Integrated Fenton-like and ozonation based advanced oxidation processes for treatment of real-time textile effluent containing azo reactive dyes.

The treatment of real-time textile effluent, collected from the Common Effluent Treatment Plant (CETP) of Kerala Industrial Infrastructure Development Corporation (KINFRA) at Kannur (District), Kerala (State), India, have been studied by utilizing the Fenton-like and ozone (O3) based advanced oxidation processes (AOPs). The Fenton-like AOP has been conducted as the pre-treatment of textile effluent involving the activation of persulfate (PS) and hydrogen peroxide (H2O2) as a single and the mixed oxidants by using the Flyash (FA)-Pd composite particles as the activator. The maximum chemical oxygen demand (COD) removal of 84% has been observed for a stand-alone O3 based treatment at an O3 flow rate of 5-6 g h-1. By conducting the pre-treatment of textile effluent with the PS, H2O2, and mixed oxidants (PS and H2O2) based Fenton-like AOPs, the COD removal after an O3 based post-treatment has been observed to be 83, 87, and 93% respectively at an O3 flow rate of 2, 3, and 5 g h-1. Hence, the Fenton-like pre-treatment involving the activation of mixed oxidants has been determined to be the best method for the highest COD removal of real-time textile effluent. The optimum values of initial oxidant-ratio (initial [H2O2]:initial [PS]), initial oxidant-dosage, and ozonation time, for the mixed oxidants based Fenton-like pre-treatment, have been determined to be 3 wt% mM-1, 6:2 wt% mM-1, and 60 min respectively. Under the most optimum conditions, the COD removal has been attributed to the combination of O2•- (for the pre-treatment) and •OOH (for the post-treatment) which possess relatively lower oxidation potential values.

Removal of methylene blue and azo reactive dyes from aqueous solution and textile effluent via modified pulsed low-frequency ultrasound cavitation process.

Organic dyes in the aqueous solutions and textile effluents cause severe environmental pollution due to their carcinogenic and mutagenic nature. Ultrasound (US) cavitation is one of the promising advanced oxidation processes (AOP) to remove the organic dyes from the aqueous solutions and textile effluents. Nevertheless, the conventional low-frequency US cavitation process exhibits very low efficiency in the dye removal process and demands effective modification to improve its performance. In this investigation, a conventional pulsed low-frequency (22 ± 2 kHz) US cavitation process has been modified by varying the US power (50-150 W), initial solution pH (2-10), and O2 flow rate (1-4 L min-1) to enhance the decomposition of cationic methylene blue (MB) dye in an aqueous solution. The operation of the classic Haber-Weiss reaction, both in the forward and backward directions, and the ozone effect have been observed, for the first time, under the modified US cavitation process, as confirmed via the radical trapping experiments. Moreover, the hydrothermally synthesized hydrogen titanate (H2Ti3O7) nanotubes (HTN) have been utilized as sonocatalyst, for the first time, for 100% dye removal, with effective regeneration obtained via an in-situ thermal activation of persulfate (PS, S2O82-). The most optimum values of US power, initial solution pH, O2 flow rate, HTN, and PS concentrations for 100% MB decomposition are observed to be 150 W, 2, 2 L min-1, 0.3 g L-1, and 10 mM, respectively. The decomposition of industrial azo reactive dyes in an aqueous solution as well as in a textile effluent has also been demonstrated using a modified pulsed low-frequency US cavitation process involving the thermal activation of PS without the use of HTN, which justifies its suitability for a commercial application.

Catalytic dye degradation by novel phytofabricated silver/zinc oxide composites.

Phytofabrication of the nanoparticles with exotic shape and size is an attractive area where nanostructures with noteworthy physicochemical and optoelectronic properties that can be significantly employed for photocatalytic dye degradation. In this study a medicinal plant, Plumbago auriculata leaf extract (PALE) was used to synthesize zinc oxide particles (ZnOPs) and silver mixed zinc oxide particles (ZnOAg1Ps, ZnOAg10Ps, ZnO10Ag1Ps) by varying the concentration of the metal precursor salts, i.e. zinc acetate and silver nitrate. The PALE showed significantly high concentrations of polyphenols, flavonoids, reducing sugar, starch, citric acid and plumbagin up to 314.3 ± 0.33, 960.0 ± 2.88, 121.3 ± 4.60, 150.3 ± 3.17, 109.4 ± 2.36, and 260.4 ± 8.90 µg/ml, respectively which might play an important role for green synthesis and capping of the phytogenic nanoparticles. The resulting particles were polydispersed which were mostly irregular, spherical, hexagonal and rod like in shape. The pristine ZnOPs exhibited a UV absorption band at 352 nm which shifted around 370 in the Ag mixed ZnOPs with concomitant appearance of peaks at 560 and 635 nm in ZnO10Ag1Ps and ZnOAg1Ps, respectively. The majority of the ZnOPs, ZnOAg1Ps, ZnOAg10Ps, and ZnO10Ag1Ps were 407, 98, 231, and 90 nm in size, respectively. Energy dispersive spectra confirmed the elemental composition of the particles while Fourier transform infrared spectra showed the involvement of the peptide and methyl functional groups in the synthesis and capping of the particles. The composites exhibited superior photocatalytic degradation of methylene blue dye, maximum being 95.7% by the ZnOAg10Ps with a rate constant of 0.0463 s-1 following a first order kinetic model. The present result clearly highlights that Ag mixed ZnOPs synthesized using Plumbago auriculata leaf extract (PALE) can play a critical role in removal of hazardous dyes from effluents of textile and dye industries. Further expanding the application of these phytofabricated composites will promote a significant complementary and alternative strategy for treating refractory pollutants from wastewater.

