Heteroaggregation of Graphene Oxide with Minerals in Aqueous

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Heteroaggregation of Graphene Oxide with Minerals in Aqueous Phase Jian Zhao,†,‡ Feifei Liu,‡,§ Zhenyu Wang,*,†,‡ Xuesong Cao,† and Baoshan Xing*,‡ †

College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Marine Environment and Ecology, and Qingdao Collaborative Innovation Center of Marine Science and Technology, Ocean University of China, Qingdao 266100, China ‡ Stockbridge School of Agriculture, University of Massachusetts, Amherst, Massachusetts 01003, United States § Shandong Provincial Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Shandong University, Jinan, Shandong 250100, China S Supporting Information *

ABSTRACT: Upon release into waters, sediments, and soils, graphene oxide (GO) may interact with fine mineral particles. We investigated the heteroaggregation of GO with different minerals, including montmorillonite, kaolinite, and goethite, in aqueous phase. GO significantly enhanced the dispersion of positively charged goethite (>50%) via heteroaggregation, while there was no interaction between GO and negatively charged montmorillonite or kaolinite. Electrostatic attraction was the dominant force in the GO−goethite heteroaggregation (pH 4.0−8.5), and the dissolved Fe ions (1 μm, Figures 1 and SI S5) and F

DOI: 10.1021/es505605w Environ. Sci. Technol. XXXX, XXX, XXX−XXX

Article

Environmental Science & Technology

Figure 5. GO−goethite (Goe) heteroaggregation in the binary system. (A) SEM image of GO; (B) SEM image of GO−Goe heteroaggregate. The images in panels C and D are enlarged from panel B; (E, F) Possible configurations of GO−Goe heteroaggregate. In the binary system, the coverage could be formed by folding the GO sheets to cover (wrap) individual goethites (E) or goethite aggregate (F).

edges and Ag nanoparticles, GO sheets are mostly singlelayered, and the thickness (1.2 nm, Figure 1C) is much lower than the diameter of goethite particles (40 nm, SI Figure S5). The sheet is not thick enough to stably support the goethite particle; the sheet flat cover is a better and stable arrangement. As a result, the multilayered structure of GO−goethite complex was formed. This stable geometric match could inhibit desorption of GO from goethite, likely the cause for desorption hysteresis observed in Figure 4.

40−100 nm), indicating that these covered particles were the aggregates of goethite. TEM imaging further showed the multilayered structure of GO−goethite complexes (Figure 6B). Goethite particles could neutralize the negative charges on GO sheets and lower the interlayer charge repulsion. Therefore, the GO sheets are prone to be aggregated together. Moreover, the multilayered structure could be formed by (1) the sheet−sheet interaction (Figure 6C), or (2) folding from a single sheet (Figure 5E and F). However, we did not observe the edge− particle attachment between GO sheets and goethite particles using any of the above microscopic techniques. The edge− particle attachment has been reported by Zhou et al.,11 in which the heteroaggregation occurred between positively charged edges of montmorillonite and negatively charged Ag nanoparticles at low pH (4.0). Expectedly, this edge−particle interaction may be not stable enough between the edges of GO sheets and goethite particles. There are two possible explanations for this unstable configuration: (1) differing from the rigid structure of montmorillonite, the graphene sheet is flexible and apt to fold (SI Figure S5) or form crimps at the edge as shown in Figure 5A, which is supported by other studies;39,42 and (2) unlike the similar size of montmorillonite

4. ENVIRONMENTAL IMPLICATIONS Our results revealed that the electrostatic attraction was critical in the heteroaggregation between GO and positively charged minerals (e.g., goethite) at the tested solution pHs (4.0−8.5). GO had no interaction with the negatively charged minerals such as montmorillonite and kaolinite due to electrostatic repulsion. However, it is worth noting that for negatively charged biocolloids such as proteins, DNA, viruses, and bacteria, the interaction cannot be simply ignored because π−π interaction and hydrogen bonding may also play important roles by overcoming the electrostatic repulsion.43−46 GO sheets were able to irreversibly interact with goethite G

DOI: 10.1021/es505605w Environ. Sci. Technol. XXXX, XXX, XXX−XXX

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Environmental Science & Technology

(E. coli) was prevented.47 GO with two-dimensional structure exhibited different configuration with minerals from Ag nanoparticles, and the alteration of GO toxicity deserves further investigation.

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ASSOCIATED CONTENT

S Supporting Information *

Ten figures and two tables as noted in the text. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Authors

*Phone: +1 413 545 5212. E-mail: [email protected]. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This research was supported by NSFC (41403086, 41325013, 41120134004) and USDA-NIFA Hatch program (MAS 00475).

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REFERENCES

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Figure 6. AFM (A) and TEM (B) images of GO−goethite heteroaggregates. Panel A is the AFM image of GO in the presence of goethite. In panel A, the values indicated by red arrows are the heights of the GO wrinkles. Panel B is the TEM image of GO− goethite heteroaggregate. The possible scheme (multilayered structure) of GO−goethite in panel B is proposed in panel C.

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DOI: 10.1021/es505605w Environ. Sci. Technol. XXXX, XXX, XXX−XXX