CO Oxidation at 20 °C on Au Catalysts Supported on Mesoporous Silica: Effects of Support Structural Properties and Modifiers.

In this work we report the effects of support structural properties and its modification with some metal oxides modifiers on the catalytic behavior of Au catalysts in the total CO oxidation at 20 °C. Au catalysts were supported on mesoporous silica materials (MSM) having different structural properties: Channel-like (SBA-15), cage-like (SBA-16), hexagonal (HMS), and disordered (DMS-1) structures. The effect of the modifier was evaluated by comparison of the catalytic response of the SBA-15-based catalysts modified with MgO, Fe2O3, TiO2, and CeO2. The chemical, structural, and electronic properties of the catalysts were investigated by a variety of techniques (metal content analysis by ICP-OES, N2 physisorption, XRD, UV-vis DRS, DRIFTS of adsorbed CO and OH regions, oxygen storage capacity (OSC), HR-TEM, and XPS). The activity of calcined catalysts in the CO oxidation reaction were evaluated at steady state conditions, at 20 °C, atmospheric pressure, and when using, as feed, a 1%CO/1%O2/98% gas mixture. The work clearly demonstrated that all Au catalysts supported on the mesoporous silicas modified with metal oxides were more active than the Au/SBA-15 and Au/MgO reference ones. The support structural properties and type of dopant were important factors influencing on the catalyst behavior. Concerning the support textural properties, it was found that the HMS substrate with the wormhole-structure offers better porosity and specific surface area than their silica counterparts having channel-like (SBA-15), cage-like (SBA-16), and disordered (DMS-1) mesoporous structures. Concerning the effect of modifier, the best catalytic response was achieved with the catalysts modified with MgO. After activation by calcination at 200 °C for 4 h, the Au/MgO/HMS catalyst exhibited the best catalytic performance, which was ascribed to the combined effects of the best structural properties, a large support oxygen storage capacity and homogeneous distribution of gold particles on the support (external and inner). Implications of the type of active sites (Au1+ or Au°), support structural properties and role of modifier on the catalytic activity are discussed.

Bioinspired Electro-Organocatalytic Material Efficient for Hydrogen Production.

Commercial carbon fibers can be used as electrodes with high conductive surfaces in reduced devices. Oxidative treatment of such electrodes results in a chemically robust material with high catalytic activity for electrochemical proton reduction, enabling the measurement of quantitative faradaic yields (>95 %) and high current densities. Combination of experiments and DFT calculations reveals that the presence of carboxylic groups triggers such electrocatalytic activity in a bioinspired manner. Analogously to the known Hantzsch esters, the oxidized carbon fiber material is able to transfer hydrides, which can react with protons, generating H2 , or with organic substrates resulting in their hydrogenation. A plausible mechanism is proposed based on DFT calculations on model systems.

Direct Detection of OXA-48 Carbapenemase Gene in Lysate Samples through Changes in Mechanical Properties of DNA Monolayers upon Hybridization.

Carbapenem-resistant Enterobacteriaceae have recently become an important cause of morbidity and mortality due to healthcare-associated infections. Most commonly used diagnostic methods are incompatible with fast and accurate directed therapy. We report here the direct identification of the blaOXA48 gene, which codes for the carbapenemase OXA-48, in lysate samples from Klebsiella pneumoniae. The method is PCR-free and label-free. It is based on the measurement of changes in the stiffness of DNA self-assembled monolayers anchored to microcantilevers that occur as a consequence of the hybridization. The stiffness of the DNA layer is measured through changes of the sensor resonance frequency upon hybridization and at varying relative humidity.

Effect of water-DNA interactions on elastic properties of DNA self-assembled monolayers.

DNA-water interactions have revealed as very important actor in DNA mechanics, from the molecular to the macroscopic scale. Given the particularly useful properties of DNA molecules to engineer novel materials through self-assembly and by bridging organic and inorganic materials, the interest in understanding DNA elasticity has crossed the boundaries of life science to reach also materials science and engineering. Here we show that thin films of DNA constructed through the self-assembly of sulfur tethered ssDNA strands demonstrate a Young's modulus tuning range of about 10 GPa by simply varying the environment relative humidity from 0% up to 70%. We observe that the highest tuning range occurs for ssDNA grafting densities of about 3.5 × 1013 molecules/cm 2, where the distance between the molecules maximizes the water mediated interactions between the strands. Upon hybridization with the complementary strand, the DNA self-assembled monolayers significantly soften by one order of magnitude and their Young's modulus dependency on the hydration state drastically decreases. The experimental observations are in agreement with molecular dynamics simulations.

