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Greener Catalysis for Environmental Applications

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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 2020) | Viewed by 34310

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Special Issue Editor

Prof. Dr. Stanisław Wacławek

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Guest Editor

Department of Nanomaterials in Natural Sciences, Institute for Nanomaterials, Advanced Technology and Innovation, Technical University of Liberec, Studentska 1402/2, Liberec 1, Czech Republic
Interests: chemical engineering; nanotechnology; environmental engineering; theoretical chemistry; environmental chemistry; adsorption; sustainable chemistry; water and wastewater treatment; anaerobic biogas; digestion; bioremediation
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Special Issue Information

Dear Colleagues,

Catalytic reactions form around 85% of all chemical reactions, being especially important in environmental science. It has been more than 20 years since Anastas and Warner introduced their 12 postulates of green chemistry, of which the 9th is catalysis. There have been continuous developments in catalysis regarding environmental applications, which are embodied in the exponential growth of scientific articles (published annually) concerning that topic.

This Special Issue is devoted to ‘’Greener Catalysis for Environmental Applications’’, and primarily covers the catalytic removal of pollutants (from water, wastewater, soil, and air) as well as the catalytic synthesis of value-added chemicals (for example, in nonthermal plasma catalytic systems).

Articles focusing on the catalytic activation of oxidants and green syntheses of sophisticated catalysts for various environmental applications are particularly welcomed. Primarily, the following topics are planned to be covered in this Special Issue:

Green synthesis of heterogeneous catalysts;
Catalytic activation of oxidants (advanced oxidation processes; sulfate radical-based processes);
Photocatalysis for the removal of, e.g., micropollutants;
Catalytic hydrogenation of carbon dioxide into value-added chemicals and fuels;
Catalytic hydrogenation of contaminants in water;
Nanozymes for environmental applications.

All studies (experimental and theoretical) in the scope of this Special Issue, including original research and review articles, short communications, and perspective articles, are invited for submission.

Dr. Stanisław Wacławek
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Catalysts is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

Greener catalysts
Green synthesis of nanoparticles
Photocatalysis
Nanozymes
Catalytic activation of oxidants
Catalytic reduction of pollutants
Catalytic water and wastewater treatment
Value-added products from renewable sources.

Published Papers (11 papers)

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Editorial

Jump to: Research

3 pages, 414 KiB

Open AccessEditorial

Greener Catalysis for Environmental Applications

by Stanisław Wacławek

Catalysts 2021, 11(5), 585; https://doi.org/10.3390/catal11050585 - 30 Apr 2021

Cited by 3 | Viewed by 1663

Abstract

Catalytic reactions account for approximately 85% of all chemical reactions, and they are particularly significant in environmental science [...] Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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Research

Jump to: Editorial

18 pages, 6737 KiB

Open AccessArticle

Transformation of Contaminants of Emerging Concern (CECs) during UV-Catalyzed Processes Assisted by Chlorine

by Edyta Kudlek

Catalysts 2020, 10(12), 1432; https://doi.org/10.3390/catal10121432 - 8 Dec 2020

Cited by 8 | Viewed by 1869

Abstract

Every compound that potentially can be harmful to the environment is called a Contaminant of Emerging Concern (CEC). Compounds classified as CECs may undergo different transformations, especially in the water environment. The intermediates formed in this way are considered to be toxic against living organisms even in trace concentrations. We attempted to identify the intermediates formed during single chlorination and UV-catalyzed processes supported by the action of chlorine and hydrogen peroxide or ozone of selected contaminants of emerging concern. The analysis of post-processing water samples containing benzocaine indicated the formation of seven compound intermediates, while ibuprofen, acridine and β-estradiol samples contained 5, 5, and 3 compound decomposition by-products, respectively. The number and also the concentration of the intermediates decreased with the time of UV irradiation. The toxicity assessment indicated that the UV-catalyzed processes lead to decreased toxicity nature of post-processed water solutions. Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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13 pages, 3116 KiB

Open AccessArticle

Cleaner Production of Epoxidized Cooking Oil Using A Heterogeneous Catalyst

by Maria Kurańska and Magdalena Niemiec

Catalysts 2020, 10(11), 1261; https://doi.org/10.3390/catal10111261 - 30 Oct 2020

