Assessing the Novel Mixed Tutton Salts K2Mn0.03Ni0.97(SO4)2(H2O)6 and K2Mn0.18Cu0.82(SO4)2(H2O)6 for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study
Abstract
:1. Introduction
2. Results and Discussions
2.1. Crystal Growth
2.2. Structure Solving and Lattice Parameters
2.3. Study of Intermolecular Interactions via Hirshfeld Surfaces
2.4. Crystal Voids
2.5. Calculated Properties of the Hexa-Aqua Transition Metal Complexes
2.6. Thermal Properties
3. Experimental and Theoretical Procedures
3.1. Single-Crystal Synthesis
3.2. Structural and Thermal Characterization
3.3. Computational Procedure
3.4. Hirshfeld Surface Analysis and Unit Cell Voids
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Empirical Formula | H12K2Mn0.03Ni0.97O14S2 | H12K2Mn0.18Cu0.82O14S2 |
---|---|---|
Formula weight [g/mol] | 437.01 | 434.32 |
Temperature [K] | 301.00 | 302.00 |
Crystal system | monoclinic | monoclinic |
Space group | P21/c | P21/c |
a [Å] | 6.1351(2) | 6.1690(2) |
b [Å] | 12.1900(3) | 12.1406(5) |
c [Å] | 9.0039(3) | 9.0784(3) |
α [°] | 90 | 90 |
β [°] | 105.0400(10) | 104.4720(10) |
γ [°] | 90 | 90 |
Volume [Å3] | 650.31(3) | 658.36(4) |
Z | 2 | 2 |
ρCalc [g/cm3] | 2.232 | 2.191 |
μ [mm−1] | 2.507 | 2.553 |
F(000) | 444.0 | 433.0 |
Crystal size [mm3] | 0.518 × 0.227 × 0.153 | 1.105 × 0.511 × 0.267 |
Radiation | MoKα (λ = 0.71073) | MoKα (λ = 0.71073) |
2θ range for data collection [°] | 5.754 to 84.544 | 5.722 to 59.982 |
Index ranges | −11 ≤ h ≤ 9, −22 ≤ k ≤ 20, −14 ≤ l ≤ 16 | −8 ≤ h ≤ 8, −17 ≤ k ≤ 17, −12 ≤ l ≤ 12 |
Reflections collected | 26,978 | 17,974 |
Independent reflections | 4046 [Rint = 0.0347, Rsigma = 0.0246] | 1912 [Rint = 0.0406, Rsigma = 0.0261] |
Data/restraints/parameters | 4046/0/93 | 1912/0/90 |
Goodness-of-fit on F2 | 1.045 | 1.081 |
Final R indexes [I ≥ 2σ (I)] | R1 = 0.0254, wR2 = 0.0620 | R1 = 0.0244, wR2 = 0.0650 |
Final R indexes [all data ] | R1 = 0.0313, wR2 = 0.0649 | R1 = 0.0247, wR2 = 0.0653 |
Largest diff. peak/hole [Å−3] | 0.52/−0.48 | 0.58/−0.41 |
KMn/Ni | KMn/Cu | ||
---|---|---|---|
Atoms | Length [Å] | Atoms | Length [Å] |
Mn/Ni–O4 | 2.021(7) | Mn/Cu–O4 | 1.961(11) |
Mn/Ni–O5 | 2.086(7) | Mn/Cu–O5 | 2.095(12) |
Mn/Ni–O6 | 2.080(7) | Mn/Cu–O6 | 2.248(12) |
S3–O7 | 1.475(7) | S3–O7 | 1.478(12) |
S3–O8 | 1.481(7) | S3–O8 | 1.481(11) |
S3–O9 | 1.478(8) | S3–O9 | 1.474(12) |
S3–O10 | 1.465(9) | S3–O10 | 1.464(13) |
KMn/Ni | KMn/Cu | ||
---|---|---|---|
Atoms | Angle [°] | Atoms | Angle [°] |
O4–Mn/Ni–O4* | 180.0(5) | O4–Mn/Cu–O4† | 180.0(5) |
O4–Mn/Ni–O5* | 90.0(3) | O4–Mn/Cu–O5† | 89.6(5) |
