Ovidiu Ersen

An Efficient Strategy to Drive Nanoparticles into Carbon Nanotubes and the Remarkable Effect of Confinement on Their Catalytic Performance

Are you in? Bimetallic PtRu nanoparticles have been selectively confined inside or deposited outside carbon nanotubes (see picture). The confined nanoparticles display significantly higher selectivity and catalytic activity in hydrogenation reactions.

Selective Deposition of Metal Nanoparticles Inside or Outside Multiwalled Carbon Nanotubes

A general method is described for the deposition of metal nanoparticles selectively either inside or outside of carbon nanotubes (CNTs). The method is based on the difference in the interface energies of organic and aqueous solutions with the CNT surface. Because of their lipophilic character, the organic solvent better wets the surface of the nanotubes compared to water and penetrates into the inner volume. The precise control of the volume of each phase allows filling the CNT with the organic phase and covering its outer surface with the aqueous one. Hence, metal nanoparticles can be put with high selectivity either inside or outside the CNT, just by choosing in which solvent the metal precursor is dissolved. SEM, TEM, and 3D-TEM investigations show that a selectivity in localization close to 75% can be reached by this technique. The nanoparticles are homogeneously dispersed and present a narrow size distribution, centered on 5 nm. In this way, one can decorate either the inner or the outer surface of open CNTs, without the need of discriminating the diameter of the opening and without any further step of functionalization than a treatment with nitric acid.

Nitrogen-doped carbon nanotubes as a highly active metal-free catalyst for selective oxidation.

Catalytic reactions are generally carried out on supported metals or oxides, which act as an active phase and require impregnation and thermal treatment steps. During tests, the metal or oxide nanoparticles could be further sintered, which would induces deactivation. Direct incorporation of the active phase into the matrix of a support could be an elegant alternative to prevent catalyst deactivation. Here, we report that nitrogen-doped carbon nanotubes (N-CNTs) can be efficiently employed as a metal-free catalyst for oxidative reactions that allow the selective transformation of the harmful, gaseous H(2)S into solid sulfur. The catalyst exhibits a high stability during the test at high space velocity. The macroscopic shaping of the catalyst on the silicon carbide foam also increases its catalytic activity by improving the contact between the reactants and the catalyst. Such macroscopic shaping allows the avoidance of problems linked with transport and handling of nanoscopic materials and also reduces the pressure drop across the catalyst bed to a large extent.

3D analysis of the morphology and spatial distribution of nitrogen in nitrogen-doped carbon nanotubes by energy-filtered transmission electron microscopy tomography.

We present here the application of the energy-filtered transmission electron microscopy (EFTEM) in the tomographic mode to determine the precise 3D distribution of nitrogen within nitrogen-doped carbon nanotubes (N-CNTs). Several tilt series of energy-filtered images were acquired on the K ionization edges of carbon and nitrogen on a multiwalled N-CNT containing a high amount of nitrogen. Two tilt series of carbon and nitrogen 2D maps were then calculated from the corresponding energy-filtered images by using a proper extraction procedure of the chemical signals. Applying iterative reconstruction algorithms provided two spatially correlated C and N elemental-selective volumes, which were then simultaneously analyzed with the shape-sensitive reconstruction deduced from Zero-Loss recordings. With respect to the previous findings, crucial information obtained by analyzing the 3D chemical maps was that, among the two different kind of arches formed in these nanotubes (transversal or rounded ones depending on their morphology), the transversal arches contain more nitrogen than do the round ones. In addition, a detailed analysis of the shape-sensitive volume allowed the observation of an unexpected change in morphology along the tube axis: close to the round arches (with less N), the tube is roughly cylindrical, whereas near the transversal ones (with more N), its shape changes to a prism. This relatively new technique is very powerful in the material science because it combines the ability of the classical electron tomography to solve 3D structures and the chemical selectivity of the EFTEM imaging.

Fischer–Tropsch Reaction on a Thermally Conductive and Reusable Silicon Carbide Support

The Fischer-Tropsch (FT) process, in which synthesis gas (syngas) derived from coal, natural gas, and biomass is converted into synthetic liquid fuels and chemicals, is a strongly exothermic reaction, and thus, a large amount of heat is generated during the reaction that could severely modify the overall selectivity of the process. In this Review, we report the advantages that can be offered by different thermally conductive supports, that is, carbon nanomaterials and silicon carbide, pure or doped with different promoters, for the development of more active and selective FT catalysts. This Review follows a discussion regarding the clear trend in the advantages and drawbacks of these systems in terms of energy efficiency and catalytic performance for this most-demanded catalytic process. It is demonstrated that the use of a support with an appropriate pore size and thermal conductivity is an effective strategy to tune and improve the activity of the catalyst and to improve product selectivity in the FT process. The active phase and the recovery of the support, which also represents a main concern in terms of the large amount of FT catalyst used and the cost of the active cobalt phase, is also discussed within the framework of this Review. It is expected that a thermally conductive support such as β-SiC will not only improve the development of the FT process, but that it will also be part of a new support for different catalytic processes for which high catalytic performance and selectivity are strongly needed.

