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
- 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
- Neiner D, AJ Karkamkar, JC Linehan, BW Arey, T Autrey, and SM Kauzlarich. 2009. "Promotion of Hydrogen Release from Ammonia Borane with Mechanically Activated Hexagonal Boron Nitride." Journal of Physical Chemistry C 113(3):1098-1103. doi:10.1021/jp8087385
- 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.
- Dietrich BL, KI Goldberg, DM Heinekey, T Autrey, and JC Linehan. 2008. "Iridium Catalyzed Dehydrogenation of Substituted Amine Boranes: Kinetics, Thermodynamics and Implications for Hydrogen Storage." Inorganic Chemistry 47(19):8583-8585. doi:10.1021/ic801161g
- Fister TT, FD Vila, GT Seidler, L Svec, JC Linehan, and JO Cross. 2008. "The Local Electronic Structure of Dicarba-closo-dodecaboranes C2B10H12." Journal of the American Chemical Society 130(3):925-932. doi:10.1021/ja074794u
- Fister TT, GT Siedler, EL Shirley, FD Vila, KP Nagle, JJ Rehr, JC Linehan, and JO Cross. 2008. "The local electronic structure of a-Li3N ." Journal of Chemical Physics 129(4):345-352; Article No. 044702.
- 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.
- Heldebrant DJ, AJ Karkamkar, JC Linehan, and T Autrey. 2008. "Synthesis of Ammonia Borane for Hydrogen Storage Applications." Energy & Environmental Science 1(1):156-160.
- Heldebrant DJ, AJ Karkamkar, JC Linehan, and T Autrey. 2008. "Synthesis of Ammonia Borane for Hydrogen Storage Applications." Energy & Environmental Science 1(1):156-160. doi:10.1039/b808865a
- Shaw WJ, JC Linehan, NK Szymczak, DJ Heldebrant, CR Yonker, DM Camaioni, RT Baker, and T Autrey. 2008. "In Situ Multinuclear NMR Spectroscopic Studies of the Thermal Decomposition of Ammonia Borane in Solution." Angewandte Chemie International Edition 47(39):7493-7496. doi:10.1002/anie.200802100
- Shaw WJ, Y Chen, JL Fulton, JC Linehan, A Gutowska, and TE Bitterwolf. 2008. "Structural Evolution of a Recoverable Rhodium Hydrogenation Catalyst." Journal of Organometallic Chemistry 693(12):2111-2118. doi:10.1016/j.jorganchem.2008.03.011
- 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
- Zheng F, SD Rassat, DJ Heldebrant, DD Caldwell, CL Aardahl, T Autrey, JC Linehan, and KG Rappe. 2008. "Automated gas burette system for evolved hydrogen measurements." Review of Scientific Instruments 79(8):Article no: 084103. doi:10.1063/1.2968715
- 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.
- Fulton JL, JC Linehan, T Autrey, M Balasubramanian, Y Chen, and NK Szymczak. 2007. "When is a Nanoparticle a Cluster? An Operando EXAFS Study of Amine Borane Dehydrocoupling by Rh4-6 Clusters." Journal of the American Chemical Society 129(39):11936-11949.
- Heldebrant DJ, JC Linehan, DM Camaioni, SD Rassat, F Zheng, and T Autrey. 2007. "EFFECT OF ADDITIVES ON THE THERMOLYSIS OF AMMONIA BORANE." In 234th American Chemical Society Conference Proceedings - Reprints of Symposia - Division of Fuel Chemistry., vol. 52, no. 2, pp. 563-564. American Chemical Society, Washington DC.
- Stowe AC, WJ Shaw, JC Linehan, B Schmid, and T Autrey. 2007. "In situ solid state B-11 MAS-NMR studies of the thermal decomposition of ammonia borane: mechanistic studies of the hydrogen release pathways from a solid state hydrogen storage material." Physical Chemistry Chemical Physics. PCCP 9(15):1831-1836. doi:10.1039/b617781f
- Linehan JC, CM Stiff, and GE Fryxell. 2006. "A simple determination of alkylsilane monolayer population density." Inorganic Chemistry Communications 9(2):239-241.
- 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.
- DuBois DL, DM Blake, A Miedaner, CJ Curtis, MR DuBois, JA Franz, and JC Linehan. 2006. "Hydride Transfer from Rhodium Complexes to Triethylborane." Organometallics 25(18):4414-4419. doi:10.1021/om060584z
- 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.
- Linehan JC, T Autrey, JL Fulton, Y Chen, and M Balasubramanian. 2005. "Catalysis for Hydrogen Storage." In Abstracts of Papers of the American Chemical Society: 230th National Meeting of the American Chemical Society, vol. 230, no. 53-FUEL, p. U1651. American Chemical Society, Washington DC.
- Chen Y, JL Fulton, JC Linehan, and T Autrey. 2005. "In-situ XAFS and NMR Study of Rhodium Catalyzed Dehydrogenation of Dimethylamine Borane. ." Journal of the American Chemical Society 127(10):3254-3255. doi:10.1021/ja0437050
- 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.
