Design of Pt-like M–V8C7 catalysts for efficient ethane dehydrogenation via integrated DFT calculations and ML-assisted theoretical phase diagram analysis

Pt-based catalysts are widely employed in ethane direct dehydrogenation (EDH) for their high activity, but their practical application is limited by high cost, susceptibility to coking and rapid deactivation. Transition metal carbide V 8 C 7 , known for its Pt-like electronic properties, offers a promising alternative. In this work, we combined DFT calculations and machine learning (ML)-assisted theoretical phase diagram analysis to systematically assess the stability of 27 single-atom doped M–V 8 C 7 structures and their EDH catalytic performance. While the V 8 C 7 (110) surface showed appreciable EDH activity, it suffered from low C 2 H 4 selectivity. Among the doped catalysts, 20 were identified as thermodynamically stable, particularly Rh-V 8 C 7 exhibited enhanced activity and high C 2 H 4 (g) selectivity. Electronic structure analysis identified Bader charge and d-band center as effective activity descriptors for the M–V 8 C 7 series. Notably, Rh-V 8 C 7 demonstrates Pt-like behavior in both catalytic function and electronic structure, highlighting its potential as an efficient and economical alternative to Pt-based catalysts for EDH.