Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification)

A special issue of Catalysts (ISSN 2073-4344). This special issue belongs to the section "Environmental Catalysis".

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 53569

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Department of Chemical Sciences, University of Catania, Viale A. Doria 6, 95125 Catania, Italy
Interests: heterogeneous catalysis; photocatalysis; TiO2-based materials; air purification; water treatment; H2 economy; VOC oxidation; H2 production and purification; CO2 valorization
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Dear Colleagues,

The quality of air and water is a crucial contemporary problem. The globalization economy and the rapid growth of new economic powers have given rise to new problems related to the environmental protection. The catalysis science has always given smart, green, and scale-up eco-friendly solutions. In the last year, together with the traditional and efficient catalytic thermal treatments, new and emerging techniques such as photothermal treatments or advanced oxidation processes (photocatalysis, Fenton and PhotoFenton, Ozonation, etc.) have provided good results both in air and in water purification.

Based on the above considerations, submissions to this Special Issue on “Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification)” are welcome in the form of original research papers, reviews or communications that highlight the state of research in the VOCs oxidation (catalytic oxidation, photocatalytic oxidation or photothermal catalytic oxidation); air purification; wastewater treatments (adsorption, membrane filtration, AOP, photocatalysis, Fenton and PhotoFenton, ozonation, etc.); development of new catalysts for environmental protection; correlation structure–activity of new catalysts applied for green solutions; new environmental friendly materials; characterization in “situ” of the oxidation processes; and supported and unsupported catalysts (metal oxide, MOF, zeolite, nanocatalyst, noble metal-based catalysts, mono and bimetallic catalysts, etc.) for environmental applications.

Dr. Roberto Fiorenza
Guest Editor

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Keywords

  • VOC
  • water treatment
  • air purification
  • AOP (advanced oxidation process)
  • photothermal conversion
  • photocatalysis
  • Fenton and PhotoFenton treatment
  • thermal catalytic treatment
  • supported and unsupported catalysts (metal oxide, MOF, zeolite, nanocatalyst, noble metal-based catalysts, mono and bimetallic catalysts, and others)

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Related Special Issue

Published Papers (12 papers)

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Editorial

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2 pages, 175 KiB  
Editorial
Heterogeneous Catalysis and Advanced Oxidation Processes (AOPs) for Environmental Protection (VOC Oxidation, Air and Water Purification)
by Roberto Fiorenza
Catalysts 2022, 12(3), 317; https://doi.org/10.3390/catal12030317 - 10 Mar 2022
Cited by 4 | Viewed by 2549
Abstract
The quality of air and water is a crucial and critical contemporary problem [...] Full article

