Prussian blue hydrogen peroxide reduction

The kinetics of hydrogen peroxide reduction catalyzed by Prussian blue has been investigated [12, 113]. In neutral media the reaction scheme of H202 reduction has been found to be the following ... 

The electrochemical rate constants for hydrogen peroxide reduction have been found to be dependent on the amount of Prussian blue deposited, confirming that H202 penetrates the films, and the inner layers of the polycrystal take part in the catalysis. For 4-6 nmol cm 2 of Prussian blue the electrochemical rate constant exceeds 0.01cm s-1 [12], which corresponds to the bi-molecular rate constant of kcat = 3 X 103 L mol 1s 1 [114], The rate constant of hydrogen peroxide reduction by ferrocyanide catalyzed by enzyme peroxidase was 2 X 104 L mol 1 s 1 [116]. Thus, the activity of the natural enzyme peroxidase is of a similar order of magnitude as the catalytic activity of our Prussian blue-based electrocatalyst. Due to the high catalytic activity and selectivity, which are comparable with biocatalysis, we were able to denote the specially deposited Prussian blue as an artificial peroxidase [114, 117]. 

Prussian blue-based nano-electrode arrays were formed by deposition of the electrocatalyst through lyotropic liquid crystalline [144] or sol templates onto inert electrode supports. Alternatively, nucleation and growth of Prussian blue at early stages results in nano-structured film [145], Whereas Prussian blue is known to be a superior electrocatalyst in hydrogen peroxide reduction, carbon materials used as an electrode support demonstrate only a minor activity. Since the electrochemical reaction on the blank electrode is negligible, the nano-structured electrocatalyst can be considered as a nano-electrode array. 

Except for Prussian blue activity in hydrogen peroxide, reduction has been shown for a number of transition metal hexacyanoferrates. The latter were cobalt [151], nickel [152], chromium [150], titanium [153], copper [154], manganese [33], and vanadium [28] hexacyanoferrates. However, as was shown in review [117], catalytic activity of the mentioned inorganic materials in H202 reduction is either very low, or is provided by impurities of Prussian blue in the material. Nevertheless, a number of biosensors based on different transition metal hexacyanoferrates have been developed. 

A.A. Karyakin, E.E. Karyakina, and L. Gorton, The electrocatalytic activity of Prussian blue in hydrogen peroxide reduction studied using a wall-jet electrode with continuous flow. J. Electroanal. Chem. 456, 97-104 (1998). 

Mediators such as 7,7,8,8-tetracyanoquinodimethane (TCNQ) [166], hexacyanoferrate(III) [168] and CoPC [169], which have been applied to a carbon paste or ink, are reduced by the reaction with thiocholine and then reoxidised at the carbon electrode (Fig. 23.6). A second type of mediator has involved the addition of Prussian blue (ferric hex-anocyanoferrate) into an AChE and choline oxidase (ChO) bienzyme biosensor. Prussian blue mediates the reduction of hydrogen peroxide produced by the conversion of choline to betaine by ChO [170]. 

The electrochemical rate constants for hydrogen peroxide reduction have been found to be dependent on the amount of Prussian blue deposited, confirming that H2O2 penetrates the films, and the inner layers of the polycrystal take part in the catalysis. For... 

In contrast to a variety of oxidizable compounds, only a few examples for the detection of strong oxidants with transition metal hexacyanoferrates were shown. Among them, hydrogen peroxide is discussed in the following section. Except for H202, the reduction of carbon dioxide [91] and persulfate [92] by Prussian blue-modified electrode was shown. The detection of the latter is important in cosmetics. It should be noted that the reduction of Prussian blue to Prussian white occurs at the lowest redox potential as can be found in transition metal hexacyanoferrates. 

It is important to compare the catalytic properties of Prussian blue with known hydrogen peroxide transducers. Table 13.2 presents the catalytic parameters, which are of major importance for analytical chemistry selectivity and catalytic activity. It is seen that platinum, which is still considered as the universal transducer, possesses rather low catalytic activity in both H202 oxidation and reduction. Moreover, it is nearly impossible to measure hydrogen peroxide by its reduction on platinum, because the rate of oxygen reduction is ten times higher. The situation is drastically improved in case of enzyme peroxidase electrodes. However, the absolute records of both catalytic activity... 

Application of transition metal hexacyanoferrates for development of biosensors was first announced by our group in 1994 [118]. The goal was to substitute platinum as the most commonly used hydrogen peroxide transducer for Prussian blue-modified electrode. The enzyme glucose oxidase was immobilized on the top of the transducer in the polymer (Nation) membrane. The resulting biosensor showed advantageous characteristics of both sensitivity and selectivity in the presence of commonly tested reductants, such as ascorbate and paracetamol. 

Karyakin and Karyakina have developed a hydrogen peroxide sensor, based on Prussian Blue deposited on glassy carbon electrodes. Prussian Blue was considered an artificial peroxidase due to its high catalytic activity and selectivity, which could be compared with biocatalysis. The application of Prussian Blue modified electrodes enabled the sensing of H2O2 at around 0 V vs. SCE. The electrocatalytic reduction of H2O2 in the presence of O2 was found to be better for Prussian Blue deposited on glassy carbon electrodes than for platinum covered electrodes. Furthermore, these electrodes were more stable and active and less expensive than the platinum and peroxidase modified electrodes. The response was linear up to 0.1-100 pM and the detection limit found to be 10 M. 

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