Distinction of the two phases of CuTCNQ by scanning electrochemical microscopy

The two known phases of CuTCNQ and TCNQ (TCNQ = 7,7',8,8'-tetracyanoquinodimethane) have been probed by scanning electrochemical microscopy (SECM) in the feedback mode. The first use of this technique for distinguishing differences in the electronic properties of semiconductor phases exploits the large differences in conductivity that exist between CuTCNQ and the parent TCNQ material and also between the CuTCNQ phases I and II. However, the packing density of the individual CuTCNQ crystals in a film structure also is shown to influence the SECM feedback response. Finally, it is shown that films of pure phase II material or mixtures of the phases can be mapped using feedback mode SECM. The SECM method provides valuable insights for elucidating properties of semiconducting solids that are mounted on insulating substrates.     

Fabrication and characterization of probes for combined scanning electrochemical/optical microscopy experiments

A technique that combines scanning electrochemical microscopy (SECM) and optical microscopy (OM) was implemented with a new probe tip. The tip for scanning electrochemicaVoptical microscopy (SECM/OM) was constructed by insulating a typical gold-coated near-field scanning optical microscopy tip using electrophoretic anodic paint. Once fabricated, the tip was characterized by steady-state cyclic voltammetry, as well as optical and electrochemical approach experiments. This tip generated a stable steady-state current and well-defined SECM approach curves for both conductive and insulating substrates. Durable tips whose geometry was a ring with < 1 microm as outer ring radius could be consistently fabricated. Simultaneous electrochemical and optical images of an interdigitated array electrode were obtained with a resolution on the micrometer scale, demonstrating good performance of the tip as both an optical and an electrochemical probe for imaging microstructures. The SECM feedback current measurements were successfully employed to determine tip-substrate distances for imaging.     

Quasi-steady-state voltammetry of rapid electron transfer reactions at the macroscopic substrate of the scanning electrochemical microscope

We report on a novel theory and experiment for scanning electrochemical microscopy (SECM) to enable quasi-steady-state voltammetry of rapid electron transfer (ET) reactions at macroscopic substrates. With this powerful approach, the substrate potential is cycled widely across the formal potential of a redox couple while the reactant or product of a substrate reaction is amperometrically detected at the tip in the feedback or substrate generation/tip collection mode, respectively. The plot of tip current versus substrate potential features the retraceable sigmoidal shape of a quasi-steady-state voltammogram although a transient voltammogram is obtained at the macroscopic substrate. Finite element simulations reveal that a short tip-substrate distance and a reversible substrate reaction (except under the tip) are required for quasi-steady-state voltammetry. Advantageously, a pair of quasi-steady-state voltammograms is obtained by employing both operation modes to reliably determine all transport, thermodynamic, and kinetic parameters as confirmed experimentally for rapid ET reactions of ferrocenemethanol and 7,7,8,8-tetracyanoquinodimethane at a Pt substrate with ～0.5 μm-radius Pt tips positioned at 90 nm-1 μm distances. Standard ET rate constants of ～7 cm/s were obtained for the latter mediator as the largest determined for a substrate reaction by SECM. Various potential applications of quasi-steady-state voltammetry are also proposed.     

Scanning electrochemical microscopy with a band microelectrode: theory and application

Scanning electrochemical microscopy (SECM) is described using a band microelectrode tip. Numerical calculations allow the determination of approach curves of an insulating or a conductive substrate, and the numerical analysis is compared to experimental curves. Natural convection provides a steady-state current at the band microelectrode at an infinite distance from the substrate, and the band tip may be used in the SECM configuration as easily as the tip of a disk. Owing to the millimetric dimension of the band microelectrode, the substrate has an influence on the current at much longer distances than with the disk. Finally, the advantage of SECM with a band microelectrode is observed with the fast electrochemical modification of a fluoropolymer surface.     

