Samvit G. Menon

Microwave solution route to ceramic ZnAl2O4 nanoparticles in 10 minutes: inversion and photophysical changes with thermal history

Microwave-assisted synthesis of ZnAl2O4 nanoparticles in minutes using metalorganic precursors is reported. Phase-pure ZnAl2O4 with an average crystallite size of ∼5 nm is formed in the solution medium at 185 °C. Annealing in air at temperatures between 500 and 1200 °C increases the crystallite size to ∼32 nm. The as-prepared particles are largely shapeless, whereas polyhedral crystallites with well-defined grain boundaries can be seen in the HR-TEM image of the annealed samples. Diffuse reflectance spectroscopy provides insight into the structural development of the oxide spinel. Rapid synthesis leads to significant crystallographic inversion (∼33%), as observed by X-ray photoelectron spectroscopy. Photoluminescence spectroscopy shows that the different emission bands are due both to anti-site defects in the form of zinc interstitials caused by cationic inversion and to oxygen and zinc vacancies. Optical measurements suggest that inhomogeneity in cationic distribution, probably caused by the rapidity of synthesis, is prevalent even after annealing at temperatures up to 1200 °C, and plays a significant role in controlling the emission properties of the spinel. The microwave-assisted technique using metalorganic precursors is an easy path to the rapid synthesis of doped ZnAl2O4 phosphors.

Diffusion-controlled growth of CuAl2O4 Nanoparticles: Effect of Sintering and Photodegradation of Methyl Orange

ABSTRACT Facile synthesis of CuAl2O4 and sintering effects on the phase composition are reported. Annealing at 500 °C showed only CuO phase and the spinel phase started evolving at 700 °C with the concurrent decrease in the CuO phase. Diffusion-mediated growth of spinel phase was also observed at higher temperatures forming CuAl2O4 at 1000 °C. The material was stoichiometric and the average particle size was 55 nm, as evidenced by EDS and FE-SEM studies, respectively. The zeta potential of +30 mV and lower (0.346) value of the poly dispersive index (PDI), confirmed the high dispersability of CuAl2O4 in water. The favourable band gap (2.2 eV) makes it suitable as visible light photocatalyst. Owing to its positive surface charge and conducive pH, material could adsorb anionic methyl orange dye. A total of 74% of the dye could be recovered by a simple methanolic extraction. The visible light photocatalysis of the same dye leads to 67% decolouration and the addition of H2O2 accelerated the photodegradation to completion. The catalyst displayed excellent reusability and stability even after five successive runs.

Adsorptive CuO/CuAl2O4 nanoparticles for the separation of aqueous methyl orange

A simple method for the separation of aqueous methyl orange, an azo dye, is reported, where CuO/CuAl2O4 nanoparticles synthesisedby co-precipitation methodwere used as the adsorbent. The presence of cubic CuAl2O4 (CAO) and monoclinic CuO phase of this composite material was confirmed by X-Ray diffraction and its specific surface area wasdetermined by BET nitrogen adsorption method.To study the nature of surface charge, theisoelectric point of the material was determined using the pH drift methodfollowing which the rate of decolouration was studied forpH 5and pH 7. Theexperiments in the absence oflight show that adsorption of the dye is prevalent even up to 6h leading to 86% decolouration.A methanolic extraction was effectivefor quantitative separation ofadsorbed dye fromCuO/CuAl2O4 nanoparticles regenerating them for reuse. The presence of methyl orange in the extracted solution and on the nanoparticles at various stages was verified byUV-Visible and FT-IR spectroscopic methods.The extent of adsorption was quantified and found tobe as high as 86%. The catalyst aftercomplete extraction ofmethyl orange (MO),could be reused for the decolouration. Stability of the nanoparticles after reuse was verified by the closematch of XRD patterns ofthe pure and reused CAOwhich show no significant changes in itscrystal structure. The separation method shown here can be extended for the removal of other azo dyesfrom textile effluents.