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

Totan Mondal, Alina Sermiagin, Dan Meyerstein, Tomer Zidki, Haya Kornweitz

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

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.

Original languageEnglish
Pages (from-to)1657-1672
Number of pages16
JournalNanoscale
Volume12
Issue number3
DOIs
StatePublished - 21 Jan 2020

ASJC Scopus subject areas

  • Materials Science (all)

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