Storing and releasing hydrogen with a redox switch.
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Journal Article↗
Biomedical subjects
Frank Marken
Publications and source records attributed to Frank Marken.
Microwave induced jet boiling investigated via voltammetry at ring-disk microelectrodes.
High intensity microwave radiation is (self-)focused at metal electrodes immersed in aqueous electrolyte solutions to generate highly localized superheating and convection effects. It is shown that, for an electrode pointing downward, low intensity microwave radiation causes density driven convective flow (upward), which at the onset of boiling abruptly switches to a fast jet of liquid moving away from the electrode surface (downward). This "jet-boiling" phenomenon allows extremely high rates of mass transport and mixing to be realized at the electrode surface. Cyclic voltammograms obtained at electrodes placed into a microwave field show very strong mass transport enhancement effects. Cyclic voltammograms recorded at a Pt/Pt ring-disk electrode system (r(1) = 25 microm, r(2) = 32 microm, r(3) = 32.4 microm) in the presence of microwave radiation are employed to further explore mass transport effects under microwave conditions. Mass transport coefficients, collection efficiencies, and temperatures are determined as a function of microwave intensity.
Chemistry, Physical↗
Self-supported and clean one-step cathodic coupling of activated olefins with benzyl bromide derivatives in a micro flow reactor.
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Journal Article↗
Redox processes in mesoporous oxide membranes: layered TiO2 phytate and TiO2 flavin adenine dinucleotide films.
Thin films of TiO2 (anatase) nanoparticles are assembled at an electrode surface via a layer-by-layer deposition process employing phytic acid, pyromellitic acid, or flavin adenine dinucleotide (FAD) as molecular binders. With all three types of binders, layers of typically 30 nm thickness are formed each deposition cycle. FAD as an electrochemically active component immobilized at the surface of the TiO2 particles is reduced to FADH2 and reoxidized in a chemically reversible two electron-two proton redox process. Two distinct voltammetric signals are observed for the immobilized FAD redox system associated with (i) hopping of electrons at the TiO2 surface (reversible) and (ii) conduction of electrons through the TiO2 assembly (irreversible). The conduction of electrons through the TiO2 assembly is possible by diffusion over considerable distances as well as through a "spacer" layer of TiO2 phytate. An order of magnitude (upper limit) estimate for the diffusion coefficient of electrons through TiO2 phytate, D(electron) approximately 10(-6) m(2) s(-1), is obtained from voltammetric data. Finally, it is demonstrated that the calcination of TiO2 assemblies causes dramatic changes in the electron transfer kinetics for the immobilized FAD/FADH2 redox system.
Adsorption↗
Microwave activation of the electro-oxidation of glucose in alkaline media.
The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme-modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)(6)(3-/4-) redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 microm diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of k(mt) > 0.01 m s(-1)(or k(mt) > 1.0 cm s(-1)) are observed at 50 microm diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 microm diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 microm diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.
Calibration↗
Microwave enhanced electroanalysis of formulations: processes in micellar media at glassy carbon and at platinum electrodes.
The direct electroanalysis of complex formulations containing alpha-tocopherol (vitamin E) is possible in micellar solution and employing microwave-enhanced voltammetry. In the presence of microwave radiation substantial heating and current enhancement effects have been observed at 330 microm diameter glassy carbon electrodes placed into a micellar aqueous solution and both hydrophilic and highly hydrophobic redox systems are detected. For the water soluble Fe(CN)(6)(3-/4-) redox system in micellar aqueous solutions of 0.1 M NaCl and 0.1 M sodium dodecylsulfate (SDS) at low to intermediate microwave power, thermal effects and convection effects are observed. At higher microwave power, thermal cavitation is induced and dominates the mass transport at the electrode surface. For the micelle-soluble redox systems tert-butylferrocene and 2,5-di-tert-butyl-1,4-benzoquinone, strong and concentration dependent current responses are observed only in the presence of microwave radiation. For the oxidation of micelle-soluble alpha-tocopherol current responses at glassy carbon electrodes are affected by adsorption and desorption processes whereas at platinum electrodes, analytical limiting currents are obtained over a wide range of alpha-tocopherol concentrations. However, for the determination of alpha-tocopherol in a commercial formulation interference from proteins is observed at platinum electrodes and direct measurements are possible only over a limited concentration range and at glassy carbon electrodes.
Carbon↗
TiO2 phytate films as hosts and conduits for cytochrome c electrochemistry.
