Dodzi Zigah

Bipolar electrochemistry: from materials science to motion and beyond.

Bipolar electrochemistry, a phenomenon which generates an asymmetric reactivity on the surface of conductive objects in a wireless manner, is an important concept for many purposes, from analysis to materials science as well as for the generation of motion. Chemists have known the basic concept for a long time, but it has recently attracted additional attention, especially in the context of micro- and nanoscience. In this Account, we introduce the fundamentals of bipolar electrochemistry and illustrate its recent applications, with a particular focus on the fields of materials science and dynamic systems. Janus particles, named after the Roman god depicted with two faces, are currently in the heart of many original investigations. These objects exhibit different physicochemical properties on two opposite sides. This makes them a unique class of materials, showing interesting features. They have received increasing attention from the materials science community, since they can be used for a large variety of applications, ranging from sensing to photosplitting of water. So far the great majority of methods developed for the generation of Janus particles breaks the symmetry by using interfaces or surfaces. The consequence is often a low time-space yield, which limits their large scale production. In this context, chemists have successfully used bipolar electrodeposition to break the symmetry. This provides a single-step technique for the bulk production of Janus particles with a high control over the deposit structure and morphology, as well as a significantly improved yield. In this context, researchers have used the bipolar electrodeposition of molecular layers, metals, semiconductors, and insulators at one or both reactive poles of bipolar electrodes to generate a wide range of Janus particles with different size, composition and shape. In using bipolar electrochemistry as a driving force for generating motion, its intrinsic asymmetric reactivity is again the crucial aspect, as there is no directed motion without symmetry breaking. Controlling the motion of objects at the micro- and nanoscale is of primary importance for many potential applications, ranging from medical diagnosis to nanosurgery, and has generated huge interest in the scientific community in recent years. Several original approaches to design micro- and nanomotors have been explored, with propulsion strategies based on chemical fuelling or on external fields. The first strategy is using the asymmetric particles generated by bipolar electrodeposition and employing them directly as micromotors. We have demonstrated this by using the catalytic and magnetic properties of Janus objects. The second strategy is utilizing bipolar electrochemistry as a direct trigger of motion of isotropic particles. We developed mechanisms based on a simultaneous dissolution and deposition, or on a localized asymmetric production of bubbles. We then used these for the translation, the rotation and the levitation of conducting objects. These examples give insight into two interesting fields of applications of the concept of bipolar electrochemistry, and open perspectives for future developments in materials science and for generating motion at different scales.

Tuning the Electronic Communication between Redox Centers Bound to Insulating Surfaces

Controlling communication: The electronic communication between ferrocenyl centers bound to insulating silicon surfaces can be efficiently controlled; scanning electrochemical microscopy (SECM) shows that both the surface coverage of the electroactive units and the nature of the redox mediator allow for this control. The lateral charge propagation can be precisely tuned from an extremely slow to a very fast process

Variations of diffusion coefficients of redox active molecules in room temperature ionic liquids upon electron transfer.

In ionic liquids, the diffusion coefficients of a redox couple vary considerably between the neutral and radical ion forms of the molecule. For a reduction, the inequality of the diffusion coefficients is characterized by the ratio gamma = D(red)/D(ox), where D(red) and D(ox) are the diffusion coefficients of the electrogenerated radical anion and of the corresponding neutral molecule, respectively. In this work, measurements of gamma have been performed by scanning electrochemical microscopy (SECM) in transient feedback mode, in three different room temperature ionic liquids (RTILs) sharing the same anion and with a series of nitro-derivative compounds taken as a test family. The smallest gamma ratios were determined in an imidazolium-based RTIL and with the charge of the radical anion localized on the nitro group. Conversely, gamma tends to unity when the radical anion is fully delocalized or when the nitro group is sterically protected by bulky substituents. The gamma ratios, standard potentials of the redox couple measured in RTILs, and those observed in a classical organic solvent were compared for the investigated family of compounds. The stabilization energies approximately follow the gamma ratios in a given RTIL but change considerably between ionic liquids with the nature of the cation.

Synthesis and immobilization of Ag(0) nanoparticles on diazonium modified electrodes: SECM and cyclic voltammetry studies of the modified interfaces.

A versatile method was used to prepare modified surfaces on which metallic silver nanoparticles are immobilized on an organic layer. The preparation method takes advantage, on one hand, of the activated reactivity of some alkyl halides with Ag-Pd alloys to produce metallic silver nanoparticles and, on the other hand, of the facile production of an anchoring polyphenyl acetate layer by the electrografting of substituted diazonium salts on carbon surfaces. Transport properties inside such modified layers were investigated by cyclic voltammetry, scanning electrochemical microscopy (SECM) in feedback mode, and conducting AFM imaging for characterizing the presence and nature of the conducting pathways. The modification of the blocking properties of the surface (or its conductivity) was found to vary to a large extent on the solvents used for surface examination (H(2)O, CH(2)Cl(2), and DMF).

