Influence of Polyoxometalate Protecting Ligands on Catalytic Aerobic Oxidation at the Surfaces of Gold Nanoparticles in Water

Mingfu Zhang, Jingcheng Hao, Alevtina Neyman, Yifeng Wang, Ira A. Weinstock

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Abstract

Metal oxide cluster-anion (polyoxometalate, or POM) protecting ligands, [α-PW11O39]7- (1), modify the rates at which 14 nm gold nanoparticles (Au NPs) catalyze an important model reaction, the aerobic (O2) oxidation of CO to CO2 in water. At 20 °C and pH 6.2, the following stoichiometry was observed: CO + O2 + H2O = CO2 + H2O2. After control experiments verified that the H2O2 product was sufficiently stable and did not react with 1 under turnover conditions, quantitative analysis of H2O2 was used to monitor the rates of CO oxidation, which increased linearly with the percent coverage of the Au NPs by 1 (0-64% coverage, with the latter value corresponding to 211 ± 19 surface-bound molecules of 1). X-ray photoelectron spectroscopy of Au NPs protected by a series of POM ligands (K+ salts): 1, the Wells-Dawson ion [α-P2W18O62]6- (2) and the monodefect Keggin anion [α-SiW11O39]8- (3) revealed that binding energies of electrons in the Au 4f7/2 and 4f5/2 atomic orbitals decreased as a linear function of the POM charge and percent coverage of Au NPs, providing a direct correlation between the electronic effects of the POMs bound to the surfaces of the Au NPs and the rates of CO oxidation by O2. Additional data show that this effect is not limited to POMs but occurs, albeit to a lesser extent, when common anions capable of binding to Au-NP surfaces, such as citrate or phosphate, are present.

Original languageEnglish
Pages (from-to)2400-2408
Number of pages9
JournalInorganic Chemistry
Volume56
Issue number5
DOIs
StatePublished - 6 Mar 2017

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