Catalytic Oxidation Degradation Research Articles

Catalytic oxidative degradation of paracetamol in water solutions over Al/Fe -pillared clay

Catalytic oxidative degradation of paracetamol in water solutions over Al/Fe -pillared clay

Study on the grading preparation of multifunctional materials and application from coal gasification fine slag

Alkali activation at high temperatures serves as a significant method for the resource reuse of coal gasification fine slag (CGFS). This experimental approach used CGFS, coal-based solid waste, to prepare multifunctional materials and neither waste acid nor alkali was discharged in the process. Using this method, MCM-41 with hexagonal mesopores and carbon/zeolite composite with NaP-type zeolite structures were prepared hierarchically. It is noteworthy that this synthetic method incorporates Al from CGFS into MCM-41, which enhances the acidic sites of the material. This modification endows MCM-41 with potential application in catalyzing guaiacol. Under the same conditions, CGFS-based MCM-41 demonstrated the capacity to convert guaiacol into cyclohexane. In contrast, commercial MCM-41 exhibited the ability to catalyze the conversion of guaiacol into cyclohexanol and cyclohexane. At the same time, the carbon/zeolite composite retains the Fe in CGFS and can be used for the catalytic oxidative degradation of tetracycline. The carbon/zeolite composite was able to degrade 100 mL of 100 mg‧L−1 tetracycline solution by 99.38 % in 120 min at dose of 30 mg, an H2O2 concentration of 25 mmol‧L−1 and solution pH of 3. This research outlines a promising approach for the innovative concept of "turning waste into treasure."

Efficient degradation of vulcanized natural rubber into liquid rubber by catalytic oxidation

Waste tire rubber based on natural rubber (NR) represents an abundant feedstock for the production of valuable products. This study investigated an efficient approach to convert NR vulcanizates into liquid rubber with the number-average molar masses of 1.3 × 104 g/mol. Compared to the anaerobic liquefaction at 300 °C for 3 min, NR vulcanizates were liquefied efficiently at 210 °C for 3 min by thermo-oxidative degradation catalyzed by manganese (II) stearate. The apparent activation energy of the NR degradation reaction decreased from 470.8 kJ/mol to 208.2 kJ/mol with catalysis, which was attributed to the formation of a coordination complex between catalysts and peroxides via the single-electron transfer redox reaction, leading to the catalytic oxidative degradation of NR vulcanizates. The main chain scission and crosslink scission occurred simultaneously during the degradation process, and the main chain scission was the primary catalytic oxidation reaction according to the Horikx theory. In addition, the obtained liquid rubber contained carbonyls, ether linkages, and sulfoxide groups, as proved by FTIR and 13CNMR . The catalytic oxidative degradation mechanism of NR vulcanizates was proposed based on the chemical structure of products and simulation results. The efficient method was proposed to highly facilitate the recycling and valorization of NR-based waste tire rubber.

Catalytic wet oxidation degradation of malachite green with Cu-coated sediment as catalyst: parameter optimization using response surface methodology

Catalytic wet oxidation degradation of malachite green with Cu-coated sediment as catalyst: parameter optimization using response surface methodology

Status of rare-earth perovskite catalysts in environmental applications

Rare-earth perovskite oxides have become a research hotspot in the fields of environment and energy owing to their structural tunability, excellent redox properties, high stability and high catalytic activity. Researchers have designed and developed different rare-earth perovskite catalysts for tackling environmental pollutants in recent years. This review summarizes recent research progress on rare-earth perovskite catalysts in the catalytic oxidation and photocatalytic degradation of pollutants, gas sensing of volatile organic compounds and photocatalytic water splitting for hydrogen production and carbon dioxide reduction and conversion, and summarizes the mechanism of these reactions. It also discusses in detail the relationship between structural modification, synthesis process and the physical–chemical properties of the catalysts. Finally, the challenges with rare-earth chalcocite catalysts in the field of environment and energy are discussed.

Fe-ZSM-5 zeolite catalyst for heterogeneous Fenton oxidation of 1,4-dioxane: effect of Si/Al ratios and contributions of reactive oxygen species.

