Unusually high oxidation states of manganese in high optical basicity silicate glasses
Unusually high oxidation states of manganese were stabilized within a cesium-barium silicate (CBS) glass system of extremely high optical basicity. The highest basicity was obtained for the metasilicate glass 40Cs2O–10BaO–50SiO2 (mol%) with an optical basicity of Λ = 0.81. The presence of Mn5+ (d2)...
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Elsevier
2024-12-01
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| Series: | Optical Materials: X |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2590147824000834 |
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| author | Amir Ashjari Brian Topper Lars H. Hess Lucas Greiner Jared Tolliver Fiona Cormack Dimitrios Palles Efstratios I. Kamitsos Mikhail G. Brik Doris Möncke |
| author_facet | Amir Ashjari Brian Topper Lars H. Hess Lucas Greiner Jared Tolliver Fiona Cormack Dimitrios Palles Efstratios I. Kamitsos Mikhail G. Brik Doris Möncke |
| author_sort | Amir Ashjari |
| collection | DOAJ |
| description | Unusually high oxidation states of manganese were stabilized within a cesium-barium silicate (CBS) glass system of extremely high optical basicity. The highest basicity was obtained for the metasilicate glass 40Cs2O–10BaO–50SiO2 (mol%) with an optical basicity of Λ = 0.81. The presence of Mn5+ (d2) as well as Mn6+ (d1) is confirmed by UV–Vis, photoluminescence, and Raman spectroscopy. The UV–Vis spectrum is dominated by the Mn3+ (d4) absorption at 526 nm for low-basicity glasses, which is replaced by a peak at 679 nm (Mn5+) and, finally, a band at 603 nm (Mn6+) in the glass with the highest basicity (Λ = 0.81). In this glass, the Mn5+/Mn6+ ratio varies with the melting conditions. Photoluminescence (PL) spectroscopy under 633 nm excitation confirms the presence of Mn5+, showing the narrow, forbidden 1E →3A2 transition located at 1191 nm with vibrational sidebands at 1245 nm and 1290 nm. The measured static fluorescence intensity due to Mn5+ grows exponentially with increasing optical basicity. The near infrared fluorescence decay was bi-exponential, with time constants of 14 and 51 μs. The absence of Mn4+ in CBS glasses was confirmed by PL and electron paramagnetic resonance (EPR) spectroscopy. Despite initial doping as MnO2, metastable Mn4+ disproportionates into lower and higher valent manganese species, followed by reduction or oxidation of manganese to a stable species as ruled by the basicity of the glass and oxygen availability during melting. A structural study of the glasses by Raman spectroscopy revealed a resonance enhancement effect for the symmetric stretching mode of MnO4-tetrahedra at ∼800 cm−1 with overtones observed at higher frequencies. |
| format | Article |
| id | doaj-art-c0511209727e45b7bb39afe30fc87756 |
| institution | Kabale University |
| issn | 2590-1478 |
| language | English |
| publishDate | 2024-12-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Optical Materials: X |
| spelling | doaj-art-c0511209727e45b7bb39afe30fc877562024-12-13T11:01:06ZengElsevierOptical Materials: X2590-14782024-12-0124100371Unusually high oxidation states of manganese in high optical basicity silicate glassesAmir Ashjari0Brian Topper1Lars H. Hess2Lucas Greiner3Jared Tolliver4Fiona Cormack5Dimitrios Palles6Efstratios I. Kamitsos7Mikhail G. Brik8Doris Möncke9Inamori School of Engineering at the New York State College of Ceramics, Alfred University, Alfred, NY, 14802, USAInamori School of Engineering at the New York State College of Ceramics, Alfred University, Alfred, NY, 14802, USA; Center for High Technology Materials, University of New Mexico, Albuquerque, NM, 87106, USA; Department of Materials Science and Engineering, Clemson University, Clemson, SC, 29634, USANorthvolt AB, Ackumulatorvägen 1, Västerås, SwedenInamori School of Engineering at the New York State College of Ceramics, Alfred University, Alfred, NY, 14802, USA; Department of Material Science and Engineering, Missouri University of Science and Technology, Rolla, MO, 65409, USACenter for High Technology Materials, University of New Mexico, Albuquerque, NM, 