| Summary: | High-efficiency and low-cost multifunctional electrocatalysts for hydrogen evolution reaction (HERs), oxygen evolution reaction (OERs) and oxygen reduction reaction (ORRs) are important for the practical applications of regenerative fuel cells. The activity trends of core–shell Ni<sub>6</sub>@M<sub>32</sub> and Ni<sub>6</sub>@Pt1M31 (M = Pt, Pd, Cu, Ag, Au) were investigated using the density functional theory (DFT). Rate constant calculations indicated that Ni<sub>6</sub>@Pt<sub>1</sub>Ag<sub>31</sub> was an efficient HER catalyst. The Volmer–Tafel process was the kinetically favorable reaction pathway for Ni<sub>6</sub>@Pt<sub>1</sub>M<sub>31</sub>. The Volmer–Heyrovsky reaction mechanism was preferred for Ni<sub>6</sub>@M<sub>32</sub>. The Pt active site reduced the energy barrier and changed the reaction mechanism. The ORR and OER overpotentials of Ni<sub>6</sub>@Pt<sub>1</sub>Ag<sub>31</sub> were calculated to be 0.12 and 0.33 V, indicating that Ni<sub>6</sub>@Pt<sub>1</sub>Ag<sub>31</sub> could be a promising multifunctional electrocatalyst. Ni<sub>6</sub>@Pt<sub>1</sub>M<sub>31</sub> core–shell clusters present abundant active sites with a moderate adsorption strength for *H, *O, *OH and *OOH. The present study shows that embedding a single Pt atom onto a Ni@M core–shell cluster is a rational strategy for designing an effective multifunctional electrocatalyst.
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