Probing the Catalytic Activity of Sulfate-Derived Pristine and Post-Treated Porous TiO2(101) Anatase Mesocrystals by the Oxidative Desulfurization of Dibenzothiophenes.

Mesocrystals (basically nanostructures showing alignment of nanocrystals well beyond crystal size) are attracting considerable attention for modeling and optimization of functionalities. However, for surface-driven applications (heterogeneous catalysis), only those mesocrystals with excellent textural properties are expected to fulfill their potential. This is especially true for oxidative desulfuration of dibenzothiophenes (hard to desulfurize organosulfur compounds found in fossil fuels). Here, we probe the catalytic activity of anatases for the oxidative desulfuration of dibenzothiophenes under atmospheric pressure and mild temperatures. Specifically, for this study, we have taken advantage of the high stability of the (101) anatase surface to obtain a variety of uniform colloidal mesocrystals (approximately 50 nm) with adequate orientational order and good textural properties (pores around 3-4 nm and surface areas around 200 m2/g). Ultimately, this stability has allowed us to compare the catalytic activity of anatases that expose a high number of aligned single crystal-like surfaces while differing in controllable surface characteristics. Thus, we have established that the type of tetrahedral coordination observed in these anatase mesocrystals is not essential for oxidative desulfuration and that both elimination of sulfates and good textural properties significantly improve the catalytic activity. Furthermore, the most active mesocrystals have been used to model the catalytic reaction in three-(oil-solvent-catalyst) and two-phase (solvent-catalyst) systems. Thus, we have been able to observe that the transfer of DBT from the oil to the solvent phase partially limits the oxidative process and to estimate an apparent activation energy for the oxidative desulfuration reaction of approximately 40 kJ/mol in the two-phase system to avoid mass transfer limitations. Our results clearly establish that (101) anatase mesocrystals with excellent textural properties show adequate stability to withstand several post-treatments without losing their initial mesocrystalline character and therefore could serve as models for catalytic processes different from the one studied here.

Targeted killing of prostate cancer cells using antibody-drug conjugated carbon nanohorns.

The ability of carbon nanohorns (CNHs) to cross biological barriers makes them potential carriers for delivery purposes. In this work, we report the design of a new selective antibody-drug nanosystem based on CNHs for the treatment of prostate cancer (PCa). In particular, cisplatin in a prodrug form and the monoclonal antibody (Ab) D2B, selective for PSMA+ cancer cells, have been attached to CNHs due to the current application of this antigen in PCa therapy. The hybrids Ab-CNHs, cisplatin-CNHs and functionalised-CNHs have also been synthesized to be used as control systems. The efficacy and specificity of the D2B-cisplatin-CNH conjugate to selectively target and kill PSMA+ prostate cancer cells have been demonstrated in comparison with other derivatives. The developed strategy to functionalise CNHs is fascinating because it can allow the fine tuning of both drug and Ab molecules attached to the nanostructure in order to modulate the activity of the nanosystem. Finally, the herein described methodology can be used for the incorporation of almost any drugs or Abs in the platforms in order to create new targeted drugs for the treatment of different diseases.

A decacobalt(ii) cluster with triple-sandwich structure obtained by partial reductive hydrolysis of a pentacobalt(ii/iii) Weakley-type polyoxometalate.

Partial reductive hydrolysis of a penta-CoII/III cluster [Co(H2O)2(CoIIIW9O34)(PW9O34)]12- (1) leads to the formation of [Co2{Co3(H2O)(Co(OH)2W7O26)(PW9O34)}2]22- (2). This polyoxometalate is made up of two capping [PW9O34]9- units and two bridging [W7O26]10- units that assemble to encapsulate a novel deca-CoII cluster core comprising octahedral and tetrahedral CoII ions.

Ga-Promoted Photocatalytic H2 Production over Pt/ZnO Nanostructures.

