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Among various advanced oxidation processes for wastewater treatment, heterogeneous catalytic ozonation (HCO) has a growing interest in pollutant degradation, e.g., pesticides, pharmaceuticals, cresols, detergents, polymers, dyes, and others. Direct oxidation with ozone can occur by this route or indirectly, generating reactive oxygen species through the catalytic activation of the ozone molecule. Then, many catalytic materials were evaluated, such as unsupported and supported oxides, activated carbon, nanocarbons, carbon nitride, and mesoporous materials. This review focuses on the properties and performance of Ni-based catalysts (NiO, supported NiO, Ni ferrites, and M-Ni bimetallic), emphasizing the reaction mechanisms and the importance of the reactive oxygen species in removing toxic organic compounds.

Diethyl phthalate (DEP) is a pollutant which can be found on soils as a result of its widespread application in plastic industry. Soil contaminated with DEP requires the application of different chemical methods to attain its remediation. Among these methods, ozonation has proven to be effective against toxic soil pollutants. The presence of metal oxides in soil is a possible source of catalytic effect. In this study, it was analyzed the catalytic effect of goethite (α-FeOOH), hematite (α-Fe2O3), and gibbsite (γ-Al(OH)3) in combination with O3 to achieve DEP decomposition. The DEP elimination efficiency by ozonation on the sand increased according to the following order: without catalyst

The carbamazepine (CBZ) abatement is herein evaluated using catalytic ozonation at different NiO concentrations as catalyst: 100, 300, and 500 mg L−1, revealing its total destruction after 5 min of reaction either by conventional or catalytic ozonation. The NiO incorporation in the reactor does not increase the destruction rate, but the catalyst presence enhances the partial mineralization of the contaminant by conversion into oxalic and formic acids and the removal of total organic carbon (TOC) associated with the formation of oxidant species such as hydroxyl radical. Evidence for this behavior is the accumulation rate of the above acids which rise proportionally to the NiO concentration. The highest NiO concentration (500 mg L−1) reached a maximum TOC removal of 79.2%, which exceeds by 50% the outcome of the conventional treatment. The accumulation-decomposition profiles of oxalic and formic acids suggest the occurrence of simultaneous reaction mechanisms (hydroxyl radicals and complex formations) on the catalyst during CBZ ozonation. According to XPS analysis, the presence of nitrogen species in the NiO-ozonated was attributable to byproducts of CBZ decomposition. The toxicity bioassay based on Lactuca sativa seeds demonstrate that ozonated samples attained similar plant germination than the reference substance (water) after 120 min of treatment. This result is comparable with or without the catalyst presence, indicating the formation of non-toxic accumulated byproducts at the end of the ozonation reaction.

A low-cost and durable BiVO4 photoelectrode (PE) is herein synthesized to improve the separation of the electron and hole pair in photoelectrochemical applications. A new synthesis method was envis...

In this work, the degradation of terephthalic acid (TA) by vanadium oxide (VxOy) supported on zinc oxide (ZnO) was evaluated in a photocatalytic ozonation treatment based on two UV-A LEDs distribut...

This study evaluates naproxen (NP) degradation efficiency by ozonation using nickel oxide films (NiO(F)NiO(F)) as a catalyst. The NiO films were synthesized by chemical vapor deposition and characterized by X-ray diffraction, scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy. NP degradation was conducted for 5 min using 10 films of NiO(F) comparing against ozonation using 100 mg/L NiO powder in suspension (NiO(s)NiO(S)) and conventional ozonation (O3-conv). Total organic carbon analysis demonstrated a mineralization degree of 12% with O3O3-conv, 35% with NiONiO as powder and 22% with NiO(F)NiO(F) after 60 min of reaction. The films of NiO(F)NiO(F) were sequentially used 4 times in ozonation demonstrating the stability of the synthesized material, as well as its properties as a catalyst for ozonation. A proposed modeling strategy using robust parametric identification techniques allows the comparison of NP decomposition pseudo-monomolecular reaction rates.

