Growth and characterization of ammonium nickel-cobalt sulfate Tutton’s salt for UV light applications

Ghosh, Santunu; Oliveira, Michelle de; Pacheco, Tiago S.; Perpétuo, Genivaldo Júlio; Franco, Carlos J.

doi:10.1016/j.jcrysgro.2018.02.027

Cited by 32 publications

(9 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Four hexahydrate examples are shown in Figure S17. The ν(OH) regions of Mg(H 2 O) 6 (BrO 3 ) 2 , (NH 4 ) 2 M(H 2 O) 6 (SO 4 ) 2 (M = 50:50 Co:Ni), K 2 Zn(H 2 O) 6 (SO 4 ) 2 , and Al(H 2 O) 6 F 3 are centered at 3293, 3277, ca. 3200, and ca.…”

Section: Resultsmentioning

confidence: 99%

“…We are studying anhydrous, hydrated, solvated, and ligated metal ion salts of the icosahedral superweak anion B 12 F 12 2– (hereinafter Z 2– ). − The structures and other properties of M(H 2 O) n (Z) hydrates can serve as models for the hydration of alkaline earth and transition metal ions in solution − or in extended solids such as clays, − zeolites, , or metal–organic frameworks (MOFs). − The degree of hydration of an alkaline earth or transition metal compound can affect its electrical or proton conductivity, − its photoluminescence intensity, its fluorescence red-shift, or its ability to act as a UV filter, − among other physicochemical properties. The dehydration/rehydration behavior of M(H 2 O) n (Z) salts is especially important in light of the interest in thermodynamic and kinetic dehydration/rehydration studies of salt hydrates for the storage of low potential heat from solar energy. − Some salt hydrates are known to change their structure when D 2 O replaces H 2 O .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

et al. 2018

View full text Add to dashboard Cite

Eight M(H2O) n (Z) salt hydrates were characterized by single-crystal X-ray diffraction (Z2– = B12F12 2–): M = Ca, Sr, n = 7; M = Mg, Co, Ni, Zn, n = 6; M = Ba, n = 4, 5. Weak O–H···F hydrogen bonding between the M(H2O) n 2+ cations and Z2– resulted in room-temperature Fourier transform infrared (FTIR) spectra having sharp ν(OH) bands, with full widths at half max of 10–30 cm–1, which are much more narrow than ν(OH) bands in room temperature FTIR spectra of most salt hydrates. Clearly resolved νasym(OH/OD) and νsym(OH/OD) bands with Δν(OH) as small as 17 cm–1 and Δν(OD) as small as 11 cm–1 were observed (Δν(OX) = νasym(OX) – νsym(OX)). The isomorphic hexahydrates (R3̅) have two fac-(H2O)3 sets of H2O ligands and nearly octahedral coordination spheres. They exhibited four resolvable ν(OH) bands, one νasym(OH)/νsym(OH) pair for H2O ligands with longer O(H)···F distances and one νasym(OH)/νsym(OH) pair for H2O ligands with shorter O(H)···F distances. The ν(OH) bands for the three H2O molecules with shorter, slightly stronger O(H)···F hydrogen bonds were broader, more intense, and red-shifted by ca. 25 cm–1 relative to the bands for the three other H2O molecules, the first time that such small differences in relatively weak O(H)···F hydrogen bonds in the same crystalline hexahydrate have resulted in observable IR spectroscopic differences at room temperature. For the first time room temperature ν(OH) values for salt hexahydrates showed the monotonic progression Mg2+ > Co2+ > Ni2+ > Zn2+, essentially the same progression as the pK a values for these metal ions in aqueous solution. A further manifestation of the weak O–H···F hydrogen bonding in these hydrates is the latent porosity exhibited by Ba(H2O)5,8(Z), Sr(H2O) n,m (Z), and Ca(H2O)4,6(Z). Finally, the H2O/D2O exchange reaction Co(D2O)6(Z) → Co(H2O)6(Z) was ca. 50% complete in 1 h at 50 °C in N2/17 Torr H2O(g).

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Several works report the synthesis of mixed Tutton salt crystals and their structural and optical properties, such as K 2 Zn x Ni 1–x (SO 4 ) 2 ·6H 2 O [ 24 ], K 2 Co x Ni 1-x (SO 4 ) 2 ·6H 2 O [ 10 ], (NH 4 ) 2 Zn x Mg 1-x (SO 4 ) 2 ·6H 2 O [ 17 ], (NH 4 ) 2 Ni x Cu 1-x (SO 4 ) 2 ·6H 2 O [ 25 ], and (NH 4 ) 2 Ni x Co 1-x (SO 4 ) 2 ·6H 2 O [ 12 ]. However, few papers provide studies involving the occupation of Mn 2+ and Zn 2+ cations in the lattice structure of an individual or mixed Tutton salt [ 15 , 26 , 27 ].…”