87106, USAInamori School of Engineering at the New York State College of Ceramics, Alfred University, Alfred, NY, 14802, USATheoretical and Physical Chemistry Institute, National Hellenic Research Foundation, Athens, GreeceTheoretical and Physical Chemistry Institute, National Hellenic Research Foundation, Athens, GreeceSchool of Optoelectronic Engineering & CQUPT-BUL Innovation Institute, Chongqing University of Posts and Telecommunications, Chongqing, 400065, People's Republic of China; Centre of Excellence for Photoconversion, Vinča Institute of Nuclear Sciences - National Institute of the Republic of Serbia, University of Belgrade, Belgrade, Serbia; Faculty of Science and Technology, Jan Długosz University, 42200, Częstochowa, Poland; Institute of Physics, University of Tartu, W. Ostwald Str. 1, Tartu, 50411, Estonia; Academy of Romanian Scientists, Ilfov Str. No. 3, Bucharest, RomaniaInamori School of Engineering at the New York State College of Ceramics, Alfred University, Alfred, NY, 14802, USA; Corresponding author.Unusually high oxidation states of manganese were stabilized within a cesium-barium silicate (CBS) glass system of extremely high optical basicity. The highest basicity was obtained for the metasilicate glass 40Cs2O–10BaO–50SiO2 (mol%) with an optical basicity of Λ = 0.81. The presence of Mn5+ (d2) as well as Mn6+ (d1) is confirmed by UV–Vis, photoluminescence, and Raman spectroscopy. The UV–Vis spectrum is dominated by the Mn3+ (d4) absorption at 526 nm for low-basicity glasses, which is replaced by a peak at 679 nm (Mn5+) and, finally, a band at 603 nm (Mn6+) in the glass with the highest basicity (Λ = 0.81). In this glass, the Mn5+/Mn6+ ratio varies with the melting conditions. Photoluminescence (PL) spectroscopy under 633 nm excitation confirms the presence of Mn5+, showing the narrow, forbidden 1E →3A2 transition located at 1191 nm with vibrational sidebands at 1245 nm and 1290 nm. The measured static fluorescence intensity due to Mn5+ grows exponentially with increasing optical basicity. The near infrared fluorescence decay was bi-exponential, with time constants of 14 and 51 μs. The absence of Mn4+ in CBS glasses was confirmed by PL and electron paramagnetic resonance (EPR) spectroscopy. Despite initial doping as MnO2, metastable Mn4+ disproportionates into lower and higher valent manganese species, followed by reduction or oxidation of manganese to a stable species as ruled by the basicity of the glass and oxygen availability during melting. A structural study of the glasses by Raman spectroscopy revealed a resonance enhancement effect for the symmetric stretching mode of MnO4-tetrahedra at ∼800 cm−1 with overtones observed at higher frequencies.http://www.sciencedirect.com/science/article/pii/S2590147824000834Cesium-barium metasilicateHigh optical basicityResonance Raman enhancementMn5+Mn6+Redox equilibria |
| spellingShingle | Amir Ashjari Brian Topper Lars H. Hess Lucas Greiner Jared Tolliver Fiona Cormack Dimitrios Palles Efstratios I. Kamitsos Mikhail G. Brik Doris Möncke Unusually high oxidation states of manganese in high optical basicity silicate glasses Optical Materials: X Cesium-barium metasilicate High optical basicity Resonance Raman enhancement Mn5+ Mn6+ Redox equilibria |
| title | Unusually high oxidation states of manganese in high optical basicity silicate glasses |
| title_full | Unusually high oxidation states of manganese in high optical basicity silicate glasses |
| title_fullStr | Unusually high oxidation states of manganese in high optical basicity silicate glasses |
| title_full_unstemmed | Unusually high oxidation states of manganese in high optical basicity silicate glasses |
| title_short | Unusually high oxidation states of manganese in high optical basicity silicate glasses |
| title_sort | unusually high oxidation states of manganese in high optical basicity silicate glasses |
| topic | Cesium-barium metasilicate High optical basicity Resonance Raman enhancement Mn5+ Mn6+ Redox equilibria |
| url | http://www.sciencedirect.com/science/article/pii/S2590147824000834 |
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