Co(OH)2 Nanoparticle‐Encapsulating Conductive Nanowires Array: Room‐Temperature Electrochemical Preparation for High‐Performance Water Oxidation Electrocatalysis

It is highly desired but still remains challenging to design and develop a Co‐based nanoparticle‐encapsulated conductive nanoarray at room temperature for high‐performance water oxidation electrocatalysis. Here, it is reported that room‐temperature anodization of a Co(TCNQ)₂ (TCNQ = tetracyanoquinodimethane) nanowire array on copper foam at alkaline pH leads to in situ electrochemcial oxidation of TCNQ^? into water‐insoluable TCNQ nanoarray embedding Co(OH)₂ nanoparticles. Such Co(OH)₂‐TCNQ/CF shows superior catalytic activity for water oxidation and demands only a low overpotential of 276 mV to drive a geometrical current density of 25 mA cm^?2 in 1.0 m KOH. Notably, it also demonstrates strong long‐term electrochemical durability with its activity being retrained for at least 25 h, a high turnover frequency of 0.97 s^?1 at an overpotential of 450 mV and 100% Faradic efficiency. This study provides an exciting new method for the rational design and development of a conductive TCNQ‐based nanoarray as an interesting 3D material for advanced electrochemical applications.     

Local feedback mode of scanning electrochemical microscopy for electrochemical characterization of one-dimensional nanostructure: theory and experiment with nanoband electrode as model substrate

Local feedback mode is introduced as a novel operation mode of scanning electrochemical microscopy (SECM) for electrochemical characterization of a single one-dimensional (1D) nanostructure, for example, a wire, rod, band, and tube with 1-100-nm width and micrometer to centimeter length. To demonstrate the principle, SECM feedback effects under diffusion limitation were studied theoretically and experimentally with a disk probe brought near a semi-infinitely long band electrode as a geometrical model for a conductive 1D nanostructure. As the band becomes narrower than the disk diameter, the feedback mechanism for tip current enhancement is predicted to change from standard positive feedback mode, to positive local feedback mode, and then to negative local feedback mode. The negative local feedback effect is the only feedback effect that allows observation of a 1D nanostructure without serious limitations due to small lateral dimension, available tip size, or finite electron-transfer rate. In line-scan and approach-curve experiments, an unbiased Pt band electrode with 100-nm width and 2.6-cm length was detectable in negative local feedback mode, even using a 25-microm-diameter disk Pt electrode. Using a 2-microm-diameter probe, both well-defined and defected sites were observed in SECM imaging on the basis of local electrochemical activity of the nanoband electrode. Noncontact and spatially resolved measurement is an advantage of this novel SECM approach over standard electrochemical approaches using electrodes based on 1D nanostructure.     

Kinetics of electron-transfer reactions at nanoelectrodes

The kinetics of several fast heterogeneous electron-transfer reactions were investigated by steady-state voltammetry at nanoelectrodes and scanning electrochemical microscopy (SECM). The disk-type, polished Pt nanoelectrodes (3.7-400-nm radius) were characterized by a combination of voltammetry, scanning electron microscopy, and SECM. A number of experimental curves were obtained at the same nanoelectrode to attain the accuracy and reproducibility similar to those reported previously for micrometer-sized probes. A new analytical approximation was developed and used for analysis of steady-state tip voltammograms. The self-consistent kinetic parameter values with the uncertainty margin of approximately 10% were obtained for electrodes of different radii and for a wide range of the SECM tip/substrate separation distances. The determined standard rate constants are compared to those previously measured at the electrodes of different dimensions, and the correlation between the heterogeneous and self-exchange rate constants is discussed.     

Scanning electrochemical microscopy of quinoprotein glucose dehydrogenase

The activity of immobilized glucose dehydrogenase (GDH), a typical PQQ-dependent quinoprotein, was studied qualitatively and quantitatively by scanning electrochemical microscopy (SECM). PQQ-dependent GDH is of interest because of its high activity and independence of dissolved oxygen in catalyzing the transfer of electrons from glucose to an electron mediator. Biotinylated glucose dehydrogenase was bound to streptavidin-coated paramagnetic beads (surface concentration > or = 1.8 x 10(-11) mol cm(-2)) which were deposited as microscopic microspots on a hydrophobic surface. The catalytic activity of immobilized GDH was mapped in SECM feedback mode and generation-collection mode using ferrocenemethanol, ferrocenecarboxylic acid, p-aminophenol, and ferricyanide as electron mediators, respectively. The apparent steady-state kinetics of catalysis were measured under conditions of high d-glucose concentration using the theory developed for the SECM feedback and generation collection (GC) modes. In feedback mode, curves of the kinetically controlled substrate current against normalized distance were plotted, and it was found that GDH catalysis follows pseudo-first-order kinetics. In GC mode detection, the catalysis follows zero-order kinetics in the presence of high concentration of both substrates for GDH. The turnover rate obtained for immobilized GDH is lower than that of native GDH but much higher than that generally observed for glucose oxidase.     