Research

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17 pages, 42324 KiB  
Article
Photocatalytic Degradation of Fluoroquinolone Antibiotics in Solution by Au@ZnO-rGO-gC3N4 Composites
by Abniel Machín, Kenneth Fontánez, José Duconge, María C. Cotto, Florian I. Petrescu, Carmen Morant and Francisco Márquez
Catalysts 2022, 12(2), 166; https://doi.org/10.3390/catal12020166 - 28 Jan 2022
Cited by 18 | Viewed by 3481
Abstract
The photocatalytic degradation of two quinolone-type antibiotics (ciprofloxacin and levofloxacin) in aqueous solution was studied, using catalysts based on ZnO nanoparticles, which were synthesized by a thermal procedure. The efficiency of ZnO was subsequently optimized by incorporating different co-catalysts of gC3N [...] Read more.
The photocatalytic degradation of two quinolone-type antibiotics (ciprofloxacin and levofloxacin) in aqueous solution was studied, using catalysts based on ZnO nanoparticles, which were synthesized by a thermal procedure. The efficiency of ZnO was subsequently optimized by incorporating different co-catalysts of gC3N4, reduced graphene oxide, and nanoparticles of gold. The catalysts were fully characterized by electron microscopy (TEM and SEM), XPS, XRD, Raman, and BET surface area. The most efficient catalyst was 10%Au@ZnONPs-3%rGO-3%gC3N4, obtaining degradations of both pollutants above 96%. This catalyst has the largest specific area, and its activity was related to a synergistic effect, involving factors such as the surface of the material and the ability to absorb radiation in the visible region, mainly produced by the incorporation of rGO and gC3N4 in the semiconductor. The use of different scavengers during the catalytic process, was used to establish the possible photodegradation mechanism of both antibiotics. Full article
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19 pages, 7819 KiB  
Article
Hydrothermal and Co-Precipitated Synthesis of Chalcopyrite for Fenton-like Degradation toward Rhodamine B
by Po-Yu Wen, Ting-Yu Lai, Tsunghsueh Wu and Yang-Wei Lin
Catalysts 2022, 12(2), 152; https://doi.org/10.3390/catal12020152 - 26 Jan 2022
Cited by 11 | Viewed by 3291
Abstract
In this study, Chalcopyrite (CuFeS2) was prepared by a hydrothermal and co-precipitation method, being represented as H-CuFeS2 and C-CuFeS2, respectively. The prepared CuFeS2 samples were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive [...] Read more.
In this study, Chalcopyrite (CuFeS2) was prepared by a hydrothermal and co-precipitation method, being represented as H-CuFeS2 and C-CuFeS2, respectively. The prepared CuFeS2 samples were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), energy dispersive X-ray spectroscopy mapping (EDS-mapping), powder X-ray diffractometer (XRD), X-ray photoelectron spectrometry (XPS), and Raman microscope. Rhodamine B (RhB, 20 ppm) was used as the target pollutant to evaluate the degradation performance by the prepared CuFeS2 samples. The H-CuFeS2 samples (20 mg) in the presence of Na2S2O8 (4 mM) exhibited excellent degradation efficiency (98.8% within 10 min). Through free radical trapping experiment, the major active species were •SO4 radicals and •OH radicals involved the RhB degradation. Furthermore, •SO4 radicals produced from the prepared samples were evaluated by iodometric titration. In addition, one possible degradation mechanism was proposed. Finally, the prepared H-CuFeS2 samples were used to degrade different dyestuff (rhodamine 6G, methylene blue, and methyl orange) and organic pollutant (bisphenol A) in the different environmental water samples (pond water and seawater) with 10.1% mineral efficiency improvement comparing to traditional Fenton reaction. Full article
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17 pages, 2074 KiB  
Article
VOCs Photothermo-Catalytic Removal on MnOx-ZrO2 Catalysts
by Roberto Fiorenza, Roberta Agata Farina, Enrica Maria Malannata, Francesca Lo Presti and Stefano Andrea Balsamo
Catalysts 2022, 12(1), 85; https://doi.org/10.3390/catal12010085 - 13 Jan 2022
Cited by 16 | Viewed by 3248
Abstract
Solar photothermo-catalysis is a fascinating multi-catalytic approach for volatile organic compounds (VOCs) removal. In this work, we have explored the performance and the chemico-physical features of non-critical, noble, metal-free MnOx-ZrO2 mixed oxides. The structural, morphological, and optical characterizations of these [...] Read more.
Solar photothermo-catalysis is a fascinating multi-catalytic approach for volatile organic compounds (VOCs) removal. In this work, we have explored the performance and the chemico-physical features of non-critical, noble, metal-free MnOx-ZrO2 mixed oxides. The structural, morphological, and optical characterizations of these materials pointed to as a low amount of ZrO2 favoured a good interaction and the ionic exchange between the Mn and the Zr ions. This favoured the redox properties of MnOx increasing the mobility of its oxygens that can participate in the VOCs oxidation through a Mars-van Krevelen mechanism. The further application of solar irradiation sped up the oxidation reactions promoting the VOCs total oxidation to CO2. The MnOx-5 wt.%ZrO2 sample showed, in the photothermo-catalytic tests, a toluene T90 (temperature of 90% of conversion) of 180 °C and an ethanol T90 conversion to CO2 of 156 °C, 36 °C, and 205 °C lower compared to the thermocatalytic tests, respectively. Finally, the same sample exhibited 84% toluene conversion and the best selectivity to CO2 in the ethanol removal after 5 h of solar irradiation at room temperature, a photoactivity similar to the most employed TiO2-based materials. The as-synthetized mixed oxide is promising for an improved sustainability in both catalyst design and environmental applications. Full article
