Understanding the Adiabatic Evolution of Surface States in Tetradymite Topological Insulators under Electrochemical Conditions

Nontrivial surface states in topological materials have emerged as exciting targets for surface chemistry research. In particular, topological insulators have been used as electrodes in electrocatalytic reactions. Herein, we investigate the robustness of the topological surface states and band topology under electrochemical conditions, specifically in the presence of an electric double layer. First-principles band structure calculations are performed on the electrified (111) surfaces of Bi2Te3, Bi2Se3, and Sb2Te3 using an implicit electrolyte model. Our results demonstrate the adiabatic evolution of the surface states upon surface charging. Under oxidizing potentials, the surface states are shifted upward in energy, preserving the Dirac point on the surface and the band inversion in the bulk. Conversely, under reduced potentials, hybridization is observed between the surface and bulk states, suggesting a likely breakdown of topological protection. The position of the Fermi level, which dictates the working states in catalytic reactions, should ideally be confined within the bulk bandgap. This requirement defines a potential window for the effective application of topological electrocatalysis.