Cited by 13 | Viewed by 2401

Abstract

A cleaner solvent-free process of used cooking oil epoxidation has been developed. The epoxidation reactions were carried out using “in situ”-formed peroxy acid. A variety of ion exchange resins with different cross-linking percentages and particle sizes such as Dowex 50WX2 50-100, Dowex 50WX2 100-200, Dowex 50WX2 200-400, Dowex 50WX4 50-100, Dowex 50WX4 100-200, Dowex 50WX4 200-400, Dowex 50WX8 50-100, Dowex 50WX8 100-200, Dowex 50WX8 200-400 were used in the synthesis as heterogeneous catalysts. No significant effect of the size as well as porosity of the catalysts on the properties of the final products was observed. In order to develop a more economically beneficial process, a much cheaper heterogeneous catalyst—Amberlite IR-120—was used and the properties of the epoxidized oil were compared with the bio-components obtained in the reaction catalyzed by the Dowex resins. The epoxidized waste oils obtained in the experiments were characterized by epoxy values in the range of 0.32–0.35 mol/100 g. To reduce the amount of waste, the reusability of the ion exchange resin in the epoxidation reaction was studied. Ten reactions were carried out using the same catalyst and each synthesis was monitored by determination of epoxy value changes vs. time of the reactions. It was noticed that in the case of the reactions where the catalyst was reused for the third and fourth time the content of oxirane rings was higher by 8 and 6%, respectively, compared to the reaction where the catalyst was used only one time. Such an observation has not been reported so far. The epoxidation process with catalyst recirculation is expected to play an important role in the development of a new approach to the environmentally friendly solvent-free epoxidation process of waste oils. Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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19 pages, 5707 KiB

Open AccessArticle

Fe₃O₄-Zeolite Hybrid Material as Hetero-Fenton Catalyst for Enhanced Degradation of Aqueous Ofloxacin Solution

by Alamri Rahmah Dhahawi Ahmad, Saifullahi Shehu Imam, Wen Da Oh and Rohana Adnan

Catalysts 2020, 10(11), 1241; https://doi.org/10.3390/catal10111241 - 27 Oct 2020

Cited by 23 | Viewed by 3070

Abstract

A hetero-Fenton catalyst comprising of Fe₃O₄ nanoparticles loaded on zeolite (FeZ) has been synthesized using a facile co-precipitation method. The catalyst was characterized using various characterization methods and then, subsequently, was used to degrade ofloxacin (OFL, 20 mg·L⁻¹), an antibiotic, via a heterogeneous Fenton process in the presence of an oxidizing agent. The effects of different parameters such as Fe₃O₄ loading on zeolite, catalyst loading, initial solution pH, initial OFL concentration, different oxidants, H₂O₂ dosage, reaction temperature, and inorganic salts were studied to determine the performance of the FeZ catalyst towards Fenton degradation of OFL under different conditions. Experimental results revealed that as much as 88% OFL and 51.2% total organic carbon (TOC) could be removed in 120 min using the FeZ catalyst. Moreover, the FeZ composite catalyst showed good stability for Fenton degradation of OFL even after five cycles, indicating that the FeZ catalyst could be a good candidate for wastewater remediation. Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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13 pages, 3350 KiB

Open AccessArticle

Glycine–Nitrate Combustion Synthesis of Cu-Based Nanoparticles for NP9EO Degradation Applications

by Hsu-Hui Cheng, Shiao-Shing Chen, Hui-Ming Liu, Liang-Wei Jang and Shu-Yuan Chang

