Bipolar Patterning of Conducting Polymers by Electrochemical Doping and Reaction
Bipolar Patterning of Conducting Polymers by Electrochemical Doping and Reaction
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DOI：
10.1002/anie.201005671
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发表时间：
2010-01-01
影响因子：
16.6
通讯作者：
Fuchigami, Toshio
中科院分区：
文献类型：
--
作者：
Inagi, Shinsuke;Ishiguro, Yutaka;Fuchigami, Toshio
当溶液中的隔离导电基底受到平行电场时，它可以变成双极电极，即同时充当阳极和阴极的电极。这种类型的电化学使得研究化学反应而不与电路物理接触成为可能，例如，在电致化学发光应用中。[1]最近，Björefors和同事成功地在双极电极上创建了分子梯度。[2]例如，通过硫醇的阴极解吸，金上的自组装单分子膜被转化为梯度表面。所报道的电化学[3]或双极[4]图案化都是基于在导电基底的表面处涉及的有机/聚合物分子或无机材料的沉积或解吸。考虑到对基于聚合物的软物质梯度的广泛扩展的研究，使用简单的技术在平面内逐渐转换分子或聚合物膜的组成的挑战是相当重要的。[5]导电聚合物通常具有高导电性，并且当氧化或还原以具有电荷和抗衡离子（掺杂剂）时显示出显著的颜色变化;因此，它们是导电和电致变色材料应用的候选者。在此，我们研究了导电聚合物薄膜的新型双极图案化，即导电聚合物薄膜在双极电极上的电化学掺杂行为。电荷和掺杂剂分布与面内梯度整个聚合物膜是预期的。基于利用电生成物种进行有机反应的电有机合成，[6]我们最近开发了一种通过电化学掺杂和随后的化学反应触发导电聚合物膜的电化学改性的技术。[7，8]例如，使用亲核盐如Et 4 NCl作为支持电解质和氯源成功地进行了聚噻吩膜在阳极上的电化学氯化。[8，9]所需的取代反应不仅在聚合物膜的表面进行，而且在聚合物膜的本体内进行。因此，我们报告
When an isolated conducting substrate in a solution is subjected to a parallel electric field, it can become a bipolar electrode, that is, an electrode that simultaneously acts as both anode and cathode. This type of electrochemistry has made possible the studying of chemical reactions without physical contact to a circuit, for instance, in electrogenerated chemiluminescence applications.[1] Recently, Björefors and co-workers successfully created molecular gradients on a bipolar electrode.[2] For example, self-assembled monolayers on gold were converted to a gradient surface by the cathodic desorption of thiols. Reported electrochemical [3] or bipolar [4] patterning has all been based on deposition or desorption of organic/polymeric molecules or inorganic materials involved at the surface of a conducting substrate. The challenge to gradually convert the composition of molecular or polymeric film in-plane using a simple technique is quite important in view of the widely expanding research into polymer-based soft matter gradients.[5]Conducting polymers generally have a high conductivity and show a significant color change when oxidized or reduced to have charges and counterions (dopants); therefore, they are candidates for conducting and electrochromic material applications. Herein, we investigate the novel bipolar patterning of a conducting-polymer film, that is, the electrochemical doping behavior of a conducting-polymer film on a bipolar electrode. Charge and dopant distributions with an inplane gradient across the polymer film are expected. Based on electroorganic synthesis that utilizes electrogenerated species for organic reactions,[6] we recently developed a technique for the electrochemical modification of a conducting-polymer film triggered by electrochemical doping and subsequent chemical reaction.[7, 8] For instance, the electrochemical chlorination of polythiophene films on an anode was successfully carried out using a nucleophilic salt such as Et4NCl as a supporting electrolyte and chlorine source.[8, 9] The desired substitution reaction proceeded not only at the surface but also within the bulk of the polymer film. Thus, we report the