Ultrafine Co Nanoparticles Encapsulated in Carbon‐Nanotubes‐Grafted Graphene Sheets as Advanced Electrocatalysts for the Hydrogen Evolution Reaction

The rational design of an efficient and inexpensive electrocatalyst based on earth-abundant 3d transition metals (TMs) for the hydrogen evolution reaction still remains a significant challenge in the renewable energy area. Herein, a novel and effective approach is developed for synthesizing ultrafine Co nanoparticles encapsulated in nitrogen-doped carbon nanotubes (N-CNTs) grafted onto both sides of reduced graphene oxide (rGO) (Co@N-CNTs@rGO) by direct annealing of GO-wrapped core-shell bimetallic zeolite imidazolate frameworks. Benefiting from the uniform distribution of Co nanoparticles, the in-situ-formed highly graphitic N-CNTs@rGO, the large surface area, and the abundant porosity, the as-fabricated Co@N-CNTs@rGO composites exhibit excellent electrocatalytic hydrogen evolution reaction (HER) activity. As demonstrated in electrochemical measurements, the composites can achieve 10 mA cm^-2 at low overpotential with only 108 and 87 mV in 1 m KOH and 0.5 m H₂ SO₄ , respectively, much better than most of the reported Co-based electrocatalysts over a wide pH range. More importantly, the synthetic strategy is versatile and can be extended to prepare other binary or even ternary TMs@N-CNTs@rGO (e.g., Co-Fe@N-CNTs@rGO and Co-Ni-Cu@N-CNTs@rGO). The strategy developed here may open a new avenue toward the development of nonprecious high-performance HER catalysts.