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Iron and Cobalt Catalysts
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Iron and Cobalt Catalysts

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

Deadline for manuscript submissions: closed (31 August 2019) | Viewed by 104197

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

Special Issue Editors

Dr. Wilson D Shafer

E-Mail Website
Guest Editor
Science and Health Department, Asbury University, Lexington, KY 40390, USA
Interests: clean energy; carbon dioxide utilization; heterogeneous catalysis processes such as Fischer-Tropsch synthesis, aromatization, steam reforming, and water–gas shift
Dr. Gary Jacobs

E-Mail Website
Guest Editor
University of Texas at San Antonio, Chemical Engineering Program – Department of Biomedical Engineering, Department of Mechanical Engineering, One UTSA Circle, San Antonio, TX 78249, USA
Interests: heterogeneous catalysis; syngas conversion; hydrogen production

Special Issue Information

Dear Colleagues,

Since the turn of the last century—when the field of catalysis was born—iron and cobalt have been key players in numerous catalysis processes. These metals, because of their ability to activate CO and CH, remain a major economic impact worldwide. Several industrial processes and synthetic routes utilize these metals:

  • Biomass-to-Liquids (BTL),
  • Coal-to-Liquids (CTL),
  • Natural Gas-to-Liquids (GTL),
  • Water-Gas-Shift,
  • Alcohol Synthesis,
  • Alcohol Steam Reforming,
  • Polymerization Processes,
  • Cross-coupling Reactions,
  • Photocatalyst activated reactions.

A vast number of materials are produced from these processes, including oil, lubricants, waxes, diesel and jet fuels, hydrogen (e.g., fuel cell applications), gasoline, rubbers, plastics, alcohols, pharmaceuticals, agrochemicals, feed-stock chemicals and other alternative materials. However, given the true complexities of the variables involved in these processes, many key mechanistic issues are still not fully defined or understood.

This Special Issue of Catalysis will be a collaborative effort to combine current catalysis research on these metals, from experimental and theoretical perspectives on both heterogeneous and homogeneous catalysts.  We welcome contributions from the catalysis community on catalyst characterization, kinetics, reaction mechanism, reactor development, theoretical modeling, and surface science are all welcome. 

Prof. Wilson D Shafer
Prof. Gary Jacobs
Guest Editors

Manuscript Submission Information

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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

  • Iron
  • Cobalt
  • Catalysis
  • CO activation
  • CH activation

Published Papers (20 papers)

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Editorial

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6 pages, 197 KiB  
Editorial
Editorial: Cobalt and Iron Catalysis
by Wilson D. Shafer and Gary Jacobs
Catalysts 2020, 10(1), 36; https://0-doi-org.brum.beds.ac.uk/10.3390/catal10010036 - 27 Dec 2019
Viewed by 2985
Abstract
Cobalt and iron have long history of importance in the field of catalysis that continues to this day [...] Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)

