Sonochemical synthesis of graphene oxide supported Pt–Pd alloy nanocrystals as efficient electrocatalysts for methanol oxidation

Pt–Pd bimetallic nanoparticles supported on graphene oxide (GO) nanosheets were prepared by a sonochemical reduction method in the presence of polyethylene glycol as a stabilizing agent. The synthetic method allowed for a fine tuning of the particle composition without significant changes in their size and degree of aggregation. Detailed characterization of GO-supported Pt–Pd catalysts was carried out by transmission electron microscopy (TEM), AFM, XPS, and electrochemical techniques. Uniform deposition of Pt–Pd nanoparticles with an average diameter of 3 nm was achieved on graphene nanosheets using a novel dual-frequency sonication approach. GO-supported bimetallic catalyst showed significant electrocatalytic activity for methanol oxidation. The influence of different molar compositions of Pt and Pd (1:1, 2:1, and 3:1) on the methanol oxidation efficiency was also evaluated. Among the different Pt/Pd ratios, the 1:1 ratio material showed the lowest onset potential and generated the highest peak current density. The effect of catalyst loading on carbon paper (working electrode) was also studied. Increasing the catalyst loading beyond a certain amount lowered the catalytic activity due to the aggregation of metal particle-loaded GO nanosheets.

Nano-biocomposite films with modified cellulose nanocrystals and synthesized silver nanoparticles

Ternary nano-biocomposite films based on poly(lactic acid) (PLA) with modified cellulose nanocrystals (s-CNC) and synthesized silver nanoparticles (Ag) have been prepared and characterized. The functionalization of the CNC surface with an acid phosphate ester of ethoxylated nonylphenol favoured its dispersion in the PLA matrix. The positive effects of the addition of cellulose and silver on the PLA barrier properties were confirmed by reductions in the water permeability (WVP) and oxygen transmission rate (OTR) of the films tested. The migration level of all nano-biocomposites in contact with food simulants were below the permitted limits in both non-polar and polar simulants. PLA nano-biocomposites showed a significant antibacterial activity influenced by the Ag content, while composting tests showed that the materials were visibly disintegrated after 15 days with the ternary systems showing the highest rate of disintegration under composting conditions.

Multicomponent Azide-Alkyne Cycloaddition Catalyzed by Impregnated Bimetallic Nickel and Copper on Magnetite

A new bimetallic catalyst derived from nickel and copper has been used successfully for the first time in the multicomponent reaction of terminal alkynes, sodium azide, and benzyl bromide derivatives. The presence of both metallic species on the surface of magnetite seems to have a positive and synergetic effect. The catalyst loading is the lowest ever published for a catalyst of copper anchored on any type of iron support. The catalyst could be easily removed from the reaction media just by magnetic decantation and it could be reused up to ten times without any negative effect on the initial results.

Combined effects of cellulose nanocrystals and silver nanoparticles on the barrier and migration properties of PLA nano-biocomposites

Poly(lactic acid) (PLA)-based high performance nano-biocomposites were prepared to be used in active food packaging. Pristine (CNC) and surfactant modified cellulose nanocrystals (s-CNC) with silver (Ag) nanoparticles were used as the matrix modifiers. Binary and ternary systems were prepared. Morphological investigations revealed the good distribution of silver nanoparticles in PLA ternary systems. The combination of s-CNC and Ag nanoparticles increased the barrier effect of the produced films while the results of overall migration for the PLA nano-biocomposites revealed that none of the samples exceeded the overall migration limit, since results were well below 60 mg kg−1 of simulant.

