Catalytic Wet Peroxide Oxidation Research Articles

Hybrid multi-core shell magnetic nanoparticles for wet peroxide oxidation of paracetamol: Application in synthetic and real matrices

Clean water availability is becoming a matter of global concern in the last decades. The responsible entities for wastewater treatment do not have the proper facilities to deal with a wide range of pollutants. Special attention should be given to emerging contaminants, whose presence in water bodies may cause adverse effects on the aquatic ecosystem and human health. Most studies in the literature do not consider the development of their solution in real matrices, which can hinder the applicability of the explored alternative in the real scenario. Therefore, in this work, we demonstrate the applicability of hybrid magnetic nanoparticles for removing paracetamol (PCM) from simulated and real matrices by catalytic wet peroxide oxidation (CWPO). To achieve carbon coating, the nanoparticles were prepared via the traditional route (resorcinol/formaldehyde, CoFe@CRF). A new methodology was also considered for synthesizing thin-layered carbon-coated magnetic nanoparticles (phloroglucinol/glyoxalic acid, CoFe@CPG). TEM images revealed a multi-core shell structure formation, with an average carbon layer size of 7.8 ± 0.5 and 3.2 ± 0.3 nm for resorcinol/formaldehyde and phloroglucinol/glyoxalic acid methodology, respectively. Screening the materials’ activity for PCM oxidation by CWPO revealed that the nanoparticle prepared by phloroglucinol/glyoxalic acid methodology has higher performance for the degradation of PCM, achieving 63.5% mineralization after 24 h of reaction, with similar results for more complex matrices. Iron leaching measured at the end of all reactions has proven that the carbon layer protects the core against leaching.

Catalytic wet peroxide oxidation with in-situ generated H2O2: An efficient strategy for improving the stability of metal-organic framework catalysts

Although catalytic wet peroxide oxidation (CWPO) may offer an efficient method for wastewater treatment, the use of metal-organic framework (MOF) catalysts for the CWPO reaction in the presence of H2O2 is challenging because the MOF structure is highly vulnerable to water and/or oxidizing agents. Herein, a range of M-1,3,5-benzenetricarboxylate (BTCs) (M = Fe, Co, Mn, and Cu) were prepared, and their catalytic activities in the CWPO of methyl orange (MO) were evaluated. To examine the stability of the M-BTCs under different reaction conditions, the CWPO reaction was performed with ready-made H2O2 (CWPO-I) or in-situ generated H2O2 using H2 and O2 (CWPO-II). In the latter, Pd was supported onto an M-BTC (Pd/M-BTC). The CWPO-I reaction rate was significantly affected by the metal nodes of the M-BTC, with the Fe-BTC catalyst showing the fastest MO degradation rate. However, regardless of the type of metal node, the M-BTC catalysts underwent significant decomposition during the CWPO-I reaction, leading to a considerable decrease in their textural properties. This result suggests that the M-BTC structure collapsed due to attack by the hydroxyl radicals generated during the reaction. Therefore, the activity of the regenerated Fe-BTC catalyst significantly decreased to 40% of that of the fresh catalyst. In contrast, the catalyst stability in CWPO-II outperformed that in CWPO-I. The Pd/Fe-BTC catalyst exhibited a moderate decrease in activity owing to the gradually reduced surface area of the catalyst during the recycling runs, and the crystallinity of Fe-BTC was preserved. Moreover, the content, particle size, and electronic properties of Pd supported on Fe-BTC showed little change after the reaction. These results demonstrate that the use of in-situ generated H2O2 is superior for impeding the catalyst deactivation caused by structural deformation of the MOF.

