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(3-Mercaptopropyl)trimethoxysilane assisted synthesis of macro- and mesoporous graphene aerogels exhibiting robust superhydrophobicity and exceptional thermal stability Shuai Zhou, Xiang Zhou, Wei Jiang, Tianhe Wang, Ning Zhang, Yue Lu, Liuhua Yu, and Zuozhu Yin Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.5b03179 • Publication Date (Web): 10 Jan 2016 Downloaded from http://pubs.acs.org on January 17, 2016

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Industrial & Engineering Chemistry Research

(3-Mercaptopropyl)trimethoxysilane

assisted

synthesis of macro- and mesoporous graphene aerogels exhibiting robust superhydrophobicity and exceptional thermal stability Shuai Zhou, Xiang Zhou, Wei Jiang*, Tianhe Wang*, Ning Zhang, Yue Lu, Liuhua Yu, Zuozhu Yin National Special Superfine Powder Engineering Research Center, Nanjing University of Science and Technology, Nanjing 210094, PR China

ACS Paragon Plus Environment

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ABSTRACT: Robust superhydrophobic and exceptionally thermostable graphene aerogels exhibiting a three-dimensional macro- and mesoporous structure have been synthesized through a (3-Mercaptopropyl)trimethoxysilane assisted two-step route with natural drying. The facile synthetic process not only guarantees their excellent performance but also greatly improves their practical production rate. The prepared graphene aerogels hold excellent superhydrophobicity, for which water contact angle exceeded 160 degrees, even after 20 ethanol washing-drying cycles. Furthermore, the self-assembly functionalized graphene sheets enhances the thermal stability of nanocomposites, due to the good dispersion of functionalized graphene sheets and the strong bonding between graphene sheets and polymer chains within the aerogels. The study implies a novel and practical methodology to efficiently fabricate three-dimensional composite materials with enhanced performances.


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1. Introduction Multi-dimensional graphene sheets have won unprecedented attentions as an exciting carbon nanomaterial in the most recent period, owing to their superior thermal stability, high Young’s modulus, excellent electronic properties and relatively economical advantages.1-4 One operable and simple route to maximize these outstanding features for large-scale applications is to efficiently incorporate polymeric substance into the graphene skeleton to fabricate the functional materials with high-performance.5-8 The trend of easy stack and re-agglomeration within graphene sheets result from the chemical inertness and the nano effect, making it difficult for the excellent performance of graphene in the composites to reflect to the greatest degree.9-12 Besides, the enhanced performance of the composites is mainly due to the formation of chemical bonds between the polymer and the graphene sheets, and the strength of the bond will further determine the extent of the performance enhancement.13-15 Multifunctional self-assembly technology and chemical modification have created an effective approach to overcome these problems.16-18 So far, different types of silane have been developed to act as multifunctional and cross-linking agents between graphene sheets and polymeric substrate to produce functionalized graphene aerogels (FGAs).19-22 However, to the best of our knowledge, the previously reported preparation process requires multi steps, such as self-assembly, high temperature treatment, lyophilisation and microwave radiation, thereby greatly limiting their practical production rate and increasing the cost of production.23-26 Furthermore, due to the tedious preparation process, it is hard to make FGAs to meet the expected performance and the demands of multifunction.


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Here we reported a (3-Mercaptopropyl)trimethoxysilane (MPS) assisted route to produce graphene aerogels, with robust superhydrophobicity and exceptional thermal stability, where a three-dimensional continuous macro- and mesoporous structure was constructed through a twostep synthesis process without lyophilisation. We defined the MPS functional graphene aerogels as MGAs to make it easier for description. The functionalized networks of the MGAs synergistically form a siloxane surface chemical composition and characteristic nano-micro substructures, contributing greatly to the enhancement of hydrophobicity. Moreover, the thermal stability of substrate is improved, resulting from the homogeneous dispersion of functionalized graphene (FGN) layers and polymer chains within the backbone network of MGAs. The MPS assisted self-assembly route displayed in this study may imply a novel and facile methodology for preparation of three-dimensional materials with enhanced performances. 2. Experimental section 2.1 Chemicals and materials All reagents were of analytical grade, and were used without purification. The deionized water was used to prepare solutions in all processes. (3-Mercaptopropyl)trimethoxysilane and hydrochloric acid (HCl) were purchased from Aladdin Chemistry Co. Ltd. Graphite oxide were obtained from Jcnano Co. Ltd, Nanjing, China. 2.2 Material synthesis MGAs were successfully synthesized with MPS assisted. 4 mL of MPS was mixed thoroughly with hydrochloric acid solution and simultaneously kept the PH between 4 and 5. Then, 20 mL of graphite oxide (GO) dispersion (3 mg mL−1) was mixed by ultrasonic dispersion with as-obtained MPS/ HCl solution. Next, the mixed solution was heated to 200 °C and held for


