preparation-hydrophobic-metal-organic-frameworks-via-plasma-enhanced

Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high ...

Science Applications International Corporation (SAIC)

A novel technique for determining the relative accessibility and reactivity of basic surface hydroxyl sites by reacting various zirconium(IV) hydroxide materials with 2,2,2-trifluoroethanol (TFE) and characterizing the resulting material using (19)F magic angle spinning (MAS) nuclear magnetic resonance (NMR) is presented here. Studied here are three zirconium hydroxide samples, two unperturbed commercial materials, and one commercial material that is crushed by a pellet press. Factors, such as the ratio of bridging/terminal hydroxyls, surface area, and pore size distribution, are examined and found to affect the ability of the zirconium(IV) hydroxide to react with TFE. X-ray diffraction, nitrogen isotherms, and (1)H MAS NMR were used to characterize the unperturbed materials, while thermogravitric analysis with gas chromatography and mass spectrometry along with the (19)F MAS NMR were used to characterize the materials that were reacted with TFE. Zirconium hydroxide materials with a high surface area and a low bridging/terminal hydroxyl ratio were found to react TFE in the greatest amounts.

Trifluoroethanol and 19F magic angle spinning nuclear magnetic resonance as a basic surface hydroxyl reactivity probe for zirconium(IV) hydroxide structures.

Metal organic frameworks (MOFs) are a leading class of porous materials for a wide variety of applications, but many of them have been shown to be unstable toward water. Cu-BTC (1,3,5 benzenetricarboxylic acid, BTC) was treated with a plasma-enhanced chemical vapor deposition (PECVD) of perfluorohexane creating a hydrophobic form of Cu-BTC. It was found that the treated Cu-BTC could withstand high humidity and even submersion in water much better than unperturbed Cu-BTC. Through Monte Carlo simulations it was found that perfluorohexane sites itself in such a way within Cu-BTC as to prevent the formation of water clusters, hence preventing the decomposition of Cu-BTC by water. This PECVD of perfluorohexane could be exploited to widen the scope of practical applications of Cu-BTC and other MOFs.

Enhanced stability of Cu-BTC MOF via perfluorohexane plasma-enhanced chemical vapor deposition.

The adsorption of ammonia on Zr(OH)(4), as well as Zr(OH)(4) treated with sulfuric acid, were examined. The results show that treating Zr(OH)(4) with sulfuric acid leads to the formation of a sulfate on the surface of the material, and that the sulfate contributes to the ammonia adsorption capacity through the formation of an ammonium sulfates species. Calcination of Zr(OH)(4) decreases the ammonia adsorption capacity of the material and limits the formation of sulfate species. NMR and FTIR spectroscopy results are presented that show the presence of two distinct ammonium species on the surface of the material. The adsorption capacity of the materials is shown to be a complex phenomenon that is impacted by the surface area, the sulfur content, and the pH of the material. The results illustrate that Zr(OH)(4), which is known to adsorb acidic gases, can be modified and used to adsorb basic gases.

Adsorption of ammonia by sulfuric acid treated zirconium hydroxide.

With the prevalence of air quality issues in our society, the ability to remove toxic gases from air is a necessity. This work addresses the development of biphasic, nanostructured, organoalkoxysilane-grafted, siliceous materials for use in single pass filters of various types for the removal of acidic and basic gases from humid air. Materials exhibit high single pass capacities for sulfur dioxide, a representative acid-forming gas, or ammonia, a representative basic gas. The nanostructured siliceous support provides initial ammonia capacity, and grafted amine and carbonyl groups provide desired functional chemistries for sulfur dioxide and enhanced ammonia capacities. Methacryloxypropyltrimethoxysilane (MAPS)-MCM-41 has the highest ammonia capacity at about 7 mol/kg at 1500 ppmv and 23 Â°C, and 3-aminopropyltriethoxysilane (APTES)-MCM-41 has the highest sulfur dioxide capacity at 0.85 mol/kg at 500 ppmv and 23 Â°C. These biphasic materials exhibit high adsorption capacity for two distinct gases and are promising candidates as adsorbents for protection from toxic industrial gases.

Organoalkoxysilane-grafted silica composites for acidic and basic gas adsorption.

Spinel ferrite magnetic nanoparticles, MnFe2O4, NiFe2O4, and CoFe2O4, were synthesized and used as gas-phase adsorbents for the removal of cyanogen chloride from dry air. Fixed-bed adsorption breakthrough experiments show adsorption wave behavior at the leading edge of the breakthrough curve that is not typical of physically adsorbed species. Fourier transform infrared spectroscopy (FTIR) results indicate that CK is reacting with the spinel ferrite surface and forming a carbamate species. The reaction is shown to be a function of the hydroxyl groups and adsorbed water on the surface of the particles as well as the metallic composition of the particles. The surface reaction decreases the remnant and saturation magnetism of the MnFe2O4 and CoFe2O4 particles by approximately 25%.

Article	Year
Trifluoroethanol and 19F magic angle spinning nuclear magnetic resonance as a basic surface hydroxyl reactivity probe for zirconium(IV) hydroxide structures. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 21699226	2011
Enhanced stability of Cu-BTC MOF via perfluorohexane plasma-enhanced chemical vapor deposition. Journal of the American Chemical Society\| PubMed ID: 22239201	2012
Adsorption of ammonia by sulfuric acid treated zirconium hydroxide. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 22686609	2012
Organoalkoxysilane-grafted silica composites for acidic and basic gas adsorption. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 23186068	2012
Chemisorption of cyanogen chloride by spinel ferrite magnetic nanoparticles. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 23540752	2013

Jared B. DeCoste

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