Graphene and titanium based semiconductors in photocatalytic hydrogen and oxygen generation and hydrogenation of organics also in membrane reactors

Dottorata di Ricerca in"Ingegneria Chimica dei Materiali" Scuola di Dottorata "Pitagora" in Scienze Ingegneristiche, Ciclo XXVI, a.a.2012-2013The development of graphene (G)-based materials as photocatalysts has become in the last years of high interest due to their sustainability and flexibility in the modification and design, particularly in the field of photocatalytic generation of hydrogen. Carbon based materials are sustainable when they are derived from renewable biomass feedstocks. G is a versatile material allowing different modification strategies to improve its activity. Thus, the present thesis reports that inserting heteroatoms, adding semiconductors or changing the layers size, the activity of the materials prepared can be improved for different applications. Sun light is one of major renewable energy resource. The use of light as driving force for chemical reactions has attracted much attention of organic chemists. Heterogeneous photocatalysis is a discipline which includes a large variety of reactions, in particular hydrogen (considered the perfect renewable energy source in the future) and oxygen generation from water and hydrogenation of multiple bonds are the target of this PhD thesis. Photocatalytic reductions represent an alternative to conventional catalytic hydrogenation and it represent a more sustainable method to synthesize organic compounds under mild conditions in the presence of affordable photocatalysts. Photocatalytic processes in membrane reactors represent a technology of great scientific interest because it allows chemical reactions and separation processes to be accomplished in one step, which in turn results in lower processing cost and minimum environmental impact. The preparation and characterization of G-based semiconductors has been carried out in the first part of the Thesis and their photocatalytic activity for hydrogen and oxygen generation from water was determined in the second part. Graphite was oxidized to graphene oxide (GO) and its photocatalytic activity for hydrogen generation from water/methanol mixtures with visible or solar light was enhanced by the presence of dyes, in the absence of any noble metal. The most efficient tested photocatalyst was the one containing a tris(2,2-bipyridyl) ruthenium(II) complex incorporated in the interlayer spaces of a few layers of GO platelets with a moderate degree of oxidation. This photocatalyst was two orders of magnitude more efficient than a titania based photocatalyst containing Au, when the reaction is performed under 532 nm laser as excitation light. Doping G with nitrogen by pyrolysis of chitosan leads to a material that behaves as a semiconductor and exhibits high efficiency for the photocatalytic generation of hydrogen from water-methanol mixtures with similar efficiency using UV or visible light. This similar photocatalytic activity wis due to the fact that, in contrast to GO, N-doped G exhibits an almost “neutral” absorption spectrum. 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. Furthermore, N-doped G was able to generate hydrogen also upon illumination of simulated sunlight. The use of G as co-catalyst of metal oxides semiconductors to enhance their photocatalytic activity has been extensively reported. Using alginate, a natural polysaccharide from algae, simultaneously as G precursor and as ceria nanoparticles template agent, a series of materials consisting of highly crystalline ceria nanoparticles embedded on a few layers G matrix has been prepared. Varying the weight percentage of ceria/alginate and the pyrolysis temperature, it was possible to prepare a ceria/G photocatalyst that exhibits about three times higher photocatalytic activity for water oxidation to oxygen than commercial ceria. Pyrolysis at 900 °C under inert atmosphere of alginate 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 leading to G quantum dots (GQDs). Accordingly, the emission intensity of these GQDs increases along the number of laser shots, the maximum emission intensity appearing at about 500 nm in the visible region increasing in intensity 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. During the second part of the present thesis the photocatalytic hydrogenation of acetophenone by using titanium based semiconductors in batch and membrane reactors under UV and visible light has been studied. Different photocatalytic tests have been performed using ethanol or water and formic acid in a batch reactor in order to optimize the reaction parameters before to be applied in membrane reactors with different substrate addition mode. The use of a membrane reactor system for the photocatalytic hydrogenation of acetophenone in water solution with formic acid as hydrogen and electron donor was found to improve the efficiency of the photocatalytic system with respect to the use of batch reactor. The most efficient system for photocatalytic hydrogenation of acetophenone in terms of productivity, amount of phenylethanol produced and extraction of desired product was found to be the membrane reactor in which acetophenone was used as both organic phase and substrate. The presence of palladium enhances the visible light photocatalytic activity of TiO2 photocatalyst, that is not active alone. The productivity by using Pd/TiO2 photocatalyst under visible light increases five times more than using TiO2 under UV lightUniversità della Calabri