Derivatized metal electrode

Electron donor molecules are oxidized in solution easily. Eor example, for TTE is 0.33V vs SCE in acetonitrile. Similarly, electron acceptors such as TCNQ are reduced easily. TCNQ exhibits a reduction wave at — 0.06V vs SCE in acetonitrile. The redox potentials can be adjusted by derivatizing the donor and acceptor molecules, and this tuning of HOMO and LUMO levels can be used to tailor charge-transfer and conductivity properties of the material. Knowledge of HOMO and LUMO levels can also be used to choose materials for efficient charge injection from metallic electrodes. 

In 1975, the fabrication of a chiral electrode by permanent attachment of amino acid residues to pendant groups on a graphite surface was reported At the same time, stimulated by the development of bonded phases on silica and aluminia surfaces the first example of derivatized metal surfaces for use as chemically modified electrodes was presented. A silanization technique was used for covalently binding redox species to hydroxy groups of SnOj or Pt surfaces. Before that time, some successful attemps to create electrode surfaces with deliberate chemical properties made use of specific adsorption techniques... 

If (23) is selected as the dihalosilane, a convenient way of modifying the nickel surface is available.64 The electrochemical properties of the treated nickel electrode are very similar to those of a similarly derivatized platinum electrode for example, both are equally effective in the elec-trocatalytic oxidation-reduction of solution ferrocene. Normally oxidation of the nickel surface would be a competing process ultimately rendering the electrode passive. The surface modification clearly eliminates this problem and opens up the possibility of using surface modified inexpensive metals as electrodes. 

Ey is the photovoltage obtained for the derivatized n-type semiconductor photoanodes. We assume E° to be the values given in brackets and Ey is the extent to which the peak of the photoanodic current is more negative than E° under >Eg illumination. Data are from references given in (a). cWe assume E° to be the same on the n-type semiconductors as on metallic electrodes but these values have not been measured, since the n-type semiconductors generally are not reversible. 

An interesting development is the application of electrochemical detection methods for improved sensitivity. Originally metal electrodes were used, without derivatization, [163-165], but sensitivity was fairly poor and varied a good deal between the amino acids. For these reasons OPA derivatization was tried [166, 167], and the latest derivatization schemes use p-dimethylamino-phenyl isothiocyanate [168] or phenyl isothiocyanate [169] for making detectable derivatives. 

The chemical modification by silani2a-tion (or other chemical reactions) of carbon, oxide, or metal electrode surfaces [21, 22] or SAM formation on gold surfaces with thiol or disulfide compounds [23] has been utilized for the tip functionalization. The systematic chemical derivatization of the tips was carried out with silane [10, 24-27] or thiol [17, 18, 20, 28-37] derivatives. Today, chemical differentiation of the terminal groups by FFM [5-20,28, 36, 37] or adhesive force measurements [17, 18, 20, 24-28, 30-37] is called chemical force microscopy (CFM) [17]. Adhesive and frictional forces can be mapped in x-y planes as CFM images. The adhesive... 

Importantly, these analytes can be quantitatively electrooxidized at boron-doped diamond thin-film electrodes without derivatization, the use of pulsed voltammetiic waveforms as is most often required for detection at metal electrodes like gold, or fouling [36,39,43,110]. Boron-doped diamond electrodes possess the requisite physicochemical properties needed to support the amine oxidation via an anodic oxygen-transfer reaction (e.g., surface boron sites for amine coordination and localized sp carbon sites where the oxidant, OH , is generated at lower overpotential than the surrounding diamond matrix), and these properties can... 

Fig. 7 (a) Catechol derivatized tetracenes self-assemble on metal oxide surfaces such as aluminum oxide, (b) Schematic and (c) scanning electron micrographs of FET structures fabricated with a 5-nm aluminum oxide layer on top of a 5-nm thermally oxidized Si wafer to allow self-assembly of the derivatized tetracene between sub-100 nm Au source and drain electrodes, (d) /d-Eds characteristics of the assembled tetracene monolayer FET for a 40 nm channel length showing hole modulation and (inset) an atomic force microscope image of the FET channel... 

The preparation of film electrodes Prussian blue films are usually prepared by cycling an electrode in a freshly prepared solution containing iron(III) and hexacyanoferrate(III) ions [70-72]. As substrate, mostly platinum is used, sometimes glassy carbon [73] is used, and very frequently ITO electrodes [74] are used because the latter are very useful for electrochromism studies. Similar procedures using solutions containing metal ions and hexacyanoferrate(III) have been used to deposit cobalt hexacyanoferrate [75] and chromium hexacyanoferrate [76, 77]. Crumbliss et al. reported a plasma deposition of iron species from a plasma containing iron pentacarbonyl and ethane, followed by electrochemical derivatization of the deposited iron sites with the help of hexacyanoferrate solutions [78]. 

The presence of a derivatized surface layer can affect the energetics as well as the kinetics of electrode reactions. It has been found that the flatband potentials of -Si and p-Si electrodes coated with conducting polypyrrole films are shifted by 300 and 500 mV in CH3CN solution." The reaction kinetics on polymer derivatized surface can further be enhanced by impregnation of noble metals such as Pt particles into the... 

---