実験番号：201905013（2 シフト）BL8S3

WAXS characterization of raw nanomaterials
Cruz Silva Rodolfo
Research Initiative for Supra-Materials Shinshu University
1．Background and research purpose
Graphene oxide membranes have become one of the most interesting nanomaterials that has potential
applications in separation technologies.1 The separation properties of the graphene oxide membranes can be
tailored by the addition of a second phase nanomaterial, such as surfactants or few layered graphene sheets,
while its adhesive properties can be modified by the introdution of polymers such as polyvinyl alcohol.2There isalso great interest in combining graphene oxide membranes with the other two dimensional crystalline materials,
since nanocomposite membranes might be the future of desalination.3 Here, we carried out an exploratory
research on the mixture of graphene oxide papers with several additives in order to understand its mechanism ofdrying and formation.
2．Experiment contents
Graphene oxide composite papers were prepared by blade coating a slurry of graphene oxide or slurries ofgraphene oxide mixtures as previously described.4 Several additives such as mineral graphite, molybdenumdisulfide, boron nitride and carbon nanotubes (CNTs) were added. These inorganic fillers were analyzed by wide
angle X-ray scattering in the form of powders. Samples were mounted on aluminum sample holders and observedat the BL8S3 line. The resulting scattering patterns were analyzed using Fit2D software.5
3．Results and discussion.
In the current stage of research, we basically characterized the raw materials to be mixed with graphene oxide
dispersions in order to prepare hybrid papers. Figure 1 shows the radially integrated wide-angle X-ray scattering
patterns of four different inorganic materials: chemically vapor deposited carbon nanotubes (Figure 1a), mineralgraphite (Figure 1b), synthetic molybdenum disulfide (Figure 1c), and synthetic boron nitride (Figure 1d). The
peaks corresponding to the CNTs are broader than those of the other materials because the interlayer spacings
are affected due to the curvature of the carbon nanotubes, as well as the presence of crystalline defects. The othercrystalline materials show very sharp peaks characteristic of crystalline materials. In the case of the graphite,
individual spots corresponding to the scattering of big single crystal flakes can be clearly seen in the inset, while
the molybdenum disulfide and boron nitride show clear rings due to the fine powder form of the sample. Since
these materials are two-dimensional, we used the 001 and 002 peaks to calculate the interlayer spacing that matchwith the reported layered structures. This work is part of the basic characterization of the materials microstructure.
4. Conclusions
The scattering patterns confirm the crystalline structure of these samples. All these materials will be exfoliatedwith high energy ultrasound to prepare dispersions of nanoribbons (in the case of nanotubes) or nanoplatelets(for the graphite, molybdenum disulfide and boron nitride) before mixing with graphene oxide.

Figure 1. Radially integrated Wide-angle X-ray scattering patterns of a) Carbon nanotubes,b) graphite, c) molybdenum disulfide, and d) boron nitride.
5．References
1. Nair, R. R.; Wu, H. A.; Jayaram, P. N.; Grigorieva, I. V.; Geim, A. K., Unimpeded Permeation of Water
Through Helium-Leak-Tight Graphene-Based Membranes. Science 2012, 335 (6067), 442-444.
2. Morelos-Gomez, A.; Cruz-Silva, R.; Muramatsu, H.; Ortiz-Medina, J.; Araki, T.; Fukuyo, T.; Tejima, S.;
Takeuchi, K.; Hayashi, T.; Terrones, M.; Endo, M., Effective NaCl and dye rejection of hybrid graphene
oxide/graphene layered membranes. Nature Nanotechnology 2017, 12 (11), 1083-+.
3. Cruz-Silva, R.; Endo, M.; Terrones, M., Graphene oxide films, fibers, and membranes. Nanotechnology
Reviews 2016, 5 (4), 377-391.
4. Cruz-Silva, R.; Morelos-Gomez, A.; Kim, H. I.; Jang, H. K.; Tristan, F.; Vega-Diaz, S.; Rajukumar, L.
P.; Elias, A. L.; Perea-Lopez, N.; Suhr, J.; Endo, M.; Terrones, M., Super-stretchable Graphene Oxide
Macroscopic Fibers with Outstanding Knotability Fabricated by Dry Film Scrolling. Acs Nano 2014, 8 (6),5959-5967.
5. Hammersley, A. P., FIT2D: a multi-purpose data reduction, analysis and visualization program. Journal ofApplied Crystallography 2016, 49, 646-652.