Professor Emeritus of Chemistry
Dr. Billups' early research interests included the synthesis of new molecular systems of theoretical interest. A major focus involved the development of a vacuum gas phase procedure for the synthesis of small ring cycloalkenes using reagents adsorbed on inert surfaces to affect elimination reactions. This approach allows the reactive species to be isolated at low temperature, and eliminates many of the undesired bimolecular side reactions that would normally be encountered in solution. Energetic compounds can thus be collected readily in cold traps for further chemical studies or spectral characterization. X-ray structural parameters of unstable low melting compounds were secured in collaboration with Dr. Roland Boese in Essen, Germany. Representative molecules whose syntheses have been accomplished include methylenecyclopropene, spiropentadiene, and spiroheptatriene. 3,3’-Bicyclopropenyl, the last (CH6) isomer benzene, was first made only in 1989 and characterized by X-Ray crystallography in the Boese laboratory. Collaborative work with Boese and an industrial sponsor led to the nucleation, growth, and structure of gas hydrates by X-Ray crystallography. Gas hydrates cause serious problems in long distance natural gas pipelines.
A second area involved studies on the activation of carbon-hydrogen bonds by first row transition metals. For example, photoexcited cobalt atoms were found to insert into the carbon-hydrogen bonds of methane to yield CH3CoH. This same species can be microsynthesized and characterized using FTIR spectroscopy by cocondensing the metal with CH2N2, H2, and argon at 11 K. Photolysis of CH3CoH using 400 nm light leads to extrusion of the metal with the formation of the spectroscopically detectable Co(CH4) σ-complex 2 shown to have C3v symmetry. Photolysis of this complex using a UV source regenerates the insertion product CH3CoH. Deuterium labeling studies have shown that the methane rotates freely on the cobalt. These studies were carried out in collaboration with the late Professor John Margrave.
Current studies in the area of carbon nanomaterials have focused on the development of routes to soluble carbon nanotubes and graphene. Reductive alkylation reactions that give nearly complete exfoliation of these materials have been developed. Application of these reactions to coal has allowed us to synthesize soluble coal nanoplatelets (liquid coal). This chemistry is described in the publications listed below.
S. C. Fritz, B. E. Brinson, W. E. Billups and Lonnie G. Thompson "Diatoms at >5000 Meters in the Quelccaya Summit Dome Glacier," Peru: Arctic, Antarctic, and Alpine Research, accepted for publication.
Y. Sun, A. G. Kvashnin, P. B. Sorokin, B.I. Yakobson, and W. E. Billups, "Radiation-Induced Nucleation of diamond from Amorphous Carbon: Effect of Hydrogen," Journal Physical Chemistry Letters, 5 2014: 1924-1928.
S. C. Fritz, B. E. Brinson, W. E. Billups and L. G. Thompson, “Diatoms at >5000 Meters in the Quelccaya Summit Dome Glacier, Peru”. Arctic, Antarctic, and Alpine Research, 47 2015: 149-154.
L. B. Alemany, M. Verma, W. E. Billups, S. L. Wellington, and M. Shammai, “Solid- and Solution-State Nuclear Magnetic Resonance Analyses of Ecuadorian Asphaltenes: Quantitative Solid-State Aromaticity Determination Supporting the “Island” Structural Model. Aliphatic Structural Information from Solution-State 1H–13C Heteronuclear Single-Quantum Coherence Experiments.” Energy Fuels, 29 2015: 6317–6329.
E. Vishnyakova, B. E. Brinson, L. B. Alemany, M. Verma, W. E. Billups, Structural Characterization and properties of a New Graphitic-Based Material. Chem. Eur. J. 2016, 22, 1452-1460.
S. Ghosh, F. Wei, S. M. Bachilo, R. H. Hauge, W. E. Billups, and R. B. Weisman, “Structure-Dependent Thermal Defunctionalization of Single-Walled Carbon Nanotubes.” ACS Nano, 9 2015: 6324–6332.
