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Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation
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Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation

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

Deadline for manuscript submissions: closed (30 September 2022) | Viewed by 25254

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editors

Dr. Magdalena Zybert

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Guest Editor
Department of Chemical Technology, Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland
Interests: heterogeneous catalysis; catalyst preparation; catalyst characterization; ammonia synthesis; cobalt catalysts; thermal analysis; sorption techniques; materials chemistry
Special Issues, Collections and Topics in MDPI journals
Dr. Katarzyna Antoniak-Jurak

E-Mail Website
Guest Editor
Łukasiewicz Research Network—New Chemical Syntheses Institute, Al. Tysiąclecia Państwa Polskiego 13a, 24-110 Puławy, Poland
Interests: heterogeneous catalysis; synthesis and characterization of nanomaterials; scale-up of catalytic materials production; water gas shift and hydrogen production

Special Issue Information

Dear Colleagues,

Catalysis is very important in terms of sustainable development, energy production, environmental protection, food production, and water purification, among others. The practical importance of catalysis is due to the fact that almost 90% of the products of the chemical industry are produced by catalytic processes. The great economic and strategic importance of catalysis makes it a rapidly evolving field. In the face of the great challenges of the present day, the acquisition of fundamental knowledge about the structure and phenomena on catalysts’ surface as well as relationships between catalysts composition, synthesis method, properties, and their performance in industrial processes is essential. Research is still needed to improve existing catalysts or design new systems which may efficiently and selectively conduct a given reaction toward the desired product.

This Special Issue is devoted to the design and characterization of heterogeneous catalytic systems for industrial inorganic chemical processes. The aim is to collect the current state of knowledge, indicate areas requiring further research, and show the direction of ongoing development work. The main attention will be focused on comprehensive experimental studies of synthesis, characterization, and evaluation of catalyst performance in industrial processes such as, but not limited to, methane conversion, water–gas–shift reaction, ammonia synthesis, ammonia decomposition, carbon oxide methanation, selective catalytic reduction of nitrogen oxides, high-temperature N2O decomposition, and low-temperature N2O decomposition.

The scope also includes an investigation of catalysts under conditions close to the industrial ones, a comparison of the studied catalytic systems with the currently operating commercial systems, and a demonstration of the validity of their application in a given chemical process.

Dr. Magdalena Zybert
Dr. Katarzyna Antoniak-Jurak
Guest Editors

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

  • Industrial inorganic chemistry
  • Nanomaterials
  • Carbon nanomaterials
  • Heterogeneous catalyst
  • Catalyst synthesis
  • Catalyst characterization
  • Catalyst design
  • Catalyst deactivation
  • Thermodynamics and kinetics
  • Modeling and simulation of catalytic reactors

Published Papers (11 papers)

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Editorial

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4 pages, 189 KiB  
Editorial
Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation
by Magdalena Zybert
Catalysts 2023, 13(3), 607; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13030607 - 17 Mar 2023
Cited by 1 | Viewed by 2093
Abstract
Catalysis is a very important process with practical significance for sustainable development, energy production, environmental protection, food production, and water purification, among others, and catalytic processes produce almost 90% of the products in the chemical industry [...] Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)

