Highly stable Fe/γ‐Al2O3 catalyst for catalytic wet peroxide oxidation

BACKGROUND: A highly stable Fe/γ‐Al₂O₃ catalyst for catalytic wet peroxide oxidation has been studied using phenol as target pollutant. The catalyst was prepared by incipient wetness impregnation of γ‐Al₂O₃ with an aqueous solution of Fe(NO₃)₃· 9H₂O. The influence of pH, temperature, catalyst and H₂O₂ doses, as well as the initial phenol concentration has been analyzed. RESULTS: The reaction temperature and initial pH significantly affect both phenol conversion and total organic carbon removal. Working at 50 °C, an initial pH of 3, 100 mg L^?1 of phenol, a dose of H₂O₂ corresponding to the stoichiometric amount and 1250 mg L^?1 of catalyst, complete phenol conversion and a total organic carbon removal efficiency close to 80% were achieved. When the initial phenol concentration was increased to 1500 mg L^?1, a decreased efficiency in total organic carbon removal was observed with increased leaching of iron that can be related to a higher concentration of oxalic acid, as by‐product from catalytic wet peroxide oxidation of phenol. CONCLUSION: A laboratory synthesized γ‐Al₂O₃ supported Fe has shown potential application in catalytic wet peroxide oxidation of phenolic wastewaters. The catalyst showed remarkable stability in long‐term continuous experiments with limited Fe leaching, < 3% of the initial loading. Copyright © 2010 Society of Chemical Industry     

New aluminum mesh from recyclable material for immobilization of TiO2 in heterogeneous photocatalysis

This study presents a new aluminium mesh made out of soda can rings as a support for titanium dioxide (TiO₂) in the degradation of the synthetic dyes Bordeaux Red (BR) and Tartrazine (TT). Three pre-treatments including calcination and acidification steps were investigated in order to select the most efficient immobilization procedure for photocatalysis application. Raw and titania-aluminum meshes were characterized by scanning electron microscopy, x-ray diffraction, diffuse reflectance, and Fourier transform infrared spectroscopy. The material presented itself as a suitable alternative in the immobilization of titania for wastewater treatment. Preliminary tests selected H₂O₂/TiO_{2(suspension)} oxidation systems under natural sunlight and germicidal lamps (UVC) exhibiting 97.2% and 99.5% of degradation in 180 minutes, respectively. Immobilized TiO₂ systems reached high degradation rates (>99%) after 180 minutes in both UVC and solar light-based processes. An experimental planning study was carried out for the processes in order to find the best operational conditions and pseudo-first-order model fit well the removal data (discolouration rates of in the order of 0.0274 and 0.0145 min⁻¹ for UVC and solar light systems, respectively). Parameters such as TOC, COD, and turbidity, revealed a great improvement in the environmental quality of the water after the treatment and acute toxicity bioassays demonstrated a significant decrease in toxicity for both systems after the treatments. The TiO₂-meshes demonstrated high performance in the removal after five cycles of operation. Therefore, the new immobilization procedure demonstrated that the TiO₂-aluminum mesh is a feasible option for wastewater treatment and photocatalysis.     

Novel Co‐Mn‐O nanosheet catalyst for CO preferential oxidation toward hydrogen purification

