Bipolar Electrochemistry: A Powerful Tool for Electrifying Functional Material Synthesis.

Electrosynthesis is a powerful method for the synthesis of organic, inorganic, and polymeric materials based on electron-transfer-driven reactions at the substrate/electrode interface. The use of electricity for synthetic reactions without the need for hazardous chemical oxidants and reductants is recognized as a green and sustainable method. Other advantages include control of the reaction selectivity by tuning the electrode potentials. A different mode for driving electrochemical reactions has recently been proposed, in which bipolar electrodes (BPEs) are available as wireless electrodes that undergo anodic and cathodic reactions simultaneously. Bipolar electrochemistry is an old technology that has recently garnered renewed attention because of the interesting features of BPEs: (i) the wireless nature of a BPE is useful for sensors and material synthesis; (ii) the gradient potential distribution on BPEs is a powerful tool for the preparation of gradient surfaces and materials; and (iii) electrophoresis is available for effective electrolysis. In addition to these unique features, a BPE system only requires a small amount of supporting electrolyte in principle, whereas a large amount of electrolyte is necessary in conventional electrochemistry. Hence, bipolar electrochemistry is an inherently green and sustainable chemical process for the synthesis of materials. In this Account, recent progress in bipolar electrochemistry for the electrosynthesis of functional materials is summarized. The wireless nature of BPEs was utilized for symmetry breaking to produce anisotropic materials based on the site-selective modification of conductive objects by electrodeposition and electropolymerization. Potential gradients on a BPE interface have been successfully used as controllable templates to form molecular or polymeric gradient materials, which are potentially applicable for high throughput analytical equipment or as biomimetic materials. The electric field necessary to drive BPEs is also potentially useful to induce the directed migration of charged species. The synergetic effects of electrophoresis and electrolysis were also successfully demonstrated to obtain various functional materials. These features of bipolar electrochemistry and the various combinations of techniques have the potential to change the methodologies of material synthesis. Furthermore, the fundamental principle of bipolar electrochemistry infers that very small amounts of supporting electrolyte are necessary for an electrode system, which is expected to lead new methods of sustainable organic electrosynthesis.