Heterogeneous Fenton oxidation using traditional catalysts with H2O2 for the degradation of 1,4-dioxane (1,4-DX) still presents challenge. In this study, we explored the potential of Fe-ZSM-5 zeolites (Fe-zeolite) with three Si/Al ratios (25, 100, 300) as heterogeneous Fenton catalysts for the removal of 1,4-DX from aqueous solution. Fe2O3 or ZSM-5 alone provided ineffective in degrading 1,4-DX when combined with H2O2. However, the efficient removal of 1,4-DX using H2O2 was observed when Fe2O3 was loaded on ZSM-5. Notably, the Brønsted acid sites of Fe-zeolite played a crucial role during the degradation of 1,4-DX. Fe-zeolites, in combination with H2O2, effectively removed 1,4-DX via a combination of adsorption and oxidation. Initially, Fe-zeolites demonstrated excellent affinity for 1,4-DX, achieving adsorption equilibrium rapidly in about 10min, followed by effective catalytic oxidative degradation. Among the Fe-ZSM-5 catalysts, Fe-ZSM-5 (25) exhibited the highest catalytic activity and degraded 1,4-DX the fastest. We identified hydroxyl radicals (·OH) and singlet oxygen (1O2) as the primary reactive oxygen species (ROS) responsible for 1,4-DX degradation, with superoxide anions (HO2·/O2·-) mainly converting into 1O2 and ·OH. The degradation primarily occurred at the Fe-zeolite interface, with the degradation rate constants proportional to the amount of Brønsted acid sites on the Fe-zeolite. Fe-zeolites were effective over a wide working pH range, with alkaline pH conditions favoring 1,4-DX degradation. Overall, our study provides valuable insights into the selection of suitable catalysts for effective removal of 1,4-DX using a heterogeneous Fenton technology.

Synthesis of Kaolin-Supported Nickel Oxide Composites for the Catalytic Oxidative Degradation of Methylene Blue Dye.

Organic dye contamination of water is a contributing factor to environmental pollution and has a negative impact on aquatic ecology. In this study, unsupported NiO and kaolin-supported NiO composites were synthesized by a one-step wet impregnation-precipitation method through the precipitation of nickel hydroxide onto locally accessible, inexpensive, and easily treated kaolin surfaces by using sodium hydroxide as a precipitating agent. The product was calcined at 500 °C and used for the catalytic oxidative degradation of methylene blue (MB) dye in an aqueous solution. The morphology, structure, and interactions of the synthesized materials were explored by SEM, XRD, and FT-IR spectroscopy. The characterization results revealed the fabrication and the growth of NiO on the kaolin surface. To determine the catalytic oxidative degradation performance of the catalyst, many experiments have been performed using the MB dye as a model dye. The catalytic degradation tests confirmed the importance of NiO and the high catalytic activity of the synthesized NiO/kaolin composite toward MB dye degradation. The oxidative degradation results showed that the optimized precursor amount on the kaolin surface could efficiently enhance the removal of MB dye. The kinetic investigation of the catalytic degradation of MB dye fitted the pseudo-first-order kinetic model. High removal efficiency was observed after eight reuse cycles, proving the exceptional stability and reusability of the composite. The catalytic process also proceeded with a low activation energy of 30.5 kJ/mol. In conclusion, the kaolin-supported NiO composite was established to be a favorable catalyst to degrade a model dye (MB) from an aqueous solution in the presence of inexpensive and easily available NaOCl with a catalytic efficiency of the material higher than 99% of the 20.3 mg catalyst within 6 min with an apparent rate constant, kapp, higher than 0.44625 min-1, which is far better than that of the unsupported catalyst with a kapp of 0.0926 min-1 at 10 mg dose in 20 min.

Recent advances in oxidative degradation of plastics.

Oxidative degradation is a powerful method to degrade plastics into oligomers and small oxidized products. While thermal energy has been conventionally employed as an external stimulus, recent advances in photochemistry have enabled photocatalytic oxidative degradation of polymers under mild conditions. This tutorial review presents an overview of oxidative degradation, from its earliest examples to emerging strategies. This review briefly discusses the motivation and the development of thermal oxidative degradation of polymers with a focus on underlying mechanisms. Then, we will examine modern studies primarily relevant to catalytic thermal oxidative degradation and photocatalytic oxidative degradation. Lastly, we highlight some unique studies using unconventional approaches for oxidative polymer degradation, such as electrochemistry.

