Carboxymethyl ß-Cyclodextrin Assistance for the 4-Nitrophenol Reduction Using Cobalt-Based Layered Double Hydroxides.

Cobalt-aluminum-layered double hydroxides containing carboxymethyl ß-cyclodextrin (CMßCD) were synthesized by coprecipitation and evaluated as a cobalt source for the 4-nitrophenol reduction in an aqueous medium. Several physicochemical techniques (XRD, FTIR, TGA) indicated the intercalation of the anionic cyclodextrin without damages to the hydrotalcite-type structure. These lamellar cobalt-aluminum hybrid materials (CoAl_CMßCD) were evaluated in the 4-nitrophenol reduction and showed higher activities in comparison with the CMßCD-free standard material (CoAl_CO3). To rationalize these results, a set of experimental controls going from physical mixtures of CoAl_CO3 with different cyclodextrins to other cobalt-based materials were investigated, highlighting the beneficial effects of both the layered double hydroxide and CMßCD-based hybrid structures. CMßCD also showed a beneficial effect as an additive during the 4-nitrophenol reduction. CoAl_CO3, dispersed in a fresh CMßCD solution could be re-used for five successive cycles without the loss of activity.

Synthesis of Gold Nanoparticles over CoAl Mixed Oxide for Ethanol Oxidation Reaction.

Catalytic total oxidation is an effective technique for the treatment of industrial VOCs principally resulting from industrial processes using solvents and usually containing mono-aromatics (BTEX) and oxygenated compounds (acetone, ethanol, butanone). The aim of this work is to deposit gold nanoparticles on CoAl mixed oxide issued from layered double hydroxide (LDH) precursor by using the deposition precipitation (DP) method, which is applied with two modifications, labeled method (A) and method (B), in order to enhance the interaction of the HAuCl4 precursor with the support. Method (A) involves the hydrolysis of the HAuCl4 precursor after addition of the support, while in method (B), the gold precursor is hydrolyzed before adding the support. The two methods were applied using as support the CoAl mixed oxide and the LDH precursor. Samples were characterized by several physical chemical techniques and evaluated for ethanol total oxidation. Method (B) allowed the ethanol oxidation activity to be enhanced for the resulting Au/CoAlOx catalysts thanks to the high surface concentration of Co2+ and improved reducibility at low temperature. The presence of gold permits to minimize the formation of by-products, notably, methanol, allowed for a total oxidation of ethanol at lower temperature than the corresponding support.

Potentiometric Chemical Sensors Based on Metal Halide Doped Chalcogenide Glasses for Sodium Detection.

Chalcogenide glasses are widely used as sensitive membranes in the chemical sensors for heavy metal ions detection. The lack of research work on sodium ion-selective electrodes (Na+-ISEs) based on chalcogenide glasses is due to the high hygroscopicity of alkali dopes chalcogenides. However, sodium halide doped Ga2S3-GeS2 glasses are more chemically stable in water and could be used as Na+-sensitive membranes for the ISEs. In this work we have studied the physico-chemical properties of mixed cation (AgI)x(NaI)30-x(Ga2S3)26(GeS2)44 chalcogenide glasses (where x = 0, 7.5, 15, 22.5 and 30 mol.% AgI) using density, DSC, and conductivity measurements. The mixed cation effect with shallow conductivity and glass transition temperature minimum was found for silver fraction r = Ag/(Na + Ag) ≈ 0.5. Silver addition decreases the moisture resistance of the glasses. Only (AgI)22.5(NaI)7.5(Ga2S3)26(GeS2)44 composition was suitable for chemical sensors application, contrary to the single cation sodium halide doped Ga2S3-GeS2 glasses, where 15 mol.% sodium-halide-containing vitreous alloys are stable in water solutions. The analytical parameters of (NaCl)15(Ga2S3)23(GeS2)62; (NaI)15(Ga2S3)23(GeS2)62 and (AgI)22.5(NaI)7.5(Ga2S3)26(GeS2)44 glass compositions as active membranes in Na+-ISEs were investigated, including detection limit, sensitivity, linearity, ionic selectivity (in the presence of K+, Mg2+, Ca2+, Ba2+, and Zn2+ interfering cations), reproducibility and optimal pH-range.

Investigation of catalysts M/CeO2 (M = Pt, Rh, or Pd) for purification of CO2 derived from oxycombustion in the absence or presence of water.

Oxyfuel combustion is a promising technology to produce a CO2-rich flue gas ready suitable for sequestration or valorization. But its storage as well as its further valorization requires to increase the CO2 purification as a small amount of CO and NOx are produced during combustion. Based on the technology developed for three-way converters, similar systems, i.e., M/CeO2 where M is Pt, Pd, or Rh, were studied for NO-CO abatement in a gas stream similar to those obtained when an oxyfuel combustion is performed. The results evidenced that the role of the metal nature influences the performances obtained on NO-CO abatement, platinum supported on ceria being the most efficient catalyst. We also measured the impact of the presence of water in the reaction stream on the catalytic activity of these materials. It appears that the presence of water has a beneficial effect on the different reactions due to a water gas shift reaction that increases the reduction of the NO and favors the formation of N2. The study pointed out that platinum supported on ceria remained the best catalyst, under these wet operating conditions close to industrial ones, for purification of oxyfuel combustion exhausts.

Mixed Oxides Issued from Hydrotalcite Precursors for Toluene and CO Total Oxidation: Comparison of Preparation Method.

