title: Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal β-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid.
abstract: Porous (Ce0.5Zr0.5)O2 solid solutions were prepared by thermolysis (T=285 °C) or sonolysis (20 kHz, I=32 W cm(-2), Pac=0.46 W mL(-1), T=200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4-6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and μ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce0.5Zr0.5)O2 solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m(2) g(-1) depending on synthesis conditions. The use of Barrett-Joyner-Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce0.5Zr0.5)O2 mixed oxides loaded with 1.5%wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C.
authors: Institut de Chimie Séparative de Marcoule (ICSM), UMR 5257, CEA, CNRS, UMII, ENSCM, Centre de Marcoule, BP 17171, 30207 Bagnols sur Cèze Cedex, France; Institut Charles Gerhardt (ICG), UMR 5253, UMII, CNRS, Chimie Moléculaire et Organisation du Solide, Université de Montpellier II, Bât 17 - CC 1701, 34095 Montpellier Cedex 5, France.
authors: Camille
authors: C
authors: Cau
authors: Institut Charles Gerhardt (ICG), UMR 5253, UMII, CNRS, Chimie Moléculaire et Organisation du Solide, Université de Montpellier II, Bât 17 - CC 1701, 34095 Montpellier Cedex 5, France. Electronic address: yannick.guari@univ-montp2.fr.
authors: Yannick
authors: Y
authors: Guari
authors: Institut de Chimie Séparative de Marcoule (ICSM), UMR 5257, CEA, CNRS, UMII, ENSCM, Centre de Marcoule, BP 17171, 30207 Bagnols sur Cèze Cedex, France.
authors: Tony
authors: T
authors: Chave
authors: Institut Charles Gerhardt (ICG), UMR 5253, UMII, CNRS, Chimie Moléculaire et Organisation du Solide, Université de Montpellier II, Bât 17 - CC 1701, 34095 Montpellier Cedex 5, France.
authors: Joulia
authors: J
authors: Larionova
authors: Institut de Chimie Séparative de Marcoule (ICSM), UMR 5257, CEA, CNRS, UMII, ENSCM, Centre de Marcoule, BP 17171, 30207 Bagnols sur Cèze Cedex, France. Electronic address: serguei.nikitenko@cea.fr.
authors: Sergey I
authors: SI
authors: Nikitenko
keywords: CWAO; Cerium–zirconium mixed oxide; Nanoparticles; Sonochemistry; Thermolysis; β-Diketonate