Addressing the Effectiveness and Molecular Mechanism of the Catalytic CO₂ Hydration in Aqueous Solutions by Nickel Nanoparticles

Hydration of carbon dioxide in water solution is the rate limiting step for the CO₂ mineralization process, a process which is at the base of many carbon capture and utilization (CCU) technologies aiming to convert carbon dioxide to added-value products and mitigate climate change. Here, we present a combined experimental and computational study to clarify the effectiveness and molecular mechanism by which nickel nanoparticles, NiNPs, may enhance CO₂ hydration in aqueous solutions. Contrary to previous literature, our kinetic experiments recording changes of pHs, conductivity, and dissolved carbon dioxide in solution reveal a minimal effect of the NiNPs in catalyzing CO₂ hydration. Our atomistic simulations indicate that the Ni metal surface can coordinate only a limited number of water molecules, leaving uncoordinated metal sites for the binding of carbon dioxide or other cations in solution. This deactivates the catalyst and limits the continuous re-formation of a hydroxyl-decorated surface, which was a key chemical step in the previously suggested Ni-catalyzed hydration mechanism of carbon dioxide in aqueous solutions. At our experimental conditions, which expand the investigation of NiNP applicability toward a wider range of scenarios for CCU, NiNPs show a limited catalytic effect on the rate of CO₂ hydration. Our study also highlights the importance of the solvation regime: while Ni surfaces may accelerate carbon dioxide hydration in water restricted environments, it may not be the case in fully hydrated conditions.