Cycloaddition of Nitrile Oxides to Graphene: a Theoretical and Experimental Approach.

Density functional theory (DFT) studies of the interaction between graphene sheets and nitrile oxides have proved the feasibility of the reaction through 1,3-dipolar cycloaddition. The viability of the approach has been also confirmed experimentally through the cycloaddition of few-layer exfoliated graphene and nitrile oxides containing functional organic groups with different electronic nature. The cycloaddition reaction has been successfully achieved in one-pot from the corresponding oximes under microwave (MW) irradiation. The successful formation of the isoxazoline ring has been confirmed by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS).

Synthesis, characterization and photoinduced charge separation of carbon nanohorn-oligothienylenevinylene hybrids.

The covalent coupling between oligo(thienylenevinylenes) (nTVs) and carbon nanohorns (CNHs) has been investigated. The resulting nanohybrids have been characterized by a combination of several techniques, including thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM) and Raman spectroscopy. The photophysical properties of the new hybrids were investigated by steady-state and time-resolved spectroscopic techniques. A transient signal characterized by two kinetic regimes, one short decay within 0.5 µs corresponding to around 80% of the total signal and another much longer-lived decay of 10 µs, has been detected. The transient absorption spectra are characterized by a continuous absorption that increases in intensity towards shorter wavelengths, with a maximum at 430 nm. These transient signals have been assigned to the charge-separated state delocalized on CNHs based on the quenching behavior and by comparison with the photophysical properties of nTV in the absence and presence of quenchers. The photophysical behavior of covalent nTV-CNH conjugates with microsecond transients due to electrons and holes on CNHs contrasts with the absence of any transient for analogous nTV-C60 conjugates, for which charge separation was not observed at timescales longer than nanoseconds. The photochemical behavior of CNHs is believed to derive from the amphoteric (electron donor and acceptor) properties of CNHs and from the larger number of carbon atoms (efficient delocalization) in CNHs compared with C60.

Modulation of the exfoliated graphene work function through cycloaddition of nitrile imines.

After the feasibility of the 1,3-dipolar cycloaddition reaction between nitrile imines and exfoliated graphene by density functional theory calculations was proved, very few-layer graphene was effectively functionalized using this procedure. Hydrazones with different electronic properties were used as precursors for the 1,3-dipoles, and microwave irradiation as an energy source enabled the reaction to be performed in a few minutes. The anchoring of organic addends on the graphene surface was confirmed by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis. Ultraviolet photoelectron spectroscopy (UPS) was used to measure the work function and band gap of these new hybrids. Our results demonstrate that it is possible to modulate these important electronic valence band parameters by tailoring the electron richness of the organic addends and/or the degree of functionalization.

Double-wall carbon nanotube-porphyrin supramolecular hybrid: synthesis and photophysical studies.

Double-wall carbon nanotubes (DWCNTs) with pyridyl units covalently attached to the external wall through isoxazolino linkers and carboxylic groups that have been esterified by pentyl chains are synthesized. The properties of these modified DWCNTs are then compared with an analogous sample based on single-wall carbon nanotubes (SWCNTs). Raman spectroscopy shows the presence of characteristic radial breathing mode vibrations, confirming that the samples partly retain the integrity of the nanotubes in the case of DWCNTs, including the internal and external nanotubes. Quantification of the pyridyl content for both samples (DWCNT and SWCNT derivatives) is based on X-ray photoelectron spectroscopy and thermogravimetric profiles, showing very similar substituent load. Both pyridyl-containing nanotubes (DWCNTs and SWCNTs) form a complex with zinc porphyrin (ZnP), as evidenced by the presence of two isosbestic points in the absorption spectra of the porphyrin upon addition of the pyridyl-functionalized nanotubes. Supramolecular complexes based on pyridyl-substituted DWCNTs and SWCNTs quench the emission and the triplet excited state identically, through an energy-transfer mechanism based on pre-assembly of the ground state. Thus, the presence of the intact inner wall in DWCNTs does not influence the quenching behavior, with respect to SWCNTs, for energy-transfer quenching with excited ZnP. These results sharply contrast with previous ones referring to electron-transfer quenching, in which the double-wall morphology of the nanotubes has been shown to considerably reduce the lifetime of charge separation, owing to faster electron mobility in DWCNTs compared to SWCNTs.