A. C. Ford, M. C. Shaughnessy-Culver, B. M. Wong, O. V. Kuznetsov, A. Kane, K. L. Krafcik, W. E. Billups, R. H. Hauge, F. Léonard Physical removal of metallic carbon nanotubes from nanotube network devices using a thermal and fluidic process. Nanotechnol., 24 2013: 105202-1:105202-8
S. Acharya, J. Alvarado, D. Banerjee, W. E. Billups, G. Chen, B. A. Cola, W. Cross, E. Duke, S. Graham, Jr., H. He, H. Hong, S. Jin, S. Karna, C. Li, C. H. Li, J. Li, G. P. Peterson, J. A. Puszynski, J. Routbort, J. Shan, D. Shin, A. Smirnova, P. Smith, X. Wang, A. Waynick, R. White, X. Yan, and W. Yu Report on Carbon and Nano Material Workshop: Challenges and Opportunities. Nanoscale Microscale Thermophys. Eng., 17 2013: 10-24
K. F. Kelly, W. E. Billups Synthesis of water soluble graphite and graphene. Acc. Chem. Res., 46 2013: 4-13
Z. Yang, Y. Sun, L. B. Alemany, T. N. Narayanan, W. E. Billups Birch reduction of graphite. Edge and Interior functionalization by hydrogen. J. Am. Chem. Soc., 134 2012: 18689-18694
O. Kuznetsov, Y. Sun, R. Thaner, A. Bratt, V. Shenoy, M. S. Wong, J. Jones and W. E. Billups Water Soluble Nano Diamond. Langmuir, 28 2012: 5243-5248
A. Kumar, A. L. M. Reddy, A. Mukherjee, M. Dubey, X. Zhan, N. Singh, L. Ci. W. E. Billups, J. Nagurny, G. Mital, P. M. Ajayan Direct Synthesis of Lithium-Intercalated Graphene for Electrochemical Energy Storage Application. ACS Nano, 5 2011: 4345-4349
Y. Sun, O. Kuznetsov, L. B. Alemany, W. E. Billups Reductive Alkylation of Anthracite: Edge Functionalization. Energy Fuels, 25 2011: 3997-4005
Y. Sun, L. B. Alemany, W. E. Billups, J. Lu, B. I. Yakobson Structural Dislocations in Anthracite. J. Phys. Chem. Lett., 2 2011: 2521-2524
V. C. Moore, L. A. McJilton, S. T. Pheasant, C. Kittrell, R. E. Anderson, D. Ogrin, F. Liang, R. H. Hauge, H. J. Schmidt, J M. Tour, W. E. Billups, A. R. Barron, and R. E. Smalley Controlled attachment of metal nanoparticles to single walled carbon nanotubes as a key step in their seeded growth and lengthening. Carbon, 48 2010: 561-565
J. Chattopadhyay, A. Mukherjee, S. Chakraborty, J. Kang, P. J. Loos. K. F. Kelly, H. K. Schmidt, and W. E. Billups Exfoliated Soluble Graphite. Carbon, 47 2009: 2945-2949
J. Chattopadhyay, C. Hamilton, A. Mukherjee, S. Chakraborty, W. Guo, A. R. Barron, and W. E. Billups Graphite Epoxide. J. Am. Chem. Soc., 130 2008: 5414
C. Ni, J. Chattopadhyay, W. E. Billups, and P. R. Bandaru Modification of the Electrical Characteristics of Single Wall Carbon Nanotubes Through Selective Functionalization. Appl. Phys. Lett., 93 2008: 243113
S. Chakraborty, W. Guo, R. H. Hauge, and W. E. Billups Reductive Alkylation of Fluorinated Graphite. Chem. Mater., 20 2008: 3134
D. Ogrin, R.E. Anderson, R. Colorado, Jr., B. Maruyama, M.J. Pender, V.C. Moore, S.T. Pheasant, L. McJilton, H.K. Schmidt, R.H Hauge, W.E. Billups, J.M. Tour, R.E. Smalley, and A.R. Barron Amplification of Single Walled Carbon Nanotubes from Designed Seeds: Separation of Nucleation and Growth. J. Phys. Chem. C, 111 2007: 17804
X. Shi, B. Sitharaman, Q.P. PHam, F. Liang, K. Wu, W.E. Billups, L.J. Wilson and A.G. Mikos Fabrication of Porous Ultra-Short Single-Walled Carbon Nanotube Nanocomposite Scaffolds for Bone Tissue Engineering. Biomaterials, 28 2007: 4078-4090
S. Chakroborty, J. Chattopadhyay, W. Guo, and W.E. Billups Functionalization of Potassium Graphite. Angew. Chem. Int. Ed., 46 2007: 4486
J. Chattopadhyay, S. Chakraborty, A. Mukherjee, R. Want, P.S. Engel, and W.E. Billups SET Mechanism in the Functionalization of Single Walled Carbon Nanotubes. J. Phys. Chem. C, 111 2007: 17928
K.J. Ziegler, Z. Gu, F. Liang, W.E. Billups, R.H. Hauge, and R.E. Smalley Statistically Accurate Lenght Measurements of Single-Walled Carbon Nanotubes. J. Nanosci. and Nanotechnol., 7, No.8 2007: 2917
M. Moniruzzaman, J. Chattopadhyay, W.E. Billups, and K.I. Winey Tuning the Mechanical Properties of SWNT/Nylon 6,10 Composits with Flexible Spacers at the Interface. Nano Lett., 7 2007: 1178