Fabrication of surface oxygen vacancies on NiMnAl-LDO catalyst by high-shear mixer-assisted preparation for low-temperature CO2 methanation

Low-temperature performance of non-noble metal Ni-based catalysts in CO2 methanation still faces great challenges. A series of NiMnAl-LDO (layered double oxides) catalysts with different processing conditions were prepared using the high-shear mixer-assisted method. The FH-C (80 °C) catalyst exhibited high activity in low-temperature CO2 methanation, and CO2 conversion and CH4 selectivity reached 85% and 97% at 200 °C. Characterization results show that the strong shear force of the high-shear mixer can improve the dispersion of the catalyst and reduce the particle size of the catalyst. The high-shear mixer treatment increases the CO2 chemisorption and the number of strongly basic sites on the catalyst. The main reason for the low-temperature activity of the catalyst is that the high-shear mixer increases the number of oxygen vacancies in the catalyst. In situ infrared probes into the surface species and intermediate products of the catalyst, confirming that formate is an intermediate product of the CO2 methanation reaction. Density functional theory calculations demonstrated that increasing the content of oxygen vacancies is beneficial for increasing the CO2 adsorption capacity of the catalyst and reducing the reaction energy barrier of CO2 → COOH*.