@article{PrimusMenskiYesteetal.2015, author = {Primus, Philipp-Alexander and Menski, Antonia and Yeste, Maria Pilar and Cauqui, Miguel Angel and Kumke, Michael Uwe}, title = {Fluorescence Line-Narrowing Spectroscopy as a Tool to Monitor Phase Transitions and Phase Separation in Efficient Nanocrystalline CexZr1-xO2:Eu3+ Catalyst Materials}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {119}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {19}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.5b01271}, pages = {10682 -- 10692}, year = {2015}, abstract = {Despite the wide range of industrial applications for ceria-zirconia mixed oxides (CexZr1-xO2), the complex correlation between their atomic structure and catalytic performance is still under debate. Catalytically interesting CexZr1-xO2 nanomaterials can form homogeneous solid solutions and, depending on the composition, show phase separation under the formation of small domains. The characterization of homogeneity and atomic structure of these materials remains a major challenge. High-resolution emission spectroscopy recorded under cryogenic conditions using Eu3+ as a structural probe in doped CeZrO2 nanoparticles offers an effective way to identify the different atomic environments of the Eu3+ dopants and, subsequently, to monitor structural parameters of the ceria-zirconia mixed oxides. It is found that, in stoichiometric CeZrO2:Eu3+, phase separation occurs at elevated temperatures beginning with the gradual formation of (pseudo)cubic crystallites in the amorphous materials at 500 degrees C and a sudden phase separation into tetragonal, zirconia-rich and cubic, ceria-rich domains over 900 degrees C. The presented technique allows us to easily monitor subtle changes even in amorphous, high surface area samples, yielding structural information not accessible by conventional techniques such as X-ray diffraction (XRD) and Raman. Moreover, in reference experiments investigating the reducibility of largely unordered Ce0.2Zr0.8O2:Eu3+, the main reduction peak in temperature-programmed reduction measurements appeared at exceptionally low temperatures below 200 degrees C, thus suggesting the outstanding potential of this oxide to activate catalytic oxidation reactions. This effect was found to be dependent on the amount of Eu3+ dopant introduced into the CeZrO2 matrix as well as to be connected to the atomic structure of the catalyst material.}, language = {en} } @article{YestePrimusAlcantaraetal.2020, author = {Yeste, Maria Pilar and Primus, Philipp-Alexander and Alcantara, Rodrigo and Cauqui, Miguel Angel and Calvino, Juan Jose and Pintado, Jos{\´e} Mar{\´i}a and Blanco, Ginesa}, title = {Surface characterization of two Ce0.62Zr0.38O2 mixed oxides with different reducibility}, series = {Applied surface science : a journal devoted to applied physics and chemistry of surfaces and interfaces}, volume = {503}, journal = {Applied surface science : a journal devoted to applied physics and chemistry of surfaces and interfaces}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0169-4332}, doi = {10.1016/j.apsusc.2019.144255}, pages = {9}, year = {2020}, abstract = {This paper presents a study of the surface properties of two Ce/Zr mixed oxides with different reducibility, obtained by applying distinct thermal ageing treatments to an oxide with the composition Ce0.62Zr0.38O2. The surface composition was investigated by XPS. Chemical reactivity of the surface was studied by adsorption of the probe molecules CO2, D-2 and methanol. Nanostructural characterization was carried out by XRD, Raman and high-resolution Eu3+ spectroscopy (FLNS). The characterization showed only slight variations in surface composition and bulk Ce-Zr distribution, but hardy differences concerning the type and strength of acidic surface centres, as well as strong differences in the ability to dissociate hydrogen. Structural variations between both samples were identified by comparing the optical spectra of Eu3+ in surface doped samples.}, language = {en} }