Combined effects of Ag nanoparticles and oxygen plasma treatment on PLGA morphological, chemical, and antibacterial properties.

The purpose of this study is to investigate the combined effects of oxygen plasma treatments and silver nanoparticles (Ag) on PLGA in order to modulate the surface antimicrobial properties through tunable bacteria adhesion mechanisms. PLGA nanocomposite films, produced by solvent casting with 1 wt % and 7 wt % of Ag nanoparticles were investigated. The PLGA and PLGA/Ag nanocomposite surfaces were treated with oxygen plasma. Surface properties of PLGA were investigated by field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), static contact angle (CA), and high resolution X-ray photoelectron spectroscopy (XPS). Antibacterial tests were performed using an Escherichia coli RB (a Gram negative) and Staphylococcus aureus 8325-4 (a Gram positive). The PLGA surface becomes hydrophilic after the oxygen treatment and its roughness increases with the treatment time. The surface treatment and the Ag nanoparticle introduction have a dominant influence on the bacteria adhesion and growth. Oxygen-treated PLGA/Ag systems promote higher reduction of the bacteria viability in comparison to the untreated samples and neat PLGA. The combination of Ag nanoparticles with the oxygen plasma treatment opens new perspectives for the studied biodegradable systems in biomedical applications.

Photochemical evidence of electronic interwall communication in double-wall carbon nanotubes.

Single- and double-wall carbon nanotubes (CNTs) having dimethylanilino (DMA) units covalently attached to the external graphene wall have been prepared by the reaction of the dimethylaminophenylnitronium ion with the corresponding CNT. The samples have been characterized by Raman and XPS spectroscopies, thermogravimetry, and high-resolution transmission electron microscopy in which the integrity of the single or double wall of the CNT and the percentage of substitution (one dimethylanilino group every 45 carbons of the wall for the single- and double-wall samples) has been determined. Nanosecond laser flash photolysis has shown the generation of transients that has been derived from the charge transfer between the dimethylanilino (as the electron donor) to the CNT graphene wall (as the electron acceptor). Importantly, the lifetime of the double-wall CNT is much shorter than that monitored for the single-wall CNT. Shorter-lived transients were also observed for the pentyl-esterified functionalized double-wall CNT with respect to the single-wall analogue in the presence of hole (CH(3)OH) and electron quenchers (O(2), N(2)O), which has led to the conclusion that the inner, intact graphene wall that is present in double-wall CNT increases the charge mobility significantly, favoring charge recombination processes. Considering the importance that charge mobility has in microelectronics, our finding suggests that double-wall CNT or two-layer graphene may be more appropriate to develop devices needing fast charge mobility.

Insights into the effects of functional groups on carbon nanotubes for the electrooxidation of methanol.

Functionalized carbon nanotubes were used as a support for PtCo nanoparticles. Their performance as electrocatalysts for the electrooxidation of methanol was evaluated by cyclic voltammetry and in situ FTIR reflectance spectroscopy. The onset potentials for both the electrooxidation of methanol and the production of CO(2) shifted to less positive values for catalysts prepared with more oxygen groups on the support. Furthermore, the production of CO(2) was higher on catalysts prepared with functionalized carbon nanotubes. The functional groups play two different but complementary roles. On the one hand, they help to stabilize smaller PtCo particles of ca. 3 nm. On the other hand, they provide the -OH groups necessary for the total oxidation of methanol to CO(2) at potentials less positive than on nonfunctionalized supports. Remarkably, the consumption of carboxylic acid groups along with the production of water is observed in the infrared spectra of the functionalized supports recorded during the electrooxidation of methanol. This observation suggests that the -OH groups of the support can also react with methanol, forming water and an ester.

