Supporting Information. Robust Bioinspired Graphene Film via π-π Cross-linking

Transcription

1 Supporting Information Robust Bioinspired Graphene Film via π-π Cross-linking Hong Ni, a Feiyu Xu, a Antoni P. Tomsia, a,b Eduardo Saiz, c Lei Jiang, a and Qunfeng Cheng* a a Key Laboratory of Bio-inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry, Beijing Advanced Innovation Center for Biomedical Engineering, Beihang University, Beijing, , P. R. China b Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA c Department of Materials, Centre for Advanced Structural Ceramics, Imperial College London, London SW7 2AZ, UK. * Correspondence should be addressed to Qunfeng Cheng, cheng@buaa.edu.cn S-1

2 Figure S1. AFM image of GO nanosheet with thickness of ~ 0.75 nm. S-2

3 Figure S2. TGA curves of GO, rgo, rgo-ap-dss-i, rgo-ap-dss-ii, rgo-ap-dss-iii and rgo-ap-dss-iv samples. The corresponding AP-DSS contents in different samples are shown on the right side of the graph. All the samples were tested in an argon atmosphere at a heating rate of 15 C min -1. Figure S3. XRD patterns of rgo, rgo-ap-dss-i, rgo-ap-dss-ii, rgo-ap-dss-iii and rgo-ap-dss-iv samples. The corresponding d-spacing is 3.53 Å, 3.63 Å, 3.64 Å, 3.72 Å and 3.72 Å, respectively. The increase of the d-spacing is due to the intercalation of AP-DSS molecules into the interspace of graphene layers. S-3

4 Figure S4. The tensile strength and toughness of rgo-ap-dss nanocomposites with different contents of AP-DSS molecules. Figure S5. Dynamic stress-strain curves of (a) rgo film, (b) rgo-ap-dss-iii nanocomposite. S-4

5 Table S1. Mechanical properties of GO, rgo, rgo-ap-dss-i, rgo-ap-dss-ii, rgo-ap- DSS-III, and rgo-ap-dss-iv samples. Sample Stress (MPa) Strain (%) Toughness (MJ m -3 ) GO ± ± ± 0.3 rgo ± ± ± 0.2 rgo-ap-dss-i ± ± ± 0.3 rgo-ap-dss-ii ± ± ± 1.0 rgo-ap-dss-iii ± ± ± 3.0 rgo-ap-dss-iv ± ± ± 0.3 S-5

6 Table S2. Electrical conductivities of rgo, rgo-ap-dss-i, rgo-ap-dss-ii, rgo-ap-dss- III and rgo-ap-dss-iv samples. Sample Electrical conductivity (S cm -1 ) rgo ± 9.6 rgo-ap-dss-i ± 6.3 rgo-ap-dss-ii ± 8.6 rgo-ap-dss-iii ± 11.8 rgo-ap-dss-iv ± 10.1 S-6

7 Table S3. Comparison of tensile strength, toughness, and conductivity of rgo-ap-dss film with other GO/rGO-based composite films cross-linked through non-covalent bonding. Sample Electrical conductivity (S. cm -1 ) Toughness (MJ. m -3 ) Tensile strength (MPa) Reference rgo-pb [1] rgo-fpeg [2] GO-PVA [3] rgo-pva [4] GO-PMMA [3] rgo-papb [5] GO-CNC [6] rgo-cnc [6] GO-Zn [7] GO-Ca [8] GO-Mg [8] GO-Al [9] GO-SL [10] rgo-sl [10] rgo-ap-dss-ii This work REFERENCE (1) Xu, Y.; Bai, H.; Lu, G.; Li, C.; Shi, G., Flexible graphene films via the filtration of watersoluble noncovalent functionalized graphene sheets. J. Am. Chem. Soc. 2008, 130, (2) Georgakilas, V.; Tiwari, J. N.; Kemp, K. C.; Perman, J. A.; Bourlinos, A. B.; Kim, K. S.; Zboril, R., Noncovalent Functionalization of Graphene and Graphene Oxide for Energy S-7

8 Materials, Biosensing, Catalytic, and Biomedical Applications. Chem. Rev. 2016, 116, (3) Putz, K. W.; Compton, O. C.; Palmeri, M. J.; Nguyen, S. T.; Brinson, L. C., High-Nanofiller- Content Graphene Oxide Polymer Nanocomposites via Vacuum-Assisted Self-Assembly. Adv. Funct. Mater. 2010, 20, (4) Li, Y. Q.; Yu, T.; Yang, T. Y.; Zheng, L. X.; Liao, K., Bio inspired nacre like composite films based on graphene with superior mechanical, electrical, and biocompatible properties. Adv. Mater. 2012, 24, (5) Zhang, M.; Huang, L.; Chen, J.; Li, C.; Shi, G., Ultratough, ultrastrong, and highly conductive graphene films with arbitrary sizes. Adv. Mater. 2014, 26, (6) Xiong, R.; Hu, K.; Grant, A. M.; Ma, R.; Xu, W.; Lu, C.; Zhang, X.; Tsukruk, V. V., Ultrarobust Transparent Cellulose Nanocrystal-Graphene Membranes with High Electrical Conductivity. Adv. Mater. 2016, 28, (7) Lam, D. V.; Gong, T.; Won, S.; Kim, J.-H.; Lee, H.-J.; Lee, C.; Lee, S.-M., A robust and conductive metal-impregnated graphene oxide membrane selectively separating organic vapors. Chem. Commun. 2015, 51, (8) Park, S.; Lee, K.-S.; Bozoklu, G.; Cai, W.; Nguyen, S. T.; Ruoff, R. S., Graphene Oxide Papers Modified by Divalent Ions Enhancing Mechanical Properties via Chemical Cross- Linking. ACS Nano 2008, 2, (9) Yeh, C.-N.; Raidongia, K.; Shao, J.; Yang, Q.-H.; Huang, J., On the origin of the stability of graphene oxide membranes in water. Nat. Chem. 2015, 7, (10) Hu, K.; Tolentino, L. S.; Kulkarni, D. D.; Ye, C.; Kumar, S.; Tsukruk, V. V., Written in Conductive Patterns on Robust Graphene Oxide Biopaper by Electrochemical Microstamping. Chem., Int. Ed. 2013, 52, S-8