Efficient treatment of veterinary pharmaceutical industrial wastewater by catalytic ozonation process: degradation of enrofloxacin via molecular ozone reactions.

The study focused on the efficacious performance of bimetallic Fe-Zn loaded 3A zeolite in catalytic ozonation for the degradation of highly toxic veterinary antibiotic enrofloxacin in wastewater of the pharmaceutical industry. Batch experiments were conducted in a glass reactor containing a submerged pump holding catalyst pellets at suction. The submerged pump provided the agitation and recirculation across the solution for effective contact with the catalyst. The effect of ozone flow (0.8-1.55 mg/min) and catalyst dose (5-15 g/L) on the enrofloxacin degradation and removal of other conventional pollutants COD, BOD5, turbidity was studied. In batch experiments, 10 g of Fe-Zn 3A zeolite efficiently removed 92% of enrofloxacin, 77% of COD, 69% BOD5, and 61% turbidity in 1 L sample of pharmaceutical wastewater in 30 min at 1.1 mg/min of O3 flow. The catalytic performance of Fe-Zn 3A zeolite notably exceeded the removal efficiencies of 52%, 51%, 52%, and 59% for enrofloxacin, COD, BOD5, and turbidity, respectively, achieved with single ozonation process. Furthermore, an increase in the biodegradability of treated pharmaceutical industrial wastewater was observed and made biodegradable easily for subsequent treatment.

Synergistic effect of plasma power and temperature on the cracking of toluene in the N2 based product gas.

In this research, a dielectric barrier discharge (DBD) reactor is used to study the cracking of the toluene into C1-C6 hydrocarbons. The combined effect of parameters such as temperature (20-400 °C) and plasma power (10-40 W) was investigated to evaluate the DBD reactor performance. The main gaseous products from the decomposition of toluene include lower hydrocarbon (C1-C6). The cracking of toluene increases with power at all temperatures (20-400 °C). On the otherhand, it decreases from 92.8 to 73.1% at 10 W, 97.2 to 80.5% at 20, 97.5 to 86.5% at 30 W, and 98.4 to 93.7% at 40 W with raising the temperature from 20 to 400 °C. Nonetheless, as the temperature and plasma input power increase, the methane yield increases. At 40 W, the maximum methane yield was 5.1%. At 10 and 20 W, the selectivity to C2 increases as the temperature rises up to 400 °C. At 30 and 40 W, it began to drop after 300 °C due to the formation of methane and the yield of methane increases significantly beyond this temperature.

A Comprehensive Review on Zeolite Chemistry for Catalytic Conversion of Biomass/Waste into Green Fuels.

Numerous attempts have been made to produce new materials and technology for renewable energy and environmental improvements in response to global sustainable solutions stemming from fast industrial expansion and population growth. Zeolites are a group of crystalline materials having molecularly ordered micropore arrangements. Over the past few years, progress in zeolites has been observed in transforming biomass and waste into fuels. To ensure effective transition of fossil energy carriers into chemicals and fuels, zeolite catalysts play a key role; however, their function in biomass usage is more obscure. Herein, the effectiveness of zeolites has been discussed in the context of biomass transformation into valuable products. Established zeolites emphasise conversion of lignocellulosic materials into green fuels. Lewis acidic zeolites employ transition of carbohydrates into significant chemical production. Zeolites utilise several procedures, such as catalytic pyrolysis, hydrothermal liquefaction, and hydro-pyrolysis, to convert biomass and lignocelluloses. Zeolites exhibit distinctive features and encounter significant obstacles, such as mesoporosity, pore interconnectivity, and stability of zeolites in the liquid phase. In order to complete these transformations successfully, it is necessary to have a thorough understanding of the chemistry of zeolites. Hence, further examination of the technical difficulties associated with catalytic transformation in zeolites will be required. This review article highlights the reaction pathways for biomass conversion using zeolites, their challenges, and their potential utilisation. Future recommendations for zeolite-based biomass conversion are also presented.

