Catalysts with Bioinorganic Metal Centres

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

Deadline for manuscript submissions: closed (31 May 2022) | Viewed by 9627

Special Issue Editors


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Guest Editor
1. LCC Laboratoire de Chimie de Coordination, Toulouse, France
2. Department of Chemistry, IUT Paul Sabatier, Castres, France
Interests: coordination chemistry; green chemistry; catalysis; catalysts grafting; DFT calculations; organic solvent-free processes; polyoxometalates; biomass valorization
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Guest Editor
1. LCC Laboratoire de Chimie de Coordination, Toulouse, France
2. Chem Dpt of IUT Paul Sabatier, Castres, France
Interests: coordination chemistry; catalysis; bioinspired chemistry; second coordination sphere

Special Issue Information

Dear Colleagues,

Metal ions are known to play an essential role in living systems. Although it is known that metal ions possess a key role in biological reactions, their exact functions have not been totally elucidated. Typical metal-containing bioactive compounds are involved as electron carriers; oxygen transportation agents; and hydrolase, oxidoreductase, and isomerase agents.

This Special Issue focusses on molecular and supported catalysts containing essential bioinorganic metal centers (for instance, Fe, Cu, Zn, Mo, V, Co, Mn, and Ni) and related catalyzed processes. Particular attention will be paid to oxidation reactions (alkanes, alkenes, alcohols, sulfides, etc.) in which high catalyst activity, stability, and selectivity towards the desired product are pivotal parameters to be reached and understood. Thus, clarifying the reaction mechanism is strongly encouraged.

Dr. Jana Pisk
Dr. Dominique Agustin
Dr. Pascal GUILLO
Guest Editors

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Keywords

  • Bioinorganic metal centres
  • Oxidation reactions
  • Molecular catalyst
  • Supported catalyst
  • Reaction mechanism

Published Papers (3 papers)

