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*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

29 Scopus citations


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 (US)
Pages (from-to)1269-1277
Number of pages9
JournalChemistry of Materials
Issue number4
StatePublished - Feb 24 2015

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Materials Chemistry


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