O4*–Mn/Ni–O5* | 89.9(3) | O4†–Mn/Cu–O5† | 90.3(5) |
O4–Mn/Ni–O5 | 90.0(3) | O4–Mn/Cu–O5 | 89.6(5) |
O4*–Mn/Ni–O5 | 89.9(3) | O4†–Mn/Cu–O5 | 90.3(5) |
O4*–Mn/Ni–O6* | 90.3(3) | O4†–Mn/Cu–O6† | 89.3(4) |
O4–Mn/Ni–O6 | 89.6(3) | O4–Mn/Cu–O6 | 90.6(4) |
O4–Mn/Ni–O6* | 89.6(3) | O4–Mn/Cu–O6† | 90.6(4) |
O4*–Mn/Ni–O6 | 90.3(3) | O4†–Mn/Cu–O6 | 89.3(4) |
O5–Mn/Ni–O5* | 180.0(4) | O5–Mn/Cu–O5† | 180.0(4) |
O5*–Mn/Ni–O6* | 91.6(3) | O5†–Mn/Cu–O6† | 90.6(5) |
O5–Mn/Ni–O6* | 91.6(3) | O5–Mn/Cu–O6† | 89.4(5) |
O5*–Mn/Ni–O6 | 88.3(3) | O5†–Mn/Cu–O6 | 89.4(5) |
O5–Mn/Ni–O6 | 88.3(3) | O5–Mn/Cu–O6 | 90.5(5) |
O6–Mn/Ni–O6* | 180.0(5) | O6–Mn/Cu–O6† | 180.0(5) |
O7–S3–O8 | 110.2(4) | O7–S3–O8 | 110.0(7) |
O7–S3–O9 | 108.0(5) | O7–S3–O9 | 110.0(8) |
O9–S3–O8 | 109.9(5) | O9–S3–O8 | 108.0(7) |
O7–S3–O10 | 108.4(5) | O7–S3–O10 | 110.4(8) |
O10–S3–O8 | 110.6(5) | O10–S3–O8 | 108.2(8) |
O10–S3–O9 | 109.5(6) | O10–S3–O9 | 109.8(9) |
Crystal | Unit Cell Volume [Å3] | Voids Volume [Å3] | Voids Percentage [%] | Voids Surface Area [Å2] |
---|---|---|---|---|
KMn/Ni | 650.31 | 10.70 | 1.64 | 60.70 |
KMn/Cu | 658.36 | 7.32 | 1.11 | 46.47 |
Complex | Spin Multiplicity | ΔcoordG298 [kcal/mol] | ΔcoordH [kcal/mol] | ΔcoordEZPVE [kcal/mol] |
---|---|---|---|---|
[Cu(H2O)6]2+ | 2 | −296.00 | −351.49 | −347.75 |
[Ni(H2O)6]2+ | 3 | −296.00 | −352.03 | −348.18 |
[Ni(H2O)4]2+ | 1 | −339.45 | −400.05 | −393.65 |
[Mn(H2O)6]2+ | 6 | −242.20 | −296.65 | −293.17 |
[Mn(H2O)6]2+ | 4 | −274.90 | −329.57 | −325.99 |
Complex | Spin Multiplicity | M–Oax [Å] | O–M–Oax [°] | M–Oeq1 [Å] | M–Oeq2 [Å] | O–M–Oeq [°] |
---|---|---|---|---|---|---|
[Cu(H2O)6]2+ | 2 | 2.28 | 89.97 | 2.01 | 2.00 | 90.03 |
[Ni(H2O)6]2+ | 3 | 2.07 | 89.99 | 2.07 | 2.07 | 90.01 |
[Ni(H2O)4]2+ | 1 | -- | -- | 1.88 | 1.88 | 91.54 |
[Mn(H2O)6]2+ | 6 | 2.20 | 89.99 | 2.20 | 2.20 | 90.01 |
[Mn(H2O)6]2+ | 4 | 2.26 | 89.93 | 2.02 | 2.10 | 91.38 |
Complex | q(O)ax | q(O)eq1 | q(O)eq2 | q(M) | ρs_ax(O) | ρs_eq1(O) | ρs_eq2(O) | ρs(M) | HOMO [eV] | LUMO [eV] | Gap [eV] |
---|---|---|---|---|---|---|---|---|---|---|---|
[Cu(H2O)6]2+ s = 2 | −0.39 | −0.37 | −0.34 | 0.98 | 0.00 | 0.03 | 0.03 | 0.84 | −17.56 | −11.95 | 5.61 |
[Ni(H2O)6]2+ s = 3 | −0.38 | −0.38 | −0.38 | 1.04 | 0.03 | 0.03 | 0.03 | 1.80 | −17.33 | −9.89 | 7.45 |
[Ni(H2O)4]2+ s = 1 | -- | −0.35 | −0.35 | 1.02 | -- | -- | -- | -- | −16.78 | −11.31 | 5.48 |
[Mn(H2O)6]2+ s = 6 | −0.39 | −0.39 | −0.39 | 1.11 | 0.01 | 0.01 | 0.01 | 4.93 | −16.11 | −8.22 | 7.89 |
[Mn(H2O)6]2+ s = 4 | −0.39 | −0.36 | −0.38 | 1.02 | 0.01 | 0.00 | −0.01 | 2.99 | −13.68 | −9.57 | 4.10 |