Cytochrome c is accumulated into a film of TiO(2) nanoparticles and phytate by adsorption from an aqueous solution into the mesoporous structure. Stable voltammetric responses and high concentrations of redox protein within the TiO(2) phytate layer can be achieved. Two types of electrode systems are reported with (i) the modified TiO(2) phytate film between electrode and aqueous solution phase and (ii) the modified TiO(2) phytate film buried under a porous gold electrode ('porotrode'). The electrical conductivity of TiO(2) phytate films is measured and compared in the dry and in the wet state. Although in the dry state essentially insulating, the TiO(2) phytate film turns into an electrical conductor (with approximately 4 Omega cm specific resistivity assuming ohmic behaviour) when immersed in aqueous 0.1 M phosphate buffer solution at pH 7. The redox protein cytochrome c is therefore directly connected to the electrode via diffusion and migration of electrons in the three dimensional mesoporous TiO(2) phytate host structure. Electron transfer from cytochrome c to TiO(2) is proposed to be the rate-determining step for this conduction mechanism.
Cytochromes c↗
Ion transfer processes at 4-(3-phenylpropyl)-pyridine/aqueous electrolyte/electrode triple phase boundary systems supported by graphite and by mesoporous TiO2.
Biphasic electrode systems allow electrochemical reactions to be driven in a microphase of organic liquid (typically 1-100 nL), which is coupled via ion transfer processes to the surrounding aqueous electrolyte medium. Microdroplet deposits on basal plane pyrolytic graphite as well as thin film deposits of the organic phase within a mesoporous titanium oxide host film are investigated. Cobalt tetraphenylporphyrin (CoTPP) is dissolved in the organic liquid 4-(3-phenylpropyl)-pyridine (PPP) and deposited in the form of microphases at suitable electrode surfaces. The electrode is immersed in aqueous electrolyte environments. It is shown that two stable and highly reversible one-electron metal-centred redox processes occur consistent with Co(III/II)TPP and Co(II/I)TPP in the presence of axial pyridine ligands. The electrochemical characteristics for both processes are strongly affected by the liquid/liquid ion exchange accompanying the redox processes. The potential for both the Co(III/II)TPP and the Co(II/I)TPP redox processes can be adjusted independently by the choice of the nature and concentration of the aqueous electrolyte. The reversible potential observed for the CoTPP metal complex is dominated by the Gibbs energy of transfer for the 'spectator ions'. Conditions can be chosen to eliminate ion transfer effects on the potential scale for biphasic oxidation and reduction processes.
Journal Article↗
Electrifying interfaces.
Electrochemical processes at electrified or polarized phase boundaries and methods for charging phase boundaries are discussed. An important type of interface, the three-phase junction, is introduced and processes at three-phase junctions are compared with those occurring at two-phase junctions. Finally, pairing charged interfaces is considered as a methodology for a more efficient use of electrical energy in microscale electrochemical processes. Chemical processes triggered by currents in the ultimate type of paired electrode system, a tunnel junction, are discussed.
Journal Article↗
Microwave activation in ionic liquids induces high temperature-high speed electrochemical processes.
Self-focusing of intense microwave radiation at the tip of a 25 microm diameter platinum disk microelectrode immersed into the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM(+)PF(6)(-)) containing 1 mM ferrocene causes dramatically (two orders of magnitude) enhanced voltammetric current signals and temperatures in excess of 600 K (at the electrode surface)--extreme conditions sufficient for condensed phase pyrolysis processes to occur.
Journal Article↗
Hydrophobic silica sol-gel films for biphasic electrodes and porotrodes.
Hydrophobic sol-gel films from methyltrimethoxysilane (MTMOS) are deposited onto glass and tin-doped indium oxide (ITO) coated glass substrates. Uniform and microporous films of ca. 200 nm thickness are obtained and investigated by scanning electron microscopy and by electrochemical techniques. From cyclic voltammograms for the oxidation of ferrocenedimethanol in aqueous 0.1 M KNO3 apparent diffusion coefficients and free volume data for processes within the film are derived and it is demonstrated that the film morphology can be controlled by the deposition timing. Two novel types of biphasic electrodes for observing liquid/liquid ion transfer reactions are introduced: (i) an ITO electrode coated with a hydrophobic sol-gel film and (ii) a hydrophobic sol-gel film on glass sputter-coated with 20 nm porous gold (porotrode). For the t-butylferrocene redox system deposited in the form of an organic liquid, very low and morphology dependent current responses are observed on modified ITO electrodes. However, the porotrode system allows biphasic electrode reactions to be driven with high efficiency and with no significant morphology effect of the hydrophobic sol-gel film. This type of nanofilm-modified electrode system will be of interest for biphasic sensor developments.
Journal Article↗
Liquid / liquid ion-transfer processes at the dioctylphosphoric acid (N,N-didodecyl-N',N'-diethylphenylenediamine) / water (electrolyte) interface at graphite and mesoporous TiO2 substrates.
