Carbon Nanomaterials

  • Carbon Nanothreads from Benzene

    We have found that benzene molecules can react in the solid state to form diamondoid nanothreads. These nanothreads differ from conventional carbon nanotubes in having tetrahedrally bonded carbon instead of trigonal carbon. See: Fitzgibbons, T.C., Guthrie, M., Xu, E., Crespi, V.H, Davidowski, S.K., Cody, G.D., Alem, N. and Badding, J.V., Benzene-derived carbon nanothreads, Nature Materials, doi: 10.1038/nmat4088.

    Ambient Temperature Reversible Hydrogenation

    Unsaturated carbon molecules and materials can change hybridization to sp3-bonded carbon upon compression (4). Hydrogen can affect this change in hybridization by bonding to compressed carbon. We are investigating the high pressure behavior of unsaturated carbon molecules as part of the Carnegie Institution of Washington DOE EFREE Energy Frontier Research Center. Applications of interest include hydrogen storage materials, luminescent materials, and high strength materials. Some solids can reversibly rehybridize from sp2 to sp3 bonding and back to the same sp2 bonding upon release of pressure (4). This behavior remains largely not understood and thus probing it is a key focus of our research.

    Ambient temperature reversible hydrogenation of carbon is of particular interest because it places strict constraints on the C-H bond energetics: 2 C-H bonds must have an energy close to that of an H-H bond. Most C-H bonds in organic molecules and organic solids have an energy closer to that of H-H.

    Our research collaboration with Angela Lueking and Vin Crespi at Penn State has shown that carbons doped with catalytic Pt nanoparticles can be hydrogenated reversibly at room temperature (28). A new mode at ~1180 cm-1 arises in the in Raman spectrum of oxidized and Pt doped activated carbon in the presence of hydrogen and disappears upon removal of hydrogen at ambient temperature. This mode also appears to arise in the Raman spectrum of hydrogen implanted graphene (28), but has not previously been recognized as such. Other carbons, such as graphene, also exhibit the mode, but it does not disappear upon removal of hydrogen. The bond can be convincingly attributed to H because it downshifts by the expected amount upon deuteration. Ambient temperature reversible hydrogenation of carbon is of particular interest because it places strict constraints on the C-H bond energetics: 2 C-H bonds must have an energy close to that of an H-H bond. Most C-H bonds in organic molecules and organic solids have an energy closer to that of H-H. Reversibility is a central issue in hydrogen storage, for example; chemical bonds are often too strong to allow for reversibility while physisorption does not allow for much storage at ambient temperature. Density functional calculations show that certain arrangements of paired H atoms bonded to a graphene sheet allow for bond strengths in the range needed for reversibility. Steric effects associated with the rehybridization of the sp2 graphene carbons to sp3 upon reaction with hydrogen weaken the bond. Unraveling the origin of the reversibility in certain carbons and the lack of it in other carbons is a central goal of this project. The experiments to date show that Raman spectroscopy can give new information at the microscopic level, i.e., the level of bonds, about the reversible and irreversible hydrogenation of carbon by catalytic Pt nanoparticles. Macroscopic measurements and inelastic neutron scattering measurements, for example, do not give such direct microsocopic level information about the C-H bonding.

