Co(III) carboxamide complexes as electrocatalysts for water splitting |
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Affiliation: | 1. Alborz Campus, University of Tehran, Tehran, Iran;2. Department of Chemistry, College of Science, University of Tehran, Tehran 14155-6455, Iran;3. Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland;4. Institute of Physics, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland |
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Abstract: | Water splitting is a promising approach for storing intermittent renewable energies, such as sunlight in the clean chemical bonds as a hydrogen fuel. Two water-soluble octahedral cobalt (III) complexes, Co(bpb)(OAc)(H2O)], 1, (bpb2? = N,N′-bis(2-pyridine carboxamide)-1,2-benzene] dianion) and Co(cbpb)(OAc)(H2O)], 2, (cbpb2? = N,N′-bis(2-pyridine carboxamide)-4-chloro-1,2-benzene] dianion) were synthesised and characterised by CHN elemental analysis, UV–Vis, FT-IR and single-crystal X-ray diffraction techniques. The two carboxamide ligands had been prepared in the ionic liquid TBAB as an environmentally benign reaction medium. The electrocatalytic water splitting activity of 1 and 2 showed that both complexes are highly active for the water splitting in aqueous solutions. Turn Over Frequency (TOF) values were, for 1 and 2 respectively, 527 and 490 mol of hydrogen in each mole of catalyst per hour at an overpotential of 738 mV (pH = 7.0). Such a performance can be ascribed to the flat ligands, the electroactivity of the metal centre and carboxamide ligands and the ability of losing the axial ligands around the metal-ion centre during the reduction process which provide different reduction pathways for an HER process. |
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Keywords: | Co(III) carboxamide complexes Crystal structure Electrocatalyst HER Water splitting |
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