Implanted metal-nitrogen active sites enhance the electrocatalytic activity of zeolitic imidazolate zinc framework-derived porous carbon for the hydrogen evolution reaction in acidic and alkaline media.

Abstract Developing electrocatalysts with excellent catalytic performance and superior durability for hydrogen evolution reaction (HER) remains a challenge. Herein, metal-nitrogen sites (M–Nx, M = Ni and Cu) are successfully implanted into zeolitic imidazolate zinc framework (ZIF-8)-derived nitrogen-doped porous carbon (ZIF/NC) to prepare Ni-ZIF/NC and Cu-ZIF/NC electrocatalysts for the HER. These M–Nx active sites significantly enhanced the electrocatalytic activities of Ni-ZIF/NC and Cu-ZIF/NC. Metal Ni acted as a catalyst for catalysis of Ni-ZIF/NC to form carbon nanotubes-like structures, which provided convenient ion transmission pathways. Owing to its special morphology and an increased number of defects, Ni-ZIF/NC displayed superior electrocatalytic activity in the HER compared to those of Cu-ZIF/NC and ZIF/NC. In an alkaline environment, Ni-ZIF/NC exhibited an overpotential at the current density of 10 mA cm−2 (η10) of 163.0 mV and Tafel slope of 85.0 mV dec−1, demonstrating an electrocatalytic property equivalent to that of Pt/C. In an acidic environment, Ni-ZIF/NC yielded a η10 of 177.4 mV and Tafel slope of 83.9 mV dec−1, which were comparable to those of 20 wt.% Pt/C. Moreover, Ni-ZIF/NC and Cu-ZIF/NC also exhibited superior stabilities in alkaline environments. This work offers a valuable strategy for controlling the morphology and implanting M–Nx active sites into carbon for designing novel catalysts for use in alternative new energy applications.