Research

Jump to: Editorial

16 pages, 6560 KiB  
Article
The Influence of Active Phase Content on Properties and Activity of Nd2O3-Supported Cobalt Catalysts for Ammonia Synthesis
by Wojciech Patkowski, Magdalena Zybert, Hubert Ronduda, Gabriela Gawrońska, Aleksander Albrecht, Dariusz Moszyński, Aleksandra Fidler, Piotr Dłużewski and Wioletta Raróg-Pilecka
Catalysts 2023, 13(2), 405; https://0-doi-org.brum.beds.ac.uk/10.3390/catal13020405 - 14 Feb 2023
Cited by 6 | Viewed by 1572
Abstract
A series of neodymium oxide-supported cobalt catalysts with cobalt content ranging from 10 to 50 wt.% was obtained through the recurrent deposition-precipitation method. The effect of active phase, i.e., metallic cobalt, content on structural parameters, morphology, crystal structure, surface state, composition and activity [...] Read more.
A series of neodymium oxide-supported cobalt catalysts with cobalt content ranging from 10 to 50 wt.% was obtained through the recurrent deposition-precipitation method. The effect of active phase, i.e., metallic cobalt, content on structural parameters, morphology, crystal structure, surface state, composition and activity of the catalysts was determined after detailed physicochemical measurements were performed using ICP-AES, N2 physisorption, XRPD, TEM, HRTEM, STEM-EDX, H2-TPD and XPS methods. The results indicate that the catalyst activity strongly depends on the active phase content due to the changes in average cobalt particle size. With the increase of the cobalt content, the productivity per catalyst mass increases, while TOF maintains a constant value. The TOF is below average only for the catalyst with the lowest cobalt content, i.e., when the average Co particle size is below 20 nm. This is due to the predominance of strong hydrogen binding sites on the surface, leading to hydrogen poisoning which prevents nitrogen adsorption, thus inhibiting the rate-determining step of the process. Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)
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13 pages, 3369 KiB  
Article
Structure Sensitivity of Ammonia Synthesis on Cobalt: Effect of the Cobalt Particle Size on the Activity of Promoted Cobalt Catalysts Supported on Carbon
by Magdalena Zybert, Aleksandra Tarka, Wojciech Patkowski, Hubert Ronduda, Bogusław Mierzwa, Leszek Kępiński and Wioletta Raróg-Pilecka
Catalysts 2022, 12(10), 1285; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12101285 - 21 Oct 2022
Cited by 6 | Viewed by 1780
Abstract
This work presents a size effect, i.e., catalyst surface activity, as a function of active phase particle size in a cobalt catalyst for ammonia synthesis. A series of cobalt catalysts supported on carbon and doped with barium was prepared, characterized (TEM, XRPD, and [...] Read more.
This work presents a size effect, i.e., catalyst surface activity, as a function of active phase particle size in a cobalt catalyst for ammonia synthesis. A series of cobalt catalysts supported on carbon and doped with barium was prepared, characterized (TEM, XRPD, and H2 chemisorption), and tested in ammonia synthesis (9.0 MPa, 400 °C, H2/N2 = 3, 8.5 mol% of NH3). The active phase particle size was varied from 3 to 45 nm by changing the metal loading in the range of 4.9–67.7 wt%. The dependence of the reaction rate expressed as TOF on the active phase particle size revealed an optimal size of cobalt particles (20–30 nm), ensuring the highest activity of the cobalt catalyst in the ammonia synthesis reaction. This indicated that the ammonia synthesis reaction on cobalt is a structure-sensitive reaction. The observed effect may be attributed to changes in the crystalline structure, i.e., the appearance of the hcp Co phase for the particles with a diameter of 20–30 nm. Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)
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14 pages, 2622 KiB  
Article
Block Copolymer and Cellulose Templated Mesoporous TiO2-SiO2 Nanocomposite as Superior Photocatalyst
by Sudipto Pal, Antonietta Taurino, Massimo Catalano and Antonio Licciulli
Catalysts 2022, 12(7), 770; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12070770 - 12 Jul 2022
Cited by 6 | Viewed by 1556
Abstract
A dual soft-templating method was developed to produce highly crystalline and mesoporous TiO2-SiO2 nanocomposites. Pluronic F127 as the structure-directing agent and pure cellulose as the surface area modifier were used as the templating media. While Pluronic F127 served as the [...] Read more.
