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Catalysts
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Cobalt Catalysis: Recent Progress and Developments
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Cobalt Catalysis: Recent Progress and Developments

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

Deadline for manuscript submissions: closed (31 January 2021) | Viewed by 21745

Special Issue Editors

Dr. Jose R. Cabrero-Antonino

E-Mail Website
Guest Editor
Instituto de Tecnología Química (Universitat Politècnica de València – Consejo Superior de Investigaciones Científicas), Avda de los Naranjos s/n, 46022 València, Spain
Interests: metal-based catalysis applied to organic synthesis; (de)hydrogenative transformations; carboxylic acid derivatives and CO2 employment
Dr. Rosa Adam

E-Mail Website
Guest Editor
Instituto de Tecnología Química (Universitat Politècnica de València – Consejo Superior de Investigaciones Científicas), Avda de los Naranjos s/n, 46022 València, Spain
Interests: organic synthesis; homogeneous and heterogeneous catalysis; CO2 utilization

Special Issue Information

Dear Colleagues,

Cobalt-based catalysts, either heterogeneous or homogeneous, have been intensively developed since the beginning of the XX century owing to their activity in Fischer–Tropsch and hydroformylation processes. Hence, cobalt catalysts have constituted key materials for humankind’s modern development. Since the new century, myriad novel cobalt-based systems have been explored, leading to the discovery of new catalytic activities previously attributed exclusively to precious metals.

This Special Issue of Catalysts intends to cover recent developments in cobalt catalysis either related to well-known reactions (Fisher–Tropsch, carbonylation, oxidation, hydrodesulfuration), as well as more recently discovered catalytic applications of this metal (de/hydrogenation, hydroaddition, C–C coupling, CH activation, electrocatalysis, photocatalysis, CO2 utilization, etc.). We would like to give a general overview of the field, including methodology development, mechanistic studies, well-defined homogeneous catalysts advances, and design and characterization of nanostructured catalysts (including nanoparticles, single atoms, MOF, etc.).

 

Dr. Jose R. Cabrero-Antonino
Dr. Rosa Adam
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 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

  • cobalt
  • homogeneous catalysis
  • heterogeneous catalysis
  • base metals

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Published Papers (5 papers)

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Research

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11 pages, 1582 KiB  
Article
Photoelectrochemical Water Oxidation by Cobalt Cytochrome C Integrated-ATO Photoanode
by Carla Casadevall, Haojie Zhang, Shaojiang Chen, Dayn J. Sommer, Dong-Kyun Seo and Giovanna Ghirlanda
Catalysts 2021, 11(5), 626; https://doi.org/10.3390/catal11050626 - 12 May 2021
Cited by 2 | Viewed by 3334
Abstract
Here, we report the immobilization of Co-protoporphyrin IX (Co-PPIX) substituted cytochrome c (Co-cyt c) on Antimony-doped Tin Oxide (ATO) as a catalyst for photoelectrochemical oxidation of water. Under visible light irradiation (λ > 450 nm), the ATO-Co-cyt c photoanode displays ~6-fold enhancement [...] Read more.
Here, we report the immobilization of Co-protoporphyrin IX (Co-PPIX) substituted cytochrome c (Co-cyt c) on Antimony-doped Tin Oxide (ATO) as a catalyst for photoelectrochemical oxidation of water. Under visible light irradiation (λ > 450 nm), the ATO-Co-cyt c photoanode displays ~6-fold enhancement in photocurrent density relative to ATO-Co-PPIX at 0.25 V vs. RHE at pH 5.0. The light-induced water oxidation activity of the system was demonstrated by detecting evolved stoichiometric oxygen by gas chromatography, and incident photon to current efficiency was measured as 4.1% at 450 nm. The faradaic efficiency for the generated oxygen was 97%, with a 671 turnover number (TON) for oxygen. The current density had a slow decay over the course of 6 h of constant irradiation and applied potential, which exhibits the robustness of catalyst-ATO interaction. Full article
(This article belongs to the Special Issue Cobalt Catalysis: Recent Progress and Developments)
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16 pages, 4367 KiB  
Article
CpCo(III) Precatalysts for [2+2+2] Cycloadditions
by Fabian Fischer, Michael Eder and Marko Hapke
Catalysts 2021, 11(5), 596; https://doi.org/10.3390/catal11050596 - 4 May 2021
Cited by 2 | Viewed by 3490
Abstract
Catalysts applied in cobalt-catalyzed cyclotrimerizations reactions in general rely on the use of Co(I) precatalysts or the in situ generation of Co(I) catalysts from Co(II) sources by reduction in the presence of steering ligands, often by addition of less noble metals. In this [...] Read more.
Catalysts applied in cobalt-catalyzed cyclotrimerizations reactions in general rely on the use of Co(I) precatalysts or the in situ generation of Co(I) catalysts from Co(II) sources by reduction in the presence of steering ligands, often by addition of less noble metals. In this paper, we report the synthesis and properties of novel stable CpCo(III) complexes as precatalysts and their exemplary evaluation for application in catalytic [2+2+2] cycloadditions. The role of phosphite neutral ligands, as well as iodide and cyanide as anionic ligands, on the reactivity of the complexes was evaluated. A modified one-pot approach to the synthesis of Cp ring-functionalized Cp’Co(III) complexes was developed. The investigations demonstrated that CpCo(III) complexes can be directly applied as catalysts in catalytic cyclotrimerizations of triynes without reducing agents as additives. Full article
(This article belongs to the Special Issue Cobalt Catalysis: Recent Progress and Developments)
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12 pages, 4283 KiB  
Article
Replacing Pyridine with Pyrazine in Molecular Cobalt Catalysts: Effects on Electrochemical Properties and Aqueous H2 Generation
by Lars Kohler, Andrea M. Potocny, Jens Niklas, Matthias Zeller, Oleg G. Poluektov and Karen L. Mulfort
Catalysts 2021, 11(1), 75; https://doi.org/10.3390/catal11010075 - 7 Jan 2021
Cited by 4 | Viewed by 3071
Abstract
Four new molecular Co(II)tetrapyridyl complexes were synthesized and evaluated for their activity as catalysts for proton reduction in aqueous environments. The pyridine groups around the macrocycle were substituted for either one or two pyrazine groups. Single crystal X-ray analysis shows that the pyrazine [...] Read more.
Four new molecular Co(II)tetrapyridyl complexes were synthesized and evaluated for their activity as catalysts for proton reduction in aqueous environments. The pyridine groups around the macrocycle were substituted for either one or two pyrazine groups. Single crystal X-ray analysis shows that the pyrazine groups have minimal impact on the Co(II)–N bond lengths and molecular geometry in general. X-band EPR spectroscopy confirms the Co(II) oxidation state and the electronic environment of the Co(II) center are only very slightly perturbed by the substitution of pyrazine groups around the macrocycle. The substitution of pyrazine groups has a substantial impact on the observed metal- and ligand-centered reduction potentials as well as the overall H2 catalytic activity in a multimolecular system using the [Ru(2,2′-bipyridine)3]Cl2 photosensitizer and ascorbic acid as a sacrificial electron donor. The results reveal interesting trends between the H2 catalytic activity for each catalyst and the driving force for electron transfer between either the reduced photosensitizer to catalyst step or the catalyst to proton reduction step. The work presented here showcases how even the difference of a single atom in a molecular catalyst can have an important impact on activity and suggests a pathway to optimize the photocatalytic activity and stability of molecular systems. Full article
(This article belongs to the Special Issue Cobalt Catalysis: Recent Progress and Developments)
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Review

