MnOx Film-Coated NiFe-LDH Nanosheets on Ni Foam as Selective Oxygen Evolution Electrocatalysts for Alkaline Seawater Oxidation

Inorg Chem. 2022 Sep 26;61(38):15256-15265. doi: 10.1021/acs.inorgchem.2c02579. Epub 2022 Sep 9.

Abstract

Compared to freshwater electrolysis, seawater electrolysis to produce hydrogen is preferable and more promising, but this technology is plagued by the electrode's corrosion and oxidative reactions of the competitive Cl- ion on the anode. To develop efficient oxygen evolution reaction (OER) catalysts for seawater electrolysis, the ultrathin MnOx film-covered NiFe-layered double-hydroxide nanosheet array is directly assembled on Ni foam (MnOx/NiFe-LDH/NF) by hydrothermal and electrodeposition in turn. This catalyst demonstrates excellent OER-selective activity in alkaline saline electrolytes. In 1 M KOH/0.5 M NaCl and 1 M KOH/seawater electrolytes, MnOx/NiFe-LDH/NF exhibits lower overpotentials at 100 mA cm-2100 values of 265 and 276 mV, respectively) and Tafel slopes (73 and 77 mV decade-1, respectively) than does the NiFe-LDH/NF electrode (η100 values of 298 and 327 mV and Tafel slopes of 91 and 140 mV decade-1, respectively). In alkaline saline solutions, the stability and durability of the former are also better than those of the latter. The good OER selectivity and catalytic performance are attributed to the MnOx overlayer that selectively blocks Cl- anions from approaching catalytic centers, and the good conductivity, fast kinetics, more oxygen vacancies, and abundant active sites of MnOx/NiFe-LDH/NF. The robust stability is due to the enhanced resistance for Cl- corrosion stemming from the MnOx protective film. Hence, MnOx/NiFe-LDH/NF can act as a promising OER electrocatalyst for alkalized natural seawater electrolysis.