Organic acid-assisted preparation of highly dispersed Co/ZrO2 catalysts with superior activity for CO2 methanation

Various organic acids were investigated for preparing the highly dispersed cobalt catalysts on zirconia support, Co/ZrO 2 , by an acid-assisted incipient wetness impregnation. The organic acid-assisted preparation results in highly dispersed Co/ZrO 2 catalysts which demonstrate superior catalytic activity with only 2 wt.% Co loading for CO 2 methanation. Among the acids, the carboxylic acids with bigger molecular weight, more carboxyl groups and hydroxyl groups are more effective. Furthermore, the amino acids can also change the charge property of ZrO 2 surface through controlling the solution pH and increase the metal dispersion through strong electrostatic adsorption. It is worth mentioning that, among the numerous organic acids, citric acid-assisted preparation gives Co/ZrO 2 catalyst with superior catalytic activity and increased the CO 2 conversion from 38% to 85% with highest turnover frequency. The linear relationship between metal dispersion and TOF with the molar ratio of acid to cobalt n CA/Co ranging from 0 to 2 demonstrates the importance of well dispersed metal particles in the enhanced activity. However, when the n CA/Co value exceeds 2 and the metal particle size further decreases, but no further enhancement is observed and the CO 2 conversion even slightly decreased at the n CA/Co value of 5. The organic acids-assisted strategy can lead to increased metal dispersion and higher TOF for Co/ZrO 2 catalysts; the appropriate metal dispersion corresponds to the suitable Co-ZrO 2 interaction with oxygen vacancy which leads to more catalytically active sites for CO 2 adsorption and catalytic hydrogenation. The organic acid-assisted strategy provides a new design approach for highly dispersed and active catalysts.