Photo- and Thermocatalytic CO2 Methanation: A Comparison of Ni/Al2O3 and Ni-Ce Hydrotalcite-Derived Materials under UV and Visible Light.

Abstract

Catalysts derived from Ni/Al/Mg/Ce hydrotalcite were prepared via a co-precipitation method, varying the Ce/Al atomic ratio. All of the catalytic systems thus prepared were tested for CO2 methanation under dark and photocatalytic conditions (visible and ultraviolet) under continuous flow with the light intensity set to 2.4 W cm-2. The substitution of Al by Ce formed a solid solution, generating oxygen vacancies and Ce3+/Ce4+ ions that helped shift the dissociation of CO2 towards the production of CH4, thus enhancing the activity of methanation, especially at lower temperatures (<523 K) and with visible light at temperatures where other catalysts were inactive. Additionally, for comparison purposes, Ni/Al2O3-based catalysts prepared via wetness impregnation were synthesized with different Ni loadings. Analytical techniques were used for the characterization of the systems. The best results in terms of activity were as follows: Hydrotalcite with Ce promoter > Hydrotalcite without Ce promoter > 25Ni/Al2O3 > 13Ni/Al2O3. Hydrotalcite, with a Ce/Al atomic ratio of 0.22 and a Ni content of 23 wt%, produced 7.74 mmol CH4 min-1·gcat at 473 K under visible light. Moreover, this catalyst exhibited stable photocatalytic activity during a 24 h reaction time with a CO2 conversion rate of 65% and CH4 selectivity of >98% at 523 K. This photocatalytic Sabatier enhancement achieved activity at lower temperatures than those reported in previous publications.