Understanding structure-activity relationships in highly active La promoted Ni catalysts for CO₂ methanation

Ni-based catalysts are selective in the hydrogenation of CO_{2} to CH_{4} but their activity and stability need improvement. Herein, we propose a hydrotalcite-derived high loaded Ni-Al_{2}O_{3} catalyst promoted by La. The effect of La on the catalyst properties is investigated and compared with that of Y and Ce. The NiO_{x} rystallite size and basic properties (rather than the nickel reducibility) as well as the catalytic activity depend on the rare-earth element. The La-catalyst achieves a more relevant activity enhancement at low temperature and high space velocity (480 L g^{-1} h^{-1}, CO_{2}/H_{2}/N_{2} = 1/4/1 v/v), high CH_{4} productivity (101 L_{CH4} gNi^{-1} h^{-1}) and stability, even under undiluted feeds. In situ DRIFTS and the characterization of spent catalysts confirm that this enhanced performance is related to the combination of dissociative and associative CO_{2} activation on more reduced, highly dispersed and stable Ni nanoparticles and basic sites in the La_{2}O_{3}-Al_{2}O_{3} matrix, respectively