Issue 3, 2020

On the mechanism of reduction of M(H2O)mn+ by borohydride: the case of Ag(H2O)2+

Abstract

The redox potentials of M(H2O)mn+/M0(atom) couples are often far too negative to enable the formation of M0(atom) by most reducing agents. Therefore, one has to reconsider the mechanism of formation of M0-NPs by the bottom-up procedure. A deep and detailed theoretical analysis of the reduction of Ag(H2O)2+ by BH4 points out that silver cations act mainly as catalysts of the reactions BH4 + 4H2O → B(OH)4 + 4H2. However, the transition states of the catalyzed process differ from those of the un-catalyzed process. The formation of (H2O)Ag–H, which is the starting stage for the formation of intermediates with Ag–Ag bonds, is only a side reaction in the process. Experimental evidence of the complexity of the process is presented, by stopped-flow; at least four processes are observed prior to the formation of Ag0-NPs. The spectra of these intermediates differ from those of Ag0atom and Ag2+aq. Though DFT calculations were performed only for silver cations, it is believed that analogous mechanisms are involved in the reductions of other cations.

Graphical abstract: On the mechanism of reduction of M(H2O)mn+ by borohydride: the case of Ag(H2O)2+

Supplementary files

Article information

Article type
Paper
Submitted
02 Oct 2019
Accepted
16 Dec 2019
First published
17 Dec 2019

Nanoscale, 2020,12, 1657-1672

On the mechanism of reduction of M(H2O)mn+ by borohydride: the case of Ag(H2O)2+

T. Mondal, A. Sermiagin, D. Meyerstein, T. Zidki and H. Kornweitz, Nanoscale, 2020, 12, 1657 DOI: 10.1039/C9NR08472J

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