Application, performance and mechanism of high-entropy catalysts for degradation of heterocyclic compounds

High-entropy catalysts have attracted great interest due to their unique microstructures, excellent thermal stability and catalytic activity for various reactions. In this study, three high-entropy catalysts were prepared by doping CeO2 with transition metal oxides that have full redox cycle capability. Their performance for the ultra-fast catalytic oxidation degradation of heterocyclic compounds was investigated. Compared with the reaction without catalysts, the high-entropy catalysts could significantly shorten the residence time and improve the reaction efficiency, indicating that they could promote the oxidation reaction. Under the conditions of reaction temperature (T) = 390 °C and oxidation coefficient (OC) = 2.90, the chemical oxygen demand (COD) removal rate of the high-entropy oxide catalyst (AlTiCeFeCu)Ox@TA reached 94.52 % after 8 min of reaction. Moreover, characterization analysis revealed that the high-entropy catalysts prepared by doping appropriate transition metal oxides exhibited excellent catalytic activity and stability, providing new insights for the research of efficient catalysts in the ultra-fast oxidation system.

Catalytic oxidative degradation of crystal violet dye using NanoCopper oxide encapsulated zeolite catalyst

A new active zeolite supported copper catalyst was developed from coal fly ash (FA) by immobilization of copper nanoparticles. Zeolite (Zeo) was created by FA via acid and hydrothermal synthesis methods. The metal salt CuCl2 was reduced to copper nanoparticle by using (nithyakalyani) Catharanthus roseus leaf extract. The formed copper nanoparticle was encapsulated into the zeolite framework by mechanical stirring followed by calcination at 550 °C. The prepared CuO-Zeo catalyst has been defined by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Scanning electron microscope (SEM) and Energy dispersive X-ray (EDX) techniques. Catalytic activity of the synthesized CuO-Zeo catalyst was investigated by crystal violet dye degradation by wet catalytic method in the presence of H2O2. Effect of catalyst dosage, catalyst variation, dye content, volume of H2O2 and pH were studied. It was observed that the catalytic activity of bare Zeo is negligible and is enhanced by copper encapsulation and also the efficiency of the catalyst is tested and 95% is maintained. The work highlights the design and development of green catalyst from waste material FA.

Catalytic wet peroxide oxidation of metronidazole over Fe and Mn supported UiO-66 catalysts: Kinetic study

The metronidazole (MNZ) antibiotic is widely used to treat infections caused by anaerobic bacteria and it is difficult to biodegrade in the pharmaceutical wastewaters. In this study, Fe-UiO-66, Mn-UiO-66 and Fe/Mn-UiO-66 catalysts were prepared for the kinetic study of catalytic wet peroxide oxidation (CWPO) degradation of metronidazole in pharmaceutical wastewater. The catalysts were characterized by XRD, FT-IR, N2 adsorption-desorption, SEM, and TGA. The effects of Fe and Mn loading rate, catalyst dosage, MNZ concentrations, calcined temperature of Mn-UiO-66 and Fe/Mn ratio on the CWPO of metronidazole wastewater were systematically studied. Fe-UiO-66 catalysts exhibited better catalytic activity for the CWPO degradation of metronidazole wastewater (XMNZ = 93 %, XH2O2 = 78 %) compared to Mn-UiO-66 catalysts (XMNZ = 20 %, XH2O2 = 30 %). The kinetics study indicates that the CWPO process is fitted for the pseudo-first-order reaction with activation energy of 89.37 kJ/mol and 95.08 kJ/mol obtained on the Fe-UiO-66 and 2Fe/Mn-UiO-66 catalysts, respectively. The supported Fe and Mn UiO-66 catalysts showed good catalytic activity for CWPO of metronidazole which exhibited potential application in the wastewater treatment process.