Application of poly aluminum chloride and alum as catalyst in catalytic ozonation process after coagulation for the treatment of textile wastewater.

Textile wastewater is ranked highly contaminated among all industrial waste. During textile processing, the consumption of dyes and complex chemicals at various stages makes textile industrial wastewater highly challenging. Therefore, conventional processes based on single-unit treatment may not be sufficient to comply with the environmental quality discharge standards and more stringent guidelines for zero discharge of hazardous chemicals (ZDHC). In this study, a novel approach was followed by recycling Poly aluminum chloride (PACl) and Alum as a catalyst for the first time in the catalytic ozonation treatment process leading to a nascent method after using them as a coagulant in Coagulation/Flocculation. In the current investigation, six different combinations were studied to remove turbidity, TSS, COD, BOD5, color, and biodegradability (BOD5/COD ratios) of wastewater. Moreover, Central Composite Design was implied using RSM in Minitab software. During the combination of treatment processes, it was found that the pre-coagulation/flocculation with coagulant PACl followed by post-catalytic ozonation with recycled PACl, a more effective treatment than others. The optimum R.E of turbidity, TSS, COD, and color were 84%, 86%, 89%, and 98%, respectively. Moreover, a decrease in toxicity and increase in biodegradability (BOD5/COD ratio from 0.29 to 0.54) was observed as well. The electrical energy demand and operational costs of treatment processes were estimated and compared with other treatment processes.

Application of Fe-RGO for the removal of dyes by catalytic ozonation process.

Due to continuous industrialization, the discharge of hazardous dyes has enormously disrupted the ecosystem causing environmental problems. Due to the stable recalcitrant nature of dyes, advanced catalytic ozonation processes with the latest catalyst are under investigation. Fe-RGO is an effective oxidation catalyst, and the metal loaded platform provides enhanced catalytic performance. This study aims to investigate the effectiveness of Fe-RGO/O3 process for the removal of dyes. In the current research, the application of iron-coated reduced graphene oxide (Fe-RGO) was studied as a catalyst in the heterogeneous catalytic ozonation process to remove dyes. Methylene blue (MB) was selected as a model pollutant. RGO was prepared using the improved Hummers method and was coated with iron (Fe) implying the impregnation method. The FTIR, SEM-EDX, XRD, and BET analyses of RG and Fe-RGO were performed to characterize the catalyst. The effect of various parameters such as pH (3-10), catalyst dose (0.01-0.04 g), and radical scavengers (NaHCO3, NaCl) on removal efficiency was elucidated. The result revealed an excellent catalytic efficiency of Fe-RGO in the ozonation process. At optimum conditions, 96% removal efficiency was achieved in catalytic ozonation at pH 7 with a catalyst dose of 0.02 g and ozone dose 0.5 mg/min, after 10 min. Interestingly, a slight decrease in removal efficiency was observed in the catalytic ozonation process in hydroxyl radical scavengers (NaCl and NaHCO3), which makes the proposed catalyst more applicable in real conditions. Therefore, it is concluded that Fe-RGO can be used as an excellent catalyst for the removal of dyes in real conditions where radical scavengers may be present in a significant amount.

Photocatalytic degradation of methylene blue using polyaniline-based silver-doped zinc sulfide (PANI-Ag/ZnS) composites.

