Pacific Northwest National Laboratory
PO Box 999
Richland, WA 99352
Dr. Linehan joined Pacific Northwest National Laboratory in 1987 as a Postdoctoral Appointee and was promoted to Research Scientist in 1988, Senior Research Scientist in 1991, and to Staff Scientist in 1996. He is a founding member of the Center for Molecular Electrocatalysis. Previous to Battelle, he was a Postdoctoral Fellow at Argonne National Laboratory, 1986-1987. His professional experience includes operando spectroscopy (XAFS, NMR, FTIR) of Catalysts, Nanophase Materials/Catalyst Synthesis, Organometallic and Organic Synthesis, Catalyst Design and Testing, State of the Art Multinuclear NMR of solids and fluids under high pressure, Organometallic and Organic Reaction Mechanisms, and Fuel Refining Mechanisms.
Green Chemistry. Dr. Linehan is active in the chemistry of a hydrogen-based economy. Design of new hydrogen storage materials and reaction mechanisms of H2 uptake and release including catalytic studies are underway. Dr. Linehan is actively pursuing research into the utilization of CO2 as a chemical feedstock through the use organo-metal catalysts and novel organic chemistry. The first spectroscopic detection of a cyclometallo-anhydride has recently been observed. This and other organometal- and organo-CO2 complexes are potential key intermediates in the utilization of CO2 as a chemical synthon.
Operando Spectroscopy of Catalysts. Dr. Linehan is extremely interested in determing the actual active catalyst through the use of operando (or spectroscopy under actual catalyst working conditions) spectroscopies. Recently he has shown that the actual catalysts in both dehydrogenation of ammonia borane and the hydrogenation of benzene are homogeneous rhodium clusters in contrast to the previously accepted rhodium nanoparticles.
Organometallic Reaction Mechanisms. Dr. Linehan successfully obtained the first complete Arrhenius parameters for hydrogen abstraction from a transition metal hydride by a series of alkyl radicals. A method for the determination of the absolute rates of heteroatom transfer from organics to transition metal radicals was designed to acquire rates of carbon-sulfur, carbon-selenium, and carbon-halide bond scission (and transfer) to a molybdenum centered radical. In addition the Arrhenius parameters for the abstraction of a hydrogen atom from a metal-sulfur-hydrogen complex have been obtained. These results yield important insight into the fundamental processes occurring in catalytic systems such as hydrocarbon-cracking and hydrodesulfurization (HDS).
Nanometer Particle Synthesis & Catalyst Design. Dr. Linehan has designed three new methods of producing nanometer-sized metal-sulfide, metal-oxide and metal particles. These particles act as very efficient selective catalysts as well as precursors to novel high strength materials. The iron-based nanoparticulates have been shown to have the highest activity for hydrocracking of any iron-based catalysts. The mechanism of these iron-based cracking catalysts has been elucidated.
High Pressure Spectroscopic Studies. Using high pressure NMR, photoacoustic and IR spectroscopies we are studying the kinetics, mechanisms and thermodynamics of stable and transient organometallic complexes. The bond strength of a weak metal-ethylene bond has been obtained.
Solid State NMR Spectroscopy. Dr. Linehan has been instrumental in advancing the quantitative aspects of solid 13C NMR spectroscopy of fossil fuels, including coals, coal macerals, lignites, and humics. He has obtained the first quantitative solid 13C NMR spectra of the International Humic Substances Society (IHSS) humic acids and the Argonne Premium Coals. Some of the first solid 195Pt NMR spectra were obtained by Dr. Linehan. The use of metal ions and 15N and 19F labelled compounds as NMR probes of functional groups such as phenols, sulfides, carboxylic acids, etc. in polymers, coals, and coal products is being explored. The first NMR of Self-Assembled Monolayers were performed by Dr. Linehan.
Organometallic Synthesis. Dr Linehan has synthesized the first air stable Rhodium-phosphine complex analogous to Wilkinson's catalyst which reversibly adds di-hydrogen at room temperature under 1 atmosphere of H2. This Rhodium trimer was found to be an active catalyst for olefin reduction under mild conditions. Dr. Linehan has also synthesized many bi-metallic species potentially useful in catalysis.
Education and Credentials
- Ph.D., University of California, Davis, Inorganic Chemistry (Dr. Alan Balch, Advisor)
- B.S., San Francisco State University, Chemistry (Dr. Jane Krevor, Advisor)
Affiliations and Professional Service
- American Chemical Society
- Affiliate Faculty University of Idaho
- Adjunct Faculty Central Washington University
- Adjunct Faculty Washington State University-Tri Cities
- Member, Editorial board of the Inorganic Chemistry Communications, 2005-present
Awards and Recognitions
- R&D 100 award winner for Rapid Thermal Decomposition of precursors in Solution (RTDS), 1993
- Glenn ACS Award for best Fuel Division paper, 2004
- Linehan, J. C.; Zemanian, T. Z.; Yonker, C.; and Franz, J.A. "Spectrometer Capillary Vessel and Method of Making Same." U.S. Patent # 5,469,061, 1995.
- Matson; D. W.; Fulton; J. L.; Linehan; J. C.; Bean; R.M.Brewer; T.D.;Werpy; T. A.; Darab; J. G. "Catalyst Material and Method of Making." U.S. Patent #5,652,192, 1998.
- Linehan, John C.; Fulton, John L.; Bean, Roger M. "Process of Forming Compounds Using Reverse Micelle or Reverse Microemulsion Systems." U.S. Patent # 5,770,172, 1998