Catalytic total oxidation is an effective technique for the treatment of industrial VOCs. This emission is generally accompanied by the presence of other products like CO, NOx or other VOC. In this paper, the development of catalysts for the total oxidation of CO and toluene mixture is performed. For this study, Mg6Al2HT hydrotalcites precursors were synthesized by three different methods: co-precipitation, microwaves and ultrasound assisted method. Hydrotalcite precursors have been used in order to develop mixed oxides after calcination for the catalytic oxidation test. Hydrotalcite structure as well as the mixed oxides obtained after calcination was studied, by several techniques: XRD, TEM, DTA/TG, BET, N2 sorption, H2-TPR. The physico chemical studies revealed modification in the structural characteristics (surface area, porosity) as well as in reducibility properties of the formed mixed oxides. The nanocatalyst issued from microwaves synthesis was the most active in these studied reactions for the total oxidation of the mixture. Moreover, addition of CO on the reaction mixture allows obtaining a beneficial effect on the toluene oxidation.

In vitro toxicological evaluation of emissions from catalytic oxidation removal of industrial VOCs by air/liquid interface (ALI) exposure system in repeated mode.

Toxicity of toluene and by-products formed during its catalytic oxidative degradation was studied in human bronchial BEAS-2B cells repeatedly exposed. BEAS-2B cells were exposed using an Air-Liquid Interface (ALI) System (Vitrocell®) for 1 h per day during 1, 3 or 5 days to gaseous flows: toluene vapors (100 and 1000 ppm) and outflow after catalytic oxidation of toluene (10 and 100%). After exposure to gaseous flow, cytotoxicity, inflammatory response and Xenobiotic Metabolism Enzymes (XME) gene expression were investigated. No significant cytotoxicity was found after 5 days for every condition of exposure. After cells exposure to catalytic oxidation flow, IL-6 level increased no significantly in a time- and dose-dependent way, while an inverted U-shaped profile of IL-8 secretion was observed. XME genes induction, notably CYP2E1 and CYP2F1 results were in line with the presence of unconverted toluene and benzene formed as a by-product, detected by analytical methods. Exposure to pure toluene also demonstrated the activation of these XMEs involved in its metabolism. Repeated exposure permits to show CYP1A1, CYP1B1 and CY2S1 expression, probably related to the formation of other by-products, as PAHs, not detected by standard analytical methods used for the development of catalysts.

Usefulness of toxicological validation of VOCs catalytic degradation by air-liquid interface exposure system.

Toluene is one of the most used Volatile Organic Compounds (VOCs) in the industry despite its major health impacts. Catalytic oxidation represents an efficient remediation technique in order to reduce its emission directly at the source, but it can release by-products. To complete the classical performance assessment using dedicated analytical chemistry methods, we propose to perform an untargeted toxicological validation on two efficient catalysts. Using biological system allows integrating synergy and antagonism in toxic effects of emitted VOCs and by-products, often described in case of multi-exposure condition. Catalysts Pd/α-Al2O3 and Pd/γ-Al2O3 developed for the oxidation of toluene were both coupled to a Vitrocell® Air-Liquid Interface (ALI) system, for exposure of human A549 lung cells during 1h to toluene or to catalysts exhaust before quantification of xenobiotics metabolizing enzymes. This study validated initially the Vitrocell® as an innovative, direct and dynamic model of ALI exposure in the assessment of the performances of new catalysts, showing the presence of chemically undetected by-products. The comparison of the two catalysts showed then that fewer organic compounds metabolizing genes were induced by Pd/γ-Al2O3 in comparison to Pd/α-Al2O3, suggesting that Pd/γ-Al2O3 is more efficient for toluene total oxidation from a toxicological point of view.

Catalytic oxidation of propylene, toluene, carbon monoxide, and carbon black over Au/CeO2 solids: comparing the impregnation and the deposition-precipitation methods.

Au/CeO2 solids were prepared by two methods: deposition-precipitation (DP) and impregnation (Imp). The prepared solids were calcined under air at 400°C. Both types of catalysts have been tested in the total oxidation of propylene, toluene, carbon monoxide, and carbon black. Au/CeO2-DP solids were the most reactive owing to the high number of gold nanoparticles and Au⁺ species and the low concentration of Cl⁻ ions present on its surface compared to those observed in Au/CeO2-Imp solids.

Noble-metal-based catalysts supported on zeolites and macro-mesoporous metal oxide supports for the total oxidation of volatile organic compounds.

The use of porous materials to eliminate volatile organic compounds (VOCs) has proven very effective towards achieving sustainability and environmental protection goals. The activity of zeolites and macro-mesoporous metal-oxide supports in the total oxidation of VOCs has been investigated, with and without noble-metal deposition, to develop highly active catalyst systems where the formation of by-products was minimal. The first catalysts employed were zeolites, which offered a good activity in the oxidation of VOCs, but were rapidly deactivated by coke deposition. The effects of the acido-basicity and ionic exchange of these zeolites showed that a higher basicity was related to exchanged ions with lower electronegativities, resulting in better catalytic performances in the elimination of VOCs. Following on from this work, noble metals were deposited onto macro-mesoporous metal-oxide supports to form mono and bimetallic catalysts. These were then tested in the oxidation of toluene to study their catalytic performance and their deactivation process. PdAu/TiO(2) and PdAu/TiO(2) -ZrO(2) 80/20 catalysts demonstrated the best activity and life span in the oxidation of toluene and propene and offered the lowest temperatures for a 50 % conversion of VOCs and the lowest coke content after catalytic testing. Different characterization techniques were employed to explain the changes occurring in catalyst structure during the oxidation of toluene and propene.