Photodegradation of dispersants in colloidal suspensions of pristine graphene

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.