Unlocking high stability and selectivity in reverse water–gas shift over a synergistic MoCO catalyst

Abstract The reverse water‐gas shift (RWGS) reaction is vital for CO 2 utilization and carbon cycling, yet catalyst stability and CO selectivity remain major challenges due to its endothermic nature and competing methanation. Here, a synergistic α‐Mo 2 C:MoO 2 (MoCO) catalyst with carbide–oxide interactions was in situ constructed via a one‐step temperature‐programmed calcination, achieving high dispersion and synergy. MoCO‐3.5 (Mo/C = 1:3.5) reached near‐equilibrium CO 2 conversions (50.56% at 500°C, 74.71% at 800°C) and >99.6% CO selectivity under H 2 /CO 2 = 3:1 at industrial space velocity (8400 mL·g cat −1 ·h −1 ), maintaining stability for 120 h without coking. Mechanistic studies revealed a hydrogen‐assisted formate pathway, and weak CO adsorption enabled rapid desorption, effectively suppressing methanation. This synergy‐driven structural regulation strategy offers a promising strategy for designing highly stable and CO‐selective non‐noble metal RWGS catalysts.