Direct Electrochemistry and Electrocatalysis of Hemoglobin on Bimetallic Au–Pt Inorganic–Organic Nanofiber Hybrid Nanocomposite and Mesoporous Molecular Sieve MCM-41

A glassy carbon electrode modified with MCM-41 and bimetallic inorganic–organic nanofiber hybrid nanocomposite was prepared and used for determination of trace levels of hydrogen peroxide (H₂O₂). The direct electron transfer (DET) and electrocatalysis of hemoglobin (Hb) entrapped in the MCM-41 modified Au–Pt inorganic–organic nanofiber hybrid nanocomposite electrode (Au–PtNP/NF/GCE) were investigated by using cyclic voltammetry in 0.1 M pH 7.0 phosphate buffer solution. Due to its uniform pore structure, high surface area and good biocompatibility, the mesoporous silica sieve MCM-41 provided a suitable matrix for immobilization of biomolecules. The MCM-41 modified Au–Pt inorganic–organic nanofiber hybrid nanocomposite electrode showed significant promotion to DET of Hb, which exhibited a pair of well-defined and quasi-reversible peaks for heme Fe(III)/Fe(II) with a formal potential of ?0.535 V (vs. Ag/AgCl). Additionally, the Hb immobilized on the MCM-41 modified electrode showed excellent electrocatalytic activity toward H₂O₂ reduction.     

MCM-41 supported CuO/Bi2O3 nanoparticles as potential catalyst for 1,4-butynediol synthesis

CuO/Bi₂O₃ (CuO/Bi₂O₃/MCM-41) nanoparticles supported on MCM-41 were synthesized by a facile impregnation method. The products were characterized by nitrogen adsorption/desorption, X-ray diffraction (XRD), H₂ temperature programmed reduction (H₂-TPR) and scanning electron microscopy (SEM). XRD patterns indicated the presence of crystalline CuO and Bi₂O₃ phase for CuO/Bi₂O₃/MCM-41 catalyst. TPR results revealed CuO nanoparticles were dispersed well on MCM-41. SEM results showed that the nanoparticles were located on the MCM-41. The activity of the catalysts towards ethynylation of formaldehyde for 1,4-butynediol synthesis was evaluated at atmospheric pressure. Compared with unsupported CuO/Bi₂O₃ and commercial Cu/Bi-based catalyst, CuO/Bi₂O₃/MCM-41 catalyst showed maximum conversion (51%) and selectivity (94%) towards 1,4-butynediol. The results show that CuO/Bi₂O₃ catalysts supported on MCM-41 have potential for 1,4-butynediol synthesis in industrial application.     

Zr (IV)-ninhydrin supported MCM-41 and MCM-48 as novel nanoreactor catalysts for the oxidation of sulfides to sulfoxides and thiols to disulfides

Modification of MCM-41 and MCM-48 mesoporous materials with bonded aminosilane species, Schiff base preparation by ninhydrin and finally complexation with zirconium, has attracted much attention in order to design catalyst with advanced applications in the oxidation of sulfides to sulfoxides and thiols to disulfides in the presence of hydrogen peroxide. In all oxidation of sulfides to sulfoxids 0.4 mL H₂O₂ used as oxidant in the presence of Zr(IV)-ninhydrin supported MCM-41 (0.01 g) or Zr(IV)-ninhydrin supported MCM-48 (0.005 g) at room temperature and solvent-free condition. Also the best conditions for oxidation of thiols to disulfides with 0.4 mL H₂O₂ were 0.005 g Zr(IV)-ninhydrin supported MCM-41 or Zr(IV)-ninhydrin supported MCM-48 at room temperature and in ethanol. These catalysts are characterized by SEM, XRD, TGA, FT-IR, EDS, ICP and BET analysis. Also the Turn over frequency (TOF) and Turn over number (TON) of catalysts are calculated. Obtained results by these heterogeneous catalysts revealed several advantages including short reaction times, simple workup, easy isolation and reusability.     

