Controlled Reduction of Graphene Oxide Using Sulfuric Acid.

Sulfuric acid under different concentrations and with the addition of SO3 (fuming sulfuric acid) was studied as a reducing agent for the production of reduced graphene oxide (RGO). Three concentrations of sulfuric acid (1.5, 5, and 12 M), as well as 12 M with 30% SO3, were used. The reduction of graphene oxide increased with H2SO4 concentration as observed by Fourier-transformed infrared spectroscopy and X-ray photoelectron spectroscopy. It was observed that GO lost primarily epoxide functional groups from 40.4 to 9.7% and obtaining 69.8% carbon when using 12 M H2SO4, without leaving sulfur doping. Additionally, the appearance of hexagonal domain structures observed in transmission electron microscopy and analyzed by selected area electron diffraction patterns confirmed the improvement in graphitization. Although the addition of SO3 in H2SO4 improved the GO reduction with 74% carbon, as measured by XPS, the use of SO3 introduced sulfur doping of 1.3%. RGO produced with sulfuric acid was compared with a sample obtained via ultraviolet (UV) irradiation, a very common reduction route, by observing that the RGO produced with sulfuric acid had a higher C/O ratio than the material reduced by UV irradiation. This work showed that sulfuric acid can be used as a single-step reducing agent for RGO without sulfur contamination.

Effect of UV radiation on the structure of graphene oxide in water and its impact on cytotoxicity and As(III) adsorption.

Graphene oxide (GO) is widely used in different applications, however once released into the environment it can change its structure and affect the transport of important contaminants such as arsenic. In this work we show that UV radiation, even in the range of 28-74 µW/cm2 of irradiance up to 120 h of exposure, can induce important changes in the structure of graphene oxide, by eliminating -OH and CO functional groups. This reduction affected the stability of graphene oxide in water by decreasing its zeta potential from -41 to -37 mV at pH=7 with the increase of the exposure time. Our results showed that after 24 and 120 h of UV exposure, As(III) adsorption capacity decreased from 5 mg/g to 4.7 and 3.8 mg/g, respectively, suggesting a lower capacity to transport contaminants with time. Computer modelling showed that even a degraded GO structure can have an interaction energy of 223.84 kJ/mol with H3AsO3. Furthermore, we observed that the cytotoxicity of graphene oxide changed after being irradiated at 74 µW/cm2 for 120 h, showing 20% more cell viability compared to as-produced GO. Our results stress the importance of considering the microstructural and compositional changes that GO undergoes even under low irradiance and short periods, when studying its fate and behavior in the environment and possible applications in water treatment.