Research

Jump to: Editorial, Review

29 pages, 14382 KiB  
Article
The Preparation and Characterization of Co–Ni Nanoparticles and the Testing of a Heterogenized Co–Ni/Alumina Catalyst for CO Hydrogenation
by Julián López-Tinoco, Rubén Mendoza-Cruz, Lourdes Bazán-Díaz, Sai Charan Karuturi, Michela Martinelli, Donald C. Cronauer, A. Jeremy Kropf, Christopher L. Marshall and Gary Jacobs
Catalysts 2020, 10(1), 18; https://doi.org/10.3390/catal10010018 - 21 Dec 2019
Cited by 10 | Viewed by 3376
Abstract
Samples of well-controlled nanoparticles consisting of alloys of cobalt and nickel of different atomic ratios were synthesized using wet chemical methods with oleylamine as the solvent and the reducing agent. These materials were characterized by a variety of techniques, including high-angle annular dark-field [...] Read more.
Samples of well-controlled nanoparticles consisting of alloys of cobalt and nickel of different atomic ratios were synthesized using wet chemical methods with oleylamine as the solvent and the reducing agent. These materials were characterized by a variety of techniques, including high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). Small amounts of heterogenized catalysts were prepared using alumina as the support. However, the potential for use of Co–Ni catalysts in CO hydrogenation was explored using a larger amount of Co–Ni/alumina catalyst prepared from standard aqueous impregnation methods and tested in a continuously stirred tank reactor (CSTR) for Fischer–Tropsch synthesis (FTS). Results are compared to a reference catalyst containing only cobalt. The heterogenized catalysts were characterized using synchrotron methods, including temperature programmed reduction with extended X-ray absorption fine structure spectroscopy and X-ray absorption near edge spectroscopy (TPR-EXAFS/XANES). The characterization results support intimate contact between Co and Ni, strongly suggesting alloy formation. In FTS testing, drawbacks of Ni addition included decreased CO conversion on a per gram catalyst basis, although Ni did not significantly impact the turnover number of cobalt, and produced slightly higher light gas selectivity. Benefits of Ni addition included an inverted induction period relative to undoped Co/Al2O3, where CO conversion increased with time on-stream in the initial period, and the stabilization of cobalt nanoparticles at a lower weight % of Co. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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27 pages, 6318 KiB  
Article
Kinetics of Fischer–Tropsch Synthesis in a 3-D Printed Stainless Steel Microreactor Using Different Mesoporous Silica Supported Co-Ru Catalysts
by Nafeezuddin Mohammad, Sujoy Bepari, Shyam Aravamudhan and Debasish Kuila
Catalysts 2019, 9(10), 872; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9100872 - 21 Oct 2019
Cited by 25 | Viewed by 5048
Abstract
Fischer–Tropsch (FT) synthesis was carried out in a 3D printed stainless steel (SS) microchannel microreactor using bimetallic Co-Ru catalysts on three different mesoporous silica supports. CoRu-MCM-41, CoRu-SBA-15, and CoRu-KIT-6 were synthesized using a one-pot hydrothermal method and characterized by Brunner–Emmett–Teller (BET), temperature programmed [...] Read more.
Fischer–Tropsch (FT) synthesis was carried out in a 3D printed stainless steel (SS) microchannel microreactor using bimetallic Co-Ru catalysts on three different mesoporous silica supports. CoRu-MCM-41, CoRu-SBA-15, and CoRu-KIT-6 were synthesized using a one-pot hydrothermal method and characterized by Brunner–Emmett–Teller (BET), temperature programmed reduction (TPR), SEM-EDX, TEM, and X-ray photoelectron spectroscopy (XPS) techniques. The mesoporous catalysts show the long-range ordered structure as supported by BET and low-angle XRD studies. The TPR profiles of metal oxides with H2 varied significantly depending on the support. These catalysts were coated inside the microchannels using polyvinyl alcohol and kinetic performance was evaluated at three different temperatures, in the low-temperature FT regime (210–270 °C), at different Weight Hourly Space Velocity (WHSV) in the range of 3.15–25.2 kgcat.h/kmol using a syngas ratio of H2/CO = 2. The mesoporous supports have a significant effect on the FT kinetics and stability of the catalyst. The kinetic models (FT-3, FT-6), based on the Langmuir–Hinshelwood mechanism, were found to be statistically and physically relevant for FT synthesis using CoRu-MCM-41 and CoRu-KIT-6. The kinetic model equation (FT-2), derived using Eley–Rideal mechanism, is found to be relevant for CoRu-SBA-15 in the SS microchannel microreactor. CoRu-KIT-6 was found to be 2.5 times more active than Co-Ru-MCM-41 and slightly more active than CoRu-SBA-15, based on activation energy calculations. CoRu-KIT-6 was ~3 and ~1.5 times more stable than CoRu-SBA-15 and CoRu-MCM-41, respectively, based on CO conversion in the deactivation studies. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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16 pages, 1989 KiB  
Article
Fischer-Tropsch Synthesis: Cd, In and Sn Effects on a 15%Co/Al2O3 Catalyst
by Wenping Ma, Gary Jacobs, Wilson D. Shafer, Yaying Ji, Jennifer L. S. Klettlinger, Syed Khalid, Shelley D. Hopps and Burtron H. Davis
Catalysts 2019, 9(10), 862; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9100862 - 16 Oct 2019
Cited by 7 | Viewed by 2627
Abstract
The effects of 1% of Cd, In and Sn additives on the physicochemical properties and Fischer-Tropsch synthesis (FTS) performance of a 15% Co/Al2O3 catalyst were investigated. The fresh and spent catalysts were characterized by BET, temperature programmed reduction (TPR), H [...] Read more.
