Pd⁰‐ and Au⁰‐Nanoparticles Catalyze the Reduction of Perchlorate by ·C(CH₃)₂OH Radicals

Abstract

Catalytic water reduction to hydrogen takes place when metal nanoparticles (M0‐NPs) of gold or palladium are charged with an excess of electrons by an electron‐transfer process from strong reducing α‐alcohol radicals such as ·C(CH3)2OH. The results reported in this study indicate that the M0‐NPs also catalyze the reduction of perchlorate by ·C(CH3)2OH radicals and by BH4–. The results point out that the M0‐NPs behave as nanoelectrodes. The catalytic reduction of perchlorate competes well with the catalytic reduction of water; that is, although the concentration of perchlorate is orders of magnitude smaller than that of water, the radicals reduce the perchlorate preferentially. Thus, we have identified a new way to deal with the residual perchlorate in water, using any reducing agent forming adsorbed hydrogen. The nature of the reactive reducing agent (M0‐NPs)n–/{(M0‐NPs) – Hm}(n–m)– [n = number of excess electrons and m = number of electrons given off after the same number of H atoms have been adsorbed] and the energetic processes, which might be different for the two M0‐NPs, are discussed. The results demonstrate that M0‐NPs can be developed as simple and effective catalysts for the removal of perchlorate from polluted aqueous solutions.

DFT Study of the BH4− Hydrolysis on Au(111) Surface

“…Catalyst Preparation : The M 0 ‐NPs suspensions, were prepared as reported elsewhere using the modified Creighton's procedure [27] by Zidki et al. [40–42] . Briefly, 30 mL of an ice‐cold aqueous solution containing NaBH 4 (2.0 mM) were added at once under vigorous stirring to 10 mL of 1.0 mM of the desired precursor salts dissolved in water (HAuCl 4 , and Ag 2 SO 4 for Ag and Au, respectively).…”

“…The M 0 -NPs suspensions, were prepared as reported elsewhere using the modified Creighton's procedure [27] by Zidki et al. [40][41][42] Briefly, 30 mL of an ice-cold aqueous solution containing NaBH 4 (2.0 mM) were added at once under vigorous stirring to 10 mL of 1.0 mM of the desired precursor salts dissolved in water (HAuCl 4 , and Ag 2 SO 4 for Ag and Au, respectively). The final metal ion concentration was 2.5 × 10 À 4 M. All the NP concentrations are stated as ion-based M n + concentrations in all experiments.…”

Preise der israelischen chemischen Gesellschaft: Y. Apeloig, S. Shaik, J. M. L. Martin, D. Meyerstein, S. Ruthstein und M. E. van der Boom / NAS Award in Chemical Sciences: J. A. Doudna / Remsen Award und Ralph N. Adams Award: C. A. Mirkin

“…Meyerstein untersucht zurzeit den Mechanismus der Fenton‐Reaktion unter verschiedenen Bedingungen, die Rolle von Carbonat als Kokatalysator in katalytischen Oxidationsprozessen sowie Reaktionen von Radikalen mit Metallnanopartikeln in wässrigen Medien. Er verfasste einen Beitrag für das European Journal of Inorganic Chemistry über Nanopartikel in der katalytischen Reduktion von Perchlorat durch Radikale, und sein Bericht über Kupferbicarbonat/carbonat‐Komplexe als Wasseroxidationskatalysatoren erschien auf dem Titelbild von Chemistry – A European Journal …”

Israel Chemical Society Prizes: Y. Apeloig, S. Shaik, J. M. L. Martin, D. Meyerstein, S. Ruthstein, and M. E. van der Boom / NAS Award in Chemical Sciences: J. A. Doudna / Remsen Award and Ralph N. Adams Award: C. A. Mirkin

“…Meyerstein's current research interests include the mechanisms of the Fenton reaction under different conditions, the role of carbonate as a co‐catalyst in catalytic oxidation processes, and reactions of radicals with metal nanoparticles immersed in aqueous solutions. He has reported in the European Journal of Inorganic Chemistry on the role of nanoparticles in the catalytic reduction of perchlorate with radicals, and his report on the role of copper bicarbonate/carbonate complexes as water oxidation catalysts was featured on a cover of Chemistry—A European Journal …”