Silane coupling agent structures on carbon nanofibers.

Carbon nanofibers (CNFs) are considered ideal materials for reinforcing polymers due to their excellent mechanical properties, among others. In order to obtain composites of optimal properties the clue is to enhance the interaction between reinforcement (CNFs) and polymer matrix. Surface modification of CNFs with silane coupling agents (SCAs) has revealed as one of the most interesting methods. The silanization process has been carried out mixing at room temperature and for one minute the hydrolysed silane with CNFs. We have use four different SCAs: 3-aminopropyltriethoxyxilane (APS), 3-aminopropyltrimethoxysilane (AMMO), N-(2-aminoethyl)-3-(aminopropyltrimethoxysilane) (DAMO), and 3-glycidoxypropyltrimethoxysilane (GLYMO), in order to elucidate the SCA-CNFs interaction and the silane structures formed on CNFs surface. XPS and FTIR-ATR techniques have pointed out that each silane adsorbs on CNFs surface through chemical bonding, forming multilayers. Silane nature determines the structure taken on CNFs surface. APS and AMO silanes adsorb taking vertical structures on CNFs surface, while DMO and GMO adsorb on CNFs taking horizontal structures, stabilized by zwitterions formed through H-bonds with hydroxyl groups from CNFs surface.

A carbon nanohorn-porphyrin supramolecular assembly for photoinduced electron-transfer processes.

A supramolecular assembly of zinc porphyrin-carbon nanohorns (CNHs) was constructed in a polar solvent. An ammonium cation was covalently connected to the CNH through a spacer (sp) (CNH-sp-NH(3)(+)) and bound to a crown ether linked to a zinc porphyrin (Crown-ZnP). Nanohybrids CNH-sp-NH(3)(+);Crown-ZnP and CNH-sp-NH(3)(+) were characterized by several techniques, such as high-resolution transmission electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and Raman spectroscopy. The photoinduced electron-transfer processes of the nanohybrids have been confirmed by using time-resolved absorption and fluorescence measurements by combining the steady-state spectral data. Fluorescence quenching of the ZnP unit by CNH-sp-NH(3)(+) has been observed, therefore, photoinduced charge separation through the excited singlet state of the ZnP unit is suggested for the hybrid material, CNH-sp-NH(3)(+);Crown-ZnP. As transient absorption spectral experiments reveal the formation of the radical cation of the ZnP unit, electron generation is suggested as a counterpart of the charge-separation on the CNHs; such an electron on the CNHs is further confirmed by migrating to the hexylviologen dication (HV(2+)). Accumulation of the electron captured from HV(*+) is observed as electron pooling in solution in the presence of a hole-shifting reagent. Photovoltaic performance with moderate efficiency is confirmed for CNH-sp-NH(3)(+);Crown-ZnP deposited onto nanostructured SnO(2) films.

Mechanistic aspects of the ethanol steam reforming reaction for hydrogen production on Pt, Ni, and PtNi catalysts supported on gamma-Al2O3.

Mechanistic aspects of ethanol steam reforming on Pt, Ni, and PtNi catalysts supported on gamma-Al(2)O(3) are investigated from the analysis of adsorbed species and gas phase products formed on catalysts during temperature-programmed desorption of ethanol and during ethanol steam reforming reaction. DRIFTS-MS analyses of ethanol decomposition and ethanol steam reforming reactions show that PtNi and Ni catalysts are more stable than the Pt monometallic counterpart. Ethanol TPD results on Ni, Pt, and NiPt catalysts point to ethanol dehydrogenation and acetaldehyde decomposition as the first reaction pathways of ethanol steam reforming over the studied catalysts. The active sites responsible for the acetaldehyde decomposition are easily deactivated in the first minutes on-stream by carbon deposits. For Ni and PtNi catalysts, a second reaction pathway, consisting in the decomposition of acetate intermediates formed over the surface of alumina support, becomes the main reaction pathway operating in steam reforming of ethanol once the acetaldehyde decomposition pathway is deactivated. Taking into account the differences observed in the mechanism of ethanol decomposition, the better stability observed for PtNi catalyst is proposed to be related with a cooperative effect between Pt and Ni activities together with the enhanced ability of Ni to gasify the methyl groups formed by decomposition of acetate species. On the contrary, monometallic catalysts are believed to dehydrogenate these methyl groups forming coke that leads to deactivation of metal particles.

