Monometallic Ultrasmall Nanocatalysts via Different Valence Atomic Interfaces Boost Hydrogen Evolution Catalysis

Abstract

Synergistic monometallic nanocatalysts have attracted much attention due to their high intrinsic activity properties. However, current synergistic monometallic nanocatalysts tend to suffer from long reaction paths due to restricted nanoscale interfaces. In this paper, we synthesized the interstitial compound N-Pt/CNT with monometallic atomic interfaces. The catalysts are enriched with atomic interfaces between higher valence Pt δ+ and Pt 0 , allowing the reaction to proceed synergistically within the same component with an ideal reaction pathway. Through ratio optimization, N 2.42 -Pt/CNT with a suitable ratio of Pt δ+ and Pt 0 is synthesized. And the calculated turnover frequency of N 2.42 -Pt/CNT is about 37.4 s −1 (−0.1 V vs reversible hydrogen electrode (RHE)), six times higher than that of the commercial Pt/C (6.58 s −1 ), which is the most intrinsically active of the Ptbased catalysts. Moreover, prepared N 2.42 -Pt/CNT exhibits excellent stability during the chronoamperometry tests of 200 h. With insights from comprehensive experiments and theoretical calculations, Pt with different valence states in monometallic atomic interfaces synergistically accelerates the H 2 O dissociation step and optimizes the Gibbs free energy of H* adsorption. And the existence of desirable hydrogen transfer paths substantially facilitates hydrogen evolution reaction kinetics.