Synthesis and characterization of graphene oxide and graphene. Aline Z. Cardosoa ( IC ) , Diego G. C. da Silvaa ( IC ) , Cssia C. Turcib,Glucio B.

Ferreiraa ( PQ ) and Mri D. Vieiraa ( PQ ).

a b

Universidade Federal Fluminense, Niteri - RJ - Brasil; Universidade Federal do Rio de Janeiro, Rio de Janeiro - RJ - Brasil. the peak 002. The other peaks are impurities present in the product due to the short reaction time with the oxidizing agent and a very difficult filtration and washing procedures. The formation of

INTRODUCTION Graphene has been extensively studied due to their nanoscale dimensions, electrical conductivity, associated to its chemical and mechanical stability1. These properties make this compound, a potential technological material in the development of sensors, composite materials, solar cells, supercapacitors, catalysts and gas storage means. Due to its diversified application, a great challenge of materials chemistry at present time is the development of methodologies capable to synthesize a graphene sheet, in an easy and reproductible way. Thus, some modifications in literature synthesis routes were adopted. In this study, the modified method of Hummer [1] was used for obtaining of the graphene oxide with thereafter reduction with aluminum in acidic media for obtaining the graphene [2]. The characterization methods used were X-ray diffraction ( XRD ) and X-ray photoelectron spectroscopy ( XPS ) with the facilities of the lab. of x ray diffraction at Federal Fluminense University LDRX-UFF, the Soft X-ray Spectroscopy (SXS) beamline at the LNLS-Campinas (research proposal SXS-14393) and the XPS- equipment at Catalysis Lab. -RECAT-UFF, respectively RESULTS AND DISCUSSION The synthesis steps were validated by analysis of X-ray diffraction, shown in Figures 1 and 2. The structural modifications found in synthesis products were compared with mineral graphite used as starting material. In Figure 1, can be observed the x-ray diffraction patterns for graphite, graphene oxide 1 (GO 1) and reduced graphene oxide (GR). The XRD 002 peak characteristic of graphite is present in GO 1 and GR. The production of GO 1 is confirmed by the appearance of a 2 band near 10 (peak 001), which is consistent with the literature for the graphene oxide [1]. However, the separation of the sheets was incomplete due to the permanence of

the GR is confirmed by the disappearance of the characteristic 2 peak of GO 1 at aprox. 10o.

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Figure 1. X-ray diffractogram of graphite, graphene oxide (GO 1) and reduced graphene oxide (GR).

The x-ray diffraction pattern of graphite, graphene oxide (D) and reduced graphene oxide (GO D), in Figure 2, shows the characteristic peak of graphene oxide with a 2 peak at around 10 (peak 001) and almost total disappearance of the peak 002 of GO D and GR D according to literature [1]. The difference between GO 1 and GO D is the oxidation reaction time of graphite (about 1h for the GO 1 and 24h to GO D). These results showed a product with higher purity and better defined peak 001 for a longer oxidation.

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GR due to greater time of the reduction (30 minutes) instead of 10 minutes , respectively. These results were corroborated by analysis of x-ray photoelectron spectroscopic (XPS). Figure 5 shows the XPS spectrum for the sample of the mineral graphite used as starting material, with the overall and specific for C1s and O1s in detail lower. Figure 5 shows the graphite with the main peak of C1s at about 284.5 eV. This is the C-C bond with little contribution of other chemical environments at the surface[3]. A

Figure 2. X-ray diffractogram of graphite, graphene oxide (GO D) and reduced graphene oxide D (GRD).
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Figure 3. X-ray diffraction pattern of graphene oxide 1 (GO 1) and graphene oxide A (GO A).

A comparison between graphene oxides reduced at different times (Fig. 4) shows that the 001 peak, characteristic of graphene oxide disappears almost completely in GR and GR D.
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Figure 5. XPS overall spectrum for the mineral graphite (a), C1s (b) Figures 6A and B show the XPS spectra for oxidized graphite samples for 1 hour (GO 1) and 4 hours (GO D). The comparison of samples GO1 and GOD (Fig. 6A e B) shows a higher intensity of peak at 286,5 for GOD indicating the existence of a greater number of C-O bonds for the sample GOD because of the greater oxidation time.

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Figure 4. X-ray diffraction pattern of graphite, reduced graphite oxide 1 (GR) and reduced graphite oxide D (GRD).

However, for the GR is present the 002peak characteristic of graphite while in the GRD, this peak is absent. This indicates that the graphene oxide GRD was reduced more effectively than the

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Figure 7. XPS spectrum for a sample of oxidized graphite GO 1 hour (A) and GOD 4 hours (B). Minor detail: left (C1s) and right. (O1s). In Figure 7, the reduced sample presents a peak corresponding to C-O bonds much lower than in the oxidized one indicating that a longer time of reduction is necessary. The samples were cleaned with distilled water normally until neutral pH and the samples GO A1 and GO A2 (Fig. 8 A e B) are examples of the corrected washing need. GO A1 sample were washed until pH= 3,0 e GP A2, until pH= 1,0. As can be seen, the sample washed until pH= 3,0 presents minor quantity of impurities than the other washed until pH= 1,0. The number of extra bands in the GO A2 sample indicates a more necessity of washing.

Figure 8. XPS spectrum of Graphene oxide cleaned until different pH value (A)-GOA1(pH=3,0) e (B)GOA2 (pH=1,0). CONCLUSIONS The study demonstrated that the synthesis of graphene can be performed in a simple and reproducible manner. The methodology for synthesis of graphene - with some modifications of the method of Hummer to graphene oxide and its subsequent reduction with aluminum - were adequate for the production of oxidized and reduced samples. However, the oxidation time and the reduction must be optimized in order to obtain a more pure materials and more controlled properties. Although the x-ray diffraction is little used in the evaluation of graphene samples, this technique can be roughly used as a fast method to monitor the synthesis with posterior more accurate XPS analysis.
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ACKNOWLEDGEMENTS UFF-IQ-GQI, LDRX- Lab. multiusurios de difrao de raios x da UFF, LNLS-Laboratrio Nacional de Luz Sncroton proposta no. SXS-14393 and Laboratrio de XPS-RECAT-UFF. ______________________________________ REFERENCES 1 Geim, A.K., Graphene: status and prospects, Science 324(5934) 1530-1534. Wu, Z.; Ren W.; Gao, L.; Liu, B.; Jiang, C. e Cheng, H. Carbon 47 2009, 493-499.
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Krishnamoorthy,K., Veerapandian,M., Yun,K. e. Kim,S.J. The chemical and structural analysis of graphene oxide with different degrees of oxidation, Carbon 53 2013, 3849. 4 Yang, D, Velamakanni,A., Bozoklu, G., Park,S., Stoller, M., Piner,R.D., Stankovich,S., Jung,I.,

Field,D.A., Ventrice Jr., C.A. and Ruoff, R.S. Chemical analysis of graphene oxide lms after heat and chemical treatments by X-ray photoelectron and Micro-Raman spectroscopy, Carbon 47, 2009, 145152