Fluid Catalysis Program

We solve the hard problems in high-pressure, high-temperature catalysis mechanisms

The Fluid Catalysis Program explores fuel-related catalysis mechanisms, new catalytic species, and new catalytic reaction chemistry using an array of powerful in-situ spectroscopic and kinetic techniques at the high pressures and temperatures that are frequently used in industrial processes. 

Our prior research on homogeneous carbonylation chemistry produced a selective catalytic ethanol synthesis route that is timely in today's energy circumstances. Our recent work and planned future activities on this system are aimed at uncovering the mechanism of an interesting and unusual synergistic catalytic effect wherein a mixture of iron and manganese carbonyl anions was demonstrated to be more active than either of the complexes when used separately.  We are probing for a suspected hetero-bimetallic intermediate using high-pressure kinetic and spectroscopic methods combined with theoretical (dft) calculations. We believe that understanding of such synergistic effects is important because this knowledge might lead to new possibilities for catalyst design. 

In Fischer-Tropsch-related research, we have recently conducted supercritical transition-metal complex catalyzed CO hydrogenation for the first time.  Because bond energies are defined in terms of gas-phase chemistry, thermochemical and kinetic measurements in the gas-like supercritical media are more easily interpretable in terms of the bond dissociation energies of the various bonds in organometallic catalysts.

Experimental thermochemical and kinetic data from supercritical fluids is highly amenable to theoretical calculation and, using high-pressure NMR and high-pressure IR spectroscopies, we are measuring homogeneous Fischer-Tropsch-related activation parameters, electronic and steric effects of ligands, product selectivities, equilibria, and kinetic isotope effects for iterative feedback with ongoing dft calculations.

In related research, we have uncovered the first cobalt catalyst for the supercritical phosphine-modified hydroformylation of olefins and measured the thermodynamics of the key hydrogen addition steps for comparison with dft calculated values.  In other research, ligand-stabilized nanoparticulate catalysts were shown to catalytically activate Si-H bonds in a variety of solution-phase processes that are highly amenable to spectroscopic scrutiny.

Research Areas

• Fischer-Tropsch/Methanol-Synthesis Related Homogeneous Catalytic CO Hydrogenation
  • Reaction Pathways in Catalytic CO Hydrogenation
• Metal-Centered Free Radicals in Olefin Hydroformylation Catalysis
• Catalytic Ethanol Synthesis via Homologation
  • Selective Catalytic Ethanol Synthesis (extended abstract, .pdf,  48 kb)
  • Selective Catalytic Ethanol Synthesis (slide show)
• Homogeneous Catalysis in Supercritical Fluids
  • "Super" Fluid Eases Catalysis
• Nanocatalysis in Solution (poster, .pdf, 78 kb)
• In-Situ Spectroscopic Devices for Studying Industrial Catalytic Processes
  • R&D 100 Award-Winning Toroid Cavity Imager

Publications

• List of Selected Fluid Catalysis Publications

Patents

• Selected patents

Personnel

• Jerome W. Rathke
• Michael J. Chen
• Robert J. Klingler
• Rex E. Gerald II

Some of Our Collaborators

• Clark Landis, University of Wisconsin
• Randall Meyer, Department of Chemical Engineering, University of Illinois at Chicago
• Zumu Zhang, Pennsylvania State University
• Klaus Woelk, Institute of Physical and Theoretical Chemistry, University of Bonn
• Jack Halpern, Chemistry Department, The University of Chicago
• Dan DuBois, Pacific Northwest National Laboratory
• Can Erkey, University of Connecticut
• Peter Ford, University of California at Santa Barbara
• Walter Leitner, Max-Planck-Institut für Kohlenforschung
• John Gladysz, Universität Erlangen-Nürnberg
• Philip Jessop, University of California-Davis

For More Information

Contact Jerome (Jerry) Rathke (630-252-4549, rathke@cmt.anl.gov).

Research funded by U.S. Department Of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences