Scalable production of graphene through liquid-phase exfoliation has been plagued by low yields. Although several recent studies have attempted to improve graphene exfoliation technology, the problem of separating colloidal nanosheets from unexfoliated parent material has received far less attention. Here we demonstrate a scalable method for improving nanosheet yield through a facile washing process. By probing the sedimentation of liquid-phase exfoliated slurries of graphene nanosheets and parent material, we found that a portion of exfoliated graphene is entrapped in the sediment, but can be recovered by repeatedly washing the slurry of nanosheet and parent material with additional solvent. We found this process to significantly increase the overall yield of graphene (graphene / parent material) and recover a roughly constant proportion of graphene with each wash. The cumulative amount of graphene recovered is only a function of total solvent volume. Moreover, we found this technique to be applicable to other types of nanosheets such as boron nitride nanosheets.
We demonstrate that UV degradation can remove polymeric dispersants from the surface of colloidal pristine graphene. In particular, we investigated the irradiation of polyvinylpyrrolidone (PVP)-dispersed graphene in water; this polymer has been established as a versatile nanosheet dispersant for a range of solvents, and it undergoes photo-oxidative degradation when exposed to UV light. We find that the molecular weight of PVP decreases with irradiation time and subsequently desorbs from the graphene surface. This causes gradual destabilization of graphene and agglomeration in water. The amount of adsorbed PVP decreases by approximately 45% after 4 h of irradiation in comparison with the non-irradiated dispersion. At this point, the majority of the stable graphene nanosheets flocculate, likely because of insufficient surface coverage as indicated by thermogravimetric analysis. Graphene aggregates were characterized as a function of irradiation time by optical microscopy, UV-vis spectroscopy, Raman spectroscopy, and conductivity measurements; the data suggest that the agglomerates maintain a graphene-like (rather than graphite-like) structure. The effect is also observed for another graphene dispersant (sapogenin), which suggests that our findings can be generalized to the broader class of photodegradable dispersants.
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