Leucophyllum frutescens mediated synthesis of silver and gold nanoparticles for catalytic dye degradation.

The application of nanotechnology is gaining worldwide attention due to attractive physico-chemical and opto-electronic properties of nanoparticles that can be also employed for catalytic dye degradation. This study reports a phytogenic approach for fabrication of silver (AgNPs) and gold nanoparticles (AuNPs) using Leucophyllum frutescens (Berl.) I. M. Johnst (Scrophulariaceae) leaf extract (LFLE). Development of intense dark brown and purple color indicated the synthesis of AgNPs and AuNPs, respectively. Further characterization using UV-visible spectroscopy revealed sharp peak at 460 nm and 540 nm for AgNPs and AuNPs, respectively that were associated to their surface plasmon resonance. High resolution transmission electron microscope (HRTEM) revealed the spherical shape of the AgNPs, whereas anisotropic AuNPs were spherical, triangular and blunt ended hexagons. The majority of the spherical AgNPs and AuNPs were ∼50 ± 15 nm and ∼22 ± 20 nm, respectively. Various reaction parameters such as, metal salt concentration, temperature and concentration of the leaf extract were optimized. Maximum synthesis of AgNPs was obtained when 5 mM for AgNO3 reacted with 10% LFLE for 48 h at 50°C. Likewise, AuNPs synthesis was highest when 2 mM HAuCl4 reacted with 10% LFLE for 5 h at 30°C. Energy dispersive spectroscopy (EDS) showed phase purity of both the nanoparticles and confirmed elemental silver and gold in AgNPs and AuNPs, respectively. The average hydrodynamic particles size of AgNPs was 34.8 nm while AuNPs was 140.8 nm as revealed using dynamic light scattering (DLS) that might be due to agglomeration of smaller nanoparticles into larger clusters. ZETA potential of AgNPs and AuNPs were 0.67 mV and 5.70 mV, respectively. X-ray diffraction (XRD) analysis confirmed the crystallinity of the nanoparticles. Fourier transform infrared spectroscopy (FTIR) confirmed that various functional groups from the phytochemicals present in LFLE played a significant role in reduction and stabilization during the biogenic synthesis of the nanoparticles. The bioreduced AgNPs and AuNPs catalytically degraded Rhodamine B dye (RhB) in presence of UV-light with degradation rate constants of 0.0231 s-1 and 0.00831 s-1, respectively. RhB degradation followed a first order rate kinetics with 23.1 % and 31.7% degradation by AgNPs and AuNPs, respectively.

Autoclave and pulsed ultrasound cavitation based thermal activation of persulfate for regeneration of hydrogen titanate nanotubes as recyclable dye adsorbent.

In the dye removal application, regeneration of hydrogen titanate nanotubes (HTN, H2Ti3O7) has been achieved via thermal activation of persulfate anion (PS, S2O82-) by using the conventional hot plate technique which has limitations from the commercial perspective since it does not provide any precise control over the thermal generation process typically during the scale-up operation. To overcome this drawback, HTN have been synthesized via hydrothermal process which exhibit the methylene blue (MB) adsorption of 93% at the initial dye concentration and solution pH of 90 µM and 10 respectively. HTN have been regenerated via the thermal activation of PS by varying its initial concentration and regeneration temperature, within the range of 0.27-1 wt% and 40-80 °C, under the thermal conditions set by the autoclave and pulsed ultrasound (US) cavitation process. The results of recycling experiments suggest that the optimum values of initial PS concentration and temperature, for the regeneration of HTN under the autoclave conditions, are 1 wt% and 70 °C with the maximum MB adsorption of 92%, while, the corresponding values for the pulsed US cavitation process are 1 wt%, 80 °C, and 91% respectively. Thus, the regeneration and recycling of HTN have been successfully demonstrated by using the autoclave and pulsed US cavitation process. Under the optimum conditions, MB degradation involves the generation and attack of SO4•- for both the thermal generation techniques. The regeneration techniques developed here may be utilized in future during the scale-up operation and also for the regeneration of adsorbents besides HTN.

Hydrothermal synthesized magnetically separable mesostructured H2Ti3O7/γ-Fe2O3 nanocomposite for organic dye removal via adsorption and its regeneration/reuse through synergistic non-radiation driven H2O2 activation.

