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There is much current interest in developing graphene-based materials as photocatalysts, particularly in the field of solar fuels and the photocatalytic generation of hydrogen. Graphene is a versatile material allowing different modification strategies to improve its activity. Thus, in the present manuscript we report that, in contrast to the lack of photocatalytic activity of undoped graphene, nitrogen doping introduces UV- and visible-light activity for hydrogen evolution; the efficiency of the material depends on the preparation conditions. The N-doped graphene is obtained by pyrolysis under an inert atmosphere of natural chitosan, which is considered a biomass waste, followed by ultrasound exfoliation, without the need of oxidation and reconstitution. The main parameter controlling the residual amount of nitrogen and the resulting photocatalytic activity is the pyrolysis temperature that produces an optimal material when the thermal treatment is carried out at 900 °C. Due to the fact that, in contrast to graphene oxide, N-doped graphene exhibits an almost "neutral" absorption spectrum, the material exhibits photocatalytic activity upon UV- (355 nm) and visible-light (532 nm) irradiation, and is able to generate hydrogen upon simulated sunlight illumination.

Pyrolysis at 900 °C under an inert atmosphere of alginate, a natural widely available biopolymer, renders a graphitic carbon that upon ablation by exposure to a pulsed 532 nm laser (7 ns, 50 mJ pulse(-1)) in acetonitrile, water, and other solvents leads to the formation of multilayer graphitic quantum dots. The dimensions and the number of layers of these graphitic nanoparticles decrease along the number of laser pulses from 100 to 10 nm average and from multiple layers to few layers graphene (1-1.5 nm thickness), respectively, leading to graphene quantum dots (GQDs). Accordingly, the emission intensity of these GQDs increases appearing at about 500 nm in the visible region along the reduction of the particle size. Transient absorption spectroscopy has allowed detection of a transient signal decaying in the microsecond time scale that has been attributed to the charge separation state.

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