Influence of the aqueous matrix on the degradation of cyanotoxins by CWPO: A study on the Iberian Peninsula freshwaters

The increasing occurrence of toxic cyanobacterial blooms worldwide represents a critical health and environmental risk. Catalytic wet peroxide oxidation (CWPO) has emerged as an efficient and environmentally friendly technology for the removal of cyanotoxins in water. Nevertheless, its effectiveness has just been demonstrated in deionized water or simple synthetic aqueous matrices. In this work, the effect of the different components of the aqueous matrix on the CWPO of cyanotoxins was deeply evaluated considering the widespread properties of the Iberian Peninsula freshwaters. The presence of Cl-, HCO3- and SO42- ions reduced the oxidation rate of cylindrospermopsin (CYN) up to 70–80% at the highest concentrations tested (2000, 250 and 500 mg L−1 for Cl-, HCO3- and SO42-, respectively) due to their hydroxyl radical scavenging capacity. The presence of natural organic matter (NOM) resulted in a similar outcome (oxidation rate reduction up to 90% at the highest concentration tested, 20 mg L−1), but in this case due to the consumption of hydroxyl radicals in competition with CYN oxidation. The presence of NO3- and H2PO4- did not show any significant effect on CYN oxidation. Similarly, the presence of cyanobacteria (Chrysosporum ovalisporum, 50 µg chlorophyll-a L−1) did not appreciably affect the CYN oxidation rate. These results were consistent with those obtained by evaluating the impact of real aqueous matrices from drinking water treatment plants (DWTPs) located in Castilla y León and Extremadura regions (Spain) on CWPO performance. This knowledge is key to the implementation of the technology for the treatment of surface waters affected by toxic cyanobacterial blooms.

Polyolefin-derived carbon nanotubes as magnetic catalysts for wet peroxide oxidation of paracetamol in aqueous solutions

This work deals with developing feasible valorization technologies to prepare carbon nanotubes (CNTs) from plastic solid waste and demonstrate their application in catalytic wet peroxide oxidation (CWPO). CNTs were synthesized by catalytic chemical vapor deposition (CCVD) at 850 ºC, considering low-density polyethylene (LDPE), high-density polyethylene (HDPE), and polypropylene (PP) as carbon precursors representative of urban plastic solid waste. Iron oxide nanoparticles supported in alumina, previously synthesized by sol-gel, were used as catalysts in the CCVD process. TEM micrographs allow us to determine 41 nm as the average outer diameter of the CNTs and to visualize magnetic iron nanoparticles (ca. 10 nm) embedded inside the CNTs (ca. 6.4 % of content measured as ashes). These magnetic nanoparticles were kept in the CNT structure even after the purification of the CNTs with sulphuric acid, allowing to obtain magnetic CNTs. All purified and non-purified CNTs prepared from the polyolefins were assessed as catalysts in CWPO of paracetamol (PCM), used as a model pharmaceutical contaminant in water at CPCM,0 = 100 μg mL−1 (CH2O2,0 = 472 μg mL−1, CCNT = 2.5 g L−1, pH0 = 3.5 and T = 80 °C). The concentrations of PCM, H2O2, aromatic and total phenolic compounds were monitored for 24 h. All CNTs showed catalytic activity, allowing the complete degradation of PCM at 6 h of reaction time. The stability and reusability of materials are tested and proved in CWPO.

Use of Fe and Al Containing Electrocoagulation Sludge as an Adsorbent and a Catalyst in Water Treatment

In this study, three different electrocoagulation (EC) sludges were studied as an adsorbent (removal of humic acids) and as a catalyst [catalytic wet peroxide oxidation (CWPO) of bisphenol A (BPA)]. The sludges originated from electrocoagulation process in which aluminum (Al) and iron (Fe) electrodes were used for the treatment of mining industry wastewater. All the materials were used as dried sludge and calcined material. The stability of these materials was studied in neutral and alkaline conditions with analysis of the leached iron content in solution. Based on the EC sludge characterization with X-ray fluorescence (XRF), X-ray diffractometer (XRD), and diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy different forms of Fe occurring in EC sludges were found. The Brunauer–Emmett–Teller (BET) method showed reduced surface area after calcination process. Stability of the sludges was studied in neutral conditions, and the amount of iron leaching was low (<1.4 ppm). Adsorption experiments showed that the removal of humic acids (measured as total organic carbon) was over 50% in all tested materials in the pH range of 3–9, and over 92% with the S3 calcined material in all studied pH range. The calcined samples were catalytically more active than raw material in CWPO of BPA. The highest removal of BPA was 85% over calcined sludge. Therefore, calcined EC sludges are suitable materials for catalyst and adsorbent use. The main novelty of this paper was the finding of sludge modification in the EC process of water treatment through different electrode material and current density. This modification can be made in EC water treatment process, and it may provide low-cost materials to different utilization of EC sludge.

