Strategies to improve hydrogen activation on gold catalysts.

Catalytic reactions involving molecular hydrogen are at the heart of many transformations in the chemical industry. Classically, hydrogenations are carried out on Pd, Pt, Ru or Ni catalysts. However, the use of supported Au catalysts has garnered attention in recent years owing to their exceptional selectivity in hydrogenation reactions. This is despite the limited understanding of the physicochemical aspects of hydrogen activation and reaction on Au surfaces. A rational design of new improved catalysts relies on making better use of the hydrogenating properties of Au. This Review analyses the strategies utilized to improve hydrogen-Au interactions, from addressing the importance of the Au particle size to exploring alternative mechanisms for H2 dissociation on Au cations and Au-ligand interfaces. These insights hold the potential to drive future applications of Au catalysis.

Solvent-Free Aerobic Oxidative Cleavage of Methyl Oleate to Biobased Aldehydes over Mechanochemically Synthesized Supported AgAu Nanoparticles.

The performance of mechanochemically synthesized supported bimetallic AgAu nanoalloy catalysts was evaluated in the oxidative cleavage of methyl oleate, a commonly available unsaturated bio-derived raw material. An extensive screening of supports (SiO2 , C, ZrO2 , Al2 O3 ), metallic ratios (Ag : Au), reaction times, temperatures, and use of solvents was carried out. The performance was optimized towards productivity and selectivity for the primary cleavage products (aldehydes and oxoesters). The optimal conditions were achieved in the absence of solvent, using Ag8 Au92 /SiO2 as catalyst, at 80 °C, reaction time of 1 h, substrate to catalyst=555 and 10 bar of molecular oxygen. A strong support effect was observed: the selectivity to aldehydes was best with silica as support, and to esters was best using zirconia. This shows not only that mechanochemical preparation of bimetallic catalysts is a powerful tool to generate useful catalyst compositions, but also that a safe, green, solventless synthesis of bio-derived products can be achieved by aerobic oxidative cleavage.

Riboflavin Surface Modification of Poly(vinyl chloride) for Light-Triggered Control of Bacterial Biofilm and Virus Inactivation.

Poly(vinyl chloride) (PVC) is the most used biomedical polymer worldwide. PVC is a stable and chemically inert polymer. However, microorganisms can colonize PVC producing biomedical device-associated infections. While surface modifications of PVC can help improve the antimicrobial and antiviral properties, the chemically inert nature of PVC makes those modifications challenging and potentially toxic. In this work, we modified the PVC surface using a derivative riboflavin molecule that was chemically tethered to a plasma-treated PVC surface. Upon a low dosage of blue light, the riboflavin tethered to the PVC surface became photochemically activated, allowing for Pseudomonas aeruginosa bacterial biofilm and lentiviral in situ eradication.

Optimizing Active Sites for High CO Selectivity during CO2 Hydrogenation over Supported Nickel Catalysts.

Controlling the selectivity of CO2 hydrogenation catalysts is a fundamental challenge. In this study, the selectivity of supported Ni catalysts prepared by the traditional impregnation method was found to change after a first CO2 hydrogenation reaction cycle from 100 to 800 °C. The usually high CH4 formation was suppressed leading to full selectivity toward CO. This behavior was also observed after the catalyst was treated under methane or propane atmospheres at elevated temperatures. In situ spectroscopic studies revealed that the accumulation of carbon species on the catalyst surface at high temperatures leads to a nickel carbide-like phase. The catalyst regains its high selectivity to CH4 production after carbon depletion from the surface of the Ni particles by oxidation. However, the selectivity readily shifts back toward CO formation after exposing the catalysts to a new temperature-programmed CO2 hydrogenation cycle. The fraction of weakly adsorbed CO species increases on the carbide-like surface when compared to a clean nickel surface, explaining the higher selectivity to CO. This easy protocol of changing the surface of a common Ni catalyst to gain selectivity represents an important step for the commercial use of CO2 hydrogenation to CO processes toward high-added-value products.

Bioinspired-Metalloporphyrin Magnetic Nanocomposite as a Reusable Catalyst for Synthesis of Diastereomeric (-)-Isopulegol Epoxide: Anticancer Activity Against Human Osteosarcoma Cells (MG-63).

