Modeling the oxidation of atrazine by H2O2/UV. Estimation of kinetic parameters

A kinetic model for the oxidation of atrazine by H₂O₂/UV in dilute aqueous solutions ([Atrazine]₀ < 2 μM) has been tested in a batch reactor. In this model, direct photolysis and oxidation by hydroxyl radicals are assumed to be the main reactions in the decomposition of atrazine by H₂O₂/UV. The data showed that the model can be used to predict the effects of some parameters (hydrogen peroxide dose, pH, bicarbonate alkalinity, …) and to estimate values of quantum yield of photolysis, rate constants for the reaction of hydroxyl radicals with atrazine and of the scavenging term (Sk_iS_i) of natural waters.     

Titanium deposited from TiCl4 on amorphous silica and silicalite-1 as catalyst in aromatic hydroxylation reactions

Titanium deposited from TiCl₄ on crystalline or amorphous SiO₂ catalyses the hydroxylation of phenol with aqueous H₂O₂. The amorphous silica-supported titanium shows a high rate of hydrogen peroxide conversion, however with a low selectivity towards aromatic hydroxylation products. A silicalite-supported titanium catalyst exhibits an efficiency towards hydroxylation products, based on hydrogen peroxide conversion, that is equal to that of titanium-silicalite-1 (TS-1), however with a lower activity.     

Direct synthesis of hydrogen peroxide from H2 and O2 and in situ oxidation using zeolite-supported catalysts

Four microporous materials, zeolites HZSM-5, Y, Beta and TS-1, were used as the supports to prepare supported gold catalysts using impregnation or deposition precipitation. The gold catalysts were tested in the direct synthesis of hydrogen peroxide from H₂ and O₂ and for CO oxidation. The effect on the catalytic activity of different metal (e.g., Pd, Pt, Cu, Ag, Rh or Ru) on the synthesis of hydrogen peroxide was also tested. Organic substrates, such as cyclohexane or cyclooctene, were introduced to investigate the possibility of in situ H₂O₂ oxidation with these catalysts.     

New insights into the influence of activated carbon surface oxygen groups on H2O2 decomposition and oxidation of pre-adsorbed volatile organic compounds

In this study, the influence of the surface oxygen groups of activated carbons (ACs) on the decomposition of H₂O₂ and the consequent OH radicals generation is investigated. The oxidation of pre-adsorbed volatile organic compounds by H₂O₂ is also studied. Four ACs, with low percentage of inorganic matter (<0.2%), similar textural properties but differing in their surface oxygen content were evaluated. The surface oxygen groups of the ACs were characterised by using appropriate characterisation techniques (temperature programmed desorption and X-ray photoelectron spectroscopy). The kinetic curves of H₂O₂ decomposition were very similar for all the ACs. However, different profiles in the production of OH radicals were observed. OH radicals generation seemed to be promoted by low surface oxygen contents. Oxidation of two volatile organic compounds (VOCs) of different polarity, methyl ethyl ketone (MEK) and toluene, pre-adsorbed onto the ACs was finally investigated. H₂O₂ was used as oxidising agent. Both VOCs presented similar maximum oxidation rates, around 70%, in spite of their different hydrophobicity. Some evidences are provided supporting that oxidation of pre-adsorbed VOCs can take place in the inner pore structure of the ACs.     

Surface smoothing of a polycrystalline diamond using an iron plate-H2O2 chemical reaction

In this study, the researchers demonstrated an ultraprecise polishing method that achieved an improved polycrystalline diamond (PCD) surface. This novel polishing technique uses hydroxyl radicals generated on an iron plate in a hydrogen peroxide (H₂O₂) solution. To demonstrate the feasibility of obtaining an ultrasmooth PCD surface, we conducted a polishing experiment using an iron plate in an H₂O₂ solution; the rotating speed of the polishing table/sample holder and the contact load were controlled. After polishing, we cleaned the PCD samples using two different methods and evaluated the surface morphology and chemical components using scanning white light interference microscopy, atomic force microscopy, and an electron-probe micro analyzer. The results showed that atomic-level smoothing of the topmost grain diamond (which constitutes the PCD substrate) could be realized using our proposed method. Moreover, cleaning with a mixed acid (H₂SO₄/H₂O₂) solution was more effective in removing residual contaminates than ultrasonic cleaning in acetone.     