Triplet photosensitizer-nanotube conjugates: synthesis, characterization and photochemistry of charge stabilizing, palladium porphyrin/carbon nanotube conjugates.

The ability of a triplet photosensitizer to generate long-lived charge separated states, in contrast to traditionally used singlet photosensitizers, in covalently functionalized single-walled carbon nanotube hybrids has been investigated. Enriched single-walled carbon nanotubes with two diameters, namely (6,5) and (7,6), were covalently modified to carry a charge-stabilizing triplet photosensitizer derived from a palladium porphyrin. The nanohybrids were fully characterized and the presence of intramolecular interactions between the porphyrin and nanotubes was established from various spectroscopic, imaging, electrochemical and thermochemical studies. Photoluminescence of palladium porphyrin was found to be quantitatively quenched in the presence of covalently appended SWCNTs and this quenching is due to excited state charge separation and has been established by femtosecond transient absorption studies. Owing to the presence of the triplet photosensitizer, the charge separated states lasted over 3 ns, i.e., much longer than those reported earlier for singlet photosensitizer-derived nanotube hybrids. The nanohybrids also exhibited efficient photocatalytic behavior in experiments involving electron pooling of one-electron reduced methyl viologen in the presence of a sacrificial electron donor. Higher yields of photoproducts were achieved from the present donor-acceptor nanohybrids when compared with those of singlet photosensitizer-derived nanohybrids, more so for (6,5) nanotube derived hybrids compared to (7,6) nanotube derived hybrids. The present findings highlight the importance of triplet photosensitizer derived nanohybrids in artificial photosynthesis of charge separation and photocatalytic applicatons.

Conjugation with carbon nanotubes improves the performance of mesoporous silicon as Li-ion battery anode.

Carbon nanotubes can be utilized in several ways to enhance the performance of silicon-based anodes. In the present work, thermally carbonized mesoporous silicon (TCPSi) microparticles and single-walled carbon nanotubes (CNTs) are conjugated to create a hybrid material that performs as the Li-ion battery anode better than the physical mixture of TCPSi and CNTs. It is found out that the way the conjugation is done has an essential role in the performance of the anode. The conjugation should be made between negatively charged TCPSi and positively charged CNTs. Based on the electrochemical experiments it is concluded that the positive charges, i.e., excess amine groups of the hybrid material interfere with the diffusion of the lithium cations and thus they should be removed from the anode. Through the saturation of the excess positive amine groups on the CNTs with succinic anhydride, the performance of the hybrid material is even further enhanced.

Partial Oxidation of Methane to Syngas Over Nickel-Based Catalysts: Influence of Support Type, Addition of Rhodium, and Preparation Method.

