Covalent organic framework-derived highly dispersed Pt single atoms collaborate with Pt nanoclusters electrocatalyst for acid hydrogen evolution

Abstract

Developing advanced composite materials with single atoms and ultrafine nanoclusters through the modulation of the interactions between these components and their corresponding supports is crucial for achieving economical and effective hydrogen evolution reaction (HER) catalysts. Additionally, enhancing mass transfer efficiency and ensuring high-throughput H₂ production are also vital in electrocatalytic processes. In this study, an electrocatalyst with ultrafine Pt nanoclusters adjacent to Pt single atoms and supported by covalent organic framework-derived hierarchical porous N-doped carbon (mCN-Pt₁) is developed for the acidic HER. More importantly, the rational implementation of hierarchical porous structures and N heteroatom doping are also realized during the material synthesis process. The well-designed mCN-Pt₁ electrocatalyst demonstrates excellent performance in the HER, exhibiting high activity (η₁₀ = 22 mV) and a TOF of 18.5 s⁻¹ at 50 mV. Experimental results and theoretical calculations reveal that the incorporation of N heteroatoms into carbon materials is beneficial for stabilizing Pt single atoms and Pt nanoclusters against agglomeration, while the strong electronic coupling effects between Pt nanoclusters and adjacent Pt single atoms significantly influence the HER activity. This work provides new insights into the design of high-performance atomic-scale catalysts for electrochemical applications.