Ordered clustering of single atomic Te vacancies in atomically thin PtTe2 promotes hydrogen evolution catalysis.

Exposing and stabilizing undercoordinated platinum (Pt) sites and therefore optimizing their adsorption to reactive intermediates offers a desirable strategy to develop highly efficient Pt-based electrocatalysts. However, preparation of atomically controllable Pt-based model catalysts to understand the correlation between electronic structure, adsorption energy, and catalytic properties of atomic Pt sites is still challenging. Herein we report the atomically thin two-dimensional PtTe₂ nanosheets with well-dispersed single atomic Te vacancies (Te-SAVs) and atomically well-defined undercoordinated Pt sites as a model electrocatalyst. A controlled thermal treatment drives the migration of the Te-SAVs to form thermodynamically stabilized, ordered Te-SAV clusters, which decreases both the density of states of undercoordinated Pt sites around the Fermi level and the interacting orbital volume of Pt sites. As a result, the binding strength of atomically defined Pt active sites to H intermediates is effectively reduced, which renders PtTe₂ nanosheets highly active and stable in hydrogen evolution reaction. Precisely regulating Pt catalytic sites is important and challenging. Herein the authors engineer the clustering of single atomic Te vacancies in atomically thin PtTe₂ to optimize the electronic structure, adsorption energy, and catalytic performance of atomically defined Pt sites. [ABSTRACT FROM AUTHOR]