Defluorination and adsorption of tetrafluoroethylene (TFE) on TiO2(110) and Cr2O3(0001)

Here, we show that metal oxide surfaces catalyze the formation of intermediate defluorinated tetrafluoroethylene (TFE) radicals, resulting in enhanced binding on the corresponding metal oxide surfaces. We attribute the preferential adsorption and radical formation of TFE on Cr2O3(0001) relative to TiO2(110) to the low oxygen coordination of Cr surface atoms. This hints at a possible dependence of the TFE binding strength to the surface stoichiometry of metal-oxide surfaces.

High-Temperature Decomposition of Diisopropyl Methylphosphonate (DIMP) on Alumina: Mechanistic Predictions from Ab Initio Molecular Dynamics

The enhanced degradation of organophosphorous-based chemical warfare agents (CWAs) on metal-oxide surfaces holds immense promise for neutralization efforts; however, the underlying mechanisms in this process remain poorly understood. We utilize large-scale quantum calculations for the first time to probe the high-temperature degradation of diisopropyl methylphosphonate (DIMP), a nerve agent simulant. Our Born-Oppenheimer molecular dynamics (BOMD) calculations show that the gamma-Al2O3 surface shows immense promise for quickly adsorbing and destroying CWAs. We find that the alumina surface quickly adsorbs DIMP at all temperatures, and subsequent decomposition of DIMP proceeds via a propene elimination. Our BOMD calculations are complemented with metadynamics simulations to produce free energy paths, which show that the activation barrier decreases with temperature and DIMP readily decomposes on gamma-Al2O3. Our first-principle BOMD and metadynamics simulations provide crucial diagnostics for sarin decomposition models and mechanistic information for examining CWA decomposition reactions on other candidate metal oxide surfaces.

Synthesis of Aminopropyltriethoxysilyl-Substituted Imines and Amides

A series of small molecules containing aminopropyltriethoxysilyl-substituted imines and amides were synthesized so that they could potentially be incorporated into self-assembled monolayers (SAMs) on metal oxide surfaces. Simple one-step imine preparations and two-step amide preparations are reported here.

Zirconia Nanotube Coatings - UV-Resistant Superhydrophobic Surfaces

Surface modifications influence material interactions such as wettability, imparting hydrophobicity or hydrophilicity. Mainstream research focused on enhancing product shelf-life, directs attention towards superhydrophobic surfaces (SHS). SHS offer several benefits for outdoor applications such as self-cleaning, anti-soiling, anti-mist etc. In this manuscript, we explore the possibility of combining structural and chemical modifications to metal substrates in order to create superhydrophobic metal oxide surfaces. ZrO2-nanotubes are evaluated with regard to their application as transparent UV-stable superhydrophobic coatings. Nanostructured oxide surfaces are created via single-step electrochemical anodization. The absence of HF acid-based pre-etching steps offer a safe and alternatively a green synthesis route. Anodized oxides are modified using octadecylphosphonic acid self-assembled monolayers, demonstrate superhydrophobicity and are evaluated for their mechanical stability under a jet of water, chemical stability under indirect sunlight irradiation in air/water and direct UV exposure. Zirconia nanotubular films were evaluated for optical transparency using light microscopy and surface wettability of the different zirconia-composites was compared to the model system-titania. Structural and compositional differences of the SAM layer upon time dependent decay were analyzed with X-ray photoelectron spectroscopy. <br>

Zirconia Nanotube Coatings - UV-Resistant Superhydrophobic Surfaces

Surface modifications influence material interactions such as wettability, imparting hydrophobicity or hydrophilicity. Mainstream research focused on enhancing product shelf-life, directs attention towards superhydrophobic surfaces (SHS). SHS offer several benefits for outdoor applications such as self-cleaning, anti-soiling, anti-mist etc. In this manuscript, we explore the possibility of combining structural and chemical modifications to metal substrates in order to create superhydrophobic metal oxide surfaces. ZrO2-nanotubes are evaluated with regard to their application as transparent UV-stable superhydrophobic coatings. Nanostructured oxide surfaces are created via single-step electrochemical anodization. The absence of HF acid-based pre-etching steps offer a safe and alternatively a green synthesis route. Anodized oxides are modified using octadecylphosphonic acid self-assembled monolayers, demonstrate superhydrophobicity and are evaluated for their mechanical stability under a jet of water, chemical stability under indirect sunlight irradiation in air/water and direct UV exposure. Zirconia nanotubular films were evaluated for optical transparency using light microscopy and surface wettability of the different zirconia-composites was compared to the model system-titania. Structural and compositional differences of the SAM layer upon time dependent decay were analyzed with X-ray photoelectron spectroscopy. <br>