Structural evolution during the reduction of chemically derived graphene oxide


The excellent electrical, optical and mechanical properties of graphene have driven the search to find methods for its large-scale production, but established procedures (such as mechanical exfoliation or chemical vapour deposition) are not ideal for the manufacture of processable graphene sheets. An alternative method is the reduction of graphene oxide, a material that shares the same atomically thin structural framework as graphene, but bears oxygen-containing functional groups. Here we use molecular dynamics simulations to study the atomistic structure of progressively reduced graphene oxide. The chemical changes of oxygen-containing functional groups on the annealing of graphene oxide are elucidated and the simulations reveal the formation of highly stable carbonyl and ether groups that hinder its complete reduction to graphene. The calculations are supported by infrared and X-ray photoelectron spectroscopy measurements. Finally, more effective reduction treatments to improve the reduction of graphene oxide are proposed.

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Figure 1: Morphology of rGO and the structure of defects formed during thermal annealing.
Figure 2: Concentration of different functional groups in rGO.
Figure 3: Formation energies and structures of defects in rGO.
Figure 4: In-situ transmission infrared and XPS spectra of rGO.
Figure 5: Improvement in reduction efficiency on annealing of rGO in a hydrogen atmosphere.


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We acknowledge support from the National Science Foundation (NSF) and Nanoelectronic Research Initiative through the Brown University Materials Research Science and Engineering Center program and from the NSF through grants CMMI-0825771 and CMMI-0855853. We thank N. Medhekar, R. Grantab and I. Milas for discussions and suggestions. Computational support for this research was provided by the grant TG-DMR090098 from the TeraGrid advanced support program and the Center for Computation and Visualization at Brown University. M.C. and C.M. acknowledge financial support from the Jacobs Chair Funds at Rutgers University and an NSF CAREER Award (ECS 0543867). The work at University of Texas Dallas was supported by the SWAN-NRI program and Texas Instruments.

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V.B.S. and M.C. conceived the project, A.B. and V.B.S. conducted the MD simulations and first-principles calculations with input from C.M. and M.C., M.A and Y.C. performed the FTIR spectroscopy measurements and analysis, M.C., C.M. and V.B.S. wrote the manuscript with input from Y.C. and M.A. All of the authors read and approved the contents of the manuscript prior to submission. A.B. and C.M. contributed equally to this work.

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Correspondence to Vivek B. Shenoy.

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Bagri, A., Mattevi, C., Acik, M. et al. Structural evolution during the reduction of chemically derived graphene oxide. Nature Chem 2, 581–587 (2010).

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