Engineering the Interfacial Microenvironment to Boost Ethane Dehydrogenation on Ga2O3-Pt Catalysts via Metal Doping Modulation

Abstract Inverse Ga2O3-Pt catalysts have exhibited better catalytic performance in propane dehydrogenation due to their tunable interfacial electronic properties. This study explores the potential of inverse Ga2O3-Pt catalysts and their single-atom-doped variant (Ga2O3-M/Pt) systems for ethane dehydrogenation using DFT calculations and kinetic Monte Carlo simulations. The results show that Ga2O3-Pt exhibits low ethylene formation activity (0.83 × 102 s–1) and selectivity (84.28%) due to its interfacial sites that weakly and uniformly adsorb hydrogen, impeding the differential regulation of key CH2CH3* intermediate adsorption behavior. Single-atom doping (M = Ti, Co, etc.) creates a Pt–M–O interfacial microenvironment, modulating the electronic structure of interfacial oxygen sites, which enables the effective differential regulation of CH2CH3* intermediate adsorption, thereby enhancing catalytic performance. Among the 14 screened dopants, the Ga2O3-Ti/Pt catalyst emerged as optimal, showing high activity (2.86 × 103 s–1) and selectivity (97.13%) for ethylene formation at the optimal 873.15 K and CH3CH3(g) partial pressure of 0.20 bar. This advantage stems from its moderate p-band center and Ti–O charge transfer, which yield an ideal hydrogen adsorption energy for CH2CH3* regulation. The H* adsorption energy can serve as a descriptor for qualitatively evaluating the activity of CH2CH2(g) formation for a series of Ga2O3-M/Pt catalysts. This work proposes the strategy of “interfacial microenvironment reconstruction to regulate the electronic structure” as a design method for developing high-efficiency alkane dehydrogenation catalysts.