The effects of 1% of Cd, In and Sn additives on the physicochemical properties and Fischer-Tropsch synthesis (FTS) performance of a 15% Co/Al2O3 catalyst were investigated. The fresh and spent catalysts were characterized by BET, temperature programmed reduction (TPR), H2-chemisorption, NH3 temperature programmed desorption (TPD), X-ray absorption near edge spectroscopy (XANES), and X ray diffraction (XRD). The catalysts were tested in a 1 L continuously stirred tank reactor (CSTR) at 220 °C, 2.2 MPa, H2/CO = 2.1 and 20–55% CO conversion. Addition of 1% of Cd or In enhanced the reduction degree of 15%Co/Al2O3 by ~20%, while addition of 1% Sn slightly hindered it. All three additives adversely impacted Co dispersion by 22–32% by increasing apparent Co cluster size based on the H2-chemisorption measurements. However, the decreased Co active site density resulting from the additives did not result in a corresponding activity loss; instead, the additives decreased the activity of the Co catalysts to a much greater extent than expected, i.e., 82–93%. The additional detrimental effect on catalyst activity likely indicates that the Cd, In and Sn additives migrated to and covered active sites during reaction and/or provided an electronic effect. XANES results showed that oxides of the additives were present during the reaction, but that a fraction of metal was also likely present based on the TPR and reaction testing results. This is in contrast to typical promoters that become metallic at or below ~350 °C, such as noble metal promoters (e.g., Pt, Ru) and Group 11 promoters (e.g., Ag, Au) on Co catalysts in earlier studies. In the current work, all three additives remarkably increased CH4 and CO2 selectivities and decreased C5+ selectivity, with the Sn and In additives having a greater effect. Interestingly, the Cd, In, or Sn additives were found to influence hydrogenation and isomerization activities. At a similar conversion level (i.e., in the range of 40–50%), the additives significantly increased 2-C4 olefin content from 3.8 to 10.6% and n-C4 paraffin from 50 to 61% accompanied by decreases in 1-C4 olefin content from 48 to 30%. The Sn contributed the greatest impact on the secondary reactions of 1-olefins, followed by the In and Cd. NH3-TPD results suggest enhanced acid sites on cobalt catalysts resulting from the additives, which likely explains the change in selectivities for the different catalysts. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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12 pages, 414 KiB  
Article
Fischer–Tropsch Synthesis: Computational Sensitivity Modeling for Series of Cobalt Catalysts
by Harrison Williams, Muthu K. Gnanamani, Gary Jacobs, Wilson D. Shafer and David Coulliette
Catalysts 2019, 9(10), 857; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9100857 - 15 Oct 2019
Cited by 6 | Viewed by 2721
Abstract
Nearly a century ago, Fischer and Tropsch discovered a means of synthesizing organic compounds ranging from C1 to C70 by reacting carbon monoxide and hydrogen on a catalyst. Fischer–Tropsch synthesis (FTS) is now known as a pseudo-polymerization process taking a mixture [...] Read more.
Nearly a century ago, Fischer and Tropsch discovered a means of synthesizing organic compounds ranging from C1 to C70 by reacting carbon monoxide and hydrogen on a catalyst. Fischer–Tropsch synthesis (FTS) is now known as a pseudo-polymerization process taking a mixture of CO as H2 (also known as syngas) to produce a vast array of hydrocarbons, along with various small amounts of oxygenated materials. Despite the decades spent studying this process, it is still considered a black-box reaction with a mechanism that is still under debate. This investigation sought to improve our understanding by taking data from a series of experimental Fischer–Tropsch synthesis runs to build a computational model. The experimental runs were completed in an isothermal continuous stirred-tank reactor, allowing for comparison across a series of completed catalyst tests. Similar catalytic recipes were chosen so that conditional comparisons of pressure, temperature, SV, and CO/H2 could be made. Further, results from the output of the reactor that included the deviations in product selectivity, especially that of methane and CO2, were considered. Cobalt was chosen for these exams for its industrial relevance and respectfully clean process as it does not intrinsically undergo the water–gas shift (WGS). The primary focus of this manuscript was to compare runs using cobalt-based catalysts that varied in two oxide catalyst supports. The results were obtained by creating two differential equations, one for H2 and one for CO, in terms of products or groups of products. These were analyzed using sensitivity analysis (SA) to determine the products or groups that impact the model the most. The results revealed a significant difference in sensitivity between the two catalyst–support combinations. When the model equations for H2 and CO were split, the results indicated that the CO equation was significantly more sensitive to CO2 production than the H2 equation. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
28 pages, 5878 KiB  
Article
The Evolution of Catalysis for Alkyd Coatings: Responding to Impending Cobalt Reclassification with Very Active Iron and Manganese Catalysts, Using Polydentate Nitrogen Donor Ligands
by Neil Simpson, Karin Maaijen, Yfranka Roelofsen and Ronald Hage
Catalysts 2019, 9(10), 825; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9100825 - 01 Oct 2019
Cited by 17 | Viewed by 7719
Abstract
Autoxidation processes to achieve curing of alkyd resins in paints, inks, and coatings are ubiquitous in many applications. Cobalt soaps have been employed for these applications for many decades and most of the paint and ink alkyd resin formulations have been optimized to [...] Read more.