Photocatalytic H2 generation is investigated over a series of Ga-modified ZnO photocatalysts that were prepared by hydrothermal methods. It is found that the structural, textural, and optoelectronic properties remarkably depend on the Ga content. The photocatalytic activity is higher in samples with Ga content equal to or lower than 5.4 wt %, which are constituted by Zn1-xGaxO phases. Structural, textural, and optoelectronic characterization, combined with theoretical calculations, reveals the effect of Ga in the doped ZnO structures. Higher Ga incorporation leads to the formation of an additional ZnGa2O4 phase with spinel structure. The presence of such a phase is detrimental for the textural and optoelectronic properties of the photocatalysts, leading to a decrease in H2 production. When Pt is used as the cocatalyst, there is an increase of 1 order of magnitude in the activity with respect to the bare photocatalysts. This is a result of Pt acting as an electron scavenger, decreasing the electron-hole recombination rate and boosting the H2 evolution reaction.

Triazine-Carbon Nanotubes: New Platforms for the Design of Flavin Receptors.

The synthesis of functionalised carbon nanotubes as receptors for riboflavin (RBF) is reported. Carbon nanotubes, both single-walled and multi-walled, have been functionalised with 1,3,5-triazines and p-tolyl chains by aryl radical addition under microwave irradiation and the derivatives have been fully characterised by using a range of techniques. The interactions between riboflavin and the hybrids were analysed by using fluorescence and UV/Vis spectroscopic techniques. The results show that the attached functional groups minimise the π-π stacking interactions between riboflavin and the nanotube walls. Comparison of p-tolyl groups with the triazine groups shows that the latter have stronger interactions with riboflavin because of the presence of hydrogen bonds. Moreover, the triazine derivatives follow the Stern-Volmer relationship and show a high association constant with riboflavin. In this way, artificial receptors in catalytic processes could be designed through specific control of the interaction between functionalised carbon nanotubes and riboflavin.

H2 oxidation versus organic substrate oxidation in non-heme iron mediated reactions with H2O2.

Herein we show that species generated upon reaction of α-[Fe(CF3SO3)2(BPMCN)] (BPMCN = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane) with H2O2 (putatively [Fe(V)(O)(OH)(BPMCN)]) is able to efficiently oxidize H2 to H2O even in the presence of organic substrates, while species formed in the presence of acetic acid (putatively [Fe(V)(O)(OAc)(BPMCN)]) prefer organic substrate oxidation over H2 activation. Mechanistic implications have been analysed with the aid of computational methods.

Complete chemical hydrolysis of cellulose into fermentable sugars through ionic liquids and antisolvent pretreatments.

This work describes a relatively simple methodology for efficiently deconstructing cellulose into monomeric glucose, which is more easily transformed into a variety of platform molecules for the production of chemicals and fuels. The approach undertaken herein first involves the dissolution of cellulose in an ionic liquid (IL), followed by a second reconstruction step aided by an antisolvent. The regenerated cellulose exhibited strong structural and morphological changes, as revealed by XRD and SEM analyses. These changes dramatically affect the hydrolytic reactivity of cellulose with dilute mineral acids. As a consequence, the glucose yield obtained from the deconstructed-reconstructed cellulose was substantially higher than that achieved through hydrolysis of the starting cellulose. Factors that affect the hydrolysis reaction include the type of cellulose substrate, the type of IL used in pretreatment, and the type of acid used in the hydrolysis step. The best results were obtained by treating cellulose with IL and using phosphotungstic acid (0.067 mol L(-1) ) as a catalyst at 413 K. Under these conditions, the conversion of cellulose was almost complete (>99%), with a glucose yield of 87% after only 5 h of reaction.

Few-layer graphenes from ball-milling of graphite with melamine.

We report a simple, practical scalable procedure to produce few-layer graphene sheets using ball-milling. Commercially available melamine can be efficiently used to exfoliate graphite and generate concentrated water or DMF dispersions.

Direct evidence of the SMSI decoration effect: the case of Co/TiO2 catalyst.

First direct images of cobalt nanoparticles covered by a few atomic layers thick TiO(x) moieties after reduction treatment of a Co/TiO(2) system with the simultaneous formation of Co-O-Ti bonds confirm the development of the SMSI decoration effect.

Ball-milling modification of single-walled carbon nanotubes: purification, cutting, and functionalization.

Single-walled carbon nanotubes (SWNTs) can be successfully cut with relatively homogeneous sizes using a planetary mill. The optimized conditions produce highly dispersible SWNTs that can be efficiently functionalized in a variety of synthetic ways. As clearly shown by Raman spectroscopy, the milling/cutting procedure compares very favorably with the most common way of purifying SWNTs, namely, treatment with strong oxidizing acids. Moreover a similar milling process can be used to functionalize and cut pristine SWNTs by one-step nitrene chemistry.

Grafting of poly(acrylic acid) onto an aluminum surface.

