Eco-Friendly 1,3-Dipolar Cycloaddition Reactions on Graphene Quantum Dots in Natural Deep Eutectic Solvent

Due to their outstanding physicochemical properties, the next generation of the graphene family-graphene quantum dots (GQDs)-are at the cutting edge of nanotechnology development. GQDs generally possess many hydrophilic functionalities which allow their dispersibility in water but, on the other hand, could interfere with reactions that are mainly performed in organic solvents, as for cycloaddition reactions. We investigated the 1,3-dipolar cycloaddition (1,3-DCA) reactions of the C-ethoxycarbonyl N-methyl nitrone 1a and the newly synthesized C-diethoxyphosphorylpropilidene N-benzyl nitrone 1b with the surface of GQDs, affording the isoxazolidine cycloadducts isox-GQDs 2a and isox-GQDs 2b. Reactions were performed in mild and eco-friendly conditions, through the use of a natural deep eutectic solvent (NADES), free of chloride or any metal ions in its composition, and formed by the zwitterionic trimethylglycine as the -bond acceptor, and glycolic acid as the hydrogen-bond donor. The results reported in this study have for the first time proved the possibility of performing cycloaddition reactions directly to the p-cloud of the GQDs surface. The use of DES for the cycloaddition reactions on GQDs, other than to improve the solubility of reactants, has been shown to bring additional advantages because of the great affinity of these green solvents with aromatic systems

Ru–Pd Bimetallic Catalysts Supported on CeO2-MnOX Oxides as Efficient Systems for H2 Purification through CO Preferential Oxidation

The catalytic performances of Ru/ceria-based catalysts in the CO preferential oxidation (CO-PROX) reaction are discussed here. Specifically, the effect of the addition of different oxides to Ru/CeO2 has been assessed. The Ru/CeO2-MnOx system showed the best performance in the 80–120 °C temperature range, advantageous for polymer-electrolyte membrane fuel cell (PEMFC) applications. Furthermore, the influence of the addition of different metals to this mixed oxide system has been evaluated. The bimetallic Ru–Pd/CeO2-MnOx catalyst exhibited the highest yield to CO2 (75%) at 120 °C whereas the monometallic Ru/CeO2-MnOx sample was that one with the highest CO2 yield (60%) at 100 °C. The characterization data (H2-temperature programmed reduction (H2-TPR), X-ray diffraction (XRD), N2 adsorption-desorption, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), X-ray photoelectron spectroscopy (XPS)) pointed out that the co-presence of manganese oxide and ruthenium enhances the mobility/reactivity of surface ceria oxygens accounting for the good CO-PROX performance of this system. Reducible oxides as CeO2 and MnOx, in fact, play two important functions, namely weakening the CO adsorption on the metal active sites and providing additional sites for adsorption/activation of O2, thus changing the mechanism from competitive Langmuir–Hinshelwood into non-competitive one-step dual site Langmuir–Hinshelwood/Mars–van Krevelen. As confirmed by H2-TPR and XPS measurements, these features are boosted by the simultaneous presence of ruthenium and palladium. The strong reciprocal interaction of these metals between them and with the CeO2-MnOx support was assumed to be responsible of the promoted reducibility/reactivity of CeO2 oxygens, thus resulting in the best CO-PROX efficiency at low temperature of the Ru-Pd/CeO2-MnOx catalyst. The higher selectivity to CO2 found on the Ru–Pd system, which reduces the undesired H2 consumption, represents a promising result of this research, being one of the key aims of the design of CO-PROX catalysts

High-Performing Au-Ag Bimetallic Catalysts Supported on Macro-Mesoporous CeO2 for Preferential Oxidation of CO in H2-Rich Gases

