Ajayan, Pulickel2017-08-022017-08-022016-052016-03-29May 2016Kabbani, Mohamad. "Ambient mechanochemical solid-state reactions of carbon nanotubes and their reactions via covalent coordinate bond in solution.." (2016) Diss., Rice University. <a href="https://hdl.handle.net/1911/96241">https://hdl.handle.net/1911/96241</a>.https://hdl.handle.net/1911/96241In its first part, this thesis deals with ambient mechanochemical solid-state reactions of differently functionalized multiple walled carbon nanotubes (MWCNTs) while in its second part it investigates the cross-linking reactions of CNTs in solution via covalent coordinate bonds with transitions metals and carboxylate groups decorating their surfaces. In the first part a series of mechanochemical reactions involving different reactive functionalities on the CNTs such as COOH/OH, COOH/NH2 and COCl/OH were performed. The solid-state unzipping of CNTs leading to graphene formation was confirmed using spectroscopic, thermal and electron microscopy techniques. The non-grapheme products were established using in-situ quadruple mass spectroscopy. The experimental results were confirmed by theoretical simulation calculations using the ‘hot spots’ protocol. The kinetics of the reaction between MWCNT-COOH and MWCNT-OH was monitored using variable temperature Raman spectroscopy. The low activation energy was discussed in terms of hydrogen bond mediated proton transfer mechanism. The second part involves the reaction of MWCNTII COOH with Zn (II) and Cu (II) to form CNT metal-organic frame (MOFs) products that were tested for their effective use as counter-electrodes in dyes sensitized solar cells (DSSC). The thesis concludes by the study of the room temperature reaction between the functionalized graphenes, GOH and G'-COOH followed by the application of compressive loads. The 3D solid graphene pellet product (~0.6gm/cc) is conductive and reflective with a 35MPa ultimate strength as compared to 10MPa strength of graphite electrode (~2.2gm/cc).application/pdfengCopyright is held by the author, unless otherwise indicated. Permission to reuse, publish, or reproduce the work beyond the bounds of fair use or other exemptions to copyright law must be obtained from the copyright holder.CNT Carbon NanotubeSWCNT Single-Walled Carbon NanotubeMWCNT Multiple-Walled Carbon NanotubeDMF N, N-dimethylformamideMOF Metal organic frameworksCVD Carbon Vapor DepositionMCR Mechanochemical ReactionDSSC Dye-Sensitized Solar CellSEM Scanning Electron MicroscopyTEM Transmission Electron MicroscopyATR-IR Attenuated Total reflectance IR spectroscopyTGA Thermal Gravimetric AnalysisDTA Differential Thermal AnalysisXPS X-ray Photoelectron SpectroscopyXRD X-Ray DiffractionDFT Density Function TheoryNEB Nudged Elastic BandReaxFF Reactive Force FieldThesis2017-08-02