Substituent‐Induced Deformed Ni–Porphyrin as an Electrocatalyst for the Electrochemical Conversion of Water into Dioxygen. Issue 14 (25th March 2018)

• Record Type: Journal Article
• Authors: Krishna, Jonnadula Venkata Suman; Krishna, Narra Vamsi; Singh, Santosh K.; Shaw, Pankaj K.; Dhavale, Vishal M.; Vardhaman, Anil Kumar; Giribabu, Lingamallu
• Is Part Of: European journal of inorganic chemistry. Issue 14(2018)
• Page Start: 1549
• Page End: 1555
• Publication Date: 2018-03-25
• Subjects: Oxygen -- Nickel -- Porphyrinoids -- Electrochemistry -- Water chemistry -- Electrocatalysts; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201701427
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : The electrochemical water oxidation ability of complexes 5, 15‐diphenylporphinatonickel(II) (A ) and 5, 15‐bis(3, 5‐di‐ tert ‐butylphenyl)porphinatonickel(II) (B ) in the oxygen evolution reaction (OER) have been investigated in an alkaline medium. ComplexB was found to be kinetically and thermodynamically more active than complexA . The overpotential and Tafel slope of complexB are lower than those of complexA by 30 mV and around 45 mV/decade, respectively, which supports the higher activity ofB . Moreover, stability tests endorse the sustainability of both samples under alkaline conditions. It has been found that the 3, 5‐di‐ tert ‐butylphenyl substituent inB plays a decisive role in achieving a better OER onset potential and current than that obtained withA, which is a result of the modulation of the structural parameters ofB . Furthermore, the measured OER activities ofA andB have been correlated with their molecular arrangement as well as differences in their bonding characteristics and dipole moments. For further insight, the obtained results have been confirmed by a theoretical study. Abstract : The activities of 5, 15‐diphenylporphinatonickel(II) (A) and 5, 15‐bis(3, 5‐di‐ tert ‐butylphenyl)porphinatonickel(II) (B) complexes in the oxygen evolution reaction (OER) have been investigated in an alkaline medium. The OER activities ofA andB have been correlated with their molecular properties.