RESUMEN
Huntsman-Merrimack MIRALON® carbon nanotubes (CNTs) are a novel, highly entangled, commercially available, and scalable format of nanotubes. As-received and acid-treated CNTs were added to aerospace grade epoxy (CYCOM® 977-3), and the composites were characterized. The epoxy resin is expected to infiltrate the network of the CNTs and could improve mechanical properties. Epoxy composites were tested for flexural and viscoelastic properties and the as-received and acid treated CNTs were characterized using Field-Emission Scanning and Transmission Electron Microscopy, X-Ray Photoelectron Spectroscopy, and Thermogravimetric Analysis. Composites containing 0.4 wt% as-received CNTs showed an increase in flexural strength, from 136.9 MPa for neat epoxy to 147.5 MPa. In addition, the flexural modulus increased from 3.88 GPa for the neat epoxy to 4.24 GPa and 4.49 GPa for the 2.0 wt% and 3.0 wt% as-received CNT/epoxy composites, respectively. FE-SEM micrographs indicated good dispersion of the CNTs in the as-received CNT/epoxy composites and the 10 M nitric acid 6 h treatment at 120 °C CNT/epoxy composites. CNTs treated with 10 M nitric acid for 6 h at 120 °C added oxygen containing functional groups (C-O, C=O, and O=C-O) and removed iron catalyst present on the as-received CNTs, but the flexural properties were not improved compared to the as-received CNT/epoxy composites.
RESUMEN
Vibrational spectroscopy techniques have evolved to measure gases, liquids, and solids at surfaces and interfaces. In the field of surface-sensitive vibrational spectroscopy, infrared spectroscopy measures the adsorption on surfaces and changes from reactions. Previous polarized modulated-infrared reflection-absorption spectroscopy (PM-IRRAS) measurements at the gas/solid interface were developed to observe catalytic reactions near reaction conditions. Other PM-IRRAS measurements use liquid cells where the sample is submerged and compressed against a prism that has traditionally been used for electrochemical reactions. This article presents a new method that is used to observe in situ adsorption of molecules using PM-IRRAS at the gas/liquid/solid interface. We demonstrate the meniscus method by measuring the adsorption of octadecanethiol on gold surfaces. Characterization of self-assembled monolayers (SAMs), the "gold standard" for PM-IRRAS calibration measurements, was measured in ethanol solutions. The condensed-phase (air/liquid) interface in addition to the liquid/solid interface was measured simultaneously in solution. These are compared with liquid attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy measurements to confirm the presence of the SAM and liquid ethanol. A model of the three-phase system is used to approximate the thickness of the liquid ethanol layer and correlate these values to signal attenuation using PM-IRRAS. This proof-of-concept study enables the measurement of reactions at the gas/liquid/solid interface that could be adapted for other reactions at the electrode and electrolyte interfaces with applications in environmental science and heterogeneous catalysis.
RESUMEN
Iron oxide nanomaterials participate in redox processes that give them ideal properties for their use as earth-abundant catalysts. Fabricating nanocatalysts for such applications requires detailed knowledge of the deposition and growth. We report the spontaneous deposition of iron oxide nanoparticles on HOPG in defect areas and on step edges from a metal precursor solution. To study the nucleation and growth of iron oxide nanoparticles, tailored defects were created on the surface of HOPG using various ion sources that serve as the target sites for iron oxide nucleation. After solution deposition and annealing, the iron oxide nanoparticles were found to nucleate and coalesce at 400 °C. AFM revealed that the particles on the sp3 carbon sites enabled the nanoparticles to aggregate into larger particles. The iron oxide nanoparticles were characterized as having an Fe3+ oxidation state and two different oxygen species, Fe-O and Fe-OH/Fe-OOH, as determined by XPS. STEM imaging and EDS mapping confirmed that the majority of the nanoparticles grown were converted to hematite after annealing at 400 °C. A mechanism of spontaneous and selective deposition on the HOPG surface and transformation of the iron oxide nanoparticles is proposed. These results suggest a simple method for growing nanoparticles as a model catalyst.
RESUMEN
Dehydrative cyclocondensation processes for semiconductor surface modification can be generally suggested on the basis of well-known condensation schemes; however, in practice this approach for organic functionalization of semiconductors has never been investigated. Here we report the modification of hydrogen-terminated silicon surfaces by cyclocondensation. The cyclocondensation reactions of nitrobenzene with hydrogen-terminated Si(100) and Si(111) surfaces are investigated and paralleled with selected cycloaddition reactions of nitro- and nitrosobenzene with Si(100)-2x1. Infrared spectroscopy is used to confirm the reactions and verify an intact phenyl ring and C-N bond in the reaction products as well as the depletion of surface hydrogen. High resolution N 1s X-ray photoelectron spectroscopy (XPS) suggests that the major product for both cyclocondensation reactions investigated is a nitrosobenzene adduct that can only be formed following water elimination. Both IR and XPS are augmented by density functional theory (DFT) calculations that are also used to investigate the feasibility of several surface reaction pathways, which are insightful in understanding the relative distribution of products found experimentally. This novel surface modification approach will be generally applicable for semiconductor functionalization in a highly selective and easily controlled manner.