Aggregation of catalytically active Ru nanoparticles to inactive bulk, monitored in situ during an allylic isomerization reaction. Influence of solvent, surfactant and stirring

The exploration of catalytic isomerization reactions of an allylic alcohol to ketone, in the presence of μ-oxo-triruthenium acetate as a precatalyst in alcohol solvents, has established that the catalyst is heterogeneous in nature and proceeds by means of the in situ formed Ru⁰ nanoparticles (Ru⁰NPs). This reaction is used as an indicator for evaluating the kinetics and mechanism for metallic NP formation and self-assembly. In ethanol, complete conversion of the reactant is achieved under all experimental conditions tested. Conversely, in iso-propanol or n-pentanol the catalytic particles swiftly lose activity and the reaction arrests after partial conversion. We conclude that, in ethanol the process of NP self-assembly results in the formation of active and stable NPs of a specific size, named C-particles. Consequently, we propose an additional step for the established mechanism of NP self-assembly, namely the aggregation of C-NPs to inactive bulk-metal, labeled as D (C + C → D). D-particles differ from other NPs present in the catalytic cycle in size and in the catalytic activity. The effect of surfactant and mixing is also explored and the acquired observations strongly support the proposed mechanism of catalyst formation and decay. Addition of surfactants and/or mixing slowed down the reaction rate but dramatically improved the lifetime of the catalyst and the observed conversions. We attribute this phenomenon to the inhibition of the aggregation step of the active C-NPs to inactive D bulk-metal. The aggregation step of C-NPs to inactive D-bulk is assumed for the first time. This assumption prompts all the experimental data to be consistent. Introduction of the new kinetic step enables the use of the proposed mechanism with the reactions, where the catalyst loses its activity in the course of the reaction, and it converts the mechanism of the metal NP self-assembly into the more universal form.