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14 pages, 4355 KiB  
Article
Optimized Synthesis Routes of MnOx-ZrO2 Hybrid Catalysts for Improved Toluene Combustion
by Xin Huang, Luming Li, Rong Liu, Hongmei Li, Li Lan and Weiqi Zhou
Catalysts 2021, 11(9), 1037; https://doi.org/10.3390/catal11091037 - 27 Aug 2021
Cited by 6 | Viewed by 2152
Abstract
In this contribution, the three Mn-Zr catalysts with MnxZr1−xO2 hybrid phase were synthesized by two-step precipitation route (TP), conventional coprecipitation method (CP) and ball milling process (MP). The components, textural and redox properties of the Mn-Zr hybrid catalysts [...] Read more.
In this contribution, the three Mn-Zr catalysts with MnxZr1−xO2 hybrid phase were synthesized by two-step precipitation route (TP), conventional coprecipitation method (CP) and ball milling process (MP). The components, textural and redox properties of the Mn-Zr hybrid catalysts were studied via XRD, BET, XPS, HR-TEM, H2-TPR. Regarding the variation of synthesis routes, the TP and CP routes offer a more obvious advantage in the adjustment of the concentration of MnxZr1−xO2 solid solution compared to the MP process, which directly commands the content of Mn4+ and oxygen vacancy and lattice oxygen, and thereby leads to the enhanced mobility of reactive oxygen species and catalytic activity for toluene combustion. Moreover, the TP-Mn2Zr3 catalyst with the enriched exposure content of 51.4% for the defective (111) lattice plane of MnxZr1−xO2 exhibited higher catalytic activity and thermal stability for toluene oxidation than that of the CP-Mn2Zr3 sample with a value of 49.3%. This new observation will provide a new perspective on the design of bimetal catalysts with a higher VOCs combustion abatement. Full article
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18 pages, 1877 KiB  
Article
Alkali-Activated Materials as Catalysts for Water Purification
by Anne Heponiemi, Janne Pesonen, Tao Hu and Ulla Lassi
Catalysts 2021, 11(6), 664; https://doi.org/10.3390/catal11060664 - 23 May 2021
Cited by 10 | Viewed by 3351
Abstract
In this study, novel and cost-effective alkali-activated materials (AAMs) for catalytic applications were developed by using an industrial side stream, i.e., blast furnace slag (BFS). AAMs can be prepared from aluminosilicate precursors under mild conditions (room temperature using non-hazardous chemicals). AAMs were synthesized [...] Read more.
In this study, novel and cost-effective alkali-activated materials (AAMs) for catalytic applications were developed by using an industrial side stream, i.e., blast furnace slag (BFS). AAMs can be prepared from aluminosilicate precursors under mild conditions (room temperature using non-hazardous chemicals). AAMs were synthesized by mixing BFS and a 50 wt % sodium hydroxide (NaOH) solution at different BFS/NaOH ratios. The pastes were poured into molds, followed by consolidation at 20 or 60 °C. As the active metal, Fe was impregnated into the prepared AAMs by ion exchange. The prepared materials were examined as catalysts for the catalytic wet peroxide oxidation (CWPO) of a bisphenol A (BPA) aqueous solution. As-prepared AAMs exhibited a moderate surface area and mesoporous structure, and they exhibited moderate activity for the CWPO of BPA, while the iron ion-exchanged, BFS-based catalyst (Fe/BFS30-60) exhibited the maximum removal of BPA (50%) during 3 h of oxidation at pH 3.5 at 70 °C. Therefore, these new, inexpensive, AAM-based catalysts could be interesting alternatives for catalytic wastewater treatment applications. Full article
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13 pages, 2809 KiB  
Article
Magnetite, Hematite and Zero-Valent Iron as Co-Catalysts in Advanced Oxidation Processes Application for Cosmetic Wastewater Treatment
by Jan Bogacki, Piotr Marcinowski, Dominika Bury, Monika Krupa, Dominika Ścieżyńska and Prasanth Prabhu
Catalysts 2021, 11(1), 9; https://doi.org/10.3390/catal11010009 - 24 Dec 2020
Cited by 9 | Viewed by 3044
Abstract
Background: There is a need for more effective methods of industrial wastewater treatment. Methods: Cosmetic wastewater was collected and subjected to H2O2/Fe3O4/Fe2O3/Fe0 and UV/H2O2/Fe3O [...] Read more.
Background: There is a need for more effective methods of industrial wastewater treatment. Methods: Cosmetic wastewater was collected and subjected to H2O2/Fe3O4/Fe2O3/Fe0 and UV/H2O2/Fe3O4/Fe2O3/Fe0 process treatment. Results: Total organic carbon (TOC) was decreased from an initial 306.3 to 134.1 mg/L, 56.2% TOC removal, after 120 min of treatment for 1:1 H2O2/COD mass ratio and 500/500/1000 mg/L Fe3O4/Fe2O3/Fe0 catalyst doses. The application chromatographic analysis allowed for the detection and identification of pollutants present in the wastewater. Identified pollutants were removed during the treatment processes. Processes carried out at a pH greater than 3.0 were ineffective. The UV process was more effective than the lightless process. Conclusions: The applied processes are effective methods for wastewater treatment. Chromatographic results confirmed the effectiveness of the treatment method. The kinetics of the process were described by the modified second-order model. On the basis of ANOVA results, the hypothesis regarding the accuracy and reproducibility of the research was confirmed. Full article
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12 pages, 8860 KiB  
Article
Eco-Friendly Cotton/Linen Fabric Treatment Using Aqueous Ozone and Ultraviolet Photolysis
by Kengo Hamada, Tsuyoshi Ochiai, Yasuyuki Tsuchida, Kyohei Miyano, Yosuke Ishikawa, Toshinari Nagura and Noritaka Kimura
Catalysts 2020, 10(11), 1265; https://doi.org/10.3390/catal10111265 - 2 Nov 2020
Cited by 7 | Viewed by 10857
Abstract