Section: Introductionmentioning

confidence: 99%

“…Thermochemical heat storage materials, which offer an alternative solution to the global energy problem, have also been in a high demand [6,7]. In this context, Tutton salts stand out due to their versatility in the various branches of science, having the potential to be used as ultraviolet light (UV) filters [8], thermal energy storage materials [9], and other applications [10][11][12][13][14].…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Crystal growth, crystal structure determination, and computational studies of a new mixed (NH4)2Mn1–xZnx(SO4)2(H2O)6 Tutton salt

et al. 2022

View full text Add to dashboard Cite

Tutton salts have been extensively explored in recent decades due to their attractive physical and chemical properties, which make them potential candidates for thermochemical heat storage systems and optical technologies. In this paper, a series of new mixed Tutton salts with the chemical formula (NH4)2Mn1–xZnx(SO4)2(H2O)6 is reported. Crystals are successfully grown by the solvent slow evaporation method and characterized by powder X-ray diffraction (PXRD) with Rietveld refinement. In particular, the crystal structure of the mixed (NH4)2Mn0.5Zn0.5(SO4)2(H2O)6 crystal is solved through PRXD data using the DICVOL06 algorithm for diffraction pattern indexing and the Le Bail method for lattice parameter and spatial group determination. The structure is refined using the Rietveld method implemented in TOPAS® and reported in the Cambridge Structural Database file number 2104098. Moreover, a computational study using Hirshfeld surface and crystal void analyses is conducted to identify and quantify the intermolecular interactions in the crystal structure as well as to determine the amount of free space in the unit cell. Furthermore, 2D-fingerprint plots are generated to evaluate the main intermolecular contacts that stabilize the crystal lattice. Density functional theory is employed to calculate the structural, thermodynamic, and electronic properties of the coordination [Zn(H2O)6]2+ and [Mn(H2O)6]2+ complexes present in the salts. Molecular orbitals, bond lengths, and the Jahn–Teller effect are also discussed. The findings suggest that in Mn-Zn salts several properties dependent on the electronic structure can be tuned up by modifying the chemical composition.

show abstract

Tutton salt (NH4)2Zn(SO4)2(H2O)6: thermostructural, spectroscopic, Hirshfeld surface, and DFT investigations

de Oliveira Neto,

Viana,

Abreu

et al. 2024

J Mol Model

View full text Add to dashboard Cite

Context Ammonium Tutton salts have been widely studied in recent years due to their thermostructural properties, which make them promising compounds for application in thermochemical energy storage devices. In this work, a detailed experimental study of the Tutton salt with the formula (NH4)2Zn(SO4)2(H2O)6 is carried out. Its structural, vibrational, and thermal properties are analyzed and discussed. Powder X-ray diffraction (PXRD) studies confirm that the compound crystallizes in a structure of a Tutton salt, with monoclinic symmetry and P21/a space group. The Hirshfeld surface analysis results indicate that the main contacts stabilizing the material crystal lattice are H···O/O···H, H···H, and O···O. In addition, a typical behavior of an insulating material is confirmed based on the electronic bandgap calculated from the band structure and experimental absorption coefficient. The Raman and infrared spectra calculated using DFT are in a good agreement with the respective experimental spectroscopic results. Thermal analysis in the range from 300 to 773 K reveals one exothermic and several endothermic events that are investigated using PXRD measurements as a function of temperature. With increasing temperature, two new structural phases are identified, one of which is resolved using the Le Bail method. Our findings suggest that the salt (NH4)2Zn(SO4)2(H2O)6 is a promising thermochemical material suitable for the development of heat storage systems, due to its low dehydration temperature (≈ 330 K), high enthalpy of dehydration (122.43 kJ/mol of H2O), and hydration after 24 h. Methods Computational studies using Hirshfeld surfaces and void analysis are conducted to identify and quantify the intermolecular contacts occurring in the crystal structure. Furthermore, geometry optimization calculations are performed based on density functional theory (DFT) using the PBE functional and norm-conserving pseudopotentials implemented in the Cambridge Serial Total Energy Package (CASTEP). The primitive unit cell optimization was conducted using the Broyden–Fletcher–Goldfarb–Shanno (BFGS) algorithm. The electronic properties of band structure and density of states, and vibrational modes of the optimized crystal lattice are calculated and analyzed. Graphical abstract

show abstract

Growth and characterization of ammonium nickel-cobalt sulfate Tutton’s salt for UV light applications

Cited by 32 publications

References 54 publications

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Crystal growth, crystal structure determination, and computational studies of a new mixed (NH4)2Mn1–xZnx(SO4)2(H2O)6 Tutton salt

Tutton salt (NH4)2Zn(SO4)2(H2O)6: thermostructural, spectroscopic, Hirshfeld surface, and DFT investigations

Contact Info

Product

Resources

About

Growth and characterization of ammonium nickel-cobalt sulfate Tutton’s salt for UV light applications

Cited by 32 publications

References 54 publications

Manifestations of Weak O–H···F Hydrogen Bonding in M(H2O)n(B12F12) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Manifestations of Weak O–H···F Hydrogen Bonding in M(H2O)n(B12F12) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Crystal growth, crystal structure determination, and computational studies of a new mixed (NH4)2Mn1–xZnx(SO4)2(H2O)6 Tutton salt

Tutton salt (NH4)2Zn(SO4)2(H2O)6: thermostructural, spectroscopic, Hirshfeld surface, and DFT investigations

Contact Info

Product

Resources

About

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)

Manifestations of Weak O–H···F Hydrogen Bonding in M(H₂O)_n(B₁₂F₁₂) Salt Hydrates: Unusually Sharp Fourier Transform Infrared ν(OH) Bands and Latent Porosity (M = Mg–Ba, Co, Ni, Zn)