Catalytic oxidation degradation of volatile organic compounds (VOCs) – a review

Abstract Volatile organic compounds (VOCs) are considered one of the significant contributors to air pollution because they are toxic, difficult to remove, come from a wide range of sources, and can easily cause damage to the environment and human health. There is an urgent need for effective means to reduce their emissions. The current treatment technologies for VOCs include catalytic oxidation, adsorption, condensation, and recovery. Catalytic oxidation technology stands out among the others thanks to its high catalytic efficiency, low energy requirement, and lack of secondary pollution. The difficulty of this technology lies in the development of efficient catalysts. The research on loaded noble metal catalysts and non-noble metal oxide catalysts in this area over the past few years is briefly described in this work. Firstly, the catalytic destruction mechanism of organic volatile compounds is introduced. Secondly, the effects of structural modulation during catalytic oxidation, such as the adjustment of noble metal particle size and morphology, metal doping, and defect engineering, on the conformational relationships are discussed. Finally, the challenges faced by thermal catalytic oxidation for the degradation of VOCs are discussed, and the prospects for its development are presented.

Artificial intelligence-aided preparation of perovskite SrFexZr1-xO3-δ catalysts for ozonation degradation of organic pollutant concentrated water after membrane treatment

Membrane technology has been widely used to treat wastewater from a variety of industries, but it also results in a large amount of concentrated wastewater containing organic pollutants after membrane treatment, which is challenging to decompose. Here in this work, a series of perovskite SrFexZr1-xO3-δ catalysts were prepared via a modified co-precipitation method and evaluated for catalytic ozone oxidative degradation of m-cresol. An artificial neural intelligence networks (ANN) model was employed to train the experimental data to optimize the preparation parameters of catalysts, with SrFe0.13Zr0.87O3-δ being the optimal catalysts. The resultant catalysts before and after reduction were then thoroughly characterized and tested for m-cresol degradation. It was found that the co-doping of Fe and Zr at the B-site and the improvement of oxygen vacancies and oxygen active species by reduction dramatically increased TOC removal rates up to 5 times compared with ozone alone, with the conversion rate of m-cresol reaching 100%. We also proposed a possible mechanism for m-cresol degradation via investigating the intermediates using GC-MS, and confirmed the good versatility of the reduced SrFe0.13Zr0.87O3-δ catalyst to remove other common organic pollutants in concentrated wastewater. This work demonstrates new prospects for the use of perovskite materials in wastewater treatment.

Ultrafine ZnCo2O4 QD-incorporated carbon nitride mediated peroxymonosulfate activation for norfloxacin oxidation: performance, mechanisms and pathways.

Recently, peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) are being actively investigated as a potential technology for water decontamination and many efforts have been made to improve the activation efficiency of PMS. Herein, a 0D metal oxide quantum dot (QD)-2D ultrathin g-C3N4 nanosheet (ZnCo2O4/g-C3N4) hybrid was facilely fabricated through a one-pot hydrothermal process and used as an efficient PMS activator. Benefiting from the restricted growth effect of the g-C3N4 support, ultrafine ZnCo2O4 QDs (∼3-5 nm) are uniformly and stably anchored onto the surface. The ultrafine ZnCo2O4 possesses high specific surface areas and shortened mass/electron transport route so that the internal static electric field (Einternal) formed in the interface between p-type ZnCo2O4 and the n-type g-C3N4 semiconductor could speed up the electron transfer during the catalytic reaction. This thereby induces the high-efficiency PMS activation for rapid organic pollutant removal. As expected, the ZnCo2O4/g-C3N4 hybrid catalysts significantly outperformed individual ZnCo2O4 and g-C3N4 in catalytic oxidative degradation of norfloxacin (NOR) in the presence of PMS (95.3% removal of 20 mg L-1 of NOR in 120 min). Furthermore, the ZnCo2O4/g-C3N4-mediated PMS activation system was systematically studied in terms of the identification of reactive radicals, the impact of control factors, and the recyclability of the catalyst. The results of this study demonstrated the great potential of a built-in electric field-driven catalyst as a novel PMS activator for the remediation of contaminated water.