Catalysts 2020, 10(9), 1061; https://doi.org/10.3390/catal10091061 - 15 Sep 2020

Cited by 8 | Viewed by 2621

Abstract

Copper-based nanoparticles were synthesized using the glycine–nitrate process (GNP) by using copper nitrate trihydrate [Cu(NO₃)₂·3H₂O] as the main starting material, and glycine [C₂H₅NO₂] as the complexing and incendiary agent. The as-prepared powders were characterized through X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy analysis. Using Cu(NO₃)₂·3H₂O as the oxidizer (N) and glycine as fuel (G), we obtained CuO, mixed-valence copper oxides (CuO + Cu₂O, G/N = 0.3–0.5), and metallic Cu (G/N = 0.7). The XRD and BET results indicated that increasing the glycine concentration (G/N = 0.7) and reducing the particle surface area increased the yield of metallic Cu. The effects of varying reaction parameters, such as catalyst activity, catalyst dosage, and H₂O₂ concentration on nonylphenol-9-polyethoxylate (NP9EO) degradation, were assessed. With a copper-based catalyst in a heterogeneous system, the NP9EO and total organic carbon removal efficiencies were 83.1% and 70.6%, respectively, under optimum operating conditions (pH, 6.0; catalyst dosage, 0.3 g/L; H₂O₂ concentration, 0.05 mM). The results suggest that the removal efficiency increased with an increase in H₂O₂ concentration but decreased when the H₂O₂ concentration exceeded 0.05 mM. Furthermore, the trend of photocatalytic activity was as follows: G/N = 0.5 > G/N = 0.7 > G/N = 0.3. The G/N = 0.5 catalysts showed the highest photocatalytic activity and resulted in 94.6% NP9EO degradation in 600 min. Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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17 pages, 3319 KiB

Open AccessArticle

Reductive Dechlorination of Chloroacetamides with NaBH₄ Catalyzed by Zero Valent Iron, ZVI, Nanoparticles in ORMOSIL Matrices Prepared via the Sol-Gel Route

by Michael Meistelman, Dan Meyerstein, Amos Bardea, Ariela Burg, Dror Shamir and Yael Albo

Catalysts 2020, 10(9), 986; https://doi.org/10.3390/catal10090986 - 1 Sep 2020

Cited by 3 | Viewed by 2642

Abstract

The efficient reductive dechlorination, as remediation of dichloroacetamide and monochloroacetamide, toxic and abundant pollutants, using sodium borohydride catalyzed by zero valent iron nanoparticles (ZVI-NPs), entrapped in organically modified hybrid silica matrices prepared via the sol-gel route, ZVI@ORMOSIL, is demonstrated. The results indicate that the extent of the dechlorination reaction depends on the nature of the substrate and on the reaction medium. By varying the amount of catalyst or reductant in the reaction it was possible to obtain conditions for full dechlorination of these pollutants to nontoxic acetamide and acetic acid. A plausible mechanism of the catalytic process is discussed. The present work expands the scope of ZVI-NP catalyzed reduction of polluting compounds, first reports the catalytic parameters of chloroacetamide reduction, and offers additional insight into the heterogeneous catalyst structure of M⁰@ORMOSIL sol-gel. The ZVI@ORMOSIL catalyst is ferromagnetic and hence can be recycled easily. Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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19 pages, 8051 KiB

Open AccessArticle

Effect of the Gallium and Vanadium on the Dibenzothiophene Hydrodesulfurization and Naphthalene Hydrogenation Activities Using Sulfided NiMo-V₂O₅/Al₂O₃-Ga₂O₃

