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Published January 21, 2018 | Supplemental Material
Journal Article Open

Catalytic synthesis of few-layer graphene on titania nanowires

Abstract

Growth mechanisms of graphitic nanostructures on metal oxides by chemical vapor deposition (CVD) are observed at 750 °C, using titania nanowire aerogel (NWAG) as a three-dimensional substrate and without metal catalysts. We temporally observed catalytic transformation of amorphous carbon into few-layer graphene on the surface of 5–10 nm diameter titania nanowires. The graphitization spontaneously terminates when the titania nanowires are encapsulated by a shell of approximately three graphene layers. Extended CVD time beyond the termination point (>1125 seconds) yields only additional amorphous carbon deposits on top of the few-layer graphene. Furthermore, it was discovered that the islands of amorphous carbon do not graphitize unless they catalytically grow beyond a threshold size of 5–7 nm along the nanowire length, even after an extended thermal treatment. The electrical conductivity of the NWAG increased by four orders of magnitude, indicating that the graphene shell mediated by titania nanowires yielded a network of graphene throughout the three-dimensional nanostructure of the aerogel. Our results help us understand the growth mechanisms of few-layer graphene on nanostructured metal oxides, and inspire facile and controllable processing of metal oxide–nanocarbon fiber–shell composites.

Additional Information

© 2018 The Royal Society of Chemistry. Received 8th August 2017, Accepted 20th November 2017, First published on 21st December 2017. This material is based upon the work supported by the National Science Foundation under Grant No. 1007793 and was also supported by Airbus Group, Embraer, Lockheed Martin, Saab AB, ANSYS, Hexcel, and TohoTenax through MIT's Nano-Engineered Composite aerospace STructures (NECST) Consortium. This work made use of the Shared Experimental Facilities supported in part by the MRSEC Program of the National Science Foundation under award number DMR-0819762 and the facilities at the MIT Institute for Soldier Nanotechnologies (ISN), supported by the U.S. Army Research Office under contract W911NF-13-D-0001. This work was performed in part at the Center for Nanoscale Systems (CNS), a member of the National Nanotechnology Infrastructure Network (NNIN), which is supported by the National Science Foundation under NSF award no. ECS-0335765. CNS is part of Harvard University. This research was also supported by the Individual Basic Science&Engineering Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (NRF-2017R1D1A1B03033694). A. Kudo also thanks Dr Kehang Cui (MIT) for the discussion regarding Raman spectrum data, Prof. George R. Rossman (Caltech) for providing access to a Renishaw M1000 Micro Raman Spectrometer System, and Pakpoom Buabthong (Caltech) for collecting XPS data. There are no conflicts to declare.

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