Ronen Bar-Ziv

Coating Platinum Nanoparticles with Methyl Radicals: Effects on Properties and Catalytic Implications

It was recently reported that the reaction of methyl radicals with Pt(0) nanoparticles (NPs), prepared by the reduction of Pt(SO4)2 with NaBH4, is fast and yields as the major product stable (Pt(0)-NPs)-(CH3)n and as side products, in low yields, C2H6, C2H4, and some oligomers. We decided to study the effect of this coating on the properties of the Pt(0)-NPs. The results show that the coating can cover up to 75% of the surface Pt(0) atoms. The rate constant of the reaction, k((.)CH3+Pt(0)-NPs), decreases with the increase in the surface coverage, leading to competing reaction paths in the solution, which gradually become dominant, affecting the composition of the products. The methyl coating also affects the zeta potential, the UV spectra, and the electrocatalytic reduction of water in the presence of the NPs. Thus, the results suggest that binding alkyl radicals to Pt(0) surfaces might poison the NPs catalytic activity. When the Pt(0)-NPs are prepared by the reduction of a different precursor salt, PtCl6(2-), nearly no C2 H4 and oligomers are formed and the methyl coating covers a larger percentage of the surface Pt(0) atoms. The difference is attributed to the morphology of the Pt(0)-NPs: those prepared from Pt(SO4)2 are twinned nanocrystals, whereas those prepared from PtCl6(2-) consist mostly of single crystals. Thus, the results indicate that the side products, or most of them at least, are formed on the twinned Pt(0) nanocrystal edges created between (111) facets. In addition, the results show that Pt(0)-NPs react very differently compared with other noble metals, for example, Au(0) and Ag(0); this difference is attributed in part to the difference in the bond strength, (M(0)-NP)-CH3, and should be considered in heterogeneous catalytic processes involving alkyl radicals as intermediates.

Effect of Hydrogen Pretreatment of Platinum Nanoparticles on their Catalytic Properties: Reactions with Alkyl Radicals – A Mechanistic Study

Methyl radicals react with platinum nanoparticles (NPs) suspended in aqueous solutions to form (Pt0‐NPs)‐(CH3)n as a stable major product. Hydrogen gas treatment of the Pt0‐NPs affects the composition of the products and the surface reactions. The results clearly point out that pretreatment of Pt0‐NPs and (Pt0‐NPs)‐(CH3)n with H2 considerably affects their reactions with methyl radicals. The implications of the results on catalytic processes are discussed.

H/D kinetic isotope effect as a tool to elucidate the reaction mechanism of methyl radicals with glycine in aqueous solutions.

The H/D kinetic isotope effect (KIE) for the reaction of methyl radicals with glycine in aqueous solutions at pH 10.6 equals 16 ± 3. This result proves that the methyl radical abstracts a hydrogen atom from the methylene group of glycine and not an electron from the unpaired couple on the nitrogen atom. The rate constant of the reaction of methyl radicals with glycine at pH 7.0 is orders of magnitude smaller than that at pH 10.6.

The effect of negatively charged metallic nanocatalysts on their reactions with alkyl radicals

Abstract Stored electrons on Au and Ag nanoparticles (NPs) have been found to catalyze various reduction processes initiated by ionizing irradiation or light illumination in which the NPs act as “nano-electrodes”. In the present study, we explored the effect of charging colloidal gold and silver NPs on their reaction with methyl radicals, ·CH3. The results show that charging the colloidal metal NPs by excess of electrons, (NP)n−, affected their reaction mechanism with methyl radicals and resulted in different product composition in comparison to the analogous reactions with uncharged particles. These results should be considered in photo(electro)catalytic processes when alkyl radicals are formed near the catalyst surface. Graphical Abstract