Structure type and disorder have become important questions in catalyst design, with the most active catalysts often noted to be “disordered” or “amorphous” in nature. To quantify the effects of disorder and structure type systematically, a test set of manganese(III,IV) oxides was developed and their reactivity as oxidants and catalysts tested against three substrates: methylene blue, hydrogen peroxide, and water. We find that disorder destabilizes the materialsthermodynamically, making them stronger chemical oxidantsbut not necessarily better catalysts. For the disproportionation of H2O2 and the oxidative decomposition of methylene blue, MnOx-mediated direct oxidation competes with catalytically mediated oxidation, making the most disordered materials the worst catalysts, whereas for water oxidation, the most disordered materials and the strongest chemical oxidants are also the best catalysts. Even though the manganese(III,IV) oxide materials were able to oxidize both methylene blue and peroxides directly,the same materials were able to act as catalysts for the oxidation of methylene blue in the presence of peroxides. This impliesthat effects of electron transfer time scales are important and strongly affected by structure type and disorder. This is discussed In the context of catalyst design.
It is often noted that disordered materials have different chemical properties to their more “ordered” cousins. Quantifying these effects in terms of thermodynamics is challenging in part because disordered materials can be difficult to characterize and are frequently relatively unstable. During the course of our experiments to understand the effects of disorder in catalysts for water oxidation we observed that many disordered manganese and cobalt oxide water oxidation catalysts directly oxidized peroxide in contrast to their more ordered analogues which catalyzed its disproportionation, that is, MnO2+2H+ +H2O2! Mn2+ +2H2O+O2(oxidation) versus H2O2!H2O+1=2 O2(disproportionation). By measuring the efficiency for one reaction over the oth
... Show MoreElectrodeposition of metal oxides on graphite electrodes can improve their ability to remove organic substances. In this work, multicomponent oxides of Mn, Co, and Ni were electrochemically deposited on both the anode and cathode of graphite electrodes to enhance their performance in removing phenol. Formation of the deposit was achieved within 2 h in current densities of 20, 25, 30, and 35 mA/cm2 for better composite properties. The deposited layer was characterized by testing the surface structure, morphology, composition, and roughness. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and Atomic force microscopy (AFM) techniques facilitated these tests. The composite electrodes have synthesized
... Show MoreKinetic and mechanism studies of the oxidation of oxalic acid by Cerium sulphate have been carried out in acid medium sulphuric acid. The uv- vis. Spectrophotometric technique was used to follow up the reaction and the selected wavelength to be followed was 320 nm. The kinetic study showed that the order of reaction is first order in Ce(IV) and fractional in oxalic acid. The effect of using different concentration of sulphuric acid on the rate of the reaction has been studied a and it was found that the rate decreased with increasing the acid concentration. Classical organic tests was used to identify the product of the oxidation reaction, the product was just bubbles of CO2.
Kinetics study on the phenol oxidation by catalytic wet air oxidation (CWAO) using CuO.NiO/Al2O3 as heterogeneous catalyst is presented. 4 g/l phenol solution of pH 7.3 was oxidized in a trickle bed reactor with gas flow rate of 80% stochiometric excess (S.E).. In order to verify the proposed kinetics, a series of CWAO experimental tests were done at two temperatures (140 and 160° C), oxygen partial pressures (9 and 12 bar), and weight hourly space velocity (WHSV) (1, 1.5, 2, 2.5, and 3 h-1). According to Power Law, the reaction orders are found to be approximately 1 and 0.5 with respect to phenol concentration and oxygen solubility, respectively. These values favorably compare with those cited in the literature for intrinsic kinetics,
... Show MoreCatalytic wet air oxidation of aqueous phenol solution was studied in a pilot plant trickle bed reactor using copper
oxide catalyst supported on alumina and silica. Catalysts were prepared by impregnating method. Effect of feed solution
pH (5.9, 7.3, and 9.2), gas flow rate (20%, 50%, 80%, and 100%), WHSV (1, 2, and 3 h-1), temperature (120°C, 140°C,
and 160°C), oxygen partial pressure (6, 9, 12 bar), and initial phenol concentration (1, 2, and 4 g/l).Generally, the
performance of the catalysts was better when the pH of feed solution was increased. The catalysts deactivation is related
to the dissolution of the metal oxides from the catalyst surface due to the acidic conditions. Phenol oxidation reaction
was strongly
Graphite nanoparticles were successfully synthesized using mixture of H2O2/NH4OH with three steps of oxidation. The process of oxidations were analysis by XRD and optics microscopic images which shows clear change in particle size of graphite after every steps of oxidation. The method depend on treatments the graphite with H2O2 in two steps than complete the last steps by reacting with H2O2/NH4OH with equal quantities. The process did not reduces the several sheets for graphite but dispersion the aggregates of multi-sheets carbon when removed the Van Der Waals forces through the oxidation process.
This work was conducted to study the oxidation of phenol in aqueous solution using copper based catalyst with zinc as promoter and different carrier, i.e. γ-Alumina and silica. These catalysts were prepared by impregnation method.
The effect of catalyst composition, pH (5.6-9), phenol to catalyst concentration ratio (2-0.5), air feed rate (30-50) ml/s, stirring speed (400-800) rpm, and temperature (80-100) °C were examined in order to find the best conditions for phenol conversion.
The best operating conditions which lead to maximum phenol conversion (73.1%) are : 7.5 pH, 4/6 phenol to catalyst concentration, 40 ml/s air feed rate, 600 rpm stirring speed, and 100 °C reaction temperature. The reaction involved an induction period
The adsorption of zirconium, on manganese dioxide from nitric
acid solutions has been studied as a function of shaking time, concentration of electrolytes, concentration of adsorbate and temperature effects (25- 90°C).
Four hours of shaking was appropriate to ensure that the
adsorption plateau was reached and the adsorption of zirconium decrease with an increase in nitric acid concentration. The limiting adsorption capacities at 3 molar nitric acid was 0.2 Zr per mole of Mn02. Working at elevated temperature was in favour
... Show More