Co‐Mn‐O composite oxide nanosheet catalyst was successfully prepared using a facile urea‐assisted one‐step hydrothermal method in the absence of organic or organic templating reagent. Co‐Mn‐O nanosheet catalyst was optimized by varying hydrothermal process parameters such as molar ratio of Co‐Mn to urea, hydrothermal temperature, and hydrothermal time. Various characterization techniques including scanning electron microscopy, X‐ray diffraction, nitrogen adsorption, X‐ray photoelectron spectroscopy, Raman spectroscopy, and H₂ temperature‐programmed reduction were used to reveal the relationship between catalyst nature and catalytic performance in CO preferential oxidation (CO PROX) in excess H₂. The developed Co‐Mn‐O nanosheet catalyst have demonstrated much superior catalytic performance to Co‐Mn‐O nanoparticle, particularly in the low temperature range, and 100% CO conversion over the developed Co‐Mn‐O nanosheet can be achieved in temperature range of 50 to 150°C at 10,000 mL g^?1 h^?1 of gas hourly space velocity in the standard feed. Furthermore, the almost complete CO removal over Co‐Mn‐O nanosheet at 125°C of low temperature with 94.9% selectivity can be achieved even in the simulated reformed gas. The excellent catalytic performance is ascribed to nanosheet morphology, more surface Co³⁺, smaller average crystallite size, higher reducibility, and strong Co‐Mn interaction. Catalytic stability investigation indicates the developed nanostructured catalyst exhibits high catalytic stability for CO PROX reaction in simulated gas. The developed Co‐Mn‐O nanosheet catalyst can be a potential candidate for catalytic elimination of trace CO from H₂‐rich gas for Proton exchange membrane fuel cell applications. © 2014 American Institute of Chemical Engineers AIChE J, 61: 239–252, 2015     

Comparison of a new immobilized Fe3+ catalyst with homogeneous Fe3+–H2O2 system for degradation of 2,4‐dinitrophenol

BACKGROUND: Heterogeneous Fenton catalysts have been used to treat various organic pollutants in an aqueous environment. The present study has investigated the degradation of 2,4‐dinitrophenol (2,4‐DNP), a priority pollutant generated by such industries as pharmaceuticals, pesticides, pigments and dyes. Degradation of 2,4‐DNP (100 mg L^?1) was studied using Fe³⁺ loaded on Al₂O₃ as a heterogeneous catalyst in the presence of H₂O₂, and the efficiency compared with the homogeneous Fe³⁺/H₂O₂ based Fenton‐like process. The effect of different parameters for both processes, such as catalyst loading, H₂O₂ concentration, initial solution pH, initial substrate concentration and temperature were investigated and the optimum operating conditions determined. RESULTS: Under optimal operating conditions of the homogeneous system ([Fe³⁺] 125 mg L^?1; [H₂O₂] 250 mg L^?1; pH 3; room temperature), 92.5% degradation was achieved in 35 min for an initial 2,4‐DNP concentration of 100 mg L^?1. In the case of immobilized Fe (Fe³⁺–Al₂O₃ catalyst), degradation improved to 98.7% under the condition 10 wt% [Fe³⁺–Al₂O₃] 1 g L^?1 catalyst loading; [H₂O₂] 250 mg L^?1; pH 3; at room temperature for the same duration. CONCLUSIONS: This study demonstrated the stability and reusability of the prepared heterogeneous catalyst. This process is a viable technique for treatment of aqueous solutions containing contaminants. Copyright © 2012 Society of Chemical Industry     

Palladium Nanoparticles in Water: A Reusable Catalytic System for the Cycloetherification or Benzannulation of α‐Allenols

A convenient ligand‐free catalytic system has been developed for the chemoselective cyclization reaction of various α‐allenol derivatives by palladium nanoparticles (PdNPs) in an aqueous reaction medium.

     

Photocatalytic oxidation of substituted toluenes with irradiated TiO2 semiconductor. Effect of zeolite

Photocatalytic oxidation of substituted toluenes was investigated on irradiated TiO₂ and TiO₂ combined with HY₁₅ and HY₂₀ zeolites. In all cases the oxidation occurred in the first step exclusively on either one substituent or the other, but never on both simultaneously. In the presence of a zeolite, photooxidation conversion was higher than that obtained without zeolite.     

A Polystyrene‐Supported,Highly Recyclable Squaramide Organocatalyst for the Enantioselective Michael Addition of 1,3‐Dicarbonyl Compounds to β‐Nitrostyrenes

A chiral squaramide has been supported onto a polystyrene (PS) resin through a copper‐catalyzed azide–alkyne cycloaddition (CuAAC) reaction and used as a very active, easily recoverable and highly reusable organocatalyst for the asymmetric Michael addition of 1,3‐dicarbonyl compounds to β‐nitrostyrenes. The PS‐supported squaramide could be recycled up to 10 times.     