Electron transfer at the class II/III borderline of mixed valency: dependence of rates on solvent dynamics and observation of a localized-to-delocalized transition in freezing solvents

The dependence of the rates of intramolecular electron transfer (ET) of mixed-valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}-1, where L is the pyridyl ligand and BL is the pyrazine on solvent type and temperature is described. Complexes were reduced chemically to obtain the mixed-valence anions in acetonitrile (CH3CN) and methylene chloride (CH2Cl2). Rate constants for intramolecular ET were estimated by simulating the observed degree of nu(CO) infrared (IR) bandshape coalescence in the mixed-valence state. In the strongly coupled mixed-valence states of these complexes, the electronic coupling, HAB, approaches lambda/2, where lambda is the total reorganization energy. The activation energy is thus nearly zero, and rate constants are in the 'ultrafast' regime where they depend on the pre-exponential terms within the frequency factor, nuN. The frequency factor contains both external (solvent dynamics) and internal (molecular vibrations) contributions. In general, external solvent motions are slower than internal vibrations, and therefore control ET rates in fluid solution. A profound increase in the degree of nu(CO) IR bandshape coalescence is observed as the temperature approaches the freezing points of the solvents methylene chloride (f.p. -92 degrees C) and acetonitrile (f.p. -44 degrees C). Decoupling the slower solvent motions involved in the frequency factor nuN for ET by freezing the solvent causes a transition from solvent dynamics to internal vibration-limited rates. The solvent phase transition causes a localized-to-delocalized transition in the mixed-valence ions that accelerates the rate of ET.     

Scanning electrochemical microscopy. 57. SECM tip voltammetry at different substrate potentials under quasi-steady-state and steady-state conditions

We discuss SECM tip voltammetry, where a UME tip is held above a conductive substrate within about a tip radius and a tip voltammogram is recorded as its potential is slowly scanned while the substrate is held at a fixed potential. When the potential of the substrate is changed, the series of steady-state tip voltammograms provide information about the reactants and products. When the potential of the substrate, ES, is set so that the reaction at the substrate is opposite to that at the tip (the usual SECM conditions), a total positive feedback (tpf) tip voltammogram is recorded. When the substrate potential is set to values where the reaction at the substrate is the same as that occurring on the tip, the tip is shielded from the species in the bulk solution. Depending upon the substrate potential, this can cause total shielding (ts) or a voltammogram that is the result of partial feedback/partial shielding (pf-ps). The result is a series of tip voltammograms that are characterized by tpf, pf-ps, or ts, depending upon ES. Experimental tip voltammograms resulting from the reversible reduction of TCNQ and oxidation of ferrocene in MeCN are reported. These are compared with those from simulations and approximate equations developed to describe the features of the tip voltammograms generated under tpf, ts, or pf-ps conditions. The effect of the diffusion coefficient ratio on the ability of the UME tip to reach a true steady state is also addressed and possible applications, e.g., obtaining information about the reversibility of an electrochemical reaction, the product of an electrochemical reaction, the stability of that product, or the diffusion coefficients of the electroactive species, are discussed.     

Specific heat and paramagnetism of TTT-TCNQ and TTT-TCNQ2 charge transfer complexes

Charge transfer complexes of tetracyanoquinodimethane (TCNQ) (namely TTT-TCNQ and TTT-TCNQ₂), are prepared with the radical cation of tetrathiotetracene (TTT). The two salts are conductive at room temperature and show (at low temperatures) a quasi constant paramagnetism and a linear specific heat term. This behaviour which is characteristic of a magnetic ground state as already found in other salts with regular TCNQ stacks is discussed.     

