Synthesis of nano-sized zeolite-Y functionalized with 5-amino-3-thiomethyl 1H-pyrazole-4-carbonitrile for effective Fe(III)-chelating strategy

摘要

Zeolite crystals having faujasite-type (FAU) topology in the nanometer range were first synthesized from amorphous rice husk ash at a low temperature of 363 K under autogenous pressure. Following this, surface functionalization of the produced zeolite with 5-amino-3-thiomethyl 1H-pyrazole-4-carbonitrile (pyrazole; Py) was carried out by two different methods, namely liquefied-period adsorption of Py (Py/Y-im) and a flexible ligand method (Py/Y-ss). The latter provides a larger amount of Py formed into as-made zeolite-Y. The sorption of Fe(III) onto Py/NaY afforded large meso-macroporosity introduced by the aggregation-assembly between Fe(III)Py complexes and NaY zeolite, which was typically evidenced for Fe(III)Py/Y-ss . The materials were characterized by XRD, FT-IR spectroscopy, thermal analysis (TGA) and porous structure by N-2 adsorption-desorption at 77 K. The XRD evaluation showed that the zeolite structure was managed right after adding Fe(III) to Py/Y, although a change in intensity of the zeolite reflections on complex formation was noticed. The FT-IR spectrum of Fe(III)Py/Y(ss )exhibited two bands at 3594 and 3542 cm(-1) assigned to bridging hydroxyl groups associated with a Bronsted site, which did not exist in the spectra of Fe(III)Py/Y-im,Y- and Fe(III)exchanged as-made NaY zeolite. This effect was ascribed to the induced greater electronegativity of the ligand towards Fe(III) species in dissociation of water molecules, producing acidic protons that are potential Bronsted acid sites. It was also evident that the Fe(III) adsorption capacity on Py/Y(ss )is greater than on as-made NaY zeolite and Py/Y-im, owing most likely to the increasing concentration of the incorporating Py ligand which leads to an increase in the number of binding sites. The Fe(III) adsorption onto Py/Y-ss was well described by the pseudo-second-order kinetic model. Density functional theory (B3LYP/6-311G*) was performed to understanding the interaction mode of the ligand and complex