A self-generated and degradation-resistive cratered stainless steel electrocatalyst for efficient water oxidation in a neutral electrolyte

Abstract

An electron-mediated CO2-to-chemical conversion system is regarded as one of the effective solutions for the depletion of fossil fuels and the accumulation of atmospheric CO2. In this process, the protons and electrons generated from the water-oxidation reaction at an anode are used during the reduction of CO2 at a cathode, in order to produce high-value hydrocarbon chemicals. Therefore, water oxidation is also a key reaction for the overall electron-mediated CO2-to-chemical conversion. In this work, a facile preparation method is developed for a highly efficient water oxidation electrocatalyst which stably operates in a neutral bicarbonate electrolyte optimized for CO2-reduction conditions. Ni-rich cratered structures were spontaneously formed on the stainless steel surface by harsh electro-oxidation, and the chemical composition changes of Fe and Ni on the catalyst surface dramatically enhance wateroxidation activity showing an overpotential value of 504 mV at 10 mA cm(-2) in a CO2-saturated bicarbonate electrolyte. In contrast to a severe degradation in the phosphate electrolyte, the cratered stainless-steel (CSS) catalyst is very stable for an 18 h reaction in the bicarbonate electrolyte. Surface spectroscopic analyses of CSS consistently revealed that the active-surface structure of the NiOOH and adsorbed water molecules is remarkably stable throughout water-oxidation in the neutral bicarbonate electrolyte, while the destruction of Ni structures by the phosphate electrolyte is proposed to cause concomitant activity loss for water oxidation.