | assessing the novel mixed tutton salts k sub 2 sub mn sub 0 03 sub ni sub 0 97 sub so sub 4 sub sub 2 sub h sub 2 sub o sub 6 sub and k sub 2 sub mn sub 0 18 sub cu sub 0 82 sub so sub 4 sub sub 2 sub h sub 2 sub o sub 6 sub for thermochemical heat storage applications an experimental theoretical study |
| topic | single-crystal growth mixed Tutton salts Hirshfeld fingerprint plots DFT calculations thermochemical compounds |
| url | https://www.mdpi.com/1420-3049/28/24/8058 |
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