Radical formation in polymer electrolyte fuel cell components as studied by ESR spectroscopy

To clarify the deterioration mechanism for polymer electrolyte fuel cells, OH radical formation at the catalyst electrodes was investigated by ESR (electron spin resonance) spectroscopy using a flow cell with the catalyst electrodes. OH radicals produced from H₂O₂ were detected by a DMPO (5,5-dimethyl-1-pyrroline N-oxide) spin-trapping method for a Nafion-coated Pt/Carbon catalyst electrode under a high potential (0.85 V versus RHE) on supplying H₂ and under low potentials (lower than 0.40 V). When Pt–Ru catalysts were employed instead of Pt catalysts, the formation of OH radicals was barely detected. The results suggest the possibility of the formation of OH radicals by the oxidation of H₂O₂ at the oxidized Pt surface under a positive potential as well as the reduction of H₂O₂ at the clean Pt surface under a low potential.     

Heterogeneously assisted oxidation of adsorbates from carbonmonoxide, methanol and ethanol by hydrogen peroxide solutions on platinum electrodes in sulphuric acid

The influence of hydrogen peroxide on the adsorption and oxidation of carbon monoxide, methanol and ethanol adlayers on porous Pt electrodes were studied in 2 M sulphuric acid solution by means of cyclic voltammetry and differential electrochemical mass spectrometry (DEMS). The oxidation of adsorbed species is observed at electrode potentials far less negative than those required for electrochemical adsorbate oxidation. The oxidation by H₂O₂ is dependent on its concentration in solution, as well as on the adsorbates and their coverages. In all cases the isolated adlayers are oxidised by dissolved H₂O₂. However, the presence of H₂O₂ during adsorption partially inhibits adlayer formation from CH₃OH and C₂H₅OH, but avoids almost completely the adsorption of carbon monoxide. The removal of the residues from the surface by dissolved hydrogen peroxide probably occurs through O_ad species formed during the heterogeneous decomposition reaction of H₂O₂ on Pt.     

The effect of H2 treatment on the activity of activated carbon for the oxidation of organic contaminants in water and the H2O2 decomposition

In this work, hydrogen peroxide reactions, i.e. H₂O₂ decomposition and oxidation of organics in aqueous medium, were studied in the presence of activated carbon. It was observed that the carbon pre-treatment with H₂ at 300, 500, 700 and 800 °C resulted in an increase in activity for both reactions. The carbons were characterized by BET nitrogen adsorption, thermogravimetric analyses (TG), temperature programmed reduction (TPR), electron paramagnetic resonance (EPR), iodometric titration and determination of the acid/basic sites. TPR experiments showed that activated carbon reacts with H₂ at temperatures higher than 400 °C. The treatment produces a slight increase in the surface area. EPR analyses indicate the absence of unpaired electrons in the carbon. Iodometric titrations and TG analyses suggested that the treatment with H₂ generates reduction sites in the carbon structure, with concentration of approximately 0.33, 0.53, 0.59, 0.65 and 0.60 mmol/g for carbons treated at 25, 300, 500, 700 and 800 °C, respectively. It was also observed the appearance of basic sites which might be related to the reduction sites. It is proposed that these reducing sites in the carbon can activate H₂O₂ to generate HO^* radicals which can lead to two competitive reactions, i.e. the hydrogen peroxide decomposition or the oxidation of organics in water.     

