The recovery of osmium from residual osmium tetroxide (OsO4) is a necessity imposed by its high toxicity, but also by the technical-economic value of metallic osmium. An elegant and extremely useful method is the recovery of osmium as a membrane catalytic material, in the form of nanoparticles obtained on a polymeric support. The subject of the present study is the realization of a composite membrane in which the polymeric matrix is the polypropylene hollow fiber, and the active component consists of the osmium nanoparticles obtained by reducing an alcoholic solution of osmium tetroxides directly on the polymeric support. The method of reducing osmium tetroxide on the polymeric support is based on the use of 10-undecenoic acid (10–undecylenic acid) (UDA) as a reducing agent. The osmium tetroxide was solubilized in t–butanol and the reducing agent, 10–undecenoic acid (UDA), in i–propanol, t–butanol or n–decanol solution. The membranes containing osmium nanoparticles (Os–NP) were characterized morphologically by the following: scanning electron microscopy (SEM), high-resolution SEM (HR–SEM), structurally: energy-dispersive spectroscopy analysis (EDAX), Fourier transform infrared (FTIR) spectroscopy. In terms of process performance, thermal gravimetric analysis was performed by differential scanning calorimetry (TGA, DSC) and in a redox reaction of an organic marker, p–nitrophenol (PNP) to p–aminophenol (PAP). The catalytic reduction reaction with sodium tetraborate solution of PNP to PAP yielded a constant catalytic rate between 2.04 × 10−4 mmol s–1 and 8.05 × 10−4 mmol s−1.

The bio-medical benefits of silver ions and 10–undecenoic acid in various chemical-pharmaceutical preparations are indisputable, thus justifying numerous research studies on delayed and/or controlled release. This paper presents the effect of the polymer matrix in the simultaneous release of silver ions and 10–undecenoic acid in an aqueous medium of controlled pH and ionic strength. The study took into consideration polymeric matrices consisting of cellulose acetate (CA) and polysulfone (PSf), which were impregnated with oxide nanoparticles containing silver and 10–undecenoic acid. The studied oxide nanoparticles are nanoparticles of iron and silver oxides obtained by an accessible electrochemical method. The obtained results show that silver can be released, simultaneously with 10–undecenoic acid, from an impregnated polymeric membrane, at concentrations that ensure the biocidal and fungicidal capacity. Concentrations of active substances can be controlled by choosing the polymer matrix or, in some cases, by changing the pH of the target medium. In the studied case, higher concentrations of silver ions are released from the polysulfone matrix, while higher concentrations of 10–undecenoic acid are released from the cellulose acetate matrix. The results of the study show that a correlation can be established between the two released target substances, which is dependent on the solubility of the organic compound in the aqueous medium and the interaction of this compound with the silver ions. The ability of 10–undecenoic acid to interact with the silver ion, both through the carboxyl and alkene groups, contributes to the increase in the content of the silver ions transported in the aqueous medium.

Regardless of the type of liquid membrane (LM) (Bulk Liquid Membranes (BLM), Supported Liquid Membranes (SLM) or Emulsion Liquid Membranes (ELM)), transport and separation of chemical species are conditioned by the operational (OP) and constructive design parameters (DP) of the permeation module. In the present study, the pH of the aqueous source phase (SP) and receiving phase (RP) of the proposed membrane system were selected as operational parameters. The mode of contacting the phases was chosen as the convective transport generator. The experiments used BLM-type membranes with spheres in free rotation as film contact elements of the aqueous phases with the membrane. The target chemical species were selected in the range of phenol derivatives (PD), 4–nitrophenol (NP), 2,4–dichlorophenol (DCP) and 2,4–dinitrophenol (DNP), all being substances of technical-economic and environmental interest. Due to their acid character, they allow the evaluation of the influence of pH as a determining operational parameter of transport and separation through a membrane consisting of n–octanol or n–decanol (n–AlcM). The comparative study performed for the transport of 4–nitrophenol (NP) showed that the module based on spheres (Ms) was more performant than the one with phase dispersion under the form of droplets (Md). The sphere material influenced the transport of 4–nitrophenol (NP). The transport module with glass spheres (Gl) was superior to the one using copper spheres (Cu), but especially with the one with steel spheres (St). In all the studied cases, the sphere-based module (Ms) had superior transport results compared to the module with droplets (Md). The extraction efficiency (EE) and the transport of 2,4–dichlorophenol (DCP) and 2,4–dinitrophenol (DNP), studied in the module with glass spheres, showed that the two phenolic derivatives could be separated by adjusting the pH of the source phase. At the acidic pH of the source phase (pH = 2), the two derivatives were extracted with good results (EE > 90%), while for pH values ranging from 4 to 6, they could be separated, with DCP having doubled separation efficiency compared to DNP. At a pH of 8 in the source phase, the extraction efficiency halved for both phenolic compounds.

Liquid membranes usually have three main constructive variants: bulk liquid membranes (BLM), supported liquid membranes (SLM) and emulsion liquid membranes (ELM). Designing hybrid variants is very topical, with the main purpose of increasing the flow of substance through the membrane but also of improving the selectivity. This paper presents the operational limits of some kind of hybrid membrane constituted as a bulk liquid membrane (BLM), but which works by dispersing the aqueous source (SP) and receiving (RP) phases, with the membrane itself being a dispersion of nanoparticles in an organic solvent (NP–OSM). The approached operational parameters were the volume of phases of the hybrid membrane system, the thickness of the liquid membrane, the working temperature, the flow of aqueous phases, the droplet size of the aqueous phases dispersed across the membrane, the nature and concentration of nanoparticles in the membrane, the pH difference between the aqueous phases, the nature of the organic solvent, the salt concentration in the aqueous phases and the nature of transported chemical species. For this study, silver ion (SI) and p-nitrophenol (PNP) were chosen as transportable chemical species, the n-aliphatic alcohols (C6…C12) as membrane organic solvents, 10–undecenoic acid (UDAc) and 10-undecylenic alcohol (UDAl) as carriers and magnetic iron oxides as nanoparticles dispersed in the membrane phase. Under the experimentally established operating conditions, separation efficiencies of over 90% were obtained for both ionic and molecular chemical species (silver ions and p-nitrophenol). The results showed the possibility of increasing the flow of transported chemical species by almost 10 times for the silver ion and approximately 100 times for p-nitrophenol, through the appropriate choice of operational parameters, but they also exposed their limits in relation to the stability of the membrane system.