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Towards Catalysts Prepared by Cold Plasma
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Towards Catalysts Prepared by Cold Plasma

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

Deadline for manuscript submissions: closed (15 November 2021) | Viewed by 24263

Special Issue Editors

Prof. Dr. Jacek Tyczkowski

E-Mail Website1 Website2
Guest Editor
Department of Molecular Engineering, Faculty of Process and Environmental Engineering, Lodz University of Technology, Wolczanska 213, 90-924 Lodz, Poland
Interests: molecular engineering; nanotechnology; surface engineering; plasma technology; cold plasma chemistry; nanocatalysts; plasma-deposited thin films; plasma biomedicine; water splitting; CO2 conversion
Prof. Dr. Hanna Kierzkowska-Pawlak

E-Mail Website1 Website2
Guest Editor
Department of Molecular Engineering, Faculty of Process and Environmental Engineering, Lodz University of Technology, Wolczanska 213, 90-924 Lodz, Poland
Interests: heterogeneous catalysis; reaction engineering; cold plasma; thin-film catalysts; CO2 capture; gas absorption; amines; CO2 conversion

Special Issue Information

Dear Colleagues,

Cold plasma techniques are widely used to create new materials with a unique structure and unique properties, which very often cannot be prepared by other methods. Among these interesting materials, a special place is occupied by new types of catalysts, starting from plasma-modified conventional catalysts, through plasma-assisted synthesized catalysts, to advanced thin catalytic films produced, for example, via plasma sputtering processes or using the ALD technique, but primarily via plasma deposition from volatile organic and organometallic precursors (PECVD). Catalytic films have recently attracted considerable attention due to the possibility of depositing them as very thin coatings on virtually all supports without causing any change in their geometry. Such coatings pave the way for new reactor designs—so-called structured reactors—leading to intensified processes on a large scale. They can also be used as a catalytic deposit on the surface of electrodes for fuel cells and photoelectrodes for water splitting processes.

The aim of this Special Issue is to cover recent developments and further prospects in the field of catalysts produced using cold plasma. Publications in the form of original research papers or short reviews regarding all aspects of plasma-modified catalysts; plasma-assisted synthesized catalysts; and, above all, plasma-deposited thin-film catalysts are welcome. Any manuscripts discussing plasma processes associated with the production of catalytic materials; the molecular and nano structures of these catalysts; as well as their catalytic, electrocatalytic, and photocatalytic activity, both at the level of basic and applied research, are expected.

Prof. Dr. Jacek Tyczkowski
Prof. Dr. Hanna Kierzkowska-Pawlak
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 2200 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

  • Cold plasma techniques;
  • Plasma-modified catalysts;
  • Plasma-assisted synthesized catalysts;
  • Plasma-deposited thin-film catalysts;
  • Molecular and nano structures;
  • Catalytic properties;
  • Structured catalysts and reactors;
  • Photo and electrocatalytic electrodes.

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Published Papers (9 papers)

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Editorial

Jump to: Research

3 pages, 192 KiB  
Editorial
Towards Catalysts Prepared by Cold Plasma
by Jacek Tyczkowski and Hanna Kierzkowska-Pawlak
Catalysts 2022, 12(1), 75; https://doi.org/10.3390/catal12010075 - 11 Jan 2022
Cited by 3 | Viewed by 1682
Abstract
Cold (non-equilibrium) plasma techniques have long been used as plasma deposition methods to create new materials, often with unique properties, which cannot be produced any other way, as well as plasma treatment methods for the sophisticated modification of conventional materials [...] Full article
(This article belongs to the Special Issue Towards Catalysts Prepared by Cold Plasma)