A dual soft-templating method was developed to produce highly crystalline and mesoporous TiO2-SiO2 nanocomposites. Pluronic F127 as the structure-directing agent and pure cellulose as the surface area modifier were used as the templating media. While Pluronic F127 served as the sacrificing media for generating a mesoporous structure in an acidic pH, cellulose templating helped to increase the specific surface area without affecting the mesoporosity of the TiO2-SiO2 nanostructures. Calcination at elevated temperature removed all the organics and formed pure inorganic TiO2-SiO2 composites as revealed by TGA and FTIR analyses. An optimum amount of SiO2 insertion in the TiO2 matrix increased the thermal stability of the crystalline anatase phase. BET surface area measurement along with low angle XRD revealed the formation of a mesoporous structure in the composites. The photocatalytic activity was evaluated by the degradation of Rhodamine B, Methylene Blue, and 4-Nitrophenol as the model pollutants under solar light irradiation, where the superior photo-degradation activity of Pluronic F127/cellulose templated TiO2-SiO2 was observed compared to pure Pluronic templated composite and commercial Evonik P25 TiO2. The higher photocatalytic activity was achieved due to the higher thermal stability of the nanocrystalline anatase phase, the mesoporosity, and the higher specific surface area. Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)
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15 pages, 3108 KiB  
Article
Physicochemical Features and NH3-SCR Catalytic Performance of Natural Zeolite Modified with Iron—The Effect of Fe Loading
by Magdalena Saramok, Marek Inger, Katarzyna Antoniak-Jurak, Agnieszka Szymaszek-Wawryca, Bogdan Samojeden and Monika Motak
Catalysts 2022, 12(7), 731; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12070731 - 01 Jul 2022
Cited by 5 | Viewed by 1623
Abstract
In modern dual-pressure nitric acid plants, the tail gas temperature usually exceeds 300 °C. The NH3-SCR catalyst used in this temperature range must be resistant to thermal deactivation, so commercial vanadium-based systems, such as V2O5-WO3 (MoO [...] Read more.
In modern dual-pressure nitric acid plants, the tail gas temperature usually exceeds 300 °C. The NH3-SCR catalyst used in this temperature range must be resistant to thermal deactivation, so commercial vanadium-based systems, such as V2O5-WO3 (MoO3)-TiO2, are most commonly used. However, selectivity of this material significantly decreases above 350 °C due to the increase in the rate of side reactions, such as oxidation of ammonia to NO and formation of N2O. Moreover, vanadium compounds are toxic for the environment. Thus, management of the used catalyst is complicated. One of the alternatives to commercial V2O5-TiO2 catalysts are natural zeolites. These materials are abundant in the environment and are thus relatively cheap and easily accessible. Therefore, the aim of the study was to design a novel iron-modified zeolite catalyst for the reduction of NOx emission from dual-pressure nitric acid plants via NH3-SCR. The aim of the study was to determine the influence of iron loading in the natural zeolite-supported catalyst on its catalytic performance in NOx conversion. The investigated support was firstly formed into pellets and then impregnated with various contents of Fe precursor. Physicochemical characteristics of the catalyst were determined by XRF, XRD, low-temperature N2 sorption, FT-IR, and UV–Vis. The catalytic performance of the catalyst formed into pellets was tested on a laboratory scale within the range of 250–450 °C using tail gases from a pilot nitric acid plant. The results of this study indicated that the presence of various iron species, including natural isolated Fe3+ and the introduced FexOy oligomers, contributed to efficient NOx reduction, especially in the high-temperature range, where the NOx conversion rate exceeded 90%. Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)
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10 pages, 1673 KiB  
Article
Toluene Decomposition in Plasma–Catalytic Systems with Nickel Catalysts on CaO-Al2O3 Carrier
by Joanna Woroszył-Wojno, Michał Młotek, Bogdan Ulejczyk and Krzysztof Krawczyk
Catalysts 2022, 12(6), 635; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12060635 - 10 Jun 2022
Cited by 1 | Viewed by 1858
Abstract
The decomposition of toluene as a tar imitator in a gas composition similar to the gas after biomass pyrolysis was studied in a plasma–catalytic system. Nickel catalysts and the plasma from gliding arc discharge under atmospheric pressure were used. The effect of the [...] Read more.
The decomposition of toluene as a tar imitator in a gas composition similar to the gas after biomass pyrolysis was studied in a plasma–catalytic system. Nickel catalysts and the plasma from gliding arc discharge under atmospheric pressure were used. The effect of the catalyst bed, discharge power, initial toluene, and hydrogen concentration on C7H8 decomposition, calorific value, and unit energy consumption were studied. The gas flow rate was 1000 NL/h, while the inlet gas composition (molar ratio) was CO (0.13), CO2 (0.15), H2 (0.28–0.38), and N2 (0.34–0.44). The study was conducted using an initial toluene concentration in the range of 2000–4500 ppm and a discharge power of 1500–2000 W. In plasma–catalytic systems, the following catalysts were compared: NiO/Al2O3, NiO/(CaO-Al2O3), and Ni/(CaO-Al2O3). The decomposition of toluene increased with its initial concentration. An increase in hydrogen concentration resulted in higher activity of the Ni/(CaO-Al2O3) catalysts. The gas composition did not change by more than 10% during the process. Trace amounts of C2 hydrocarbons were observed. The conversion of C7H8 was up to 85% when NiO/(CaO-Al2O3) was used. The products of the toluene decomposition reactions were not adsorbed onto its surface. The calorific value was not changed during the process and was higher than required for turbines and engines in every system studied. Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)