Mn-doped ZrO2 nanoparticles as an efficient catalyst for green oxidative degradation of methylene blue

Manganese doped on cubic phase nanoparticles of ZrO₂ was synthesized by an impregnation method. These novel particles were carefully analyzed by various chemico-physical methods. The catalytic degradation of an organic dye, methylene blue, in the presence of Mn-doped ZrO₂ nanoparticles, as well as ZrO₂ nanoparticles as catalyst with aqueous hydrogen peroxide, H₂O₂, as an oxidizing agent has been studied in aqueous solution at room temperature. Effects of solution pH, catalyst composition and radical scavenging agents on the degree of degradation of methylene blue were also studied. Finally, the recoverability and reusability of the Mn-doped ZrO₂ catalyst were evaluated.     

Assessment of Fe2O3/SiO2 catalysts for the continuous treatment of phenol aqueous solutions in a fixed bed reactor

Different iron-containing catalysts have been tested for the oxidation of phenol aqueous solutions in a catalytic fixed bed reactor in the presence of hydrogen peroxide. All the catalysts consist of iron oxide, mainly crystalline hematite particles, over different silica supports (mesostructured SBA-15 silica and non-ordered mesoporous silica). The immobilization of iron species over different silica supports was addressed by direct incorporation of metal during the synthesis or post-synthesis impregnation. The synthesis conditions were tuned up to yield agglomerated catalysts with iron loadings between 10 and 15 wt.%. The influence of the preparation method and the type of silica support was evaluated in a catalytic fixed bed reactor for the continuous oxidation of phenol in terms of catalysts activity (phenol and total organic carbon degradation) as well as their stability (catalyst deactivation by iron leaching). Those catalysts prepared by direct synthesis, either in presence of a structure-directing agent (Fe₂O₃/SBA-15(DS)) or in absence (Fe₂O₃/SiO₂(DS)), achieved high catalytic performances (TOC reduction of 65% and 52%, respectively) with remarkable low iron leaching in comparison with their silica-based iron counterparts prepared by impregnation. Catalytic results have demonstrated that the synthesis method plays a crucial role in the dispersion and stability of active species and hence resulting in superior catalytic performances.     

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     

Ozone-Based Advanced Oxidation Processes for the Decomposition of N-Methyl-2-Pyrolidone in Aqueous Medium

The present study investigates the decomposition of N-Methyl-2-Pyrolidone (NMP) using conventional ozonation (O₃), ozonation in the presence of UV light (UV/O₃), hydrogen peroxide (O₃/H₂O₂), and UV/H₂O₂ processes under various experimental conditions. The influence of solution pH, ozone gas flow dosage, and H₂O₂ dosage on the degradation of NMP was studied. All ozone-based advanced oxidation processes (AOPs) were efficient in alkaline medium, whereas the UV/H₂O₂ process was efficient in acidic medium. Increasing ozone gas flow dosage would accelerate the degradation of NMP up to certain level beyond which no positive effect was observed in ozonation as well as UV light enhanced ozonation processes. Hydrogen peroxide dosage strongly influenced the degradation of NMP and a hydrogen peroxide dosage of 0.75 g/L and 0.5 g/L was found to be the optimum dosage in UV/H₂O₂ and O₃/H₂O₂ processes, respectively. The UV/O₃ process was most efficient in TOC removal. Overall it can be concluded that ozonation and ozone-based AOPs are promising processes for an efficient removal of NMP in wastewater.     

Semiconductor-mediated photocatalytic degradation of anazo dye, chrysoidine Y in aqueous suspensions

The photocatalytic degradation of an azo dye derivative, chrysoidine Y (1), was investigated in aqueous suspensions of titanium dioxide and zinc oxide by monitoring the change in substrate concentration employing UV spectroscopic analysis and decrease in total organic carbon content as a function of irradiation time under a variety of conditions. The degradation of the dye was studied under different conditions such as pH, catalyst concentration, substrate concentration and in the presence of electron acceptors such as hydrogen peroxide (H₂O₂) and potassium bromate (KBrO₃) besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient as compared with zinc oxide     

Titanium dioxide mediated photocatalyzed degradation of a textile dye derivative, acid orange 8, in aqueous suspensions

Titanium dioxide mediated photocatalysed degradation of a textile dye derivative, acid orange 8(1), was investigated in aqueous suspensions of titanium dioxide by monitoring the depletion of total organic carbon (TOC) content as a function of irradiation time under a variety of conditions. The degradation kinetics were studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO₂ and in the presence of electron acceptors such as hydrogen peroxide (H₂O₂) and potassium bromate (KBrO₃) besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient compared with other photocatalysts. The dye was found to be adsorbed on the surface of the photocatalyst at acidic pH.     