Research

Jump to: Editorial

41 pages, 11457 KiB  
Article
The Effect of Cobalt Catalyst Loading at Very High Pressure Plasma-Catalysis in Fischer-Tropsch Synthesis
by Byron Bradley Govender, Samuel Ayodele Iwarere and Deresh Ramjugernath
Catalysts 2021, 11(11), 1324; https://doi.org/10.3390/catal11111324 - 31 Oct 2021
Cited by 3 | Viewed by 2332
Abstract
The influence of different catalyst cobalt loadings on the C1–C3 hydrocarbon product yields and energy consumption in plasma-catalytic Fischer-Tropsch synthesis (FTS) was investigated from the standpoint of various reactor operating conditions: pressure (0.5 to 10 MPa), current (250 to 450 [...] Read more.
The influence of different catalyst cobalt loadings on the C1–C3 hydrocarbon product yields and energy consumption in plasma-catalytic Fischer-Tropsch synthesis (FTS) was investigated from the standpoint of various reactor operating conditions: pressure (0.5 to 10 MPa), current (250 to 450 mA) and inter-electrode gap (0.5 to 2 mm). This was accomplished by introducing a mullite substrate, coated with 2 wt%-Co/5 wt%-Al2O3, 6 wt%-Co/5 wt%-Al2O3 or 0 wt%-Co/5 wt%-Al2O3 (blank catalyst), into a recently developed high pressure arc discharge reactor. The blank catalyst was ineffective in synthesizing hydrocarbons. Between the blank catalyst, 2 wt%, and the 6 wt% Co catalyst, the 6 wt% improved C1–C3 hydrocarbon production at all conditions, with higher yields and relatively lower energy consumption at (i) 10 MPa at 10 s, and 2 MPa at 60 s, for the pressure variation study; (ii) 250 mA for the current variation study; and (iii) 2 mm for the inter-electrode gap variation study. The inter-electrode gap of 2 mm, using the 6 wt% Co catalyst, led to the overall highest methane, ethane, ethylene, propane and propylene yields of 22 424, 517, 101, 79 and 19 ppm, respectively, compared to 40 ppm of methane and <1 ppm of C1–C3 hydrocarbons for the blank catalyst, while consuming 660 times less energy for the production of a mole of methane. Furthermore, the 6 wt% Co catalyst produced carbon nanotubes (CNTs), detected via transmission electron microscopy (TEM). In addition, scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX) and x-ray diffraction (XRD) showed that the cobalt catalyst was modified by plasma treatment. Full article
(This article belongs to the Special Issue Towards Catalysts Prepared by Cold Plasma)
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13 pages, 3636 KiB  
Article
Cold Plasma Synthesis and Testing of NiOX-Based Thin-Film Catalysts for CO2 Methanation
by Martyna Smolarek, Hanna Kierzkowska-Pawlak, Ryszard Kapica, Maciej Fronczak, Maciej Sitarz, Magdalena Leśniak and Jacek Tyczkowski
Catalysts 2021, 11(8), 905; https://doi.org/10.3390/catal11080905 - 26 Jul 2021
Cited by 8 | Viewed by 2168
Abstract
An essential problem in managing CO2 and transforming it into methane as a useful fuel is the quest for adequately efficient and cheap catalysts. Another condition is imposed by the new designs of structured reactors, which require catalysts in the form of [...] Read more.
An essential problem in managing CO2 and transforming it into methane as a useful fuel is the quest for adequately efficient and cheap catalysts. Another condition is imposed by the new designs of structured reactors, which require catalysts in the form of the thinnest possible films. The aim of this work was to produce Ni-based thin-film catalysts by the cold plasma deposition method (PECVD) from a volatile metal complex (Ni(CO)4) and to study their structure and catalytic properties in the CO2 methanation process. We tested three basic types of films: as-deposited, calcined in Ar, and calcined in air. The nanostructure and molecular structure of the films were investigated by electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The catalytic activity was evaluated in the methanation process (CO2 + H2), which was performed in a tubular reactor operating in the temperature range of 300–400 °C. The films calcined in air showed the highest activity in this process but behaved unstably. However, their regeneration by recalcination in air restored the initial catalytic activity. An important conclusion emerged from the obtained results, namely that the active phase in the tested films is Ni3+ (most likely in the form of Ni2O3), contrary to the common opinion that this phase is metallic Ni0. In our case, Ni0 quenches the catalytic activity. Full article