Autoxidation processes to achieve curing of alkyd resins in paints, inks, and coatings are ubiquitous in many applications. Cobalt soaps have been employed for these applications for many decades and most of the paint and ink alkyd resin formulations have been optimized to achieve optimal benefits of the cobalt soaps. However, cobalt soaps are under increased scrutiny because of likely reclassification as carcinogenic under REACH (Registration, Evaluation, Authorisation, and Restrictions of Chemicals) legislation in Europe. This is critical, since such coatings are available for regular human contact. Alternative manganese- and iron-based siccatives have been developed to address this need for over a decade. They often show very high curing activity depending on the organic ligands bound to the metal centers. Recently, new classes of catalysts and modes of application have been published or patented to create safe paints, whilst delivering performance benefits via their unique reaction mechanisms. Besides the use of well-defined, preformed catalysts, paint formulations have also been developed with mixtures of metal soaps and ligands that form active species in-situ. The change from Co-soaps to Mn- and Fe-based siccatives meant that important coating issues related to radical-based curing, such as skinning, had to be rethought. In this paper we will review the new catalyst technologies and their performance and modes of action, as well as new compounds developed to provide anti-skinning benefits. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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18 pages, 3865 KiB  
Article
Effect of Operating Temperature, Pressure and Potassium Loading on the Performance of Silica-Supported Cobalt Catalyst in CO2 Hydrogenation to Hydrocarbon Fuel
by Rama Achtar Iloy and Kalala Jalama
Catalysts 2019, 9(10), 807; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9100807 - 26 Sep 2019
Cited by 21 | Viewed by 3533
Abstract
Potassium (1–5 wt.%)-promoted and unpromoted Co/SiO2 catalysts were prepared by impregnation method and characterized by nitrogen physisorption, temperature-programmed reduction (TPR), CO2 temperature-programmed desorption (TPD), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. They were evaluated for CO2 hydrogenation in [...] Read more.
Potassium (1–5 wt.%)-promoted and unpromoted Co/SiO2 catalysts were prepared by impregnation method and characterized by nitrogen physisorption, temperature-programmed reduction (TPR), CO2 temperature-programmed desorption (TPD), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. They were evaluated for CO2 hydrogenation in a fixed bed reactor from 180 to 300 °C within a pressure range of 1–20 bar. The yield for hydrocarbon products other than methane (C2+) was found to increase with an increase in the operating temperature and went through a maximum of approximately 270 °C. It did not show any significant dependency on the operating pressure and decreased at potassium loadings beyond 1 wt.%. Potassium was found to enhance the catalyst ability to adsorb CO2, but limited the reduction of cobalt species during the activation process. The improved CO2 adsorption resulted in a decrease in surface H/C ratio, the latter of which enhanced the formation of C2+ hydrocarbons. The highest C2+ yield was obtained on the catalyst promoted with 1 wt.% of potassium and operated at an optimal temperature of 270 °C and a pressure of 1 bar. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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14 pages, 5306 KiB  
Article
Cobalt-Based Fischer–Tropsch Synthesis: A Kinetic Evaluation of Metal–Support Interactions Using an Inverse Model System
by Anna P. Petersen, Michael Claeys, Patricia J. Kooyman and Eric van Steen
Catalysts 2019, 9(10), 794; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9100794 - 24 Sep 2019
Cited by 23 | Viewed by 4185
Abstract
Metal–support interactions in the cobalt–alumina system are evaluated using an inverse model system generated by impregnating Co3O4 with a solution of aluminum sec-butoxide in n-hexane. This results in the formation of nano-sized alumina islands on the surface of cobalt oxide. [...] Read more.
Metal–support interactions in the cobalt–alumina system are evaluated using an inverse model system generated by impregnating Co3O4 with a solution of aluminum sec-butoxide in n-hexane. This results in the formation of nano-sized alumina islands on the surface of cobalt oxide. The activated model systems were kinetically evaluated for their activity and selectivity in the Fischer–Tropsch synthesis under industrially relevant conditions (220 °C, 20 bar). The kinetic measurements were complemented by H2-chemisorption, CO-TPR, and pyridine TPD. It is shown that the introduction of aluminum in the model system results in the formation of strong acid sites and enhanced CO dissociation, as evidenced in the CO-TPR. The incorporation of aluminum in the model systems led to a strong increase in the activity factor per surface atom of cobalt in the rate expression proposed by Botes et al. (2009). However, the addition of aluminum also resulted in a strong increase in the kinetic inhibition factor. This is accompanied by a strong decrease in the methane selectivity, and an increase in the desired C5+ selectivity. The observed activity and selectivity changes are attributed to the increase in the coverage of the surface with carbon with increasing aluminum content, due to the facilitation of CO dissociation in the presence of Lewis acid sites associated with the alumina islands on the catalytically active material. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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24 pages, 4945 KiB  
Article
Synthesis and Catalytic Application of Knölker-Type Iron Complexes with a Novel Asymmetric Cyclopentadienone Ligand Design
by Christian A. M. R. van Slagmaat, Khi Chhay Chou, Lukas Morick, Darya Hadavi, Burgert Blom and Stefaan M. A. De Wildeman
Catalysts 2019, 9(10), 790; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9100790 - 22 Sep 2019