Surface modification of cellulose nanocrystals by grafting with poly(lactic acid)

The use of biopolymers obtained from renewable resources is currently growing and they have found unique applications as matrices and/or nanofillers in ‘green’ nanocomposites. Grafting of polymer chains to the surface of cellulose nanofillers was also studied to promote the dispersion of cellulose nanocrystals in hydrophobic polymer matrices. The aim of this study was to modify the surface of cellulose nanocrystals by grafting from L-lactide by ring-opening polymerization in order to improve the compatibility of nanocrystals and hydrophobic polymer matrices. The effectiveness of the grafting was evidenced by the long-term stability of a suspension of poly(lactic acid)-grafted cellulose nanocrystals in chloroform, by the presence of the carbonyl peak in modified samples determined by Fourier transform infrared spectroscopy and by the modification in C1s contributions observed by X-ray photoelectron spectroscopy. No modification in nanocrystal shape was observed in birefringence studies and transmission electron microscopy.

Steam reforming of ethanol over bimetallic RhPt/La2O3: Long-term stability under favorable reaction conditions

Recently, the steam reforming of biofuels has been presented as a potential hydrogen source for fuel cells. Because this scenario represents an interesting opportunity for Colombia (South America), which produces large amounts of bioethanol, the steam reforming of ethanol was studied over a bimetallic RhPt/La2O3 catalyst under bulk mass transfer conditions. The effect of temperature and the initial concentrations of ethanol and water were evaluated at space velocities above 55,000 h−1 to determine the conditions that maximize the H2/CO ratio and reduce CH4 production while maintaining 100% conversion of ethanol. These requirements were accomplished when 21 mol% H2O and 3 mol% C2H5OH (steam/ethanol molar ratio = 7) were reacted at 600 °C. The catalyst stability was assessed under these reaction conditions during 120 h on stream, obtaining ethanol conversions above 99% during the entire test. The effect of both H2 and air flows as catalyst regeneration treatments were evaluated after 44 and 67 h on stream, respectively. The results showed that H2 treatment accelerated catalyst deactivation, and air regeneration increased both the catalyst stability and the H2 selectivity while decreasing CH4 generation. Fresh and spent catalyst samples were characterized by TEM/EDX, XPS, TPR, and TGA. Although the Rh and Pt in the fresh catalyst were completely reduced, the spent samples showed a partial oxidation of Rh and small amounts of carbonaceous residue. A possible Rh–Pt–Rh2O3 structure was proposed as the active site on the catalyst, which was regenerated by air treatment.

Palladium and Bimetallic Palladium–Nickel Nanoparticles Supported on Multiwalled Carbon Nanotubes: Application to Carbon–Carbon Bond-Forming Reactions in Water

Palladium and bimetallic Pd–Ni nanoparticles (NPs) protected by polyvinylpyrrolidone were prepared by the reduction-by-solvent method and deposited on multiwalled carbon nanotubes (MWCNTs). The catalytic activity of these NPs to carbon–carbon bond-forming reactions was studied by using 0.1 mol % Pd loading, at 120 °C for 1 h and water as a solvent under ligand-free conditions. The Suzuki–Miyaura reaction took place quantitatively for the cross-coupling of 4-bromoanisole with phenylboronic acid, better than those obtained with potassium phenyltrifluoroborate, with Pd50Ni50/MWCNTs as a catalyst and K2CO3 as a base and TBAB as an additive, with good recyclability during 4 cycles with some Ni leaching. The Hiyama reaction of 4-iodoanisole with trimethoxyphenylsilane, under fluoride-free conditions using 50 % aqueous NaOH solution, was performed with Pd/MWCNTs as a catalyst in 83 % yield with low recyclability. For the Mizoroki-Heck reaction 4-iodoanisole and styrene gave the corresponding 4-methoxystilbene quantitatively with Pd50Ni50/MWCNTs using K2CO3 as a base and TBAB as an additive although the recycle failed. In the case of the Sonogashira-Hagihara reaction, Pd/MWCNTs had to be used as a catalyst and pyrrolidine as a base for the coupling of 4-iodoanisole with phenylacetylene under copper-free conditions. The corresponding 4-methoxytolane was quantitatively obtained allowing the recycling of the catalyst during 3 cycles.

