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.

The effects of formation and functionalization of graphene-based membranes on their gas and water vapor permeation properties.

The gas and water vapor permeabilities of graphene-based membranes can be affected by the presence of different functional groups directly bound to the graphene network. In this work, one type of carboxylated graphene oxide (GO-COOH) and two types of graphene oxide synthesized i) under strong oxidative conditions directly from graphite (GO-1) and ii) under mild oxidative conditions from exfoliated graphene (GO-2) were used as precursors of self-standing membranes prepared with thicknesses in the range of 12-55 µm via slow-vacuum filtration preparation method. It was observed that the permeabilities for all tested gases decreased in order GO-2 > GO-1 > GO-COOH and depended on both the arrangement of graphene sheets and their functionalization. The GO-1 membrane with a high content of oxygen-containing groups showed the best performance for water vapor permeability. The GO-2 membrane with a thickness of 43 µm exhibited a disordered GO sheet morphology and, therefore, unique gas-separation performance towards H2/CO2 gas pair, showing high hydrogen permeability while keeping extremely high H2/CO2 ideal selectivity that exceeds the Robeson 2008 upper bound of polymer membranes.

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.

Effect of Multiply Twinned Ag(0) Nanoparticles on Photocatalytic Properties of TiO2 Nanosheets and TiO2 Nanostructured Thin Films.

Ag-decorated TiO2 nanostructured materials are promising photocatalysts. We used non-standard cryo-lyophilization and ArF laser ablation methods to produce TiO2 nanosheets and TiO2 nanostructured thin films decorated with Ag nanoparticles. Both methods have a common advantage in that they provide a single multiply twinned Ag(0) characterized by {111} twin boundaries. Advanced microscopy techniques and electron diffraction patterns revealed the formation of multiply twinned Ag(0) structures at elevated temperatures (500 °C and 800 °C). The photocatalytic activity was demonstrated by the efficient degradation of 4-chlorophenol and Total Organic Carbon removal using Ag-TiO2 nanosheets, because the multiply twinned Ag(0) served as an immobilized photocatalytically active center. Ag-TiO2 nanostructured thin films decorated with multiply twinned Ag(0) achieved improved photoelectrochemical water splitting due to the additional induction of a plasmonic effect. The photocatalytic properties of TiO2 nanosheets and TiO2 nanostructured thin films were correlated with the presence of defect-twinned structures formed from Ag(0) nanoparticles with a narrow size distribution, tuned to between 10 and 20 nm. This work opens up new possibilities for understanding the defects generated in Ag-TiO2 nanostructured materials and paves the way for connecting their morphology with their photocatalytic activity.

Room-temperature synthesis of nanoceria for degradation of organophosphate pesticides and its regeneration and reuse.

A simple low-temperature water-based and one-pot synthesis was developed for the preparation of nanocrystalline CeO2 that was used for degradation of the toxic organophosphate pesticide parathion methyl. By changing the reaction temperature in the range from 5 °C to 95 °C, several properties (i.e., crystallinity, grain size and surface area) of nanoceria can be easily controlled. The catalytic decomposition of parathion methyl to its degradation product 4-nitrophenol was highly dependent on the CeO2 preparation temperature. It was demonstrated that at low temperature (i.e. 5 °C), CeO2 with very small crystallites (<2 nm) and high surface area can be obtained. For practical use, it was demonstrated that highly crystalline CeO2 can be prepared at room-temperature (30 °C) in at least 100 g batches. It was shown that precipitated nanoceria had high thermal stability and its post-synthesis annealing up to 400 °C did not significantly alter the material properties and hence the catalytic activity. Furthermore, as shown by the reusability tests, the sorbent can be reactivated by simply washing with water which demonstrated its durability.

Synthesis and characterization of TiO2/Mg(OH)2 composites for catalytic degradation of CWA surrogates.

