Jiao-Jing Shao

On the origin of the stability of graphene oxide membranes in water

Graphene oxide (GO) films are known to be highly stable in water and this property has made their use in membrane applications in solution possible. However, this state of affairs is somewhat counterintuitive because GO sheets become negatively charged on hydration and the membrane should disintegrate owing to electrostatic repulsion. We have now discovered a long-overlooked reason behind this apparent contradiction. Our findings show that neat GO membranes do, indeed, readily disintegrate in water, but the films become stable if they are crosslinked by multivalent cationic metal contaminants. Such metal contaminants can be introduced unintentionally during the synthesis and processing of GO, most notably on filtration with anodized aluminium oxide filter discs that corrode to release significant amounts of aluminium ions. This finding has wide implications in interpreting the processing-structure-property relationships of GO and other lamellar membranes. We also discuss strategies to avoid and mitigate metal contamination and demonstrate that this effect can be exploited to synthesize new membrane materials.

Self‐Assembly of Graphene Oxide at Interfaces

Due to its amphiphilic property, graphene oxide (GO) can achieve a variety of nanostructures with different morphologies (for example membranes, hydrogel, crumpled particles, hollow spheres, sack-cargo particles, Pickering emulsions, and so on) by self-assembly. The self-assembly is mostly derived from the self-concentration of GO sheets at various interfaces, including liquid-air, liquid-liquid and liquid-solid interfaces. This paper gives a comprehensive review of these assembly phenomena of GO at the three types of interfaces, the derived interfacial self-assembly techniques, and the as-obtained assembled materials and their properties. The interfacial self-assembly of GO, enabled by its fantastic features including the amphiphilicity, the negatively charged nature, abundant oxygen-containing groups and two-dimensional flexibility, is highlighted as an easy and well-controlled strategy for the design and preparation of functionalized carbon materials, and the use of self-assembly for uniform hybridization is addressed for preparing hybrid carbon materials with various functions. A number of new exciting and potential applications are also presented for the assembled GO-based materials. This contribution concludes with some personal perspectives on future challenges before interfacial self-assembly may become a major strategy for the application-targeted design and preparation of functionalized carbon materials.

Graphene oxide assisted hydrothermal carbonization of carbon hydrates.

Hydrothermal carbonization (HTC) of biomass such as glucose and cellulose typically produces micrometer-sized carbon spheres that are insulating. Adding a very small amount of Graphene oxide (GO) to glucose (e.g., 1:800 weight ratio) can significantly alter the morphology of its HTC product, resulting in more conductive carbon materials with higher degree of carbonization. At low mass loading level of GO, HTC treatment results in dispersed carbon platelets of tens of nanometers in thickness, while at high mass loading levels, free-standing carbon monoliths are obtained. Control experiments with other carbon materials such as graphite, carbon nanotubes, carbon black, and reduced GO show that only GO has significant effect in promoting HTC conversion, likely due to its good water processability, amphiphilicity, and two-dimensional structure that may help to template the initially carbonized materials. GO offers an additional advantage in that its graphene product can act as an in situ heating element to enable further carbonization of the HTC products very rapidly upon microwave irradiation. Similar effect of GO is also observed for the HTC treatment of cellulose.

Graphene Emerges as a Versatile Template for Materials Preparation

Graphene and its derivatives are emerging as a class of novel but versatile templates for the controlled preparation and functionalization of materials. In this paper a conceptual review on graphene-based templates is given, highlighting their versatile roles in materials preparation. Graphene is capable of acting as a low-dimensional hard template, where its two-dimensional morphology directs the formation of novel nanostructures. Graphene oxide and other functionalized graphenes are amphiphilic and may be seen as soft templates for formatting the growth or inducing the controlled assembly of nanostructures. In addition, nanospaces in restacked graphene can be used for confining the growth of sheet-like nanostructures, and assemblies of interlinked graphenes can behave either as skeletons for the formation of composite materials or as sacrificial templates for novel materials with a controlled network structure. In summary, flexible graphene and its derivatives together with an increasing number of assembled structures show great potentials as templates for materials production. Many challenges remain, for example precise structural control of such novel templates and the removal of the non-functional remaining templates.

A wavy graphene/platinum hybrid with increased electroactivity for the methanol oxidation reaction

Two distinct graphene sheets, highly flat graphene and wavy graphene, were used as support materials for in situ nucleation and growth of platinum nanoparticles (Pt NPs) to synthesize graphene/Pt catalysts. The average size of Pt NPs on the wavy graphene sheets is around 2 nm and is smaller than those on the flat graphene sheets. The electrochemical activity of the two as-prepared catalysts towards methanol oxidation was investigated and compared with that of a commercial Pt/carbon black (Pt/C) catalyst, and electrochemical results showed that the wavy graphene/Pt catalyst possessed the best poison tolerance and comparable electrochemical surface area to the commercial Pt/C catalyst. The wavy microstructure is believed to be responsible for the stable dispensability of the as-prepared wavy graphene and the acquisition of small size Pt NPs, since the abundant ripples coming from the wavy microstructure effectively prevent the aggregation of the graphene sheets, and also act as barriers to prevent agglomeration of Pt NPs during their in situ nucleation and growth process. This work indicates that the microstructure of the supporting material plays a crucial role in the electrochemical performance of platinum-based catalysts.