Sonophotocatalytic degradation of malachite green in aqueous solution using six competitive metal oxides as a benchmark.

A comparison study examines six different metal oxides (CuO, ZnO, Fe3O4, Co3O4, NiO, and α-MnO2) for the degradation of malachite green dye using four distinct processes. These processes are as follows: sonocatalysis (US/metal oxide), sonocatalysis under ultra-violet irradiation (US/metal oxide/UV), sonocatalysis in the presence of hydrogen peroxide (US/metal oxide/H2O2), and a combination of all these processes (US/metal oxide/UV/H2O2). The effective operating parameters, such as the dosage of metal oxide nanoparticles (MONPs), the type of the process, and the metal oxides' efficiency order, were studied. At the same reaction conditions, the sonophotocatalytic is the best process for all six MOsNPs, CuO was the better metal oxide than other MOsNPs, and at the sonocatalysis process, ZnO was the best metal oxide in other processes. It was found that the metal oxide order for sonocatalytic process is CuO > α-MnO2 ≥ ZnO > NiO ≥ Fe3O4 ≥ Co3O4 within 15-45 min. The order of (US/metal oxide/UV) process is ZnO ≥ NiO ≥ α-MnO2 > Fe3O4 ≥ CuO ≥ Co3O4 within 5-40 min. The order of (US/ MOsNPs/ H2O2) process is ZnO ≥ CuO ≥ α-MnO2 ≥ NiO > Co3O4 > Fe3O4 within 5-20 min. The maximum removal efficiency order of the sonophotocatalytic process is ZnO ≥ CuO > α-MnO2 > NiO > Fe3O4 ≥ Co3O4 within 2-8 min. The four processes degradation efficiency was in the order US/MOsNPs ˂ US/MOsNPs/UV ˂ US/MOsNPs/H2O2 ˂ (UV/Ultrasonic/MOsNPs/H2O2). Complete degradation of MG was obtained at 0.05 g/L MONPs and 1 mM of H2O2 using 296 W/L ultrasonic power and 15 W ultra-violet lamp (UV-C) within a reaction time of 8 min according to the MOsNPs type at the same sonophotocatalytic/H2O2 reaction conditions. The US/metal oxide/UV/H2O2 process is inexpensive, highly reusable, and efficient for degrading dyes in colored wastewater.

Amine-rich quartz nanoparticles for Cu(II) chelation and their application as an efficient catalyst for oxidative degradation of Rhodamine B dye.

The study describes the loading of the quartz SiO2 nanoparticles (NPs) with (3-aminopropyl)triethoxysilane (APTES) linker with simultaneous lengthening of the linker through the terminal amine group by glutaraldehyde (GA). The reactive polyethylenimine (PEI) was introduced to the surface to increase the ability to capture Cu(II) ions. The composite got the abbreviation SiO2/PEI-Cu(II). The Cu(II) ions were the active center with a peroxo-complex activation state. The composite characterization included scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron-dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and Brunauer-Emmett-Teller (BET) surface analyzer. The kinetics of the oxidative degradation of Rhodamine B (RhB) dye obeyed the pseudo-first order under flooding conditions. The reaction parameters including the catalyst dose, solution pH, initial concentration of reactants, and temperature got some attention. The obtained results showed that more than 91.7 ± 1% of RhB dye was degraded to CO2, NH4+, NO3-, H2O, and some inorganic acids after 30 min as confirmed by gas chromatography mass spectrometry and total organic carbon (TOC) measurements. Also, GC-MS spectra for water samples drawn from the reaction in successive periods had suggested a conceivable degradation pathway for RhB by hydroxyl radicals. Degradation starts with de-alkylation then carboxyphenyl removal followed by two successive ring-opening stages. Both the effects of the catalyst recycling and treated water reusability on the reaction rate were studied. The catalyst provided noticeable stability over three consecutive cycles.

Homogeneous and heterogeneous catalytic oxidation of some azo dyes using copper(II) ions.

The kinetics of the homogeneous and heterogeneous catalytic oxidation processes of three azo dyes in presence of copper (II) - ions, copper (II) - ions - supported on alumina and on zinc oxide as well as copper ammonia complex supported on alumina were investigated in aqueous solutions. The dyes are Chromotrope 2B (C2B), Chromotrope 2R (C2R) and Chrysophenen (CRY). The reaction progress was followed by monitoring the decrease in absorbance at ℷmax 512, 511 and 401 nm, respectively. The rate of reaction increased with increasing either the concentration of the dye or the catalyst, giving a plateau at high concentrations of the catalyst. On the other hand, the rate of reaction increased gradually with increasing hydrogen peroxide concentration attaining a maximum then decreased thereafter. The reaction rate was also increased with increasing pH and temperature and was found to be entropy controlled. This work could be applied for dye baths water reuse to reduce costs in textile and dyeing factories as will as for environmental purposes.

Chemical insight into the adsorption of reactive wool dyes onto amine-functionalized magnetite/silica core-shell from industrial wastewaters.