Optimized preparation and scanning electrochemical microscopy analysis in feedback mode of glucose oxidase layers grafted onto conducting carbon surfaces.

An optimized immobilization procedure based on the electroreduction of aryldiazonium salt followed by covalent attachment of a cross-linked hydrogel was used to graft glucose oxidase on a carbon surface. Scanning electrochemical microscopy (SECM) and cyclic voltammetry were used to follow the construction steps of the modified electrode. By adjusting the compactness of the layer through the electrografting reaction, the penetration of the mediator through the layer can be controlled to allow the monitoring of the enzymatic activity by both cyclic voltammetry and SECM in feedback mode. The enzymatic activity of the film is finally characterized by SECM.

Wireless Electrografting of Molecular Layers for Janus Particle Synthesis

The chemical functionalization of surfaces with biological, redox-active or photosensitive molecules has been shown to be useful for applications ranging from molecular electronics, catalysis and energy conversion to chemical or biochemical sensors. Among several methods proposed to tailor the properties of conducting surfaces, electrografting of diazonium salts is one of the most popular strategies for tuning the chemical nature of substrate surfaces without losing its bulk properties. This electrochemical reduction of diazonium salts allows a covalent attachment of various functional groups to a wide range of substrates, and especially to carbon surfaces. These grafted organic layers are frequently used to fine-tune the surface properties of such substrates. The grafting is usually carried out by normal electrochemical reduction, meaning that the substrate has to be physically connected to an electrode. However in some situations it might be interesting and even mandatory to modify objects that are suspended in a solution, and thus not being in direct contact with an electrode. This is for example the case for the bulk production of Janus particles. It has been shown recently that this can be achieved by bipolar electrochemistry for the asymmetric deposition of metal layers. Herein we present an original method in which this attractive concept is for the first time used to generate a grafted organic layer, localized on one half sphere of carbon beads, thus leading to Janus particles bearing organic functional groups. The concept of bipolar electrochemistry applied to microspheres has been described by Fleischmann et al. Briefly, when a high electric field polarizes an object with sufficient electrical conductivity suspended in a solution, redox reactions can be carried out at the opposite side of the object, namely reductions at the cathodically polarized side and oxidations at the anodically polarized side (Figure 1). The polarization (DV) of the object is directly proportional to the effective length of the particle. This concept has recently become the driving force for the detec-

Electrokinetic Assembly of One-Dimensional Nanoparticle Chains with Cucurbit(7)uril Controlled Subnanometer Junctions

One-dimensional (1D) nanoparticle chains with defined nanojunctions are of strong interest due to their plasmonic and electronic properties. A strategy is presented for the assembly of 1D gold-nanoparticle chains with fixed and rigid cucurbit[n]uril-nanojunctions of 9 Å. The process is electrokinetically accomplished using a nanoporous polycarbonate membrane and controlled by the applied voltage, the nanoparticle/CB[n] concentration ratio, time and temperature. The spatial structure and time-resolved analysis of chain plasmonics confirm a growth mechanism at the membrane nanopores.

Electropolymerization of Polypyrrole by Bipolar Electrochemistry in an Ionic Liquid

Bipolar electrochemistry has been recently explored for the modification of conducting micro- and nanoobjects with various surface layers. So far, it has been assumed that such processes should be carried out in low-conductivity electrolytes in order to be efficient. We report here the first bipolar electrochemistry experiment carried out in an ionic liquid, which by definition shows a relatively high conductivity. Pyrrole has been electropolymerized on a bipolar electrode, either in ionic liquid or in acetonitrile. The resulting polymer films were characterized by scanning electron microscopy and by contact profilometry. We demonstrate that the films obtained in an ionic liquid are thinner and smoother than the films synthesized in acetonitrile. Furthermore, a well-defined band of polypyrrole can be obtained in ionic liquid, in contrast to acetonitrile for which the polypyrrole film is present on the whole anodic part of the bipolar electrode.

One-step preparation of bifunctionalized surfaces by bipolar electrografting

Bipolar electrochemistry (BPE) is widely used to trigger electrochemical reactions on conducting objects without direct electrical wiring. In this study a novel methodology is reported, which for the first time allows simultaneous deposition of two different organic films at each end of a glassy carbon substrate (1 × 1 cm2). The approach is based on the use of an organic bifunctional molecule, which may be oxidatively and reductively electrografted at the same time. The reduction process goes through the diazonium group, while the oxidation proceeds via the primary amine. The double functionalized plates are investigated by ellipsometry, cyclic voltammetry, condensation imaging, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. Post-modification of one of the anchoring layers illustrates the versatility of the system, pointing to its potential use in fields going from molecular electronics to targeted drug delivery.