This study set out to determine the photocatalytic degradation potential of polyaniline-based silver-doped zinc sulfide composite (PANI-Ag/ZnS) for effective degradation of methylene blue. The heterogeneous photocatalytic experiments were carried out by irradiating aqueous dye solutions with ultraviolet light (UV-254 nm). The catalysts (ZnS, Ag/ZnS, PANI-ZnS, and PANI-Ag/ZnS) were prepared successfully and characterized by Fourier Transforms Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), and Energy-dispersive X-ray diffraction (EDX). Combined with density functional theory calculations, a set of calculations has been performed for optimization, computation, and accuracy of the structure. After the optimization, the equilibrium lattice were a=b= (0.54447 nm), in good agreement with experimental results (a=b=c=0.54093 nm). Fermi energy levels Ef, indicating Ag-doped in ZnS as the impurity acceptor and for better visible-light photo-catalysis, narrow bandgap, and acceptor states are beneficial. The optimization of effective parameters like pH, catalyst dose, oxidant dose, dye concentration, and reaction time was carried out. The best degradation efficiency (> 95%) of PANI-Ag/ZnS composite against methylene was achieved within 60 min of reaction time under optimized conditions. The optimized conditions were recoded as follows: pH = 7, catalysts dose = 30 mg/L, oxidant dose = 3 mM, and irradiation time = 60 min under UV-254 nm for all catalysts. The central composite design (CCD) under the Response Surface Methodology (RSM) was chosen as a statistical tool to obtain the correlation of influential parameters. Five successive reusability trials were carried out to check the stability of catalysts.

Subcritical and supercritical water oxidation for dye decomposition.

The total annual output of synthetic dyes exceeds 7 × 105 tons. About 1,000 tons of non-biodegradable synthetic dyes are released every year into the natural streams and water sources from textile wastes. The release of these colored wastewater exerts negative impact on aquatic ecology and human beings because of the poisonous and carcinogenic repercussions of dyes involved in coloration production. Therefore, with a growing interest in the environment, efficient technologies need to be developed to eliminate dyes from local and industrial wastewater. Supercritical water oxidation as a promising wastewater treatment technology has many advantages, such as a rapid reaction and pollution-free products. However, due to corrosion, salt precipitation and operational problems, supercritical water oxidation process did not gain expected industrial development. These technical difficulties can be overcome by application of non-corrosive subcritical water as a reaction medium. This work summarizes the negative impacts of dyes and role of subcritical and supercritical water and their efficiencies in dye oxidation processes.

Efficient Cr(vi) photoreduction under natural solar irradiation using a novel step-scheme ZnS/SnIn4S8 nanoheterostructured photocatalysts.

Removal of heavy metal pollutants from water is a challenge to water security and the environment. Therefore, in this work, multinary chalcogenide based nanoheterostructures such as ZnS/SnIn4S8 nanoheterostructure with different loading amounts were prepared. The prepared nanoheterostructures were utilized as photocatalysts for chromium (Cr(vi)) photoreduction. The prepared nanoheterostructures were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), UV-Vis spectroscopy, dynamic light scattering (DLS), and X-ray photoelectron spectroscopy (XPS) and BET measurements. The absorption spectra of the prepared nanoheterostructures revealed that they are widely absorbed in the visible range with bandgap values 2.4-3.5 eV. The photocatalytic activities of prepared nanoheterostructures were studied toward the photoreduction of heavy metal, chromium (Cr(vi)), under irradiation of natural solar light. The ZnS/SnIn4S8 (with ZnS molar ratio 20%) nanoheterostructures results showed a high photocatalytic activity (92.3%) after 120 min which could be attributed to its enhanced charge carrier separation with respect to the bare ZnS and SnIn4S8 NPs. Also, the optoelectronic, valence-band XPS and electrochemical properties of the investigated photocatalysts were studied and the results revealed that the photocatalysts behave the step-scheme mechanism. The recyclability tests revealed a beneficial role of the surface charge in efficient regeneration of the photocatalysts for repeated use.

Treatment of leachate through constructed wetlands using Typha angustifolia in combination with catalytic ozonation on Fe-zeolite A.