Chitosan-promoted sepiolite supported Ag as efficient catalyst for catalytic oxidative degradation of formaldehyde at low temperature

The chitosan (CTs) modified high purity sepiolite (HP-Sep) supported Ag nanoparticles catalyst (CTs-Ag/HP-Sep) was prepared by impregnation and applied in the catalytic oxidation of HCHO. 5CTs-10Ag/HP-Sep-300 (5 and 10 represent the weight percentage of 5% chitosan and 10% Ag, and 300 represents the calcination temperature of 300 °C) with abundant amino and hydroxyl groups, smaller highly dispersed metallic Ag nanoparticles presented superior adsorbability of HCHO and better oxidative degradation performance. The 100 ppm HCHO under the GHSV of 6000 mL/g·h can be completely oxidized to H2O and CO2 at low temperature of 52 °C. The addition of CTs was conducive to the HCHO adsorption, the formation of smaller Ag nanoparticles with lattice oxygen and the transformation of formate into carbonate species, hence promoting the HCHO oxidative degradation. The possible reaction route was discussed in detail based on the results of XPS and in-situ DRIFTS. This study will provide a promising way for designing highly efficient heterogeneous catalysts by combining nature clay with polymers supported active metal for the oxidative degradation of HCHO at low temperature.

Preparation of a transition metal-supported TiO2 catalyst and the catalytic oxidative degradation of toluene

The synthesis of supported transition metal oxides with satisfactory low-temperature catalytic performance and application potential is still a challenge for the complete degradation of VOCs. Ni-Cu-loaded TiO2 catalysts were prepared by an impregnation method. The lattice defect and oxygen vacancy concentrations of the prepared materials could be tuned by controlling the Ni/Cu molar ratio and the mass proportion of the TiO2 support. 5Ni-Cu/TiO2 exhibited the best catalytic activity and showed superior catalytic stability during complete toluene oxidation. The obtained catalysts were fully characterized by XRD, FT-IR, TEM, N2 adsorption analysis, XPS, H2-TPR, O2-TPD, TPD analysis, and XPS. The 5Ni-Cu/TiO2 catalyst had improved pore sizes and specific surface area, had more oxygen vacancies on its surface, had increased concentrations of adsorbed and lattice oxygen species, and had good redox properties; these characteristics were favorable for low-temperature catalytic performance and catalytic stability. Cyclic transformations of metal valence states between Cu+ and Cu and between Ni and Ni2+ were observed in the catalytic system. A potential catalytic reaction process based on the M-vK mechanism was proposed. This work serves as a reference for the application of supported transition metal catalysts for the degradation of VOCs.

Metal-organic frameworks-derived CoFeN-NC materials with the enhanced catalytic activity and selectivity for the degradation of organic dyes via adsorption and heterogeneous photo-Fenton

Nanoscale iron-based materials are widely used as photocatalytic materials for catalytic oxidative degradation of organic dyes in water. Here, a series of MOFs derived nitrogen doped cobalt iron bimetallic carbon composite nanomaterials (CoxFe1-xN-NCs) were prepared by self-assembly and annealing treatment, and their application in the removal of organic dyes in water was investigated by the synergistic effect of adsorption and photo-Fenton. The study found that the Co0.8Fe0.2N-NC exhibit superior catalytic performance for different types of organic dyes. For example, when the concentration of MB was 40 mg L-1, the degradation rate constant was 3.88 × 10-2 min−1, which were 2.9 and 25.2 times the corresponding values of the Fenton-like and photocatalytic system, respectively. Meanwhile, compared with azo dyes Methyl Orange and Congo Red (MO and CR), Co0.8Fe0.2N-NC has obvious selective catalysis for non-azo dyes Methylene Blue, Malachite Green, Rhodamine B and Neutral Red (MB, MG, RhB and NR). Moreover, the reaction of cobalt iron active centers with hydrogen peroxide (H2O2) further promotes the generation of active substances (·OH, ·O2– and h+), speeding up the degradation of organic dyes. These results suggest that the synergistic effect of adsorption and photo-Fenton may provide new clues for the treatment of organic pollutants in wastewater.

