Frédéric Kanoufi

Electron transfer properties of a monolayer of hybrid polyoxometalates on silicon

As electroactive molecules, polyoxometalates (POMs) have potential in charge trapping or resistive molecular memories, yet scarcely investigated until very recently. Since charge–discharge processes as well as transport properties are dependent upon the organization of the thin layers, we chose to explore a covalent approach and we prepared a diazonium post-functionalized Keggin-type polyoxometalate [PW11O39{Ge(p-C6H4–CC–C6H4–N2+)}]3− that was subsequently anchored on hydrogenated n-type Si(100) surfaces. A flat and homogeneous hybrid POM monolayer is obtained and characterized by AFM, ellipsometry and XPS techniques. Vertical and lateral electron transfers are studied by cyclic voltammetry and scanning electrochemical microscopy (SECM). If the electron transfer between the POM layer and the silicon surface is quite slow (kETvert = 5 s−1), SECM suggests that the monolayer displays a good lateral conductivity. Interestingly, SECM experiments evidence the influence of the organization of the layer on the lateral charge transfer and show the possibility to accumulate negative charges within the POM monolayer.

Synergistic effect on corrosion resistance of Phynox substrates grafted with surface-initiated ATRP (co)polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) and 2-hydroxyethyl methacrylate (HEMA).

Phynox is of high interest for biomedical applications due to its biocompatibility and corrosion resistance. However, some Phynox applications require specific surface properties. These can be imparted with suitable surface functionalizations of its oxide layer. The present work investigates the surface-initiated atom transfer radical polymerization (ATRP) of 2-methacryloyoxyethyl phosphorylcholine (MPC), 2-hydroxyethyl methacrylate (HEMA), and ATRP copolymerization of (HEMA-co-MPC) (block and statistic copolymerization with different molar ratios) on grafted Phynox substrates modified with 11-(2-bromoisobutyrate)-undecyl-1-phosphonic acid (BUPA) as initiator. It is found that ATRP (co)polymerization of these monomers is feasible and forms hydrophilic layers, while improving the corrosion resistance of the system.

Electrochemical transformation of individual nanoparticles revealed by coupling microscopy and spectroscopy

Although extremely sensitive, electrical measurements are essentially unable to discriminate complex chemical events involving individual nanoparticles. The coupling of electrochemistry to dark field imaging and spectroscopy allows the triggering of the electrodissolution of an ensemble of Ag nanoparticles (by electrochemistry) and the inference of both oxidation and dissolution processes (by spectroscopy) at the level of a single nanoparticle. Besides the inspection of the dissolution process from optical scattering intensity, adding optical spectroscopy reveals chemical changes through drastic spectral changes. The behaviours of single NPs and NP agglomerates are differentiated: in the presence of thiocyanate ions, the transformation of Ag single nanoparticles to AgSCN is investigated in the context of plasmonic coupling with the electrode; tentative interpretations for optically unresolved groups of nanoparticles are proposed.

Opto-electrochemical in situ monitoring of cathodic single-cobalt nanoparticle formation

Single-particle electrochemistry at a nanoelectrode is explored by dark-field optical microscopy. The analysis of the scattered light allows in situ dynamic monitoring of the electrodeposition of single cobalt nanoparticles down to a radius of 65u2005nm. Larger sub-micrometer particles are directly sized optically by super-localization of the edges and the scattered light contains complementary information concerning the particle redox chemistry. This opto-electrochemical approach is used to derive mechanistic insights about electrocatalysis that are not accessible from single-particle electrochemistry.

Platinum Nanoparticle Impacts at a Liquid|Liquid Interface

Single nanoparticle (NP) electrochemistry detection at a micro liquid|liquid interface (LLI) is exploited using the catalyzed oxygen reduction reaction (ORR). In this way, current spikes reminiscent of nanoimpacts were recorded, which corresponded to electrocatalytic enhancement of the ORR by Pt NPs. The nature of the LLI allows exploration of new phenomena in single NP electrochemistry. The recorded impacts result from a bipolar reaction occurring at the Pt NP straddling the LLI. O2 reduction takes place in the aqueous phase, while ferrocene hydride (Fc-H+ ; a complex generated upon facilitated interfacial proton transfer by Fc) is oxidized in the organic phase. Ultimately, the role of reactant partitioning, NP bouncing, or the ability of NPs to induce Marangoni effects, is demonstrated.

