(Invited) Electrochemically Driven Ion-Exchange Remediation of Water Containing High Fluoride Content
Authors: Hillman A. Robert , Yavuz Abdulcabbar , Unal Asuman , Cihangir Salih , Ryder Karl 
Published: February 2024

Remediation of water contaminated by anthropogenic activities is required to provide clean water for human consumption and prevent damage to the environment. The scale of the challenge is signaled by its inclusion in the UN 17 Sustainable Development Goals [1]. Major contributors to the problem are industrial activity and agriculture. The former commonly results in the release of metals; analysis and separation of such cationic species have received considerable attention [2]. In the latter instance, run-off of fertilizers used to enhance crop yields can result in unacceptable levels of nitrate or phosphate in natural waters. While monitoring of anionic species is widely undertaken using ion selective electrodes [3], the promise of electrochemical separation technologies [4] in this area is less well developed.
For anthropogenic causes, remediation is the last resort following failure to prevent release of toxic materials into the environment. In contrast, there are instances where the “contaminant” is natural: fluoride is a prime example. The beneficial dental health effects of fluoride are widely appreciated, but excessive amounts are harmful to teeth, bones and various organs [5]. The World Health Organization (WHO) identifies the optimum fluoride level in drinking water to be 0.5-1.0 mg/L. In many regions, water is fluoridated to realize the health benefits. However, local geological conditions many countries can result in natural water fluoride levels significantly above the recommended upper limit of 1.5 mg/L.
This presentation addresses the challenges associated with remediation of anions, with particular focus on fluoride. At the outset, it is recognized that for potable water the requirement is not full de-ionization but selective removal of contaminants: this is a separation challenge. The attributes, performance and potential for scale-up of a range of (electro)chemical remediation strategies will be discussed in general. We then focus on electrochemically switched ion-exchange (ESIX) [6], for which application to water softening [7] and perchlorate removal [8] has been demonstrated.
We explore the facility of aniline-based (co-)polymer films to reversibly extract and eject fluoride ions as the charge (oxidation state) of the films are subject to electrochemical control. Homopolymer and copolymer films based on aniline, o-aminophenol and o-toluidine were deposited potentiodynamically. Film thickness was controlled via the number of potential cycles: the resultant electroactive site population was assayed coulometrically in monomer-free background electrolyte. Film mass was assayed gravimetrically using the EQCM. For relatively thin films, correlation of film mass and charge capacity revealed the solvent content. During deposition of thicker films, acoustic admittance data revealed the progressive evolution of viscoelastic effects. Co-monomer feedstock has a significant influence on film deposition rate, absolute solvent population and redox-driven solvent population change [9].
The ion-exchange capacity of the films for redox-driven fluoride uptake was determined upon exposure to aqueous solutions of varying fluoride concentration, both in the absence and presence of chloride as a competing anion. EQCM mass and charge responses, respectively, provide overall “ion+solvent” and “solvent” population changes: correlation permits separation of fluoride and water uptake/release. Copolymer composition significantly influences the ease of fluoride uptake and release and reveals ion trapping. Complementary data on the dynamics of ion and solvent transfers are provided by shorter timescale experiments, involving voltammetry at faster scan rates and chronoamperometry. Correlation of gravimetric and coulometric data permits temporal separation of fluoride and solvent entry and exit.
Practical exploitation of these promising fundamental observations will require scale-up and optimization of cycle life, film viscoelasticity and response time as functions of film thickness. We speculate that spatially variant film solvation will be a critical parameter. To this end, we consider the viability of neutron reflectivity measurements with isotopic substitution to determine the spatial distributions of fluoride and solvent in films of graded composition.
References
[1] https://sdgs.un.org/goals/goal6
[2] P. Srimuk, X. Su, J. Yoon, D. Aurbach, V. Presser, Nature Reviews Materials, 5 (2020) 517.
[3] G.A. Crespo, Electrochimica Acta, 245 (2017) 1023.
[4] X. Su, Current Opinion in Colloid & Interface Science, 46 (2020) 77.
[5] WHO report WHO/CED/PHE/EPE/19.4.5 (2019).
[6] C. Weidlich, K. M. Mangold and K. Jüttner, Electrochim. Acta, 47 (2001) 741.
[7] C. Weidlich, K. Mangold, K. Jüttner, Electrochim. Acta, 50 (2005) 1547.
[8] S. Zhang, Y. Shao, J. Liu, I. A. Aksay, Y. Lin, ACS Appl. Mater. Interf., 3 (2011) 3633.
[9] A. Unal, A.R. Hillman, K.S. Ryder, S. Cihangir, J. Electrochem. Soc., 168 (2021) 022502.