| dc.description.abstract | Due to the negative impact on the environment and the associated biological risks on human and animal life, the need for eco-friendly synthetic protocols is critical. With the rapid advancement in nanotechnology, this extends to the synthesis of nanomaterials. Eco-friendly nanoparticle synthesis protocols have led to the use of fungi, plants and other biological substances, due to their remarkable ability in reducing metal ions. This led to the formation of very efficient hybrid catalysts, which are partially organic/inorganic composites. Palladium nanoparticles have drawn much interest due to its potential in catalytic applications and in photovoltaic cell development. In this study, the brown marine algae, Ecklonia radiata, was employed as a putative palladium nanoparticle bioreactor. Aqueous extracts of the algae were used as a supporting matrix for the synthesis of palladium nanoparticle (AE-PdNPs) catalysts according to the principles of green chemistry. The catalysts were then assessed for their capability in various carbon-carbon coupling reactions such as Suzuki-Miyaura, Sonogashira, and Heck coupling reactions. Selectivity studies were also performed. The PdNPs were compared to “model” polyvinylpyrrolidone palladium nanoparticles (PVP-PdNPs), synthesized according to literature methods. A variety of spectroscopic techniques were used to characterize the nanoparticles and the organic reaction products, including HRTEM, EDX, NMR, FTIR, DLS, TGA, UV-Vis, ICP-AES, GC-MS and XRD spectroscopy. qNMR was used to determine the product % yields. The aqueous extracts were characterised using NMR and a variety of assays, including total antioxidant potential, total reducing power and radical scavenging ability) to assess its ability to reduce the Pd metal salt. 2D NMR revealed polysaccharides and polyphenols to be the major and minor components, respectively, present in the extract. HRTEM images revealed the average size of the AE-PdNPs and PVP-PdNPs to be 12 nm and 8 nm, respectively. The images also showed the shapes of the NPs to be cubic for the AE-PdNPs and cubic or triangular for the PVP-PdNPs. SAED and XRD spectroscopy revealed the face-centred cubic phase and polycrystalline nature of the AE-PdNPs. No reliable data, other than the HRTEM images was obtained for the PVP-PdNPs. Zeta potential and DLS measurements confirmed the negative charge present on the surface of the nanoparticles, while the hydrodynamic radii were found to be 65 nm and 99 nm for the AE- and PVP-PdNPs, respectively, substantiating the presence of the capping agents. ICP-AES analysis revealed the Pd content of the NPs to be 48.8 and 28.9 ppm for the AE- and PVP-PdNPs. Following characterization, the PdNPs were assessed as potential catalysts in the Suzuki-Miyaura, Heck and Sonogashira carbon-carbon coupling reactions. Bromo and iodo substrates were employed, together with sterically hindered substrates, with a nitro moiety in the ortho or para positions. For the Suzuki-Miyaura reactions, both sets of PdNPs revealed slightly higher yields for the products synthesized using the bromo substrate (>90%), while low yields (40 – 55% yields) were obtained for the ortho substituted substrate in comparison to the para substrate (>90% yields). The Heck coupling reactions with butyl acrylate and 4-iodoacetphenone were successful (~70% yields), while reactions with 4-bromoacetophenone failed. However, the Sonogashira couplings did not proceed at all. With the series of reactions NPs showed some selectivity, with the AE-PdNPs consistently producing higher yields for the products obtained. This may be due to overall nature of the NPs, or due to the higher platinum loading content for the AE-PdNPs. | en_US |
