Electrocatalytic Water Oxidation by a Ni(ii) Salophen-type Complex

Overview

Journal RSC Adv

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 May 11

PMID 35542637

Authors

Mehri Aligholivand

Zohreh Shaghaghi

Rahman Bikas

Anna Kozakiewicz

Affiliations

Soon will be listed here.

Abstract

A new mononuclear Ni(ii) complex, NiL (1), was synthesized from the reaction of Ni(OAc)·4HO and salophen-type NO-donor ligand, HL (where HL = 2,2'-((1,1')-((4-chloro-5-methyl-1,2-phenylene)bis(azanylylidene))bis(methanylylidene))diphenol), in ethanol. The obtained complex was characterized by elemental analysis, spectroscopic techniques and single crystal X-ray analysis. The complex was studied as a water oxidizing catalyst and its electrocatalytic activity in the water oxidation reaction was tested in 0.5 M of borate buffer at pH = 3, 7 and 11 in a typical three-electrode setup with a carbon paste electrode modified by complex 1 as a working electrode. The linear sweep voltammetry (LSV) curves indicated that complex 1 has a much superior activity and only needs 21 mV Ag/AgCl overvoltage to reach a geometrical catalytic current density of 2.0 mA cm at pH = 11. The onset potential decreased from 1.15 V to 0.67 V Ag/AgCl with an increase of pH from 3 to 13 under a constant current density of 1.0 mA cm. Then, to determine the true catalyst for the water oxidation reaction in the presence of complex 1 at pH = 3, 7 and 11, cyclic voltammetry was also performed. The continuous CVs for complex 1 at neutral and alkaline solutions showed significant progress for the water oxidation reaction. In addition, the amperometry tests exhibited excellent stability and high constant current density for water oxidation by CPE-complex 1 under electrochemical conditions at pH = 11 and 7. Although X-ray powder diffraction analysis did not show a pure and crystalline structure for NiO , the scanning electron microscopy images showed that nickel oxide at pH = 11 and nickel oxide or other Ni-based compounds at pH = 7 are true water oxidizing catalysts on the surface of a CPE electrode. Moreover at pH = 3, no clear water oxidation or NiO formation was observed.

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