Copper Chloro-Complexes Concentrated Solutions: An Electrochemical Study

Basic studies on concentrated solutions are becoming more and more important due to the practical industrial and geological applications. The use in redox flow batteries is one of the most important applications of these solutions. Specifically, in this paper we investigated high-concentrated copper chloro-complexes solutions with different additives. The concentration of ligands and additives affects the physicochemical and electrochemical properties of 2 M solutions of Cu(I) and Cu(II). Solutions with calcium chloride and HCl as Cl− source were investigated with Cu:Cl ratios of 1:5 and 1:7, the 1:5 Cu:Cl ratio being the best performing. The substitution of calcium chloride with ammonium chloride increased the conductivity. However, while the effect on the positive electrode process was not very evident, the reversibility of the copper deposition–stripping process was greatly improved. Orthophosphoric acid could be a viable additive to decrease the complexation of calcium with chloride anions and to improve the stability of Cu(II) chloro-complexes. Absorption spectroscopy demonstrated that phosphate ions do not coordinate copper(II) but lead to a shift in the distribution of copper chloro-complexes toward more coordinated species. Electrochemically, the increased availability of chloride anions in solution stabilized the Cu(II)-rich solution and led to increased reversibility of the Cu(II)/Cu(I) redox process.

Green Graphene–Chitosan Sorbent Materials for Mercury Water Remediation

The development of new graphene-based nanocomposites able to provide synergistic effects for the adsorption of toxic heavy metals in realistic conditions (environment) is of higher demand for future applications. This work explores the preparation of a green nanocomposite based on the self-assembly of graphene oxide (GO) with chitosan (CH) for the remediation of Hg(II) in different water matrices, including ultrapure and natural waters (tap water, river water, and seawater). Starting at a concentration of 50 μg L–1, the results showed that GO–CH nanocomposite has an excellent adsorption capacity of Hg (II) using very small doses (10 mg L–1) in ultrapure water with a removal percentage (% R) of 97 % R after only two hours of contact time. In the case of tap water, the % R was 81.4% after four hours of contact time. In the case of river and seawater, the GO–CH nanocomposite showed a limited performance due the high complexity of the water matrices, leading to a residual removal of Hg(II). The obtained removal of Hg(II) at equilibrium in river and seawater for GO–CH was 13% R and 7% R, respectively. Our studies conducted with different mimicked sea waters revealed that the removal of mercury is not affected by the presence of NO3– and Na+ (>90% R of Hg(II)); however, in the presence of Cl–, the mercury removal was virtually nonexistent (1% R of Hg(II)), most likely because of the formation of very stable chloro-complexes of Hg(II) with less affinity towards GO–CH.

Diffusion Dialysis for Separation of Hydrochloric Acid, Iron and Zinc Ions from Highly Concentrated Pickling Solutions

Acid recovery from pickling waste solutions is an important step to enhance hot-dip-galvanizing industry process sustainability. Diffusion dialysis (DD) can be used to separate acids and heavy metals (e.g., iron and zinc) from pickling waters, promoting the circular use of such raw materials. In the present study, a laboratory scale unit operating in batch and a continuous large scale unit, both equipped with Fumasep anionic exchange membranes, were tested. Results obtained show that zinc and iron concentration affect the HCl recovery in opposite ways. Iron chlorides enhance acid recovery, while zinc chlorides considerably tend to diffuse through the membrane because of negatively charged chloro-complexes formation and slightly reduce the acid diffusion. A multi-components mathematical model, with a time-dependent and distributed-parameters architecture, was adopted enabling the prediction of operations with hydrochloric acid, zinc, and iron metals both in batch and in continuous dialyzers. As a result, a good comparison between model simulations and experiments was achieved in both configurations.

Platinum Group Elements Recovery from Used Catalytic Converters by Acidic Fusion and Leaching

The recovery of platinum group elements (PGE (platinum group element coating); Pd, Pt, and Rh) from used catalytic converters, using low energy and fewer chemicals, was developed using potassium bisulfate fusion pretreatment, and subsequently leached using hydrochloric acid. In the fusion pre-treatment, potassium bisulfate alone (without the addition of an oxidant) proved to be an effective and selective fusing agent. It altered PGE into a more soluble species and did not react with the cordierite support, based on X-Ray Diffraction (XRD) and metallographic characterization results. The fusion efficacy was due to the transformation of bisulfate into pyrosulfate, which is capable of oxidizing PGE. However, the introduction of potassium through the fusing agent proved to be detrimental, in general, since potassium formed insoluble potassium PGE chloro-complexes during leaching (decreasing the recovery) and required higher HCl concentration and a higher leaching temperature to restore the solubility. Optimization on the fusion and leaching parameter resulted in 106% ± 1.7%, 93.3% ± 0.6%, and 94.3% ± 3.9% recovery for Pd, Pt, and Rh, respectively. These results were achieved at fusion conditions: temperature 550 °C, potassium bisulfate/raw material mass ratio 2.5, and fusion time within 30 min. The leaching conditions were: HCl concentration 5 M, temperature 80 °C, and time within 20 min.

Single-molecule magnet behavior in heterolopetic Dy3+-chloro-diazabutadiene complexes: influence of the nuclearity and ligand redox state

We report the synthesis, structure and magnetic properties investigations of a series of new dysprosium mono- and dinuclear chloro complexes based on different diazabutadiene ligands (DAD2R = [2,6-iPr2C6H3N–CRCR–NC6H3iPr2-2,6]; R = H, Me).