Proximity effects in graphene‐supported single-atom catalysts for hydrogen evolution reaction

The interaction between adjacent active sites is crucial to balance the efficiency and utilization of functional atoms in single-atom catalysts. Herein, the catalytic activity of hydrogen evolution reaction at different site (nitrogen coordinated transition metal centers embedded in graphene) distances was comprehensively investigated by density functional theory calculations. The results show that a proximity effect of reactivity and site spacing can be identified in the Co-series single-atom catalysts. Although the proximity effect is more linearly responded with the site spacing along x direction, an optimal distance of ∼0.8 and ∼2.8 nm are found for Co and Rh, Ir atoms, respectively. An in-depth analysis of the electronic property reveals that the proximity effect is caused by the distinct net charge of the active site, which is affected by the $dz2$ position relative to E_F. Subsequently, an excess electron nodal channel in x direction was found to serve as a communication pathway between the active sites. Through the finding in this work, an optimal Fe-N2C2 structure was deliberately designed and has shown prominent proximity effect as Co-series do. The results reported in this work provide a simple and effective tuning method for the reactivity of a single-atom catalyst.