Changes in Surface Property and Catalysis of Mesoporous Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> from Amorphous to Crystalline Pore Walls

Abstract  

The amorphous inorganic phase of an ordered amorphous mesoporous Nb₂O₅ with two dimensional hexagonal (2D-hex) structure was crystallized with maintaining the original well arranged porous structure. The difference in surface property between amorphous and crystalline Nb₂O₅ with similar ordered mesoporous structure was compared. It was found from water adsorption–desorption isotherms and observation by infrared (IR) spectroscopy that the amorphous sample was hydrophilic and that the surface OH groups were acidic. On the other hand, the OH groups on crystalline mesoporous Nb₂O₅ were non-acidic and inside the pores was less hydrophilic. The surface property was also compared by a catalytic reaction, oxidation of cyclohexe by an aqueous solution of H₂O₂. The high (95%) selectivity for 1,2-epoxycyclohexane was obtained at 40 °C for 2 h in methanol solvent over crystalline mesoporous Nb₂O₅ at 12% conversion, while amorphous mesoporous Nb₂O₅ showed high (68%) selectivity for 1,2-cyclohexanediol in acetonitrile solvent at 60 °C for 2 h at 22% conversion. The differences in selectivity and the optimal solvent between amorphous and crystalline samples were interpreted in terms of the acidic feature of surface OH groups and hydrophilicity. While similar selectivity was observed over non-porous crystalline Nb₂O₅, much higher conversion over crystalline mesoporous Nb₂O₅ was attained at the same surface area. Thus, an advantage of mesoporous structure is attributed to the higher contact time of molecules inside the pores to the catalyst surface than those outside the particles.     

Iodination of arachidonic acid by the iron/H2O2/iodide system

The newly described iron/hydrogen peroxide (H₂O₂)/iodide antimicrobial system iodinates arachidonic acid to form the same products which are generated by peroxidase/H₂O₂/iodide systems. Arachidonic acid is multiply iodinated with the formation ofbis-iodohydrins and monoiodinated products which were identified as iodolactones by their high performance liquid chromatography elution patterns and by gas chromatography-mass spectrometric analysis. Iodination of arachidonic acid by the iron/H₂O₂/iodide system appears to proceed via the formation of hydroxyl radicals as an intermediate species. Iodination of unsaturated lipids may contribute to the cytotoxicity of the iron/H₂O₂/iodide system. Recipient of Allergic Diseases Academic Award AI00487 from the National Institute of Allergy and Infectious Diseases.     

Decolorization of Methyl Orange Dye at IrO2‐SnO2‐Sb2O5 Coated Titanium Anodes

A film of iridium and tin dioxides doped with antimony oxide (IrO₂‐SnO₂‐Sb₂O₅) was deposited onto Ti mesh and plate substrates by the Pechini method. The electrode surface morphology and composition were characterized by SEM‐EDS. The ternary oxide coating was used for the anodic oxidation of methyl orange (MO) azo dye. Linear sweep voltammetry was used to identify the electrode potentials that favour MO degradation. Batch electrolyses were then carried out at a constant electrode potential of 1.5, 1.75 and 2.0 V vs. SHE using either a three‐electrode batch cell or a flow reactor. The dye solutions were totally decolorized via reactive oxygen species, such as ^?OH, H₂O₂ and O₃ formed in situ from water oxidation at the Ti/IrO₂‐SnO₂‐Sb₂O₅ surface.     

Oxidation of several chlorophenolic derivatives by UV irradiation and hydroxyl radicals

The oxidation of some chlorophenols: 4‐chlorophenol, 2,4‐dichlorophenol, 2,4,6‐trichlorophenol, 2,3,4,6‐tetrachlorophenol, tetrachlorocatechol (3,4,5,6‐tetrachloro‐2‐hydroxy phenol) and 4‐chloroguaiacol (4‐chloro‐2‐methoxy phenol) has been studied via single photodecomposition produced by polychromatic UV irradiation, oxidation by hydroxyl radicals generated by Fenton's reagent (hydrogen peroxide plus ferrous ions), and degradation by hydroxyl radicals produced by combinations of UV irradiation plus hydrogen peroxide, and UV irradiation plus hydrogen peroxide and ferrous ions (photo‐Fenton system). These organics have been selected as models of chloro‐phenolic derivative pollutants present in wastewaters and groundwaters. The degradation levels obtained in each process are reported. The quantum yields in the single photodecomposition reaction and the rate constants between the chlorophenols and the hydroxyl radicals in the reaction with Fenton's reagent are determined. Finally, the additional contributions to the photodecomposition promoted by the radical reaction in the combined UV/H₂O₂ and photo‐Fenton systems are also evaluated. © 2001 Society of Chemical Industry     

