Systematische Entwicklung der Reaktionschromatographie für das Hochdurchsatzscreening von Katalysatoren

• Applicant: Professor Dr. Oliver Trapp
• Subject Area: Analytical Chemistry
• Term: from 2005 to 2013
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 5457487

• Final Report Year: 2013

Final Report Abstract

To achieve a high-throughput in the screening of catalytic properties of new materials typically reactors and reaction vessels in a highly parallelized fashion are developed. The advantages are manifold, because reaction batches are prepared with a high reproducibility, reactions are performed under comparable reaction conditions, typically less reagents are used and therefore the chemical waste is reduced, in average shorter testing cycles are achieved and the overall expenses per test are reduced. For the reactant and product analysis several analytical techniques were adapted to match the throughput of these screening assays. Despite these advances there is still a bottle-neck in the application of chromatographic techniques, which have the advantage that even complex reaction mixtures can be analyzed and the field of applications is very broad. In this research project two chromatographic techniques have been developed and investigated to increase the throughput in catalyst screening: On-column reaction chromatography and electrophoresis and multiplexing gas chromatography. For the kinetic investigation of hydrogenation over highly active palladium nanoparticles a throughput of up to 5880 reactions in only 40 hours could be demonstrated (highlighted in Nature). To achieve such a high-throughput the separation selectivity of common stationary phases was combined with catalytic activity, e.g. Pd nanoparticles, metathesis catalysts. This allows studying not only one reaction at a time but by injection of reactant libraries complete sets of reactions under the same reaction conditions without any competing reaction. This gave access to comprehensive kinetic data sets which gave further insight into the reaction mechanisms and how to control reaction conditions. The investigation of (catalyzed) reactions in any chromatographic The here developed concept was then successfully extended to the study of various catalytic processes including C-C-coupling reactions, metathesis, immobilized NHC-ligands, immobilized salen type ligands, immobilized camphor ligands, and the investigation of higher order reactions in capillary electrophoresis. Multiplexing gas chromatography, which is a combination of information technology and chemical analysis, has been developed as a versatile tool to investigate reactions with large catalyst libraries. A maximum throughput of up to 453 samples/ h could be achieved on a single separation column. These results have been highlighted in the Editors’ Choice section of Science.

Publications

• Anal. Chem. 2006, 78, 189-198. Unified Equation for Access to Rate Constants of First-Order Reactions in Dynamic and On-Column Reaction Chromatography
  O. Trapp
  
• Electrophoresis 2006, 27, 534-541. The Unified Equation for the Evaluation of First Order Reactions in Dynamic Electrophoresis
  O. Trapp
  
• Angew. Chem. 2007, 119, 5706-5710. Durchsatzsteigerung von Trenntechniken mittels Multiplexing
  O. Trapp
  
• Angew. Chem. 2007, 119, 7447-7451. Hochdurchsatzscreening von Katalysatoren durch Integration von Reaktion und Analyse
  O. Trapp, S.K. Weber, S. Bauch, W. Hofstadt
  
• Angew. Chem. Int. Ed. 2007, 46, 5609-5613. Boosting the Throughput of Separation Techniques by Multiplexing
  O. Trapp
  
• Angew. Chem. Int. Ed. 2007, 46, 7307- 7310. High-throughput screening of catalysts by combining chemical reaction and analysis
  O. Trapp, S.K. Weber, S. Bauch, W. Hofstadt
  
• Chem. Eur. J. 2008, 14, 4657- 4666. High Throughput Kinetic Study of Hydrogenations over Palladium Nanoparticles - Combination of Reaction and Analysis
  O. Trapp, S.K. Weber, S. Bauch, T. Bäcker, B. Spliethoff
  
• Electrophoresis 2009, 30, 329-336. Stereodynamics of Tris-(α-diimine)-transition metal-complexes by Enantioselective Dynamic Micellar Electrokinetic Chromatography
  S. Bremer, O. Trapp
  
• Chem. Eng. Sci. 2010, 65, 2410-2416. Integration of reaction and separation in a micro capillary column reactor - Palladium nanoparticle catalyzed C-C bond forming reactions
  S.K. Weber, S. Bremer, O. Trapp
  
• Electrophoresis 2010, 31, 786-813. Investigation of the stereodynamics of molecules and catalyzed reactions by CE
  O. Trapp
  
• Chem. Commun. 2011, 47, 391-393. Catalysts by the meter: rapid screening approach of N-heterocyclic carbene ligand based catalysts
  C. Lang, U. Gärtner, O. Trapp
  
• Electrophoresis 2012, 33, 1060-1067. Integration of On-column Catalysis and EKC Analysis: Investigation of Enantioselective Sulfoxidations
  S. Fuessl, O. Trapp