Surface Mobility and Nucleation of a Molecular Switch: Tetraaniline on Hematite

Understanding the dynamics of organic thin film formation is crucial to quality control in organic electronics and smart coatings. We have studied the nucleation and growth of the reduced and the oxidized states of phenyl-capped aniline tetramer (PCAT) deposited on hematite(1000) surfaces by physical vapor deposition. The fully reduced PCAT molecules form 2D islands on the surface, whereas the fully oxidized molecules form 3D islands. Through scaled island size distribution, it was found that the critical island sizes, <i>i</i>, for the reduced and oxidized molecules are <i>i</i> = 4 and 5, respectively. From the dependence of the island density on substrate temperature, the activation energies for the diffusion of the molecules away from the critical cluster were calculated to be 1.30 and 0.55 eV, respectively. At low temperatures, the reduced and the oxidized PCAT molecules form compact islands on the surface. At higher temperatures, the reduced islands become dendritic, whereas the oxidized islands become slightly dendritic. The attempt frequencies for surface diffusion of the reduced and the oxidized islands were estimated to be about 5 × 10²⁵ and 8 × 10¹¹ s^–1, respectively. The former value is in line with the high degree of surface wetting by the reduced PCAT, whereas the latter value shows the higher degree of intermolecular interaction in the fully oxidized PCAT and the low degree of its interaction with the iron oxide surface. Interconversion between oxidized and reduced islands through exposure to a reducing environment, and its impact on island morphology was examined. We also found that the presence of Fe²⁺ defects on the hematite surface did not impact the nucleation and growth of the molecular islands, likely due to a discrepancy in time scale. This study elucidates the interactions between an oligoaniline-based molecular switch (PCAT) and hematite surfaces as a function of molecular oxidation state, with applications in molecular electronics, chemical sensors, and smart coatings

Ultrasmooth Gold Surfaces Prepared by Chemical Mechanical Polishing for Applications in Nanoscience

For over 20 years, template stripping has been the best method for preparing ultrasmooth metal surfaces for studies of nanostructures. However, the organic adhesives used in the template stripping method are incompatible with many solvents, limiting the conditions that may subsequently be used to prepare samples; in addition, the film areas that can be reliably prepared are typically limited to ∼1 cm². In this article, we present chemical–mechanical polishing (CMP) as an adhesive-free, scalable method of preparing ultrasmooth gold surfaces. In this process, a gold film is first deposited by e-beam evaporation onto a 76-mm-diameter silicon wafer. The CMP process removes ∼4 nm of gold from the tops of the grains comprising the gold film to produce an ultrasmooth gold surface supported on the silicon wafer. We measured root-mean-square (RMS) roughness values using atomic force microscopy of 12 randomly sampled 1 μm × 1 μm areas on the surface of the wafer and repeated the process on 5 different CMP wafers. The average RMS roughness was 3.8 ± 0.5 Å, which is comparable to measured values for template-stripped gold (3.7 ± 0.5 Å). We also compared the use of CMP and template-stripped gold as bottom electrical contacts in molecular electronic junctions formed from <i>n</i>-alkanethiolate self-assembled monolayers as a sensitive test bed to detect differences in the topography of the gold surfaces. We demonstrate that these substrates produce statistically indistinguishable values for the tunneling decay coefficient β, which is highly sensitive to the gold surface topography

Continuous Hydrothermal Decarboxylation of Fatty Acids and Their Derivatives into Liquid Hydrocarbons Using Mo/Al₂O₃ Catalyst

In this study, we report a single-step continuous production of straight-chain liquid hydrocarbons from oleic acid and other fatty acid derivatives of interest including castor oil, frying oil, and palm oil using Mo, MgO, and Ni on Al₂O₃ as catalysts in subcritical water. Straight-chain hydrocarbons were obtained via decarboxylation and hydrogenation reactions with no added hydrogen. Mo/Al₂O₃ catalyst was found to exhibit a higher degree of decarboxylation (92%) and liquid yield (71%) compared to the other two examined catalysts (MgO/Al₂O₃, Ni/Al₂O₃) at the maximized conditions of 375 °C, 4 h of space time, and a volume ratio of 5:1 of water to oleic acid. The obtained liquid product has a similar density (0.85 kg/m³ at 15.6 °C) and high heating value (44.7 MJ/kg) as commercial fuels including kerosene (0.78–0.82 kg/m³ and 46.2 MJ/kg), jet fuel (0.78–0.84 kg/m³ and 43.5 MJ/kg), and diesel fuel (0.80–0.96 kg/m³ and 44.8 MJ/kg). The reaction conditions including temperature, volume ratio of water-to-feed, and space time were maximized for the Mo/Al₂O₃ catalyst. Characterization of the spent catalysts showed that a significant amount of amorphous carbon deposited on the catalyst could be removed by simple carbon burning in air with the catalyst recycled and reused