Investigation of Charge Transfer Kinetics of Polyaniline Supercapacitor Electrodes by Scanning Electrochemical Microscopy

Scanning Electrochemical Microscopy (SECM) is introduced as a promising technique to probe localized interfacial kinetics at the interface of electrolyte/supercapacitor electrode based on polyaniline (PANI) by measuring approach curves from which heterogeneous charge transfer rate constants (k _eff) are extracted. The values correlate with the effectiveness of the electrode material for supercapacitor application. Specifically, measurements on PANI films of different thicknesses show that potential‐dependent rate constants are observed only for PANI films of up to 5 μm thickness. In addition to the thickness of PANI, k _eff is also found to be affected by the applied potential and surface morphology of PANI electrodes. These findings correlate with the macroscopic electrochemical performance of PANI electrodes which shows enhanced specific charge storage ability when their thickness is below 5 μm. Under these conditions, they deliver a specific capacitance of 486 F g⁻¹ and a rate capability of 89%. The observed correlation between microscopic kinetic data determined by SECM and macroscopic device characteristics provides rational guidelines for the optimization of the physical and structural properties of high performance supercapacitor electrodes.     

Use of catechol as selective redox mediator in scanning electrochemical microscopy investigations

The use of catechols, and more specifically of dopamine, as a specific redox mediator for scanning electrochemical microscopy (SECM) investigations was evaluated in the challenging situation of an ultrathin layer deposited on a conductive substrate (carbon materials). Experiments show that dopamine is a well-adapted redox system for SECM in feedback mode and in unbiased conditions. Used as a redox mediator, catechol permits the investigations of modified surfaces without an electrical connection of the sample thanks to fast charge transfer kinetics but with a surface selectivity that does not exist in classical outer-sphere redox mediators. The interest of catechol in SECM as a sensitive redox mediator is exemplified by monitoring several modification steps of an ultrathin (<1 nm) hierarchically porous organic monolayer deposited on carbon substrates. For quantitative analysis, the SECM approach curves using dopamine could simply be characterized with an irreversible electron transfer kinetics model in a large range of pH.     

Scanning electrochemical microscopy in nonusual solvents: inequality of diffusion coefficients problem

Scanning electrochemical microscopy offers interesting possibilities for investigating both transport properties in room-temperature ionic liquids (RTILs) and reactions occurring at the ionic liquid/substrate interface. Besides the expected difficulties related to the lower diffusion coefficients for species dissolved in RTILs arising from the higher viscosity of RTILs, the major problem comes from the inequality of the diffusion coefficients between the oxidized and reduced forms of the redox mediator used to probe the interfaces. This question was treated by an extension of the model originally presented by Martin and Unwin (Martin, R. D.; Unwin, P. R. J. Electroanal. Chem. 1997, 439, 123) and was adapted to the specific aspects of SECM in ionic liquids. The inequalities of diffusion coefficients lead to large anomalies in the current responses, which in extreme cases impede the recording of stationary approach curves. Conditions for recording steady-state approach curves into ionic liquids and consequences of erroneous data treatment were examined. These discrepancies with the simple models (when diffusion coefficients have been taken as equal), could be transformed in a convenient method for characterizing the transport properties of species dissolved in RTIL. The analysis is based on transient SECM experiments and determinations from nonambiguous dimensionless parameters. Experimental examples based on SECM in common RTILs, using the O2/ O2*- couple, were analyzed taking into account the presented model.     

Thin-film phases of organic charge-transfer complexes formed by chemical vapor deposition

Thin films of organic charge-transfer salts, (TTF)(TCNQ) and (TTF)(DMDCNQI), are prepared by the chemical vapor deposition method, where TTF is tetrathiafulvalene, TCNQ is tetracyanoquinodimethane, and DMDCNQI is dimethyldicyanoquinonediimine. Depending on the substrate temperatures, we have obtained randomly oriented polycrystalline phases composed of relatively large crystals and microcrystalline thin-film phases, which sometimes contain well-grown nanowires. The latter shows much different conducting properties from the bulk crystals, and particularly the (TTF)(DMDCNQI) film is nearly as conductive as the (TTF)(TCNQ) film in spite of the bulk insulating property coming from the mixed-stack crystal structure.     

