ABSTRACT
In this paper, novel mixed Tutton salts with the chemical formulas K2Mn0.03Ni0.97(SO4)2(H2O)6 and K2Mn0.18Cu0.82(SO4)2(H2O)6 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 [MII(H2O)6]2+ (MII = 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.
ABSTRACT
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.
ABSTRACT
Photocatalytic activity of TiO2 nanoparticles is highly dependent on their phase composition. The coexistence of anatase and rutile phases in a single nanoparticle eases the electron transfer process between the phases, and favors the separation of photogenerated pairs. In this work, highly photoactive mixed-phase TiO2 nanostructures were prepared by supercritical antisolvent precipitation (SAS), an environmentally friendly technology. It is shown here that this methodology has the remarkable ability to produce highly porous (515â¯m2/g) and crystalline TiO2 nanoparticles. The phase composition of as-prepared TiO2 samples can be tailored through annealing process. Several mixed-phase TiO2 samples were tested to assess the correlation between photocatalytic activity and phase composition. The photocatalytic performance is strongly affected by the anatase-rutile ratio, since the synergism between phases enhances the charge separation, reducing the recombination effect of the photogenerated pairs (e-/h+). It was found that the nanocatalyst composed by 7.0â¯wt% of rutile phase and 93.0â¯wt% of anatase phase, named as TiO2_650, presented the highest photodegradation for both methyl orange (MO) and methylene blue (MB) dyes. Interestingly, TiO2 samples prepared by SAS have superior photoactivity than the benchmark photocatalyst names as P25, which is a widely used TiO2 material composed of anatase and rutile phases.
