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Controlled Generation of TiOx–Au Interface Using Titanium Molecular Complex Bearing Pyridyl Anchors: Synthesis, Characterization and Catalysis

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Abstract

Interfacial perimeter sites between metal and support are often important for catalysis. A mononuclear titanium siloxy complex III, Ti(acac)2[OSiC6H5N(OCH3)2]2 was synthesized to generate TiOx units of different degrees of clustering to decorate Au nanoparticles. Two different methods of preparation were examined; one was to deposit III onto Au/SiO2 and the other was to form III-covered Au nanoparticle first before deposition onto SiO2. The former method generated more highly dispersed TiOx units, while larger domains of TiO2 were formed with the latter method, as deduced by UV–vis and XAS characterization. A model was proposed to explain how TiOx dispersity could be related to the preparative procedures. These samples were further tested as catalysts in selective oxidation of propane in a stream of O2 and H2. They exhibited different product selectivities. The sample with more dispersed TiOx units were more selective for acetone formation versus propene formation. The results confirmed the important role of both the Au–TiOx interface at the perimeter and the extent of Ti isolation in the TiOx phase in the reaction.

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Acknowledgements

The authors acknowledge support of this work by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DOE DE-FG02-03-ER15457. Linping Qian for experimental assistance, China Scholarship Council for support of Z.W. and X. H. This work made use of the EPIC, Keck-II, and/or SPID facility(ies) of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1121262) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois, through the IIN. XRD patterns were collected in the J.B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation (DMR-1121262) at the Materials Research Center of Northwestern University. XAS were collected at Sector 5 of the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) at the Advanced Photon Source (APS). DND-CAT was supported by Northwestern University, E.I. DuPont de Nemours & Co., and The Dow Chemical Company and the Advanced Photon Source is a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. The CleanCat Core facility was funded in part by the U.S. Department of Energy (DE-FG02-03ER15457). We also thank the Cabot Corporation for the gift of Cab-O-Sil L-90.

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    Authors and Affiliations

    1. Faculty of Printing, Packaging Engineering and Digital Media Technology, Xi’an University of Technology, Xi’an, 710048, People’s Republic of China

      Zhen Wang & Changqing Fang

    2. Chemical and Biological Engineering Department, Northwestern University, Evanston, IL, 60208, USA

      Zhen Wang, Yi Y. Wu, Jingmei Shen, Mayfair C. Kung & Harold H. Kung

    3. School of Materials Science and Engineering, Northwestern Polytechnical University, Xi’an, 710072, Shaanxi, People’s Republic of China

      Xianliang Hou & Tiehu Li

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    Correspondence to Mayfair C. Kung or Harold H. Kung.

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    X. Hou and Y. Wu have contributed equally in this work.

    Zhen Wang—Experimental work were conducted at Northwestern University.

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    Wang, Z., Hou, X., Wu, Y.Y. et al. Controlled Generation of TiOx–Au Interface Using Titanium Molecular Complex Bearing Pyridyl Anchors: Synthesis, Characterization and Catalysis. Top Catal 61, 800–809 (2018). https://doi.org/10.1007/s11244-018-0941-2

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