by Esneyder Puello-Polo, Yina Pájaro and Edgar Márquez

Catalysts 2020, 10(8), 894; https://doi.org/10.3390/catal10080894 - 7 Aug 2020

Cited by 6 | Viewed by 2572

Abstract

The effect of Ga and V as support-modifier and promoter of NiMoV/Al2O3-Ga2O3 catalyst on hydrogenation (HYD) and hydrodesulfurization (HDS) activities was studied. The catalysts were characterized by elemental analysis, textural properties, XRD, XPS, EDS elemental mapping and High-resolution transmission electron microscopy (HRTEM). The chemical analyses by X-ray Fluorescence (XRF) and CHNS-O elemental analysis showed results for all compounds in agreement, within experimental accuracy, according to stoichiometric values proposed to Mo/Ni = 6 and (V+Ni)/(V+Ni+Mo) = 0.35. The sol-gel synthesis method increased the surface area by incorporation of Ga³⁺ ions into the Al₂O₃ forming Ga-O-Al bonding; whereas the impregnation synthesis method leads to decrease by blocking of alumina pores, as follows NiMoV/Al-Ga(1%-I) < NiMoV/Al-Ga(1%-SG) < NiMo/Al₂O₃ < Al₂O₃-Ga₂O₃(1%-I) < Al₂O₃-Ga₂O₃(1%-SG) < Al₂O₃, propitiating Dp-BJH between 6.18 and 7.89 nm. XRD confirmed a bulk structure typical of (NH₄)_4[NiMo₆O₂₄H₆]•5H₂O and XPS the presence at the surface of Mo⁴⁺, Mo⁶⁺, NixSy, Ni²⁺, Ga³⁺ and V⁵⁺ species, respectively. The EDS elemental mapping confirmed that Ni, Mo, Al, Ga, V and S are well-distributed on Al₂O₃-Ga₂O₃(1%-SG) support. The HRTEM analysis shows that the length and stacking distribution of MoS₂ crystallites varied from 5.07 to 5.94 nm and 2.74 to 3.58 with synthesis method (SG to I). The results of the characterization sulfided catalysts showed that the synthesis method via impregnation induced largest presence of gallium on the surface influencing the dispersion V⁵⁺ species, this effect improves the dispersion of the MoS₂ phase and increasing the number of active sites, which correlates well with the dibenzothiophene HDS and naphthalene HYD activities. The dibenzothiophene HDS activities with overall pseudo-first-order rate constants’ values (k_HDS) from 1.65 to 7.07 L/(h·mol·m²) follow the order: NiMoV-S/Al-Ga(1%-I) < NiMo-S/Al₂O₃ < NiMoV-S/Al-Ga(1%-SG), whereas the rate constants’ values (k) of naphthalene HYD from 0.022 to 2.23 L/(h·mol·m²) as follow: NiMoV-S/Al-Ga(1%-SG) < NiMo-S/Al₂O₃ < NiMoV-S/Al-Ga(1%-I). We consider that Ga and V act as structural promoters in the NiMo catalysts supported on Al₂O₃ that allows the largest generation of BRIM sites for HYD and CUS sites for DDS. Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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12 pages, 5376 KiB

Open AccessArticle

Montmorillonite K10: An Efficient Organo-Heterogeneous Catalyst for Synthesis of Benzimidazole Derivatives

by Sonia Bonacci, Giuseppe Iriti, Stefano Mancuso, Paolo Novelli, Rosina Paonessa, Sofia Tallarico and Monica Nardi

Catalysts 2020, 10(8), 845; https://doi.org/10.3390/catal10080845 - 28 Jul 2020

Cited by 26 | Viewed by 4873

Abstract

The use of toxic solvents, high energy consumption, the production of waste and the application of traditional processes that do not follow the principles of green chemistry are problems for the pharmaceutical industry. The organic synthesis of chemical structures that represent the starting point for obtaining active pharmacological compounds, such as benzimidazole derivatives, has become a focal point in chemistry. Benzimidazole derivatives have found very strong applications in medicine. Their synthesis is often based on methods that are not convenient and not very respectful of the environment. A simple montmorillonite K10 (MK10) catalyzed method for the synthesis of benzimidazole derivatives has been developed. The use of MK10 for heterogeneous catalysis provides various advantages: the reaction yields are decidedly high, the work-up procedures of the reaction are easy and suitable, there is an increase in selectivity and the possibility of recycling the catalyst without waste formation is demonstrated. The reactions were carried out in solvent-free conditions and in a short reaction time using inexpensive and environmentally friendly heterogeneous catalysis. It has been shown that the reaction process is applicable in the industrial field. Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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17 pages, 12504 KiB

Open AccessArticle

CoMn Catalysts Derived from Hydrotalcite-Like Precursors for Direct Conversion of Syngas to Fuel Range Hydrocarbons