Cited by 15 | Viewed by 5932
Abstract
Asymmetric catalysis is an essential tool in modern chemistry, but increasing environmental concerns demand the development of new catalysts based on cheap, abundant, and less toxic iron. As a result, Knölker-type catalysts have emerged as a promising class of iron catalysts for various [...] Read more.
Asymmetric catalysis is an essential tool in modern chemistry, but increasing environmental concerns demand the development of new catalysts based on cheap, abundant, and less toxic iron. As a result, Knölker-type catalysts have emerged as a promising class of iron catalysts for various chemical transformations, notably the hydrogenation of carbonyls and imines, while asymmetric versions are still under exploration to achieve optimal enantio-selectivities. In this work, we report a novel asymmetric design of a Knölker-type catalyst, in which the C2-rotational symmetric cyclopentadienone ligand possesses chiral substituents on the 2- and 5-positions near the active site. Four examples of the highly modular catalyst design were synthesized via standard organic procedures, and their structures were confirmed with NMR, IR, MS, and polarimetry analysis. Density functional theory (DFT) calculations were conducted to elucidate the spatial conformation of the catalysts, and therewith to rationalize the influence of structural alterations. Transfer- and H2-mediated hydrogenations were successfully established, leading to appreciable enantiomeric excesses (ee) values up to 70%. Amongst all reported Knölker-type catalysts, our catalyst design achieves one of the highest ee values for hydrogenation of acetophenone and related compounds. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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11 pages, 1960 KiB  
Article
Selective CO Hydrogenation Over Bimetallic Co-Fe Catalysts for the Production of Light Paraffin Hydrocarbons (C2–C4): Effect of Space Velocity, Reaction Pressure and Temperature
by Seong Bin Jo, Tae Young Kim, Chul Ho Lee, Jin Hyeok Woo, Ho Jin Chae, Suk-Hwan Kang, Joon Woo Kim, Soo Chool Lee and Jae Chang Kim
Catalysts 2019, 9(9), 779; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9090779 - 19 Sep 2019
Cited by 8 | Viewed by 2887
Abstract
Synthetic natural gas (SNG) using syngas from coal and biomass has attracted much attention as a potential substitute for fossil fuels because of environmental advantages. However, heating value of SNG is below the standard heating value for power generation (especially in South Korea [...] Read more.
Synthetic natural gas (SNG) using syngas from coal and biomass has attracted much attention as a potential substitute for fossil fuels because of environmental advantages. However, heating value of SNG is below the standard heating value for power generation (especially in South Korea and Japan). In this study, bimetallic Co-Fe catalyst was developed for the production of light paraffin hydrocarbons (C2–C4 as well as CH4) for usage as mixing gases to improve the heating value of SNG. The catalytic performance was monitored by varying space velocity, reaction pressure and temperature. The CO conversion increases with decrease in space velocities, and with an increase in reaction pressure and temperature. CH4 yield increases and C2+ yield decreases with increasing reaction temperature at all reaction pressure and space velocities. In addition, improved CH4 yield at higher reaction pressure (20 bar) implies that higher reaction pressure is a favorable condition for secondary CO2 methanation reaction. The bimetallic Co-Fe catalyst showed the best results with 99.7% CO conversion, 36.1% C2–C4 yield and 0.90 paraffin ratio at H2/CO of 3.0, space velocity of 4000 mL/g/h, reaction pressure of 20 bar, and temperature of 350 °C. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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17 pages, 2019 KiB  
Article
Reverse Water-Gas Shift Iron Catalyst Derived from Magnetite
by Chen-Yu Chou, Jason A. Loiland and Raul F. Lobo
Catalysts 2019, 9(9), 773; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9090773 - 14 Sep 2019
Cited by 43 | Viewed by 7747
Abstract
The catalytic properties of unsupported iron oxides, specifically magnetite (Fe3O4), were investigated for the reverse water-gas shift (RWGS) reaction at temperatures between 723 K and 773 K and atmospheric pressure. This catalyst exhibited a fast catalytic CO formation rate [...] Read more.
The catalytic properties of unsupported iron oxides, specifically magnetite (Fe3O4), were investigated for the reverse water-gas shift (RWGS) reaction at temperatures between 723 K and 773 K and atmospheric pressure. This catalyst exhibited a fast catalytic CO formation rate (35.1 mmol h−1 gcat.−1), high turnover frequency (0.180 s−1), high CO selectivity (>99%), and high stability (753 K, 45000 cm3h−1gcat.−1) under a 1:1 H2 to CO2 ratio. Reaction rates over the Fe3O4 catalyst displayed a strong dependence on H2 partial pressure (reaction order of ~0.8) and a weaker dependence on CO2 partial pressure (reaction order of 0.33) under an equimolar flow of both reactants. X-ray powder diffraction patterns and XPS spectra reveal that the bulk composition and structure of the post-reaction catalyst was formed mostly of metallic Fe and Fe3C, while the surface contained Fe2+, Fe3+, metallic Fe and Fe3C. Catalyst tests on pure Fe3C (iron carbide) suggest that Fe3C is not an effective catalyst for this reaction at the conditions investigated. Gas-switching experiments (CO2 or H2) indicated that a redox mechanism is the predominant reaction pathway. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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18 pages, 5996 KiB  
Article
Comparative Studies of Fischer-Tropsch Synthesis on Iron Catalysts Supported on Al2O3-Cr2O3 (2:1), Multi-Walled Carbon Nanotubes or BEA Zeolite Systems
