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
- Bayram E, JC Linehan, JL Fulton, N Szymczak, and RG Finke. 2015. "Determination of the Dominant Catalyst Derived from the Classic [RhCp*Cl2]2 Precatalyst System: Is it Single-Metal Rh1Cp*-Based, Subnanometer Rh4 Cluster-Based, or Rh(0)n Nanoparticle-Based Cyclohexene Hydrogenation Catalysis at Room Temperature and Mild Pressures?" ACS Catalysis 5(6):3876-3886. doi:10.1021/acscatal.5b00315
- Bays JT, N Priyadarshani, MS Jeletic, E Hulley, DL Miller, JC Linehan, and WJ Shaw. 2014. "The Influence of the Second and Outer Coordination Spheres on Rh(diphosphine)2 CO2 Hydrogenation Catalysts." ACS Catalysis 4(10):3663-3670. doi:10.1021/cs5009199
- Galan BR, ES Wiedner, ML Helm, JC Linehan, and AM Appel. 2014. "Effects of Phosphine-Carbene Substitutions on the Electrochemical and Thermodynamic Properties of Nickel Complexes." Organometallics 33(9):2287-2294. doi:10.1021/om500206e
- Ginovska-Pangovska B, A Dutta, ML Reback, JC Linehan, and WJ Shaw. 2014. "Beyond the Active Site: The Impact of the Outer Coordination Sphere on Electrocatalysts for Hydrogen Production and Oxidation." Accounts of Chemical Research 47(8):2621-2630. doi:10.1021/ar5001742
- Ginovska-Pangovska B, MH Ho, JC Linehan, Y Cheng, M Dupuis, S Raugei, and WJ Shaw. 2014. "Molecular Dynamics Study of the Proposed Proton Transport Pathways in [FeFe]-Hydrogenase." Biochimica et Biophysica Acta--Bioenergetics 1837(1):131-138. doi:10.1016/j.bbabio.2013.08.004
- Jeletic MS, ML Helm, EB Hulley, MT Mock, AM Appel, and JC Linehan. 2014. "A Cobalt Hydride Catalyst for the Hydrogenation of CO2: Pathways for Catalysis and Deactivation." ACS Catalysis 4(10):3755-3762. doi:10.1021/cs5009927
- Lercher JA, AM Appel, T Autrey, RM Bullock, DM Camaioni, HM Cho, DA Dixon, Z Dohnalek, F Gao, VA Glezakou, MA Henderson, JZ Hu, E Iglesia, AJ Karkamkar, BD Kay, GA Kimmel, JC Linehan, J Liu, I Lyubinetsky, D Mei, CHF Peden, RJ Rousseau, GK Schenter, WJ Shaw, J Szanyi, H Wang, Y Wang, and RS Weber. 2014. "Multifunctional Catalysts to Synthesize and Utilize Energy Carriers." In Frontiers at the Interface between Homogeneous and Heterogeneous Catalysis, II, pp. 207-219. U.S. Department of Energy, Office of Science, Washington, DC.
