Reduction of superintegrable systems: the anisotropic harmonic oscillator

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

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

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

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

HMF Selective Photo-oxidation in Aqueous Suspension of Both Bare and H2O2 Treated Carbon Nitride Carried out in a Solar Pilot Plant

HMF Selective Photo-oxidation in Aqueous Suspension of Both Bare and H2O2 Treated Carbon Nitride Carried out in a Solar Pilot Plan

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

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

Selective photocatalytic oxidation of 5-hydroxymethyl-2-furfural in aqueous suspension of polymeric carbon nitride and its adduct with H2O2in a solar pilot plant

This work reports a study on the reactivity of polymeric carbon nitride (PCN) and PCN-H2O2adduct samples for sunlight photocatalytic selective oxidation reactions. The characterization of these materials was reported in a previous paper where the reactivity towards the partial oxidation of 5-hydroxymethylfurfural (HMF) was studied by using two different laboratory scale photoreactors; one irradiated by UV lamps and the other one by natural sunlight. In the present study it has been confirmed the effectiveness of these C3N4based materials for the selective partial oxidation of HMF to FDC (2,5-furandicarboxaldehyde) in aqueous medium in a pilot plant photoreactor irradiated by natural sunlight. The reactivity results and, in particular, the selectivity to FDC formation have been very encouraging, mostly by considering that the reaction was carried out in water. Moreover, they are comparable with those obtained in the laboratory scale photoreactors irradiated by both UV lamps and natural sunlight. Interestingly, the pristine PCN sample has shown a higher HMF conversion with respect to that of the PCN-H2O2adduct, but the last one is more selective to the FDC formation. A kinetic study indicates that the pseudo-first-order rate constant of HMF oxidation is higher in the case of pristine photocatalyst and that the equilibrium adsorption constants of HMF is higher in the case of PCN-H2O2adduct catalyst. Finally, the partial oxidation of two aromatic alcohols, i.e. benzyl alcohol (BA) and 4-methoxy benzyl alcohol (4-MBA) to benzaldehyde (BAL) and 4-methoxy benzaldehyde (4-MBAL), respectively, has also been studied

Selective photocatalytic oxidation of 5-hydroxymethyl-2-furfural in aqueous suspension of polymeric carbon nitride and its adduct with H2O2 in a solar pilot plant

This work reports a study on the reactivity of polymeric carbon nitride (PCN) and PCN-H2O2 adduct samples for sunlight photocatalytic selective oxidation reactions. The characterization of these materials was reported in a previous paper where the reactivity towards the partial oxidation of 5-hydroxymethylfurfural (HMF) was studied by using two different laboratory scale photoreactors; one irradiated by UV lamps and the other one by natural sunlight. In the present study it has been confirmed the effectiveness of these C3N4 based materials for the selective partial oxidation of HMF to FDC (2,5-furandicarboxaldehyde) in aqueous medium in a pilot plant photoreactor irradiated by natural sunlight. The reactivity results and, in particular, the selectivity to FDC formation have been very encouraging, mostly by considering that the reaction was carried out in water. Moreover, they are comparable with those obtained in the laboratory scale photoreactors irradiated by both UV lamps and natural sunlight. Interestingly, the pristine PCN sample has shown a higher HMF conversion with respect to that of the PCN-H2O2 adduct, but the last one is more selective to the FDC formation. A kinetic study indicates that the pseudo-first-order rate constant of HMF oxidation is higher in the case of pristine photocatalyst and that the equilibrium adsorption constants of HMF is higher in the case of PCN-H2O2 adduct catalyst. Finally, the partial oxidation of two aromatic alcohols, i.e. benzyl alcohol (BA) and 4-methoxy benzyl alcohol (4-MBA) to benzaldehyde (BAL) and 4-methoxy benzaldehyde (4-MBAL), respectively, has also been studied.Authors wish to thank CIEMAT-PSA and European Commission for the funding in the framework of the EU-DG RTD’s project: SFERA II contract no. 312643. University of Oviedo acknowledges the financial support from Spanish MINECO (MAT2013-40950-R, CTQ2014-52956-C3-1-R and MAT2016-78155-C2-1-R) and Gobierno del Principado de Asturias (GRUPIN14-060, GRUPIN14-078 and Severo Ochoa PhD grant BP-14-029 to MI). IK thanks for the support the Ministry of Education and Science of the Russian Federation (grant no. 4.9722.2017/8.9).Peer reviewe

Valorisation of microalga Chlorella sp. into furans in the presence of Nb2O5 catalysts

Despite the interest in niobia-based catalysts and the importance of biomass valorisation, studies on these catalysts typically utilize model substrates like simple sugars. In this study, a series of niobium oxide-based catalysts was prepared for the application in aqueous phase catalytic conversion of sugars extracted from Chlorella sp. microalga into value-added furans. The solid catalysts were firstly characterized by various techniques including X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), Raman and X-ray photoelectron (XPS) spectroscopy as well as low-temperature N2 physisorption. Moreover, the acidity of the catalysts was assessed by using the temperature-programmed NH3 desorption (NH3-TPD), by titration of water suspended catalyst with NaOH solution, and by P-bearing molecular probes loaded catalysts through 31P and 1H solid-state nuclear magnetic resonance (NMR) techniques. Herein, we focused on the catalytic transformation of Chlorella sp. and glucose solution as model molecule into furans. The best Nb2O5 catalysts for valorizing Chlorella sp. into furans exhibited a larger number of Brønsted acid sites, achieving conversion yields to 5-HMF and furfural of ca. 20–22 % with respect to the extracted sugars from algae. The results showed a discernible dependence of the conversion yields to 5-HMF and furfural on catalyst acidity, specific surface area, and the presence of the Brønsted acid sites. Conversely, when using the glucose solution as substrate is concerning, the highest yield to 5-HMF was reached by using a catalyst that showed also the presence of Lewis acid sites. A systematic investigation of the structure–activity relationships in niobium oxide application for aqueous phase dehydration using real biomass substrates to obtain furanic derivatives has not been documented thus far. Therefore, the current research is significant as it demonstrates the feasibility of transforming the carbohydrate content in microalgal biomass into furans by identifying the best catalyst to use