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8 h in a Teflon reactor to complete the hydrolysis, functionalization and self-assembly process. As depicted in Figure S1, under hydrothermal conditions, the high concentrations MPS produced a hydrolysis reaction, forming silanols with abundant hydroxyl functional group. As a result, the generated silanols produced hydration reaction with hydroxyl functional group on the surface of GO, thus completing the reduction process as well as creating space between graphene sheets by in situ growth of silicone polymer. And then the multi-functionalized graphene hydrogel (FGH) was

fabricated. Finally, the residual solvent was removed by natural drying way. The

experimental method and mechanism for the preparation of MGAs were schematically shown in Figure 1.

Figure 1. Schematic illustration of the fabrication process of the MGAs 2.3 Characterization Raman spectra were used to characterize the changes in carbon-based materials, and the recorded section was from 500 to 4000 cm-1 on a Labram Aramis. X-ray powder diffraction patterns of the products were collected on a Bruker D8-Advanced diffractometer in the 2θ range of 5°-80° with Cu Kα1 radiation (λ=0.15406 nm) operated at 40 kV and 40 mA. Fourier transform infrared (FTIR) spectra were recorded on a Bruker Vector 22 spectrometer. The size


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and morphology of the material were observed by a scanning electron microscope (ModelS4800). Transmission electron microscopy (TEM, Tecnai 12) was used to further confirm the microscopic structure and morphology. A Water contact angles (WCAs) instrument (SL200B, Solon Tech. Co. Ltd) was adopted to evaluate the WCAs. The enhanced thermal stability is verified by the thermogravimetric analyses (TGA) test with a Model TA2100, (TA Instruments, USA). The temperature range is controlled at 25-1000 °C under nitrogen atmosphere. The composition for the surface of materials was determined by X-ray photoelectron spectroscopy (XPS)with a PHI QUANTERA II spectrometer. 3. Results and discussion Figure 2 shows Raman spectra of GO and MGAs. Compared with GO in Figure 2a, the intensity of characteristic D band relative to and G band of MGAs (Figure 2b) is significantly higher, suggesting that GO has been converted into graphene and well-defined graphene plates are dispersed in the reticulated structure of MGAs.27-28

Figure 2. Raman spectra of (a) GO and (b) MGAs.


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Figure 3 shows the XRD diffraction patterns of GO and MGAs. As shown in Figure 3a, GO has a strong diffraction peak, which appears at 11° 29 For MGAs (Figure 3b), the diffused peak at 21° is attributed to the combined effect of graphene and polymer matrix30. Taking into account that the characteristic peak at 11° do not appear in the XRD patterns for MGAs, we can make sure that GO powder has been reduced to graphene sheets. These above results indicate that graphene sheets are successfully functionalized and the functionalized graphene plates were dispersed in the backbone network of aerogels. 31

Figure 3. XRD patterns for (a) GO and (b) MGAs. In order to determine the composition of GO and MGAs, X-ray photoelectron spectroscopy (XPS) are carried out. The C1s XPS spectra of (a) GO, (c) MGAs and XPS survey scans of (b) GO and (d) MGAs are displayed in Figure 4. As shown in the C1s XPS spectrum of Figure 4a, there are four divided peaks at 284.8, 285.8, 286.8 and 288.7 eV, which are attributed to the four typical oxygen-containing functional groups of GO, respectively.32 Most interestingly, the C1s peak of MGAs in Figure 4c, in addition to unoxidized graphite carbon, are completely disappeared, confirming that a large number of oxygenated functional groups are removed during the hydrothermal and assembly process. And a new characteristic peak at 283.5 eV,


