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

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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 53614

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Dr. Roberto Fiorenza

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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

Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification), 2nd Edition in Catalysts (6 articles)

Published Papers (12 papers)

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Editorial

Jump to: Research, Review

2 pages, 175 KiB

Open AccessEditorial

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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

Research

Jump to: Editorial, Review

17 pages, 42324 KiB

Open AccessArticle

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 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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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19 pages, 7819 KiB

Open AccessArticle

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 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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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17 pages, 2074 KiB

Open AccessFeature PaperArticle

VOCs Photothermo-Catalytic Removal on MnO_x-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 MnO_x-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 MnO_x 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 MnO_x-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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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14 pages, 4355 KiB

Open AccessArticle

Optimized Synthesis Routes of MnO_x-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 Mn_xZr_1−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 Mn_xZr_1−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 Mn_xZr_1−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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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18 pages, 1877 KiB

Open AccessArticle

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 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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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13 pages, 2809 KiB

Open AccessArticle

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 10 | 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/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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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12 pages, 8860 KiB

Open AccessArticle

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 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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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13 pages, 3401 KiB

Open AccessArticle

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 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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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16 pages, 5378 KiB

Open AccessArticle

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 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 CeO_2, 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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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Review

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49 pages, 5874 KiB

Open AccessReview

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. 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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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25 pages, 3329 KiB

Open AccessFeature PaperReview

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 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

(This article belongs to the Special Issue Heterogeneous Catalysis and Advanced Oxidation Processes (AOP) for Environmental Protection (VOCs Oxidation, Air and Water Purification))

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