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Research

14 pages, 1948 KiB  
Article
Alcohol Oxidation Assisted by Molybdenum Hydrazonato Catalysts Employing Hydroperoxide Oxidants
by Josipa Mihalinec, Matea Pajski, Pascal Guillo, Mirna Mandarić, Nikol Bebić, Jana Pisk and Višnja Vrdoljak
Catalysts 2021, 11(8), 881; https://doi.org/10.3390/catal11080881 - 22 Jul 2021
Cited by 9 | Viewed by 2524
Abstract
Molybdenum(VI) catalysts were obtained from methanol or acetonitrile by the reaction of [MoO2(C5H7O2)2] and isonicotinoyl- or nicotinoyl-based aroylhydrazones. Reactions in methanol resulted in the formation of the mononuclear complexes [MoO2(L1–4 [...] Read more.
Molybdenum(VI) catalysts were obtained from methanol or acetonitrile by the reaction of [MoO2(C5H7O2)2] and isonicotinoyl- or nicotinoyl-based aroylhydrazones. Reactions in methanol resulted in the formation of the mononuclear complexes [MoO2(L1–4)(MeOH)] (1a4a), while the ones in acetonitrile provided polynuclear complexes [MoO2(L1–4)]n (14). Crystals of polynuclear compound, [MoO2(L3)]n∙H2O (3∙H2O), suitable for X-ray diffraction analysis were obtained by the solvothermal procedure at 110 °C. Complexes were characterized by infrared spectroscopy (IR-ATR), nuclear magnetic resonance (NMR), elemental analysis (EA), and thermogravimetric analysis (TGA). The prepared catalysts were tested in alcohol oxidation reactions. Carveol, cyclohexanol, and butan-2-ol were investigated substrates. Because the alcohol oxidations are very challenging due to various possible pathways, the idea was to test different oxidants, H2O2, TBHP in water and decane, to optimize the researched catalytic system. Full article
(This article belongs to the Special Issue Catalysts with Bioinorganic Metal Centres)
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14 pages, 1707 KiB  
Article
Efficient Molybdenum Hydrazonato Epoxidation Catalysts Operating under Green Chemistry Conditions: Water vs. Decane Competition
by Silvija Mrkonja, Edi Topić, Mirna Mandarić, Dominique Agustin and Jana Pisk
Catalysts 2021, 11(7), 756; https://doi.org/10.3390/catal11070756 - 22 Jun 2021
Cited by 4 | Viewed by 2790
Abstract
Molybdenum compounds containing benzaldehyde-based hydrazones were obtained. The reaction in MeOH resulted with monomeric Mo complexes, [MoO2(L)(MeOH)], while the reaction in dichloromethane (DCM) provided oligomeric complexes, [MoO2(L)]n. The solid-state structures of the obtained compounds were investigated through [...] Read more.
Molybdenum compounds containing benzaldehyde-based hydrazones were obtained. The reaction in MeOH resulted with monomeric Mo complexes, [MoO2(L)(MeOH)], while the reaction in dichloromethane (DCM) provided oligomeric complexes, [MoO2(L)]n. The solid-state structures of the obtained compounds were investigated through Infrared Spectroscopy - Attenuated Total Reflection (IR-ATR), Thermogravimetric analysis (TGA), and via X-ray diffraction. The prepared molybdenum species were employed as cyclooctene epoxidation catalysts. TBHP (tert-butylhydroperoxide) in water and TBHP in decane were employed and compared as oxidants, with 0.25 mol% [Mo]. The catalyst activity and selectivity towards epoxide is >90% for all the reactions. The results have been linked to theoretical calculations, showing the importance of the first step, i.e., the transformation of [MoO2(L)(MeOH)] into the pentacoordinate [MoO2(L)]. Full article
(This article belongs to the Special Issue Catalysts with Bioinorganic Metal Centres)
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15 pages, 1956 KiB  
Article
Alkali Earth Metal Molybdates as Catalysts for the Selective Oxidation of Methanol to Formaldehyde—Selectivity, Activity, and Stability
by Joachim Thrane, Lars Fahl Lundegaard, Pablo Beato, Uffe Vie Mentzel, Max Thorhauge, Anker Degn Jensen and Martin Høj
Catalysts 2020, 10(1), 82; https://doi.org/10.3390/catal10010082 - 6 Jan 2020
Cited by 16 | Viewed by 3277
Abstract
Alkali earth metal molybdates (MMoO4, M = Mg, Ca, Sr, and Ba) were investigated as catalysts for the selective oxidation of methanol to formaldehyde in the search for more stable alternatives to the current industrial iron molybdate catalyst. The catalysts were [...] Read more.
Alkali earth metal molybdates (MMoO4, M = Mg, Ca, Sr, and Ba) were investigated as catalysts for the selective oxidation of methanol to formaldehyde in the search for more stable alternatives to the current industrial iron molybdate catalyst. The catalysts were prepared by either sol-gel synthesis or co-precipitation with both stoichiometric ratio (Mo:M = 1.0) and 10 mol% to 20 mol% excess Mo (Mo:M = 1.1 to 1.2). The catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, Raman spectroscopy, temperature programmed desorption of CO2 (CO2-TPD), and inductively coupled plasma (ICP). The catalytic performance of the catalysts was measured in a lab-scale, packed bed reactor setup by continuous operation for up to 100 h on stream at 400 °C. Initial selectivities towards formaldehyde of above 97% were achieved for all samples with excess molybdenum oxide at MeOH conversions between 5% and 75%. Dimethyl ether (DME) and dimethoxymethane (DMM) were the main byproducts, but CO (0.1%–2.1%) and CO2 (0.1%–0.4%) were also detected. It was found that excess molybdenum oxide evaporated from all the catalysts under operating conditions within 10 to 100 h on stream. No molybdenum evaporation past the point of stoichiometry was detected. Full article
(This article belongs to the Special Issue Catalysts with Bioinorganic Metal Centres)
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