  • Selected Publications

    • (1) Badding, J. V. High-pressure synthesis, characterization, and tuning of solid-state materials. Annual Review of Materials Science 28, 631 (1998).
    • (2) Parker, L. J., Atou, T. & Badding, J. V. Transition element-like chemistry for potassium under pressure. Science 273, 95 (1996).
    • (3) Atou, T., Hasegawa, M., Parker, L. J. & Badding, J. V. Unusual Chemical Behavior for Potassium under Pressure: Potassium-Silver Compounds. Journal of the American Chemical Society 118, 12104 (1996).
    • (4) Badding, J.V., Lueking, A.L., Reversible High Pressure sp2-sp3 Transformations in Carbon, Phase Transitions, 80, 1033 (2007)
    • (5) Miller, E. D., Nesting, D. C. & Badding, J. V. Quenchable Transparent Phase of Carbon. Chemistry of Materials 9, 18 (1997).
    • (6) Jackson, B. R., Trout, C. C. & Badding, J. V. UV Raman Analysis of the C:H Network Formed by Compression of Benzene. Chemistry of Materials 15, 1820 (2003).
    • (7) Ravindran, T. R. & Badding, J. V. Ultraviolet Raman analysis of the formation of diamond from C60. Solid State Communications 121, 391 (2002).
    • (8) Badding, J. V. Solid-state carbon nitrides. Advanced Materials 9, 877 (1997).
    • (9) Ravindran, T. R., Jackson, B. R. & Badding, J. V. UV Raman Spectroscopy of Single-Walled Carbon Nanotubes. Chemistry of Materials 13, 4187 (2001).
    • (10) Polvani, D. A., Meng, J. F., Shekar, N. V. C., Sharp, J. & Badding, J. V. Large Improvement in Thermoelectric Properties in Pressure-Tuned p-Type Sb1.5Bi0.5Te3. Chemistry of Materials 13, 2068 (2001).
    • (11) Baril, N.F, He, R., Day, T.D., Sparks, J.R., Keshavarzi, B, , Krishnamurthi, M, Borhan, A, Gopalan, V, Peacock, A.C, Heal, N, . Sazio, P.J.A., and Badding, J. V. Confined High-Pressure Chemical Deposition of Hydrogenated Amorphous Silicon, Journal of the American Chemical Society, 134, 19-22 (2012).
    • (12) Sazio, P. J. A., Amezcua-Correa, A., Finlayson, C. E., Hayes, J. R., Scheidemantel, T. J., Baril, N. F., Jackson, B. R., Won, D.-J., Zhang, F., Margine, E. R., Gopalan, V., Crespi, V. H. & Badding, J. V. Microstructured Optical Fibers as High-Pressure Microfluidic Reactors. Science 311, 1583 (2006).
    • (13) Sparks, J.R., He, R., Healy, N., Krishnamurthi, M, Peacock, A.M., Sazio, P.J.A., Gopalan, V. Badding, J.V. Zinc Selenide Optical Fibers, Advanced Materials, 23, 1647 (2011).
    • (14) Healy, N., Lagonigro, L., Sparks, J.R., Boden, S., Sazio, P.J.A., Badding, J.V., and Peacock, A.C., Polycrystalline silicon optical fibers with atomically smooth surfaces, Optics Letters, 36, 12480-2482 (2011).
    • (15) He, R.,Sazio, P.J.A., Peacock, A.C, Heal, N., Sparks, J.R., Krishnamurthi, M, Gopalan, V, and Badding, J. V., Integration of GHz Bandwidth Semiconductor Devices inside Microstructured Optical Fibres, Nature Photonics, 6, 174-179 (2012).
    • (16) Calkins, J.A., Peacock, A.C, Sazio, P. J. A., Allara, D.L., and Badding, J. V. Spontaneous Waveguide Raman Spectroscopy of Self-Assembled Monolayers in Silica Micropores, Langmuir, 27, 630 (2011).
    • (17) Mehta, P., Krishanmurthi, M., Healy, N., Baril, N. F., Sparks, J., Sazio, P. J. A., Gopalan,V., Badding, J. V. and Peacock, A. C. Mid-infrared transmission properties of amorphous germanium optical fibers, Applied Physics Letters, 97, 071117 (2010).
    • (18) Vukovic, N, Healy, N, Horak, P., Sparks, J.R., Sazio, P.J.A., Badding, J.V., and, Peacock, A.C., Ultra-smooth microcylindrical resonators fabricated from silicon optical fibers, Applied Physics Letters, 99. 03117 (2011).
    • (19) Krishnamurthi, M, Sparks, J.R., He, R.,Temkyh, I., Baril, N.F., Liu, Z., Sazio, P.J.A., Badding, J. V., and Gopalan, V, An Array of Tapered Semiconductor Waveguides in a Fiber for Infrared Image Transfer and Magnification Optics Express, 20, 4168-4175 (2012).
    • (20) Mehta, P., Healy, N., Baril,N. F., Sazio, P. J. A., Badding, J. V. and Peacock, A. C. Nonlinear transmission properties of hydrogenated amorphous silicon core optical fibers, Optics Express, 18, 16826 (2010).
    • (21) Danisman, M.F, Calkins, J.A. Sazio, P.J.A., Allara, D.A., Badding, J.V. Organosilane Self Assembled Monolayer Growth from Supercritical Carbon Dioxide in Microstructured Optical Fiber Capillary Arrays, Langmuir, 24, 3636 (2008).
    • (22) Baril, N. F., Keshavarzi, B., Sparks, J. Krishnamurthi, M., Temnykh, I., Sazio, P. J. A., Peacock, A. C., Borhan, A., Gopalan, V., Badding, J. V. High Pressure Chemical Deposition for Void-Free Filling of Extreme Aspect Ratio Templates, Advanced Materials, 22, 4605 (2010).
    • (23) Jackson, B.R., Sazio, P.J., Badding,J.V., Single Crystal Silicon Wires Integrated into Microstructured Optical Fiber Templates, Advanced Materials, 20, 1135 (2008).
    • (24) Borkar, S., Gu, B., Dirmyer, M., Delicado, R., Sen, A., Jackson, B. R. & Badding, J. V. Polytetrafluoroethylene nano/microfibers by jet blowing. Polymer 47, 8337-8343 (2006).
    • (25) Ainslie, K. M., Bachelder, E. M., Borkar, S., Zahr, A. S., Sen, A., Badding, J. V. & Pishko, M. V.Albumin Adsorption and Cell Adhesion on Nanofibrous Polytetrafluoroethylene (nPTFE). Langmuir, 23, 747-754 (2007).
    • (26) Sparks, J.R., He, R., Healy, N., Chaudhuri, S., Peacock, A.C., Sazio, P.J.A., and Badding, J. V., Conformal Coating by High Pressure Chemical Deposition for Patterned Microwires of II-VI Semiconductors, Advanced Functional Materials 10.1002/adfm.201202224.
    • (27) He, R., Day, T.D., Krishnamurthi, M., Sparks, J.R., Sazio, P.J.A., Gopalan, V., and Badding, J. V., Silicon p-i-n Junction Fibers, Advanced Materials 10.1002/adma.201203879.
    • (28) Liu, X., Tang, Y., Xu, E., Fitzgibbons, T., Larsen, G., Gutierrez, H., Tseng, H.-H., Yu, M.-S., Tsao, C.-S., Badding, J., Crespi, V., Lueking, A., Evidence for Ambient-Temperature Reversible Catalytic Hydrogenation in Pt-doped Carbons, Nano Letters 10.1021/nl303673z.
    • (29) Mehta, P., Healy, N., Day, T.D., Badding, J. V., and Peacock, A. C. Ultrafast wavelength conversion via cross-phase modulation in hydrogenated amorphous silicon optical fibers, Optics Express 20, 26110-26116 (2012).
    • (30) Sparks, J.R., Sazio, P.J.A., Gopalan, V., Badding, J. V., Templated Chemically Deposited Semiconductor Optical Fiber Materials, Annual Review of Materials Research, 0.1146/annurev-matsci-073012-125958.