Efficient degradation of <Emphasis Type="Italic">para</Emphasis>-chlorobenzoic acid in water by catalytic ozonation with La–Ce–MCM-41

La–Ce–MCM-41 was directly synthesized by a hydrothermal method and applied as heterogeneous catalyst for the ozonation process of para chlorobenzoic-acid (pCBA). La³⁺ and Ce³⁺ were successfully incorporated into the framework of MCM-41 and the formation of degradation products (p-chlorophenol, p-dihydroxybenzene, maleic acid and oxalic acid) were monitored qualitatively using gas chromatography–mass spectrometer and high performance liquid chromatography. Due to the synergy of bimetal and the fast degradation of accumulated intermediates, total organic carbon (TOC) removal efficiency was significantly improved (92 %) in La–Ce–MCM-41/O₃ process compared with ozonation (40 %) at identical reaction condition. The presence of tert-butanol (TBA) in La–Ce–MCM-41/O₃ process indicated that the oxidation of pCBA was mainly due to the function of hydroxyl radicals in the liquid bulk, and a plausible degradation pathway was proposed. TOC removal slightly decreased from 90 to 86 % after La–Ce–MCM-41 being re-utilized three times, which illustrated that La–Ce–MCM-41 was an efficient of promising catalyst for ozonation of pCBA.     

The role of activated carbon as a catalyst in GAC/iron oxide/H2O2 oxidation process

The catalytic properties of granular activated carbon (GAC) in GAC/iron oxide/hydrogen peroxide (H₂O₂) system was investigated in this research. Batch experiments were carried out in de-ionized water at the desired concentrations of ethylene glycol and phenol. Rate constants for the degradation of hydrogen peroxide and the formation rate of iron species were determined and correlated with mineralization of ethylene glycol at various GAC concentrations. The observed first order degradation rate of hydrogen peroxide in the absence of iron oxide and organic matter increases linearity with the increasing of the GAC concentration. The decomposition rate of hydrogen peroxide was suppressed significantly as the solution pH became acidic or by reducing the surface area of the GAC. The reduction of the surface area was obtained by loading an organic compound (such as phenol) on the GAC or by using the oxidizing agent (H₂O₂). The addition of both chemicals, phenol and H₂O₂, affects mainly the surface area of the small pores, resulting in reducing the catalytic activity inside the micropores.The catalytic properties of the GAC were used to accelerate the formation rate of the ferrous ions, which is known in the literature to be the limiting rate reaction in the classic Fenton like reagent. It was shown that the ethylene glycol mineralization rate was increased by more than 50%.Finally, optimization of the GAC consumption leading to the fastest mineralization of the ethylene glycol, resulting in decreasing of the decomposition rate of H₂O₂ while enhancing the generation rate of ferrous ions.     

Study of iron sources and hydrogen peroxide supply in the photo‐Fenton process using acetaminophen as model contaminant

BACKGROUND: The aim of this study was the evaluation of iron (II) D‐gluconate and iron (II) sulfate as iron sources for the photo‐Fenton process at initial neutral pH. Acetaminophen was used as the contaminant for this purpose. The evaluation was carried out at laboratory and pilot‐plant scales. In addition, hydrogen peroxide dosage was analyzed in order to decrease reactant consumption. RESULTS: 20 mg Fe L^?1 was added as iron salt or iron D‐gluconate; hydrogen peroxide dosage proved to be efficient when using iron sulfate, obtaining similar mineralization levels for one large H₂O₂ addition, two smaller additions and continuous dosage (78%, 74% and 78% mineralization, respectively). However, when D‐gluconate was used, H₂O₂ dosage resulted in a slower process rate: 74% mineralization for one large H₂O₂ addition versus 49% mineralization for two smaller additions. CONCLUSIONS: Results showed that iron complexes could form between iron and degradation by‐products increasing reaction efficiency. The ratio between the dissolved organic carbon concentrations of the contaminant and the iron complex proved to be important as well. H₂O₂ dosage confirmed that two reactant additions led to the best results, which was then corroborated with real wastewater. © 2012 Society of Chemical Industry     

