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Oxidation-stable plasmonic copper nanoparticles in photocatalytic TiO2 nanoarchitectures† Paul A. DeSario, *a Jeremy J. Pietron,*a Todd H. Brintlinger,b Monica McEntee,c Joseph F. Parker,a Olga Baturina,a Rhonda M. Stroud b and Debra R. Rolison a Ultraporous copper/titanium dioxide (Cu/TiO2) aerogels supporting 10 for typical oxide supported metal catalysts—should increase the
Published on 04 August 2017. Downloaded by Naval Research Laboratory - Washington on 21/11/2017 18:02:53.
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Fig. 1 (a) Scanning electron micrograph of TiO2 aerogel and schematic representation of Cu/TiO2 aerogel depicting the extensive contact between the bonded, non-agglomerated TiO2 nanoparticulate network and the supported Cu nanoparticles; (b) schematic representation of a conventional Cu/TiO2 nanocomposite illustrating the single interfacial boundary between the Cu nanoparticles and the TiO2 support and a scanning electron micrograph of commercial TiO2. Note: Scales of the micrographs are fixed to be the same.
ability of aerogel TiO2 to limit oxidation of supported Cu nanoparticles. The interfacial contact between metal nanoparticles hosted in oxide aerogels, which we previously described for catalytic Au–TiO2 aerogels,32–35 ensures contact of the metal nanoparticle with multiple supporting oxide particles. To determine how interfacial contact impacts the metallic and plasmonic character of the hosted Cu nanoparticle, we photodeposit Cu nanoparticles on two drastically different TiO2 nanomaterials: TiO2 aerogels comprising a mesoporous architecture defined by a network of 10–15 nm, covalently bonded TiO2 nanoparticles (Fig. 1a) and a commercially available nanoparticulate TiO2, comprising non-networked, ∼50–100 nm particles (Fig. 1b). The key difference between the two nanoscopic realizations of Cu junctions with TiO2—multiple contacts per Cu nanoparticle vs. a one-dimensional line boundary contact—are seen schematically by contrasting Fig. 1a with Fig. 1b. Herein, we demonstrate that photodeposition of small ( primarily
