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https://hdl.handle.net/20.500.14279/32215
Title: | Mechanism of the Reductive Activation of O2 to O22- from a Vanadium(IV) Species and Its Potential Use in Fuel Cells | Authors: | Keramidas, Anastasios D. Papanikolaou, Michael G. Hadjithoma, Sofia Keramidas, Odysseas Amoiridis, Aggelos Drouza, Chryssoula Themistokleous, Alexandros Hayes, Sofia C. Lianos, Panagiotis Tsipis, Athanassios C. Kabanos, Themistoklis A. |
Major Field of Science: | Natural Sciences | Field Category: | Chemical Sciences | Keywords: | Electron reductive activation;Green oxidants;Powerful fuel-cells | Issue Date: | 8-May-2023 | Source: | Joint CTMNM/NAGC Conference, 2023, 8-12 May, Spetses Island, Greece | Link: | https://christou.chem.ufl.edu/2023-joint-ctmnm-nagc-conference/ | Conference: | Joint CTMNM/NAGC Conference | Abstract: | The two electron reductive activation of O2 to O22- is of particular interest to scientific community mainly due to the use of peroxides as green oxidants and in powerful fuel-cells. Among the metal-ions which activate O2, vanadium is of particular interest because of its numerous oxidative catalytic properties. Reaction of either VIVOSO4.3.5H2O or VIVOCl2 with N-(8-quinolyl)pyridine-2-carboxamide (Hpbq) in CH3OH solution under atmospheric O2, at room temperature, resulted in the quick formation of [VVO(k2-O2)(pbq)(H2O)](1). Compound 1 constitutes a rare example of formation of a (peroxo)oxidovanadium(V) complex from molecular O2 and an oxidovanadium(IV) complex. The reaction of formation of compound 1vs. time was monitored by 51V and 1H NMR, UV-vis, cw-X-EPR, Resonance Raman spectroscopiesand cyclic voltammetry revealing the formation of a stable radical intermediate [VVO(k2-O2)(pbq)(H2O)]•+. Dynamic experiments in combination with computational calculations were used to elucidate the mechanism of the reaction. The galvanic cell {Zn|VIII,VII||cis-[VVO2(bpq)], [VVO(O2)(bpq)(H2O)],[VIVO(bpq)(H2O)2]+|O2|C(s)} was manufactured, demonstrating that this technology can be used in Zn|H2O2 fuel cells generating H2O2 in situ from atmospheric O2. | URI: | https://hdl.handle.net/20.500.14279/32215 | Type: | Conference Papers | Affiliation : | Cyprus University of Technology University of Cyprus University of Patras University of Ioannina |
Publication Type: | Peer Reviewed |
Appears in Collections: | Δημοσιεύσεις σε συνέδρια /Conference papers or poster or presentation |
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