by Zahra Gholami, Zdeněk Tišler, Romana Velvarská and Jaroslav Kocík

Catalysts 2020, 10(8), 813; https://doi.org/10.3390/catal10080813 - 22 Jul 2020

Cited by 3 | Viewed by 2587

Abstract

Two different groups of CoMn catalysts derived from hydrotalcite-like precursors were prepared through the co-precipitation method, and their performance in the direct production of gasoline and jet fuel range hydrocarbons through Fischer–Tropsch (FT) synthesis was evaluated in a batch autoclave reactor at 240 °C and 7 MPa and H₂/CO of 2. The physicochemical properties of the prepared catalysts were investigated and characterized using different characterization techniques. Catalyst performance was significantly affected by the catalyst preparation method. The crystalline phase of the catalyst prepared using KOH contained Co₃O₄ and some Co₂MnO_4.5 spinels, with a lower reducibility and catalytic activity than cobalt oxide. The available cobalt active sites are responsible for the chain growth, and the accessible acid sites are responsible for the cracking and isomerization. The catalysts prepared using KOH + K₂CO₃ mixture as a precipitant agent exhibited a high selectivity of 51–61% for gasoline (C₅–C₁₀) and 30–50% for jet fuel (C₈–C₁₆) range hydrocarbons compared with catalysts precipitated by KOH. The CoMn-HTC-III catalyst with the highest number of available acid sites showed the highest selectivity to C₅–C₁₀ hydrocarbons, which demonstrates that a high Brønsted acidity leads to the high degree of cracking of FT products. The CO conversion did not significantly change, and it was around 35–39% for all catalysts. Owing to the poor activity in the water-gas shift reaction, CO₂ formation was less than 2% in all the catalysts. Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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15 pages, 2193 KiB

Open AccessFeature PaperArticle

UV-Catalyzed Persulfate Oxidation of an Anthraquinone Based Dye

by Kamil Krawczyk, Stanisław Wacławek, Edyta Kudlek, Daniele Silvestri, Tomasz Kukulski, Klaudiusz Grübel, Vinod V. T. Padil and Miroslav Černík

Catalysts 2020, 10(4), 456; https://doi.org/10.3390/catal10040456 - 23 Apr 2020

Cited by 20 | Viewed by 3912

Abstract

Wastewater from the textile industry has a substantial impact on water quality. Synthetic dyes used in the textile production process are often discharged into water bodies as residues. Highly colored wastewater causes various of problems for the aquatic environment such as: reducing light penetration, inhibiting photosynthesis and being toxic to certain organisms. Since most dyes are resistant to biodegradation and are not completely removed by conventional methods (adsorption, coagulation-flocculation, activated sludge, membrane filtration) they persist in the environment. Advanced oxidation processes (AOPs) based on hydrogen peroxide (H₂O₂) have been proven to decolorize only some of the dyes from wastewater by photocatalysis. In this article, we compared two very different photocatalytic systems (UV/peroxydisulfate and UV/H₂O₂). Photocatalyzed activation of peroxydisulfate (PDS) generated sulfate radicals (SO₄^•−), which reacted with the selected anthraquinone dye of concern, Acid Blue 129 (AB129). Various conditions, such as pH and concentration of PDS were applied, in order to obtain an effective decolorization effect, which was significantly better than in the case of hydroxyl radicals. The kinetics of the reaction followed a pseudo-first order model. The main reaction pathway was also proposed based on quantum chemical analysis. Moreover, the toxicity of the solution after treatment was evaluated using Daphnia magna and Lemna minor, and was found to be significantly lower compared to the toxicity of the initial dye. Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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16 pages, 3448 KiB

Open AccessArticle

Tuning the Selectivity of LaNiO₃ Perovskites for CO₂ Hydrogenation through Potassium Substitution

by Constantine Tsounis, Yuan Wang, Hamidreza Arandiyan, Roong Jien Wong, Cui Ying Toe, Rose Amal and Jason Scott

Catalysts 2020, 10(4), 409; https://doi.org/10.3390/catal10040409 - 8 Apr 2020

Cited by 19 | Viewed by 4836

Abstract

Herein, we demonstrate a method used to tune the selectivity of LaNiO₃ (LNO) perovskite catalysts through the substitution of La with K cations. LNO perovskites were synthesised using a simple sol-gel method, which exhibited 100% selectivity towards the methanation of CO₂ at all temperatures investigated. La cations were partially replaced by K cations to varying degrees via control of precursor metal concentration during synthesis. It was demonstrated that the reaction selectivity between CO₂ methanation and the reverse water gas shift (rWGS) could be tuned depending on the initial amount of K substituted. Tuning the selectivity (i.e., ratio of CH₄ and CO products) between these reactions has been shown to be beneficial for downstream hydrocarbon reforming, while valorizing waste CO₂. Spectroscopic and temperature-controlled desorption characterizations show that K incorporation on the catalyst surface decrease the stability of C-based intermediates, promoting the desorption of CO formed via the rWGS prior to methanation. Full article

(This article belongs to the Special Issue Greener Catalysis for Environmental Applications)

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