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The molecular design of polymer interfaces has been key for advancing electrochemical separation processes. Precise control of molecular interactions at electrochemical interfaces has enabled the removal or recovery of charged species with enhanced selectivity, capacity, and stability. In this Perspective, we provide an overview of recent developments in polymer interfaces applied to liquid-phase electrochemical separations, with a focus on their role as electrosorbents as well as membranes in electrodialysis systems. In particular, we delve into both the single-site and macromolecular design of redox polymers and their use in heterogeneous electrochemical separation platforms. We highlight the significance of incorporating both redox-active and non-redox-active moieties to tune binding toward ever more challenging separations, including structurally similar species and even isomers. Furthermore, we discuss recent advances in the development of selective ion-exchange membranes for electrodialysis and the critical need to control the physicochemical properties of the polymer. Finally, we share perspectives on the challenges and opportunities in electrochemical separations, ranging from the need for a comprehensive understanding of binding mechanisms to the continued innovation of electrochemical architectures for polymer electrodes.

We have previously demonstrated up to 5 × 10(5)-fold enrichment of anionic analytes in a microchannel using a technique called bipolar electrode focusing (BEF). Here, we demonstrate that BEF can also be used to enrich a cationic fluorescent tracer. The important point is that chemical modification of the microchannel walls enables reversal of the electroosmotic flow (EOF), enabling cations, instead of anions, to be enriched via an electric field gradient focusing mechanism. Reversal of the EOF has significant consequences on the formation and shape of the region of the buffer solution depleted of charge carriers (depletion zone). Electric field measurements and numerical simulations are used to elucidate the factors influencing the depletion zone. This information is used to understand and control the location and shape of the depletion zone, which in turn influences the stability and concentration of the enriched band.

Bipolar electrode (BPE) focusing locally enriches charged analytes in a microchannel along an electric field gradient that opposes a counter-flow. This electric field gradient forms at the boundary of an ion depletion zone generated by the BPE. Here, we demonstrate concentration enrichment of a fluorescent tracer by up to 500,000-fold. The use of a dual-channel microfluidic configuration, composed of two microchannels electrochemically connected by a BPE, enhances the rate of enrichment (up to 71-fold/s). Faradaic reactions at the ends of the BPE generate ion depletion and enrichment zones in the two, separated channels. This type of device is equivalent to previously reported micro/nanochannel junction arrangements used for ion concentration polarization, but it is experimentally more flexible and much simpler to construct.