Mechanisms of Reduction of M(H2O)k n+ to Form M°-Nano-Particles in Aqueous Solutions Differs from That Commonly Assumed: The Reduction of Ag(H2O)2 + by H2

Haya Kornweitz, Dan Meyerstein

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Abstract

The redox potentials of M(H2O)l n+/M°(H2O)k are far too negative for the reduction of M(H2O)l n+ by most common reducing agents. Therefore, the question raised is how do relatively weak reducing agents reduce M(H2O)l n+ to form M°-nanoparticles, M°-NPs? Density functional theory calculations concerning the mechanism of reduction of Ag(H2O)2 + by H2 prove that AgHaq is formed as an intermediate. The AgHaq agglomerize to form a variety of {(AgH)n}aq and {(AgH)nAg}+ aq. H2 release occurs only from these agglomerates. It is suggested that the first agglomeration step is {(AgH)n}aq + Ag(H2O)2 + → (Ag2H)+ aq. Thus, M°(solvated) are not transients in the formation of M°-NPs except when very strong reducing agents, for example e- aq, are used. Therefore, one has to re-evaluate the results concerning the mechanisms of formation of M°-NPs.

Original languageEnglish
Pages (from-to)25043-25050
Number of pages8
JournalJournal of Physical Chemistry C
Volume122
Issue number43
DOIs
StatePublished - 1 Nov 2018

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