Evolution from Monolayers to Two-Dimensional Heterostructures for Enhanced Hydrogen Evolution Reaction: A Theoretical Study.

Two-dimensional heterostructures have attracted considerable attention in electrocatalytic hydrogen evolution due to their pronounced interfacial effects, tunable electronic properties, and large specific surface areas. In this work, two representative oxygen-terminated transition metal carbides (MXenes) and three typical transition metal dichalcogenides (TMDs) were selected to construct six heterostructures. Using first-principles density functional theory (DFT) calculations, their binding energies, structural stability, electronic structures, and HER catalytic performance were systematically investigated. The results showed that all heterostructures possessed good thermodynamic stability and favorable electronic properties. In particular, SnS2/Ti2CO2, SnSe2/Ti2CO2, SnTe2/Ti2CO2, and SnTe2/Zr2CO2 exhibited near-optimal hydrogen adsorption Gibbs free energy, indicating excellent HER activity. Moreover, the variation in Gibbs free energy of hydrogen adsorption from isolated monolayers to heterostructures could be effectively correlated with the work function difference. The predicted trends provided a useful descriptor for catalytic performance. Overall, this study provides theoretical insights into the rational design of efficient, advanced HER catalysts and contributes to the advancement of sustainable energy conversion technologies. As this work is based solely on first-principles calculations, the predicted catalytic activity of the heterostructure should be regarded as a theoretical prediction and awaits experimental confirmation.