Integrated Calendar

The 100-year old Sabatier reaction, i.e. catalytic CO2 hydrogenation, is now seeing a renaissance due to its application in Power-to-Methane processes for electric grid stability and potential CO2 emission mitigation [1]. To date however, the fundamentals of this important catalytic reaction are still a matter of debate. This is partly due to the structure sensitive nature of CO2 hydrogenation: not all surface atoms of the active phase nanoparticles have the same specific activity. Recently, we have showed how the mechanism of catalytic CO2 methanation depends on Ni nanoparticle size using a unique set of well-defined silica-supported Ni nanoclusters (in the range 1-7 nm) and advanced characterization methods (i.e., operando FT-IR, and operando quick X-ray absorption spectroscopy) [2]. By utilizing fundamental theoretical concepts proving why CO2 is structure sensitive, and how CO2 is activated mechanistically and linking spectroscopic descriptors to these fundamental findings we ultimately leverage our understanding with a toolbox of structure sensitivity, and a library of reducible and non-reducible supports (SiO2, Al2O3, CeO2, ZrO2 and TiO2), tuning the selectivity and activity of methanation over Ni [3]. For example, we show that CO2 hydrogenation over Ni can and does form propane. This work contributes to our ability to produce “ideal” catalysts by improving the understanding of the catalytic sites and reaction pathways responsible for higher activity and even C-C coupling. This toolbox is thus not only useful for the highly active and selective production of methane within the Power-to-Methane concept, but also provides new insights for CO2 activation towards value-added chemicals thereby reducing the deleterious effects of this environmentally harmful molecule.