- Yadav M, JC Linehan, AJ Karkamkar, EF Van Der Eide, and DJ Heldebrant. 2014. "Homogeneous Hydrogenation of CO2 to Methyl Formate Utilizing Switchable Ionic Liquids." Inorganic Chemistry 53(18):9849-9854. doi:10.1021/ic501378w
- Jeletic MS, MT Mock, AM Appel, and JC Linehan. 2013. "A Cobalt-based Catalyst for CO2 Hydrogenation Under Ambient Conditions." Journal of the American Chemical Society 135(31):11533-11536. doi:10.1021/ja406601v
- Jain A, GW Buchko, ML Reback, MJ O'Hagan, B Ginovska-Pangovska, JC Linehan, and WJ Shaw. 2012. "Active Hydrogenation Catalyst with a Structured, Peptide-Based Outer-Coordination Sphere." ACS Catalysis 2(10):2114-2118. doi:10.1021/cs3004177
- Jain A, ML Helm, JC Linehan, DL DuBois, and WJ Shaw. 2012. "Biologically Inspired Phosphino Platinum Complexes." Inorganic Chemistry Communications 22:65-67. doi:10.1016/j.inoche.2012.04.039
- Lense S, MH Ho, S Chen, A Jain, S Raugei, JC Linehan, JA Roberts, AM Appel, and WJ Shaw. 2012. "Incorporating Amino Acid Esters into Catalysts for Hydrogen Oxidation: Steric and Electronic Effects and the Role of Water as a Base." Organometallics 31(19):6719-6731. doi:10.1021/om300409y
- Bayram E, JC Linehan, JL Fulton, JA Roberts, N Szymczak, TD Smurthwaite, S Ozkar, M Balasubramanian, and RG Finke. 2011. "Is It Homogeneous or Heterogeneous Catalysis Derived from [RhCp*Cl2]2? In Operando-XAFS, Kinetic and Crucial Kinetic Poisoning Evidence for Subnanometer Rh4 Cluster-Based Benzene Hydrogenation Catalysis." Journal of the American Chemical Society 133(46):18889-18902. doi:10.1021/ja2073438
- Galan BR, J Schoffel, JC Linehan, C Seu, AM Appel, JA Roberts, ML Helm, UJ Kilgore, JY Yang, DL DuBois, and C Kubiak. 2011. "Electrocatalytic Oxidation of Formate by [Ni(PR2NR`2)2(CH3CN)]2+ Complexes." Journal of the American Chemical Society 113(35):12767-12779. doi:10.1021/ja204489e
- Jain A, S Lense, JC Linehan, S Raugei, HM Cho, DL DuBois, and WJ Shaw. 2011. "Incorporating Peptides in the Outer Coordination Sphere of Bio-inspired Electrocatalysts for Hydrogen Production ." Inorganic Chemistry 50(9):4073-4085. doi:10.1021/ic1025872
- Rainbolt JE, PK Koech, CR Yonker, F Zheng, D Main, ML Weaver, JC Linehan, and DJ Heldebrant. 2010. "Anhydrous Tertiary Alkanolamines as Hybrid Chemical and Physical CO2 Capture Reagents with Pressure-Swing Regeneration." Energy & Environmental Science 4(2):480-484. doi:10.1039/C0EE00506A
- Shaw WJ, ME Bowden, AJ Karkamkar, CJ Howard, DJ Heldebrant, NJ Hess, JC Linehan, and T Autrey. 2010. "Characterization of a New Phase of Ammonia Borane." Energy & Environmental Science 3(6):796-804.
- Baer DR, PG Tratnyek, JE Amonette, CL Chun, P Nachimuthu, J Nurmi, RL Penn, DW Matson, JC Linehan, Y Qiang, and A Sharma. 2009. "Tuning the Properties of Iron Nanoparticles: Doping Effects on Reactivity and Aging." In International Perspectives on Environmental Nanotechnology: Applications and Implications, vol. 1, no. EPA 905/R-09/032, pp. 73-78. Environmental Protection Agency, Washington DC.
- Getty AD, CC Tai, JC Linehan, PG Jessop, MM Olmstead, and A Rheingold. 2009. "Hydrogenation of Carbon Dioxide Catalyzed by Ruthenium Trimethylphosphine Complexes: A Mechanistic Investigation using High-Pressure NMR Spectroscopy." Organometallics 28(18):5466-5477. doi:10.1021/om900128s
- Kathmann SM, VM Parvanov, GK Schenter, AC Stowe, LL Daemen, MA Hartl, JC Linehan, NJ Hess, AJ Karkamkar, and T Autrey. 2009. "Experimental and Computational Studies on Collective Hydrogen Dynamics in Ammonia Borane: Incoherent Inelastic Neutron Scattering." Journal of Chemical Physics 130(2):article no. 024507. doi:10.1063/1.3042270
- Pons V, RT Baker, NK Szymczak, DJ Heldebrant, JC Linehan, MH Matus, DJ Grant, and DA Dixon. 2009. "Coordination of aminoborane, NH2BH2, dictates selectivity and extent of H2 release in metal-catalysed ammonia borane dehydrogenation." Chemical Communications 48: 6597-6599. doi:10.1039/b809190k
- Rousseau RJ, GK Schenter, JL Fulton, JC Linehan, MH Engelhard, and T Autrey. 2009. "Defining Active Catalyst Structure and Reaction Pathways from ab Initio Molecular Dynamics and Operando XAFS: Dehydrogenation of Dimethylaminoborane by Rhodium Clusters ." Journal of the American Chemical Society 131(30):10516-10524.