Fe3O4 NPs are synthesized by the co-precipitation technique. Moreover, the pristine was coated by silica layer and then functionalized by 3-aminopropyltrimethoxysilane (APTS). The sample possessed saturation magnetization with value equals 37 emu/g which made them to easily separate using external magnet. FT-IR, TGA, EDX, and VSM confirmed the aminosilane loading. The surface topography and composition were characterized using XRD, TEM, SEM, BJH, and BET methods. Where adsorption capacity of the surface toward the removal of four commercial reactive wool dyes (RD), Itowol black (IB), Itowol Red (IR), Sunzol black (SB), and Lanasol blue (LB) have been investigated. The influence variables such as pH, adsorbent dose, dye concentration, and temperature were calculated. Where experimental results fitted to Langmuir isotherm model with qmax equals 161.29, 151.51, 123.45, and 98.20 mg/g, for IR, LB, SB, and IB respectively. The results showed that the RD adsorption described by pseudo-second-order kinetics. The calculated thermodynamic parameters indicated that RD adsorption onto Fe3O4@SiO2-NH2 was spontaneous and exothermic in nature. The possible mechanisms monitoring RD adsorption on the surface included hydrogen bonding and electrostatic interactions. The reusability of adsorbent carried with four cycles without releasing of magnetite and thus excluding the potential hazardous of nanomaterial to the environment. Graphical abstract.

Kinetics of degradation of allura red, ponceau 4R and carmosine dyes with potassium ferrioxalate complex in the presence of H(2)O(2).

The degradation of title dyes with ferrioxalate and H(2)O(2) couple has been investigated spectrophotometrically. In the absence of either one of the oxidizing agents no degradation occurred. The reaction rate was proportional to moderate concentrations of the dye and H(2)O(2). At high concentration of the dye and H(2)O(2) the reaction rate decreased. With regard to the concentration of the ferrioxalate complex the rate of reaction increased even over a wide range of complex concentration. Degradation of dyes does not occur in acidic medium. It is slow in neutral but thoroughly fast in alkaline medium. The reaction rate reaches a maximum value at pH 11.5. This behavior was again observed if HCl or NaOH were added. With HCl the reaction rate decreases with increasing acid concentration but greatly increases with NaOH concentration. Isopropanol showed inhibiting effect due to scavenging the in situ generated hydroxyl radical (()OH). Oxalate ion enhanced the rate, confirming an outer sphere mechanism. The activation parameters of the reaction are estimated and a possible mechanism is proposed. The mechanism is well confirmed with data simulation procedure.

Preparation and characterization of polyaniline/manganese dioxide composites and their catalytic activity.

This paper is devoted to the preparation of polyaniline/MnO2 (PANI/MnO2) composites via chemical oxidation of aniline in H2SO4 medium using beta-MnO2 as an oxidant. The parameters affecting the polymerization reaction are considered. These parameters are [aniline], amount of beta-MnO2, stirring time, and polymerization temperature. SEM, FT-IR, XRD, and TGA techniques are used to characterize the resulting composites. XRD measurements reveal the distortion of the crystal structure of beta-MnO2 after the polymerization reaction. Thus, the XRD pattern of PANI is predominating. The crystalline composites are obtained using higher molar ratio of [Ox]/[ANI] and at higher temperature. Increasing the amount of beta-MnO2 led to an increase in the acidic character of the obtained composites due to adsorption of excess H+ on the oxide surface. The thermal stability of the composites decreased with increasing both [aniline] and stirring time, while it increased with increasing amount of beta-MnO2. The applications of the composites in the oxidative degradation of Direct Red 81, Acid Blue 92, and Indigo Carmine dyes exhibited good catalytic activity in the presence of H2O2 as an oxidant. The reactions followed first-order kinetics and the rate constants were determined. The degradation reaction involved the catalytic action of the PANI counterpart of the composite toward H2O2 decomposition, which can lead to the generation of HO radicals as a highly efficient oxidant attacking the target dyes. The detailed kinetic studies and the mechanism of these catalytic reactions are under consideration in our group.

Catalytic effect of supported metal ion complexes on the induced oxidative degradation of pyrocatechol violet by hydrogen peroxide.

Kinetics of the oxidative degradation of pyrocatechol violet dye (PCV) [2-[(3,4-dihydroxyphenyl)(3-hydroxy-4-oxocyclohexa-2,5-dien-1-ylidene) methyl]-benzenesulfonic acid] by H(2)O(2) catalyzed by supported transition metal complexes have been studied. The reaction was followed by conventional UV-vis spectrophotometer at lambda(max)=440 nm in a buffer solution at pH 5.1. The supports used were silica gel and cation exchange resins (Dowex-50W, 2 and 8% DVB), while the complexes were [Cu(amm)(4)](2+), [Cu(en)(2)](2+), [Cu(ma)(4)](2+), [Co(amm)(6)](2+), and [Ni(amm)(6)](2+) (amm=ammonia, en=ethylenediamine, and ma=methylamine). The reaction exhibited first-order kinetics with respect to [PCV] and [H(2)O(2)]. The reactivity of the catalysts is correlated with the redox potential of the metal ions, the type of support, and the amount of supported complexes. The rate of the reaction increases with increasing pH and the addition of NaCl. Addition of SDS and CTAB showed inhibiting effects. The reaction is enthalpy-controlled as confirmed from the isokinetic relationship. A reaction mechanism involved the generation of free radicals as an oxidant has been proposed.