by Pawel Mierczynski, Bartosz Dawid, Karolina Chalupka, Waldemar Maniukiewicz, Izabela Witoska, Krasimir Vasilev and Malgorzta I. Szynkowska
Catalysts 2019, 9(7), 605; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9070605 - 15 Jul 2019
Cited by 7 | Viewed by 3320
Abstract
The main goal of the presented paper is to study the influence of a range of support materials, i.e., multi-walled carbon nanotubes (MWCNTs), Al2O3-Cr2O3 (2:1), zeolite β-H and zeolite β-Na on the physicochemical and catalytic properties [...] Read more.
The main goal of the presented paper is to study the influence of a range of support materials, i.e., multi-walled carbon nanotubes (MWCNTs), Al2O3-Cr2O3 (2:1), zeolite β-H and zeolite β-Na on the physicochemical and catalytic properties in Fischer-Tropsch (F-T) synthesis. All tested Fe catalysts were synthesized using the impregnation method. Their physicochemical properties were extensively investigated using various characterization techniques such as the Temperature-Programmed Reduction of hydrogen (TPR-H2), X-ray diffraction, Temperature-Programmed Desorption of ammonia (TPD-NH3), Temperature-Programmed Desorption of carbon dioxide (TPD-CO2), Fourier transform infrared spectrometry (FTIR), Brunauer Emmett Teller method (BET) and Thermogravimetric Differential Analysis coupled with Mass Spectrometer (TG-DTA-MS). Activity tests were performed in F-T synthesis using a high-pressure fixed bed reactor and a gas mixture of H2 and CO (50% CO and 50% H2). The correlation between the physicochemical properties and reactivity in F-T synthesis was determined. The highest activity was from a 40%Fe/Al2O3-Cr2O3 (2:1) system which exhibited 89.9% of CO conversion and 66.6% selectivity toward liquid products. This catalyst also exhibited the lowest acidity, but the highest quantity of iron carbides on its surface. In addition, in the case of iron catalysts supported on MWCNTs or a binary oxide system, the smallest amount of carbon deposit formed on the surface of the catalyst during the F-T process was confirmed. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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12 pages, 2617 KiB  
Article
Investigation of C1 + C1 Coupling Reactions in Cobalt-Catalyzed Fischer-Tropsch Synthesis by a Combined DFT and Kinetic Isotope Study
by Yanying Qi, Jia Yang, Anders Holmen and De Chen
Catalysts 2019, 9(6), 551; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9060551 - 19 Jun 2019
Cited by 16 | Viewed by 3654
Abstract
Understanding the chain growth mechanism is of vital importance for the development of catalysts with enhanced selectivity towards long-chain products in cobalt-catalyzed Fischer-Tropsch synthesis. Herein, we discriminate various C1 + C1 coupling reactions by theoretical calculations and kinetic isotope experiments. CH [...] Read more.
Understanding the chain growth mechanism is of vital importance for the development of catalysts with enhanced selectivity towards long-chain products in cobalt-catalyzed Fischer-Tropsch synthesis. Herein, we discriminate various C1 + C1 coupling reactions by theoretical calculations and kinetic isotope experiments. CHx(x=0−3), CO, HCO, COH, and HCOH are considered as the chain growth monomer respectively, and 24 possible coupling reactions are first investigated by theoretical calculations. Eight possible C1 + C1 coupling reactions are suggested to be energetically favorable because of the relative low reaction barriers. Moreover, five pathways are excluded where the C1 monomers show low thermodynamic stability. Effective chain propagation rates are calculated by deconvoluting from reaction rates of products, and an inverse kinetic isotope effect of the C1 + C1 coupling reaction is observed. The theoretical kinetic isotope effect of CO + CH2 is inverse, which is consistent with the experimental observation. Thus, the CO + CH2 pathway, owing to the relatively lower barrier, the high thermodynamic stability, and the inverse kinetic isotope effect, is suggested to be a favorable pathway. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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13 pages, 4201 KiB  
Article
Liquid-Phase Catalytic Oxidation of Limonene to Carvone over ZIF-67(Co)
by Yizhou Li, Yepeng Yang, Daomei Chen, Zhifang Luo, Wei Wang, Yali Ao, Lin Zhang, Zhiying Yan and Jiaqiang Wang
Catalysts 2019, 9(4), 374; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9040374 - 21 Apr 2019
Cited by 13 | Viewed by 4445
Abstract
Liquid-phase catalytic oxidation of limonene was carried out under mild conditions, and carvone was produced in the presence of ZIF-67(Co), cobalt based zeolitic imidazolate framework, as catalyst, using t-butyl hydroperoxide (t-BHP) as oxidant and benzene as solvent. As a heterogeneous catalyst, the zeolitic [...] Read more.
Liquid-phase catalytic oxidation of limonene was carried out under mild conditions, and carvone was produced in the presence of ZIF-67(Co), cobalt based zeolitic imidazolate framework, as catalyst, using t-butyl hydroperoxide (t-BHP) as oxidant and benzene as solvent. As a heterogeneous catalyst, the zeolitic imidazolate framework ZIF-67(Co) exhibited reasonable substrate–product selectivity (55.4%) and conversion (29.8%). Finally, the X-ray diffraction patterns of the catalyst before and after proved that ZIF-67(Co) acted as a heterogeneous catalyst, and can be reused without losing its activity to a great extent. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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8 pages, 1012 KiB  
Article
The Effect of Potassium on Cobalt-Based Fischer–Tropsch Catalysts with Different Cobalt Particle Sizes
by Ljubiša Gavrilović, Jonas Save and Edd A. Blekkan
Catalysts 2019, 9(4), 351; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9040351 - 10 Apr 2019
Cited by 13 | Viewed by 3778
Abstract