There is great economic incentive in developing efficient catalysts to produce hydrogen or syngas by catalytic partial oxidation of methane (CPOM) since this is a much less energy-intensive reaction than the highly endothermic methane steam reforming reaction, which is the prominent reaction in industry. Herein, we report the catalytic behavior of nickel-based catalysts supported on different oxide substrates (Al2O3, CeO2, La2O3, MgO, and ZrO2) synthesized via wet impregnation and solid-state reaction. Furthermore, the impact of Rh doping was investigated. The catalysts have been characterized by X-ray diffraction, N2 adsorptiondesorption at -196°C, temperature-programmed reduction, X-ray photoelectron spectroscopy, O2-pulse chemisorption, transmission electron microscopy, and Raman spectroscopy. Supported Ni catalysts were found to be active for CPOM but can suffer from fast deactivation caused by the formation of carbon deposits as well as via the sintering of Ni nanoparticles (NPs). It has been found that the presence of Rh favors nickel reduction, which leads to an increase in the methane conversion and yield. For both synthesis methods, the catalysts supported on alumina and ceria show the best performance. This could be explained by the higher surface area of the Ni NPs on the alumina surface and presence of oxygen vacancies in the CeO2 lattice, which favor the proportion of oxygen adsorbed on defect sites. The catalysts supported on MgO suffer quick deactivation due to formation of a NiO/MgO solid solution, which is not reducible under the reaction conditions. The low level of carbon formation over the catalysts supported on La2O3 is ascribed to the very high dispersion of the nickel NPs and to the formation of lanthanum oxycarbonate, through which carbon deposits are gasified. The catalytic behavior for catalysts with ZrO2 as support depends on the synthesis method; however, in both cases, the catalysts undergo deactivation by carbon deposits.

Modulating charge carrier density and mobility in doped graphene by covalent functionalization.

Covalent B-functionalization of B-doped graphene has been performed for the first time. The electronic properties and Hall effect of functionalized N- and B-doped graphene can be tuned by tailoring the electron-donating/-withdrawing properties of the organic addend.

Na-doped ruthenium perovskite electrocatalysts with improved oxygen evolution activity and durability in acidic media.

The design of active and durable catalysts for the H2O/O2 interconversion is one of the major challenges of electrocatalysis for renewable energy. The oxygen evolution reaction (OER) is catalyzed by SrRuO3 with low potentials (ca. 1.35 VRHE), but the catalyst's durability is insufficient. Here we show that Na doping enhances both activity and durability in acid media. DFT reveals that whereas SrRuO3 binds reaction intermediates too strongly, Na doping of ~0.125 leads to nearly optimal OER activity. Na doping increases the oxidation state of Ru, thereby displacing positively O p-band and Ru d-band centers, weakening Ru-adsorbate bonds. The enhanced durability of Na-doped perovskites is concomitant with the stabilization of Ru centers with slightly higher oxidation states, higher dissolution potentials, lower surface energy and less distorted RuO6 octahedra. These results illustrate how high OER activity and durability can be simultaneously engineered by chemical doping of perovskites.

N-Doped graphene/C60 covalent hybrid as a new material for energy harvesting applications.

N-Doped graphene (N-G) was chemically functionalized by N-alkylation with the well-known electron acceptor C60. The degree of functionalization and the key structural features of the N-G/C60 hybrid were systematically investigated by a number of techniques including thermogravimetric analysis, X-ray photoelectron and Raman spectroscopies and transmission electron and atomic force microscopies. Absorption and electrochemical studies revealed interactions between the N-G and C60 while the fluorescence of C60 within the hybrid was found to be fully quenched. Evidence for the occurrence of excited state charge transfer from the singlet excited C60 to N-G in the hybrid was obtained from femtosecond transient absorption studies covering the visible-near-IR regions. Electron-pooling experiments performed in the presence of a sacrificial electron donor and a second electron acceptor, methyl viologen, revealed the accumulation of the one-electron reduced product of methyl viologen upon continuous irradiation of the N-G/C60 nanohybrid, thus revealing the utility of this material in photocatalytic energy harvesting applications.

Edge-on and face-on functionalized Pc on enriched semiconducting SWCNT hybrids.

