Metastable LaOClx Phase Stabilization as an Effective Strategy for Controllable Chlorination of Ethane into 1,2-Dichloroethane

LaOCl-mediated ethane chlorination into 1,2-dichloroethane offers a promising pathway for low-temperature, large-scale ethane upgrading. However, under Cl₂-rich conditions, LaOCl undergoes detrimental chlorination into lanthanum chloride (LaCl₃), accompanied by extensive surface hydroxylation. Such severe structural evolution limits the practical application of La-based catalysts under industrially relevant conditions. In this study, an alumina-stabilized La catalyst was prepared via a coprecipitation method. We demonstrated that strong La-O-Al interactions effectively resist structural degradation of La species under reaction conditions, enabling the modified catalyst to maintain exceptional stability under high Cl₂ concentrations. At a C₂H₆/Cl₂ ratio of 4:9, the optimized catalyst achieves an ethane conversion of 61%, with 1,2-dichloroethane selectivity sustained above 74% for 12 h without noticeable deactivation. In contrast, the bulk LaOCl counterpart suffers from rapid over-chlorination, shifting product dominance to trichloroethane within 10 h. Advanced spectroscopy characterization reveals that selectivity loss in LaOCl originates from phase collapse into LaCl₃, whereas Al₂O₃ stabilization preserves the metastable LaOCl<i>_x</i> phase in a highly dispersed state, ensuring selective C-Cl bond formation. These results highlight the critical role of stabilizing metastable oxychloride phases through robust metal oxide interactions, establishing a design framework for rare-earth catalysts in high-concentration chlorine environments.