Supported Palladium Nanoparticles for Sustainable Cross-Coupling and Oxidation Reactions
2014 (English)Licentiate thesis, monograph (Other academic)
The work presented in this thesis aims to combine the rich chemistry ofpalladium and the benefits of heterogeneous catalysis with metal-organic frameworks(MOFs) in developing robust materials that are recyclable and adaptable to operationunder a continuous flow regime.
Two new catalysts were created based on palladium nanoparticles in themesoporous MOFs MIL-101 and MIL-88B. They were synthesized and rigorouslycharacterized. All the parameters that can influence the outcome of the desiredchemical transformations were investigated, leading to the development of veryefficient methodologies.
Pd@MIL-101-NH2 was employed in the Suzuki-Miyaura cross-couplingreaction and it displayed a remarkable efficiency in some of the mildest conditionsreported to date. Moreover, it displays a very good tolerance to highly functionalizedsubstrates, obtaining biaryl motifs that are of potential interest for the pharmaceuticalindustry. Also, a small library of 11 compounds could be synthesized in a singlecontinuous flow experiment proving that the catalyst is amenable to a packed-bedmicro-flow reactor.
An innovative double support was also used for encapsulating palladiumnanoparticles in a mixed MOF-silica matrix. The resulting material was denotedPd@MIL-88B-NH2@SiO2 and it was employed in a greener approach towards theaerobic oxidation of alcohols. The increased protection of the support allows thecatalyst to maintain a very good performance profile over 7 days of continuousoperation under high mechanical and chemical stress, with no sign of deactivation.
Place, publisher, year, edition, pages
Stockholm University, 2014. , 57 p.
IdentifiersURN: urn:nbn:se:su:diva-102562OAI: oai:DiVA.org:su-102562DiVA: diva2:711231
2014-04-29, 14:00 (English)