Chiara Gionco

Cerium-Doped Zirconium Dioxide, a Visible-Light-Sensitive Photoactive Material of Third Generation

The dispersion of small amounts of Ce(4+) ions in the bulk of ZrO2 leads to a photoactive material sensitive to visible light. This is shown by monitoring with EPR the formation and the reactivity of photogenerated (λ > 420 nm) charge carriers. The effect, as confirmed by DFT calculations, is due to the presence in the solid of empty 4f Ce states at the mid gap, which act as intermediate levels in a double excitation mechanism. This solid can be considered an example of a third-generation photoactive material.

Structural and spectroscopic characterization of CeO2–TiO2 mixed oxides

Mixed CeO2–TiO2 systems have been synthesized using the sol–gel technique in a symmetric range of nominal compositions (10, 50 and 90 mol% CeO2). The solid materials were characterised using a variety of diffractometric and spectroscopic techniques. The intimate contact between the two components during the synthesis leads to heterogeneous systems which are based on the presence, besides the two individual oxide phases, of a mixed phase of a cerium titanate (Ce2Ti2O7, pyrochlore structure) which contains Ce3+ ions that impart particular optical properties to the solid (a pronounced red shift with respect to the band gap transition of the two oxides). Ce3+ ions are present at the surface of the systems together with tetravalent Ce and Ti ions. The mixed solids can be reduced by annealing under vacuum and, upon reoxidation under mild conditions with O2, form superoxide species adsorbed on Ce4+ which have, as already reported for low loading CeO2–TiO2 systems, peculiar spectroscopic properties with respect to superoxide adsorbed on bare cerium dioxide.

Synthesis, Characterization, and Photocatalytic Tests of N-Doped Zinc Oxide

Fast and simple synthetic methods for the preparation of bare and N-doped zinc oxide, involving a stirring or microwave assisted process, are proposed. All samples were characterized by XRD analysis, BET, and DRS-UV-Vis spectroscopy. The photocatalytic activity of these nanostructured oxides was investigated using phenol and 2,4-dichlorophenol as model molecules under UV-A and visible light irradiation. N-doping in ZnO nanostructures provided a significant increase in phenol and 2,4-dichlorophenol degradation rate under Vis light, leading to a degradation rate higher than that obtained with bare ZnO. The release of chlorine as chloride ions from 2,4-dichlorophenol with N-doped ZnO was faster achieved as well and complete dechlorination was reached within 2 h of irradiation (N-doped ZnO) instead of 3 h (bare ZnO).

Insights Into the Sunlight-Driven Water Oxidation by Ce and Er-Doped ZrO2

In the present work, the activity of Ce and Er-doped ZrO2 nanopowders for sun-driven photocatalytic water oxidation has been investigated. ZrO2 powders with tunable amounts of tetragonal, monoclinic and cubic polymorphs have been synthesized by introducing Ce and Er (from 0.5 to 10 mol % on an oxide basis) through hydrothermal method. The aim of this work is to investigate the role of rare earth (RE) ions rich of electrons (Er3+) and with entirely empty levels (Ce4+) in the ZrO2 matrix for the sun-driven photocatalytic water oxidation reaction. The samples have been characterized by means of UV-Vis spectroscopy, X-Ray diffraction (XRD), N2 adsorption, X-ray photoelectron spectrophotometry (XPS) and transmission electronic microscopy (TEM) with energy dispersive spectroscopy (EDS). With respect to the bare ZrO2 mainly containing monoclinic (m-) phase, an increasing amount of rare-earth (RE) dopant was found to improve the specific BET surface area and to stabilize the tetragonal (t-) or cubic (c-) polymorphs of ZrO2 at room temperature. XRD data confirmed that dopants were mainly inserted in the t-ZrO2 phase. The photocatalytic O2 evolution from water under AM 1.5 G simulated sunlight illumination of the prepared samples have been correlated with their optical, structural and chemical properties. The effect of the dopant concentration on the chemical-physical and photocatalytic properties of the Er- and Ce-doped ZrO2 materials was elucidated. The samples with 5% of RE oxide were the most active, i.e., three times more than pure zirconia. Their superior photocatalytic activity was found to be mainly correlated to two factors: (i) an optimal surface concentration of RE ions of about 3.7%, which increased charge carriers separation in the photocatalysts surface due more superficial defects of the t-ZrO2 and a higher surface area, thus enhancing the reaction kinetics, (ii) a controlled amount of monoclinic vs. tetragonal (or cubic) polymorphs of zirconia with an optimum ratio of about 70/30 of t-ZrO2/m-ZrO2. Instead, the increased ability of the RE-doped ZrO2 to harvest visible light was found to have a secondary role on the photocatalytic activity of the Ce-doped ZrO2 material.