The effect of K on 20%Co/0.5%Re/γ-Al2O3 Fischer–Tropsch catalysts with two different cobalt particle sizes (small, in the range 6–7 nm and medium size, in the range 12–13 nm) was investigated. The catalyst with the smaller cobalt particle size had a [...] Read more.
The effect of K on 20%Co/0.5%Re/γ-Al2O3 Fischer–Tropsch catalysts with two different cobalt particle sizes (small, in the range 6–7 nm and medium size, in the range 12–13 nm) was investigated. The catalyst with the smaller cobalt particle size had a lower catalytic activity and C5+ selectivity while selectivities towards CH4 and CO2 were slightly higher than over the catalyst with larger particles. These effects are ascribed to lower hydrogen concentration on the surface as well as the lower reducibility of smaller cobalt particles. Upon potassium addition all samples showed decreased catalytic activity, reported as Site Time Yield (STY), increased C5+ and CO2 selectivities, and a decrease in CH4 selectivity. There was no difference in the effect of potassium between the sample with small cobalt particles compared to the sample with medium size particles). In both cases the specific activity (STY) fell and the C5+ selectivity increased in a similar fashion. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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57 pages, 19782 KiB  
Article
Fischer–Tropsch: Product Selectivity–The Fingerprint of Synthetic Fuels
by Wilson D. Shafer, Muthu Kumaran Gnanamani, Uschi M. Graham, Jia Yang, Cornelius M. Masuku, Gary Jacobs and Burtron H. Davis
Catalysts 2019, 9(3), 259; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9030259 - 14 Mar 2019
Cited by 72 | Viewed by 18829
Abstract
The bulk of the products that were synthesized from Fischer–Tropsch synthesis (FTS) is a wide range (C1–C70+) of hydrocarbons, primarily straight-chained paraffins. Additional hydrocarbon products, which can also be a majority, are linear olefins, specifically: 1-olefin, trans-2-olefin, and [...] Read more.
The bulk of the products that were synthesized from Fischer–Tropsch synthesis (FTS) is a wide range (C1–C70+) of hydrocarbons, primarily straight-chained paraffins. Additional hydrocarbon products, which can also be a majority, are linear olefins, specifically: 1-olefin, trans-2-olefin, and cis-2-olefin. Minor hydrocarbon products can include isomerized hydrocarbons, predominantly methyl-branched paraffin, cyclic hydrocarbons mainly derived from high-temperature FTS and internal olefins. Combined, these products provide 80–95% of the total products (excluding CO2) generated from syngas. A vast number of different oxygenated species, such as aldehydes, ketones, acids, and alcohols, are also embedded in this product range. These materials can be used to probe the FTS mechanism or to produce alternative chemicals. The purpose of this article is to compare the product selectivity over several FTS catalysts. Discussions center on typical product selectivity of commonly used catalysts, as well as some uncommon formulations that display selectivity anomalies. Reaction tests were conducted while using an isothermal continuously stirred tank reactor. Carbon mole percentages of CO that are converted to specific materials for Co, Fe, and Ru catalysts vary, but they depend on support type (especially with cobalt and ruthenium) and promoters (especially with iron). All three active metals produced linear alcohols as the major oxygenated product. In addition, only iron produced significant selectivities to acids, aldehydes, and ketones. Iron catalysts consistently produced the most isomerized products of the catalysts that were tested. Not only does product selectivity provide a fingerprint of the catalyst formulation, but it also points to a viable proposed mechanistic route. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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18 pages, 5409 KiB  
Article
Pilot-Scale Production, Properties and Application of Fe/Cu Catalytic-Ceramic-Filler for Nitrobenzene Compounds Wastewater Treatment
by Bingchuan Yang, Yuanfeng Qi and Rutao Liu
Catalysts 2019, 9(1), 11; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9010011 - 25 Dec 2018
Cited by 3 | Viewed by 2684
Abstract
Iron powder, Kaolin powder and CuSO4∙5H2O were employed as the main materials for the pilot-scale production of Fe/Cu catalytic- ceramic-filler (CCF) by way of wet type replacement-thermo-solidification. The physical properties, half-life, microstructure, removal rate of nitrobenzene compounds and the [...] Read more.
Iron powder, Kaolin powder and CuSO4∙5H2O were employed as the main materials for the pilot-scale production of Fe/Cu catalytic- ceramic-filler (CCF) by way of wet type replacement-thermo-solidification. The physical properties, half-life, microstructure, removal rate of nitrobenzene compounds and the biodegradability-improvement of military chemical factory comprehensive wastewater were tested in comparison with commercial Fe/C ceramic-filler (CF). Catalytic micro-electrolysis bed reactors (CBRs) designed as pretreatment process and BAFs (Biological Aerated Filters) were utilized in a 90 days field pilot-scale test at last. The results showed the characteristics of optimum CCF were: 1150 kg/m3 of bulk density, 1700 kg/m3 of grain density, lower than 3.5% of shrinking ratio, 3.5% of 24 h water absorption, 6.0 Mpa of numerical tube pressure, 0.99 acid-resistance softening co-efficiency and 893.55 days of half-life. 25% addition of Fe with 1% of copper plating rate was efficient for the removal of nitrobenzene compounds and significant in promoting the biodegradability of military chemical factory comprehensive wastewater. The two-stage design of CBRs and BAFs showed high dependability and stability for the practical engineering application. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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Review

