Metal organic framework-derived transition metal-doped CoS nanocage for enhanced visible light-assisted methanol...

Designing noble metal-free anode catalysts for visible light-assisted direct methanol fuel cells still remains a significant challenge. In this study, combining the photocatalytic and electrocatalytic properties of CoS, a visible light-assisted methanol electrocatalytic oxidation strategy was provided. Doping engineering was employed to adjust the electronic structure of CoS and improve their photoassisted methanol electrocatalytic oxidation activity. Using ZIF-67 as precursor, transition metal-doped CoS (M-CoS, M = Zn, Cu, Ni, and Cd) nanocage was synthesized by cation exchange and L-cysteine-controlled etching. Cd doping not only widens the light adsorption to the visible region but also enhances the separation efficiency of photogenerated electron-hole pairs. The electrochemical and photochemical results indicated that the strong oxidative photogenerated hole, OH˙, and O₂˙^- are beneficial for methanol electrocatalytic oxidation. The synergistic electrocatalytic and photocatalytic effect will be a practical strategy for improving the methanol electrocatalytic oxidation activity of noble metal-free semiconductor catalysts.