Operando Studies of Palladium-Catalysed Cross-Coupling Surface Chemistry

Lead Research Organisation: University of York
Department Name: Chemistry


Pd-catalysed cross-coupling reactions represent key technologies employed within academia and industry, however the fine chemicals sector urgently needs new catalytic systems for large-scale, continuous processing. This proposal underpins the development of alternative, heterogeneous Pd-catalysed processes to meet this demand. Commercialization of such catalytic clean technologies awaits detailed knowledge of their optimal formulation and associated reaction conditions. This information in turn requires insight into both the mechanisms of such surface reactions and their associated deactivation pathways in order to control both activity and selectivity (homo- versus cross-coupling). Here we propose to obtain microscopic-level understanding of Heck and Suzuki-Miyaura chemistry over well-defined model palladium surfaces through the use of operando surface spectroscopies and mechanistic reaction probes. We have recently pioneered the application of in-situ, X-ray photoelectron spectroscopy for real-time investigations of industrially significant, surface catalysed processes including alkyne trimerisation, C-H activation and VOC destruction. These methodologies will also allow us to determine whether heterogeneously catalysed cross-coupling shares common reaction intermediates and rate-limiting steps with its more conventional homogeneous counterparts. The intellectual output from this project will be invaluable in designing a new toolbox of high performance dispersed Pd catalysts that will revolutionise organic synthetic chemistry.


10 25 50

publication icon
Lee A (2007) Selective Oxidation of Crotyl Alcohol over Pd(111) in The Journal of Physical Chemistry C

publication icon
Lee A (2007) Hydrodebromination of Bromobenzene over Pt(111) in The Journal of Physical Chemistry C

publication icon
Lee AF (2010) Surface catalysed Suzuki-Miyaura cross-coupling by Pd nanoparticles: an operando XAS study. in Dalton transactions (Cambridge, England : 2003)

publication icon
Lee, A.F. (2010) Evidence for the surface catalysed Suzuki-Miyaura reaction over Pd nanocatalysts: An operando XAS study in ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY

Description The first direct evidence for surface catalysed C-C bond-forming reactions (Suzuki-Miyaura) over Pd nanoparticles was discovered through dynamic X-ray spectroscopic studies of tunable palladium nanoparticles and single crystals.
Exploitation Route The time-resolved methodologies developed at the Elettra and ESRF synchrotrons have wide application for structure-reactivity studies across the physical sciences, and are broadly applicable to a range of commercially important solution phase catalytic transformations employed across the fine chemical and pharmaceutical sectors. New opportunities have been identifed for the synthesis of nanoparticulate Pd catalysts to effect C-C cross-coupling chemistry under mild conditions, opening the possibility for intensified processing under continuous flow.
Sectors Chemicals,Pharmaceuticals and Medical Biotechnology

Description Synchtrotron studies of nanostructured materials 
Organisation Elettra Sincrotrone Trieste
Country Italy 
Sector Academic/University 
PI Contribution New research areas in catalysis and materials science developed resulting in numerous jointly authored publications over 17 years.
Collaborator Contribution Access to synchtrotron facilities and training of 8 PhD students and PDRAs
Impact Joint publications, contributions to annual highlights, invited seminar and Fonda-Fasella 2004 award