(This article belongs to the Special Issue Towards Catalysts Prepared by Cold Plasma)
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18 pages, 3097 KiB  
Article
Enhancing CO2 Conversion to CO over Plasma-Deposited Composites Based on Mixed Co and Fe Oxides
by Hanna Kierzkowska-Pawlak, Małgorzata Ryba, Maciej Fronczak, Ryszard Kapica, Jan Sielski, Maciej Sitarz, Patryk Zając, Klaudia Łyszczarz and Jacek Tyczkowski
Catalysts 2021, 11(8), 883; https://doi.org/10.3390/catal11080883 - 22 Jul 2021
Cited by 8 | Viewed by 2944
Abstract
The hydrogenation of CO2 to produce CO and H2O, known as reverse-water-gas shift reaction (RWGS) is considered to be an important CO2 valorization pathway. This work is aimed at proposing the thin-film catalysts based on iron and cobalt oxides [...] Read more.
The hydrogenation of CO2 to produce CO and H2O, known as reverse-water-gas shift reaction (RWGS) is considered to be an important CO2 valorization pathway. This work is aimed at proposing the thin-film catalysts based on iron and cobalt oxides for this purpose. A series of Fe–Co nanocomposites were prepared by the plasma-enhanced chemical vapor deposition (PECVD) from organic cobalt and iron precursors on a wire-mesh support. The catalysts were characterized by SEM/EDX, XPS, XRD, and Raman spectroscopy and studied for hydrogenation of CO2 in a tubular reactor operating in the temperature range of 250–400 °C and atmospheric pressure. The Co-based catalyst, containing crystalline CoO phase, exhibited high activity toward CH4, while the Fe-based catalyst, containing crystalline Fe2O3/Fe3O4 phases, was less active and converted CO2 mainly into CO. Regarding the Fe–Co nanocomposites (incl. Fe2O3/Fe3O4 and CoO), even a small fraction of iron dramatically inhibited the production of methane. With increasing the atomic fraction of iron in the Fe–Co systems, the efficiency of the RWGS reaction at 400 °C increased up to 95% selectivity to CO and 30% conversion of CO2, which significantly exceeded the conversion for pure iron–based films (approx. 9%). The superior performance of the Fe–Co nanocomposites compared to “pure” Co and Fe–based films was proposed to be explained by assuming changes in the electronic structure of the catalyst resulting from the formation of p–n junctions between nanoparticles of cobalt and iron oxides. Full article
(This article belongs to the Special Issue Towards Catalysts Prepared by Cold Plasma)
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14 pages, 5752 KiB  
Article
Plasma-Catalytic Process of Hydrogen Production from Mixture of Methanol and Water
by Bogdan Ulejczyk, Łukasz Nogal, Paweł Jóźwik, Michał Młotek and Krzysztof Krawczyk
Catalysts 2021, 11(7), 864; https://doi.org/10.3390/catal11070864 - 19 Jul 2021
Cited by 14 | Viewed by 3367
Abstract
In the present work the process of hydrogen production was conducted in the plasma-catalytic reactor, the substrates were first treated with plasma and then introduced into the catalyst bed. Plasma was produced by a spark discharge. The discharge power ranged from 15 to [...] Read more.
In the present work the process of hydrogen production was conducted in the plasma-catalytic reactor, the substrates were first treated with plasma and then introduced into the catalyst bed. Plasma was produced by a spark discharge. The discharge power ranged from 15 to 46 W. The catalyst was metallic nickel supported on Al2O3. The catalyst was active from a temperature of 400 °C. The substrate flow rate was 1 mol/h of water and 1 mol/h of methanol. The process generated H2, CO, CO2 and CH4. The gas which formed the greatest amount was H2. Its concentration in the gas was ~60%. The conversion of methanol and the production of hydrogen in the plasma-catalytic reactor were higher than in the plasma and catalytic reactors. The synergy effect of the interaction of two environments, i.e., plasma and the catalyst, was observed. The highest hydrogen production was 1.38 mol/h and the highest methanol conversion was 64%. The increased in the discharge power resulted in increasing methanol conversion and hydrogen production. Full article