This work reports the study of the decomposition of three PAHs (anthracene, phenanthrene, and fluorene) in aqueous solution at different pHs (2, 7, and 11) and in the presence of methanol as a co-s...

The aim of this study was to characterize the ozone reaction with phenanthrene adsorbed in two types of soils (sand and agricultural). The effect of soil physicochemical properties (texture, bulk density, particle density, porosity, elemental composition, permeability, surface area and pore volume) on the phenanthrene decomposition was evaluated. Commercial sand has a uniform morphology (spherical) with a particle size range between 0.178 and 0.150 mm in diameter, regular elemental composition SiO2, specific density of 1701.38 kg/m3, a true density of 2492.50 kg/m3, with an effective porosity of 31%. On the other hand, the agricultural soil had heterogeneous morphology, particle size between 0.1779 and 0.05 mm in diameter, elemental composition was montmorrillonite silicon oxide, apparent density of 999.52 kg/m3, a true density of 2673.55 kg/m3, surface area of 34.92 m2/g and porosity of 57%. The percentage of phenanthrene decomposition in the sand was 79% after 2 h of treatment. On the other hand, the phenanthrene degradation in the agricultural soil was 95% during the same reaction time. The pore volume of soil limited the crystal size of phenanthrene and increased the contact surface with ozone confirming the direct impact of physicochemical properties of soils on the decomposition kinetics of phenanthrene. In the case of agricultural soil, the effect of organic matter on phenanthrene decomposition efficiency was also investigated. A faster decomposition of initial contaminant and byproducts formed in ozonation was obtained in natural agricultural soil compared to the sand. The partial identification of intermediates and final accumulated products produced by phenanthrene decomposition in ozonation was developed. Among others, phenanthroquinone, hydroquinone, phenanthrol, catechol as well as phthalic, diphenic, maleic and oxalic acids were identified.

In the present study, ozone was applied for the removal of dimethyl phthalate (DMP) from soil. The effect of several experimental parameters was investigated considering, the initial DMP concentration, ozone flow, the type of soil (sand and agricultural soil) and the presence of α-FeOOH as a potential catalyst in the reaction system with sand. The elimination of DMP using ozone is significantly affected by the type of soil. In the case of sand, conventional ozonation was capable to degrade 74% of the initial DMP concentration (0.5 mg g−1) after 8 h of the reaction, however, the mineralization degree was below 50%. Under the same experimental conditions, the complete elimination of DMP was achieved when calcined agricultural soil was present reaching a 70% of mineralization. The presence of metal oxides in calcined agricultural soil combined with ozone produced oxidants species which were responsible of incrementing the mineralization degree (around 20% in comparison with the sand). The toxicity tests on lettuce seed demonstrated lower toxicity of DMP byproducts after ozonation. The DMP high removal efficiencies and the lower toxicity of generated byproducts in soil prove the applicability of ozone treatment for soil remediation.

This work evaluated the inhibition effect of low molecular weight alcohol (ethanol) on naproxen (NAP) degradation by conventional and catalytic ozonation. The reaction system considered the ethanol as complementary organic matter in water. The conventional ozonation and in the presence of nickel oxide (O3–NiO) achieved 98% NAP degradation during the first 15 min of reaction despite the presence of ethanol. However, NAP degradation presented a delaying effect during the first minutes of treatment with this alcohol. The latter phenomenon indicates that ethanol concentration played a meaningful role in ozonation effectiveness in comparison with the presence of NiO catalyst. The presence of NiO did not generate differences in the byproducts in comparison with conventional ozonation. The intermediates were detected using the Electrospray Ionization Mass Spectrometry technique and have only one aromatic ring in their chemical structure. In samples without ethanol, these byproducts appeared only in the first 5 min of reaction. The TOC study demonstrated the increment of 25% in the mineralization degree with the presence of NiO due to the formation of ·OH species.

