Design and preparation of three-dimensional hetero-electrocatalysts of NiCo-layered double hydroxide nanosheets incorporated with silver nanoclusters for enhanced oxygen evolution reactions.

Layered double hydroxides (LDHs) are one of the most effective electrocatalysts. However, it is still necessary to improve the lower conductivity and limited active sites of LDHs to enhance their catalytic performance. Targeted generation of vacancies on the catalyst's surface by the incorporation of metal nanoparticles has been explored as a promising strategy to synthesize highly efficient electrocatalysts. Herein, we designed and prepared novel three-dimensional (3D) hetero-electrocatalysts of NiCo-layered double hydroxide nanosheets incorporated with silver nanoclusters on a Ni foam (labeled as Ag@NiCo-LDH/NF) by a one-pot hydrothermal method. We also conducted experimental and theoretical investigations to demonstrate the high electrocatalytic performance of the Ag@NiCo-LDH/NF hetero-electrocatalysts for OERs and the underlying mechanism. The resulting hetero-electrocatalysts show a low overpotential of 262 mV at a current density of 10 mA cm, and even exhibit low overpotentials of 300 mV at a high current density of 50 mA cm and 324 mV at 100 mA cm, and a small Tafel slope of 41 mV dec as well as excellent durability for 80 h for OERs in 1.0 M KOH. The excellent performance is attributed to the synergistic effects between Ag nanoclusters and LDHs. The population engineering effect of silver not only helps to modulate the intrinsic properties of active sites but also induces the generation of abundant oxygen vacancies on the surface; finally, it facilitates the rate-determining step of OERs (ΔG (O* → OOH*) = 1.31 eV) to gain high performance. The one-pot silver incorporating strategy and the resulting high performance pave new ways for the further development of highly efficient electrocatalysts for OERs.