In the present study, we developed a green epoxidation approach for the synthesis of the diastereomers of (-)-isopulegol benzyl ether epoxide using molecular oxygen as the oxidant and a hybrid manganese(III)-porphyrin magnetic reusable nanocomposite as the catalyst. High activity, selectivity, and stability were obtained, with up to four recycling cycles without the loss of activity and selectivity for epoxide. The anticancer effect of the newly synthesized isopulegol epoxide diastereomers was evaluated on a human osteosarcoma cell line (MG-63); both diastereomers showed similar in vitro potency. The measured IC50 values were significantly lower than those reported for other monoterpene analogues, rendering these epoxide isomers as promising anti-tumor agents against low prognosis osteosarcoma.

Controlling Reaction Selectivity over Hybrid Plasmonic Nanocatalysts.

The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles has been used to accelerate several catalytic transformations under visible-light irradiation. In order to fully harness the potential of plasmonic catalysis, multimetallic nanoparticles containing a plasmonic and a catalytic component, where LSPR-excited energetic charge carriers and the intrinsic catalytic active sites work synergistically, have raised increased attention. Despite several exciting studies observing rate enhancements, controlling reaction selectivity remains very challenging. Here, by employing multimetallic nanoparticles combining Au, Ag, and Pt in an Au@Ag@Pt core-shell and an Au@AgPt nanorattle architectures, we demonstrate that reaction selectivity of a sequential reaction can be controlled under visible light illumination. The control of the reaction selectivity in plasmonic catalysis was demonstrated for the hydrogenation of phenylacetylene as a model transformation. We have found that the localized interaction between the triple bond in phenylacetylene and the Pt nanoparticle surface enables selective hydrogenation of the triple bond (relative to the double bond in styrene) under visible light illumination. Atomistic calculations show that the enhanced selectivity toward the partial hydrogenation product is driven by distinct adsorption configurations and charge delocalization of the reactant and the reaction intermediate at the catalyst surface. We believe these results will contribute to the use of plasmonic catalysis to drive and control a wealth of selective molecular transformations under ecofriendly conditions and visible light illumination.

The role and fate of capping ligands in colloidally prepared metal nanoparticle catalysts.

Metal nanoparticles have received intense scientific attention in the field of catalysis. Precise engineering of nanomaterials' size, shape and surface composition, including adsorbed capping ligands, is of utmost importance to control activity and selectivity, and distinguish colloidally prepared metal nanoparticle catalysts from traditional heterogeneous catalysts. The interface between the material and the reaction medium is where the key interactions occur; therefore, catalysis occurs under the influence of capping ligands. In this Perspective review, we focus on the choice of capping ligands (or stabilizing agents), and their role and fate in different steps from preparation to catalysis. Evaluating the influence of the ligands on the catalytic response is not trivial, but the literature provides examples where the ligands adsorbed on the nanoparticle surface dramatically change the activity and selectivity for a particular reaction, while acting either as a dynamic shell or a passivation coating. Steric and electronic effects resulting from the presence of adsorbed ligands have been proposed to influence the catalytic properties. Attempts to remove the capping ligands are discussed, even though they are not always successful or even necessary. Finally, we outline our personal understanding and perspectives on the use of ligands or functionalized supports to tune the activity and selectivity of supported metal nanoparticles.

Reaction Pathway Dependence in Plasmonic Catalysis: Hydrogenation as a Model Molecular Transformation.

The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles can enhance or mediate chemical transformations. Increased reaction rates for several reactions have been reported due to this phenomenon; however, the fundamental understanding of mechanisms and factors that affect activities remains limited. Here, by investigating hydrogenation reactions as a model transformation and employing different reducing agents, H2 and NaBH4 , which led to different hydrogenation reaction pathways, we observed that plasmonic excitation of Au nanoparticle catalysts can lead to negative effects over the activities. The underlying physical reason was explored using density functional theory calculations. We observed that positive versus negative effects on the plasmonic catalytic activity is reaction-pathway dependent. These results shed important insights on our current understanding of plasmonic catalysis, demonstrating reaction pathways must be taken into account for the design of plasmonic nanocatalysts.

One-pot organometallic synthesis of alumina-embedded Pd nanoparticles.

Herein we report a one pot organometallic strategy to access alumina-embedded Pd nanoparticles. Unexpectedly, the decomposition of the organometallic complex tris(dibenzylideneacetone)dipalladium(0), Pd2(dba)3, by dihydrogen in the presence of aluminum isopropoxide, Al(iPrO)3, and without extra stabilizers, was found to be an efficient method to generate a Pd colloidal solution. Careful characterization studies revealed that the so-obtained Pd nanoparticles were stabilized by an aluminum isopropoxide tetramer and 1,5-diphenyl-pentan-3-one, which was produced after reduction of the dba ligand from the organometallic precursor. Moreover, calcination of the obtained nanomaterial in air at 773 K for 2 h resulted in a nanocomposite material containing Pd nanoparticles embedded in Al2O3. This stabilization strategy opens new possibilities for the preparation of transition metal nanoparticles embedded in oxides.

