Copper Deposition from Chloride-Containing Aqueous Solutions: Catalysis and the Role of the Water Structure

COLOMBO, ESTEFANÍA; BELLETTI, GUSTAVO D.; FONSECA, SARAH; PINTO, LEANDRO M. C.; JUAREZ, M. FERNANDA; NAZMUTDINOV, RENAT; SANTOS, ELIZABETH; SCHMICKLER, WOLFGANG; QUAINO, PAOLA

JOURNAL OF PHYSICAL CHEMISTRY C

AMER CHEMICAL SOC

Lugar: Washington; Año: 2021 vol. 125 p. 1811 - 1818

1932-7447

The formation of complexes and the effect of a water network close to the surface on the copper deposition are investigated by means of molecular dynamics simulations.Surprisingly, the presence of chloride has a little effect on the potential of mean force for theapproach of a copper ion to an electrode. In addition, the electronic transmission coefficients forCu2+/Cu+ and [CuCl2]/[CuCl2]− redox couples are calculated in the framework of the moderntheory of charge transfer in condensed media. Our results show that the metal influence on theelectron transfer (ET) kinetics at the copper deposition results from two important quantities: thework terms and the electronic transmission coefficient. The ET first step proceeds in a near-−adiabatic regime for both reactants. The catalytic effect of Cl is confirmed; the ratio of the calculated rate constants for [CuCl2]/[CuCl2]− and Cu2+ /Cu+ was found to be more than two orders of magnitude.