- Yonker CR, and JC Linehan. 2005. "The Use of Supercritical Fluids as Solvents for NMR Spectroscopy." Progress in Nuclear Magnetic Resonance Spectroscopy 47(1-2):95-109.
- Bitterwolf TE, JD Newell, CT Carver, RS Addleman, JC Linehan, and GE Fryxell. 2004. "Rhodium catalysts bound to functionalized mesoporous silica." Inorganica Chimica Acta 357(10):3001-3006.
- Franz JA, DS Kolwaite, JC Linehan, and E Rosenberg. 2004. "Comparison of Hydrogen Atom Abstraction Rates of Terminal and Bridging Hydrides in Triosmium Clusters: Absolute Abstraction Rate Constants for Benzyl Radical." Organometallics 23(3):441-445.
- Franz JA, JC Birnbaum, DS Kolwaite, JC Linehan, DM Camaioni, and M Dupuis. 2004. "Activation of the Sulfhydryl Group by Mo Centers: Kinetics of Reaction of Benzyl Radical with a Binuclear Mo(mu-SH)Mo Complex and with Arene and Alkane Thiols." Journal of the American Chemical Society 126(21):6680-6691.
- 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.
- 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.
- Yonker CR, and JC Linehan. 2004. "A High-Pressure NMR Investigation of Reaction Chemistries in a Simple Salt Hydrate." Journal of Supercritical Fluids 29(3):257-263.
- Yonker CR, and JC Linehan. 2002. "Investigation of the Hydroformylation of Ethylene in Liquid Carbon Dioxide." Journal of Organometallic Chemistry 650((1-2)):249-257.
- 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
- Linehan JC, CR Yonker, RS Addleman, T Autrey, JT Bays, TE Bitterwolf, and JL Daschbach. 2001. "Solvent Study of the Kinetics of Molybdenum Radical Self-Termination." Organometallics 20(3):401-407.
- Bitterwolf TE, JC Linehan, and JE Shade. 2001. "Solution and Nujol Matrix Photochemistry of (n5-C5H5)2OS2(CO)4 and Nujol Matrix Photochemistry of (n5-C5H4CH3)2Ru2(CO)4 and (n5-C5H5)M(CO)2H, where M = Ru and Os." Organometallics 20(4):775-781. doi:10.1021/om000845j
- Bitterwolf TE, DL Klein, JC Linehan, CR Yonker, and RS Addleman. 2001. "Photochemical Carbonylation of Ethane Under Supercritical Conditions." Angewandte Chemie International Edition 40(14):2692-2694.
- Bitterwolf TE, JC Linehan, and JE Shade. 2000. "Dihydrogen as a Reactant in the Photochemistry of Bimetallic Cyclopentadienyl Carbonyl Compounds." Organometallics 19(23):4915-4917. doi:10.1021/om000292c
- Franz JA, DM Camaioni, T Autrey, JC Linehan, and MS Alnajjar. 2000. "Measurement of Select Radical Processes in Hydrocarbon Pyrolysis." Journal of Analytical and Applied Pyrolysis 54(1-2):37-64.
- Linehan JC, CR Yonker, JT Bays, T Autrey, TE Bitterwolf, and S Gallagher. 1999. "A Kinetic Study of the Thermal Loss of Ethylene from CpNb(CO)(3)(eta(2)-C2H4) in Supercritical Fluid Solvents." Journal of the American Chemical Society 120(23):5826-5827.
- Autrey T, JC Linehan, LE Kaune, TR Powers, EF Mcmillan, CJ Stearns, and JA Franz. 1999. "FeS Assisted Scission of Strong Bonds in Phenoxydiphenylmethanes. Competition between Hydrogen Atom Transfer and Free Radical Rearrangement Pathways." Energy and Fuels 13(4):927-933.
- Darab JG, JC Linehan, and BP McGrail. 1999. "NMR characterization of simulated Hanford low-activity waste glasses and its use in understanding waste form chemical durability." In Scientific Basis For Nuclear Waste Management XXII, Materials Research Society Symposium Procedings, vol. 556, pp. 337-344. Materials Research Society, Warrendale.
- Franz JA, JC Linehan, JC Birnbaum, KL Hicks, and MS Alnajjar. 1999. "Absolute Rate Expressions for Hydrogen Atom Abstraction from Molybdenum Hydrides by Carbon-Centered Radicals." Journal of the American Chemical Society 121:9824-9830.
- Yonker CR, JC Linehan, and JL Fulton. 1999. "The Use of High-Pressure NMR for the Determination of Phase-Behavior for Select Binary Solvent Systems." Journal of Supercritical Fluids 14(1):9-16.
- Yonker CR, JC Linehan, and JL Fulton. 1999. "UV, EPR, X-ray and Related Spectroscopie Techniques." Chapter 3.3 in Chemical Synthesis Using Supercritical fluids, ed. Philip G. Jessop and Walter Leitner, pp. 195-212. Wiley-VCH, Weinheim, Germany.