Insights on the removal of the azole pesticides included in the EU Watch List by Catalytic Wet Peroxide Oxidation

Insights on the removal of the azole pesticides included in the EU Watch List by Catalytic Wet Peroxide Oxidation

Cu-based perovskite as a novel CWPO catalyst for petroleum refining wastewater treatment: Performance, toxicity and mechanism

For the first time, Cu-based perovskite oxides were used as catalysts to treat highly toxic and refractory petroleum refining wastewater based on catalytic wet peroxide oxidation (CWPO) technology. Perovskite La2CuO4 was synthesized by sol-gel method. A series of characterizations showed that the synthesized catalyst particles are tetragonal phase perovskite structure. The experimental results showed that under the conditions of catalyst dosage of 0.75 g, temperature of 100 ℃ and reaction time of 30 min, the COD removal rate was 89.58 %, the TOC removal rate was 87.38 %. The morphology and structure of the catalyst before and after the reaction proved that the catalyst has strong stability and catalytic activity. The components of raw water, Wet Air Oxidation (WAO) effluent and CWPO effluent were compared and analyzed by Gas Chromatography-Mass Spectrometry (GC-MS), and the possible mechanism and path of WAO and CWPO degradation of petroleum refining wastewater were further explored. The changes of Cu components in La2CuO4 before and after CWPO reaction and the transformation of lattice oxygen and adsorbed oxygen were analyzed by X-ray Photoelectron Spectroscopy (XPS). The involvement of Cu (Ⅱ) /Cu (Ⅰ) in the activation of H2O2 was speculated. Finally, the biotoxicity of raw water, WAO effluent and CWPO effluent was predicted. The results provide reference value for the application of catalyst La2CuO4 in various petrochemical wastewater.

Selective denitrification of simulated oily wastewater by oxidation using Janus-structured carbon nanotubes

The intense industrial development has resulted in several consequences for human and environmental health, including the increased discharge of oily products in water bodies. Oily products are widely used in industry, often bearing an associated high cost. Finding alternatives to treat oily wastewater aiming at recovering oily and water phases is an approach allowing recovery of products of economic interest. In this work, Janus-like carbon nanotubes (CNTs) were synthesized by varying the feed time of acetonitrile and ethylene, respectively, as nitrogen/carbon and carbon precursors in a chemical vapor deposition (CVD) approach. The CVD approach allowed the synthesis of completely undoped, completely doped and partially doped CNTs with a Janus structure. The CNTs were then tested as catalysts for the selective oxidation of 4-nitrophenol (4-NP) contained in a simulated oily wastewater (2,2,4-trimethylpentane/water (O/W) = 1:9, volume basis) by catalytic wet peroxide oxidation (CWPO). The CWPO experiments were conducted for 24 h, 80 °C, 2.5 g L−1 of catalyst, and the stoichiometric concentration of H2O2 (3.6 g L−1) for the degradation of 4-NP (1 g L−1). The same conditions were kept for experiments conducted under a biphasic system. The catalysts bearing a Janus-like structure were demonstrated to be more effective in CWPO experiments in aqueous-only and biphasic systems for the abatement of 4-NP.

Calcination temperature effects on the physicochemical properties of copper-based wire-meshes: The implications in the CWPO of phenol

