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.

Ruthenium Trichloride Catalyst in Water: Ru Colloids versus Ru Dimer Characterization Investigations.

An easy-to-prepare ruthenium catalyst obtained from ruthenium(III) trichloride in water demonstrates efficient performances in the oxidation of several cycloalkanes with high selectivity toward the ketone. In this work, several physicochemical techniques were used to demonstrate the real nature of the ruthenium salt still unknown in water and to define the active species for this Csp3-H bond functionalization. From transmission electron microscopy analyses corroborated by SAXS analyses, spherical nanoobjects were observed with an average diameter of 1.75 nm, thus being in favor of the formation of reduced species. However, further investigations, based on X-ray scattering and absorption analyses, showed no evidence of the presence of a metallic Ru-Ru bond, proof of zerovalent nanoparticles, but the existence of Ru-O and Ru-Cl bonds, and thus the formation of a water-soluble complex. The EXAFS (extended X-ray absorption fine structure) spectra revealed the presence of an oxygen-bridged diruthenium complex [Ru(OH) xCl3- x]2(µ-O) with a high oxidation state in agreement with catalytic results. This study constitutes a significant advance to determine the true nature of the RuCl3·3H2O salt in water and proves once again the invasive nature of the electron beam in microscopy experiments, routinely used in nanochemistry.

Copper-Based Silica Nanotubes as Novel Catalysts for the Total Oxidation of Toluene.

Cu (10 wt%) materials on silica nanotubes were prepared via two different synthetic approaches, co-synthesis and wetness impregnation on preformed SiO2 nanotubes, both as dried or calcined materials, with Cu(NO3)2.5H2O as a material precursor. The obtained silica and the Cu samples, after calcination at 550 °C for 5 h, were characterized by several techniques, such as TEM, N2 physisorption, XRD, Raman, H2-TPR and XPS, and tested for toluene oxidation in the 20-450 °C temperature range. A reference sample, Cu(10 wt%) over commercial silica, was also prepared. The copper-based silica nanotubes exhibited the best performances with respect to toluene oxidation. The Cu-based catalyst using dried silica nanotubes has the lowest T50 (306 °C), the temperature required for 50% toluene conversion, compared with a T50 of 345 °C obtained for the reference catalyst. The excellent catalytic properties of this catalyst were ascribed to the presence of easy copper (II) species finely dispersed (crystallite size of 13 nm) on the surface of silica nanotubes. The present data underlined the impact of the synthetic method on the catalyst properties and oxidation activity.

Regeneration of Hopcalite used for the adsorption plasma catalytic removal of toluene by non-thermal plasma.

A dielectric barrier discharge reactor packed with both Hopcalite & glass beads has been investigated for the total oxidation of toluene adsorbed on Hopcalite. The catalytic activity and selectivity through the possible formation of by-products during the NTP discharge for the abatement of irreversibly adsorbed toluene have been investigated by FT-IR and mass spectrometer. The regeneration of the used Hopcalite by NTP discharge has been established by (i) determining the amount of toluene adsorbed on NTP regenerated Hopcalite, (ii) investigating the catalytic activity of NTP regenerated Hopcalite and (iii) comparing the bulk and surface properties of the fresh calcined and NTP regenerated Hopcalite. The ratio of amount of irreversibly adsorbed toluene to that of the total amount of adsorbed toluene adsorbed is similar for the fresh calcined and NTP (I) regenerated Hopcalite. The catalytic activity of the NTP (I) regenerated Hopcalite is slightly enhanced when compared to that of the fresh calcined Hopcalite. Although the first NTP treatment induces partial transformation of Hopcalite into Mn3O4 with no detected related CuOx and reduces specific surface area by a factor of 2, the toluene adsorption capacity remains less affected. A plausible reaction scheme for toluene decomposition in Hopcalite PBDBD reactor is proposed.

Hydroxyapatite, a multifunctional material for air, water and soil pollution control: A review.

Hydroxyapatite (Ca10(PO4)6(OH)2), a calcium phosphate biomaterial, is a very promising candidate for the treatment of air, water and soil pollution. Indeed, hydroxyapatite (Hap) can be extremely useful in the field of environmental management, due in one part to its particular structure and attractive properties, such as its great adsorption capacities, its acid-base adjustability, its ion-exchange capability and its good thermal stability. Moreover, Hap is able to constitute a valuable resource recovery route. The first part of this review will be dedicated towards presenting Hap's structure and defining properties that result in its viability as an environmental remediation material. The second will focus on its use as adsorbent for wastewater and soil treatment, while indicating the mechanisms involved in this remediation process. Finally, the last part will impart all findings on Hap's applications in the field of catalysis, whether it be as catalyst, as photocatalyst, or as active phase support. Hence, all of the above will have served in showcasing the benefits gained by employing hydroxyapatite in air, water and soil clean-up.