Coupling TiO2 with narrow band gap semiconductors has been a strategy to obtain visible light active photocatalysts. In this work we present, the characterization and photocatalytic results of high-loaded CuO–TiO2 composites prepared by impregnation of TiO2 powder (Evonik, P25) with copper acetate followed by calcination. The resulting composite materials were characterized by X-ray diffraction, nitrogen adsorption/desorption, UV–vis diffuse reflectance, scanning electron microscopy, X-ray photoelectron spectroscopy and time-resolved microwave conductivity. The photocatalysts were used to degrade gallic acid by using low power ultraviolet and visible light emitting diodes (UV-LED and Vis-LED) as light sources. According to the results, the photocatalytic degradation of the pollutant was efficiently converted to several intermediate products and partially mineralized to CO2 by using visible light. These results were explained in terms of an enhancement of the optical and electronic properties of TiO2 by the presence of Cu2O and CuO phases.

Naphthalene (NA) is a polycyclic aromatic hydrocarbon with toxic properties in aquatic systems. Ozonation (O3) and catalytic ozonation (O3-cat) processes are attractive alternatives of degradation for this kind of compound. NA (20 mg L−1) degradation by conventional and catalytic ozonation in the presence of a cosolvent (ethanol) was the aim of this study. This solution was proposed to simulate some aspects of real wastewaters where not only water acts as solvent. Two proportions of the mixture ethanol/water were selected (30:70 and 50:50) with the purpose of studying the cosolvent effect on NA degradation system by ozonation. O3-cat process used nickel oxide as catalyst (0.1 g L−1). The degradation analysis of NA by O3-cat in two different proportions of cosolvent showed that in the case of 30:70 (ethanol/water), a 95 % of NA elimination in 60 min was obtained, while in the case 50:50 (ethanol/water), only 55 % was achieved. The O3 process showed similar results of degradation to the initial compound in comparison with catalytic system. According to these results, there is an inhibition effect in pollutant removal by ethanol due to the higher ethanol concentration; the lower elimination rate of NA was obtained (by 40 % during the 60 min). The by-products analysis of ozonation process detected oxalic and formic acids. Treatments with NiO presented less production of organic acids in comparison with conventional ozonation process. The high concentration of ethanol has a relevant factor in the elimination of NA and formation of organic acids; samples with 50 % of cosolvent have showed a higher concentration of organic acids. X-ray photoelectron spectroscopy (XPS) study of O3-cat of diluent (O3-NiO control) and O3-NA-NiO showed the presence of –CO3 absorbed on catalyst due to ethanol decomposition.

With the aim of exploring and comparing the photocatalytic degradation of 2,4-Dichlorophenoxyacetic acid (2,4-D) under visible light, BiVO4 was synthesized by using coprecipitation and hydrothermal methods and modified with silver nanoparticles (AgNP) employing a photo-deposition method. X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy were some of the characterization techniques used. A particular synergy was observed when decorating the hydrothermally prepared BiVO4 with AgNP, showing the higher degradation/mineralization of 2,4-D. According to the results, AgNP served as efficient co-catalysts of BiVO4, allowing the electron separation/transfer to generate the OH radicals required for the reaction. A parallel pathway of 2,4-D photodegradation was proposed, including 2,4-Dichlorophenol and oxalic acid as the main intermediary compounds. Active species trapping experiments demonstrated that the photogenerated holes play a fundamental role in promoting both the direct oxidation of 2,4-D and generation of OH radicals.

Ceria films (CeO2(f)) were deposited on glass substrate by a spray pyrolysis method. The catalytic oxidation performance of CeO2(f) was evaluated in the removal of 4-chlorophenol (4-CPh) and 4-phenolsulfonic acid (4-SPh). The catalytic oxidation reactions were carried out in water with ozone as an oxidant agent. Conventional and catalytic ozonation achieved complete removal of both compounds. Furthermore, TOC results showed higher catalytic activity with six CeO2(f) films in comparison with conventional ozonation after 120 min for the oxidation of both 4-CPh and 4-SPh. After five consecutive reuses of CeO2(f), the similar TOC removal for 4-CPh demonstrated the ceria films stability.