Deactivation characteristics of Ce-modified Cu-based carbon materials for catalytic wet air oxidation of phenol wastewater

In this paper, Ce-modified Cu-based carbon materials (Cu-Ce/AC) were prepared by impregnation method using walnut shell as the carbon precursor, Cu-ammonia solution as Cu source and Ce as modifier. The catalytic wet air oxidation (CWAO) degradation of phenol wastewater was carried out in a self-assembled fixed-bed reactor. The stability of Cu-Ce/AC catalyst under different pH conditions was studied. This study combines XRD, BET, FT-IR, ICP-OES and XPS characterization techniques to study the main reasons for the deactivation of Cu-Ce/AC catalysts. The reaction mechanism of Cu-Ce/AC catalytic wet air oxidation degradation of phenol was clarified. The result indicates that although phenol was completely converted in the CWAO process, the acidic intermediate product produced were difficult to completely degraded. Therefore, the pH of the solution gradually decreased. In acidic environment, the interaction between active component Cu and carbon carrier is weak, resulting in a large amount of metal leaching into the solution. As a result, the COD conversion gradually decreases. The alkaline environment can effectively slow down the leaching of catalyst Cu while maintaining its high catalytic activity. In addition, the incompletely degraded intermediate products are easy to accumulate and deposit on the Cu-Ce/AC surface, block the micropores and cover the surface-active sites, which reduces the catalyst activity. The study also found that there is a redox cycle between Cu+, Cu2+ Ce3+ and Ce4+ during phenol degradation, which enables Cu and Ce to form a strong interaction. The redox cycle can also promote the formation of oxygen vacancy (h+), O2−·, and HO·, making the degradation of phenol more thorough. At the same time, the mutual conversion between metal lattice oxygen and surface chemisorbed oxygen can generate high concentration of oxygen defect sites, which can improve the oxygen storage capacity of Cu-Ce/AC. These oxygen vacancies also provide more reactive sites to further promote adsorption and catalytic oxidation degradation of phenol and intermediate products.

Adsorptive removal of Ag/Au quantum dots onto covalent organic frameworks@magnetic zeolite@arabic gum hydrogel and their catalytic microwave-Fenton oxidative degradation of Rifampicin antibiotic

Recent progress in nanotechnology via incorporation of small particle size as quantum dots (QDs) (1–10 nm) in many industrial activities and commercial products has led to significant undesired environmental impacts. Therefore, QDs removal from wastewater represents an interesting research topic with a lot of challenges for scientists and engineers nowadays. In this work, the coagulative removal of metal quantum dots as silver and gold from industrial water samples is explored. A novel biosorbent was assembled via binding of covalent organic frameworks (COFs) with magnetic zeolite and Arabic gum hydrogel (COFs@MagZ@AGH) as a promising removal material for Ag-QDs and Au-QDs. This was fully characterized by EDX, SEM, TEM, FT-IR, XPS, XRD and surface area and applied in coagulative removal of Au-QDs and Ag-QDs in presence of several experimental factors as pH, presence of other electrolytes, stirring time, initial QDs concentration, coagulant dosage, and temperature in order to optimize the removal processes. At optimum conditions, COFs@MagZ@AGH was able to recover 99.19% and 87.57% of Ag-QDs and Au-QDs QDs, respectively via chemical adsorption mechanism with perfect fitting to pseudo-second order model. Reuse of the recovered Ag/Au-QDs@COFs@MagZ@AGH as efficient catalysts in catalytic degradation of Rifampicin antibiotic (Rf) from water was additionally investigated and optimized via microwave-Fenton catalysts with excellent oxidative degradation efficiency (100%). Reusability and applicability of the biosorbent (COFs@MagZ@AGH) and catalysts (Ag/Au-QDs@COFs@MagZ@AGH) in real industrial water samples were also explored and successfully accomplished.

Mechanism research of catalytic degradation of 1, 2-dichlorobenzene over highly efficient hollow calcium ferrite by in situ FTIR spectra

The hierarchical CaFe2O4 core-shell hollow microspheres are successfully fabricated by a facile solvothermal approach following heat treatment process. The hollow architecture exhibits high surface area and strong visible-light absorption capability. Meanwhile, the formation mechanism of hollow structure is proposed based on characterization results. Furthermore, the photocatalytic activity is tested by 1, 2-dichlorobenzene degradation under visible light irradiation, and the degradation ratio of CaFe2O4 core-shell hollow microspheres can reach 82.0% after 8 h. Moreover, relying on the in situ Fourier transform infrared technology, the catalytic oxidation process and degradation mechanism is clarified on CaFe2O4 surface, and the intermediate product (formate, acetate, maleate species, etc.) and the mineralized products (CO2 and H2O) are identified finally.