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12. The role of nano-sized manganese oxides in the oxygen-evolution reactions by manganese complexes: towards a complete picture.

Author

Najafpour, Mohammad Mahdi, Hołyńska, Małgorzata, Shamkhali, Amir Nasser, Kazemi, Sayed Habib, Hillier, Warwick, Amini, Emad, Ghaemmaghami, M., Sedigh, Davood Jafarian, Moghaddam, Atefeh Nemati, Mohamadi, Rahim, Zaynalpoor, Sasan, and Beckmann, Katrin

Subjects
MANGANESE oxides, OXYGEN evolution reactions, METAL complexes, METAL nanoparticles, CARBOXYLATES, CHEMICAL synthesis, LIGANDS (Chemistry)
Abstract

Eighteen Mn complexes with N-donor and carboxylate ligands have been synthesized and characterized. Three Mn complexes among them are new and are reported for the first time. The reactions of oxygen evolution in the presence of oxone (2KHSO5·KHSO4·K2SO4) and cerium(IV) ammonium nitrate catalyzed by these complexes are studied and characterized by UV-visible spectroscopy, X-ray diffraction spectrometry, dynamic light scattering, Fourier transform infrared spectroscopy, electron paramagnetic resonance spectroscopy, transmission electron microscopy, scanning electron microscopy, membrane-inlet mass spectrometry and electrochemistry. Some of these complexes evolve oxygen in the presence of oxone as a primary oxidant. CO2 and MnO4 - are other products of these reactions. Based on spectroscopic studies, the true catalysts for oxygen evolution in these reactions are different. We proposed that for the oxygen evolution reactions in the presence of oxone, the true catalysts are both high valent Mn complexes and Mn oxides, but for the reactions in the presence of cerium(IV) ammonium nitrate, the active catalyst is most probably a Mn oxide. [ABSTRACT FROM AUTHOR]

Published
2014
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14. A dinuclear iron complex with a single oxo bridge as an efficient water-oxidizing catalyst in the presence of cerium(iv) ammonium nitrate: new findings and current controversiesElectronic supplementary information (ESI) available. CCDC 955723. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3cy00644a

Author

Najafpour, Mohammad Mahdi, Moghaddam, Atefeh Nemati, Sedigh, Davood Jafarian, and Hoyska, Magorzata

Abstract

In this paper a dinuclear Fe complex, [tpa(H2O)FeOFe(H2O)tpa](ClO4)4(tpa: tris(2-pyridylmethyl)amine) is reported as an efficient catalyst for water oxidation in the presence of cerium(iv) ammonium nitrate. The turnover frequency of this dimer is 6 times greater than the turnover frequency reported for the [Fe(OTf or Cl)2(tpa)] complex (OTf: trifluoromethanesulfonate). The role of FeO42−ions in the water oxidation reaction is also discussed.

Published
2013
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