Electrochemical surface pretreatment

Electrochemical reactions at semiconductor electrodes have a number of special features relative to reactions at metal electrodes these arise from the electronic structure found in the bulk and at the surface of semiconductors. The electronic structure of metals is mainly a function only of their chemical nature. That of semiconductors is also a function of other factors acceptor- or donor-type impurities present in bulk, the character of surface states (which in turn is determined largely by surface pretreatment), the action of light, and so on. Therefore, the electronic structure of semiconductors having a particular chemical composition can vary widely. This is part of the explanation for the appreciable scatter of experimental data obtained by different workers. For reproducible results one must clearly define all factors that may influence the state of the semiconductor. 

Many dehydrogenase enzymes catalyze oxidation/reduction reactions with the aid of nicotinamide cofactors. The electrochemical oxidation of nicotinamide adeniiw dinucleotide, NADH, has been studied in depthThe direct oxidation of NADH has been used to determine concentration of ethanol i s-isv, i62) lactate 157,160,162,163) pyTuvate 1 ), glucose-6-phosphate lactate dehydrogenase 159,161) alanine The direct oxidation often entails such complications as electrode surface pretreatment, interferences due to electrode operation at very positive potentials, and electrode fouling due to adsorption. Subsequent reaction of the NADH with peroxidase allows quantitation via the well established Clark electrode. 

The different possibilities of surface pretreatment are left unconsidered in the systematics of adhesive selection. Except for very special conditions regarding climate and humidity in case of long-term effects, which require expensive chemical and electrochemical treatment, it is assumed that the process combination ... 

TCO thin films can exhibit tremendous variability in transparency, microstructure (and surface roughness), surface composition, conductivity, chemical stability at high current densities (in OLEDs, OPVs, and chemical sensors), and in their chemical compatibihty with contacting organic layers. Variability is often noticeable from production batch to production batch and within batches of the same metal oxide material [34]. Surface pretreatment conditions have also been shown to dramatically impact the electrochemical, physical, and photophysical properties of metal oxide films [8, 9, 24, 26, 27, 35]. Modification... 

Adsorption of small redox-active molecules (e.g. ferrocene [326]) on ITO can be used to probe changes in electrochemical activity of ITO surface as a function of surface pretreatment [314]. Adsorption of ferrocene dicarboxylic add (Fc(COOH)2) and 3-thiophene acetic acid (3-TAA) onto ITO was achieved by soaking ITO in a 1 mM solution of these small molecules in pure ethanol for 10 min and then rinsing briefly with acetonitrile [314-316]. To ensure reproducibility, the adsorption of Fc(COOH)2 on pretreated ITO was repeated a minimum of three times on three separate ITO samples, for each pretreatment condition [314]. Chemisorbed small molecules on ITO will provide for better direct contact of added conducting polymer layers and/or hole transport layers (HTLs) in the devices [316],... 

ITO Chemisorption of small redox-active molecules on ITO can be used to probe changes in electrochemically activity of ITO surface as a function of surface pretreatment [314-316, 326]. The modification of ITO surface with electroactive small molecules such as Fc(COOH)2 and 3-T7VA provides for better wettability of organic layers to the polar ITO surface and enhanced electrical contact between ITO and copper phthalocyanine (CuPc) layers in multilayer excitonic organic EL and PV technologies [316]. Ferrocene terminated SAMs (Fc-SAMs) [326] are one of the most studied redox-active two dimensional aggregates on metal surfaces [630]. 

Figure 6. Hole injection efficiency figure of merit for substrate contacts of varying work function vs. energy step across the contact polymer interface estimated from published work function data and electrochemical redox potential data. The height of each bar reflects the variability in injection efficiency due primarily to variation in substrate surface pretreatment and for the particular case of Au, diffusion to the interface of metal atoms from underlying binder layers.

The catalytic activity of an electrode is determined not only by the nature of the electrode metal (its bulk properties) but also by the composition and structure of the surface on which the electrochemical reaction takes place. These parameters, in turn, depend on factors such as the method of electrode preparation, the methods of surface pretreatment, the conditions of storage, and other factors all having little effect on the bulk properties. 

M. Nishizawa, Y. Miwa, T. Matsue, and I. Uchida, Surface pretreatment for electrochemical fabrication of ultrathin patterned conducting polymers. J. Elec-trochem. Soc. 74(7(6) 1650 (1993). 

Abstract. This chapter is concerned with an in-depth examination of the adherend surface pretreatments used prior to structural adhesive bonding. It encompasses the various substrates encountered, particularly but not exclusively, in the aerospace industry. It compares and contrasts mechanical, chemical and electrochemical methods used for substrates comprising aluminium alloys, titanium, stainless steel, thermoplastic and thermoset fibre reinforced composites and non-metallic honeycomb. Scanning and transmission electron microscope techniques are used to analyse and characterise many of the pretreated surfaces so produced. 

By using different surface pretreatment methods, such as electrochemical oxidation and reduction cycles, chemical etching, or electrodeposition, they obtained good-quality surface Raman signals from Pt, Pd, Ru, Rh, Fe, Co, Ni, and Zn electrodes, and investigated some fuel cell and corrosion systems that are not possible to investigate previously. These efforts have... 

Immobilized Enzymes. The immobilized enzyme electrode is the most common immobilized biopolymer sensor, consisting of a thin layer of enzyme immobilized on the surface of an electrochemical sensor as shown in Figure 6. The enzyme catalyzes a reaction that converts the target substrate into a product that is detected electrochemicaHy. The advantages of immobilized enzyme electrodes include minimal pretreatment of the sample matrix, small sample volume, and the recovery of the enzyme for repeated use (49). Several reviews and books have been pubHshed on immobilized enzyme electrodes (50—52). 

Brewis et al. used TOF-SIMS to determine the surface composition of hydrocarbon polymers after electrochemical pretreatment with nitric acid alone or in the presence of silver ions [58J. AgNO was generated by electrolysis of a 0.1 M solution of silver nitrate in 3.25 M nitric acid in the anode compartment of a... 

Fe electrodes with electrochemically polished (cathodically pretreated for 1 hr) and renewed surfaces have been investigated in H20 + KF and H20 + Na2S04 by Rybalka et al.721,m by impedance. A diffuse-layer minimum was observed at E = -0.94 V (SCE) in a dilute solution of Na2S04 (Table 19). In dilute KC1 solutions E,njn was shifted 40 to 60 mV toward more negative potentials. The adsorbability of organic compounds (1-pentanol, 1-hexanol, cyclohexanol, diphenylamine) at the Fe electrode was very small, which has been explained in terms of the higher hydro-philicity of Fe compared with Hg and Hg-like metals. 

For instance, in our laboratory, we have recently successfully coupled ex situ STM experiments with electrochemical treatment of Pt single crystals, and we have been able to assign certain changes in surface morphology to electrochemical pretreatment [Strmcnik et al., 2008]. 

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