Abstract
Doped ceria-based metal oxides are widely used as supports and stand-alone catalysts in reactions where CO2 is involved. Thus, it is important to understand how to tailor their CO(2 )adsorption behavior. In this work, steering the CO2 activation behavior of Ce-La- Cu-O ternary oxide surfaces through the combined effect of chemical and mechanical strain was thoroughly examined using both experimental and ab initio modeling approaches. Doping with aliovalent metal cations (La3+ or La3+/Cu2+) and post-synthetic ball milling were considered as the origin of the chemical and mechanical strain of CeO2, respectively. Experimentally, microwave-assisted reflux-prepared Ce-La-Cu-O ternary oxides were imposed into mechanical forces to tune the structure, redox ability, defects, and CO2 surface adsorption properties; the latter were used as key descriptors. The purpose was to decouple the combined effect of the chemical strain (epsilon C) and mechanical strain (epsilon M) on the modification of the Ce-La-Cu-O surface reactivity toward CO2 activation. During the ab initio calculations, the stability (energy of formation, EOvf) of different configurations of oxygen vacant sites (Ov) was assessed under biaxial tensile strain (epsilon > 0) and compressive strain (epsilon < 0), whereas the CO2-philicity of the surface was assessed at different levels of the imposed mechanical strain. The EOv f values were found to decrease with increasing tensile strain. The Ce-La-Cu-O(111) surface exhibited the lowest EOv f values for the single subsurface sites, implying that Ov may occur spontaneously upon Cu addition. The mobility of the surface and bulk oxygen anions in the lattice contributing to the Ov population was measured using 16O/18O transient isothermal isotopic exchange experiments; the maximum in the dynamic rate of 16O18O formation, Rmax(16O18O), was 13.1 and 8.5 mu mol g-1 s-1 for pristine (chemically strained) and dry ball-milled (chemically and mechanically strained) oxides, respectively. The CO2 activation pathway (redox vs associative) was experimentally probed using in situ diffuse reflectance infrared Fourier transform spectroscopy. It was demonstrated that the mechanical strain increased up to 6 times the CO2 adsorption sites, though reducing their thermal stability. This result supports the mechanical actuation of the "carbonate "-bound species; the latter was in agreement with the density functional theory (DFT)-calculated C-O bond lengths and O-C-O angles. Ab initio studies shed light on the CO2 adsorption energy (Eads), suggesting a covalent bonding which is enhanced in the presence of doping and under tensile strain. Bader charge analysis probed the adsorbate/surface charge distribution and illustrated that CO2 interacts with the dual sites (acidic and basic ones) on the surface, leading to the formation of bidentate carbonate species. Density of states (DOS) studies revealed a significant Eg drop in the presence of double Ov and compressive strain, a finding with design implications in covalent type of interactions. To bridge this study with industrially important catalytic applications, Ni-supported catalysts were prepared using pristine and ball-milled oxides and evaluated for the dry reforming of methane reaction. Ball milling was found to induce modification of the metal-support interface and Ni catalyst reducibility, thus leading to an increase in the CH4 and CO2 conversions.
This study opens new possibilities to manipulate the CO2 activation for a portfolio of heterogeneous reactions.