Poly electrodeposition

Conducting polymer composites have also been formed by co-electrodeposition of matrix polymer during electrochemical polymerization. Because both components of the composite are deposited simultaneously, a homogenous film is obtained. This technique has been utilized for both neutral thermoplastics such as poly(vinyl chloride) (159), as well as for a large variety of polyelectrolytes (64—68, 159—165). When the matrix polymer is a polyelectrolyte, it serves as the dopant species for the conducting polymer, so there is an intimate mixing of the polymer chains and the system can be appropriately termed a molecular composite. 

Poly crystalline silver layer electrodeposited on a polycrystalline platinum electrode. 

Bouroushian M, Kosanovic T, Karoussos D, SpyreUis N (2009) Electrodeposition of poly-crystaUine ZnTe from simple and citrate-complexed acidic aqueous solutions. Electrochim Acta 54 2522-2528... 

There is one report of the redox properties of poly(ferrocenylene) by Oyama et al. noting that the cyclic voltammetry of low molecular weight poly(ferrocenylene) (Mw 900) dissolved in CH2C12 or electrodeposited on Pt gives a broad redox wave with two (or three) peaks between 0.2 and 0.8 V vs. SSCE (70). 

One problem for the coated system is that the film is peeled off after prolonged irradiation. In order to have a more adhesive film, the surface of n-Si was modified with N-(3-trimethoxysilyIpropyl)pyrrole (22). Pyrrole was then electrodeposited on this modified electrode as shown in Eq. (24) 85). The durability of the coated poly(pyrrole) was improved by such a treatment of n-Si surface. The n-Si electrode coated only with poly(pyrrole) gave a declined photocurrent from 6.5 to 1.8 mA cm-2 in less than 18 h, while the poly(pyrrole) coated n-Si treated at first with 22 as Eq. (24) gave a stable photocurrent of 7.6 mA cm-2 for 25 h. When an n-Si electrode was coated with Pt layer before the deposition of poly(pyrrole), the stability of the semiconductor was improved remarkably (ca. 19 days)85b). A power conversion efficiency of 5.5% was obtained with iodide/iodine redox electrolytes. 

It is interesting to conclude this section with an example that, in a sense, brings the chapter full circle. The metallization of plastic materials used as metal substitutes is a process with actual and future commercial potential. Usually, plastics are plated after appropriate sensitization by an electroless process which involves reduction of metal ions (e.g. Ni2+, Cu2+) by chemical rather than electrical means.19 There seems no reason why the reducing agent should not be incorporated in the polymer and Murray and his collaborators101 have demonstrated that copper, silver, cobalt and nickel may each be electrodeposited on to films of [poly-Ru(bipy)2(4-vinylpyridine)2]2+ coated on to platinum electrodes. The metal reductions are mediated by the Ru1 and Ru° states of the polymer. 

Poly(3,4-ethylenedioxythiophene) (PEDOT) is a particularly popular conducting polymer as it can have good conductivity and stability and has a low band gap, which is pertinent to its use in photovoltaic devices. A number of authors have now studied the electrochemical synthesis of this polymer in different ionic liquids. Lu et al. [77] first demonstrated the use of [C4mim][BF4] to electrodeposit PEDOT onto ITO, and its application in an electrochromic numeric display. 

As in any electrode process, the potential applied to the electrode determines the reaction rate. In electrodeposition, we expect that it affects the rate of deposition and thence the structure of the deposit a low overpotential signifies more time available to form an electrodeposit of perfectly crystalline structure. This can be observed experimentally (Fig. 15.7). Another factor arises from differences in current density between different parts of the electrode owing to electrode shape, which affects mass transport and thus accessibility to the cations to be deposited. Generally, it is best to apply a potential corresponding to the formation of poly crystalline deposits. A more perfect crystalline structure would be desirable, but the low rate of electrodeposition does not compensate for using such low overpotentials. 

Using a different approach, the research gronps of Fabre and Freund have synthesized boronate-functionalized conjugated polymers, which serve as electrochemical sensors. For example, a conjugated redox-active film of polypyrrole (174) was electrodeposited onto a platinum electrode from acetonitrile solution. Addition of fluoride anions led to a new redox system that showed an anodic shift relative to polypyrrole itself, which was attributed to fluoride binding to the boronate group. A related poly(aniline boronic acid) (175) was also reported and studied for saccharide detection. " ... 

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