Shape-selective sieving layers on an oxide catalyst surface

Christian P. Canlas, Junling Lu, Natalie A. Ray, Nicolas A. Grosso-Giordano, Sungsik Lee, Jeffrey W. Elam, Randall E. Winans, Richard P. Van Duyne, Peter C. Stair, Justin M. Notestein*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

114 Scopus citations


New porous materials such as zeolites, metal-organic frameworks and mesostructured oxides are of immense practical utility for gas storage, separations and heterogeneous catalysis. Their extended pore structures enable selective uptake of molecules or can modify the product selectivity (regioselectivity or enantioselectivity) of catalyst sites contained within. However, diffusion within pores can be problematic for biomass and fine chemicals, and not all catalyst classes can be readily synthesized with pores of the correct dimensions. Here, we present a novel approach that adds reactant selectivity to existing, non-porous oxide catalysts by first grafting the catalyst particles with single-molecule sacrificial templates, then partially overcoating the catalyst with a second oxide through atomic layer deposition. This technique is used to create sieving layers of Al 2O 3 (thickness, 0.4-0.7 nm) with 'nanocavities' (<2 nm in diameter) on a TiO 2 photocatalyst. The additional layers result in selectivity (up to 9:1) towards less hindered reactants in otherwise unselective, competitive photocatalytic oxidations and transfer hydrogenations.

Original languageEnglish (US)
Pages (from-to)1030-1036
Number of pages7
JournalNature chemistry
Issue number12
StatePublished - Dec 2012

ASJC Scopus subject areas

  • General Chemical Engineering
  • General Chemistry


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