Electrocatalysts electrochemical deposition

The direct electrochemical deposition methods for the preparation of electrocatalysts allow to localize the catalyst particles on the top surface of the carbon support, as close as possible to the solid polymer electrolyte and does not need heat (oxidative and/or reducing) treatment, as most of the chemical methods do, in order to clean the catalytic particles from surfactant contamination [27,28], This will prevent catalyst sintering due to the agglomeration of nanoparticles under thermal treatment. 

On the other hand, the selectivity of the electrochemical deposition of the metal on the substrate must be 100% of the current efficiency, with no interference from the other metal deposition processes. Therefore, the potential distribution needs to be presented for any serious electrochemical reactor study and the electrocatalyst selection problem. The major problem of current distribution depends on the type of the process that controls the entire reaction rate, such as charge transfer, ohmic contributions, or mass transport to or from the electrode. Many parameters have to be evaluated in the course of an electrochemical process to obtain the desired uniform potential and current distributions. One of the conditions that has to be fulfilled is the continuity equation for the current density vector, j ... 

To improve the electrocatalytic activity of platinum and palladium, the ethanol oxidation on different metal adatom-modified, alloyed, and oxide-promoted Pt- and Pd-based electrocatalysts has been investigated in alkaline media. Firstly, El-Shafei et al. [76] studied the electrocatalytic effect of some metal adatoms (Pb, Tl, Cd) on ethanol oxidation at a Pt electrode in alkaline medium. All three metal adatoms, particularly Pb and Tl, improved the EOR activity of ft. More recently, Pt-Ni nanoparticles, deposited on carbon nanofiber (CNE) network by an electrochemical deposition method at various cycle numbers such as 40, 60, and 80, have been tested as catalysts for ethanol oxidadmi in alkaline medium [77]. The Pt-Ni alloying nature and Ni to ft atomic ratio increased with increasing of cycle number. The performance of PtNi80/CNF for the ethanol electrooxidation was better than that of the pure Pt40/CNF, PtNi40/CNF, and PtNi60/CNF. 

Maillard F, Gloaguen F, Leger JM. Preparation of methanol oxidation electrocatalysts ruthenium deposition on carbon-supported platinum nanoparticles. J Appl Electrochem 2003 33 1-8. 

Most of the electrocatalysts we will discuss in this book are in the form of porous metal films deposited on solid electrolytes. The same film will be also used as a catalyst by cofeeding reactants (e.g. C2H4 plus 02) over it. This idea of using the same conductive film as a catalyst and simultaneously as an electrocatalyst led to the discovery of the phenomenon of electrochemical promotion. 

Of special Interest as O2 reduction electrocatalysts are the transition metal macrocycles In the form of layers adsorptlvely attached, chemically bonded or simply physically deposited on an electrode substrate Some of these complexes catalyze the 4-electron reduction of O2 to H2O or 0H while others catalyze principally the 2-electron reduction to the peroxide and/or the peroxide elimination reactions. Various situ spectroscopic techniques have been used to examine the state of these transition metal macrocycle layers on carbon, graphite and metal substrates under various electrochemical conditions. These techniques have Included (a) visible reflectance spectroscopy (b) laser Raman spectroscopy, utilizing surface enhanced Raman scattering and resonant Raman and (c) Mossbauer spectroscopy. This paper will focus on principally the cobalt and Iron phthalocyanlnes and porphyrins. 

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. 

Nafion and PDDA [58]. Thermal treatment of the resulting films gave a mesoporous Ti02 matrix with Au NPs embedded within and dispersed on top of the Ti02 matrix. Only about 10% of the Au surface area was electrochemically active, suggesting that a large fraction of the Au NPs was not well coimected to the underlying electrode surface. These mesoporous deposits were shown to be effective electrocatalysts for NO and nitrite oxidation. 

The development of new and improved electrocatalysts begins with the discovery of materials displaying improved intrinsic electrochemical activity. Intrinsic activity is best observed and compared in a well-controlled catalyst environment where variables that may disguise the intrinsic activity trends are minimized or absent. Particle size, particle size distribution, surface area, catalyst utilization and the distribution of crystallographic phases are parameters that are typically difficult to control. Vapor deposition of unsupported thin film electrocatalysts eliminates many of these variables. This method provides a controlled synthetic route to smooth, single-phase or multi-phase, ordered or disordered metal alloy phases depending on deposition and processing conditions. 

It would obviously be informative if the release of insulin could be monitored spatially and on a useful time scale. In many microelectrode studies in biology, the substances concerned are easy to reduce or oxidize electrochemically. This is not so with sulfur-containing insulin, and it was not until a suitable (if complex) electrocatalyst was discovered that fast scan cychc voltammetry with microelectrodes could be used to monitor it. The substance that promotes reaction with the sulfide atoms in insulin is a mixed-valent RuOz-cyanoruthenate mixture. The catalyst is prepared in situ and deposited onto the carbon fiber of the microelectrode. The response time of electrodes thus prepared (Kennedy and Huang, 1995) is < 100 ms, and detection limits are as low as 5 pM. 

The activities of CNTs have been evaluated by Girishkumar et al. [7] using ex situ EIS. Their study was conducted in a three-compartment electrochemical cell using a GDE electrode (a carbon fibre paper coated with SWCNTs and Pt black as an anode or cathode). Electrophoretic deposition was used to deposit both the commercially available carbon black (CB) for comparison and the SWCNT onto the carbon Toray paper. Commercially available Pt black from Johnson Matthey was used as the catalyst. In both cases, the loading of the electrocatalyst (Pt), the carbon support, and the geometric area of the electrode were kept the same. EIS was conducted in a potentiostatic mode at either an open circuit potential or controlled potentials. 

Taylor et al.8 were the first to report an electrochemical method for preparation of MEAs for PEMFCs. In their technique, Pt was electrochemically reduced and deposited at the electrode membrane interface, where it was actually utilized as an electrocatalyst. Nation, which is an ion exchange polymer membrane, is first coated on a noncatalyzed carbon support. The Nafion-coated carbon support is then immersed into a commercial acidic Pt plating solution for electrodeposition. Application of a cathodic potential results in diffusion of platinum cations through the active Nation layer. The migrated platinum species are reduced and form Pt particle at the electrode/membrane interface only on the sites which are both electronically and ionically conductive. The deposition of Pt particles merely at the electrode/membrane interface maximizes the Pt utilization. The Pt particles of 2-3.5 nm and a Pt loading of less than 0.05 mg cm-2 were obtained employing this technique.8 The limitation of this method is the difficulty of the diffusion of platinum... 

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