This work investigates phenol elimination from water through the Catalytic Wet Peroxide Oxidation (CWPO) reaction using CuO/TiO2-ZrO2 supported on wire-meshes, all with 5 wt.% Cu and calcined at different temperatures. These were characterized by SEM/EDX, elemental mappings, XRD, LRS and XPS, and their mechanical stability was studied. The increment in the calcination temperature generated less reducible Cu2+ species, which impacted in phenol conversion rate, slowing it down. Particularly, when the lower temperatures were applied (500 – 800 °C), copper was found well-distributed on the support and high mineralization values (above 85%) were obtained. Nevertheless, these high TOC conversions were the result of elevated copper leaching (∼ 40 ppm), markedly contributing as a homogeneous catalyst. Contrarily, the application of more extreme temperatures, such as 850 and 900 °C, led to the migration of copper to the inner part of the coating, and consequently to lower copper leaching (7.6 and 0.9 ppm, respectively), due to a protective effect of the support. Accordingly, the corresponding mineralization degrees were lower, 60 and 40%, respectively. An adequate temperature was found (850 °C), with higher mineralization and better mechanical resistance than the catalyst calcined at 900 °C.

Cu(II) impregnated clay-derived HS zeolite: Synthesis, characterization and catalytic activity on catalytic wet peroxide oxidation (CWPO) of phenol

The majority of phenol-containing liquid industrial wastes are discharged into natural waters. As a result, several investigations, such as catalytic wet peroxide oxidation (CWPO), have been conducted to remediate these effluents. Copper-supported heterogeneous catalysts were prepared by an impregnation technique and tested in CWPO of phenol. Both the raw pyrophyllite clay and its zeolite form were used as supports. The samples were characterized by BET specific surface area analysis, X-ray diffraction, X-ray fluorescence, and X-ray photoelectron spectra. The effect of temperature (25–70 °C), the concentration of hydrogen peroxide (2–10 mmol·L−1), and the amount of catalyst (0.5–3 g·L−1) were selected for optimization of the catalytic system H2O2-2.5% Cu/ZP using the response surface methodology based on central composite design. The catalyst (2.5% Cu/ZP), with support of synthesized hydroxysodalite zeolite form, showed the best catalytic activity in comparison to that based on raw pyrophyllite support (2.5% Cu/RP). The maximized degradation was 100% after 4 h at optimum conditions (T = 50 °C, [H2O2] = 6.39 mmol·L−1, catalyst amount = 1.82 g·L−1) with 87.73% of mineralization.

Catalytic Wet Peroxide Oxidation of Anionic Pollutants over Fluorinated Fe3O4 Microspheres at Circumneutral pH Values

Fluorinated Fe3O4 microspheres with 7.1 ± 1.4 wt% of fluoride (F-Fe3O4-1) were prepared via glycothermal synthesis. Fluorination significantly enhanced the activity of F-Fe3O4-1 in catalytic wet peroxide oxidation of anionic dyes (including orange G (OG) and congo red) at pH ~7. However, the promotional effect of fluorination became less obvious for amphoteric rhodamine B and was not observed for cationic methylene blue. After reacting with H2O2 (40 mM) for 2 h at pH 6.5 and 40 °C, the decolorization rates of OG (0.1 mM) and the pseudo-first-order rate constant were 96.8% and 0.0284 min−1 over F-Fe3O4-1 versus 17.6% and 0.0011 min−1 over unmodified Fe3O4. The effects of reaction parameters (initial H2O2 concentration and pH value and reaction temperature) on OG decolorization with H2O2 over F-Fe3O4-1 were investigated. The reusability of F-Fe3O4-1 was demonstrated by OG decolorization in eight consecutive runs. Fluorination increased the isoelectric point of F-Fe3O4-1 to 8.7 and facilitated the adsorption and degradation of anionic dyes on the surface of F-Fe3O4-1 at pH ~7. Scavenging tests and EPR spectra supported that hydroxyl radicals were the main reactive species for the OG decolorization over F-Fe3O4-1.

