RESUMO
The electrochemical ion pumping device is a promising alternative for the development of the industry of recovering metals from natural sources-such as seawater, geothermal water, well brine, or reverse osmosis brine-using electrochemical systems, which is considered a non-evaporative process. This technology is potentially used for metals like Li, Cu, Ca, Mg, Na, K, Sr, and others that are mostly obtained from natural brine sources through a combination of pumping, solar evaporation, and solvent extraction steps. As the future demand for metals for the electronic industry increases, new forms of marine mining processing alternatives are being implemented. Unfortunately, both land and marine mining, such as off-shore and deep sea types, have great potential for severe environmental disruption. In this context, a green alternative is the mixing entropy battery, which is a promising technique whereby the ions are captured from a saline natural source and released into a recovery solution with low ionic force using intercalation materials such as Prussian Blue Analogue (PBA) to store cations inside its crystal structure. This new technique, called "electrochemical ion pumping", has been proposed for water desalination, lithium concentration, and blue energy recovery using the difference in salt concentration. The raw material for this technology is a saline solution containing ions of interest, such as seawater, natural brines, or industrial waste. In particular, six main ions of interest-Na+, K+, Mg2+, Ca2+, Cl-, and SO42--are found in seawater, and they constitute 99.5% of the world's total dissolved salts. This manuscript provides relevant information about this new non-evaporative process for recovering metals from aqueous salty solutions using hexacianometals such as CuHCF, NiHCF, and CoHCF as electrodes, among others, for selective ion removal.
RESUMO
Two new d10 metal supramolecular metal-organic frameworks (SMOFs) with general formula [ML2(H2O)2]n (M = Zn, Cd) have been synthetized using the sodium salt of the anionic 1-(3,4-dimethylphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylate ligand (Na+L-). Both SMOFs have been structurally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The compounds are isostructural and form supramolecular aggregates via hydrogen bonds with the presence of less common dihydrogen bonds. Interestingly, they show ionic conductivity and porosity. The luminescent properties have been also studied by means of the excitation and emission spectra. Periodic DFT and molecular TD-DFT calculations have been used to unravel the emergence of luminescence in the otherwise non-emitting 1-(3,4-dimethylphenyl)-5-methyl-1H-1,2,3-triazole-4-carboxylate ligand once incorporated in the SMOFs. Our results also illustrate the importance of considering the dielectric environment in the crystal when performing excited state calculations for isolated fragments to capture the correct electronic character of the low-lying states, a practice which is not commonly adopted in the community.
RESUMO
The new compound (CH3NH3)3Tl2Cl9 was synthesized and fully characterized. X-ray photoelectron spectroscopy and Raman spectroscopy are consistent with the crystal structure solved by single-crystal X-ray diffraction. This compound is a semiconductor with a measured band gap of Eg = 2.91 eV. It is the first thallium-based hybrid perovskite and shows remarkably high stability to ambient conditions.
RESUMO
Three new Ag(I) and one Cu(I) coordination compounds with two different positional isomers, propane-1,3-diyl bis(pyridine-4-carboxylate) (L1) and propane-1,3-diyl bis(pyridine-3-carboxylate) (L2), of a bis-(pyridyl-carboxylate) ligand have been synthesized. X-ray diffraction analysis revealed that the self-assembly of L1 with AgCF3SO3 and AgClO4 salts leads to the formation of discrete binuclear metallocycles {Ag(L1)CF3SO3}2 (1) and {Ag(L1)ClO4}2 (2), respectively. However, self-assembly of the other ligand, L2, with AgCF3SO3 and CuCl salts, results in a 1-D zig-zag chain {Ag(L2)CF3SO3}∞ (3) and a 1-D double-stranded helical chain {Cu2Cl2(L2)2}∞ (4) coordination polymers, respectively. Solid emission spectra recorded at room temperature show interesting luminescence properties for all four compounds in the range from 438 to 550 nm, especially for compound 4 that was found to change its emission color when the wavelength of the excitation radiation is switched from 332 to 436 nm.