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Shape-selective sieving layers on an oxide catalyst surface

Nature Chemistry volume 4, pages 1030–1036 (2012)Cite this article

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Abstract

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 Al2O3 (thickness, 0.4–0.7 nm) with ‘nanocavities’ (<2 nm in diameter) on a TiO2 photocatalyst. The additional layers result in selectivity (up to 9:1) towards less hindered reactants in otherwise unselective, competitive photocatalytic oxidations and transfer hydrogenations.

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Figure 1: Nanocavity oxides selectively allow access only to molecules able to penetrate the <2-nm-diameter supermicroporous cavities.
Figure 2: Nanocavity dimensions determined by QCM and SAXS.
Figure 3: TEM images show ALD-coated SrTiO3 nanocuboids.
Figure 4: Adding nanocavity-containing films adds reactant selectivity to intrinsically unselective TiO2 photocatalysts.

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  • 09 November 2012

    In the version of this Article originally published online, the affiliation for Sungsik Lee and Randall E. Winans was incorrect, it should have read 'X-ray Science Division, Argonne National Laboratory'. This has now been corrected in all versions of the Article.

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Acknowledgements

This material is based on work supported as part of the Institute for Atom-efficient Chemical Transformations (IACT), an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Science. The authors thank K. Poeppelmeier for the gift of SrTiO3 nanocuboids. J.M.N. acknowledges a 3M Non-Tenured Faculty Grant, a DuPont Young Professor Grant, a Camille and Henry Dreyfus New Faculty Award and a US Department of Energy award (DE-SC0006718). S. Seifert and B. Lee are thanked for assistance with acquiring and analysing SAXS data. Use of the Advanced Photon Source, an Office of Science User Facility operated for the US DOE Office of Science by Argonne National Laboratory, was supported under contract no. DE-AC02-06CH11357. TEM was performed in the Electron Probe Instrumentation Center of NUANCE (supported by NSF-NSEC, NSF-MRSEC, Keck Foundation and the State of Illinois) at Northwestern University.

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Authors and Affiliations

  1. Center for Catalysis and Surface Science, Northwestern University, Evanston, 60208, Illinois, USA

    Christian P. Canlas, Richard P. Van Duyne, Peter C. Stair & Justin M. Notestein

  2. Energy Systems Division, Argonne National Laboratory, Argonne, 60439, Illinois, USA

    Junling Lu & Jeffrey W. Elam

  3. Department of Chemistry, Northwestern University, Evanston, 60208, Illinois, USA

    Natalie A. Ray, Richard P. Van Duyne & Peter C. Stair

  4. Department of Chemical and Biological Engineering, Northwestern University, Evanston, 60208, Illinois, USA

    Nicolas A. Grosso-Giordano & Justin M. Notestein

  5. X-ray Science Division, Argonne National Laboratory, Argonne, 60439, Illinois, USA

    Sungsik Lee & Randall E. Winans

  6. Chemical Sciences and Engineering Sciences Division, Argonne National Laboratory, Argonne, 60439, Illinois, USA

    Peter C. Stair

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  1. Christian P. Canlas
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Contributions

C.P.C. grafted templates, performed TGA, UV-vis, N2 physisorption, TEM and catalysis experiments, and wrote the paper. N.A.G.G. performed catalysis experiments. J.L. and J.W.E. performed ALD with in situ QCM. S.L. and R.E.W. performed SAXS. N.A.R. performed ALD with supervision by P.C.S. and R.P.v.D. J.M.N. wrote the paper, managed the collaboration and developed the initial concept.

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Correspondence to Justin M. Notestein.

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Canlas, C., Lu, J., Ray, N. et al. Shape-selective sieving layers on an oxide catalyst surface. Nature Chem 4, 1030–1036 (2012). https://doi.org/10.1038/nchem.1477

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