We report here an investigation on the preferential oxidation of carbon monoxide in an H2-rich stream (CO-PROX reaction) over mono and bimetallic Au-Ag samples supported on macro-mesoporous CeO2. The highly porous structure of ceria and the synergistic effect, which occurs between the bimetallic Au-Ag system and the support, led to promising catalytic performance at low temperature (CO2 yield of 88% and CO2 selectivity of 100% at 60 °C), which is suitable for a possible application in the polymer electrolyte membrane fuel cell (PEMFC). The morphological, structural, textural and surface features of the catalysts were determined by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), N2-adsoprtion-desorption measurements, Temperature Programmed Reduction in hydrogen (H2-TPR), Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS). Furthermore, the catalytic stability of the best active catalyst, i.e., the AuAg/CeO2 sample, was evaluated also in the presence of water vapor and carbon dioxide in the gas stream. The excellent performances of the bimetallic sample, favored by the peculiar porosity of the macro-mesoporous CeO2, are promising for possible scale-up applications in the H2 purification for PEM fuel cells

Sb-Doped Titanium Oxide: A Rationale for Its Photocatalytic Activity for Environmental Remediation

The problem of water purification is one of the most urgent issues in developing countries, where large infrastructures and energy resources are limited. Among the possibilities for a cheap route to clean water, photocatalytic materials in the form of coatings or nanostructures are among the most promising. The most widely studied photocatalytic material is titanium dioxide (TiO2). Here, we investigate the photocatalytic properties of 1.5% Sb-doped TiO2 and laser-irradiated Sb-doped TiOx. Calcined Sb-doped TiO2 was found to adopt the rutile structure, but it turned amorphous after laser irradiation. Photocatalytic tests for Sb-doped TiO2 showed an activity 1 order of magnitude higher than that of an undoped TiO2 control sample under both ultraviolet and visible irradiation. A further sizeable enhancement resulted from laser irradiation. The increased photocatalytic activity is ascribed to both enhanced visible region absorption associated with Sb-induced lone pair surface electronic states and trapping of the holes at the lone pair surface sites, thus inhibiting the recombination of the electrons and holes generated in the initial photoexcitation step. This study shows the first rationalization of the photocatalytic properties of Sb-TiO2 in terms of its electronic structure

Exploring the Photothermo-Catalytic Performance of Brookite TiO2-CeO2 Composites

The thermocatalytic, photocatalytic and photothermo-catalytic oxidation of some volatile organic compounds (VOCs), 2-propanol, ethanol and toluene, was investigated over brookite TiO2-CeO2 composites. The multi-catalytic approach based on the synergistic effect between solar photocatalysis and thermocatalysis led to the considerable decrease in the conversion temperatures of the organic compounds. In particular, in the photothermo-catalytic runs, for the most active samples (TiO2-3 wt% CeO2 and TiO2-5 wt% CeO2), the temperature at which 90% of VOC conversion occurred was about 60 °C, 40 °C and 20 °C lower than in the thermocatalytic tests for 2-propanol, ethanol and toluene, respectively. Furthermore, the addition of cerium oxide to brookite TiO2 favored the total oxidation to CO2 already in the photocatalytic tests at room temperature. The presence of small amounts of cerium oxide allowed to obtain efficient brookite-based composites facilitating the space charge separation and increasing the lifetime of the photogenerated holes and electrons as confirmed by the characterization measurements. The possibility to concurrently utilize the photocatalytic properties of brookite and the redox properties of CeO2, both activated in the photothermal tests, is an attractive approach easily applicable to purify air from VOCs

Functional Brain Network Topology Discriminates between Patients with Minimally Conscious State and Unresponsive Wakefulness Syndrome

Consciousness arises from the functional interaction of multiple brain structures and their ability to integrate different complex patterns of internal communication. Although several studies demonstrated that the fronto-parietal and functional default mode networks play a key role in conscious processes, it is still not clear which topological network measures (that quantifies different features of whole-brain functional network organization) are altered in patients with disorders of consciousness. Herein, we investigate the functional connectivity of unresponsive wakefulness syndrome (UWS) and minimally conscious state (MCS) patients from a topological network perspective, by using resting-state EEG recording. Network-based statistical analysis reveals a subnetwork of decreased functional connectivity in UWS compared to in the MCS patients, mainly involving the interhemispheric fronto-parietal connectivity patterns. Network topological analysis reveals increased values of local-community-paradigm correlation, as well as higher clustering coefficient and local efficiency in UWS patients compared to in MCS patients. At the nodal level, the UWS patients showed altered functional topology in several limbic and temporo-parieto-occipital regions. Taken together, our results highlight (i) the involvement of the interhemispheric fronto-parietal functional connectivity in the pathophysiology of consciousness disorders and (ii) an aberrant connectome organization both at the network topology level and at the nodal level in UWS patients compared to in the MCS patients