Sample | Temperature [°C] | TG | DTA [°C] | ||||
---|---|---|---|---|---|---|---|
Weight Loss [%] | Weight Loss [mg] | Molar Mass [g·mol−1] | Molecular Fragment | [↓] Endothermal [↑] Exothermal | Event Type | ||
KMn/Ni | 30–200 | 25.0 | 0.59 | 109.2 | 6.0(H2O) | 101.8 ↓ 137.2 ↓ | dehydration dehydration |
200–900 | 12.6 | 0.30 | 55.2 | SO + 0.3O | 361.7 ↑ 563.4 ↓ 575.6 ↓ 644.8 ↓ | crystallization phase transition -- MnSO4 melting | |
KMn/Cu | 30–100 | 17.5 | 0.48 | 76.2 | 4.2(H2O) | 85.3 ↓ | dehydration |
100–200 | 7.5 | 0.21 | 32.4 | 1.8(H2O) | 131.2 ↓ | dehydration | |
200–900 | 18.8 | 0.52 | 81.9 | SO3 | 498.5 ↓ 515.1 ↓ 565.8 ↓ | phase transition -- MnSO4 melting |
Crystal | Temperature Range [°C] | Enthalpy [kJ/mol H2O] | Total Enthalpy [kJ/mol] | Energy Density [GJ/m3] |
---|---|---|---|---|
KMn/Ni | 80.7–176.2 | 79.4 | 476.5 | 2.43 |
KMn/Cu | 56.4–129.6 | 70.6 | 423.9 | 2.14 |
K2SO4 [g] | MnSO4(H2O) [g] | MIISO4(H2O)n [g] | Salt Abbreviation |
---|---|---|---|
1.3768 | 1.3521 | NiSO4(H2O)7 2.2468 | KMn/Ni |
1.3768 | 1.3521 | CuSO4(H2O)5 1.9974 | KMn/Cu |
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© 2023 by the authors. His Majesty the King in Right of Canada, as represented by the Minister of Natural Resources, 2023. Submitted for possible open access publication under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
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de Oliveira Neto, J.G.; Viana, J.R.; Lima, A.D.d.S.G.; Lopes, J.B.O.; Ayala, A.P.; Lage, M.R.; Stoyanov, S.R.; dos Santos, A.O.; Lang, R. Assessing the Novel Mixed Tutton Salts K2Mn0.03Ni0.97(SO4)2(H2O)6 and K2Mn0.18Cu0.82(SO4)2(H2O)6 for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study. Molecules 2023, 28, 8058. https://doi.org/10.3390/molecules28248058
de Oliveira Neto JG, Viana JR, Lima ADdSG, Lopes JBO, Ayala AP, Lage MR, Stoyanov SR, dos Santos AO, Lang R. Assessing the Novel Mixed Tutton Salts K2Mn0.03Ni0.97(SO4)2(H2O)6 and K2Mn0.18Cu0.82(SO4)2(H2O)6 for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study. Molecules. 2023; 28(24):8058. https://doi.org/10.3390/molecules28248058
Chicago/Turabian Stylede Oliveira Neto, João G., 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, and Rossano Lang. 2023. "Assessing the Novel Mixed Tutton Salts K2Mn0.03Ni0.97(SO4)2(H2O)6 and K2Mn0.18Cu0.82(SO4)2(H2O)6 for Thermochemical Heat Storage Applications: An Experimental–Theoretical Study" Molecules 28, no. 24: 8058. https://doi.org/10.3390/molecules28248058