Ultrathin layers of oxides deposited on atomically flat metal surfaces have been shown to significantly influence the electronic structure of the underlying metal, which in turn alters the catalytic performance. Upscaling of the specifically designed architectures as required for technical utilization of the effect has yet not been achieved. Here, we apply liquid crystalline phases of fluorohectorite nanosheets to fabricate such architectures in bulk. Synthetic sodium fluorohectorite, a layered silicate, when immersed into water spontaneously and repulsively swells to produce nematic suspensions of individual negatively charged nanosheets separated to more than 60 nm, while retaining parallel orientation. Into these galleries oppositely charged palladium nanoparticles were intercalated whereupon the galleries collapse. Individual and separated Pd nanoparticles were thus captured and sandwiched between nanosheets. As suggested by the model systems, the resulting catalyst performed better in the oxidation of carbon monoxide than the same Pd nanoparticles supported on external surfaces of hectorite or on a conventional Al2 O3 support. XPS confirmed a shift of Pd 3d electrons to higher energies upon coverage of Pd nanoparticles with nanosheets to which we attribute the improved catalytic performance. DFT calculations showed increasing positive charge on Pd weakened CO adsorption and this way damped CO poisoning.

Bavarian Polymer Institute and Department of Chemistry University of Bayreuth Universitätsstraße 30 95447 Bayreuth Germany

Department of Inorganic Chemistry Fritz Haber Institut der Max Planck Gesellschaft Faradayweg 4 6 14195 Berlin Germany

Department of Physical and Macromolecular Chemistry Charles University Hlavova 8 128 00 Prague 2 Czech Republic

Faculty of Natural Sciences Institute of Chemistry Materials for Innovative Energy Concepts Chemnitz University of Technology Straße der Nationen 62 09111 Chemnitz Germany

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