Covalently conjugated gold–porphyrin nanostructures

none8noGold nanoparticles show important electronic and optical properties, owing to their size, shape, and electronic structures. Indeed, gold nanoparticles containing no more than 30–40 atoms are only luminescent, while nanometer-sized gold nanoparticles only show surface plasmon resonance. Therefore, it appears that gold nanoparticles can alternatively be luminescent or plasmonic and this represents a severe restriction for their use as optical material. The aim of our study was the fabrication of nanoscale assembly of Au nanoparticles with bi-functional porphyrin molecules that work as bridges between different gold nanoparticles. This functional architecture not only exhibits a strong surface plasmon, due to the Au nanoparticles, but also a strong luminescence signal due to porphyrin molecules, thus, behaving as an artificial organized plasmonic and fluorescent network. Mutual Au nanoparticles–porphyrin interactions tune the Au network size whose dimension can easily be read out, being the position of the surface plasmon resonance strongly indicative of this size. The present system can be used for all the applications requiring plasmonic and luminescent emitters.openSpitaleri L.; Gangemi C.M.A.; Purrello R.; Nicotra G.; Sfrazzetto G.T.; Casella G.; Casarin M.; Gulino A.Spitaleri, L.; Gangemi, C. M. A.; Purrello, R.; Nicotra, G.; Sfrazzetto, G. T.; Casella, G.; Casarin, M.; Gulino, A

Polyethersulfone Mats Functionalized with Porphyrin for Removal of Para-nitroaniline from Aqueous Solution

The dispersion of para-nitroaniline (p-NA) in water poses a threat to the environment and human health. Therefore, the development of functional adsorbents to remove this harmful compound is crucial to the implementation of wastewater purification strategies, and electrospun mats represent a versatile and cost-effective class of materials that are useful for this application. In the present study, we tested the ability of some polyethersulfone (PES) nanofibers containing adsorbed porphyrin molecules to remove p-NA from water. The functional mats in this study were obtained by two different approaches based on fiber impregnation or doping. In particular, meso-tetraphenyl porphyrin (H2TPP) or zinc(II) meso-tetraphenyl porphyrin (ZnTPP) were immobilized on the surface of PES fiber mats by dip-coating or added to the PES electrospun solution to obtain porphyrin-doped PES mats. The presence of porphyrins on the fiber surfaces was confirmed by UV–Vis spectroscopy, fluorescence measurements, and XPS analysis. p-NA removal from water solutions was spectrophotometrically detected and evaluated

Density of States evaluation of Molybdenum Oxide for c-Si solar cell

Silicon-based heterojunction technology (HJT) is one of the most promising candidates for high performance and low cost solar cells with world-record efficiency close to 27% in IBC architecture. The HJT exploits the excellent passivation properties of hydrogenated amorphous silicon (a-Si:H); although, the use of doped a-Si:H has drawbacks such as parasitic absorption and low-thermal budget to cope with back-end metallization. Replacing the p-type a-Si:H with molybdenum oxide (MoOx) is a viable alternative. Optimizing this hole-selective layer is needed; however information on the defect density of states (DOS), linked to oxygen vacancies is still lacking

Recognition and optical sensing of amines by a quartz-bound 7-chloro-4-quinolylazopillar[5]arene monolayer

Covalent bonding of 7-chloro-4-quinolylazo-octamethoxypillar[5]arene molecules to silylated quartz substrates readily produced a new chromogenic reusable pillararene-coated quartz slide, for the direct UV detection of \u201ctransparent\u201d analytes in solution. This device provides an analyte-selective optical response towards linear (di)amines with a highly reproducible optical read-out