Bimetallic Nickel-Substituted Cobalt-Borate Nanowire Array: An Earth-Abundant Water Oxidation Electrocatalyst with Superior Activity and Durability at Near Neutral pH.

Abstract

There is an urgent demand to develop earth-abundant electrocatalysts for efficient and durable water oxidation under mild conditions. A nickel-substituted cobalt-borate nanowire array is developed on carbon cloth (Ni-Co-Bi/CC) via oxidative polarization of NiCo2 S4 nanoarray in potassium borate (K-Bi). As a bimetallic electrocatalyst for water oxidation, such Ni-Co-Bi/CC is superior in catalytic activity and durability in 0.1 m K-Bi (pH: 9.2), with a turnover frequency of 0.33 mol O2 s-1 at the overpotential of 500 mV and nearly 100% Faradaic efficiency. To drive a geometrical catalytic current density of 10 mA cm-2 , it only needs overpotential of 388 mV, 34 mV less than that for Co-Bi/CC, outperforming reported non-noble-metal catalysts operating under benign conditions. Notably, its activity is maintained over 80 000 s. Density functional theory calculations suggest that the O* to OOH* conversion is the rate-determining step and Ni substitution decreases the free energy on Co-Bi from 2.092 to 1.986 eV.