Immobilization of Uranyl Schiff Base in Mesoporous MCM-41

A uranyl Schiff base complex [UO₂{ OC₆H₄N = C(H)C₆H₄O} H₂O] has been immobilized inside the periodic mesopore channels of MCM-41 by the impregnation route. The samples have been characterized by XRD, N₂ adsorption/desorption, TG-DTA, DR UV-vis, ²⁹Si MAS NMR and FTIR techniques. While the host is found to retain its structural integrity, the surface area and the pore volume decrease considerably as a result of the intrapore confinement of complex molecules. The spectroscopy results indicate that the complex molecules are anchored with the silanol groups of MCM-41 via hydrogen bonding.     

Advanced oxidation of cork‐processing wastewater using Fenton's reagent: kinetics and stoichiometry

This work evaluates Fenton oxidation for the removal of organic matter (COD) from cork‐processing wastewater. The experimental variables studied were the dosages of iron salts and hydrogen peroxide. The COD removal ranged from 17% to 79%, depending on the reagent dose, and the stoichiometric reaction coefficient varied from 0.08 to 0.43 g COD (g H₂O₂)^?1 (which implies an efficiency in the use of hydrogen peroxide varying from 17% to 92%). In a study of the process kinetics, based on the initial rates method, the COD elimination rate was maximum when the molar ratio [H₂O₂]_o:[Fe²⁺]_o was equal to 10. Under these experimental conditions, the initial oxidation rate was 50.5 mg COD dm^?3 s^?1 with a rate of consumption of hydrogen peroxide of 140 mg H₂O₂ dm^?3 s^?1, implying an efficiency in the use of the hydrogen peroxide at the initial time of 77%. The total amount of organic matter removed by Fenton oxidation was increased by spreading the H₂O₂ and ferrous salt reagent over several fractions by 15% for two‐fractions and by 21% for three‐fractions. Copyright © 2004 Society of Chemical Industry     

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.     

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     

Monitoring the Physicochemical and Chemical Treatment of Textile Wastewater using GC/MS,LC/MS and ‐MS/MS Techniques

Abstract

Conventional biological wastewater treatment processes often fail in the elimination of finishing agents contained in textile wastewater such as dyes, surfactants, and softeners. Therefore, discharges from the textile industry are known as a major source of water pollution reaching groundwater and even drinking water treatment. Physicochemical treatment and advanced treatment processes (AOP) were applied to eliminate the pollutants prior to discharge. Ozone (O₃), O₃/UV, hydrogen peroxide/UV (H₂O₂/UV), Fenton's reagent (Fe²⁺/H₂O₂) were applied to eliminate by oxidation while ultrasonication (US) alone, US/UV or powdered activated carbon (PAC) were used for the physicochemical treatment. Elimination was monitored by a conventional sum parameter analyses (COD, BOD, DOC) while gas chromatography/mass spectrometry (GC/MS) and liquid chromatography coupled with MS and tandem mass spectrometry (LC/MS and ‐MS/MS) was applied for follow‐up of pollutants and their degradation products. The application of PAC, Fenton, and O₃/UV resulted in the highest dissolved organic carbon elimination. A complete or partial elimination and/or degradation of non‐polar or polar pollutants was observed by GC/MS or flow injection analysis/MS (FIA/MS) respectively. LC/MS and MS/MS analyses confirmed that ethoxylated surfactants (AEO) present in the original wastewater could be oxidized or destroyed resulting in carboxylated AEO and polyethylene glycol (PEG) or even carboxylated PEG.     