Decomposition of hydrogen peroxide in the presence of activated carbons with different characteristics

BACKGROUND: Catalytic ozonation promoted by activated carbon is a promising advanced oxidation process used in water treatment. Hydrogen peroxide generated as a by‐product from the reaction of ozone with some surface groups on the activated carbon or from the oxidation of some organic compounds present in the water being treated seems to play a key role in the catalytic ozonation process. Hydrogen peroxide decomposition promoted by two granular activated carbons (GAC) of different characteristics (Hydraffin P110 and Chemviron SSP‐4) has been studied in a batch reactor. The operating variables investigated were the stirring speed, temperature, pH and particle size. Also, the influence of metals on the GAC surface, that can catalyze hydrogen peroxide decomposition, was observed. RESULTS: Chemviron SSP‐4 showed a higher activity to decompose hydrogen peroxide than HydraffinP110 (70 and 50% of hydrogen peroxide removed after 2 h process, respectively). Regardless of the activated carbon used, hydrogen peroxide decomposition was clearly controlled by the mass transfer, although temperature and pH conditions exerted a remarkable influence on the process. Catalytic ozonation in the presence of activated carbon and hydrogen peroxide greatly improved the mineralization of oxalic acid (a very recalcitrant target compound). About 70% TOC (total organic carbon) depletion was observed after 1 h reaction in this combined system, much higher than the mineralization achieved by the single processes used. CONCLUSIONS: Of the two activated carbons studied, Chemviron SSP‐4 with an acidic nature presented a higher activity to decompose hydrogen peroxide. However the influence of the operating variables was quite similar in both cases. Experiments carried out in the presence of tert‐butanol confirmed the appearance of radical species. A kinetic study indicated that the process was controlled by the internal mass transfer and the chemical reaction on the surface of the activated carbon. The catalytic activity of hydrogen peroxide in oxalic acid ozonation promoted by activated carbon (O₃/AC/H₂O₂) was also studied. The results revealed the synergetic activity of the system O₃/AC/H₂O₂ to remove oxalic acid. Copyright © 2010 Society of Chemical Industry     

Preparation and Study of Pd Catalysts Supported on Activated Carbon Cloth (ACC) for Direct Synthesis of H2O2 from H2 and O2

Activated carbon cloths (ACCs) were used as supports for Pd catalysts. The catalyst preparation was carried out by the impregnation method using acidic solution of palladium dichloride (PdCl₂) as metal precursor. The effects of the oxidation state of the loaded metal, heat treatment of the catalysts in different atmosphere (H₂, air) at different temperatures and surface chemistry of the support on the catalyst characterizations and the catalytic activities were investigated. Wet oxidation of ACC was done by nitric acid in order to induce oxygen-containing surface functional groups. Surface chemistry of the support and oxidation state of the metallic phase was investigated by means of XPS, TPD, SEM, DTA and TGA tests. Direct synthesis of hydrogen peroxide from H₂ and O₂ was performed batch wise in a stainless steel autoclave. The reactions were conducted under high pressure (38 bar) at 0 °C and methanol was used as reaction medium. The direct synthesis results showed that the oxygen-containing surface functional groups increase the selectivity of the catalysts by reducing the rate of water production. Existence of the oxidized state of Pd (PdO) also makes the catalyst more selective than the corresponding zerovalent state (Pd0). PdO affected on selectivity by increasing the rate of H₂O₂ production and reducing the amount of production of water, simultaneously.     

From Renewable to Fine Chemicals Through Selective Oxidation: The Case of Glycerol

Catalytic selective oxidation of glycerol is presented in terms of catalytic systems and experimental conditions. Unsupported gold nanoparticles (AuNPs), AuNPs on carbon and on TiO₂ were employed and compared in terms of reaction selectivity and activity. The role of the base and the formed hydrogen peroxide has been considered. Gold based catalysts showed selectivity that is strongly dependent of the reaction conditions. In particular C–C scission products increases by increasing the reaction temperature but correlated only partially with the rate of degradation of the H₂O₂ formed under the operative conditions. Moreover, under neutral/acidic conditions glycerol can be oxidised also by increasing the temperature slightly, but it leads to a detrimental effect on selectivity and catalyst life.     

