Nano-architecture of silica nanoparticles as a tool to tune both electrochemical and catalytic behavior of Ni II @SiO 2

• Published in: RSC advances 2019-07, Vol.9 (39), p.22627-22635
• Main Authors: Khrizanforov, Mikhail N, Fedorenko, Svetlana V, Mustafina, Asia R, Khrizanforova, Vera V, Kholin, Kirill V, Nizameev, Irek R, Gryaznova, Tatyana V, Grinenko, Valeriya V, Budnikova, Yulia H
• Format: Article
• Language: English
• ISSN: 2046-2069; 2046-2069
• DOI: 10.1039/c9ra03421h

The present work introduces a facile synthetic route for efficient doping of [Ni (bpy) ] into silica nanoparticles with various sizes and architectures. Variation of the latter results in different concentrations of the Ni complexes at the interface of the composite nanoparticles. The UV-Vis analysis of the nanoparticles reveals changes in the inner-sphere environment of the Ni complexes when embedded into the nanoparticles, while the inner-sphere of Ni is invariant for the nanoparticles with different architecture. Comparative analysis of the electrochemically generated redox transformations of the Ni complexes embedded in the nanoparticles of various architectures reveals the latter as the main factor controlling the accessibility of Ni complexes to the redox transitions which, in turn, controls the electrochemical behavior of the nanoparticles. The work also highlights an impact of the nanoparticulate architecture in catalytic activity of the Ni complexes within the different nanoparticles in oxidative C-H fluoroalkylation of caffeine. Both low leakage and high concentration of the Ni complexes at the interface of the composite nanoparticles enables fluoroalkylated caffeine to be obtained in high yields under recycling of the nanocatalyst five times at least.