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21 pages, 10718 KiB  
Article
Effect of Potassium Promoter on the Performance of Nickel-Based Catalysts Supported on MnOx in Steam Reforming of Ethanol
by Magdalena Greluk, Marek Rotko, Grzegorz Słowik, Sylwia Turczyniak-Surdacka, Gabriela Grzybek, Kinga Góra-Marek and Andrzej Kotarba
Catalysts 2022, 12(6), 600; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12060600 - 31 May 2022
Cited by 6 | Viewed by 1896
Abstract
The effect of a potassium promoter on the stability of and resistance to a carbon deposit formation on the Ni/MnOx catalyst under SRE conditions was studied at 420 °C for different H2O/EtOH molar ratios in the range from 4/1 to [...] Read more.
The effect of a potassium promoter on the stability of and resistance to a carbon deposit formation on the Ni/MnOx catalyst under SRE conditions was studied at 420 °C for different H2O/EtOH molar ratios in the range from 4/1 to 12/1. The catalysts were prepared by the impregnation method and characterized using several techniques to study their textural, structural, and redox properties before being tested in a SRE reaction. The catalytic tests indicated that the addition of a low amount of potassium (1.6 wt.%) allows a catalyst with high stability to be obtained, which was ascribed to high resistance to carbon formation. The restriction of the amount of carbon deposits originates from the potassium presence on the Ni surface, which leads to (i) a decrease in the number of active sites available for methane decomposition and (ii) an increase in the rate of the steam gasification of carbon formed during SRE reactions. Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)
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24 pages, 9962 KiB  
Article
Kinetic Study and Modeling of the Degradation of Aqueous Ammonium/Ammonia Solutions by Heterogeneous Photocatalysis with TiO2 in a UV-C Pilot Photoreactor
by Juan C. García-Prieto, Luis A. González-Burciaga, José B. Proal-Nájera and Manuel García-Roig
Catalysts 2022, 12(3), 352; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12030352 - 21 Mar 2022
Cited by 5 | Viewed by 2377
Abstract
The degradation mechanism of NH4+/NH3 in aqueous solutions by heterogeneous photocatalysis (TiO2/SiO2) and photolysis in UV-C pilot photoreactor has been studied. Under the conditions used, NH4+/NH3 can be decomposed both by [...] Read more.
The degradation mechanism of NH4+/NH3 in aqueous solutions by heterogeneous photocatalysis (TiO2/SiO2) and photolysis in UV-C pilot photoreactor has been studied. Under the conditions used, NH4+/NH3 can be decomposed both by photolytically and photocatalytically, without disregarding stripping processes. The greatest degradation is achieved at the highest pH studied (pH 11.0) and at higher lamp irradiation power used (25 W) with degradation performances of 44.1% (photolysis) and 59.7% (photocatalysis). The experimental kinetic data fit well with a two parallel reactions mechanism. A low affinity of ammonia for adsorption and surface reaction on the photocatalytic fiber was observed (coverage not higher than 10%), indicating a low influence of surface phenomena on the reaction rate, the homogeneous phase being predominant over the heterogeneous phase. The proposed reaction mechanism was validated, confirming that it is consistent with the photocatalytic and photolytic formation of nitrogen gas, on the one hand, and the formation of nitrate, on the other hand. At the optimal conditions, the rate constants were k3 = 0.154 h−1 for the disappearance of ammonia and k1 = 3.3 ± 0.2 10−5 h−1 and k2 = 1.54 ± 0.07 10−1 h−1 for the appearance of nitrate and nitrogen gas, respectively. Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)
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12 pages, 30427 KiB  
Article
A Promising Cobalt Catalyst for Hydrogen Production
by Bogdan Ulejczyk, Paweł Jóźwik, Michał Młotek and Krzysztof Krawczyk
Catalysts 2022, 12(3), 278; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12030278 - 01 Mar 2022
Cited by 7 | Viewed by 3526
Abstract
In this work, a metal cobalt catalyst was synthesized, and its activity in the hydrogen production process was tested. The substrates were water and ethanol. Activity tests were conducted at a temperature range of 350–600 °C, water to ethanol molar ratio of 3 [...] Read more.
