Abstract
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•Microwave assisted sol gel method produces selective CO2 methanation Ni catalysts.•The incorporation of Sm3+ and Pr3+ into the CeO2 lattice generates basic positions.•Sm3+ and Pr3+ oxygen vacancies suppress the agglomeration of Ni sites.•Presence of Mg2+ increases basicity and prevents Ni sintering during reaction.•Ni on Pr-Ce highly active, selective and stable for CO2 methanation reaction.
The present work reports on the investigation of the catalytic performance for the methanation of CO2 over Ni catalysts based on CeO2, and for the first time, of Ni catalysts supported on binary CeO2-based oxides, namely, Sm2O3-CeO2, Pr2O3-CeO2 and MgO-CeO2. The supports were obtained using the microwave assisted sol-gel method under reflux, while the catalysts were prepared by the wet impregnation method. For the investigation of the morphological, textural, structural and other intrinsic properties of the catalytic materials a variety of characterization techniques were used, i.e., Raman spectroscopy, XRD, N2 physisorption-desorption, CO2-TPD, H2-TPR, H2-TPD, XPS and TEM. Carbon deposition and sintering were investigated using TEM. It was shown that the addition of Sm3+ or Pr3+, incorporated into the lattice of CeO2, generated oxygen vacancies, but the Ni/Pr-Ce catalyst was found to possess more surface oxygen vacancies (e.g. Ce4+-Ov-Pr3+ entities). Moreover, modification of CeO2 using Sm3+ or Pr3+ restricted the agglomeration of nickel active sites and led to the genesis of Lewis basic positions. These characteristics improved the hydrogenation reaction at lower temperature. On the other hand, the addition of Mg2+ resulted at strong metal support interactions reinforcing the resistance of the Ni/Mg-Ce catalyst against sintering. Furthermore, the addition of Sm3+, Pr3+ and Mg2+ cations increased the overall basicity and the moderate adsorption sites and led to the formation of smaller Ni nano particles; these physico-chemical properties enhanced the CO2 methanation reaction. Finally, the activity experiments (WGHSV = 25,000 mL g−1 h−1, H2/CO2 = 4:1, T =350 °C) showed that at lower reaction temperature the Ni/Pr-Ce had the highest catalytic performance in terms of CO2 conversion (54.5%) and CH4 yield (54.5%) and selectivity (100%). The TOF values were found to follow the order Ni/Pr-Ce >> Ni/Mg-Ce > Ni/Sm-Ce > Ni/Ce.