ChemInform Abstract: The Reaction of Barium Manganate with Acids and Their Precursors.

Kótai, László; Keszler, Ágnes; Pató, János; Holly, S.; Banerjii, Kalyan K.

doi:10.1002/chin.200012028

Cited by 8 publications

(9 citation statements)

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“…Compound 1 is slightly soluble in water at 25 °C (0.324 g/100 mL), and due to the relatively strong acidic character of permanganic acid, , its saturated aqueous solution pH was 1.93. It is not soluble in benzene, toluene, chloroform, or carbon tetrachloride at all.…”

Section: Resultsmentioning

confidence: 99%

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

et al. 2022

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Research on new reaction routes and precursors to prepare catalysts for CO 2 hydrogenation has enormous importance. Here, we report on the preparation of the permanganate salt of the urea-coordinated iron(III), [hexakis(urea- O )iron(III)]permanganate ([Fe(urea-O) 6 ](MnO 4 ) 3 ) via an affordable synthesis route and preliminarily demonstrate the catalytic activity of its (Fe,Mn)O x thermal decomposition products in CO 2 hydrogenation. [Fe(urea-O) 6 ](MnO 4 ) 3 contains O-coordinated urea ligands in octahedral propeller-like arrangement around the Fe 3+ cation. There are extended hydrogen bond interactions between the permanganate ions and the hydrogen atoms of the urea ligands. These hydrogen bonds serve as reaction centers and have unique roles in the solid-phase quasi-intramolecular redox reaction of the urea ligand and the permanganate anion below the temperature of ligand loss of the complex cation. The decomposition mechanism of the urea ligand (ammonia elimination with the formation of isocyanuric acid and biuret) has been clarified. In an inert atmosphere, the final thermal decomposition product was manganese-containing wuestite, (Fe,Mn)O, at 800 °C, whereas in ambient air, two types of bixbyite (Fe,Mn) 2 O 3 as well as jacobsite (Fe,Mn) T-4 (Fe,Mn) OC-6 2 O 4 ), with overall Fe to Mn stoichiometry of 1:3, were formed. These final products were obtained regardless of the different atmospheres applied during thermal treatments up to 350 °C. Disordered bixbyite formed first with inhomogeneous Fe and Mn distribution and double-size supercell and then transformed gradually into common bixbyite with regular structure (and with 1:3 Fe to Mn ratio) upon increasing the temperature and heating time. The (Fe,Mn)O x intermediates formed under various conditions showed catalytic effect in the CO 2 hydrogenation reaction with <57.6% CO 2 conversions and <39.3% hydrocarbon yields. As a mild solid-phase oxidant, hexakis(urea- O )iron(III) permanganate, was found to be selective in the transformation of (un)substituted benzylic alcohols into benzaldehydes and benzonitriles.

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Section: Resultsmentioning

confidence: 99%

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

et al. 2022

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“…shows that protons are reactants, thus explaining the increasing rate and yield with the acid concentration seen in Figure 1. The released oxygen may combine with Mn 2+ from (1) to produce MnO 2 [22].…”

Section: Discussionmentioning

confidence: 99%

“…The reduction potentials suggest that the manganic ion, Mn(III), produced by the reduction of permanganate ion by H 2 SO 4 is unstable with respect to the decomposition reaction [22][23][24]: The Mn(II) produced is then oxidized to Mn(IV) by permanganate (2). This can be a clue to the presence of traces of Mn(III) in the oxide.…”

Section: Discussionmentioning

confidence: 99%

The Effect of Stirring on the Morphology of Birnessite Nanoparticles

Cheney

Bhowmik

Moriuchi

et al. 2008

Journal of Nanomaterials

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The effect of mechanical stirring on the morphology of hexagonal layer-structure birnessite nanoparticles produced from decomposition ofKMnO4in dilute aqueousH2SO4is investigated, with characterization by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), thermogravimetric analysis (TGA), andN2adsorption (BET). Mechanical stirring during an initial stage of synthesis is shown to produce black birnessite containing nanofibers, whereas granular particulates of brown birnessite are produced without stirring. This is the first reduction synthesis of black birnessite nanoparticles with dendritic morphology without any use of organic reductant, and suggests that a particular morphology can arise from structural preferences of Mn in acidic conditions rather than particular organic reactants. These results enlighten the possibility of synthesizing nanoparticles with controlled size and morphology.