Biphasic electrode systems are studied for the case of the oxidation of the water-insoluble liquid N,N-didodecyl-N',N'-diethylphenylenediamine (DDPD) neat and dissolved in bis(2-ethylhexyl) phosphate (HDOP) and immersed in aqueous electrolyte media. The oxidation process in the absence of HDOP is accompanied by transfer of the anion (perchlorate or phosphate) from the water into the organic phase. However, in the presence of HDOP, oxidation is accompanied by proton exchange instead. This electrochemically driven proton exchange process occurs over a wide pH range. Organic microdroplet deposits of DDPD in HDOP at basal plane pyrolytic graphite electrodes are studied by voltammetric techniques and compared in their behavior to organic microphase deposits in mesoporous TiO2 thin films. The mesoporous TiO2 thin film acts as a host for the organic liquid and provides an alternative biphasic electrode system compared to the random microdroplet/graphite system. Two types of mesoporous TiO2 thin-film electrodes, (i) a 300-400-nm film on ITO and (ii) a 300-400-nm film on ITO sputter-coated with a 20-nm porous gold layer, are investigated.
Electrochemistry↗
Large-amplitude Fourier transformed high-harmonic alternating current cyclic voltammetry: kinetic discrimination of interfering Faradaic processes at glassy carbon and at boron-doped diamond electrodes.
Significant advantages of Fourier transformed large-amplitude ac higher (second to eighth) harmonics relative to responses obtained with conventional small-amplitude ac or dc cyclic voltammetric methods have been demonstrated with respect to (i) the suppression of capacitive background currents, (ii) the separation of the reversible reduction of [Ru(NH(3))(6)](3+) from the overlapping irreversible oxygen reduction process under conditions where aerobic oxygen remains present in the electrochemical cell, and (iii) the kinetic resolution of the reversible [Ru(NH(3))(6)](3+/2+) process in mixtures of [Fe(CN)(6)](3-) and [Ru(NH(3))(6)](3+) at appropriately treated boron-doped diamond electrodes, even when highly unfavorable [Fe(CN)(6)](3-) to [Ru(NH(3))(6)](3+) concentration ratios are employed. Theoretical support for the basis of kinetic discrimination in large-amplitude higher harmonic ac cyclic voltammetry is provided.
Journal Article↗
Microwave activation of electrochemical processes: enhanced electrodehalogenation in organic solvent media.
The effect of high-intensity microwave radiation focused into a "hot spot" region in the vicinity of an electrode on electrochemical processes with and without coupled chemical reaction steps has been investigated in organic solvent media. First, the electrochemically reversible oxidation of ferrocene in acetonitrile and DMF is shown to be affected by microwave-induced thermal activation, resulting in increased currents and voltammetric wave shape effects. A FIDAP simulation investigation allows quantitative insight into the temperature distribution and concentration gradients at the electrode / solution interface. Next, the effect of intense microwave radiation on electroorganic reactions is considered for the case of ECE processes. Experimental data for the reduction of p-bromonitrobenzene, o-bromonitrobenzene, and m-iodonitrobenzene in DMF and acetonitrile are analyzed in terms of an electron transfer (E), followed by a chemical dehalogenation step (C), and finally followed by another electron-transfer step (E). The presence of the "hot spot" in the solution phase favors processes with high activation barriers.
Journal Article↗
An electrochemical redox couple activitated by microelectrodes for confined chemical patterning of surfaces.
Microelectrodes, printed as an array on the surface of a silicon chip, generate chemically active species in a solution of electrolyte held between the electrode array and a glass plate. The active species induce chemical change in molecules coupled to the surface of the glass plate, which is separated from the electrode array by a gap of several micrometers. This paper explores the nature and pattern of the induced chemical change. The patterning is discussed with respect to the electrolyte composition and the magnitude and duration of current applied to the microelectrodes. We show that under suitable conditions the active species is confined to micrometer-sized features and diffusion does not obscure the surface pattern produced.
Journal Article↗
Voltammetric analysis of iron oxide pigments.
Eighteen earthy and four pure synthetic pigments containing alpha-Fe2O3 (hematite), alpha-FeOOH (goethite) and poorly crystalline Fe and Mn oxide species were analyzed by voltammetry of microparticles. Three natural samples were subjected to an interlaboratory test to evaluate the reproducibility of the voltammetric peak potentials and peak shapes. The results confirmed that linear-sweep voltammetry is able to distinguish between poorly crystalline, ferrihydrite-like oxides and well-crystalline hematite and goethite and to detect XRD-amorphous Mn(III,IV) oxides via the peak occurrence. Voltammetry is further able to distinguish between pigments containing well-crystalline goethite (according to its structural features) and hematite (according to its particle size). The microsamples of primers from two baroque paintings were also analyzed by XRD and voltammetry and shown to be analogous to common clayey ochres.
Journal Article↗