- Franz JA, JC Linehan, DW Matson, TD Smurthwaite, J Bekhazi, and MS Alnajjar. 2008. "Development of Highly Reactive Nanometer Fe-Based Catalysts for Coal Liquefaction." In 24th Annual International Pittsburgh Coal Conference 2007 , p. 50. Pittsburgh Coal Conference, Pittsburgh, PA.
- Xiong Z, YS Chua, G Wu, WL Xu, P Chen, WJ Shaw, AJ Karkamkar, JC Linehan, TD Smurthwaite, and T Autrey. 2008. "Interaction of Lithium Hydride and Ammonia Borane in THF ." Chemical Communications 43:5595-5597. doi:10.1039/b812576g
- Baer DR, PG Tratnyek, Y Qiang, JE Amonette, JC Linehan, V Sarathy, JT Nurmi, CM Wang, and J Antony. 2007. "Synthesis, Characterization, and Properties of Zero-Valent Iron Nanoparticles." Chapter 3 in Environmental Applications of Nanomaterials: Synthesis, Sorbents and Sensors, ed. GE Fryxell and G Cao, pp. 49-86. Imperial College Press, London, United Kingdom.
- Brown C, T Jacques, NJ Hess, LL Daemen, E Mamontov, JC Linehan, AC Stowe, and T Autrey. 2006. "Dynamics of Ammonia Borane Using Neutron Scattering." Physica B Condensed Matter 385(Pt.1 ):266-268.
- Fulton JL, DW Matson, KH Pecher, JE Amonette, and JC Linehan. 2006. "Metal-based Nanoparticle Synthesis from the Rapid Expansion of Carbon Dioxide Solutions." Journal of Nanoscience and Nanotechnology 6(2):562-567.
- Gutowska A, L Li, Y Shin, CM Wang, XS Li, JC Linehan, RS Smith, BD Kay, BA Schmid, WJ Shaw, MS Gutowski, and T Autrey. 2005. "Nano-Scaffold Mediates Hydrogen Release and Reactivity of Ammonia Borane." Angewandte Chemie International Edition 44(23):3578-3582.
- Nurmi JT, PG Tratnyek, V Sarathy, DR Baer, JE Amonette, KH Pecher, CM Wang, JC Linehan, DW Matson, RL Penn, and MD Driessen. 2005. "Characterization and Properties of Metallic Iron Nanoparticles: Spectroscopy, Electrochemistry, and Kinetics." Environmental Science and Technology 39(5):1221-1230.
- Shaw WJ, JC Linehan, A Gutowska, DJ Newell, TE Bitterwolf, JL Fulton, Y Chen, and CF Windisch, Jr. 2005. "Synthesis and Characterization of a Recoverable Rhodium Catalyst with a Stimulus Sensitive Polymer Ligand." Inorganic Chemistry Communications 8(10):894-896.
- Fryxell GE, H Wu, Y Lin, WJ Shaw, JC Birnbaum, JC Linehan, Z Nie, KM Kemner, and S Kelly. 2004. "Lanthanide Selective Sorbents: Self-Assembled Monolayers on Mesoporous Supports (SAMMS)." Journal of Materials Chemistry 14(22):3356-3363.
- Camaioni DM, JT Bays, WJ Shaw, JC Linehan, and JC Birnbaum. 2001. "Radical and Non-Radical Mechanisms for Alkane Oxidations by Hydrogen Peroxide-Trifluoroacetic Acid." Journal of Organic Chemistry 66(3):789-795. doi:10.1021/jo005617d