Removal of diazinon by various advanced oxidation processes

Diazinon is a widely used organophosphorus insecticide that is an important pollutant in aquatic environments. The chemical removal of diazinon has been studied using UV radiation, ozone, Fenton's reagent, UV radiation plus hydrogen peroxide, ozone plus hydrogen peroxide and photo‐Fenton as oxidation processes. In the photodegradation process the observed quantum yields had values ranging between 2.42 × 10^?2 and 6.36 × 10^?2 mol E^?1. Similarly, the ozonation reaction gave values for the rate constant ranging between 0.100 and 0.193 min^?1. In the combined systems UV/H₂O₂ and O₃/H₂O₂ the partial contributions to the global oxidation reaction of the direct and radical pathways were deduced. In the Fenton's reagent and photo‐Fenton systems, the mechanism of reaction has been partially discussed, and the predominant role of the radical pathway pointed out. Additionally, the rate constant for the reaction between diazinon and the hydroxyl radicals was determined, with the value 8.4 × 10⁹ L mol^?1 s^?1 obtained. A comparison of the different oxidation systems tested under the same operating conditions revealed that UV radiation alone had a moderate oxidation efficiency, which is enhanced in the case of ozone, while the most efficient oxidant is the photo‐Fenton system. Copyright © 2007 Society of Chemical Industry     

Direct synthesis of H2O2 on monometallic and bimetallic catalytic membranes using methanol as reaction medium

Tubular catalytic membranes (TMCs) active in the direct synthesis of hydrogen peroxide were prepared, characterized, and tested using methanol as the reaction medium. Low hydrogen peroxide selectivity was found when only palladium was used as a catalyst, whereas palladium/platinum bimetallic samples gave higher productivity and selectivity, with an optimum molar ratio of 18. The H₂O₂ decomposition rate is influenced by the feed gases. O₂ improves H₂O₂ stability, whereas H₂ causes hydrogen peroxide to decompose at a higher rate. The most likely decomposition pathway should be the reduction of H₂O₂ to water by H₂. Bromide ion was used as a promoter and when used in excess (60 ppm) causes a decrease in overall catalytic activity.     

Direct synthesis of hydrogen peroxide from H2/O2 and oxidation of thiophene over supported gold catalysts

Direct synthesis of hydrogen peroxide from H₂ and O₂ was performed over supported gold catalysts. The catalysts were characterized by means of UV–vis, H₂-TPR, TEM and XPS. Based on the results we conclude that metallic Au is the active species in the direct synthesis of hydrogen peroxide from H₂ and O₂. During preparation process of catalyst by deposition–precipitation with urea, the pH value increased and the gold particle size decreased with increasing the urea concentration. The catalyst prepared with higher urea concentration showed a higher activity and its stability also was efficiently improved. Gold nanoparticles, supported on TiO₂ or Ti contained supports, gave a higher catalytic activity. Thiophene can be efficiently oxidized by hydrogen peroxide synthesized in situ from H₂ and O₂ over Au/TS-1.     

Benzaldehyde synthesis via styrene oxidation by O2 over TiO2 and TiO2/SiO2

Styrene was oxidized by molecular oxygen over TiO₂ and TiO₂/SiO₂ for the formation of benzaldehyde. In the absence of catalyst at 100 °C and 10 atm O₂, polystyrene is the major product. Over the catalysts, the oxidation of styrene is enhanced with benzaldehyde and formaldehyde being the major whereas phenylacetaldehyde, acetophenone, styrene oxide, benzoic acid, and polymer being the minor products. The polymerization of styrene was initiated by the radicals formed in the oxidation reaction. The addition of radical inhibitor nitrobenzene and/or the employment of a catalyst of high specific surface area can promote the termination of the radicals, and hence improve the selectivity of benzaldehyde.