Organic acids (OAs) are usually used as refractory model compounds that require prolonged reaction time for their mineralization by different treatments. In this study, benzoic and phthalic acids in aqueous solution were significantly degraded and mineralized by catalytic ozonation in the presence of nickel oxide (NiO). For instance, only 42% mineralization was obtained by direct reaction with molecular ozone, while by catalytic ozonation 98% was achieved. These surprising results led to study in depth the role of NiO in the catalytic ozonation of both organic acids. With the aim of identifying the surface species responsible for the high activity of NiO, X-ray photoelectron spectroscopy (XPS) and high performance liquid chromatography (HPLC) were used as the main analytical tools. According to the results, the mineralization of both organic acids was directly influenced by the organic groups adsorbed onto the NiO surface. Therefore, NiO plays a relevant role as a catalyst forming complex surface compounds which are subsequently decomposed increasing the mineralization efficiency. In addition, a simplified kinetic study was conducted to characterize the effect of NiO concentration on the removal efficiency of both organic acids and the accumulation and degradation of the main byproduct (oxalic acid). These results were explained in terms of a combination of two reaction mechanisms such as conventional ozonation and indirect reaction based on ˙OH radicals.

The heterogeneous catalytic ozonation on unsupported and supported oxides has been successfully tested for the removal of several refractory compounds in aqueous solution. In this work, alumina-supported nickel catalysts prepared by photodeposition and impregnation methods were compared in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). The catalysts were characterized by high-resolution electron microscopy and X-ray photoelectron spectroscopy. The photochemical decomposition of Ni acetylacetonate to produce Ni(OH)2, NiO, and traces of Ni° deposited on alumina was achieved in the presence of benzophenone as a sensitizer. A similar surface composition was found with the impregnated catalyst after its reduction with hydrogen at 500 °C and exposed to ambient air. Results indicated a higher initial activity and maleic acid (byproduct) concentration with the photodeposited catalyst (1 wt% Ni) compared to the impregnated catalyst (3 wt% Ni). These findings suggest the use of the photodeposition method as a simple and reliable procedure for the preparation of supported metal oxide/metal catalysts under mild operating conditions.

Efficient degradation of 2,4-dichlorophenoxyacetic acid (2,4-D, herbicide) aqueous solutions was achieved on NiO/SiO 2 catalysts in presence of ozone. NiO nanoparticles were deposited on the silica surface by impregnation (I) and liquid phase photodeposition (P) in presence of sensitizers (acetone or benzophenone). The most promising method of preparation appears to be the sensitized photodeposition allowing a higher reduction of the precursor (Ni(acac) 2 ) at short irradiation time. The resulting catalysts were characterized by transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM–EDS), and X-ray photoelectron spectroscopy (XPS). It was found from TEM observations, that the size of NiO nanoparticles was smaller than 2 nm for both preparation methods, however the particle size distribution for impregnated catalyst was broader than that of photodeposited catalyst. On the other hand, the surface composition of both catalysts was similar, showing Ni(0), NiO, Ni(OH) 2 as the main species for impregnation, in the case of photodeposition an additional contribution of Ni(acac) 2 were detected. According to the results of catalytic ozonation of 2,4-D, the initial specific activity of the photodeposited catalyst was almost 7 times higher compared with that of impregnation catalyst.

Terephthalic acid (TA) is considered as a refractory model compound. For this reason, the TA degradation usually requires a prolonged reaction time to achieve mineralization. In this study, vanadium oxide (VxOy) supported on titanium oxide (TiO2) served as a photocatalyst in the ozonation of the TA with light-emitting diodes (LEDs), having a bandwidth centered at 452 nm. The modified catalyst (VxOy/TiO2) in combination with ozone and LEDs improved the TA degradation and its by-products. The results obtained by this system were compared with photolysis, single ozonation, catalytic ozonation, and photocatalytic ozonation of VxOy/TiO2 with UV lamp. The LED-based photocatalytic ozonation showed almost the same decomposition efficiency of the TA, but it was better in comparison with the use of UV lamp. The oxalic acid accumulation, as the final product of the TA decomposition, was directly influenced by either the presence of VxOy or/and the LED irradiation. Several by-products formed during the TA degradation, such as muconic, fumaric, and oxalic acids, were identified. Besides, two unidentified by-products were completely removed during the observed time (60 min). It was proposed that the TA elimination in the presence of VxOy/TiO2 as catalyst was carried out by the combination of different mechanisms: molecular ozone reaction, indirect mechanism conducted by ·OH, and the surface complex formation.