Plasma assisted Cu-Mn mixed oxide catalysts for trichloroethylene abatement in moist air.

The removal of dilute trichloroethylene (TCE) in moist air by post-plasma catalysis (PPC) using Cu-Mn mixed oxides heated at 150 °C was investigated. Cu-Mn mixed oxides were prepared by redox- and co-precipitation method. In comparison to the catalytic oxidation and non-thermal plasma (NTP) process, PPC was found to be the best process to convert TCE into CO2, in particular when Cu-Mn oxide was synthetized by redox precipitation method. The highest TCE conversion efficiency of more than 80% was obtained at the energy density of 60 J.L-1 using the catalyst prepared by redox-precipitation process in PPC configuration. The performance of Cu-Mn oxide prepared by redox-precipitation method did not show increase in TCE conversion with energy density which is attributed to the changes on the catalyst surface (such as reduction in SBET, chlorine poisoning and Mn enrichment). Although, Cu-Mn oxide prepared by co-precipitation method showed a lower TCE conversion, it exhibited a better stability in the PPC process for TCE abatement.

Polarization field effects at liquid-crystal-droplet-polymer interfaces.

The influence of confinement (droplet size) and liquid crystal orientational order (smectic-A and nematic) on the interfacial polarization field effects [Maxwell-Wagner-Sillars (MWS) effect] existing in liquid-crystal-droplets-polymer systems is investigated by broadband dielectric spectroscopy and a forward transmittance measurement technique. A relaxation process observed in the low frequency domain of the dielectric spectrum has been associated with a MWS effect for both micron-size and submicron-size droplets. Using electro-optical measurements and numerical simulations of the field inside droplets, it is shown that a depolarization field takes place in the same frequency range as that determined by dielectric spectroscopy. Differential scanning calorimetry measurements allowed to estimate the phase-separated liquid crystal [4,4'-octylcyanobiphenyl (8CB)] fraction, which was found in the range of 55% for both micron-size and submicron-size droplets. X-ray diffraction experiments showed that smectic 8CB confined to micron-size cavities adopt bulklike properties, i.e., a partial bilayer structure, whereas in submicron-size droplets the layer spacing of the smectic phase is increased due to the strong bending deformations induced by the high curvature of the cavity walls.

Capture of formaldehyde by adsorption on nanoporous materials.

The aim of this work is to assess the capability of a series of nanoporous materials to capture gaseous formaldehyde by adsorption in order to develop air treatment process and gas detection in workspaces or housings. Adsorption-desorption isotherms have been accurately measured at room temperature by TGA under very low pressure (p<2 hPa) on various adsorbents, such as zeolites, mesoporous silica (SBA15), activated carbon (AC NORIT RB3) and metal organic framework (MOF, Ga-MIL-53), exhibiting a wide range of pore sizes and surface properties. Results reveal that the NaX, NaY and CuX faujasite (FAU) zeolites are materials which show strong adsorption capacity and high affinity toward formaldehyde. In addition, these materials can be completely regenerated by heating at 200°C under vacuum. These cationic zeolites are therefore promising candidates as adsorbents for the design of air depollution process or gas sensing applications.

Formaldehyde: catalytic oxidation as a promising soft way of elimination.

Compared to other molecules such as benzene, toluene, xylene, and chlorinated compounds, the catalytic oxidation of formaldehyde has been studied rarely. However, standards for the emission level of this pollutant will become more restrictive because of its extreme toxicity even at very low concentrations in air. As a consequence, the development of a highly efficient process for its selective elimination is needed. Complete catalytic oxidation of formaldehyde into CO2 and H2 O using noble-metal-based catalysts is a promising method to convert this pollutant at room temperature, making this process energetically attractive from an industrial point of view. However, the development of a less expensive active phase is required for a large-scale industrial development. Nanomaterials based on oxides of manganese are described as the most promising catalysts. The objective of this Minireview is to present promising recent studies on the removal of formaldehyde through heterogeneous catalysis to stimulate future research in this topic.

Removal of oxygenated volatile organic compounds by catalytic oxidation over Zr-Ce-Mn catalysts.

The composition-activity relationship of Zr-Ce-Mn-O materials was investigated for the catalytic removal of Oxygenated Volatile Organic Compounds (OVOC) emitted by stationary sources. Using a sol-gel method, very high surface specific areas, small crystallite sizes and high redox properties were obtained for Zr(0.4)Ce(0.6-x)Mn(x)O(2) catalytic systems after calcination at 500°C. The textural and redox properties were improved when Mn content increased in the material, especially for x=0.36. As a result the most active and selective catalyst in the butanol (model of OVOC) oxidation was obtained for the nominal composition Zr(0.4)Ce(0.24)Mn(0.36)O(2) due to a high oxygen mobility and surface Mn(4+) concentration.

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.