RESUMEN
Redox-mediated electrosorption is a promising platform for selective electrochemical (EC) separations, due to its molecular selectivity, high uptake, and tunability for target ions. However, the electrical energy required is mainly generated by non-renewable energy sources, which limits its sustainability and overall impact to decarbonization. Here, a redox-mediated photoelectrochemical (PEC) separation process using polyvinyl ferrocene functionalized TiO2 nanorod electrodes is proposed, which integrates direct solar energy as a driver for the selective electrosorption. The photoelectrochemically-driven oxidation and reduction with both homogeneous and heterogeneous ferrocene-systems is investigated to establish the underlying mechanism. The PEC system can separate heavy metal oxyanions at lower voltages or even without electrical energy. At 0.3 V versus SCE, a 124 mg g-1 uptake for Mo is achieved, which is comparable to the performance of EC cells at 0.75 V versus SCE. Thus, PEC systems not only can generate energy for spontaneous redox-separations, but also can reduce electrical energy consumption by 51.4% compared to EC cells for separation processes when coupled with an external electrical energy.
RESUMEN
Electro-responsive metallopolymers can possess highly specific and tunable ion interactions, and have been explored extensively as electrode materials for ion-selective separations. However, there remains a limited understanding of the role of solvation and polymer-solvent interactions in ion binding and selectivity. The elucidation of ion-solvent-polymer interactions, in combination with the rational design of tailored copolymers, can lead to new pathways for modulating ion selectivity and morphology. Here, we present thermo-electrochemical-responsive copolymer electrodes of N-isopropylacrylamide (NIPAM) and ferrocenylpropyl methacrylamide (FPMAm) with tunable polymer-solvent interactions through copolymer ratio, temperature, and electrochemical potential. As compared to the homopolymer PFPMAm, the P(NIPAM0.9-co-FPMAm0.1) copolymer ingressed 2 orders of magnitude more water molecules per doping ion when electrochemically oxidized, as measured by electrochemical quartz crystal microbalance. P(NIPAM0.9-co-FPMAm0.1) exhibited a unique thermo-electrochemically reversible response and swelled up to 83% after electrochemical oxidation, then deswelled below its original size upon raising the temperature from 20 to 40 °C, as measured through spectroscopic ellipsometry. Reduced P(NIPAM0.9-co-FPMAm0.1) had an inhomogeneous depth profile, with layers of low solvation. In contrast, oxidized P(NIPAM0.9-co-FPMAm0.1) displayed a more uniform and highly solvated depth profile, as measured through neutron reflectometry. P(NIPAM0.9-co-FPMAm0.1) and PFPMAm showed almost a fivefold difference in selectivity for target ions, evidence that polymer hydrophilicity plays a key role in determining ion partitioning between solvent and the polymer interface. Our work points to new macromolecular engineering strategies for tuning ion selectivity in stimuli-responsive materials.
RESUMEN
Advanced redox-polymer materials offer a powerful platform for integrating electroseparations and electrocatalysis, especially for water purification and environmental remediation applications. The selective capture and remediation of trivalent arsenic (As(III)) is a central challenge for water purification due to its high toxicity and difficulty to remove at ultra-dilute concentrations. Current methods present low ion selectivity, and require multistep processes to transform arsenic to the less harmful As(V) state. The tandem selective capture and conversion of As(III) to As(V) is achieved using an asymmetric design of two redox-active polymers, poly(vinyl)ferrocene (PVF) and poly-TEMPO-methacrylate (PTMA). During capture, PVF selectively removes As(III) with exceptional uptake (>100 mg As/g adsorbent), and during release, synergistic electrocatalytic oxidation of As(III) to As(V) with >90% efficiency can be achieved by PTMA, a radical-based redox polymer. The system demonstrates >90% removal efficiencies with real wastewater and concentrations of arsenic as low as 10 ppb. By integrating electron-transfer through the judicious design of asymmetric redox-materials, an order-of-magnitude energy efficiency increase can be achieved compared to non-faradaic, carbon-based materials. The study demonstrates for the first time the effectiveness of asymmetric redox-active polymers for integrated reactive separations and electrochemically mediated process intensification for environmental remediation.