Structure and Chemical Reactivity of Y-Stabilized ZrO2 Surfaces: Importance for the Water-Gas Shift Reaction.

The surface structure and chemical properties of Y-stabilized zirconia (YSZ) have been subjects of intense debate over the past three decades. However, a thorough understanding of chemical processes occurring at YSZ powders faces significant challenges due to the absence of reliable reference data acquired for well-controlled model systems. Here, we present results from polarization-resolved infrared reflection absorption spectroscopy (IRRAS) obtained for differently oriented, Y-doped ZrO2 single-crystal surfaces after exposure to CO and D2O. The IRRAS data reveal that the polar YSZ(100) surface undergoes reconstruction, characterized by an unusual, red-shifted CO band at 2132 cm-1. Density functional theory calculations allowed to relate this unexpected observation to under-coordinated Zr4+ cations in the vicinity of doping-induced O vacancies. This reconstruction leads to a strongly increased chemical reactivity and water spontaneously dissociates on YSZ(100). The latter, which is an important requirement for catalysing the water-gas-shift (WGS) reaction, is absent for YSZ(111), where only associative adsorption was observed. Together with a novel analysis Scheme these reference data allowed for an operando characterisation of YSZ powders using DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy). These findings facilitate rational design and tuning of YSZ-based powder materials for catalytic applications, in particular CO oxidation and the WGS reaction.

Polarization-dependent effects in vibrational absorption spectra of 2D finite-size adsorbate islands on dielectric substrates.

In the last few years, infrared reflection-absorption spectroscopy (IRRAS) has become a standard technique to study vibrational excitations of molecules. These investigations are strongly motivated by potential applications in monitoring chemical processes. For a better understanding of the adsorption mechanism of molecules on dielectrics, the polarization-dependence of an interaction of infrared light with adsorbates on dielectric surfaces is commonly used. Thus, the peak positions in absorption spectra could be different for s- and p-polarized light. This shift between the peak positions depends on both the molecule itself and the dielectric substrate. While the origin of this shift is well understood for infinite two-dimensional adsorbate layers, finite-size samples, which consist of 2D islands of a small number of molecules, have never been considered. Here, we present a study on polarization-dependent finite-size effects in the optical response of such islands on dielectric substrates. The study uses a multi-scale modeling approach that connects quantum chemistry calculations with Maxwell scattering simulations. We distinguish the optical response of a single molecule, a finite number of molecules, and a two-dimensional adsorbate layer. We analyze CO and CO2 molecules deposited on CeO2 and Al2O3 substrates. The evolution of the shift between the polarization-dependent absorbance peaks is first studied for a single molecule, which does not exhibit any shifting at all, and for finite molecular islands, where it increases with increasing island size, as well as for an infinite two-dimensional adsorbate layer. In the latter case, the agreement between the obtained results and the experimental IRRAS data and more traditional three/four-layer model theoretical studies supports the predictive power of the multi-scale approach.

CuO decorated vacancy-rich CeO2 nanopencils for highly efficient catalytic NO reduction by CO at low temperature.

With the rapid development of transportation and vehicles, the elimination of NOx and CO has highly attracted public attention. In this work, vacancy-rich CeO2 nanopencil supported CuO catalysts (CuO/CeO2-NPC) were successfully prepared for NO reduction by CO. Importantly, CeO2 with nanopencil-like shape (CeO2-NPC) have been synthesis by solvothermal method for the first time. The physicochemical properties of all samples were studied in detail by combining the means of X-ray diffraction (XRD), Raman spectroscopy, electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), H2-temperature-programmed reduction (H2-TPR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), N2 physisorption (Brunauer-Emmett-Teller), and NO and CO temperature-programmed desorption (NO-TPD and CO-TPD) techniques. Compared with CeO2 nanorods and nanoparticles supported CuO catalysts (CuO/CeO2-NR and CuO/CeO2-NP), the CuO/CeO2-NPC catalysts showed the highest catalytic activity, affording more than 90% NO conversion at 69 °C as well as excellent H2O tolerance at 150 °C, which is superior to catalysts previously reported. Characterization results indicated that the synergistic effect between the well-dispersed CuO and the CeO2 nanopencil support enables a favorable electron transfer between these components and enhances the density of surface oxygen vacancies and Cu+ species, which consequently accelerating the redox cycle. The results indicated that the morphology control of CeO2 support could be an efficient way to evidently enhance the catalytic performance for NO + CO reaction.