(This article belongs to the Special Issue Towards Catalysts Prepared by Cold Plasma)
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8 pages, 1780 KiB  
Article
Decomposition of Tars on a Nickel Honeycomb Catalyst
by Joanna Woroszył-Wojno, Michał Młotek, Michalina Perron, Paweł Jóźwik, Bogdan Ulejczyk and Krzysztof Krawczyk
Catalysts 2021, 11(7), 860; https://doi.org/10.3390/catal11070860 - 19 Jul 2021
Cited by 2 | Viewed by 2838
Abstract
Biomass can be considered a renewable energy source. It undergoes a gasification process to obtain gaseous fuel, which converts it into combustible gaseous products such as hydrogen, carbon monoxide, and methane. The process also generates undesirable tars that can condense in gas lines [...] Read more.
Biomass can be considered a renewable energy source. It undergoes a gasification process to obtain gaseous fuel, which converts it into combustible gaseous products such as hydrogen, carbon monoxide, and methane. The process also generates undesirable tars that can condense in gas lines and cause corrosion, and after processing, can be an additional source of combustible gases. This study focused on the processing of tar substances with toluene as a model substance. The effect of discharge power and carrier gas composition on toluene conversion was tested. The process was conducted in a plasma-catalytic system with a new Ni3Al system in the form of a honeycomb. The toluene conversion reached 90%, and small amounts of ethane, ethylene, acetylene, benzene, and C3 and C4 hydrocarbons were detected in the post-reaction mixture. Changes in the surface composition of the Ni3Al catalyst were observed throughout the experiments. These changes did not affect the toluene conversion. Full article
(This article belongs to the Special Issue Towards Catalysts Prepared by Cold Plasma)
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13 pages, 2701 KiB  
Article
Nonthermal Plasma Induced Fabrication of Solid Acid Catalysts for Glycerol Dehydration to Acrolein
by Lu Liu and Xiaofei Philip Ye
Catalysts 2021, 11(3), 391; https://doi.org/10.3390/catal11030391 - 19 Mar 2021
Cited by 11 | Viewed by 2475
Abstract
The feasibility of fabricating better solid acid catalysts using nonthermal plasma (NTP) technology for biobased acrolein production is demonstrated. NTP discharge exposure was integrated in catalyst fabrication in air or argon atmosphere. The fabricated catalysts were characterized by Brunauer–Emmett–Teller surface area analysis, temperature-programmed [...] Read more.
The feasibility of fabricating better solid acid catalysts using nonthermal plasma (NTP) technology for biobased acrolein production is demonstrated. NTP discharge exposure was integrated in catalyst fabrication in air or argon atmosphere. The fabricated catalysts were characterized by Brunauer–Emmett–Teller surface area analysis, temperature-programmed desorption of ammonia, X-ray powder diffraction and Fourier-transform infrared spectroscopy of pyridine adsorption, in comparison to regularly prepared catalysts as a control. Further, kinetic results collected via glycerol dehydration experiments were compared, and improvement in acrolein selectivity was displayed when the catalyst was fabricated in the argon NTP, but not in the air NTP. Possible mechanisms for the improvement were also discussed. Full article
(This article belongs to the Special Issue Towards Catalysts Prepared by Cold Plasma)
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25 pages, 5357 KiB  
Article
