Significantly enhanced electrocatalytic activity of copper for hydrogen evolution reaction through femtosecond laser blackening.

In this work, we report on the creation of a black copper via femtosecond laser processing and its application as a novel electrode material. We show that the black copper exhibits an excellent electrocatalytic activity for hydrogen evolution reaction (HER) in alkaline solution. The laser processing results in a unique microstructure: microparticles covered by finer nanoparticles on top. Electrochemical measurements demonstrate that the kinetics of the HER is significantly accelerated after bare copper is treated and turned black. At -0.325 V (v.s. RHE) in 1 M KOH aqueous solution, the calculated area-specific charge transfer resistance of the electrode decreases sharply from 159 Ω cm for the untreated copper to 1 Ω cm for the black copper. The electrochemical surface area of the black copper is measured to be only 2.4 times that of the untreated copper and therefore, the significantly enhanced electrocatalytic activity of the black copper for HER is mostly a result of its unique microstructure that favors the formation and enrichment of protons on the surface of copper. This work provides a new strategy for developing high-efficient electrodes for hydrogen generation.