Jump to: Editorial, Research

32 pages, 9255 KiB  
Review
Bimetallic Iron–Cobalt Catalysts and Their Applications in Energy-Related Electrochemical Reactions
by Kai Li, Yang Li, Wenchao Peng, Guoliang Zhang, Fengbao Zhang and Xiaobin Fan
Catalysts 2019, 9(9), 762; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9090762 - 11 Sep 2019
Cited by 18 | Viewed by 6623
Abstract
Since the persistently increasing trend of energy consumption, technologies for renewable energy production and conversion have drawn great attention worldwide. The performance and the cost of electrocatalysts play two crucial roles in the globalization of advanced energy conversion devices. Among the developed technics [...] Read more.
Since the persistently increasing trend of energy consumption, technologies for renewable energy production and conversion have drawn great attention worldwide. The performance and the cost of electrocatalysts play two crucial roles in the globalization of advanced energy conversion devices. Among the developed technics involving metal catalysts, transition-metal catalysts (TMC) are recognized as the most promising materials due to the excellent properties and stability. Particularly, the iron–cobalt bimetal catalysts exhibit exciting electrochemical properties because of the interior cooperative effects. Herein, we summarize recent advances in iron–cobalt bimetal catalysts for electrochemical applications, especially hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). Moreover, the components and synergetic effects of the composites and catalytic mechanism during reaction processes are highlighted. On the basis of extant catalysts and mechanism, the current issues and prospective outlook of the field are also discussed. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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15 pages, 1771 KiB  
Review
Effect of Co-Feeding Inorganic and Organic Molecules in the Fe and Co Catalyzed Fischer–Tropsch Synthesis: A Review
by Adolph Anga Muleja, Joshua Gorimbo and Cornelius Mduduzi Masuku
Catalysts 2019, 9(9), 746; https://0-doi-org.brum.beds.ac.uk/10.3390/catal9090746 - 04 Sep 2019
Cited by 8 | Viewed by 4397
Abstract
This short review makes it clear that after 90 years, the Fischer–Tropsch synthesis (FTS) process is still not well understood. While it is agreed that it is primarily a polymerization process, giving rise to a distribution of mainly olefins and paraffins; the mechanism [...] Read more.
This short review makes it clear that after 90 years, the Fischer–Tropsch synthesis (FTS) process is still not well understood. While it is agreed that it is primarily a polymerization process, giving rise to a distribution of mainly olefins and paraffins; the mechanism by which this occurs on catalysts is still a subject of much debate. Many of the FT features, such as deactivation, product distributions, kinetics and mechanism, and equilibrium aspects of the FT processes are still subjects of controversy, regardless of the progress that has been made so far. The effect of molecules co-feeding in FTS on these features is the main focus of this study. This review looks at some of these areas and tries to throw some light on aspects of FTS since the inception of the idea to date with emphasis and recommendation made based on nitrogen, water, ammonia, and olefins co-feeding case studies. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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21 pages, 8529 KiB  
Review
Polynuclear Cobalt Complexes as Catalysts for Light-Driven Water Oxidation: A Review of Recent Advances
by Dmytro S. Nesterov and Oksana V. Nesterova
Catalysts 2018, 8(12), 602; https://0-doi-org.brum.beds.ac.uk/10.3390/catal8120602 - 02 Dec 2018
Cited by 31 | Viewed by 5572
Abstract
Photochemical water oxidation, as a half-reaction of water splitting, represents a great challenge towards the construction of artificial photosynthetic systems. Complexes of first-row transition metals have attracted great attention in the last decade due to their pronounced catalytic efficiency in water oxidation, comparable [...] Read more.
Photochemical water oxidation, as a half-reaction of water splitting, represents a great challenge towards the construction of artificial photosynthetic systems. Complexes of first-row transition metals have attracted great attention in the last decade due to their pronounced catalytic efficiency in water oxidation, comparable to that exhibited by classical platinum-group metal complexes. Cobalt, being an abundant and relatively cheap metal, has rich coordination chemistry allowing construction of a wide range of polynuclear architectures for the catalytic purposes. This review covers recent advances in application of cobalt complexes as (pre)catalysts for water oxidation in the model catalytic system comprising [Ru(bpy)3]2+ as a photosensitizer and S2O82− as a sacrificial electron acceptor. The catalytic parameters are summarized and discussed in view of the structures of the catalysts. Special attention is paid to the degradation of molecular catalysts under catalytic conditions and the experimental methods and techniques used to control their degradation as well as the leaching of cobalt ions. Full article
(This article belongs to the Special Issue Iron and Cobalt Catalysts)
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