Grafting of poly(acrylic acid) (PAA) onto an aluminum surface was successfully achieved by free radical polymerization of acrylic acid using typical radical initiators, benzoyl peroxide and 2,2'-azobisisobutyronitrile. Both spotlike and brush morphologies were achieved. A complete coverage of PAA on an aluminum surface was then achieved by using a thermal chemical vapor deposition process. The PAA thickness was determined by ellipsometry and the superficial chemical composition by X-ray photoelectron spectroscopy (XPS). Grazing angle Fourier transform infrared (FTIR) spectroscopy confirmed the presence of carboxylic acid groups on the surface, and the contact angle measurements revealed a decreasing free surface energy of aluminum due to the polymer surface covering.

Water splitting on semiconductor catalysts under visible-light irradiation.

Sustainable hydrogen production is a key target for the development of alternative, future energy systems that will provide a clean and affordable energy supply. The Sun is a source of silent and precious energy that is distributed fairly all over the Earth daily. However, its tremendous potential as a clean, safe, and economical energy source cannot be exploited unless the energy is accumulated or converted into more useful forms. The conversion of solar energy into hydrogen via the water-splitting process, assisted by photo-semiconductor catalysts, is one of the most promising technologies for the future because large quantities of hydrogen can potentially be generated in a clean and sustainable manner. This Minireview provides an overview of the principles, approaches, and research progress on solar hydrogen production via the water-splitting reaction on photo-semiconductor catalysts. It presents a survey of the advances made over the last decades in the development of catalysts for photochemical water splitting under visible-light irradiation. The Minireview also analyzes the energy requirements and main factors that determine the activity of photocatalysts in the conversion of water into hydrogen and oxygen using sunlight. Remarkable progress has been made since the pioneering work by Fujishima and Honda in 1972, but he development of photocatalysts with improved efficiencies for hydrogen production from water using solar energy still faces major challenges. Research strategies and approaches adopted in the search for active and efficient photocatalysts, for example through new materials and synthesis methods, are presented and analyzed.

Grafting of poly(methyl vinyl ketone) onto aluminum surface.

Polymers were grafted on aluminum surfaces in order to modify the chemical and physical properties of the interface. The properly cleaned and activated surface of the aluminum substrate was first "silanized" either with 3-(trimethoxysilyl)propylamine or allyltrimethoxysilane. The grafting was carried out following two methods: (i) by the reaction of preformed poly(methyl vinyl ketone) with the aminosilane-modified surface; and (ii) by polymerization of methyl vinyl ketone with the vinylsilane-modified surface. The modified aluminum surfaces were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy. The new surfaces were examined by contact-angle measurements, and determinations of the Lewis basicity.

Spectroscopic and DFT study of tungstic acid peroxocomplexes.

The catalytic system formed by tungstic acid and its complexes with H2O2 and phenylphosphonic acid has been analyzed from the experimental and theoretical points of view. Previous structural studies by XRD proved the validity of the DFT proposed models and methodology. Hydrogen peroxide reacts with tungstic acid to form a peroxo complex. Vibrational and electronic spectra showed significant changes upon interaction with H2O2. The DFT and TD-DFT for IR and UV-vis calculations not only are in agreement with experimental data but also allow for a deeper characterization of the species formed in in situ conditions. A SCRF/PCM methodology was chosen to account for the solvent effect. The solvent effect of water was considered for geometry re-optimization of the structure and for the TD-DFT calculations.

Hydrogen peroxide synthesis: an outlook beyond the anthraquinone process.

Hydrogen peroxide (H2O2) is widely used in almost all industrial areas, particularly in the chemical industry and environmental protection. The only degradation product of its use is water, and thus it has played a large role in environmentally friendly methods in the chemical industry. Hydrogen peroxide is produced on an industrial scale by the anthraquinone oxidation (AO) process. However, this process can hardly be considered a green method. It involves the sequential hydrogenation and oxidation of an alkylanthraquinone precursor dissolved in a mixture of organic solvents followed by liquid-liquid extraction to recover H2O2. The AO process is a multistep method that requires significant energy input and generates waste, which has a negative effect on its sustainability and production costs. The transport, storage, and handling of bulk H2O2 involve hazards and escalating expenses. Thus, novel, cleaner methods for the production of H2O2 are being explored. The direct synthesis of H2O2 from O2 and H2 using a variety of catalysts, and the factors influencing the formation and decomposition of H2O2 are examined in detail in this Review.