33 research outputs found

    Reduction of superintegrable systems: the anisotropic harmonic oscillator

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    We introduce a new 2N--parametric family of maximally superintegrable systems in N dimensions, obtained as a reduction of an anisotropic harmonic oscillator in a 2N--dimensional configuration space. These systems possess closed bounded orbits and integrals of motion which are polynomial in the momenta. They generalize known examples of superintegrable models in the Euclidean plane.Comment: 6 pages. Version accepted in Physical Review

    Selective Photocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxaldehyde by Polymeric C3N4-H2O2 Adduct

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    Selective Photocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxaldehyde by Polymeric C3N4-H2O2 Adduc

    Effect of Substituents on Partial Photocatalytic Oxidation of Aromatic Alcohols Assisted by Polymeric C3N4

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    In the present work we scrutinize the effect of substituents in the phenyl ring of the benzyl alcohol on its photo-oxidation to the corresponding benzaldehyde driven by polymeric carbon nitride photocatalyst in aqueous medium. It has been established that electron donating (ED) substituents in para- and ortho-position with respect to the CH2OH-group promote the reactivity of the substrate without compromising the selectivity towards benzaldehyde formation, maintaining it in the range of 84–98 %, if compared to the unsubstituted molecule. The same observation is true for meta-substituted benzyl alcohol with an electron withdrawing (EW) group. On the other hand, the presence of ED-group in meta-position or EW-group in para-position with respect to the CH2OH-group reduces the reactivity as well as the selectivity towards the aldehyde production, resulting in the values of selectivity ranging from 40 to 80 %. Quantum chemical calculations have allowed to establish that the reactivity correlates with the positive charge on the benzylic carbon in benzyl alcohol cation intermediate, while the selectivity, most probably, is conditioned by a negative charge on the carbon atoms in the phenyl ring being a target for an electrophile attack. The modification of the polymeric C3N4 photocatalyst with H2O2 reduces the unselective benzyl alcohol oxidation, thus favouring the higher selectivity towards benzaldehyde production

    Photoelectrochemical and EPR features of polymeric C3N4 and O-modified C3N4 employed for selective photocatalytic oxidation of alcohols to aldehydes

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    Four different C 3 N 4 specimens have been prepared, a bulk one (MCN), a thermally etched (MCN-TE), a solid prepared by hydrothermally treating MCN with H 2 O 2 (MCN-H 2 O 2 ) and a polymeric carbon nitride-hydrogen peroxide adduct (MCN-TE-H 2 O 2 ). The principal aim of this work was to correlate the capability of the prepared material to generate reactive oxygen species (ROS), under irradiation, with their photocatalytic activities in terms of conversion and selectivity for partial oxidation reactions. Photoelectrochemical studies revealed that MCN-TE represented the best material in terms of photoconductivity, whereas MCN-H 2 O 2 was defective and evidenced a poor mobility of carriers. EPR studies showed a maximum generation of reactive oxygen species irradiating the MCN-TE sample. The photocatalytic activity of these materials in the selective oxidation of three different alcohols to the corresponding aldehydes, both under UV and natural solar light, showed that the highest conversion was obtained in the presence of the MCN-TE sample, whereas the most selective one was MCN-TE-H 2 O 2 . Under solar light irradiation the performances of the powders were generally better than those under UV light. The characterization of the C 3 N 4 -based materials well justified their photocatalytic activity. The pristine C 3 N 4 materials were more active but less selective than those prepared in the presence of H 2 O 2

    Selective photocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxaldehyde by polymeric carbon nitride-hydrogen peroxide adduct

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    Polymeric carbon nitride-hydrogen peroxide adduct (PCN-H2O2) has been prepared, thoroughly characterised and its application for selective photocatalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxaldehyde (FDC) in aqueous suspension has been studied. The PCN-H2O2adduct is stable in aqueous suspension under UV and solar irradiation up to 100 \uc2\ub0C. It is also stable up to 200 \uc2\ub0C if heated in air, while at temperatures close to 300 \uc2\ub0C its decomposition takes place. Based on the obtained characterisation data it has been proposed that H2O2attaches to the non-polymerised carbon nitride species and to the heptazine nitrogen atoms, thus producing strong hydrogen bonding within the PCN-H2O2adduct. The blockage of the surface amino-groups in PCN-H2O2by H2O2hinders the interaction of HMF with these sites, which are responsible for unselective substrate conversion. PCN-H2O2, although being less active, possesses a superior selectivity in natural solar light assisted oxidation of HMF to FDC reaching 80% with respect to its thermally etched PCN counterpart, which gives rise to a 40\ue2\u80\u9350% selectivity. We believe that the exceptional performance of the applied photocatalyst in the selective photocatalytic conversion of HMF to a high added value FDC in a green solvent under natural illumination makes a significant contribution to the development of environmentally friendly technologies for biomass valorisation
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