On the Capabilities of Transition Metal Carbides for Carbon Capture and Utilization Technologies.

The search for cheap and active materials for the capture and activation of CO has led to many efforts aimed at developing new catalysts. In this context, earth-abundant transition metal carbides (TMCs) have emerged as promising candidates, garnering increased attention in recent decades due to their exceptional refractory properties and resistance to sintering, coking, and sulfur poisoning. In this work, we assess the use of Group 5 TMCs (VC, NbC, and TaC) as potential materials for carbon capture and sequestration/utilization technologies by combining experimental characterization techniques, first-principles-based multiscale modeling, vibrational analysis, and catalytic experiments. Our findings reveal that the stoichiometric phase of VC exhibits weak interactions with CO, displaying an inability to adsorb or dissociate it. However, VC often exhibits the presence of surface carbon vacancies, leading to significant activation of CO at room temperature and facilitating its catalytic hydrogenation. In contrast, stoichiometric NbC and TaC phases exhibit stronger interactions with CO, capable of adsorbing and even breaking of CO at low temperatures, particularly notable in the case of TaC. Nevertheless, NbC and TaC demonstrate poor catalytic performance for CO hydrogenation. This work suggests Group 5 TMCs as potential materials for CO abatement, emphasizes the importance of surface vacancies in enhancing catalytic activity and adsorption capability, and provides a reference for using the infrared spectra as a unique identifier to detect oxy-carbide phases or surface C vacancies within Group 5 TMCs.