Hydrogen peroxide electrode surface

Yang KS, Mull G, Moulijn JA (2007) Electrochemical generation of hydrogen peroxide using surface area-enhanced Ti-mesh electrodes. Electrochim Acta 52 6304-6309... 

FIGURE 11.5 Approach curve of a HjOj-selective amperometric tip electrode toward a polymer layer loaded with GOx. The tip was produced by immobilizing horseradish peroxidase onto the cross section of an insulated carbon fiber of 7 pm diameter. Solution composition 1 mM glucose in air-saturated 0.2 M phosphate buffer, pH 7. (Reprinted with permission from Horrocks, B.R., Schmidtke, D., Heller, A., and Bard, A.J., Scanning electrochemical microscopy. 24. Enzyme ultramicroelectrodes for the measurement of hydrogen peroxide at surfaces, Anal. Chem., 65, 3605-3614, 1993. Copyright 1993 American Chemical Society.)... 

Two major pathways exist for this reaction, one bypassing hydrogen peroxide (first pathway) and the other involving intermediate peroxide formation via reaction (15.21) (second pathway). The peroxide formed is either electrochemically reduced to water via reaction (15.22) or decomposed catalytically on the electrode surface via reaction (15.23), in which case half of the oxygen consumed to form it reemerges [in both cases the overall reaction corresponds to Eq. (15.20)]. 

Great promise exists in the use of graphitic carbons in the electrochemical synthesis of hydrogen peroxide [reaction (15.21)] and in the electrochemical reduction of carbon dioxide to various organic products. Considering the diversity in structures and surface forms of carbonaceous materials, it is difficult to formulate generalizations as to the influence of their chemical and electron structure on the kinetics and mechanism of electrochemical reactions occurring at carbon electrodes. 

Armstrong FA, Bond AM, Buchi FN, Hanmett A, Hill HAO, Lannon AM, Lettington OC, Zoski CG. 1993. Electrocatalytic reduction of hydrogen-peroxide at a stationary pyrol3ftic-graphite electrode surface in the presence of cytochrome-c peroxidase— A description based on a microelectrode array model for adsorbed enzyme molecules. Analyst 118 973-978. 

Sonoelectrochemistry has also been used for the efficient employment of porous electrodes, such as carbon nanofiber-ceramic composites electrodes in the reduction of colloidal hydrous iron oxide [59], In this kind of systems, the electrode reactions proceed with slow rate or require several collisions between reactant and electrode surface. Mass transport to and into the porous electrode is enhanced and extremely fast at only modest ultrasound intensity. This same approach was checked in the hydrogen peroxide sonoelectrosynthesis using RVC three-dimensional electrodes [58]. 

C.H. Lei and J.Q. Deng, Hydrogen peroxide sensor based on coimmobilized methylene green and horseradish peroxidase in the same montonorillonite-modified bovine serum albumin-glutaraldehyde matrix on a glassy carbon electrode surface. Anal. Chem. 68, 3344—3349 (1996). 

Y. Xiao, H.X. Ju, and H.Y. Chen, Hydrogen peroxide sensor based on horseradish peroxidase-labeled Au colloids immobilized on gold electrode surface by cysteamine monolayer. Anal. Chim. Acta. 391,... 

Haapakka and Kankare have studied this phenomenon and used it to determine various analytes that are active at the electrode surface [44-46], Some metal ions have been shown to catalyze ECL at oxide-covered aluminum electrodes during the reduction of hydrogen peroxide in particular. These include mercu-ry(I), mercury(II), copper(II), silver , and thallium , the latter determined to a detection limit of <10 10 M. The emission is enhanced by organic compounds that are themselves fluorescent or that form fluorescent chelates with the aluminum ion. Both salicylic acid and micelle solubilized polyaromatic hydrocarbons have been determined in this way to a limit of detection in the order of 10 8M. 

Fig. 18b.9. Example cychc voltammograms due to (a) multi-electron transfer redox reaction two-step reduction of methyl viologen MV2++e = MV++e = MV. (b) ferrocene confined as covalently attached surface-modified electroactive species—peaks show no diffusion tail, (c) follow-up chemical reaction A and C are electroactive, C is produced from B through irreversible chemical conversion of B, and (d) electrocatalysis of hydrogen peroxide decomposition by phosphomolybdic acid adsorbed on a graphite electrode.

A new electrolysis system comprising two metal redox couples, Bi(0)/Bi(III) and A1(0)/A1(III), has been shown to be effective for electroreductive Barbier-type allylation of imines [533]. The electrode surface structure has been correlated with the activity towards the electroreduction of hydrogen peroxide for Bi monolayers on Au(III) [578], Electroreductive cycliza-tion of the 4-(phenylsulfonylthio)azetidin-2-one derivative (502) as well as the allenecarboxylate (505) leading to the corresponding cycKzed compounds (504) and (506) has been achieved with the aid of bimetallic metal salt/metal redox systems, for example, BiCh/Sn and BiCh /Zn (Scheme 175) [579]. The electrolysis of (502) is carried out in a DMF-BiCh/Py-(Sn/Sn) system in an undivided cell by changing the current direction every 30 s, giving the product (504)in 67% yield. 

Redox-based biosensors. Noble metals (platinum and gold) and carbon electrodes may be functionalized by oxidation procedures leaving oxidized surfaces. In fact, the potentiometric response of solid electrodes is strongly determined by the surface state [147]. Various enzymes have been attached (whether physically or chemically) to these pretreated electrodes and the biocatalytic reaction that takes place at the sensor tip may create potential shifts proportional to the amount of reactant present. Some products of the enzyme reaction that may alter the redox state of the surface e.g. hydrogen peroxide and protons) are suspected to play a major role in the observed potential shifts [147]. 

---