Enriched semiconducting single-walled carbon nanotubes (SWCNT (6,5) and SWCNT (7,6)) and HiPco nanotubes were covalently functionalized with either zinc phthalocyanine or silicon phthalocyanine as electron donors. The synthetic strategy resulted in edge-on and face-on geometries with respect to the phthalocyanine geometry, with both phthalocyanines held by an electronically conducting diphenylacetylene linker. The extent of functionalization in the MPc-SWCNT (M = Zn or Si) donor-acceptor nanohybrids was determined by systematic studies involving AFM, TGA, XPS, optical and Raman techniques. Intramolecular interactions in MPc-SWCNT nanohybrids were probed by studies involving optical absorbance, Raman, luminescence and electrochemical studies. Different degrees of interactions were observed depending on the type of MPc and mode of attachment. Substantial quenching of MPc fluorescence in these hybrids was observed from steady-state and three-dimensional fluorescence mapping, which suggests the occurrence of excited state events. Evidence for the occurrence of excited state charge transfer type interactions was subsequently secured from femtosecond transient absorption studies covering both the visible and near-infrared regions. Furthermore, electron-pooling experiments performed in the presence of a sacrificial electron donor and a second electron acceptor revealed accumulation of one-electron reduced product upon continuous irradiation of the nanohybrids. In such experiments, the ZnPc-SWCNT (6,5) nanohybrid outperformed other nanohybrids and this suggests that this is a superior donor-acceptor system for photocatalytic applications.

Characterization of trimetallic Pt-Pd-Au/CeO2 catalysts combinatorial designed for methane total oxidation.

In the present work, the role and the effect of platinum and gold on the catalytic performance of ceria supported tri-metallic Pt-Pd-Au catalysts have been studied. The optimum composition of these tri-metallic supported catalysts has been discovered using methods and tools of combinatorial catalyst library design. Detailed catalytic, spectroscopic and physico-chemical characterization of catalysts in the vicinity of the optimum in the given compositional space has been performed. The temperature-programmed oxidation of methane revealed that the addition of Pt and Au to Pd/CeO2 catalyst resulted in higher conversion values in the whole investigated temperature range compared to the monometallic Pd catalyst. The time-on-stream experiments provided further evidence for the high-stability of tri-metallic catalysts compared to the monometallic one. Kinetic studies revealed the stronger adsorption of methane on Pt-Pd/CeO2 catalysts than over Pd/CeO2. XPS analysis showed that Pt and Au stabilize Pd in a more reduced form even under condition of methane oxidation. FTIR spectroscopy of adsorbed CO and hydrogen TPD measurements provided indirect evidences for alloying of Pt and Au with Pd. CO chemisorption data indicated that tri-metallic catalysts have increased accessible metallic surface area. It is suggested that advantageous catalytic properties of tri-metallic Pt-Au-Pd/CeO2 catalysts compared to the monometallic one can be attributed to (i) suppression of the formation of ionic forms of Pd(II), (ii) reaching an optimum ratio between Pd0 and PdO species, and (iii) stabilization of Pd in high dispersion. The results also indicate that Pd0 - PdO ensemble sites are required for methane activation.

Dissolution Kinetics of Hot Compressed Oxide Glasses.

The chemical durability of oxide glasses is an important property for a wide range of applications and can in some cases be tuned through composition optimization. However, these possibilities are relatively limited because around 3/5 of the atoms in most oxide glasses are oxygens. An alternative approach involves post-treatment of the glass. In this work, we focus on the effect of hot compression on dissolution kinetics because it is known to improve, for example, elastic moduli and hardness, whereas its effect on chemical durability is poorly understood. Specifically, we study the bulk glass dissolution rate of phosphate, silicophosphate, borophosphate, borosilicate, and aluminoborosilicate glasses, which have been compressed at 0.5, 1.0, and 2.0 GPa at the glass transition temperature (Tg). We perform weight loss and supplementary modifier leaching measurements of bulk samples immersed in acid (pH 2) and neutral (pH 7) solutions. Compression generally improves the chemical durability as measured from weight loss, but the effect is highly composition- and pressure-dependent. As such, we show that the dissolution mechanisms depend on the topological changes induced by permanent densification, which in turn are a function of the changes in the number of nonbridging oxygens and the network cross-linking. We also demonstrate a direct relationship between the chemical durability and the number of chemical topological constraints per atom (nc) acting within the molecular network.