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“…Therefore, a chloride ion has to be introduced into the inner coordination sphere of the cobalt in the absence of a permanganate ion-for example, with the preparation of [Co(NH 3 ) 5 Cl]Cl 2 (compound 4) [14]-and the outer sphere chloride ions have to be exchanged with permanganate ions, such as occurred with the perrhenate ions in the preparation of compound 3-Re [15,16]. A possible reaction route is the reaction of [Co(NH 3 ) 5 Cl]SO 4 [14] with barium permanganate [17][18][19][20]; however, this method was not used due to the relatively low solubility of compound 3-Mn in water that causes problems in the separation of compound 3-M from the insoluble barium sulfate by-product. The reaction of compound 4 and an excess of NaMnO 4 in a 40% aq.…”

Section: Synthesis and Properties Of Compound 3-mnmentioning

confidence: 99%

“…The IR spectra of the decomposition product formed from compound 3-Mn at 125 °C (Figure 9) showed that the permanganate ion IR bands almost completely disappeared. There were no signs of manganate (VI) or manganate (V) ions [17,19]. Thus, manganese The first thermal decomposition step of the compound 3-Mn was also studied in refluxing toluene.…”

Section: Thermal Decomposition Of Compound 3-mnmentioning

confidence: 99%

Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel

et al. 2022

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We synthesized and structurally characterized the previously unknown [Co(NH3)5Cl](MnO4)2 complex as the precursor of CoMn2O4. The complex was also deuterated, and its FT-IR, far-IR, low-temperature Raman and UV-VIS spectra were measured as well. The structure of the complex was solved by single-crystal X-ray diffraction and the 3D-hydrogen bonds were evaluated. The N-H…O-Mn hydrogen bonds act as redox centers to initiate a solid-phase quasi-intramolecular redox reaction even at 120 °C involving the Co(III) centers. The product is an amorphous material, which transforms into [Co(NH3)5Cl]Cl2, NH4NO3, and a todorokite-like solid Co-Mn oxide on treatment with water. The insoluble residue may contain {Mn4IIIMnIV2O12}n4n-, {Mn5IIIMnIVO12}n5n- or {MnIII6O12}n6n- frameworks, which can embed 2 × n (CoII and/or CoIII) cations in their tunnels, respectively, and 4 × n ammonia ligands are coordinated to the cobalt cations. The decomposition intermediates decompose on further heating via a series of redox reactions, forming a solid CoIIMIII2O4 spinel with an average size of 16.8 nm, and gaseous N2, N2O and Cl2. The CoMn2O4 prepared in this reaction has photocatalytic activity in Congo red degradation with UV light. Its activity strongly depends on the synthesis conditions, e.g., Congo red was degraded 9 and 13 times faster in the presence of CoMn2O4 prepared at 550 °C (in air) or 420 °C (under N2), respectively.

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ChemInform Abstract: The Reaction of Barium Manganate with Acids and Their Precursors.

Cited by 8 publications

References 0 publications

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

The Effect of Stirring on the Morphology of Birnessite Nanoparticles

Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel

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ChemInform Abstract: The Reaction of Barium Manganate with Acids and Their Precursors.

Cited by 8 publications

References 0 publications

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)Ox Catalysts for CO2 Hydrogenation

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)Ox Catalysts for CO2 Hydrogenation

The Effect of Stirring on the Morphology of Birnessite Nanoparticles

Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn2O4 Spinel

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Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation

Thermally Induced Solid-Phase Quasi-Intramolecular Redox Reactions of [Hexakis(urea-O)iron(III)] Permanganate: An Easy Reaction Route to Prepare Potential (Fe,Mn)O_x Catalysts for CO₂ Hydrogenation