Highly Dispersed Ni Catalyst on Metal–Organic Framework-Derived Porous Hydrous Zirconia for CO2 Methanation

We report the preparation of porous hydrous zirconia by treatment of zirconium-based metal–organic framework (MOF) UiO-66 with a strong base. Microporosity of the original MOF was partially retained in the resultant porous hydrous zirconia. Ni II centers were then adsorbed onto the OH-rich hydrous zirconia and in situ converted to highly dispersed Ni 0 for CO 2 hydrogenation to CH 4 . The activated catalyst after an induction period showed a turnover frequency of 345 h –1 or a space–time yield of 5851 mmol·g Ni –1 ·h –1 with a CH 4 selectivity of over 99%. The catalyst was tested for 100 h on stream, showing only a 4% decrease in activity, and was found to convert atmospheric CO 2 to CH 4 via CO 2 collection through Na 2 CO 3 /NaHCO 3 cycling. Thermal decomposition of NaHCO 3 released CO 2 for hydrogenation to CH 4, and the resultant Na 2 CO 3 absorbed CO 2 from air to form NaHCO 3 . This work highlights the opportunity in using MOFs as precursors to prepare highly porous metal oxide/hydroxide supports for solid–gas phase catalysis.