Leachate control and management is a major challenge faced during solid waste management as it may pollute surface and groundwaters. In the current research, constructed wetlands (CWs) vegetated with Typha angustifolia plant in combination with catalytic ozonation by ferrous (Fe)-coated zeolite A was studied for the treatment of leachate. The CWs treatment with 9 days detention reduced the chemical oxygen demand (COD) and biochemical oxygen demand (BOD) up to 75.81% and 69.84%, respectively. Moreover, total suspended solids (TSS), total dissolved solids (TDS), and total kjeldahl nitrogen (TKN) removal of 91.16%, 33.33%, and 25.22% were achieved, respectively. The Fe-coated zeolite A catalytic ozonation further reduced the COD up to 90.7%. Comparison of the processes showed the effective performance of the combined process (CW/O3/Fe-zeolite) with 97.76% COD reduction of leachate. It is, therefore, concluded that the studied combined process (CW/O3/Fe-zeolite A) was more efficient as compared with single ozonation and CW alone, hence it can be implied for the leachate treatment in real conditions.

UV-Accelerated Photocatalytic Degradation of Pesticide over Magnetite and Cobalt Ferrite Decorated Graphene Oxide Composite.

Pesticides are one of the main organic pollutants as they are highly toxic and extensively used worldwide. The reclamation of wastewater containing pesticides is of utmost importance. For this purpose, GO-doped metal ferrites (GO-Fe3O4 and GO-CoFe2O4) were prepared and characterized using scanning electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopic techniques. Photocatalytic potentials of catalysts were investigated against acetamiprid's degradation. A detailed review of the parametric study revealed that efficiency of overall Fenton's process relies on the combined effects of contributing factors, i.e., pH, initial oxidant concentration, catalyst dose, contact time, and acetamiprid load. ~97 and ~90% degradation of the acetamiprid was achieved by GO-CoFe2O4 and GO-Fe3O4, respectively during the first hour under UV radiations at optimized reaction conditions. At optimized conditions (i.e., pH:3, [H2O2]: 14.5 mM (for Fe3O4, GO-Fe3O4, and GO-CoFe2O4) and 21.75 mM (for CoFe2O4), catalysts: 100 mgL-1, time: 60min) the catalysts exhibited excellent performance, with high degradation rate, magnetic power, easy recovery at the end, and efficient reusability (up to 5 cycles without any considerable loss in catalytic activity). A high magnetic character offers its easy separation from aqueous systems using an external magnet. Moreover, the combined effects of experimental variables were assessed simultaneously and justified using response surface methodology (RSM).

Enhanced High-Temperature (600 °C) NO2 Response of ZnFe2O4 Nanoparticle-Based Exhaust Gas Sensors.

Fabrication of gas sensors to monitor toxic exhaust gases at high working temperatures is a challenging task due to the low sensitivity and narrow long-term stability of the devices under harsh conditions. Herein, the fabrication of a chemiresistor-type gas sensor is reported for the detection of NO2 gas at 600 °C. The sensing element consists of ZnFe2O4 nanoparticles prepared via a high-energy ball milling and annealed at different temperatures (600-1000 °C). The effects of annealing temperature on the crystal structure, morphology, and gas sensing properties of ZnFe2O4 nanoparticles are studied. A mixed spinel structure of ZnFe2O4 nanoparticles with a lattice parameter of 8.445 Å is revealed by X-ray diffraction analysis. The crystallite size and X-ray density of ZnFe2O4 nanoparticles increase with the annealing temperature, whereas the lattice parameter and volume are considerably reduced indicating lattice distortion and defects such as oxygen vacancies. ZnFe2O4 nanoparticles annealed at 1000 °C exhibit the highest sensitivity (0.13% ppm-1), sharp response (τres = 195 s), recovery (τrec = 17 s), and linear response to 100-400 ppm NO2 gas. The annealing temperature and oxygen vacancies play a major role in determining the sensitivity of devices. The plausible sensing mechanism is discussed. ZnFe2O4 nanoparticles show great potential for high-temperature exhaust gas sensing applications.

Catalytic Oxidation Process for the Degradation of Synthetic Dyes: An Overview.

