Studies of Cobalt(III) and Chromium(III) Complexes as Mediators in the Silver Nanoparticle Electrosynthesis in Aqueous Media

摘要

Metal complexes [Cr(bipy)~(3)]_(3+), [Co(bipy)~(3)]_(3+), and [Co(sep)]_(3+)in aqueous media at the potentials of M(III)/M(II) redox couple are shown playing a role of mediators in the electrosynthesis of silver nanoparticles, stabilized in a polyvinylpyrrolidone shell, by means of Ag(I) reduction. [Cr(bipy)~(3)]_(3+)is consumed under the conditions of long-term preparative electrolysis, the reduction process is accompanied by cathode passivation, therefore, the Ag+ ions complete conversion to the Ag-nanoparticles is unattainable. The two other metal complexes are fully remained unimpaired; the mediated electrosynthesis of the Ag-nanoparticles is carried out well effectively: the Ag-nanoparticles are produced in the solution bulk with a nearly quantitative yield, a theoretical charge being consumed. the [Co(bipy)~(3)]_(3+)-mediated reduction of the Ag_(+)ions, generated by a silver anode in situ dissolution in the course of single compartment cell electrolysis, is accompanied by the anode metal dispersion and results in the formation of polydisperse Ag-nanoparticles. The summary Ag-nanoparticle current efficiency in the solution bulk comes to 128%. Thus formed Ag-nanoparticles are characterized by using dynamic light scattering, scanning and transmission electron microscopy, and X-ray powder diffraction. The Ag-nanoparticles are spherical, with a mean size of 83 ± 53 nm, or have a form of nanowires, with a length of l = 1216 ± 664 nm and diameter of d = 94 ± 17 nm. The [Co(sep)]_(3+)-mediated AgCl reduction gives ellipsoidal Ag-nanoparticles sized l = 46 ± 19 nm, d = 27 ± 7 nm; the silver crystallite mean size is 20(1)–34.4(9) nm.