Simultaneously quantitative and qualitative regulation of active sites of Ni-phyllosilicate for enhanced CO2 hydrogenation to methane

Abstract

To address the problems of low metal utilization rate and poor low-temperature activity of the nickel phyllosilicate catalysts for CO2 methanation, this work prepared ultrathin defect-rich Ni-phyllosilicate through ball milling method in the presence of H2O2 modifier, which simultaneously created active sites with more quantity and higher quality. The instantaneous temperature and high pressure derived from the collision and friction of grinding balls provided driving force for the Ni-phyllosilicate synthesis, and the shear force destroyed the interlayer forces to construct the ultrathin layers. H2O2 molecule could insert the layers and dissociate to O2 bubbles, whose cavitation effect created holes and defects in the nickel phyllosilicate nanosheets and SiO2 spheres. H2O2 amount was crucial for the defect construction and the optimum Ni-AA-1H catalyst possessed the ultrathin nanosheet of 0.68 nm and high Ni dispersion of 15.6 %, whose TOFCO2 reached 3.76 × 10−2 s−1 at 160 °C. The in-situ DRIFTS results confirmed the enhanced low-temperature activity and the HCOO− reaction pathway over Ni-AA-1H for CO2 methanation. Nickel precursor effect was also investigated, and nickel acetylacetonate was determined as the optimal one compared with nickel acetate and nickel chloride, owing to the high steric effect of CH3COCHCOCH3− group and strong basicity environment during ball milling process.