RESUMEN
The study reported in this article has shown for the first time that strongly acidic solutions (pH < 0.5) obtained after hydrometallurgical treatment of spent automotive converters (SAC) may be valuable secondary sources of platinum group metal (PGM) nanoparticles (NPs). The PGM precipitation strongly depended on the solution pH; the yield of the precipitated PGM NPs increased considerably from 40% to almost 100% when the pH was adjusted to 7-8. To improve the NPs stability, commercial TiO2 was used as support to obtain efficient recyclable PGM@TiO2 catalysts. The size of the PGM NPs was smaller than 5 nm, while the diameter of the supported particles varied from 10 to 50 nm. The size and dispersion of PGM NPs on the support strongly depended on the pH of the medium: at pH < 0.5, the Pt and Pd NPs were significantly smaller than the NPs obtained at pH 7-8. Also, in the case of Pt@TiO2 and Rh@TiO2, the NPs were well dispersed on the support in contrast to the large agglomerates of Pd@TiO2. The PGM@TiO2 showed catalytic properties in the reduction of 4-nitrophenol to 4-aminophenol, particularly, at pH above 11. The highest conversion of 98% was obtained with 1% Pd@TiO2 at pH 14 after only 15 min. The catalyst was easily separated from the reaction mixture and reused in 7 consecutive cycles without significant loss of activity. The PGM@TiO2 synthesized from the real solution showed a similar catalytic activity (70% conversion at pH 14) as that obtained from model solution.
Asunto(s)
Nanopartículas , Platino (Metal) , Platino (Metal)/química , Titanio/química , Nanopartículas/química , CatálisisRESUMEN
The paper presents basic studies on the precipitation of platinum, palladium, rhodium, and ruthenium nanoparticles from model acidic solutions using sodium borohydride, ascorbic acid, and sodium formate as reducing agents and polyvinylpyrrolidone as a stabilizing agent. The size of the obtained PGM particles after precipitation with NaBH4 solution does not exceed 55 nm. NaBH4 is an efficient reducer; the precipitation yields for Pt, Pd, Ru, Rh are 75, 90, 65 and 85%, respectively. By precipitation with ascorbic acid, it is possible to efficiently separate Pt, Rh, and Ru from Pd from the two-component mixtures. The obtained Pt, Pd, and Rh precipitates have the catalytic ability of the catalytic reaction of p-nitrophenol to p-aminophenol. The morphological characteristic of the PGM precipitates was analyzed by AFM, SEM-EDS, and TEM.
RESUMEN
Recovery of platinum group metals (PGM) from complex aqueous solutions generated as a result of leaching of various spent materials (e.g., spent automotive converters) is a vital issue in the context of the circular economy. In this study pyridinium derivatives containing an imidoamide or imine moiety (i.e., 3-[1-(2-ethylhexyloxyimine)methane]-1-propylpyridinium chloride, 3-[1-(decyloxyimine)methane]-1-propylpyridinium chloride, 3-[1-(decyloxyimine)ethane]-1-propylpyridinium chloride and 4-[1-amine(2-ethylhexyloxyimine)]-1-propylpyridinium chloride) are proposed as novel extractants for recovery of palladium(II) and platinum(IV) from model chloride aqueous solutions. The results of liquid-liquid extraction from one-component solutions of palladium(II) or platinum(IV) showed that quaternary pyridinium salts can be used as effective extractants for platinum metal ions. Moreover, PGM extraction from a two-component mixture proved no evident selectivity in the transfer of one of the metal ions to the organic phase. As the best extractant among the investigated ones, D3EI-PrCl (with straight alkyl chain at substituent) can be pointed out, however, problems with effective stripping or phase disengagement after stripping should be indicated as a drawback of the organic phases used. Further investigation should focus on the improvement of the organic phase properties (e.g., increase in hydrophobicity of the extractants and addition of an organic phase modifier) towards stripping efficiency.