TY - JOUR
T1 - Mechanisms of Reduction of M(H2O)k n+ to Form M°-Nano-Particles in Aqueous Solutions Differs from That Commonly Assumed
T2 - The Reduction of Ag(H2O)2 + by H2
AU - Kornweitz, Haya
AU - Meyerstein, Dan
N1 - Publisher Copyright:
Copyright © 2018 American Chemical Society.
PY - 2018/11/1
Y1 - 2018/11/1
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85055318722&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.8b07331
DO - 10.1021/acs.jpcc.8b07331
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AN - SCOPUS:85055318722
SN - 1932-7447
VL - 122
SP - 25043
EP - 25050
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 43
ER -