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28 pages, 1278 KiB  
Review
Recent Advances in Applications of Co-B Catalysts in NaBH4-Based Portable Hydrogen Generators
by Valentina I. Simagina, Anna M. Ozerova, Oksana V. Komova and Olga V. Netskina
Catalysts 2021, 11(2), 268; https://doi.org/10.3390/catal11020268 - 17 Feb 2021
Cited by 31 | Viewed by 4223
Abstract
This review highlights the opportunities of catalytic hydrolysis of NaBH4 with the use of inexpensive and active Co-B catalysts among the other systems of hydrogen storage and generation based on water reactive materials. This process is important for the creation of H [...] Read more.
This review highlights the opportunities of catalytic hydrolysis of NaBH4 with the use of inexpensive and active Co-B catalysts among the other systems of hydrogen storage and generation based on water reactive materials. This process is important for the creation of H2 generators required for the operation of portable compact power devices based on low-temperature proton exchange membrane fuel cells (LT PEM FC). Special attention is paid to the influence of the reaction medium on the formation of active state of Co-B catalysts and the problem of their deactivation in NaBH4 solution stabilized by alkali. The novelty of this review consists in the discussion of basic designs of hydrogen generators based on NaBH4 hydrolysis using cobalt catalysts and the challenges of their integration with LT PEM FC. The potential of using batch reactors in which there is no need to use aggressive alkaline NaBH4 solutions is discussed. Solid-phase compositions or pellets based on NaBH4 and cobalt-containing catalytic additives are proposed, the hydrogen generation from which starts immediately after the addition of water. The review made it possible to formulate the most acute problems, which require new sci-tech solutions. Full article
(This article belongs to the Special Issue Cobalt Catalysis: Recent Progress and Developments)
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25 pages, 7872 KiB  
Review
Cobalt-Based Metal Organic Frameworks as Solids Catalysts for Oxidation Reactions
by Amarajothi Dhakshinamoorthy, Eva Montero Lanzuela, Sergio Navalon and Hermenegildo Garcia
Catalysts 2021, 11(1), 95; https://doi.org/10.3390/catal11010095 - 12 Jan 2021
Cited by 18 | Viewed by 5731
Abstract
Metal organic frameworks (MOFs) are porous crystalline solids whose frameworks are constituted by metal ions/nodes with rigid organic linkers leading to the formation of materials having high surface area and pore volume. One of the unique features of MOFs is the presence of [...] Read more.
Metal organic frameworks (MOFs) are porous crystalline solids whose frameworks are constituted by metal ions/nodes with rigid organic linkers leading to the formation of materials having high surface area and pore volume. One of the unique features of MOFs is the presence of coordinatively unsaturated metal sites in their crystalline lattice that can act as Lewis acid sites promoting organic transformations, including aerobic oxidation reactions of various substrates such as hydrocarbons, alcohols, and sulfides. This review article summarizes the existing Co-based MOFs for oxidation reactions organized according to the nature of substrates like hydrocarbon, alcohol, olefin, and water. Both aerobic conditions and peroxide oxidants are discussed. Emphasis is placed on comparing the advantages of using MOFs as solid catalysts with respect to homogeneous salts in terms of product selectivity and long-term stability. The final section provides our view on future developments in this field. Full article
(This article belongs to the Special Issue Cobalt Catalysis: Recent Progress and Developments)
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