Silica Microparticles Supported Gold and Copper Ferrite Nanoparticles: A Magnetically Recyclable Bimetallic Catalyst for Sonogashira Reaction

Novel silica supported gold and copper ferrite nanoparticles (NPs) have been synthesized, characterized and used as a separable dual catalyst in Sonogashira type reaction. These Au.CuFe2O4@Silica NPs show a high efficiency as catalyst in the alkynylation not only of aryl iodides but also aryl bromides. By using only 0.5 mol% loading and t-BuOK as base in N,N-dimethylacetamide as solvent, aryl iodides react at 115 ºC in 1 d, whereas for aryl bromides the cross-coupling takes place at 130 ºC in 2 d. The catalyst can be successfully recycled using an external magnet for four consecutive runs.

Bimetallic PtSn/C catalysts obtained via SOMC/M for glycerol steam reforming

A detailed study on the preparation of bimetallic PtSn/C catalysts using surface-controlled synthesis methods, and on their catalytic performance in the glycerol steam reforming reaction has been carried out. In order to obtain these well-defined bimetallic phases, techniques derived from Surface Organometallic Chemistry on Metals (SOMC/M) were used. The preparation process involved the reaction between an organometallic compound ((C4H9)4Sn) and a supported transition metal (Pt) in a H2 atmosphere. Catalysts with Sn/Pt atomic ratios of 0.2, 0.3, 0.5, and 0.7 were obtained, and characterized using several techniques: ICP, H2 chemisorption, TEM and XPS. These systems were tested in the glycerol steam reforming varying the reaction conditions (glycerol concentration and reaction temperature). The best performance was observed for the catalysts with the lowest tin contents (PtSn0.2/C and PtSn0.3/C). It was observed that the presence of tin increased the catalysts’ stability when working under more severe reaction conditions.

Single-walled carbon nanotube buckypapers as electrocatalyst supports for methanol oxidation

This work studies the use of various single-walled carbon nanotube (SWCNT) buckypapers as catalyst supports for methanol electro-oxidation in acid media. Buckypapers were obtained by vacuum filtration from pristine and oxidized SWCNT suspensions in different liquid media. Pt–Ru catalysts supported on the buckypapers were prepared by multiple potentiostatic pulses using a diluted solution of Pt and Ru salts (2 mM H2PtCl6 + 2 mM RuCl3) in acid media. The resulting materials were characterized via SEM, TEM, EDX and ICP-OES analysis. Well dispersed rounded nanoparticles between 2 and 15 nm were successfully electrodeposited on the SWCNT buckypapers. The ruthenium content in the bimetallic deposits was between 32 and 48 at. %, while the specific surface areas of the catalysts were in the range of 72–113 m2 g−1. It was found that the solvent used to prepare the SWCNT buckypaper films has a strong influence on the catalyst dispersion, particle size and metal loading. Cyclic voltammetry and chronoamperometry experiments point out that the most active electrodes for methanol electro-oxidation were prepared with the buckypaper supports that were obtained from SWCNT dispersions in N-methyl-pyrrolidone.

Sulfur resistance of Pt-W catalysts

The sulfur resistance of low-loaded monometallic Pt catalysts and bimetallic Pt-W catalysts during the partial selective hydrogenation of styrene, a model compound of Pygas streams, was studied. The effect of metal impregnation sequence on the activity and selectivity was also evaluated. Catalysts were characterized by ICP, TPR, XRD, and XPS techniques. Catalytic tests with sulfur-free and sulfur-doped feeds were performed. All catalysts showed high selectivities (>98%) to ethylbenzene. Activity differences between the catalysts were mainly attributed to electronic effects due to the presence of different electron-rich species of Pt0 and electron-deficient species of Ptδ+. Pt0 promotes the cleavage of H2 while Ptδ+ the adsorption of styrene. The catalyst successively impregnated with W and Pt (WPt/Al) was more active and sulfur resistant than the catalyst prepared with an inverse impregnation order (PtW/Al). The higher poison resistance of WPt/Al was attributed to both steric and electronic effects.