Dyes are used in various industries as coloring agents. The discharge of dyes, specifically synthetic dyes, in wastewater represents a serious environmental problem and causes public health concerns. The implementation of regulations for wastewater discharge has forced research towards either the development of new processes or the improvement of available techniques to attain efficient degradation of dyes. Catalytic oxidation is one of the advanced oxidation processes (AOPs), based on the active radicals produced during the reaction in the presence of a catalyst. This paper reviews the problems of dyes and hydroxyl radical-based oxidation processes, including Fenton's process, non-iron metal catalysts, and the application of thin metal catalyst-coated tubular reactors in detail. In addition, the sulfate radical-based catalytic oxidation technique has also been described. This study also includes the effects of various operating parameters such as pH, temperature, the concentration of the oxidant, the initial concentration of dyes, and reaction time on the catalytic decomposition of dyes. Moreover, this paper analyzes the recent studies on catalytic oxidation processes. From the present study, it can be concluded that catalytic oxidation processes are very active and environmentally friendly methods for dye removal.

Intrinsic peroxidase-like activity and enhanced photo-Fenton reactivity of iron-substituted polyoxometallate nanostructures.

Heteropolyacids (HPAs) are a class of polyoxometallates (POMs) with oxygen-rich surfaces. Herein, we have developed an Fe-containing heteropolyacid by cation-exchange and employed KFePW12O40 nanostructures for Fenton, photo-Fenton and enzyme-mimetic reactions. The as-prepared KFePW12O40 catalyst exhibits efficient degradation of Rhodamine B (RhB) via the photo-Fenton reaction. As an enzyme-mimetic, this material can effectively oxidize TMB and dopamine. The obtained nanomaterials were characterized via SEM, TEM, XPS, BET surface area, TGA, UV-Vis spectroscopy, FT-IR, and XRD techniques. The photocatalyst has a relatively large surface area of 38 m2 g-1, and the Keggin structure of phosphotungstic ions is kept intact during the preparation. The RhB dye pollutants can be efficiently bleached and degraded up to about 80% within a one hour photo-Fenton reaction under visible light irradiation. Our results indicate that the KFePW12O40 nanomaterial can effectively mimic the enzyme cascade reaction of horseradish peroxidase (HRP). It also has a high affinity toward 3,3',5,5'-tetramethylbenzidine (TMB) for oxidation and henceforth, it has been used for the colorimetric assay of dopamine and H2O2. Overall, our study suggests that KFePW12O40 can be used for the efficient degradation of environmental pollutants. The KFePW12O40 catalyst is stable and can be easily separated from the reaction system for reuse without an obvious loss of activity.

Highly dispersed ultra-small Pd nanoparticles on gadolinium hydroxide nanorods for efficient hydrogenation reactions.

Heterogeneous catalytic hydrogenation reactions are of great importance to the petrochemical industry and fine chemical synthesis. Herein, we present the first example of gadolinium hydroxide (Gd(OH)3) nanorods as a support for loading ultra-small Pd nanoparticles for hydrogenation reactions. Gd(OH)3 possesses a large number of hydroxyl groups on the surface, which act as an ideal support for good dispersion of Pd nanoparticles. Gd(OH)3 nanorods are prepared by hydrothermal treatment, and Pd/Gd(OH)3 catalyst with a low loading of 0.95 wt% Pd is obtained by photochemical deposition. The catalytic hydrogenation of p-nitrophenol (4-NP) to p-aminophenol (4-AP) and styrene to ethylbenzene is performed as a model reaction. The obtained Pd/Gd(OH)3 catalyst displays excellent activity as compared to other reported heterogeneous catalysts. The rate constant of 4-NP reduction is measured to be 0.047 s-1 and the Pd/Gd(OH)3 nanocatalyst shows no marked loss of activity even after 10 consecutive cycles. Additionally, the hydrogenation of styrene to ethylbenzene over Pd/Gd(OH)3 nanorods exhibits a turnover frequency (TOF) as high as 6159 h-1 with 100% selectivity. Moreover, the catalyst can be recovered by centrifugation and recycled for up to 5 consecutive cycles without obvious loss of activity. Our results indicate that Gd(OH)3 nanorods act as a promoter to enhance the catalytic activity by providing a synergistic effect from the strong metal support interaction and the large surface area for high dispersion of small sized Pd nanoparticles enriched with hydroxyl groups on the surface. The high performance of Pd/Gd(OH)3 in heterogeneous catalysis offers a new, efficient and facile strategy to explore other metal hydroxides or oxides as supports for organic transformations.