Economically attractive route for the preparation of high quality magnetic nanoparticles by the thermal decomposition of iron(III) acetylacetonate.

The thermal decomposition (TD) methods are among the most successful in obtaining magnetic nanoparticles with a high degree of control of size and narrow particle size distribution. Here we investigated the TD of iron(III) acetylacetonate in the presence of oleic acid, oleylamine, and a series of alcohols in order to disclose their role and also investigate economically attractive alternatives for the synthesis of iron oxide nanoparticles without compromising their size and shape control. We have found that some affordable and reasonably less priced alcohols, such as 1,2-octanediol and cyclohexanol, may replace the commonly used and expensive 1,2-hexadecanediol, providing an economically attractive route for the synthesis of high quality magnetic nanoparticles. The relative cost for the preparation of Fe3O4 NPs is reduced to only 21% and 9% of the original cost when using 1,2-octanediol and cyclohexanol, respectively.

Tuning the Catalytic Activity and Selectivity of Pd Nanoparticles Using Ligand-Modified Supports and Surfaces.

The organic moiety plays an essential role in the design of homogeneous catalysts, where the ligands are used to tune the catalytic activity, selectivity, and stability of the transition metal centers. The impact of ligands on the catalytic performance of metal nanoparticle catalysts is still less understood. Here, we prepared supported nanoparticle (NP) catalysts by the immobilization of preformed Pd NPs on the ligand-modified silica surfaces bearing amine, ethylenediamine, and diethylenetriamine groups. After excluding any size effect, we were able to study the influence of the ligands grafted on the support surface on the catalytic activity of the supported nanoparticles. Higher activity was observed for the Pd NPs supported on propylamine-functionalized support, whereas the presence of ethylenediamine and diethylenetriamine groups was detrimental to the activity. Upon the addition of excess of these amine ligands as surface modifiers, the hydrogenation of alkene to alkane was fully suppressed and, therefore, we were able to tune Pd selectivity. The selective hydrogenation of alkynes into alkenes, although a considerable challenge on the traditional palladium catalysts, was achieved here for a range of alkynes by combining Pd NPs and amine ligands.

Cost-efficient method for unsymmetrical meso-aryl porphyrins and iron oxide-porphyrin hybrids prepared thereof.

Herein, the synthesis and characterisation of magnetic iron oxide-porphyrin hybrids, constituted of iron-oxide magnetic nanoparticles covalently linked to an unsymmetrically substituted meso-aryl porphyrin, are described. The methodology features for the preparation of the key unsymmetrically substituted meso-aryl porphyrin synthons are discussed, with emphasis on sustainability and in economical terms. The "NaY method" herein reported allows large scale and economical preparation, which are demonstrated by its reusability and at least two-fold yields, when compared with classical porphyrin synthetic methods and also presents a much better cost-efficiency rationale and lower environmental impact. Upon covalent linking to iron-oxide magnetic nanoparticles, the new hybrids are fully characterised by thermogravimetry/differential scanning calorimetry, transmission electron microscopy and infrared spectroscopy and their photophysical properties were measured, which demonstrate that the presence of the magnetic nanoparticle counterparts does not affect these properties, thus allowing the materials to keep the photophysical features imparted by their porphyrin counterparts.

Catalytic oxidation of cinnamyl alcohol using Au-Ag nanotubes investigated by surface-enhanced Raman spectroscopy.

Surface-enhanced Raman spectroscopy (SERS) enables ultrasensitive detection of adsorbed species at the catalyst surface. However, it is quite difficult to combine catalytic and SERS activities on the same material. Here we report the application of well-defined Au-Ag nanotubes as both SERS substrates and catalysts for the oxidation of cinnamyl alcohol. The species adsorbed on the catalyst surfaces at different reaction times were analyzed by SERS. The bimetallic nanotubes prepared via a simple galvanic replacement reaction are highly active in the oxidation of cinnamyl alcohol, but do not avoid a radical-chain reaction and the cleavage of the carbon-carbon double bond. A comparison between changes in bulk composition and the nature of adsorbed species at the surface of the catalyst over time suggests that cinnamaldehyde is formed on the catalyst surface (metal-catalyzed oxidation) and benzaldehyde is probably formed in the bulk solution via a radical-chain pathway. In the presence of 2,6-di-tert-butyl-4-methylphenol, the radical-chain reaction is suppressed and the oxidation reaction produces cinnamaldehyde.

