Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> hollow spheres and their activity in methylene blue photodecomposition

PSA [poly-(styrene-methyl acrylic acid)] latex particle has been taken into account as template material in SiO₂ hollow spheres preparation. TiO₂-doped SiO₂ hollow spheres were obtained by using the appropriate amount of Ti(SO₄)₂ solution on SiO₂ hollow spheres. The photodecomposition of the MB (methylene blue) was evaluated on these TiO₂-doped SiO₂ hollow spheres under UV light irradiation. The catalyst samples were characterized by XRD, UV-DRS, SEM and BET. A TiO₂-doped SiO₂ hollow sphere has shown higher surface area in comparison with pure TiO₂ hollow spheres. The 40 wt% TiO₂-doped SiO₂ hollow sphere has been found as the most active catalyst compared with the others in the process of photodecomposition of MB (methylene blue). The BET surface area of this sample was found to be 377.6 m²g⁻¹. The photodegradation rate of MB using the TiO₂-doped SiO₂ catalyst was much higher than that of pure TiO₂ hollow spheres.     

CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> catalyst prepared by physical mixing for NH<Subscript>3</Subscript> selective catalytic reduction: Evidence about the migration of sulfates from TiO<Subscript>2</Subscript> to CeO<Subscript>2</Subscript> via simple calcination

A mechanical mixture of CeO₂ and TiO₂ powder with a small amount of sulfate was applied for the selective catalytic reduction (SCR) of NO with NH₃. After calcination at 500 oC, the mixed sample showed significantly enhanced activity and selectivity compared to the uncalcined one and, moreover, demonstrated even higher activity than the conventional V₂O₅/TiO₂ catalyst above 300 °C. Combined characterization results revealed that the main active sites were newly formed sulfate species on CeO₂, the number of which increased with calcination. Temperatureresolved DRIFT spectra provided convincing evidence about the migration of sulfate species from TiO₂ to CeO₂, as confirmed from the shift of v(S=O) band as a result of the mechanical mixing and the subsequent calcination.     

Effect of CeO<Subscript>2</Subscript>-addition sequence on the performance of CeO<Subscript>2</Subscript>-modified Ni/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst in autothermal reforming of iso-octane

Two types of CeO₂-modified Ni/Al₂O₃ catalysts were prepared by a consecutive impregnation method with different sequences in the impregnation of Ni and CeO₂, and their performance in autothermal reforming (ATR) of isooctane was investigated. Catalysts prepared by adding CeO₂ prior to the addition of Ni, Ni/CeO₂-Al₂O₃, produced larger amounts of hydrogen than those obtained using catalysts prepared by adding the two components in an opposite sequence, Ni-CeO₂/Al₂O₃. The results of H₂ chemisorption and temperature-programmed reduction revealed that added CeO₂ increased the dispersion of the Ni species on Al₂O₃ and suppressed the formation of NiAl₂O₄ in the catalyst such that large amounts of Ni species were present as NiO, the active species for the ATR. The elemental and thermogravimetric analyses of deactivated catalysts indicated that Ni/CeO₂-Al₂O₃, which showed a longer lifetime than Ni-CeO₂/Al₂O₃, contained lesser amounts and different types of coke on the surface.     

CeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZSM-5 sorbents for high-temperature H<Subscript>2</Subscript>S removal

Performance of CeO₂-La₂O₃/ZSM-5 sorbents for sulfur removal was examined at temperature ranging from 500 oC to 700 oC. The sulfur capacity of 5Ce5La/ZSM-5 was much bigger than that of CeO₂/ZSM-5. H₂ had a negative impact on the sulfidation; however, CO had little influence on sulfur removal. The characterization results showed that CeO₂ and La₂O₃ were well dispersed on ZSM-5 because of the intimate admixing of La₂O₃ and CeO₂, the major sulfidation products were Ce₂O₂S and La₂O₂S, the XRD and SEM results revealed that ZSM-5 structure could remain intact during preparation and sulfidation process, the H₂-TPR showed that the reducibility of CeO₂ can be remarkably enhanced by addition of La.     

Optical Properties of CeO<Subscript>2</Subscript> Doped SiO<Subscript>2</Subscript>-Na<Subscript>2</Subscript>O-CaO-P<Subscript>2</Subscript>O<Subscript>5</Subscript> Glasses

Cerium oxide is one of the most important rare earth elements that is introduced into glass compositions due to its great effects on the optical properties. CeO₂ was introduced in Hench’s patented SiO₂-Na₂O-CaO-P₂O₅ glasses with different concentrations in order to study its effect on the optical behavior of this glass including optical band gap, transmittance, reflectance and refractive index and to give a complete view for the optical properties on cerium oxide-doped silicate glasses.     

