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Highly Dispersed Mixed Zirconia and Hafnia Nanoparticles in a Silica Matrix: First Example of a ZrO 2 –HfO 2 –SiO 2 Ternary Oxide System
Author(s) -
Armelao L.,
Bertagnolli H.,
Bleiner D.,
Groenewolt M.,
Gross S.,
Krishnan V.,
Sada C.,
Schubert U.,
Tondello E.,
Zattin A.
Publication year - 2007
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.200600458
Subject(s) - materials science , calcination , x ray photoelectron spectroscopy , analytical chemistry (journal) , fourier transform infrared spectroscopy , nanoparticle , oxide , crystallization , mixed oxide , x ray absorption fine structure , spectroscopy , chemical engineering , nanotechnology , catalysis , chemistry , biochemistry , chromatography , engineering , metallurgy , physics , quantum mechanics
Abstract ZrO 2 and HfO 2 nanoparticles are homogeneously dispersed in SiO 2 matrices (supported film and bulk powders) by copolymerization of two oxozirconium and oxohafnium clusters (M 4 O 2 (OMc) 12 , M = Zr, Hf; OMc = OC(O)–C(CH 3 )CH 2 ) with (methacryloxypropyl)trimethoxysilane (MAPTMS, (CH2C(CH 3 )C(O)O)–(CH 2 ) 3 Si(OCH 3 ) 3 ). After calcination (at a temperature ≥800 °C), a silica matrix with homogeneously distributed MO 2 nanocrystallites is obtained. This route yields a spatially homogeneous dispersion of the metal precursors inside the silica matrix, which is maintained during calcination. The composition of the films and the powders is studied before and after calcination by using Fourier transform infrared (FTIR) analysis, X‐ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and laser ablation inductively coupled plasma mass spectrometry (LA‐ICPMS). The local environment of the metal atoms in one of the calcined samples is investigated by using X‐ray Absorption Fine Structure (XAFS) spectroscopy. Through X‐ray diffraction (XRD) the crystallization of Hf and Zr oxides is seen at temperatures higher than those expected for the pure oxides, and transmission electron microscopy (TEM) shows the presence of well‐distributed and isolated crystalline oxide nanoparticles (5–10 nm).