Catalytic wet peroxide oxidation of phenol through mesoporous silica-pillared clays supported iron and/or titanium incorporated catalysts

Catalytic performances of Silica Pillared Clay (SPC) supports synthesized in different silica amounts both from standard SWy-2 clay mineral and Hançılı region bentonite rock (HWB), and iron (Fe) and/or titanium (Ti) incorporated SPCs in different combinations were evaluated in various advanced Catalytic Wet Peroxide Oxidation (CWPO) of phenol. Host clay mineral type led to different oxidation performances and metal loading created significant increases in the catalytic performance. CWPO performance of Fe-loaded SPCs was better than Ti-loaded ones, so oxidation parameters for Fe–SPCs were studied in detail. Catalyst amount and rise in temperature increased phenol conversion values significantly, and catalysts were more effective in lower pH reaction medium. Aromatic intermediates such as catechol, hydroquinone and benzoquinone formed at the beginning of oxidation were oxidized to carboxylic acids with an advancing oxidation time. The presence of carboxylic acids such as oxalic and formic acid resulted in relatively low total organic carbon (TOC) conversion values. The highest catalytic activity was obtained with high silica content Fe–SPCs synthesized with both host clays. Complete conversion was nearly achieved within 60 min with an experimental condition of T = 30 °C, pH = 3.7 and catalyst/solution ratio = 2 g/L for SWy-2 based catalyst by applying either CWPO or PCWPO (Photo Catalytic Wet Peroxide Oxidation) techniques. SCWPO (Sono Catalytic Wet Peroxide Oxidation) technique also yielded this value at the same oxidation conditions for HWB based catalyst. TOC conversion values at 240 min oxidation time were determined as 33% and 48% for SWy-2 based catalyst with CWPO and PCWPO techniques, respectively, and 37% for HWB based catalyst with SCWPO technique. SWy-2 based catalyst still retained its performance after 3 cycles.

Highly active Mn-Cu bimetallic oxide catalyst assembled as 3D-printed monolithic agitating paddles for advanced oxidation process

Catalytically agitating paddles are essential to perform liquid-solid heterogeneous catalytic reactions on an industrial scale due to the improved mass transfer and easy catalyst recovery. Herein, bimetallic oxides were formed after the calcination of nanomaterials derived from metal-organic frameworks (MOFs). Particularly, Mn(M)-BTC nanomaterials were synthesized by self-assembly of Mn2+ ions (mixed with various dopants such as Cu2+, Ce3+, or Fe2+) and H3BTC ligands in a mixed solvent of ethanol and water. It was found that in the powdery form, the Mn-Cu oxide derivate exhibited the highest degradation rate in the catalytic wet peroxide oxidation process (CWPO process), which was significantly higher than that of single metal oxide as well as Mn-Fe and Mn-Ce oxide derivates. The reason was caused by the synergistic effect between Mn-Cu promoted the formation of Mn3+ and Cu+ species to boost the CWPO reaction. Furthermore, the obtained Mn-Cu powdery catalysts were 3D-printed to obtain monolithic agitating paddles with different geometries, which were then mounted on a central shaft in the stirred reactor. An advanced oxidation process was used to investigate the effect of 3D patterns on the degradation efficiency of various organic dyes. It was discovered that the 3D-printed grid with higher cell density (484 cpsi) had better liquid mixing efficiency and thus better catalytic performance, which could be repeatedly used more than seven times. Additionally, the numerical simulation analysis (computational fluid dynamics) revealed a good mixing efficiency and improved mass transfer in the entire reactor equipped with the designed monolithic agitating impellers.

Removal of Malachite Green Dye from Aqueous Solution by Catalytic Wet Oxidation Technique Using Ni/Kaolin as Catalyst.

In this study, natural Algerian kaolin was used as a support and impregnated with nickel at different loading amounts (2 wt.%, 5 wt.%, and 7 wt.%) in order to prepare a supported catalyst. The wet impregnation technique was used in this preparation; nickel oxide (NiO) was the active phase precursor of the catalyst, and the catalysts were designated as follows: 2%, 5%, and 7% Ni/kaolin. These catalysts were put to the test in catalytic wet peroxide oxidation (CWPO) for degrading the organic contaminant malachite green dye (MG). Analytical techniques such as FTIR spectroscopy, X-ray diffraction, BET, and X-fluorescence were used to examine the structure, morphology, and chemical composition of the support and the produced catalysts. Several parameters, including temperature, catalytic dose, metal loading, hydrogen peroxide volume, and kinetic model were systematically investigated. The combination of improved parameters resulted in a significant increase in the catalytic activity, achieving a high removal rate of MG dye of 98.87%.