2,4-Dichlorophenoxyacetic acid (2,4-D) is usually used as a refractory model compound that requires a prolonged reaction time for mineralization. In this study, we found that nickel oxide (NiO) significantly improved 2,4-D degradation and mineralization in reaction with ozone. Other metal oxides, such as titania, silica and alumina, were also tested in this reaction, so that, the mineralization degree was almost the same for all of them (ca. 25%), whereas NiO showed more than 60% in 1 h. These outstanding results led us to study in more depth the role of NiO as catalyst in the degradation of 2,4-D. For instance, the optimum NiO loading amount was 0.3 g L −1 . The catalytic ozonation showed a high stability after three reaction cycles. With the aim of identifying the surface species responsible for the high activity of NiO, besides knowing the byproducts during the degradation of 2,4-D, XPS and HPLC were mainly used as analytical tools. According to the results, the mineralization of 2,4-D was directly influenced by the adsorbed chlorate organic compounds and oxalate group onto NiO. Therefore, NiO plays a true role as a catalyst forming surface compounds which are subsequently decomposed causing an increase in the mineralization efficiency. In addition, it was possible to identify several degradation byproducts (2,4-diclorophenol, glycolic, fumaric, maleic and oxalic acids) that were included in a rational reaction pathway. It was proposed that 2,4-D elimination in presence of NiO as catalyst is a combination of processes such as: conventional ozonation, indirect mechanism ( OH) and surface complex formation.

Surface modifications of catalysts (TiO2 and Ni/TiO2) were studied after ozonation using isoelectric point determination (IEP) and X-ray photoelectron spectroscopy (XPS) techniques. The catalysts were tested in the degradation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in aqueous solution. According to the results, the initial activity of Ni/TiO2 catalysts was 26% higher compared with the conventional ozonation. This behavior was explained in terms of a change in the surface chemical composition of the catalysts after ozonation, supported by XPS results in the region O1s and Ti2p. In general, the oxidation of metallic Ni to NiO, the formation of ∗Ti4+ and ∗O species in the Ni/TiO2 (P) catalyst, and the presence of abundant –OH groups in the catalytic surface was observed.

Different photochemical approaches have been investigated to prepare supported nickel nanoparticles to be used in the catalytic ozonation of 2,4-dichlorophenoxyacetic acid (2,4-D). Direct photochemical ( λ = 365 nm, without TiO 2 ) and photocatalytic deposition in presence or absence of sensitizers (TiO 2 , acetone or benzophenone) were employed. The characterization of the catalysts was carried out by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The photocatalytic deposition without any sensitizer resulted to be the most suitable method to obtain in very short irradiation time, Ni nanoparticles randomly distributed over the support with a particle size ranging from 7 to 15 nm. An optimization of this technique was performed by varying the mass of TiO 2 and the light intensity. According to the results of 2,4-D degradation, the catalytic ozonation with Ni/TiO 2 catalyst presented a slightly higher conversion than TiO 2 or ozonation alone. These results were explained in terms of the two phases (NiO/Ni) present on the surface of TiO 2 which favor the ozone decomposition forming OH radicals useful for 2,4-D degradation. A reaction pathway including all the intermediates formed during the direct attack of ozone and the produced OH radicals was proposed.

Metallic nanoparticles may be tailored to obtain specific size and morphology. In this work we present the synthesis of Ni/TiO2 catalysts by a photodeposition method. Our investigation included the photochemical and photocatalytic reduction of the nickel organometallic precursor (Ni (II) acetylacetonate) over titania (Degussa P-25) support. The photo-reduction kinetics was followed by UV-Vis and the catalysts were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). According to the results, the photochemical reduction of the Ni precursor was only 30% at λ= 254 nm, whereas, the photocatalytic route was approximately 90 % (λ= 365 nm) yielding Ni nanoparticles with diameter ranging from 10 to 40 nm.