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attributed to C-Si groups, is apparently the result of intercalated polymer chains and functionalized graphene layers in the reticulated structures of the MGAs.33-34 Compared with the spectrum of GO in Figure 4b, the significantly increased intensities in S2s, S2p, Si2s and Si2p peaks of MGAs are presented in Figure 4d, suggesting the formed polymer chains are successfully attached to the graphene layers within the MGAs structure,35-36 further confirming that graphite oxide was converted into functionalized graphene in the self-assembly process.

Figure 4. C1s XPS spectra of (a) GO, (c) MGAs and XPS survey scans of (b) GO and (d) MGAs. Characteristic FT-IR spectra of GO and MGAs are shown in Figure 5. As shown in Figure 5a, GO has four strong peaks at 3205, 1714, 1615, and 1046 cm−1, which are corresponding with O−H stretching, C=O stretching, C=C stretching, and alkoxy C−O stretching, respectively.37


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After functionalization with MPS, it is clearly found in Figure 5b for MGAs that the intensity of these peaks are significantly reduced, further indicating that the hydrothermal process with MPS ensures graphite oxide to convert into graphene. Simultaneously, the peak at 2930 cm-1, belonging to asymmetric vibration of -CH2- groups in the polymer chain, is also found in Figure 5b, demonstrating that the formed polymer chain has been bonded with the surface of graphene sheets. Furthermore, the peaks at 799, 1003, 1084 and 1241 cm-1, which are typical of the Si-O, further give strong evidence to verify the successful functionalization of siloxane within the MGAs.38 Obviously, the peak at 2549 cm-1 resulting from the stretching vibrations of S-H, further confirms the structure of the functionalized composite networks.39

Figure 5. FTIR spectra for (a) GO and (b) MGAs Figure 6 shows the typical micrographs of MGAs. As shown in Figure 6a, MGAs has typical macroporous structures, for which pore sizes are evenly distributed in the range of 1-5 um. In Figure 6b, the SEM image with high magnification exhibits highly wrinkled graphene surfaces, chain-like and pie-like polysiloxane nanoparticles, incorporated into reticulated substructure. The generated polysiloxane particles with different sizes result from that the intense hydrolysis process with high concentrations MPS. It is believed that the formed polymer chain


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with different sizes may provided key roles in the reduction and self-assembly of graphene sheets within the backbone network of the MGAs, thus allowing macro- and mesoporous structures to be fabricated. Furthermore, the TEM image of MGAs (Figure 6c) shows mesoporous structures (with sized below 50 nm), allowing the MGAs to form characteristic nano- and micro substructures. As shown in Figure S2, there are mesopores distributed (with sized below 50 nm) in the pore-diameter distributions of MGAs, corresponding with the TEM image with high magnification. The high concentrations MPS and hydrothermal process can play a positive role in the hydrolysis reaction and make the hydrolysis and polycondensation process more rapid and violent. It is likely that the formed silicone polymer particles in nanoscale presents as a sloppy and porous structure and acts as a spacer in graphene sheets, thereby leading to the building of interesting mesoporous structure accompanied by the typical self-assembly of graphene sheets. An important outcome of the particulate incorporation brought benefits as to increasing the surface roughness of aerogels as well as rendering the material with excellent superhydrophobicity and exceptional thermal stability.

Figure 6. (a, b) SEM images with different magnifications for MGAs, (c)TEM image for MGAs. As known to all, the wettability of a solid surface depends on two factors: its surface chemical composition and its microstructure.40 Due to oxygen-containing functional groups, GO