Chemicals for the scouring and bleaching of fabrics have a high environmental load. In addition, in recent years, the high consumption of these products has become a problem in the manufacture of natural fabric products. Therefore, environmentally friendly, low-waste processes for fabric treatment [...] Read more.
Chemicals for the scouring and bleaching of fabrics have a high environmental load. In addition, in recent years, the high consumption of these products has become a problem in the manufacture of natural fabric products. Therefore, environmentally friendly, low-waste processes for fabric treatment are required. In this paper, we discuss the bleaching of fabrics using advanced oxidation processes (AOP). These processes use electrochemically generated aqueous ozone and ultraviolet (UV) irradiation to achieve bleaching. However, colour reversion often occurs. In this study, we suppressed unwanted colour reversion by treatment with rongalite. After treatment, changes in fabric colour were determined by measuring the colour difference and reflectance spectra. The best bleaching effect was obtained when ozone and UV irradiation treatments were combined, achieving results similar to those of a conventional bleaching method after 60 min of UV irradiation. In addition, the AOP treatment resulted in the simultaneous scouring of the fabric, as shown by the increased hydrophilicity of the fabric after AOP treatment. Thus, this AOP process represents a new fabric bleaching process that has an extremely low environmental impact. Full article
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13 pages, 3401 KiB  
Article
Comparative Study of ZnO Thin Films Doped with Transition Metals (Cu and Co) for Methylene Blue Photodegradation under Visible Irradiation
by William Vallejo, Alvaro Cantillo, Briggitte Salazar, Carlos Diaz-Uribe, Wilkendry Ramos, Eduard Romero and Mikel Hurtado
Catalysts 2020, 10(5), 528; https://doi.org/10.3390/catal10050528 - 11 May 2020
Cited by 71 | Viewed by 4673
Abstract
We synthesized and characterized both Co-doped ZnO (ZnO:Co) and Cu-doped ZnO (ZnO:Cu) thin films. The catalysts’ synthesis was carried out by the sol–gel method while the doctor blade technique was used for thin film deposition. The physicochemical characterization of the catalysts was carried [...] Read more.
We synthesized and characterized both Co-doped ZnO (ZnO:Co) and Cu-doped ZnO (ZnO:Cu) thin films. The catalysts’ synthesis was carried out by the sol–gel method while the doctor blade technique was used for thin film deposition. The physicochemical characterization of the catalysts was carried out by Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction, and diffuse reflectance measurements. The photocatalytic activity was studied under visible irradiation in aqueous solution, and kinetic parameters were determined by pseudo-first-order fitting. The Raman spectra results evinced the doping process and suggested the formation of heterojunctions for both dopants. The structural diffraction patterns indicated that the catalysts were polycrystalline and demonstrated the presence of a ZnO wurtzite crystalline phase. The SEM analysis showed that the morphological properties changed significantly, the micro-aggregates disappeared, and agglomeration was reduced after modification of ZnO. The ZnO optical bandgap (3.22 eV) reduced after the doping process, these being ZnO:Co (2.39 eV) and ZnO:Co (3.01 eV). Finally, the kinetic results of methylene blue photodegradation reached 62.6% for ZnO:Co thin films and 42.5% for ZnO:Cu thin films. Full article
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16 pages, 5378 KiB  
Article
CeO2 for Water Remediation: Comparison of Various Advanced Oxidation Processes
by Roberto Fiorenza, Stefano Andrea Balsamo, Luisa D’Urso, Salvatore Sciré, Maria Violetta Brundo, Roberta Pecoraro, Elena Maria Scalisi, Vittorio Privitera and Giuliana Impellizzeri
Catalysts 2020, 10(4), 446; https://doi.org/10.3390/catal10040446 - 21 Apr 2020
Cited by 28 | Viewed by 3736
Abstract
Three different Advanced Oxidation Processes (AOPs) have been investigated for the degradation of the imidacloprid pesticide in water: photocatalysis, Fenton and photo-Fenton reactions. For these tests, we have compared the performance of two types of CeO2, employed as a non-conventional photocatalyst/Fenton-like [...] Read more.
Three different Advanced Oxidation Processes (AOPs) have been investigated for the degradation of the imidacloprid pesticide in water: photocatalysis, Fenton and photo-Fenton reactions. For these tests, we have compared the performance of two types of CeO2, employed as a non-conventional photocatalyst/Fenton-like material. The first one has been prepared by chemical precipitation with KOH, while the second one has been obtained by exposing the as-synthetized CeO2 to solar irradiation in H2 stream. This latter treatment led to obtain a more defective CeO2 (coded as “grey CeO2”) with the formation of Ce3+ sites on the surface of CeO2, as determined by Raman and X-ray Photoelectron Spectroscopy (XPS) characterizations. This peculiar feature has been demonstrated as beneficial for the solar photo–Fenton reaction, with the best performance exhibited by the grey CeO2. On the contrary, the bare CeO2 showed a photocatalytic activity higher with respect to the grey CeO2, due to the higher exposed surface area and the lower band-gap. The easy synthetic procedures of CeO2 reported here, allows to tune and modify the physico-chemical properties of CeO2, allowing a choice of different CeO2 samples on the basis of the specific AOPs for water remediation. Furthermore, neither of the samples have shown any critical toxicity. Full article
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Review

