Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn<sub>2</sub>O<sub>4</sub> Spinel
We synthesized and structurally characterized the previously unknown [Co(NH<sub>3</sub>)<sub>5</sub>Cl](MnO<sub>4</sub>)<sub>2</sub> complex as the precursor of CoMn<sub>2</sub>O<sub>4</sub>. The complex was also deuterated, and...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-02-01
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| Series: | Inorganics |
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| Online Access: | https://www.mdpi.com/2304-6740/10/2/18 |
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| author | Fernanda Paiva Franguelli Éva Kováts Zsuzsanna Czégény Laura Bereczki Vladimir M. Petruševski Berta Barta Holló Kende Attila Béres Attila Farkas Imre Miklós Szilágyi László Kótai |
| author_facet | Fernanda Paiva Franguelli Éva Kováts Zsuzsanna Czégény Laura Bereczki Vladimir M. Petruševski Berta Barta Holló Kende Attila Béres Attila Farkas Imre Miklós Szilágyi László Kótai |
| author_sort | Fernanda Paiva Franguelli |
| collection | DOAJ |
| description | We synthesized and structurally characterized the previously unknown [Co(NH<sub>3</sub>)<sub>5</sub>Cl](MnO<sub>4</sub>)<sub>2</sub> complex as the precursor of CoMn<sub>2</sub>O<sub>4</sub>. 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(NH<sub>3</sub>)<sub>5</sub>Cl]Cl<sub>2</sub>, NH<sub>4</sub>NO<sub>3</sub>, and a todorokite-like solid Co-Mn oxide on treatment with water. The insoluble residue may contain {Mn<sub>4</sub><sup>III</sup>Mn<sup>IV</sup><sub>2</sub>O<sub>12</sub>}<sub>n</sub><sup>4n−</sup>, {Mn<sub>5</sub><sup>III</sup>Mn<sup>IV</sup>O<sub>12</sub>}<sub>n</sub><sup>5n−</sup> or {Mn<sup>III</sup><sub>6</sub>O<sub>12</sub>}<sub>n</sub><sup>6n−</sup> frameworks, which can embed 2 × n (Co<sup>II</sup> and/or Co<sup>III</sup>) 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 Co<sup>II</sup>M<sup>III</sup><sub>2</sub>O<sub>4</sub> spinel with an average size of 16.8 nm, and gaseous N<sub>2</sub>, N<sub>2</sub>O and Cl<sub>2</sub>. The CoMn<sub>2</sub>O<sub>4</sub> 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 CoMn<sub>2</sub>O<sub>4</sub> prepared at 550 °C (in air) or 420 °C (under N<sub>2</sub>), respectively. |
| first_indexed | 2024-03-09T21:43:24Z |
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| id | doaj.art-c01e477a1e6b43cd9510ff7c598c50e2 |
| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-03-09T21:43:24Z |
| publishDate | 2022-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Inorganics |
| spelling | doaj.art-c01e477a1e6b43cd9510ff7c598c50e22023-11-23T20:26:10ZengMDPI AGInorganics2304-67402022-02-011021810.3390/inorganics10020018Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn<sub>2</sub>O<sub>4</sub> SpinelFernanda Paiva Franguelli0Éva Kováts1Zsuzsanna Czégény2Laura Bereczki3Vladimir M. Petruševski4Berta Barta Holló5Kende Attila Béres6Attila Farkas7Imre Miklós Szilágyi8László Kótai9Research Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudósok krt. 2, H-1117 Budapest, HungaryWigner Research Centre for Physics (RCP), 761 Institute for Solid State Physics and Optics, Konkoly-Thege Miklós út 29-33, H-1121 Budapest, HungaryResearch Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudósok krt. 2, H-1117 Budapest, HungaryResearch Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudósok krt. 2, H-1117 Budapest, HungaryFaculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, 1000 Skopje, North MacedoniaDepartment of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg Dositeja Obradovića 3, 21000 Novi Sad, SerbiaResearch Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudósok krt. 2, H-1117 Budapest, HungaryDepartment of Organic Chemistry, Budapest University of Technology and Economics, Budafoki út 8, H-1111 Budapest, HungaryDepartment of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Műegyetem rakpart 3, H-1111 Budapest, HungaryResearch Centre for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudósok krt. 2, H-1117 Budapest, HungaryWe synthesized and structurally characterized the previously unknown [Co(NH<sub>3</sub>)<sub>5</sub>Cl](MnO<sub>4</sub>)<sub>2</sub> complex as the precursor of CoMn<sub>2</sub>O<sub>4</sub>. 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(NH<sub>3</sub>)<sub>5</sub>Cl]Cl<sub>2</sub>, NH<sub>4</sub>NO<sub>3</sub>, and a todorokite-like solid Co-Mn oxide on treatment with water. The insoluble residue may contain {Mn<sub>4</sub><sup>III</sup>Mn<sup>IV</sup><sub>2</sub>O<sub>12</sub>}<sub>n</sub><sup>4n−</sup>, {Mn<sub>5</sub><sup>III</sup>Mn<sup>IV</sup>O<sub>12</sub>}<sub>n</sub><sup>5n−</sup> or {Mn<sup>III</sup><sub>6</sub>O<sub>12</sub>}<sub>n</sub><sup>6n−</sup> frameworks, which can embed 2 × n (Co<sup>II</sup> and/or Co<sup>III</sup>) 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 Co<sup>II</sup>M<sup>III</sup><sub>2</sub>O<sub>4</sub> spinel with an average size of 16.8 nm, and gaseous N<sub>2</sub>, N<sub>2</sub>O and Cl<sub>2</sub>. The CoMn<sub>2</sub>O<sub>4</sub> 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 CoMn<sub>2</sub>O<sub>4</sub> prepared at 550 °C (in air) or 420 °C (under N<sub>2</sub>), respectively.https://www.mdpi.com/2304-6740/10/2/18permanganateamminequasi-intramolecular redox reactioncobalt manganite catalystspineltodorokite |
| spellingShingle | Fernanda Paiva Franguelli Éva Kováts Zsuzsanna Czégény Laura Bereczki Vladimir M. Petruševski Berta Barta Holló Kende Attila Béres Attila Farkas Imre Miklós Szilágyi László Kótai Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn<sub>2</sub>O<sub>4</sub> Spinel Inorganics permanganate ammine quasi-intramolecular redox reaction cobalt manganite catalyst spinel todorokite |
| title | Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn<sub>2</sub>O<sub>4</sub> Spinel |
| title_full | Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn<sub>2</sub>O<sub>4</sub> Spinel |
| title_fullStr | Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn<sub>2</sub>O<sub>4</sub> Spinel |
| title_full_unstemmed | Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn<sub>2</sub>O<sub>4</sub> Spinel |
| title_short | Multi-Centered Solid-Phase Quasi-Intramolecular Redox Reactions of [(Chlorido)Pentaamminecobalt(III)] Permanganate—An Easy Route to Prepare Phase Pure CoMn<sub>2</sub>O<sub>4</sub> Spinel |
| title_sort | multi centered solid phase quasi intramolecular redox reactions of chlorido pentaamminecobalt iii permanganate an easy route to prepare phase pure comn sub 2 sub o sub 4 sub spinel |
| topic | permanganate ammine quasi-intramolecular redox reaction cobalt manganite catalyst spinel todorokite |
| url | https://www.mdpi.com/2304-6740/10/2/18 |
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