Metal-organic framework-derived cation regulation of metal sulfides for enhanced oxygen evolution activity

Heteroatom doping serves as an important strategy to improve the oxygen evolution reaction (OER) activity of transition-metal compounds, while the investigation of intrinsic active sites and mechanisms remains insufficient. In this work, a facile cation regulation strategy is reported to boost the OER activity of metal sulfides via pyrolysis of the Ni-Co bimetallic metal-organic framework. The obtained Ni-substituted CoS nanoparticles on nitrogen-doped mesoporous carbon (Ni-CoS/NC) catalyst achieves a current density of 10 mA cm−2 at a small overpotential of 270 mV with a Tafel slope of 37 mV dec−1 in 1.0 mol L−1 KOH. Through a combination of spectroscopy study and theoretical computations, the activity origin is revealed at the atomic level. The CoxNi1–xOOH serves as the real active site for the OER generated by the Ni-CoS/NC reconstruction under oxidation potential during OER. The Ni substitution results in a strong electronic interaction between the two metals, thus generating more negatively charged Co atoms and more positively charged Ni atoms in the electrocatalyst. The metal sites with regulated electronic structure exhibit enhanced surface adsorption of OOH* and reduce the OER overpotential. Meanwhile, the conductive porous carbon scaffold facilitates electron transfer, mass diffusion, and the accessibility of active sites. This work not only provides a feasible cation regulation strategy for the design of high-performance electrocatalysts for low-cost energy storage and conversion systems, but also yields fresh insight into the activity enhancement mechanisms and intrinsic active sites.