Easy Access to Metallic Copper Nanoparticles with High Activity and Stability for CO Oxidation.

Copper catalysts are very promising, affordable alternatives for noble metals in CO oxidation; however, the nature of the active species remains unclear and differs throughout previous reports. Here, we report the preparation of 8 nm copper nanoparticles (Cu NPs), with high metallic content, directly deposited onto the surface of silica nanopowders by magnetron sputtering deposition. The as-prepared Cu/SiO2 contains 85% Cu0 and 15% Cu2+ and was enriched in the Cu0 phase by H2 soft pretreatment (96% Cu0 and 4% Cu2+) or further oxidized after treatment with O2 (33% Cu0 and 67% Cu2+). These catalysts were studied in the catalytic oxidation of CO under dry and humid conditions. Higher activity was observed for the sample previously reduced with H2, suggesting that the presence of Cu-metal species enhances CO oxidation performance. Inversely, a poorer performance was observed for the sample previously oxidized with O2. The presence of water vapor caused only a small increase in the temperature require for the reaction to reach 100% conversion. Under dry conditions, the Cu NP catalyst was able to maintain full conversion for up to 45 h at 350 °C, but it deactivated with time on stream in the presence of water vapor.

Volcano-like behavior of Au-Pd core-shell nanoparticles in the selective oxidation of alcohols.

Gold-palladium (AuPd) nanoparticles have shown significantly enhanced activity relative to monometallic Au and Pd catalysts. Knowledge of composition and metal domain distributions is crucial to understanding activity and selectivity, but these parameters are difficult to ascertain in catalytic experiments that have primarily been devoted to equimolar nanoparticles. Here, we report AuPd nanoparticles of varying Au:Pd molar ratios that were prepared by a seed growth method. The selective oxidation of benzyl alcohol was used as a model reaction to study catalytic activity and selectivity changes that occurred after varying the composition of Pd in bimetallic catalysts. We observed a remarkable increase in catalytic conversion when using a 10:1 Au:Pd molar ratio. This composition corresponds to the amount of Pd necessary to cover the existing Au cores with a monolayer of Pd as a full-shell cluster. The key to increased catalytic activity derives from the balance between the number of active sites and the ease of product desorption. According to density functional theory calculations, both parameters are extremely sensitive to the Pd content resulting in the volcano-like activity observed.

Effect of lipid coating on the interaction between silica nanoparticles and membranes.

Lipid coating is a method highly used to improve the biocompatibility of nanoparticles (NPs), even though its effect on the NP properties is still object of investigation. Herein, silica NPs containing methylene blue, which is a photosensitizer used in a variety of biomedical applications, were coated with a phospholipid bilayer. Regarding the photophysical properties, lipid-coating did not cause significant changes since bare and lipid-coated NPs presented very similar absorption spectra and generated singlet oxygen with similar efficiencies. However, NP interaction with cells and membrane mimics was totally different for bare and lipid-coated NPs. Lipid-coated NPs were distributed through the cell cytoplasm whereas bare NPs were detected only in some vacuolar regions within the cells. Since cellular uptake and cytolocalization are influenced by NP adsorption on cell membranes, the interaction of lipid-coated and bare NPs were studied on a membrane mimic, i.e., Hybrid Bilayer Membranes (HBMs) made of different compositions of negatively charged and neutral lipids. Interactions of bare and lipid-coated NPs with HBMs were analyzed by Surface Plasmon Resonance Imaging. Bare NPs presented high adsorption and aggregation on HBMs independently of the surface charge. Conversely, lipid-coated NPs presented less aggregation on the membrane surface and the adsorption was dependent on the charges of the NPs and of the HBMs. Our results indicated that NPs aggregation on the membrane surface can be modulated by lipid coating, which affects the cytosolic distribution of the NPs.

Insights into the active surface species formed on Ta2O5 nanotubes in the catalytic oxidation of CO.

Freestanding Ta2O5 nanotubes were prepared by an anodizing method. As-anodized amorphous nanotubes were calcined at high temperature to obtain a crystalline phase. All materials were studied by means of BET analysis, XRD, TEM, SEM, XPS, and FTIR and were evaluated in the catalytic oxidation of CO. An XPS study confirmed the formation of different tantalum surface species after high temperature treatment of amorphous Ta2O5 nanotubes. Calcination at 800 °C generated Ta(4+) while higher temperature (1000 °C) treatment led to the formation of Ta(3+) species. These materials also showed significant differences in catalytic activity. Higher activity was observed for samples calcined at 800 °C than at 1000 °C, suggesting that Ta(4+) species are active sites for CO oxidation.