Encapsulation of Bimetallic Metal Nanoparticles into Robust Zirconium-Based Metal-Organic Frameworks: Evaluation of the Catalytic Potential for Size-Selective Hydrogenation

Christoph Rösler; Stefano Dissegna; Victor L Rechac; Max Kauer; Penghu Guo; Stuart Turner; Kevin Ollegott; Hirokazu Kobayashi; Tomokazu Yamamoto; Daniel Peeters; Yuemin Wang; Syo Matsumura; Gustaaf Van Tendeloo; Hiroshi Kitagawa; Martin Muhler; Francesc X Llabrés I Xamena; Roland A Fischer

doi:10.1002/chem.201603984

Encapsulation of Bimetallic Metal Nanoparticles into Robust Zirconium-Based Metal-Organic Frameworks: Evaluation of the Catalytic Potential for Size-Selective Hydrogenation

Chemistry. 2017 Mar 13;23(15):3583-3594. doi: 10.1002/chem.201603984. Epub 2017 Feb 7.

Authors

Christoph Rösler¹, Stefano Dissegna², Victor L Rechac³, Max Kauer¹, Penghu Guo⁴, Stuart Turner⁵, Kevin Ollegott⁴, Hirokazu Kobayashi⁶, Tomokazu Yamamoto⁷, Daniel Peeters¹, Yuemin Wang⁸, Syo Matsumura⁷, Gustaaf Van Tendeloo⁵, Hiroshi Kitagawa⁶, Martin Muhler⁴, Francesc X Llabrés I Xamena³, Roland A Fischer²

Affiliations

¹ Chair of Inorganic Chemistry II, Ruhr-University Bochum, Universitätsstr. 150, 44780, Bochum, Germany.
² Chair of Inorganic and Metal-organic Chemistry, Technical University Munich, Lichtenbergstraße 4, 85748, Garching, Germany.
³ Instituto de Tecnología Química, Universitat Politècnica de València, Consejo Superior de Investigaciones Científicas, Avda. de los Naranjo, s/n, 46022, Valencia, Spain.
⁴ Laboratory of Industrial Chemistry, Ruhr-University Bochum, Universitätsstr. 150, 44780, Bochum, Germany.
⁵ EMAT, University of Antwerp, Groenenborgerlaan 171, 2020, Antwerp, Belgium.
⁶ Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto, 606-8502, Japan.
⁷ Department of Applied Quantum Physics and Nuclear Engineering, Graduate School of Engineering, Kyushu University and the Ultramicroscopy Research Center, Motooka 744, Nishi-ku, Fukuoka, 819-0395, Japan.
⁸ Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Campus Nord, B330, 76344, Eggenstein-Leopoldshafen, Germany.

PMID: 27922204
DOI: 10.1002/chem.201603984

Abstract

The realization of metal nanoparticles (NPs) with bimetallic character and distinct composition for specific catalytic applications is an intensively studied field. Due to the synergy between metals, most bimetallic particles exhibit unique properties that are hardly provided by the individual monometallic counterparts. However, as small-sized NPs possess high surface energy, agglomeration during catalytic reactions is favored. Sufficient stabilization can be achieved by confinement of NPs in porous support materials. In this sense, metal-organic frameworks (MOFs) in particular have gained a lot of attention during the last years; however, encapsulation of bimetallic species remains challenging. Herein, the exclusive embedding of preformed core-shell PdPt and RuPt NPs into chemically robust Zr-based MOFs is presented. Microstructural characterization manifests partial retention of the core-shell systems after successful encapsulation without harming the crystallinity of the microporous support. The resulting chemically robust NP@UiO-66 materials exhibit enhanced catalytic activity towards the liquid-phase hydrogenation of nitrobenzene, competitive with commercially used Pt on activated carbon, but with superior size-selectivity for sterically varied substrates.

Keywords: heterogeneous catalysis; hydrogenation; metal-organic frameworks; nanoparticles; nanostructures.