Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy
Graphitic carbon nitride (gCN) materials have been shown to efficiently perform light-induced water splitting, carbon dioxide reduction, and environmental remediation in a cost-effective way. However, gCN suffers from rapid charge-carrier recombination, inefficient light absorption, and poor long-te...
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| Format: | Article |
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MDPI AG
2023-09-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/18/6475 |
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| author | Elizaveta Kobeleva Ekaterina Shabratova Adi Azoulay Rowan W. MacQueen Neeta Karjule Menny Shalom Klaus Lips Joseph E. McPeak |
| author_facet | Elizaveta Kobeleva Ekaterina Shabratova Adi Azoulay Rowan W. MacQueen Neeta Karjule Menny Shalom Klaus Lips Joseph E. McPeak |
| author_sort | Elizaveta Kobeleva |
| collection | DOAJ |
| description | Graphitic carbon nitride (gCN) materials have been shown to efficiently perform light-induced water splitting, carbon dioxide reduction, and environmental remediation in a cost-effective way. However, gCN suffers from rapid charge-carrier recombination, inefficient light absorption, and poor long-term stability which greatly hinders photocatalytic performance. To determine the underlying catalytic mechanisms and overall contributions that will improve performance, the electronic structure of gCN materials has been investigated using electron paramagnetic resonance (EPR) spectroscopy. Through lineshape analysis and relaxation behavior, evidence of two independent spin species were determined to be present in catalytically active gCN materials. These two contributions to the total lineshape respond independently to light exposure such that the previously established catalytically active spin system remains responsive while the newly observed, superimposed EPR signal is not increased during exposure to light. The time dependence of these two peaks present in gCN EPR spectra recorded sequentially in air over several months demonstrates a steady change in the electronic structure of the gCN framework over time. This light-independent, slowly evolving additional spin center is demonstrated to be the result of oxidative processes occurring as a result of exposure to the environment and is confirmed by forced oxidation experiments. This oxidized gCN exhibits lower H<sub>2</sub> production rates and indicates quenching of the overall gCN catalytic activity over longer reaction times. A general model for the newly generated spin centers is given and strategies for the alleviation of oxidative products within the gCN framework are discussed in the context of improving photocatalytic activity over extended durations as required for future functional photocatalytic device development. |
| first_indexed | 2024-03-10T22:24:55Z |
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| id | doaj.art-2b2c1bbf4d8d490c90f3fee450d71873 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T22:24:55Z |
| publishDate | 2023-09-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-2b2c1bbf4d8d490c90f3fee450d718732023-11-19T12:07:54ZengMDPI AGMolecules1420-30492023-09-012818647510.3390/molecules28186475Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance SpectroscopyElizaveta Kobeleva0Ekaterina Shabratova1Adi Azoulay2Rowan W. MacQueen3Neeta Karjule4Menny Shalom5Klaus Lips6Joseph E. McPeak7Berlin Joint EPR Laboratory and EPR4Energy, Department Spins in Energy Conversion and Quantum Information Science (ASPIN), Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, GermanyBerlin Joint EPR Laboratory and EPR4Energy, Department Spins in Energy Conversion and Quantum Information Science (ASPIN), Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, GermanyDepartment of Chemistry, Ilse Katz Institute for Nanoscale Science and Technology, Ben-Gurion University of the Negev, Beer-Sheva 8410501, IsraelBerlin Joint EPR Laboratory and EPR4Energy, Department Spins in Energy Conversion and Quantum Information Science (ASPIN), Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, GermanyDepartment of Chemistry, Ilse Katz Institute for Nanoscale Science and Technology, Ben-Gurion University of the Negev, Beer-Sheva 8410501, IsraelDepartment of Chemistry, Ilse Katz Institute for Nanoscale Science and Technology, Ben-Gurion University of the Negev, Beer-Sheva 8410501, IsraelBerlin Joint EPR Laboratory and EPR4Energy, Department Spins in Energy Conversion and Quantum Information Science (ASPIN), Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, GermanyBerlin Joint EPR Laboratory and EPR4Energy, Department Spins in Energy Conversion and Quantum Information Science (ASPIN), Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, Hahn-Meitner-Platz 1, 14109 Berlin, GermanyGraphitic carbon nitride (gCN) materials have been shown to efficiently perform light-induced water splitting, carbon dioxide reduction, and environmental remediation in a cost-effective way. However, gCN suffers from rapid charge-carrier recombination, inefficient light absorption, and poor long-term stability which greatly hinders photocatalytic performance. To determine the underlying catalytic mechanisms and overall contributions that will improve performance, the electronic structure of gCN materials has been investigated using electron paramagnetic resonance (EPR) spectroscopy. Through lineshape analysis and relaxation behavior, evidence of two independent spin species were determined to be present in catalytically active gCN materials. These two contributions to the total lineshape respond independently to light exposure such that the previously established catalytically active spin system remains responsive while the newly observed, superimposed EPR signal is not increased during exposure to light. The time dependence of these two peaks present in gCN EPR spectra recorded sequentially in air over several months demonstrates a steady change in the electronic structure of the gCN framework over time. This light-independent, slowly evolving additional spin center is demonstrated to be the result of oxidative processes occurring as a result of exposure to the environment and is confirmed by forced oxidation experiments. This oxidized gCN exhibits lower H<sub>2</sub> production rates and indicates quenching of the overall gCN catalytic activity over longer reaction times. A general model for the newly generated spin centers is given and strategies for the alleviation of oxidative products within the gCN framework are discussed in the context of improving photocatalytic activity over extended durations as required for future functional photocatalytic device development.https://www.mdpi.com/1420-3049/28/18/6475EPR spectroscopyphotocatalysiscarbon nitrideelectronic relaxationsemiconductoroxidation processes |
| spellingShingle | Elizaveta Kobeleva Ekaterina Shabratova Adi Azoulay Rowan W. MacQueen Neeta Karjule Menny Shalom Klaus Lips Joseph E. McPeak Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy Molecules EPR spectroscopy photocatalysis carbon nitride electronic relaxation semiconductor oxidation processes |
| title | Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy |
| title_full | Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy |
| title_fullStr | Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy |
| title_full_unstemmed | Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy |
| title_short | Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy |
| title_sort | long term characterization of oxidation processes in graphitic carbon nitride photocatalyst materials via electron paramagnetic resonance spectroscopy |
| topic | EPR spectroscopy photocatalysis carbon nitride electronic relaxation semiconductor oxidation processes |
| url | https://www.mdpi.com/1420-3049/28/18/6475 |
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