RESUMO
Barium titanate nanoparticles (BTO-NPs) in the size range 8-12â¯nm, prepared by gel collection, are found to be a photoreactive detoxifier for Chemical Warfare Agent vapors, specifically, the sulfur mustard surrogate (2-chloroethyl ethyl sulfide). The relatively monodisperse, uniformly spherical BTO-NPs, initially dispersed in alcohol solvents, form a stable and porous aggregated structure reminiscent of a nanostructured material with voids/pores of an average diameter of 4.6â¯nm and a relatively narrow distribution of their sizes (2.5-8.7â¯nm). Due to the interparticle porosity and a polar, chemically active surface, signifcant amounts of CWA surrogate and its decomposition products were adsorbed on the BTO-NPs. The recorded weight uptake on the perovskite was the highest among a series of materials and nanocomposites known for their detoxification activity and tested at the same conditions (169â¯mg/g, compared to 117â¯mg/g for zinc oxide and <100â¯mg/g for other transition metal oxides). Besides adsorption, BTO nanomaterial acts simultaneously as an efficient heterogeneous catalyst by degrading the toxic vapors to alcohols, sulfides and thiols - molecules of significantly lower toxicity than the CWA surrogate. Hydrolysis and dehydrohalogenation were the predominant detoxification pathways, via the formation of the intermediate cyclic sulfonium, whether under light or in the dark. Ambient light irradiation promoted the photo-oxidation and photo-degradation by radical intermediates formed. With an unhindered oxygen rich surface, underlying highly polarizable lattice structure, and large accessible surface area, barium titanate nanoparticles are investigated as a potentially useful medium for photoreactive detoxification of chemical warfare agent vapors.
RESUMO
Frequency stable, high permittivity nanocomposite capacitors produced under mild processing conditions offer an attractive replacement to MLCCs derived from conventional ceramic firing. Here, 0-3 nanocomposites were prepared using gel-collection derived barium titanate nanocrystals, suspended in a poly(furfuryl alcohol) matrix, resulting in a stable, high effective permittivity, low loss dielectric. The nanocrystals are produced at 60 °C, emerging as fully crystallized cubic BTO, 8 nm, paraelectric with a highly functional surface that enables both suspension and chemical reaction in organic solvents. The nanocrystals were suspended in furfuryl alcohol inside a uniquely prepared mold, in which volume fraction of nanocrystal filler (νf) could be varied. Polymerization of the matrix in situ at 70-90 °C resulted in a nanocomposite with a higher than anticipated effective permittivity (up to 50, with νf only 0.41, 0.5-2000 kHz), exceptional stability as a function of frequency, and very favorable dissipation factors (tan δ < 0.01, νf < 0.41; tan δ < 0.05, νf < 0.5). The increased permittivity is attributed to the covalent attachment of the poly(furfuryl alcohol) matrix to the surface of the nanocrystals, homogenizing the particle-matrix interface, limiting undercoordinated surface sites and reducing void space. XPS and FTIR confirmed strong interfacial interaction between matrix and nanocrystal surface. Effective medium approximations were used to compare this with similar nanocomposite systems. It was found that the high effective permittivity could not be attributed to the combination of two components alone, rather the creation of a hybrid nanocomposite possessing its own dielectric behavior. A nondispersive medium was selected to focus on the frequency dependent permittivity of the 8 nm barium titanate nanocrystals. Experimental corroboration with known theory is evident until a specific volume fraction (νf ≈ 0.3) where, due to a sharp increase in the effective permittivity, approximations fail to adequately describe the nanocomposite medium.