Plasma-Catalytic Fischer–Tropsch Synthesis at Very High Pressure
by Byron Bradley Govender, Samuel Ayodele Iwarere and Deresh Ramjugernath
Catalysts 2021, 11(3), 297; https://doi.org/10.3390/catal11030297 - 25 Feb 2021
Cited by 8 | Viewed by 2586
Abstract
This study explored Fischer–Tropsch synthesis (FTS) by combining a non-thermal plasma (NTP), generated by an arc discharge reactor at pressures >> 1 MPa, coupled with a mullite-coated 2 wt%-Co/5 wt%-Al2O3 catalyst. The FTS product yields and electrical energy consumption for [...] Read more.
This study explored Fischer–Tropsch synthesis (FTS) by combining a non-thermal plasma (NTP), generated by an arc discharge reactor at pressures >> 1 MPa, coupled with a mullite-coated 2 wt%-Co/5 wt%-Al2O3 catalyst. The FTS product yields and electrical energy consumption for the pure plasma (no catalyst) and plasma-catalytic FTS processes were compared under the scope of various reactor operating parameters, namely, pressure (0.5 to 10 MPa), current (250 to 450 mA) and inter-electrode gap (0.5 to 2 mm). The major products, obtained in low concentrations for both processes, were gaseous C1–C3 hydrocarbons, synthesised in the order: methane >> ethane > ethylene > propane. The hydrocarbon product yields were observed to increase, while the specific required energy generally decreased with increasing pressure, decreasing current and increasing inter-electrode gap. Plasma-catalysis improved the FTS performance, with the optimum conditions as: (i) 10 MPa at 10 s and 2 MPa at 60 s for the pressure variation study with the longer treatment time producing higher yields; (ii) 250 mA for the current variation study; (iii) 2 mm for the inter-electrode gap variation study. Plasma-catalysis at a gap of 2 mm yielded the highest concentrations of methane (15,202 ppm), ethane (352 ppm), ethylene (121 ppm) and propane (20 ppm), thereby indicating the inter-electrode gap as the most influential parameter. Full article
(This article belongs to the Special Issue Towards Catalysts Prepared by Cold Plasma)
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11 pages, 2731 KiB  
Article
Non-Thermal Plasma-Modified Ru-Sn-Ti Catalyst for Chlorinated Volatile Organic Compound Degradation
by Yujie Fu, You Zhang, Qi Xin, Zhong Zheng, Yu Zhang, Yang Yang, Shaojun Liu, Xiao Zhang, Chenghang Zheng and Xiang Gao
Catalysts 2020, 10(12), 1456; https://doi.org/10.3390/catal10121456 - 13 Dec 2020
Cited by 3 | Viewed by 2618
Abstract
Chlorinated volatile organic compounds (CVOCs) are vital environmental concerns due to their low biodegradability and long-term persistence. Catalytic combustion technology is one of the more commonly used technologies for the treatment of CVOCs. Catalysts with high low-temperature activity, superior selectivity of non-toxic products, [...] Read more.
Chlorinated volatile organic compounds (CVOCs) are vital environmental concerns due to their low biodegradability and long-term persistence. Catalytic combustion technology is one of the more commonly used technologies for the treatment of CVOCs. Catalysts with high low-temperature activity, superior selectivity of non-toxic products, and resistance to chlorine poisoning are desirable. Here we adopted a plasma treatment method to synthesize a tin-doped titania loaded with ruthenium dioxide (RuO2) catalyst, possessing enhanced activity (T90%, the temperature at which 90% of dichloromethane (DCM) is decomposed, is 262 °C) compared to the catalyst prepared by the conventional calcination method. As revealed by transmission electron microscopy, X-ray diffraction, N2 adsorption, X-ray photoelectron spectroscopy, and hydrogen temperature-programmed reduction, the high surface area of the tin-doped titania catalyst and the enhanced dispersion and surface oxidation of RuO2 induced by plasma treatment were found to be the main factors determining excellent catalytic activities. Full article
(This article belongs to the Special Issue Towards Catalysts Prepared by Cold Plasma)
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