Suzuki–Miyaura reaction and solventfree oxidation of benzyl alcohol by Pd/nitrogen-doped CNTs catalyst

• Published in: Journal of materials science 2018-12, Vol.53 (23), p.15817-15836
• Main Authors: Labulo, Ayomide H., Omondi, Bernard, Nyamori, Vincent O.
• Format: Article
• Language: English
• Subjects: Acetonitrile; Alcohol; Analysis; Aromatic compounds; Benzaldehyde; Benzyl alcohol; Carbon; Carbon nanotubes; Catalysis; Catalysts; Catalytic activity; Characterization and Evaluation of Materials; Chemical reactions; Chemical Routes to Materials; Chemistry and Materials Science; Classical Mechanics; Coupling; Crystallography and Scattering Methods; Ethanol; Iron constituents; Materials Science; Metalorganic chemical vapor deposition; Nanomaterials; Nanoparticles; Nanotubes; Nitriles; Nitrogen; Organic chemicals; Organic chemistry; Oxidation; Oxidation-reduction reaction; Palladium; Palladium catalysts; Polymer Sciences; Potassium carbonate; Sodium carbonate; Sodium hydroxide; Solid Mechanics; Solvents; Substrates; Surface properties
• ISSN: 0022-2461; 1573-4803
• DOI: 10.1007/s10853-018-2748-8

Suzuki–Miyaura C–C coupling reactions were investigated with Pd/nitrogen-doped carbon nanotubes (Pd/N-CNTs) as a catalyst. Also, the same catalyst was examined for the solventfree oxidation of benzyl alcohol to benzaldehyde. Nitrogen-doped carbon nanotubes (N-CNTs) were synthesized from 1-ferrocenylmethyl(2-methylimidazole) and benzophenone via a chemical vapour deposition technique. Acetonitrile was used as a solvent and source of both carbon and nitrogen constituents of N-CNTs. Pd nanoparticles (Pd NPs) were successfully dispersed on N-CNTs via a metal organic chemical vapour deposition method. SEM, TEM, XRD, elemental analysis and ICP-OES measurements were used to characterize the nanomaterials. From the TEM analysis, it was observed that Pd NPs were spherical and with particle sizes ranging from 3 to 8 nm. For Suzuki C–C coupling reactions, phenylboronic acid, aryl halide, Pd/N-CNTs catalyst and a base (NaOAc, K 2 PO 4 , K 2 CO 3 , NaOH, Et 3 N and Na 2 CO 3 ) were used. The optimized experiments indicate that K 2 CO 3 , as the base, and ethanol/water (1:1 v/v, 10 mL) mixture, as a solvent, are the best reaction conditions. The solventfree oxidation reactions of benzyl alcohol were also done with Pd/N-CNTs catalyst and benzyl alcohol as a substrate. In both sets of reactions, C–C coupling and oxidation, the increase in pyrrolic nitrogen species was found to be responsible for higher catalytic activities of Pd/N-CNT catalysts, and this was attributed to the ease of Pd NP dispersion on N-CNTs, relative to pristine CNTs. Also, the higher catalytic activity of Pd/N-CNTs could be ascribed not only to the smaller Pd NP size or surface area, but to also the surface properties and the nature of the support when compared with the undoped counterpart, Pd/CNTs.