Harnessing the Liquid‐Phase Exfoliation of Graphene Using Aliphatic Compounds: A Supramolecular Approach

The technological exploitation of the extraordinary properties of graphene relies on the ability to achieve full control over the production of a high-quality material and its processing by up-scalable approaches in order to fabricate large-area films with single-layer or a few atomic-layer thickness, which might be integrated in working devices. A simple method is reported for producing homogenous dispersions of unfunctionalized and non-oxidized graphene nanosheets in N-methyl-2-pyrrolidone (NMP) by using simple molecular modules, which act as dispersion-stabilizing compounds during the liquid-phase exfoliation (LPE) process, leading to an increase in the concentration of graphene in dispersions. The LPE-processed graphene dispersion was shown to be a conductive ink. This approach opens up new avenues for the technological applications of this graphene ink as low-cost electrodes and conducting nanocomposite for electronics.

Design of covalently functionalized carbon nanotubes filled with metal oxide nanoparticles for imaging, therapy, and magnetic manipulation.

Nanocomposites combining multiple functionalities in one single nano-object hold great promise for biomedical applications. In this work, carbon nanotubes (CNTs) were filled with ferrite nanoparticles (NPs) to develop the magnetic manipulation of the nanotubes and their theranostic applications. The challenges were both the filling of CNTs with a high amount of magnetic NPs and their functionalization to form biocompatible water suspensions. We propose here a filling process using CNTs as nanoreactors for high-yield in situ growth of ferrite NPs into the inner carbon cavity. At first, NPs were formed inside the nanotubes by thermal decomposition of an iron stearate precursor. A second filling step was then performed with iron or cobalt stearate precursors to enhance the encapsulation yield and block the formed NPs inside the tubes. Water suspensions were then obtained by addition of amino groups via the covalent functionalization of the external surface of the nanotubes. Microstructural and magnetic characterizations confirmed the confinement of NPs into the anisotropic structure of CNTs making them suitable for magnetic manipulations and MRI detection. Interactions of highly water-dispersible CNTs with tumor cells could be modulated by magnetic fields without toxicity, allowing control of their orientation within the cell and inducing submicron magnetic stirring. The magnetic properties were also used to quantify CNTs cellular uptake by measuring the cell magnetophoretic mobility. Finally, the photothermal ablation of tumor cells could be enhanced by magnetic stimulus, harnessing the hybrid properties of NP loaded-CNTs.

Unravelling Kinetic and Thermodynamic Effects on the Growth of Gold Nanoplates by Liquid Transmission Electron Microscopy

The growth of colloidal nanoparticles is simultaneously driven by kinetic and thermodynamic effects that are difficult to distinguish. We have exploited in situ scanning transmission electron microscopy in liquid to study the growth of Au nanoplates by radiolysis and unravel the mechanisms influencing their formation and shape. The electron dose provides a straightforward control of the growth rate that allows quantifying the kinetic effects on the planar nanoparticles formation. Indeed, we demonstrate that the surface-reaction rate per unit area has the same dose-rate dependent behavior than the concentration of reducing agents in the liquid cell. Interestingly, we also determine a critical supply rate of gold monomers for nanoparticle faceting, corresponding to three layers per second, above which the formation of nanoplates is not possible because the growth is then dominated by kinetic effects. At lower electron dose, the growth is driven by thermodynamic and the formation and shape of nanoplates are directly related to the twin-planes formed during the growth.

Growth conditions to optimize chemical order and magnetic properties in molecular-beam-epitaxy-grown CoPt/MgO(001) thin films

CoPt films grown on MgO(001) substrates by molecular-beam epitaxy are expected to develop a very large uniaxial magnetocrystalline anisotropy and a high coercivity when the [001] single variant L10 structure develops along the growth direction. The present study investigates the growth conditions that provide the best structural quality of the films and their related magnetic properties. The quality of the substrate surface, the thickness, and the texture of the Pt buffer layer, the presence or absence of a Cr seed layer, are found to be determinants for the fraction of well-oriented grains in the films, whereas the growth temperature mainly pilots the degree of L10 order η. The uniaxial magnetocrystalline anisotropy energy of the [001] grains (Ku001) is maximum at the stoichiometric composition and shows a linear increase with η. The coercive fields and the magnetic domain size are discussed in relation to the microstructure, the degree of L10 order and the magnetic microscopic constants of the films.

Melanin‐Containing Films: Growth from Dopamine Solutions versus Layer‐by‐Layer Deposition

Films formed by oxidation of dopamine are of interest for functionalisation of solid-liquid interfaces owing to their versatility. However, the ability to modulate the properties of such films, for example, permeability to ionic species and the absorption coefficient, is urgently needed. Indeed, melanin films produced by oxidation of dopamine absorb strongly over the whole UV/Vis part of the electromagnetic spectrum and are impermeable to anions even for a film thickness as low as a few nanometers. Herein we combine oxidation of dopamine to produce a solution containing dopamine-melanin particles and their alternating deposition with poly(diallyldimethylammonium chloride) to produce films which have nearly the same morphology as pure dopamine-melanin films but are less compact, more transparent and more permeable to ferrocyanide anions.