Surface catalyzed reactions can be a convenient way to deactivate toxic chemical warfare agents (CWAs) and remove them from the contaminated environment. In this study, pure titanium oxide, magnesium hydroxide, and their composites TiO2/Mg(OH2) were prepared by thermal decomposition and precipitation of the titanium peroxo-complex and/or magnesium nitrate in an aqueous solution. The as-prepared composites were examined by XRD, XPS, HRTEM, and nitrogen physisorption. Their decontamination ability was tested on CWA surrogates and determined by high-performance liquid chromatography (HPLC) and gas chromatography coupled with mass spectrometry (GC-MS). Dimethyl methyl phosphonate (DMMP) was used as a G simulant for the nerve agents sarin (GB) and soman (GD) while 2-chloroethyl ethyl sulfide (2-CEES) and 2-chloroethyl phenyl sulfide (2-CEPS) were used as surrogates of sulfur mustard (HD). The activity of the as-prepared composites was correlated with acid-base properties determined by potentiometric titrations and pyridine adsorption studied by in situ DRIFTS. The mixing of Ti and Mg led to an increase of the surface area and the amount of surface -OH groups (with an increasing amount of Ti) that caused improved degradation of DMMP.

Ultrasound exfoliation of graphite in biphasic liquid systems containing ionic liquids: A study on the conditions for obtaining large few-layers graphene.

Herein we describe a successful protocol for graphite exfoliation using a biphasic liquid system (water/dichloromethane, DCM) containing ionic liquids (ILs; 1,3-dibenzylimidazolium benzoate- and 1-naphthoate). The use of (surface active) IL and sonication led to stable DCM/water (O/W) emulsion, which enhanced graphene formation, suppressed its re-aggregation and decreased shear/cavitation damage. The O/W emulsion stabilization by the ILs was studied by dynamic light scattering (DLS), whereas their interaction with the graphene sheets were described by Density Functional Theory (DFT) calculations. Moreover, a comprehensive investigation on cavitation-based exfoliation in the O/W systems was performed to assess the importance of operational parameters, including, the type of ultrasound processor, ultrasound power and insonation, and the influence of the exfoliation medium.

Chemical warfare agent simulant DMMP reactive adsorption on TiO2/graphene oxide composites prepared via titanium peroxo-complex or urea precipitation.

Two water-based methods were used to produce TiO2/graphene oxide (GO) nanocomposites with 1 and 2 wt.% GO. Both procedures exclude the use of organometallic precursors, as well as the high-pressure and high-temperature treatments, which facilitate pure and energy efficient synthesis amenable for larger scale synthesis. Nanocomposites with narrow (<10 nm) and long spindle-like (<100 nm) TiO2 nanoparticles supported on GO flakes were obtained (TiO2/GO), and their properties for reactive destruction of the organophosphorus simile chemical warfare agent (CWA) dimethyl methylphosphonate (DMMP) were investigated by in situ DRIFTS spectroscopy. Both synthesis procedures yielded highly reactive nanocomposites with markedly different properties compared to similarly prepared pure TiO2 nanoparticles. GO also induced morphology and texture changes, which were observed to have a significant impact on the adsorption and reactivity of the nanocomposites, and which were strongly related to synthesis procedure. In particular, the reduction state of GO, as measured by Raman spectroscopy, was observed to play a major role for the reactivity of the TiO2/GO nanocomposites.

Doping of Zinc Oxide with Selected First Row Transition Metals for Photocatalytic Applications.

ZnO doped with Cr, Mn, Fe, Co, Ni and Cu was prepared by homogeneous hydrolysis of sulfates with urea. The samples were annealed at various temperatures and characterized by X-ray powder diffraction, UV/VIS reflectance spectroscopy, BET (Brunauer-Emmet-Teller) surface area and porosity measurements. The photocatalytic activity of the samples was evaluated by measuring the degradation of an organic dye Reactive Black 5. The morphology of the samples was determined by scanning electron microscopy and atomic force microscopy. For the Cu-doped ZnO sample, EPR spectra were obtained. All samples annealed at 800°C contained hexagonal ZnO. In the VIS region, the best photocatalytic performance had the ZnO samples doped with Cr, Fe and Cu.