Single wall carbon nanotubes loaded with Pd and NiPd nanoparticles for H2 sensing at room temperature

Pd and bimetallic Ni50Pd50 nanoparticles protected by polyvinylpyrrolidone (PVP) have been synthesized by the reduction-by-solvent method and deposited on single wall carbon nanotubes (SWCNTs) to be tested as H2 sensors. The SWCNTs were deposited by drop casting from different suspensions. The Pd nanoparticles-based sensors show a very reproducible performance with good sensitivity and very low response times (few seconds) for different H2 concentrations, ranging from 0.2% to 5% vol. H2 in air at atmospheric pressure. The influence of the metal nanoparticle composition, the quality of SWCNTs suspension and the metal loading have been studied, observing that all these parameters play an important role in the H2 sensor performance. Evidence for water formation during the H2 detection on Pd nanoparticles has been found, and its repercussion on the behaviour of the assembled sensors is discussed. The sensor preparation procedure detailed in this work has proven to be simple and reproducible to prepare cost-effective and highly efficient H2 sensors that perform very well under real application conditions.

Growth of Carbon Nanotubes on Surfaces: The Effects of Catalyst and Substrate

We report a study of synthesising air-stable, nearly monodispersed bimetallic colloids of Co/Pd and Fe/Mo of varying compositions as active catalysts for the growth of carbon nanotubes. Using these catalysts we have investigated the effects of catalyst and substrate on the carbon nanostructures formed in a plasma-enhanced chemical vapour deposition (PECVD) process. We will show how it is possible to assess the influence of both the catalyst and the support on the controlled growth of carbon nanotube and nanofiber arrays. The importance of the composition of the catalytic nuclei will be put into perspective with other results from the literature. Furthermore, the influence of other synthetic parameters such as the nature of the nanoparticle catalysts will also be analysed and discussed in detail.

Interplay Between Structure, Stoichiometry, and Electron Transfer Dynamics in SILAR-based Quantum Dot-Sensitized Oxides

We quantify the rate and efficiency of picosecond electron transfer (ET) from PbS nanocrystals, grown by successive ionic layer adsorption and reaction (SILAR), into a mesoporous SnO2 support. Successive SILAR deposition steps allow for stoichiometry- and size-variation of the QDs, characterized using transmission electron microscopy. Whereas for sulfur-rich (p-type) QD surfaces substantial electron trapping at the QD surface occurs, for lead-rich (n-type) QD surfaces, the QD trapping channel is suppressed and the ET efficiency is boosted. The ET efficiency increase achieved by lead-rich QD surfaces is found to be QD-size dependent, increasing linearly with QD surface area. On the other hand, ET rates are found to be independent of both QD size and surface stoichiometry, suggesting that the donor–acceptor energetics (constituting the driving force for ET) are fixed due to Fermi level pinning at the QD/oxide interface. Implications of our results for QD-sensitized solar cell design are discussed.

Titania–Silica Materials for Enhanced Photocatalysis

Mesoporous titania–organosilica nanoparticles comprised of anatase nanocrystals crosslinked with organosilica moieties have been prepared by direct co-condensation of a titania precursor, tetrabuthylortotitanate (TBOT), with two organosilica precursors, 1,4-bis(triethoxysilyl) benzene (BTEB) and 1,2-bis(triethoxysilyl) ethane (BTEE), in mild conditions and in the absence of surfactant. These hybrid materials show both high surface areas (200–360 m2 g−1) and pore volumes (0.3 cm3 g−1) even after calcination, and excellent photoactivity in the degradation of rhodamine 6G and in the partial oxidation of propene under UV irradiation, especially after the calcination of the samples. During calcination, there is a change in the TiIV coordination and an increase in the content of Si[BOND]O[BOND]Ti moieties in comparison with the uncalcined materials, which seems to be responsible for the enhanced photocatalytic activity of hybrid titania–silica materials as compared to both uncalcined samples and the control TiO2.