Selective oxidation of H<Subscript>2</Subscript>S to sulfur over CeO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> catalyst

The catalytic oxidation of hydrogen sulfide (H₂S) to elemental sulfur was studied over CeO₂-TiO₂ catalysts. The synthesized catalysts were characterized by various techniques such as X-ray diffraction, BET, X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption of ammonia, and scanning electron microscopy (SEM). Catalytic performance studies of the CeO₂-TiO₂ catalysts showed that H₂S was successfully converted to elemental sulfur without considerable emission of sulfur dioxide. CeO₂-TiO₂ catalysts with Ce/Ti=1/5 and 1/3 exhibited the highest H₂S conversion, possibly due to the uniform dispersion of metal oxides, high surface area, and high amount of acid sites.     

Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and CeO<Subscript>2</Subscript>-promoted MgO sorbents for CO<Subscript>2</Subscript> capture at moderate temperatures

A series of Al₂O₃ and CeO₂ modified MgO sorbents was prepared and studied for CO₂ sorption at moderate temperatures. The CO₂ sorption capacity of MgO was enhanced with the addition of either Al₂O₃ or CeO₂. Over Al₂O₃-MgO sorbents, the best capacity of 24.6 mg- CO₂/g-sorbent was attained at 100 °C, which was 61% higher than that of MgO (15.3 mg-CO₂/g-sorbent). The highest capacity of 35.3 mg-CO₂/g-sorbent was obtained over the CeO₂-MgO sorbents at the optimal temperature of 200 °C. Combining with the characterization results, we conclude that the promotion effect on CO₂ sorption with the addition of Al₂O₃ and CeO₂ can be attributed to the increased surface area with reduced MgO crystallite size. Moreover, the addition of CeO₂ increased the basicity of MgO phase, resulting in more increase in the CO₂ capacity than Al₂O₃ promoter. Both the Al₂O₃-MgO and CeO₂-MgO sorbents exhibited better cyclic stability than MgO over the course of fifteen CO₂ sorption-desorption cycles. Compared to Al₂O₃, CeO₂ is more effective for promoting the CO₂ capacity of MgO. To enhance the CO₂ capacity of MgO sorbent, increasing the basicity is more effective than the increase in the surface area.

Open image in new window

     

Reduction of CO<Subscript>2</Subscript> to CO via reverse water-gas shift reaction over CeO<Subscript>2</Subscript> catalyst

CeO₂ catalysts with different structure were prepared by hard-template (Ce-HT), complex (Ce-CA), and precipitation methods (Ce-PC), and their performance in CO₂ reverse water gas shift (RWGS) reaction was investigated. The catalysts were characterized using XRD, TEM, BET, H₂-TPR, and in-situ XPS. The results indicated that the structure of CeO₂ catalysts was significantly affected by the preparation method. The porous structure and large specific surface area enhanced the catalytic activity of the studied CeO₂ catalysts. Oxygen vacancies as active sites were formed in the CeO₂ catalysts by H₂ reduction at 400 °C. The Ce-HT, Ce-CA, and Ce-PC catalysts have a 100% CO selectivity and CO₂ conversion at 580 °C was 15.9%, 9.3%, and 12.7%, respectively. The highest CO₂ RWGS reaction catalytic activity for the Ce-HT catalyst was related to the porous structure, large specific surface area (144.9 m²?g^?1) and formed abundant oxygen vacancies.     

Metabolomic effects of CeO<Subscript>2</Subscript>, SiO<Subscript>2</Subscript> and CuO metal oxide nanomaterials on HepG2 cells

Background

To better assess potential hepatotoxicity of nanomaterials, human liver HepG2 cells were exposed for 3 days to five different CeO₂ (either 30 or 100 μg/ml), 3 SiO₂ based (30 μg/ml) or 1 CuO (3 μg/ml) nanomaterials with dry primary particle sizes ranging from 15 to 213 nm. Metabolomic assessment of exposed cells was then performed using four mass spectroscopy dependent platforms (LC and GC), finding 344 biochemicals.