One-Step Growth of Iron-Nickel Bimetallic Nanoparticles on FeNi Alloy Foils: Highly Efficient Advanced Electrodes for the Oxygen Evolution Reaction.

Electrochemical water splitting is an important process to produce hydrogen and oxygen for energy storage and conversion devices. However, it is often restricted by the oxygen evolution reaction (OER) due to its sluggish kinetics. To overcome the problem, precious metal oxide-based electrocatalysts, such as RuO2 and IrO2, are widely used. The lack of availability and the high cost of precious metals compel researchers to find other resources for the development of cost-effective, environmentally friendly, earth-abundant, nonprecious electrocatalysts for OER. Such catalysts should have high OER performance and good stability in comparison to those of available commercial precious metal-based electrocatalysts. Herein, we report an inexpensive fabrication of bimetallic iron-nickel nanoparticles on FeNi-foil (FeNi4.34@FeNi-foil) as an integrated OER electrode using a one-step calcination process. FeNi4.34@FeNi-foil obtained at 900 °C shows superior OER activity in alkaline solution with an overpotential as low as 283 mV to achieve a current density of 10 mA cm-2 and a small Tafel slope of 53 mV dec-1. The high performance and durability of the as-prepared nonprecious metal electrode even exceeds those of the available commercial RuO2 and IrO2 catalysts, showing great potential in replacing the expensive noble metal-based electrocatalysts for OER.

One-Step In Situ Growth of Iron-Nickel Sulfide Nanosheets on FeNi Alloy Foils: High-Performance and Self-Supported Electrodes for Water Oxidation.

Efficient and durable oxygen evolution reaction (OER) catalysts are highly required for the cost-effective generation of clean energy from water splitting. For the first time, an integrated OER electrode based on one-step direct growth of metallic iron-nickel sulfide nanosheets on FeNi alloy foils (denoted as FeNi3 S2 /FeNi) is reported, and the origin of the enhanced OER activity is uncovered in combination with theoretical and experimental studies. The obtained FeNi3 S2 /FeNi electrode exhibits highly catalytic activity and long-term stability toward OER in strong alkaline solution, with a low overpotential of 282 mV at 10 mA cm-2 and a small Tafel slope of 54 mV dec-1 . The excellent activity and satisfactory stability suggest that the as-made electrode provides an attractive alternative to noble metal-based catalysts. Combined with density functional theory calculations, exceptional OER performance of FeNi3 S2 /FeNi results from a combination of efficient electron transfer properties, more active sites, the suitable O2 evolution kinetics and energetics benefited from Fe doping. This work not only simply constructs an excellent electrode for water oxidation, but also provides a deep understanding of the underlying nature of the enhanced OER performance, which may serve as a guide to develop highly effective and integrated OER electrodes for water splitting.

Highly efficient decomposition of Remazol Brilliant Blue R using tubular reactor coated with thin layer of PdO.

In this work, we propose a novel approach to dye decomposition under subcritical water conditions using a continuous-flow tubular reactor coated with thin layer of PdO as a catalyst. Remazole Brilliant Blue R was used as an example of synthetic dyes. Hydrogen peroxide was used as an environmental-friendly oxidant as it leaves no residues after treatment. The effect of temperature, pressure and dye concentration on total organic carbon (TOC) removal were studied. 99.9% of TOC removal was achieved at 300 °C and 10 MPa pressure within a short residence time of 3.2 s. This method provided an efficient and rapid process that has a potential for treating a wide range of textile wastewaters.