Utilisation of waste Cu-, Mn- and Fe-loaded zeolites generated after wastewater treatment as catalysts for air treatment.

Disposal of copper, manganese and iron is particularly problematic in wastewater of metallurgical and galvanization plants, the electronics industry and agriculture. On the other hand, volatile organic compounds (VOCs), emitted from industrial processes, transportation and consumer products are the main class of air pollutants. The study revealed the potential of waste metal-loaded zeolite, generated through wastewater treatment procedures, to be utilised as an effective VOC removal catalyst for air treatment. In the first step, we have evaluated the sorption performance of natural zeolite clinoptilolite (HEU type), and synthetic zeolite 4A (LTA type) for the simultaneous removal of Cu2+, Mn2+ and Fe3+ species from aqueous solution. By a detailed sorption study, we determined the optimum sorption conditions and maximum metal concentrations in wastewater that can be after treatment disposed of in rivers or municipal plants. The efficiency of both zeolites for metal immobilization was demonstrated for concentrations up to 5 mg metals/1 g zeolite. These waste Cu-, Mn- and Fe-loaded zeolites were thermally treated at 540 °C before the second step, where we evaluated their catalytic performance in removing VOC. The thermally treated waste Cu-, Mn- and Fe-loaded natural zeolite clinoptilolite showed good catalytic performance in total toluene oxidation as a model VOC (conversion rate up to 96% at 510°C) and cycling stability (less than 15% drop in conversion rate in 4 h). In contrast, this is not the case for thermally treated waste Cu-, Mn- and Fe-loaded synthetic zeolite 4A.

Low-Temperature Toluene Oxidation on Fe-Containing Modified SBA-15 Materials.

Transition metals as catalysts for total VOC oxidation at low temperatures (150-280 °C) are a big challenge nowadays. Therefore, iron-modified SBA-15, AlSBA-15, and ZrSBA-15 materials with 0.5 to 5.0 wt.% Fe loading were prepared and tested for toluene oxidation. It was found that increasing Fe loading significantly improved the rate of oxidation and lowered the temperature of achieving 100% removal of toluene from above 500 °C for the supports (AlSBA-15 and ZrSBA-15) to below 400 °C for 5FeZrSBA-15. The formation of finely dispersed iron oxide active sites with a particle size less than 5 nm was observed on all the SBA-15, AlSBA-15, and ZrSBA-15 supports. It was found that the surface properties of the mesoporous support due to the addition of Al or Zr predetermined the type of formed iron oxide species and their localization on the support surface. Fe-containing SBA-15 and AlSBA-15 showed activity in total toluene oxidation at higher temperatures (280-450 °C). However, 5 wt. % Fe-containing ZrSBA-15 showed excellent activity in the total oxidation of toluene as a model VOC at lower temperatures (150-380 °C) due to the synergistic effect of Fe-Zr and the presence of accessible and stable Fe2+/Fe3+ active sites.

In†situ generation of Ni nanoparticles from metal-organic framework precursors and their use for biomass hydrodeoxygenation.

So far, in situ-generated Ni nanoparticles have been reported to be efficient catalysts for tar cracking during wood liquefaction by pyrolysis. Herein, their performance in further bio-oil conversion steps is evaluated. Nanoparticles were generated for the first time from a Ni-containing metal-organic framework, MIL-77, during the hydrotreatment of glycerol-solvolyzed lignocellulosic (LC) biomass. Reactions were conducted at 300 °C and the H2 pressure was 8 MPa in a slurry reactor. The catalytic activity and selectivity of the deoxygenation and hydrocracking reactions for real biomass-derived feedstock using in situ-generated nanoparticles was compared with Ni nanoparticles dispersed on a silica-alumina support (commercial Ni/SiO2 -Al2 O3 catalyst). The mass activity of the in situ-generated nanoparticles for hydrogenolysis was more than ten times higher in comparison to their commercial analogues, and their potential for the use in LC biorefinery is discussed.

Active Iron Sites of Disordered Mesoporous Silica Catalyst FeKIL-2 in the Oxidation of Volatile Organic Compounds (VOC).

Iron-functionalized disordered mesoporous silica (FeKIL-2) is a promising, environmentally friendly, cost-effective and highly efficient catalyst for the elimination of volatile organic compounds (VOCs) from polluted air via catalytic oxidation. In this study, we investigated the type of catalytically active iron sites for different iron concentrations in FeKIL-2 catalysts using advanced characterization of the local environment of iron atoms by a combination of X-ray Absorption Spectroscopy Techniques (XANES, EXAFS) and Atomic-Resolution Scanning Transmission Electron Microscopy (AR STEM). We found that the molar ratio Fe/Si ≤ 0.01 leads to the formation of stable, mostly isolated Fe3+ sites in the silica matrix, while higher iron content Fe/Si > 0.01 leads to the formation of oligonuclear iron clusters. STEM imaging and EELS techniques confirmed the existence of these clusters. Their size ranges from one to a few nanometers, and they are unevenly distributed throughout the material. The size of the clusters was also found to be similar, regardless of the nominal concentration of iron (Fe/Si = 0.02 and Fe/Si = 0.05). From the results obtained from sample characterization and model catalytic tests, we established that the enhanced activity of FeKIL-2 with the optimal Fe/Si = 0.01 ratio can be attributed to: (1) the optimal concentration of stable isolated Fe3+ in the silica support; and (2) accelerated diffusion of the reactants in disordered mesoporous silica (FeKIL-2) when compared to ordered mesoporous silica materials (FeSBA-15, FeMCM-41).

Photocatalytic degradation of gaseous toluene by using immobilized titania/silica on aluminum sheets.

PURPOSE: The aim of this study was to prepare a highly active immobilized titania/silica photocatalyst and to test its performance in situ toward degradation of toluene as one of the major toxic indoor contaminants. METHODS: In this work, two different titania layers immobilized on Al sheets were synthesized via low temperature sol-gel method employing presynthesized highly active titania powders (Degussa P25 and Millennium PC500, mass ratio 1:1): (a) with a silica/titania binder and a protective layer and (b) without the binder. The photocatalysts were characterized by X-ray diffraction, nitrogen sorption measurements, scanning electron microscopy (SEM), infrared spectroscopy, and UV-vis diffuse reflectance spectroscopy (DRS). The in situ photocatalytic degradation of gaseous toluene was selected as a probe reaction to test photocatalytic activity and to verify the potential application of these materials for air remediation. RESULTS: Results show that nontransparent highly photocatalytically active coatings based on the silica/titania binder and homogeneously dispersed TiO(2) powders were obtained on the Al sheets. The crystalline structure of titania was not altered upon addition of the binder, which also prevented inhomogeneous agglomeration of particles on the photocatalyst surface. The photoactivity results indicate that the adsorption properties and photocatalytic activity of immobilized photocatalysts with the silica/titania binder and an underlying protective layer were very effective and additionally, they exhibited considerably improved adhesion and uniformity. CONCLUSION: We present a new highly photocatalytically active immobilized catalyst on a convenient metallic support, which has a potential application in an air cleaning device.