EPR Study of the Electronic States of β’-(BEDT-TTF)(TCNQ)

β’-(BEDT-TTF)(TCNQ) is a compound of BEDT-TTF (=ET) and TCNQ molecules aligned orthogonally with each other, forming two-dimensional sheets and one-dimensional columns of 1/4-filled π band, respectively. It is known that the metal-insulator transition occurs at 330 K at ambient pressure. We have measured the electronic spin susceptibility by means of the EPR-NMR method at 50 MHz, and the angular dependence of g-factor and line width of EPR both at Q (34 GHz) and W (94 GHz) band. We successfully confirmed that the antiferromagnetic transition occurs in ET sheets and TCNQ columns, independently.     

EPR study of the electronic states of β′-(BEDT-TTF)(TCNQ)

β′-(BEDT-TTF)(TCNQ) is a compound of BEDT-TTF (=ET) and TCNQ molecules aligned orthogonally with each other, forming two-dimensional sheets and one-dimensional columns of 1/4-filled π band, respectively. It is known that the metal-insulator transition occurs at 330 K at ambient pressure. We have measured the electronic spin susceptibility by means of the EPR-NMR method at 50 MHz, and the angular dependence of g-factor and line width of EPR both at Q (34 GHz) and W (94 GHz) band. We successfully confirmed that the antiferromagnetic transition occurs in ET sheets and TCNQ columns, independently.     

Scanning electrochemical microscopy with slightly recessed nanotips

Slightly recessed nanoelectrodes were prepared by controlled etching of nanometer-sized, flat Pt electrodes. By using high-frequency (e.g., 2 MHz) ac voltage, the layer of Pt as thin as greater, approximately >3 nm was removed to produce a cylindrical cavity inside the insulating glass sheath. The etched electrodes were characterized by combination of voltammetry and scanning electrochemical microscopy (SECM) to determine the radius and the effective depth of the recess. The theory was developed for current versus distance curves obtained with a recessed tip approaching either a conductive or an insulating substrate. Good agreement between the theoretical and experimental approach curves indicated that recessed nanotips are suitable for quantitative feedback mode SECM experiments.     

Scanning electrochemical microscopy: theory and application of the transient (chronoamperometric) SECM response

A study of the transient (chronoamperometric) response of the scanning electrochemical microscope (SECM) is presented. SECM transients were simulated digitally with a novel integrator based on a Krylov algorithm. The transients observed with planar electrodes (PE), microdisks (MD), and thin-layer cells (TLC) are shown to be limiting cases that fit the simulated SECM transients at very short, intermediate, and long times, respectively. A procedure is established that, provided the tip radius is known, allows the determination of the diffusion coefficient of the species in solution independent of its concentration and the number of electrons transferred in the electrode reaction. Experimental SECM transients are reported for the electrochemical oxidation of Fe(CN)6(4-) in KCl; the diffusion coefficient of Fe(CN)6(4-) was found to agree very well with the literature value.     

Scanning electrochemical microscopy. 58. Application of a micropipet-supported ITIES tip to detect Ag+ and study its effect on fibroblast cells

We report the use of a micropipet-supported ITIES (interface between two immiscible electrolyte solutions, also called a liquid/liquid (L/L) or water/oil (W/O) interface) as a scanning electrochemical microscopy (SECM) tip to detect silver ion and explore Ag+ toxicity in living cells. A 1,2-dichloroethane solution containing a commercially available calixarene-based Ag+ ionophore (IV) was injected into a micrometer-size glass pipet to construct an Ag+-selective SECM tip. The local Ag+ concentration, down to the micromolar level, in the vicinity of living fibroblast cells, was monitored by SECM approach curves and through imaging of the uptake and efflux of Ag+ by living fibroblast cells in real time. The results show that several stages of interaction between Ag+ and fibroblast cells exist. Since a number of biological processes of cells are involved with non-redox-active ions, the work presented here provides a new way to explore cell metabolism, drug delivery, and toxicity assessment by SECM.