In this work, a metal cobalt catalyst was synthesized, and its activity in the hydrogen production process was tested. The substrates were water and ethanol. Activity tests were conducted at a temperature range of 350–600 °C, water to ethanol molar ratio of 3 to 5, and a feed flow of 0.4 to 1.2 mol/h. The catalyst had a specific surface area of 1.75 m2/g. The catalyst was most active at temperatures in the range of 500–600 °C. Under the most favorable conditions, the ethanol conversion was 97%, the hydrogen production efficiency was 4.9 mol (H2)/mol(ethanol), and coke production was very low (16 mg/h). Apart from hydrogen and coke, CO2, CH4, CO, and traces of C2H2 and C2H4 were formed. Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)
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14 pages, 2234 KiB  
Article
On Optimal Barium Promoter Content in a Cobalt Catalyst for Ammonia Synthesis
by Aleksandra Tarka, Magdalena Zybert, Hubert Ronduda, Wojciech Patkowski, Bogusław Mierzwa, Leszek Kępiński and Wioletta Raróg-Pilecka
Catalysts 2022, 12(2), 199; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12020199 - 06 Feb 2022
Cited by 6 | Viewed by 2583
Abstract
High priority in developing an efficient cobalt catalyst for ammonia synthesis involves optimizing its composition in terms of the content of promoters. In this work, a series of cobalt catalysts doubly promoted with cerium and barium was prepared and tested in ammonia synthesis [...] Read more.
High priority in developing an efficient cobalt catalyst for ammonia synthesis involves optimizing its composition in terms of the content of promoters. In this work, a series of cobalt catalysts doubly promoted with cerium and barium was prepared and tested in ammonia synthesis (H2/N2 = 3, 6.3 MPa, 400 °C). Barium content was studied in the range of 0–2.6 mmol gCo−1. Detailed characterization studies by nitrogen physisorption, SEM-EDX, XRPD, H2-TPR, and H2-TPD showed the impact of barium loading in CoCeBa catalysts on the physicochemical properties and activity of the catalysts. The most pronounced effect was observed in the development of the active phase surface, a differentiation of weakly and strongly binding sites on the catalyst surface and changes in cobalt surface activity (TOF). Barium content in the range of 1.1–1.6 mmol gCo−1 leads to obtaining a catalyst with the most favorable properties. Its excellent catalytic performance is ascribed to the appropriate Ba/Ce molar ratio, i.e., greater than unity, which results in not only a structural promotion of barium, but also a modifying action associated with the in-situ formation of the BaCeO3 phase. Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)
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10 pages, 1158 KiB  
Article
Thermal Stability of Potassium-Promoted Cobalt Molybdenum Nitride Catalysts for Ammonia Synthesis
by Paweł Adamski, Wojciech Czerwonko and Dariusz Moszyński
Catalysts 2022, 12(1), 100; https://0-doi-org.brum.beds.ac.uk/10.3390/catal12010100 - 16 Jan 2022
Cited by 5 | Viewed by 2443
Abstract
The application of cobalt molybdenum nitrides as ammonia synthesis catalysts requires further development of the optimal promoter system, which enhances not only the activity but also the stability of the catalysts. To do so, elucidating the influence of the addition of alkali metals [...] Read more.
The application of cobalt molybdenum nitrides as ammonia synthesis catalysts requires further development of the optimal promoter system, which enhances not only the activity but also the stability of the catalysts. To do so, elucidating the influence of the addition of alkali metals on the structural properties of the catalysts is essential. In this study, potassium-promoted cobalt molybdenum nitrides were synthesized by impregnation of the precursor CoMoO4·3/4H2O with aqueous KNO3 solution followed by ammonolysis. The catalysts were characterized with the use of XRD and BET methods, under two conditions: as obtained and after the thermal stability test. The catalytic activity in the synthesis of ammonia was examined at 450 °C, under 10 MPa. The thermal stability test was carried out by heating at 650 °C in the same apparatus. As a result of ammonolysis, mixtures of two phases: Co3Mo3N and Co2Mo3N were obtained. The phase concentrations were affected by potassium admixture. The catalytical activity increased for the most active catalyst by approximately 50% compared to non-promoted cobalt molybdenum nitrides. The thermal stability test resulted in a loss of activity, on average, of 30%. Deactivation was caused by the collapse of the porous structure, which is attributed to the conversion of the Co2Mo3N phase to the Co3Mo3N phase. Full article
(This article belongs to the Special Issue Applied Catalysis in Chemical Industry: Synthesis, Catalyst Design, and Evaluation)
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