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49 pages, 5874 KiB  
Review
Development of Pharmaceutical VOCs Elimination by Catalytic Processes in China
by Lilong Zhou, Chen Ma, Jonathan Horlyck, Runjing Liu and Jimmy Yun
Catalysts 2020, 10(6), 668; https://doi.org/10.3390/catal10060668 - 13 Jun 2020
Cited by 26 | Viewed by 6643
Abstract
As a byproduct of emerging as one of the world’s key producers of pharmaceuticals, China is now challenged by the emission of harmful pharmaceutical VOCs. In this review, the catalogue and volume of VOCs emitted by the pharmaceutical industry in China was introduced. [...] Read more.
As a byproduct of emerging as one of the world’s key producers of pharmaceuticals, China is now challenged by the emission of harmful pharmaceutical VOCs. In this review, the catalogue and volume of VOCs emitted by the pharmaceutical industry in China was introduced. The commonly used VOC removal processes and technologies was recommended by some typical examples. The progress of catalytic combustion, photocatalytic oxidation, non-thermal plasma, and electron beam treatment were presented, especially the development of catalysts. The advantages and shortages of these technologies in recent years were discussed and analyzed. Lastly, the development of VOCs elimination technologies and the most promising technology were discussed. Full article
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25 pages, 3329 KiB  
Review
Bimetallic Catalysts for Volatile Organic Compound Oxidation
by Roberto Fiorenza
Catalysts 2020, 10(6), 661; https://doi.org/10.3390/catal10060661 - 12 Jun 2020
Cited by 25 | Viewed by 4696
Abstract
In recent years, the impending necessity to improve the quality of outdoor and indoor air has produced a constant increase of investigations in the methodologies to remove and/or to decrease the emission of volatile organic compounds (VOCs). Among the various strategies for VOC [...] Read more.
In recent years, the impending necessity to improve the quality of outdoor and indoor air has produced a constant increase of investigations in the methodologies to remove and/or to decrease the emission of volatile organic compounds (VOCs). Among the various strategies for VOC elimination, catalytic oxidation and recently photocatalytic oxidation are regarded as some of the most promising technologies for VOC total oxidation from urban and industrial waste streams. This work is focused on bimetallic supported catalysts, investigating systematically the progress and developments in the design of these materials. In particular, we highlight their advantages compared to those of their monometallic counterparts in terms of catalytic performance and physicochemical properties (catalytic stability and reusability). The formation of a synergistic effect between the two metals is the key feature of these particular catalysts. This review examines the state-of-the-art of a peculiar sector (the bimetallic systems) belonging to a wide area (i.e., the several catalysts used for VOC removal) with the aim to contribute to further increase the knowledge of the catalytic materials for VOC removal, stressing the promising potential applications of the bimetallic catalysts in the air purification. Full article
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