Sophie Carenco

The use of ceria as catalyst in hydrogenation reactions is a recent trend, as they were uncovered to be active on a number of substrates, including alkynes, alkenes, and enones. While some studies focused on the use of well‐defined shapes, others emphasized the interest of defective structures. Overall, the meeting point of these studies is the need to characterize the surface reactivity vs . H 2 , by considering a number of interesting textures (films, nanopowders with various grain size or porosity), using monitoring techniques that preserve the original features of the materials. A key question is in particular to assess the possibility to form surface hydride through homolytic H 2 splitting at cerium sites rather than at the oxygen one, a route recently highlighted as plausible. To address this question on small crystallites of CeO 2 , we designed a low‐temperature synthetic route for nanorods with an average grain size of 10 nm. Then, we employed near‐ambient‐pressure X‐ray photoelectron spectroscopy as an operando tool to monitor the cerium surface oxidation state during the initial annealing of the nanopowders, followed by exposure to a moderate pressure of H 2 (0.52 mbar). We demonstrate that H 2 homolytic splitting at cerium sites is the main activation process on this surface at 100 °C, leading to the oxidation of ca . 30 % of the surface cerium atoms from Ce 3+ to Ce 4+ . The surface hydride species were however not stable at 250 °C, H 2 was released, and cerium reduced back to Ce 3+ . A similar mechanism was observed on a defective ceria material obtained by calcination of CeO(OH) 2 , with comparable intensities. Overall, we report here CeO 2 nanorods, exposing predominantly {100} and {110} facets, as showing an interesting surface reactivity for potential application in hydrogenation reactions, and we expose a straight operando methodology to delineate suitable temperatures to be used.