Graphitic Nanocarbon Supports For Molecular Transport, Sensing, and Catalysis

Graphitic Nanocarbon Supports for Molecular Transport, Sensing, and Catalysis John Russell, Department of Chemistry, University of Illinois at Chicago, IL 60607 In this thesis, we theoretically investigate catalysis, molecular transport, and molecular sensing on nanocarbon supporting materials. First, we use ab-initio quantum chemistry methods to study sub-nanometer Pd and Pt clusters binding to graphene and carbon nanotubes [1]. We calculate reaction barriers for methane dehydrogenation on these clusters and show that the curvature and chirality of carbon supporting materials affect both the binding energies of clusters and their reaction barriers. Next, we investigate by classical molecular dynamics simulations how water nanodroplets attached by van der Waals coupling to carbon nanotubes can be dragged on their surfaces vibrated by coherent acoustic phonon waves [2]. We reveal a rich nanodroplet dynamics resembling material surfing. We also model sensing of small (explosive) molecules selectively nested on boron-and-nitrogen doped and vibrated graphene sheets [3]. The selectively attached molecules are recognized from the shifts of resonant frequencies of the vibrated sheets. Then, we study buckling of graphene bilayers, model a related diamond to rhombohedral graphite transition, and simulate graphitization of diamond nanowires by thermal annealing [4]. Finally, we develop a computationally inexpensive molecular dynamics approach to evaluate electrostatic interactions. [1] J. Russell, P. Zapol, P. Král, and L. A. Curtiss, Methane bond activation by Pt and Pd sub-nanometer clusters supported on graphene and carbon nanotubes, Chem. Phys. Lett. 536, 9 (2012). [2] J. Russell, B. Wang and P. Král, Nanodroplet Transport on Vibrated Nanotubes, J. Phys. Chem. Lett 3, 353 (2012) [3] J. Russell and P. Král, Configuration-sensitive Molecular Sensing on Doped Graphene Sheets, Nano Research 3, 472 (2010). [4] J. Russell, P. Zapol, P. Král, and L. A. Curtiss, in preparation.