Preparing Cu2O/Al2O3 Coating via an Electrochemical Method for the Degradation of Methyl Orange in the Process of Catalytic Wet Hydrogen Peroxide Oxidation

To improve the catalytic efficiency and decrease the reaction temperature of wet air oxidation technology, a Cu2O/Al2O3 coating was prepared on the surface of aluminium alloys by anodizing technology, and subsequent heating treatment. Then, the Cu2O/Al2O3 coating and 3 wt.% H2O2 was used to degrade methyl orange. The influence of the coating’s microstructure, crystalline component on the degradation rate of the methyl orange was studied. The microstructure of the coating was observed by scanning electron microscope. Results proved that the coating was composed of micropores, and Cu2O was evenly dispersed on the surface and pores in the Al2O3 coating. X-ray diffraction pattern analysis demonstrated Cu2O and Al2O3 characteristic peaks were found after the coating was treated at 300 °C, showing that amorphous Cu2O and Al2O3 were transformed into crystalline oxide. A UV-vis spectrophotometer was used to measure the absorbance of methyl orange, and it was found that the maximum absorption wavelength of methyl orange is 460 nm. At that wavelength, the suitable degradation condition of methyl orange was studied, and results showed that when electrochemical deposition time was 30 min and catalyst dosage was 8 g, the degradation rate of methyl orange could reach 92% at 25 °C for 120 min. Furthermore, when the catalyst was reused 9 times, the degradation rate still reached 75%. Based on the above results, a kinetic equation between the degradation rate of methyl orange and catalyst dosage was derived. The microstructure and crystalline component of the catalyst after different reuse times were characterized, and results showed that the catalytic efficiency of the Cu2O/Al2O3 coating decreased with a decrease in the coating’s specific surface area and the ratio of Cu2O in the coating.

Efficient degradation of m-cresol during catalytic wet peroxide oxidation with biochar derived from the pyrolysis of persulfate-ZVI treated sludge

Sludge dewatering is crucial for cutting the cost of sludge post-disposal in wastewater treatment plants. Response surface methodology (RSM) was used in this study to sufficiently investigate the interaction among persulfate, zero-valent iron (ZVI) and reaction time on the sludge dewatering. Under the experimental condition at the central point in RSM, the sludge moisture content was reduced to 54%. The sludge-based biochar obtained from the pyrolysis of persulfate-ZVI treated sludge at the central point in RSM was marked as SC-M and tested for catalytic activity. With the catalyst SC-M, the removal rates of m-cresol and total organic carbon (TOC) were 98.1% and 84.2%, respectively. The persulfate-ZVI treatment for sludge dewatering facilitated increasing the proportion of iron species in SC-M, which contributed to its high catalytic activity. M-cresol degradation with SC-M was a two-period reaction including an induction period and a rapid reaction with the apparent activation energy at a low level. This study integrates the sludge dewatering by persulfate-ZVI treatment and m-cresol degradation by catalytic oxidation with the biochar SC-M prepared from the dewatered iron-rich sludge, providing an effective, economic and environment-friendly approach for sewage sludge utilization and management.

Magnetic CoFe2O4@carbon yolk-shell nanoparticles as catalysts for the catalytic wet peroxide oxidation of paracetamol: kinetic insights

&lt;p&gt;This work focuses on the use of carbon-coated magnetic cobalt ferrite nanoparticles as catalysts for catalytic wet peroxide oxidation (CWPO) of the emerging concern pollutant paracetamol (PCM). The magnetic core of the catalyst is composed of CoFe2O4 developed by a sol-gel method. The core is subsequently coated with a formaldehyde-resorcinol resin and TEOS, further carbonized at 600 ºC, and etched with NaOH to create a yolk-shell structure denoted as CoFe2O4@void@C. X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transformed infra-red (FTIR) analysis revealed that the uncoated core is composed of a CoFe2O4 cubic spinel structure with a crystallite size of 53 nm calculated using the Williamson-Hall (W-H) method, matching very well the average size observed by TEM (53.51  4.2 nm). Comparing the performances of CoFe2O4@void@C and the bare CoFe2O4 in the CWPO of paracetamol, total organic carbon (TOC) removals of 58% and 46% are obtained respectively after 24 h of reaction. An empirical kinetic model based on second-order and autocatalytic expressions was developed to suitably describe the decomposition of H2O2 and the removal of paracetamol using CoFe2O4@void@C as catalyst. The disappearance of TOC was well-described (r2 = 0.98) by a lumped kinetic model as the sum of TOCA, TOCB and TOCC, where TOCA is the TOC of the PCM, TOCB refers the intermediate products and TOCC is the TOC of the final products obtained during the CWPO of PCM.&lt;/p&gt;&#x0D;

