Strained Ni-WC nano-islands by localized accelerated carbonization emulate noble-metal RWGS activity

Among CO2 emission mitigation strategies, the reverse water-gas shift (RWGS) reaction represents a promising route for selective CO2-to-CO conversion, enabling subsequent valorization. However, designing selective and stable non-noble metal catalysts for RWGS remains a persistent challenge. In this study, we report a Ni site-induced localized accelerated carbonization process to produce noble metal-like active Ni-WC nano-islands for high-performance RWGS catalysis. Benefiting from the unique structures, the Ni0.02WC/WO2-NIs catalyst exhibits exceptionally high RWGS activities, with a CO production rate of 2340 molCO·molWC-1·h-1 and over 97% CO selectivity. Even after 100 hours of continuous testing at 500 °C, the activity loss of Ni0.02WC/WO2-NIs was only 0.5%. Unlike the conventional catalyst structure in the RWGS reaction, we demonstrate that the nano-island WC structure with stretch strain ensures the space limitation of electron-rich Ni sites for CO desorption and H2 dissociation. Integrated in-situ DRIFTS, Raman spectroscopy, and DFT calculations reveal that dual-functional WC/WOx interfaces enhance catalyst activity through bidentate carbonate formation and intensified hydrogen spillover. We suggest that the design of new, efficient, and selective Ni-based noble-metal-like catalysts with nano-island structure through interface synergistic effects offers a promising path to engineering superior RWGS catalysts for CO2 reduction. Converting carbon dioxide into useful chemicals needs catalysts that are fast, selective and long-lasting. This study creates nickel–tungsten carbide nano-islands that efficiently make carbon monoxide and stay stable for 100 hours.