Ceria-Catalyzed Hydrolytic Cleavage of Sulfonamides.

Nanoceria is a promising nanomaterial for the catalytic hydrolysis of a wide variety of substances. In this study, it was experimentally demonstrated for the first time that CeO2 nanostructures show extraordinary reactivity toward sulfonamide drugs (sulfadimethoxine, sulfamerazine, and sulfapyridine) in aqueous solution without any illumination, activation, or pH adjustment. Hydrolytic cleavage of various bonds, including S-N, C-N, and C-S, was proposed as the main reaction mechanism and was indicated by the formation of various reaction products, namely, sulfanilic acid, sulfanilamide, and aniline, which were identified by HPLC-DAD, LC-MS/MS, and NMR spectroscopy. The kinetics and efficiency of the ceria-catalyzed hydrolytic cleavage were dependent on the structure of the sulfonamide molecule and physicochemical properties of Nanoceria prepared by three different precipitation methods. However, in general, all three ceria samples were able to cleave SA drugs tested, proving the robust and unique surface reactivity toward these compounds inherent to cerium dioxide. The demonstrated reactivity of CeO2 to molecules containing sulfonamide or even sulfonyl (and similar) functional groups may be significant for both heterogeneous catalysis and environmentally important degradation reactions.

Effect of Surface Treatment of Nanocrystalline CeO2 on Its Dephosphorylation Activity and Adsorption of Inorganic Phosphates.

The surface of nanocrystalline cerium oxide (CeO2) was treated with various chemical agents by a simple postmodification method at 25 °C and atmospheric pressure. Hydrogen peroxide, ammonium persulfate, deionized water, ascorbic acid, and ortho-phosphoric acid were used in order to study and evaluate their effect on surface materials, such as surface area, crystallite size, number of surface hydroxyl groups, particle morphology, and Ce3+/Ce4+ ratio. Paraoxon-methyl (PO) decomposition and inorganic phosphate adsorption were used to evaluate the effect of surface treatment on catalytic and adsorption properties. CeO2 surface was studied by Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and acid-base titration. While the treatment procedure affected the number of surface hydroxyl groups and the amount of bulk surface oxygen vacancies, only negligible changes were observed in the Ce3+/Ce4+ ratio. Interestingly, surface treatment affected the ability to decompose PO, but only a small effect on inorganic phosphate adsorption was observed, indicating the robustness of CeO2 for the latter. A mechanism for possible interaction of the used chemicals with the CeO2 surface was proposed.

Electrospun PA6 Nanofibers Bearing the CeO2 Dephosphorylation Catalyst.

Two types of CeO2 nanoparticles (CeNPs) prepared by low-temperature (<100 °C) precipitation methods in water were successfully immobilized in a matrix of electrospun PA6 nanofibers. The colloidal solutions of CeNPs in AcOH were directly mixed with the polymer solution before the needle electrospinning process, thereby achieving their good dispersion in the nanofibers. CeNPs embedded in the structure and on the surface of nanofibers exposing their reactive surfaces showed robust dephosphorylation catalytic activity, as demonstrated by monitoring the hydrolytic cleavage of three phosphodiester molecules (p-NP-TMP, p-NPPC, BNPP) in water by the HPLC method. This procedure allowed us to study the kinetics and mechanism of the hydrolytic cleavage and the ability of immobilized CeNPs to cleave different types of P-O bonds. One of the main hydrolysis products, p-nitrophenol, was effectively adsorbed on PA6 nanofibers, which may allow the selective separation of the degradation products after hydrolysis.

Cerium-Bismuth Oxides/Oxynitrates with Low Toxicity for the Removal and Degradation of Organophosphates and Bisphenols.

Nanoscale cerium-bismuth oxides/oxynitrates were prepared by a scalable low-temperature method at ambient pressure using water as the sole solvent. Solid solutions were formed up to a 1:1 Ce/Bi molar ratio, while at higher doping levels, bismuth oxynitrate photocatalysts with a pronounced layered structure were formed. Bismuth caused significant changes in the structure and surface properties of nanoceria, such as the formation of defects, oxygen-containing surface groups, and Lewis and Brønsted acid sites. The prepared bifunctional adsorbents/photocatalysts were efficient in the removal of toxic organophosphate (methyl paraoxon) from water by reactive adsorption followed by photocatalytic decomposition of the parent compound and its degradation product (p-nitrophenol). Bi-doped ceria also effectively adsorbed and photodegraded the endocrine disruptors bisphenols A and S and outperformed pure ceria and the P25 photocatalyst in terms of efficiency, durability, and long-term stability. The very low toxicity of Bi-nanoceria to mammalian cells, aquatic organisms, and bacteria has been demonstrated by comprehensive in vivo/in vitro testing, which, in addition to its simple "green" synthesis, high activity, and durability, makes Bi-doped ceria promising for safe use in abatement of toxic chemicals.