Size-selective synthesis and stabilization of small silver nanoparticles on TiO2 partially masked by SiO2

Zhenyu Bo, Todd R. Eaton, James R. Gallagher, Christian P. Canlas, Jeffrey T. Miller, Justin M Notestein

Research output: Contribution to journalArticle

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Abstract

Controlling metal nanoparticle size is one of the principle challenges in developing new supported catalysts. Typical methods where a metal salt is deposited and reduced can result in a polydisperse mixture of metal nanoparticles, especially at higher loading. Polydispersity can exacerbate the already significant challenge of controlling sintering at high temperatures, which decreases catalytic surface area. Here, we demonstrate the size-selective photoreduction of Ag nanoparticles on TiO2 whose surface has been partially masked with a thin SiO2 layer. To synthesize this layered oxide material, TiO2 particles are grafted with tert-butylcalix[4]arene molecular templates (∼2 nm in diameter) at surface densities of 0.05-0.17 templates.nm-2, overcoated with ∼2 nm of SiO2 through repeated condensation cycles of limiting amounts of tetraethoxysilane (TEOS), and the templates are removed oxidatively. Ag photodeposition results in uniform nanoparticle diameters ≤3.5 nm (by transmission electron microscopy (TEM)) on the partially masked TiO2, whereas Ag nanoparticles deposited on the unmodified TiO2 are larger and more polydisperse (4.7 ± 2.7 nm by TEM). Furthermore, Ag nanoparticles on the partially masked TiO2 do not sinter after heating at 450 °C for 3 h, while nanoparticles on the control surfaces sinter and grow by at least 30%, as is typical. Overall, this new synthesis approach controls metal nanoparticle dispersion and enhances thermal stability, and this facile synthesis procedure is generalizable to other TiO2-supported nanoparticles and sizes and may find use in the synthesis of new catalytic materials.

Original languageEnglish
Pages (from-to)1269-1277
Number of pages9
JournalChemistry of Materials
Volume27
Issue number4
DOIs
Publication statusPublished - Feb 24 2015

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Silver
Stabilization
Nanoparticles
Metal nanoparticles
Transmission electron microscopy
Control surfaces
Polydispersity
Catalyst supports
Oxides
Condensation
Thermodynamic stability
Sintering
Salts
Metals
Heating
Polymers
Temperature

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Size-selective synthesis and stabilization of small silver nanoparticles on TiO2 partially masked by SiO2. / Bo, Zhenyu; Eaton, Todd R.; Gallagher, James R.; Canlas, Christian P.; Miller, Jeffrey T.; Notestein, Justin M.

In: Chemistry of Materials, Vol. 27, No. 4, 24.02.2015, p. 1269-1277.

Research output: Contribution to journalArticle

Bo, Zhenyu ; Eaton, Todd R. ; Gallagher, James R. ; Canlas, Christian P. ; Miller, Jeffrey T. ; Notestein, Justin M. / Size-selective synthesis and stabilization of small silver nanoparticles on TiO2 partially masked by SiO2. In: Chemistry of Materials. 2015 ; Vol. 27, No. 4. pp. 1269-1277.
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