Characteristics of photocatalytic oxidation of gaseous 2‐propanol using thin‐film TiO2 photocatalyst

This work presents a photocatalysis‐based method to treat and purify air because of its broad applicability to common, oxidizable, air contaminants. The effect of oxygen content, temperature, water vapor, and 2‐propanol concentration on the TiO₂ surface was investigated. The rate of 2‐propanol decomposition increased with increasing the oxygen content, but was reduced at temperatures higher than 100°C. When water vapor concentration was in the range of 10–355 mmol m^?3, the rate of 2‐propanol decomposition was proportional to the water content. However, an opposite result was observed at a higher concentration of water vapor. 2‐Propanol was photooxidized to acetone, and eventually to carbon dioxide and water. The kinetic model of 2‐propanol photooxidation was successfully developed by the competitive Langmuir–Hinshelwood rate form, incorporating the inhibition effect coming from the formation of acetone. Copyright © 2004 Society of Chemical Industry     

Effect of pre‐treatments based on UV photocatalysis and photo‐oxidation on toluene biofiltration performance

BACKGROUND: The integration of UV photocatalysis and biofiltration seems to be a promising combination of technologies for the removal of hydrophobic and poorly biodegradable air pollutants. The influence of pre‐treatments based on UV_{254 nm} photocatalysis and photo‐oxidation on the biofiltration of toluene as a target compound was evaluated in a controlled long‐term experimental study using different system configurations: a standalone biofilter, a combined UV photocatalytic reactor‐biofilter, and a combined UV photo‐oxidation reactor (without catalyst)‐biofilter. RESULTS: Under the operational conditions used (residence time of 2.7 s and toluene concentrations 600–1200 mg C m^?3), relatively low removal efficiencies (6–3%) were reached in the photocatalytic reactor and no degradation of toluene was found when the photo‐oxidation reactor was operated without catalyst. A noticeable improvement in the performance of the biofilter combined with a photocatalytic reactor was observed, and the elimination capacity of the biological process increased by more than 12 g C h^?1 m^?3 at the inlet loads studied of 50–100 g C h^?1 m^?3. No positive effect on toluene removal was observed for the combination of UV photoreactor and biofilter. CONCLUSIONS: Biofilter pre‐treatment based on UV_{254 nm} photocatalysis showed promising results for the removal of hydrophobic and recalcitrant air pollutants, providing synergistic improvement in the removal of toluene. Copyright © 2011 Society of Chemical Industry     

Enantioselective Addition of Malonates and β‐Keto Esters to Nitroalkenes over an Organonickel‐Functionalized Periodic Mesoporous Organosilica

A periodic mesoporous organosilica (PMO) with chiral cyclohexyldiamine‐based nickel(II) complexes incorporated within the silica framework was prepared through a co‐condensation of (1R,2R)‐cyclohexyldiamine‐derived silane and Ph‐bridged silane followed by complexation of nickel(II) bromide in the presence of (1R,2R)‐N,N′‐dibenzylcyclohexyldiamine. Structural analyses by X‐ray powder diffraction, nitrogen sorption and transmission electron microscopy disclosed its orderly mesostructure while characterization by solid‐state NMR and X‐ray photoelectron spectroscopy demonstrated the well‐defined single‐site chiral bis(cyclohexyldiamine)‐based nickel(II) active centers incorporated within the PMO material. In particular, as a heterogeneous chiral catalyst, this periodic mesoporous organosilica showed high catalytic activity and excellent enantioselectivity in asymmetric Michael addition of 1,3‐dicarbonyl compounds to nitroalkenes (more than 92% conversions and up to 99% ee values). More importantly, this heterogeneous catalyst could be recovered easily and reused repeatedly nine times without obviously affecting its ee value, showing good potential for industrial applications.