@misc{PozarowskaPleinesPrietoetal., author = {Pozarowska, Emilia and Pleines, Linus and Prieto, Mauricio J. and Tănase, Liviu Christian and Souza Caldas, Lucas de and Tiwari, Aarti and Schmidt, Thomas and Falta, Jens and Morales, Carlos and Flege, Jan Ingo}, title = {The relation between structure sensitivity and doping of ceria(111) vs. ceria(100)}, series = {Verhandlungen der DPG}, journal = {Verhandlungen der DPG}, publisher = {Deutsche Physikalische Gesellschaft}, address = {Bad Honnef}, issn = {0420-0195}, abstract = {CeOx-Cu inverse catalysts have been shown to convert CO2 into valuable chemicals through catalytic hydrogenation. The catalytic activity may further be enhanced by alloying ceria with trivalent, catalytically active metals, such as Sm, promoting the formation of Ce3+ active sites. In this work, the structural and chemical properties of (111)- and (100)- oriented CeOx islands alloyed with samarium were explored by low-energy electron microscopy and X-ray photoemission electron microscopy. After Sm deposition on the as-grown CeOx islands, the near-surface region of (100)-oriented CeOx is reduced after exposure to H2 at 470 ∘C, whereas the deeper layers as well as the whole (111)-oriented islands retain the Ce4+ state. Subsequent reoxidation with O2 leads to the complete Ce4+ state recovery, suggesting the healing of oxygen vacancies. Additional annealing at 470 ∘C induces samarium diffusion into the ceria matrix. Yet, subsequent exposure to H2 reduces neither the (111)- nor the (100)-oriented CeSmOx islands, suggesting a quite unexpected stability of this system.}, language = {en} } @misc{PożarowskaPleinesEwertetal., author = {Pożarowska, Emilia and Pleines, Linus and Ewert, Moritz and Prieto, Mauricio J. and Tănase, Liviu Christian and Souza Caldas, Lucas de and Tiwari, Aarti and Schmidt, Thomas and Falta, Jens and Krasovskii, Eugene and Morales, Carlos and Flege, Jan Ingo}, title = {Preparation and stability of the hexagonal phase of samarium oxide on Ru(0001)}, series = {Ultramicroscopy}, volume = {250}, journal = {Ultramicroscopy}, issn = {0304-3991}, doi = {10.1016/j.ultramic.2023.113755}, abstract = {We have used low-energy electron microscopy (LEEM), micro-illumination low-energy electron diffraction (µLEED) supported by ab initio calculations, and X-ray absorption spectroscopy (XAS) to investigate in-situ and in real-time the structural properties of Sm2O3 deposits grown on Ru(0001), a rare-earth metal oxide model catalyst. Our results show that samarium oxide grows in a hexagonal A-Sm2O3 phase on Ru(0001), exhibiting a (0001) oriented-top facet and (113) side facets. Upon annealing, a structural transition from the hexagonal to cubic phase occurs, in which the Sm cations exhibit the +3 oxidation state. The unexpected initial growth in the A-Sm2O3 hexagonal phase and its gradual transition to a mixture with cubic C-Sm2O3 showcases the complexity of the system and the critical role of the substrate in the stabilization of the hexagonal phase, which was previously reported only at high pressures and temperatures for bulk samaria. Besides, these results highlight the potential interactions that Sm could have with other catalytic compounds with respect to the here gathered insights on the preparation conditions and the specific compounds with which it interacts.}, language = {en} } @misc{TschammerBussPożarowskaetal., author = {Tschammer, Rudi and Buß, Lars and Pożarowska, Emilia and Morales, Carlos and Senanayake, Sanjaya D. and Prieto, Mauricio J. and Tănase, Liviu C. and de Souza Caldas, Lucas and Tiwari, Aarti and Schmidt, Thomas and Ni{\~n}o, Miguel A. and Foerster, Michael and Falta, Jens and Flege, Jan Ingo}, title = {High-temperature growth of CeOx on Au(111) and behavior under reducing and oxidizing conditions}, series = {The journal of physical chemistry C}, volume = {129}, journal = {The journal of physical chemistry C}, number = {7}, publisher = {American Chemical Society (ACS)}, address = {Washington, DC}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.4c08072}, pages = {3583 -- 3594}, abstract = {Inverse oxide-metal model catalysts can show superior activity and selectivity compared with the traditional supported metal-oxide architecture, commonly attributed to the synergistic overlayer-support interaction. We have investigated the growth and redox properties of ceria nanoislands grown on Au(111) between 700 and 890 °C, which yields the CeO2-Au(111) model catalyst system. We have observed a distinct correlation between deposition temperature, structural order, and oxide composition through low-energy electron microscopy, low-energy electron diffraction, intensity-voltage curves, and X-ray absorption spectroscopy. Improved structural order and thermal stability of the oxide have been achieved by increasing the oxygen chemical potential at the substrate surface using reactive oxygen (O/O2) instead of molecular O2 during growth. In situ characterization under reducing (H2) and oxidizing atmospheres (O2, CO2) indicates an irreversible loss of structural order and redox activity at high reduction temperatures, while moderate temperatures result in partial decomposition of the ceria nanoislands (Ce3+/Ce4+) to metallic cerium (Ce0). The weak interaction between Au(111) and CeOx would facilitate its reduction to the Ce0 metallic state, especially considering the comparatively strong interaction between Ce0 and Au0. Besides, the higher reactivity of atomic oxygen promotes a stronger interaction between the gold and oxide islands during the nucleation process, explaining the improved stability. Thus, we propose that by driving the nucleation and growth of the ceria/Au system in a highly oxidizing regime, novel chemical properties can be obtained.}, language = {en} } @misc{PożarowskaPleinesPrietoetal., author = {Pożarowska, Emilia and Pleines, Linus and Prieto, Mauricio J. and Tănase, Liviu C. and de Souza Caldas, Lucas and Tiwari, Aarti and Schmidt, Thomas and Falta, Jens and Morales, Carlos and Flege, Jan Ingo}, title = {The relationship between Sm alloying and structure sensitivity of ceria(111)- and (100)-oriented nanoislands on Cu(111)}, series = {Physical chemistry, chemical physics}, volume = {27}, journal = {Physical chemistry, chemical physics}, number = {29}, publisher = {Royal Society of Chemistry (RSC)}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/D5CP01171J}, pages = {15691 -- 15703}, abstract = {We have investigated the complex dynamics of samarium deposition on ceria islands of different orientations, namely (111) and (100), grown side by side on a Cu(111) single-crystal substrate, followed by post-oxidation and annealing under ultra-high vacuum conditions. Only the (100)-oriented ceria islands undergo substantial initial reduction upon samarium deposition at 740 K via a pathway similar to the strong Ce-ceria interfacial interaction, while the (111)-oriented islands remain in the Ce4+ oxidation state. This remarkable structure sensitivity is explained by the different energies required for oxygen vacancy formation for both oxide orientations. Subsequent mild re-oxidation with O2 results in the complete recovery of the Ce4+ oxidation state in the (100)-oriented islands, indicating the complete healing of oxygen vacancies. In contrast, extended annealing at moderate temperatures likely induces persistent samarium incorporation into the cerium oxide matrix. Our results provide new insights into the complex structure-activity relationships in mixed rare-earth metal oxide systems and have promising implications for optimizing catalytic reactions over such compounds in reducing environments.}, language = {en} }