Elsevier

Carbon

Volume 182, September 2021, Pages 366-372
Carbon

Self-assembled graphene oxide-based paper/hollow sphere hybrid with strong bonding strength

https://doi.org/10.1016/j.carbon.2021.06.034Get rights and content

Abstract

Graphene-based nanomaterials possess broad applications because of their excellent multi-functional properties. In this work, a facile self-assembling method was presented for preparing one kind of graphene oxide-based paper/hollow microspheres hybrid. It was found that most of the hollow microspheres can strongly anchored on the surface of graphene oxide paper (GOP) by an in-situ scanning electron microscope peeling testing combining with molecular dynamics (MD) simulation. In addition, the uniform distribution of hollow microspheres on the surface of GOP cannot only provide a better surface wettability, but also can effectively improve the interfacial stress-transfer capability between such hybrid and polymer matrix. Our work provides a guidance for the structural designs of graphene-based nanomaterials and broaden their applications.

Introduction

Graphene oxide (GO) is the product of graphite powders through chemical oxidation methods [[1], [2], [3]]. This kind of typical two-dimensional nanomaterial possesses a series of excellent mechanical, optical and chemical properties, etc., showing greatly potential applications in various high-tech fields [4,5]. In particular, compared with graphene, GO is amphiphilic with an edge-to-center distribution of hydrophilic and hydrophobic domains, owing to the active functional groups on the surfaces of GO [6], which makes it easier to assemble into various GO-based nanomaterials with unique structures and multi-functional properties, including spheres, fibers, films/papers and blocks [[7], [8], [9], [10], [11], [12], [13], [14], [15]].

Recently, much interest has been focused on the GO hollow spheres (GHSs) due to their broad applications in catalyst carriers, energy storage devices, and electromagnetic devices, etc [[16], [17], [18], [19], [20], [21], [22], [23]]. So far, various methods have been developed to produce the GHSs, such as arc plasma method, hydrothermal synthesis, templating method and chemical vapor deposition (CVD) method [15,20,[24], [25], [26], [27], [28], [29]]. For examples, Mehraban et al. [24] successfully prepared carbon spheres with diameters ranging from 650 to 1000 nm in the presence of cobalt silicon-mesoporous aluminum silicate by CVD using C2H2 as the carbon source at 850 °C. Yoon et al. [20] prepared multi-layer graphene spheres using nickel nanoparticles as template by directional carburizing. Nevertheless, it has been pointed out that the GHSs cannot be directly utilized in actual applications due to their small size. Therefore, some researchers tried to assemble these GHSs onto other macro-scale nanomaterials, such as films and porous blocks [[30], [31], [32]]. However, the cluster of GHSs and the weak interfacial bonding between GHSs and nanomaterials is always an issue.

In this study, we proposed a facile self-assembling method for preparing one kind of novel GOP/GHSs hybrid (GGH), by which the GHSs can be uniformly distributed on the surface of GOP. The bonding strength between individual GHS and GOP was quantified for the first time, by an in-situ scanning electron microscope (SEM) peeling testing. Meanwhile, a molecular dynamics (MD) simulation was performed to study the peeling process from molecular level and reveal potential mechanical enhancement and failure mechanisms. Then, a GGH/polydimethylsiloxane (PDMS) laminated nanocomposite was designed and prepared. It was found that the GHSs at the interface between GOP and PDMS matrix can effectively improve the in-plane tensile mechanical properties of such nanocomposite. This work is helpful in understanding the mechanical behaviors of GO-based nanomaterials and their nanocomposites.

Section snippets

Materials

The graphite (99.95%, 2000 mesh), KMnO4, P2O5, H2SO4, K2S2O8, H2O2 and HCl were purchased from Macklin (Shanghai, China) Co., Ltd. The PDMS was purchased from Trademark of Dow. The polyvinylidene fluoride (PVDF) membrane with a pore size of 0.65 μm was purchased from Merck Millipore (Germany) Co., Ltd. The GO was synthesized from pure natural graphite by improved Hummers’ method [33,34]. The obtained GO was dispersed in water, ultrasonic for 1 h, and dried in a vacuum drying oven at 50 °C for

Structure and self-assembling of GGH

With using this self-assembling method, the GHSs are uniformly distributed on the surface of GOP and the sphericity morphology of GHSs are very regular (Fig. 1c and d). The size of GHSs conforms to typical normal distribution (Fig. 1e), and the distribution of the distance d between GHSs is presented in Fig. S2. When the electron beam is focused on a single GHS, an interesting phenomenon can be observed, by which the hollow structure with thin shell can be realized (Fig. 1f). From the view of

Conclusion

In this study, a facile solution method was developed to self-assemble the novel GGH. An in-situ SEM peeling testing was employed to investigate the bonding property between GHSs and GOP, and the peeling strength values for two samples were measured to be 38.5 MPa and 23.9 MPa, respectively. Meanwhile, the peeling failures of GHSs with strong and weak interface adhesions were investigated by the MD simulation from molecular level. On the other hand, it was found that the GHSs can effectively

CRediT authorship contribution statement

Yue Zhao: Conceptualization, Investigation, Data curation, Visualization, Writing – original draft. Fan Wu: Methodology, Software, Investigation. Yifan Zhao: Software. Ben Jiang: Resources. Linlin Miao: Resources. Junjiao Li: Resources. Chao Sui: Supervision, Resources. Huifeng Tan: Conceptualization, Project administration, Supervision, Funding acquisition, Resources. Chao Wang: Conceptualization, Supervision, Writing – review & editing, Resources.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Grant No. 11872164, 51702064). Thanks to Professor Daqing Wei, Engineer Qing Du, Engineer Yongchun Zou, and Senior Engineer Shu Guo (Center for Analysis, Measurement and Computing, Harbin Institute of Technology) for their experimental cooperation in nanomechanics analysis and in-situ testing.

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