Results

Four CeO₂, 1 SiO₂ and 1 CuO nanomaterials increased hepatocyte concentrations of many lipids, particularly free fatty acids and monoacylglycerols but only CuO elevated lysolipids and sphingolipids. In respect to structure-activity, we now know that five out of six tested CeO₂, and both SiO₂ and CuO, but zero out of four TiO₂ nanomaterials have caused this elevated lipids effect in HepG2 cells. Observed decreases in UDP-glucuronate (by CeO₂) and S-adenosylmethionine (by CeO₂ and CuO) and increased S-adenosylhomocysteine (by CuO and some CeO₂) suggest that a nanomaterial exposure increases transmethylation reactions and depletes hepatic methylation and glucuronidation capacity. Our metabolomics data suggests increased free radical attack on nucleotides. There was a clear pattern of nanomaterial-induced decreased nucleotide concentrations coupled with increased concentrations of nucleic acid degradation products. Purine and pyrimidine alterations included concentration increases for hypoxanthine, xanthine, allantoin, urate, inosine, adenosine 3′,5′-diphosphate, cytidine and thymidine while decreases were seen for uridine 5′-diphosphate, UDP-glucuronate, uridine 5′-monophosphate, adenosine 5′-diphosphate, adenosine 5′-monophophate, cytidine 5′-monophosphate and cytidine 3′-monophosphate. Observed depletions of both 6-phosphogluconate, NADPH and NADH (all by CeO₂) suggest that the HepG2 cells may be deficient in reducing equivalents and thus in a state of oxidative stress.

Conclusions

Metal oxide nanomaterial exposure may compromise the methylation, glucuronidation and reduced glutathione conjugation systems; thus Phase II conjugational capacity of hepatocytes may be decreased. This metabolomics study of the effects of nine different nanomaterials has not only confirmed some observations of the prior 2014 study (lipid elevations caused by one CeO₂ nanomaterial) but also found some entirely new effects (both SiO₂ and CuO nanomaterials also increased the concentrations of several lipid classes, nanomaterial induced decreases in S-adenosylmethionine, UDP-glucuronate, dipeptides, 6-phosphogluconate, NADPH and NADH).

     

Oxychlorination of methane over FeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/CeO<Subscript>2</Subscript> catalysts

Methane activation through oxychlorination is in the spotlight due to the relatively mild reaction conditions at atmospheric pressure and in the temperature range of 450–550 °C. Although CO₂ is known to exhibit good activity for methane oxychlorination, significant amounts of by-products such as CO₂, CO and carbon deposits are produced during the reaction over CO₂. We investigated the effect of iron in FeO_x/CO₂ catalysts on methane oxychlorination. FeO_x/CO₂ with 3 wt% iron shows the maximum yield at 510 °C with 23% conversion of methane and 65% selectivity of chloromethane. XRD and H₂ TPR results indicate that iron-cerium solid solution was formed, resulting in the production of more easily reduced cerium oxide and the suppression of catalysts sintering during the reaction. Furthermore, the selectivity of by-products decreased more significantly over FeO_x/CO₂ than cerium oxide, which can be attributed to the facilitation of HCl oxidation arising from the enhanced reducibility of the former sample.     

Preparation of H<Subscript>5</Subscript>PMo<Subscript>10</Subscript>V<Subscript>2</Subscript>O<Subscript>40</Subscript> catalyst immobilized on spherical carbon and its application to the vapor-phase 2-propanol conversion reaction

Spherical carbon (SC) with a diameter of ca. 9 μm was synthesized by a hydrothermal method using sucrose as a carbon precursor. The spherical carbon was then modified to have a positive charge, and thus, to provide a site for the immobilization of H₅PMo₁₀V₂O₄₀ (PMo₁₀V₂) catalyst. The PMo₁₀V₂ catalyst was immobilized on the surface-modified spherical carbon by taking advantage of the overall negative charge of [PMo₁₀V₂O₄₀]⁵⁻. The PMo₁₀V₂ catalyst immobilized on the spherical carbon (PMo₁₀V₂/SC) was applied to the vapor-phase 2-propanol conversion reaction. In the catalytic reaction, the PMo₁₀V₂/SC catalyst showed a higher 2-propanol conversion than the unsupported PMo₁₀V₂ catalyst. Furthermore, the PMo₁₀V₂/SC catalyst showed enhanced oxidation catalytic activity (formation of acetone) and the suppressed acid catalytic activity (formation of propylene and isopropyl ether) compared to the unsupported PMo₁₀V₂ catalyst. The enhanced oxidation activity of PMo₁₀V₂/SC catalyst was due to the fine dispersion of [PMo₁₀V₂O₄₀]⁵⁻ on the spherical carbon formed via chemical immobilization.     

Interaction of O<Subscript>2</Subscript>, O<Subscript>3</Subscript>, and H<Subscript>2</Subscript>O<Subscript>2</Subscript> with an activated carbon

The results of the modification of AG-OV-1 activated carbon under various conditions (by atmospheric oxygen at elevated temperatures and by hydrogen peroxide or ozone) are given. The effect of the used modifier on changes in the porosity, surface state, and adsorption capacity of activated carbon is evaluated.