Alkyl Modified Gold Surfaces: Characterization of the Au-C bond

The surface of gold can be modified with alkyl groups through a radical crossover reaction involving alkyliodides or bromides in the presence of a sterically hindered diazonium salt. In this paper, we characterize the Au-C(alkyl) bond by surface-enhanced Raman spectroscopy (SERS); the corresponding peak appears at 387 cm-1 close to the value obtained by theoretical modeling. The Au-C(alkyl) bond energy is also calculated, it reaches -36.9 kcal mol-1 similar to that of an Au-S-alkyl bond but also of an Au-C(aryl) bond. In agreement with the similar energies of Au-C(alkyl) and Au-S-(alkyl), we demonstrate experimentally that these groups can be exchanged on the surface of gold.

Monitoring Cobalt-Oxide Single Particle Electrochemistry with Subdiffraction Accuracy

By partially overcoming the diffraction limit, superlocalization techniques have extended the applicability of optical techniques down to the nanometer size-range. Herein, cobalt oxide-based nanoparticles are electrochemically grown onto carbon nanoelectrodes and their individual catalytic properties are evaluated through a combined electrochemical-optical approach. Using dark-field white light illumination, edges superlocalization techniques are applied to quantify changes in particle size during electrochemical activation with down to 20 nm precision. It allows the monitoring of (i) the anodic electrodeposition of cobalt hydroxide material and (ii) the large and reversible volume expansion experienced by the cobalt hydroxide particle during its oxidation. Meanwhile, the particle light scattering provides chemical information such as the Co redox state transformation, which complements both the particle size and the recorded electrochemical current and provides in operando mechanistic information on particle electrocatalytic properties.

Light Driven Design of Dynamical Thermosensitive Plasmonic Superstructures: A Bottom-Up Approach Using Silver Supercrystals

When narrowly distributed silver nanoparticles (NPs) are functionalized by dodecanethiol, they acquire the ability to self-organize in organic solvents into 3D supercrystals (SCs). The NP surface chemistry is shown to introduce a light-driven thermomigration effect, thermophoresis. Using a laser beam to heat the NPs and generate steep thermal gradients, the migration effect is triggered dynamically, leading to tailored structures with high density of plasmonic hot spots. This work describes how to manipulate the hot spots and monitor the effect by holography, thus providing a complete characterization of the migration process on a single object basis. Extensive single object tracking strategies are employed to measure the SCs trajectories, evaluate their size, drift velocity magnitude and direction, allowing the identification of the physical chemical origins of the migration. The phenomenon is shown to happen as a result of the combination of thermophoresis (at short length scales) and convection (long-range), and does not require a metallic substrate. This constitutes a fully optical method to dynamically generate plasmonic platforms in situ and on demand, without requiring substrate nanostructuration and with minimal interference on the chemistry of the system. The importance of the proof-of-concept herein described stems from the numerous potential applications, spanning over a variety of fields such as microfluidics and biosensing.

Grafting of an aluminium surface with organic layers

The grafting of organic films on an aluminum surface with its native oxide is demonstrated in protic or aprotic media by various methods: (i) spontaneous reduction of aryldiazonium salts, (ii) simultaneous electrochemical grafting of diazonium salts and alkyl iodides, (iii) spontaneous reaction of perfluoroalkylamine in an organic solvent and (iv) photochemical grafting of acetonitrile. The films are characterized by IRRAS, XPS, electrochemistry, water contact angles and ToF-SIMS; the latter demonstrates that aryl groups derived from diazonium salts are attached by an O–aryl bond. With all methods, the organic layers are strongly attached to the aluminum surface as they resist ultrasonic cleaning. Superhydrophobic films can be obtained when perfluoroalkyl groups are bonded on the surface.