Pt Atomic Layers Boosted Hydrogen Evolution Reaction in Nonacidic Media

Abstract Pt‐based electrocatalysts exhibit high performance toward hydrogen evolution reaction (HER) since they can boost sluggish kinetics of water dissociation. To develop efficient Pt catalysts in nonacidic media, Pt electrocatalysts with a Rh core and a shell of a few Pt atomic layers (Rh@Pt nL , n = 1, 2, 2.6) are designed. Ultrathin Pt atomic layers on a Rh core modulate electronic structures of Rh@Pt nL electrocatalysts, generating a combined effect of ligand, compressive strain, and electron transfer. The Rh@Pt nL electrocatalysts thus offer significantly higher HER activity in alkaline and neutral media than the RhPt alloy, Rh/C, and commercial Pt/C catalysts. The overpotential of a Rh@Pt 2L electrocatalyst is only 5 mV at 10 mA cm −2 in 1.0 M KOH. The density functional theory calculations confirm that the excellent HER activity of this Rh@Pt 2L electrocatalyst in nonacidic media is attributed to an enhanced hydrogen desorption and a decreased energetic barrier during the hydrogen generating process. These Rh@Pt nL electrocatalysts shed the light on the design of advanced catalysts to efficiently produce green hydrogen in nonacidic media.