Hydrogen titanate (H2Ti3O7) nanotubes/nanosheets (HTN) are emerging class of adsorbent material which possess unique property of activating hydrogen peroxide (H2O2) to generate the reactive oxygen species (ROS), such as superoxide radical ions (O2.-) and hydroxyl radicals (·OH), effective in the decomposition of surface-adsorbed dye. However, HTN are non-magnetic which create hurdle in their effective separation from the treated aqueous solution. To overcome this issue, magnetic nanocomposites (HTNF) composed of HTN and maghemite (γ-Fe2O3) nanoparticles have been processed by subjecting the core-shell magnetic photocatalyst consisting of γ-Fe2O3/silica (SiO2)/titania (TiO2), having varying amounts of TiO2 in the shell to the hydrothermal conditions. HTNF-5 magnetic nanocomposite consisting of 31 wt% H2Ti3O7, typically having nanotube morphology with the highest specific surface area (133 m2 g-1) and pore-volume (0.22 cm3 g-1), exhibits the highest capacity (74 mg g-1) for the adsorption of cationic methylene blue (MB) dye from an aqueous solution involving the electrostatic attraction mechanism and pseudo-second-order kinetics. Very fast magnetic separation followed by regeneration of HTNF-5 magnetic nanocomposite has been demonstrated via non-radiation driven H2O2 activation. It has been ascertained for the first time that the underlying mechanism of dye decomposition involves the synergy effect between the constituents of HTNF magnetic nanocomposite.

Dye-adsorption capacity of high surface-area hydrogen titanate nanosheets processed via modified hydrothermal method.

High surface-area (380 m2 x g(-1)) hydrogen titanate nanosheets (HTNS) processed via the modified hydrothermal method have been utilized for the removal of methylene blue (MB) dye from an aqueous solution via the surface-adsorption process involving the electrostatic attraction mechanism. The HTNS have been characterized using the transmission electron microscope (TEM), selected-area electron diffraction (SAED), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) specific surface-area measurement techniques. The amount of MB dye adsorbed on the surface of HTNS at equilibrium (q(e)) has been examined as a function of contact time, initial dye-concentration, and initial solution-pH. Within the investigated range of initial solution-pH (2.5-11), the MB dye adsorption on the surface of HTNS has been observed to follow the pseudo-second-order kinetics with the dye-adsorption capacity of 119 mg x g(-1) at the initial solution-pH of - 10. The adsorption equilibrium follows the Langmuir isotherm within the initial solution-pH range of 2.5-10. However, in a highly basic solution (initial solution-pH -11), the adsorption equilibrium has been observed to follow the Langmuir, Freundlich, and Dubinin-Kaganer-Radushkevich (DKR) models in the different ranges of initial MB dye concentration. The mere dependence on the DKR model has not been observed within the investigated range of initial solution-pH. The differences in the dye-adsorption characteristics and capacity of HTNS, compared with those of hydrogen titanate nanotubes, have been attributed to the difference in their specific surface-area. Irrespective of the morphology, the maximum coverage of MB dye on the surface of hydrogen titanate has been noted to be the same (52%).

Effect of air-pressure on room temperature hydrogen sensing characteristics of nanocrystalline doped tin oxide MEMS-based sensor.

Nanocrystalline indium oxide (In2O3)-doped tin oxide (SnO2) thin film sensor has been sol-gel dip-coated on a microelectrochemical system (MEMS) device using a sol-gel dip-coating technique. Hydrogen (H2) at ppm-level has been successfully detected at room temperature using the present MEMS-based sensor. The room temperature H2 sensing characteristics (sensitivity, response and recovery time, and recovery rate) of the present MEMS-based sensor has been investigated as a function of air-pressure (50-600 Torr) with and without the ultraviolet (UV) radiation exposure. It has been demonstrated that, the concentration of the surface-adsorbed oxygen-ions (which is related to the sensor-resistance in air), the ppm-level H2, and the oxygen (O2) partial pressure are the three major factors, which determine the variation in the room temperature H2 sensing characteristics of the present MEMS-based sensor as a function of air-pressure.

High-resolution and analytical TEM investigation of metastable-tetragonal phase stabilization in undoped nanocrystalline zirconia.

Submicron and nano-sized nanocrystalline pure zirconia (ZrO2) powders having metastable tetragonal and tetragonal-plus-monoclinic crystal structures, respectively, were synthesized using the sol-gel technique. The as-precipitated and the calcinated ZrO2 powders were analyzed for their morphology, nanocrystallite size and structures, aggregation tendency, local electronic properties, and elemental compositions by conventional and high-resolution transmission electron microscopy and field-emission analytical electron microscopy, including energy-dispersive X-ray and electron energy-loss spectroscopies. The results from this study indicate that a combination of nanocrystallite size, strain-induced grain-growth confinement, and the simultaneous presence of the monoclinic phase can lead to stabilization of the metastable tetragonal-phase in undoped ZrO2. As a result, the tetragonal phase is stabilized within ZrO2 nanocrystallites up to 100 nm in size, which is 16 times larger than the previously reported critical size of 6 nm.