Pillared clay-based catalysts for treatment of 4-nitrophenol solutions by catalytic wet peroxide oxidation

&lt;p&gt;The constant development of technological processes aggravates the problem of pollution, due to a significant change in the composition of effluents, which makes necessary new (and/or improved) treatment methods and catalytic materials. In this sense, the use of natural clays in the synthesis of low-cost pillared clays for application as catalysts in oxidation technologies for the treatment of wastewaters is relevant from an environmental and sustainable point of view. In this work, inexpensive natural clays from different regions of Kazakhstan (Akzhar, Karatau, and Kokshetau) were used in the preparation of pillared clays for the catalytic oxidation of organic pollutants with H2O2. Since nitrophenols are commonly found in many types of industrial wastewaters (e.g. plastic, pharmaceutical, paper, or pesticides industries), 4-nitrophenol (4-NP) was used as a representative model compound in the catalyst screening studies. The pillaring process of the targeted natural clays involved the incorporation of active metals such as Zr, Fe, and Cu, which were responsible for increasing the catalytic activity of the materials relative to the natural clays. High conversions of TOC (85%) and of 4-NP (100%) were obtained with the Zr-pillared clay from the Akzhar region.&lt;/p&gt;&#x0D;

Coupling photocatalytic water oxidation on decahedron BiVO4 crystals with catalytic wet peroxide oxidation for removing organic pollutions in wastewater

Catalytic wet peroxide oxidation (CWPO) is widely used to remove organic pollutants in industrial wastewater, however, the remained challenges in circulating Fe3+/Fe2+ ions, inevitably forming iron sludge and massively consuming H2O2 limit its applications. Herein, the coupling of CWPO and photocatalytic water oxidation on decahedron BiVO4 crystals was reported to solve the above challenges. Using spatial photogenerated charge separation between different facets of BiVO4, efficiently circulating Fe3+ to Fe2+ was realized with a selectivity of ~100%, which greatly inhibits the formation of iron sludge. Moreover, in-situ formation of H2O2 through two-hole-involved photocatalytic water oxidation on BiVO4 replenishes the H2O2 consuming in the CWPO process. The coupling system exhibits a much higher total organic carbon (TOC) removal than the CWPO process in various pollutants, giving an improvement of rate constant to more than 10 times. This work provides a potential coupling route for advanced degradation of organic pollutants in wastewater treatment.

Synthesis design of Cu/Al2O3 catalysts to decrease copper leaching in the catalytic wet peroxide oxidation of phenol

This work aims to study the catalytic performance of Cu/Al2O3 catalysts in the catalytic reaction of oxidation of phenol. The addition of La and Mn to Al2O3 support and the calcination temperature influence on the catalytic performance and Cu leaching were studied. The addition of either La or Mn to the support triggered less Cu leaching compared to the unmodified support. The catalysts modified with Mn and calcined at 650ºC and 900 °C yielded low Cu leaching values and high phenol conversions at 120 min of reaction, achieving total consumption of H2O2. The catalysts prepared in the same way but modified with La and calcined at 900 °C, achieved 100% phenol conversion and higher TOC conversion. Copper leaching was higher when the support was modified with La, but improved when compared to the unmodified support, suggesting that the presence of Mn allowed a better anchoring of Cu on the support. However, this was not beneficial for the reaction since a certain amount of Cu in the homogeneous phase was required for the reaction to start. Cu-La-Al2O3 showed stability after consecutive reaction cycles with the corresponding calcinations in each cycle.