Removal of organic load and phenolic compounds from olive mill wastewater by Fenton oxidation with zero-valent iron

Pre-treatment of olive mill wastewater (OMW) by Fenton Oxidation with zero-valent iron and hydrogen peroxide was investigated to improve phenolic compounds degradation and the chemical oxygen demand (COD) removal. Experimental procedure is performed with diluted OMW with COD 19 g/L and pH 5.2. The application of zero-valent Fe/H₂O₂ procedure allows high removal efficiency of pollutants from OMW. The optimal experimental conditions were found to be continuous presence of iron metal, acidic pH (2–4) and 1 M hydrogen peroxide solution. The experimental results show that the removal of 1 g of COD need 0.06 M of H₂O₂. At pH 1, the maximum COD removal (78%) is achieved after 1 h. Therefore, with a pH value within 2 and 4 the maximum COD removal reached 92%. Phenolic compounds are identified in treated and untreated OMW by gas chromatography coupled to mass spectrometry (GC–MS). The result shows a total degradation of phenolic compounds and an increasing biodegradability of treated OMW.     

Selective oxidation of benzaldehyde by molecular oxygen over molybdovanadophosphoric acid supported MCM-41

A series of molybdovanadophosphoric acid (MVPA) supported on mesoporous silica was synthesized by an incipient wetness impregnation method. The catalysts were characterized by nitrogen adsorption?Cdesorption, X-ray powder diffraction, Fourier-Transform Infra red spectroscopy (FT-IR), UV?CVis Diffused reflectance spectroscopy (UV?CVis DRS), Temperature programmed reduction (TPR) and ³¹P MAS Nuclear magnetic resonance(NMR) study. The characterization data reveals the incorporation of vanadium in phosphomolybdic acid and retention of intact Keggin ion on the support. The catalytic activities were evaluated for oxidation of benzaldehyde using molecular oxygen as oxidant as the new green reaction system. Among all the promoted catalysts, 50wt% molybdovanadophosphoric acid supported on MCM-41 exhibits highest catalytic activity in oxidation of benzaldehyde, giving 95% conversion. Other oxidants like H₂O₂ and tert-butyl hydrogen peroxide (TBHP) were also tested for benzaldehyde oxidation reaction.     

UVA-LED assisted persulfate/nZVI and hydrogen peroxide/nZVI for degrading 4-chlorophenol in aqueous solutions

Photocatalytic degradation of 4-chlrophenol (4-CP) using UVA-LED assisted persulfate and hydrogen peroxide activated by the nZVI (Nano Zero Valent Iron) in a batch photocatalytic reactor was investigated. The reaction involved a lab-scale photoreactor irradiated with UVA-LED light emitted at 390 nm. The efficiency of the reaction was evaluted in terms of 4-CP degradation and mineralization degree at different pH of solution, initial concentrations of nZVI, persulfate, hydrogen peroxide and 4-CP. In UVA-LED/H₂O₂/nZVI process, complete degradation of 4-CP (>99%) and 75% mineralization was achieved at pH of 3, hydrogen peroxide concentration of 0.75 mM, nZVI dosage of 1mM and initial 4-CP concentration of 25mg/L at the reaction time of 30 min. The optimum conditions obtained for the best 4-CP degradation rate were at an initial concentration of 25mg/l, persulfate concentration of 1.5mM, nZVI dosage of 1mM, pH of 3 and reaction time of 120min for UVA-LED/persulfate/nZVI process. It was also observed that the 4-CP degradation rate is dependent on initial 4-CP concentrations for both processes. The pseudo-first-order kinetic constant at 25mg/L initial concentration of 4-CP was found to be 1.4×10^?1 and 3.8×10^?2 in UVA-LED/H₂O₂/nZVI and UVA-LED/persulfate/nZVI processes, respectively. Briefly, the UVA-LED/H₂O₂/nZVI process enhanced the degradation rate of 4-CP by 3.67-times in comparison to UVA-LED/persulfate/nZVI process at 30min contact time, which serves as a new and feasible approach for the degradation of 4-CP as well as other organic contaminants containing wastewater.