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is naturally hydrophilic, as shown in Figure 7a. With the large number of oxygen-containing group removed, the WCA of RGO reaches 104 degrees, which is still far lower than that of MGAs. Surprisingly, compared with GO, RGO and other functionalized graphene aerogels MGAs (Figure 7a,b) display the extraordinary hydrophobicity, where water contact angle exceeds 160 degrees (even after 20 ethanol washing-drying cycles), confirming the excellent superhydrophobicity and stability.41-44 The excellent superhydrophobicity of graphene aerogels may be attributed to two factors. On the one hand, under hydrothermal conditions, the MPS produced a hydrolysis reaction, forming silanols with abundant hydroxyl functional group. As a result, the generated silanols produced hydration reaction with hydroxyl functional group on the surface of graphite oxide, thus removing the hydrophilic oxygen-containing functional groups as well as forming hydrophobic silicone polymer attached to the backbones of graphene aerogels. On the other hand, the very low surface energy derived from the in situ growth of silicone polymer, the nanoscale roughness from silicone polymer and graphene plates, as well as the large number of macropores existed, synergistically contributed to the satisfactory results.

Figure 7. Water contact angles of (a) GO, RGO and MGAs, (b) Photographs of water contact angle tests of MGAs after 20 ethanol washing-drying cycles.


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In order to better verify the enhanced thermal stability, we conducted the TGA test for GO and MGAs under the same conditions. From the Figure 8a, GO below 100 °C began to have much of the weight loss, caused by the released free water molecules from the hydrophilic material itself. The main weight loss of GO lay within the range of 150-900 °C, in the process, the oxygen-containing functional groups were completely decomposed and removed. However, as shown in the curve of MGAs, there were no significant weight loss below 250°C, which reason was that among the hydrothermal process, the unstable oxygen-containing functional groups were removed, and simultaneously a more stable functionalized graphene threedimensional structure with the polymer chain bonded was fabricated. Consistent with the previously reported results, the embedded polymer chain greatly enhanced the thermal stability of MGAs in a low temperature region.45-46 The homogeneous dispersion of functionalized graphene sheets and the incorporation of polysiloxane chain within the MGAs played crucial roles in improving the thermal stability of substrate. After the self-assembly and reduction process, there were numerous generated graphene and polysilanes presented in the threedimensional structure of the aerogels, for which thermal stability was far higher than the graphite oxide. Taking into account that a large number of unstable oxygen-containing groups had been removed, thereby the thermal stability of formed functionalized graphene sheets was much higher than that of the graphite oxide. Moreover, functionalized graphene plates and other sheetlike materials had a certain similarity in performance, and created a “tortuous path” effect, which served as ramparts to hinder the escape of degradation products from the backbone network and simultaneously propel the building of a relatively stable three-dimensional structure.30, 47 When it came to the char residues at 1000 °C, MGAs maintained 43 wt% residues, lower than that of


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pure graphene, which can be attributed to the incorporated polymer chain and the formed functionalized graphene nanosheets within the aerogels composites. 45

Figure 8. TGA curves of (b) GO and MGAs. 4. Conclusion In conclusion, we have created graphene aerogels with robust superhydrophobicity and exceptional thermal stability through a (3-Mercaptopropyl)trimethoxysilane assisted two-step route during the self-assembly process. A three-dimensional macro- and mesoporous structure was constructed. The facile synthetic process not only ensured the excellent performance of the graphene aerogels but also greatly improved their practical production rate. The water contact angle of graphene aerogels exceeded 160 degrees, and the superhydrophobicity was maintained even after 20 ethanol washing-drying cycles. The exceptional thermal stability originated from the orderly stack of functionalized graphene plates and the bonding between graphene sheets and polymer chains within the aerogels, which presented the novelty of our study. It is believed that this study can provide a novel and practical methodology to efficiently prepare three-dimensional composite materials with enhanced performances.


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AUTHOR INFORMATION Corresponding Author *Tel: +86 25 84315042. Fax: +86 25 84315042. E-mail: [email protected] (Wei Jang) or [email protected] (Tianhe Wang). Notes The authors declare no competing financial interest. Acknowledgements This work was financially supported by the Natural Science Foundation of China (Project No. 50972060), the Fundamental Research Funds of the Central University (No. 30920130112003) and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD). Supporting Information Schematic illustration of the hydrolysis and self-polymerization process of the MPS (Figure S1), pore-diameter distributions of MGAs (Figure S2).


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and Mesoporous Graphene Aerogels Exhibiting ... - ACS Publications

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