Selective fluoride removal from groundwater using CNT-CeO2 electrodes in capacitive deionization (CDI)

Abstract

Selective capacitive deionization (SCDI) is a promising process for preferentially removing specific ions from waters with complex compositions. The selectivity towards certain species in CDI is most frequently achieved through novel electrode materials with high affinities towards targeted species. In this study, we investigate the selective removal of fluoride ions from groundwater containing concentrated co-existing chloride ions. A carbon nanotube-CeO2 (CNT-CeO2) electrode is employed for the electro-sorption of fluoride ions. Our findings are compelling: when processing a mixed F−/Cl− solution comprising 10 mg/L F− and 100 mg/L Cl−, the CNT-CeO2 electrode is seen to reduce the concentration of F− ions to 1.5 mg/L in just 150 min, amounting to an 85 % F− removal efficiency, while the Cl− removal efficiency remains below 2 %. Importantly, this translates to a F−/Cl− separation factor of up to 4.16 when using the CeO2-based electrodes, which is 40 times higher than that achieved with conventional activated carbon (AC) electrodes. Furthermore, the energy consumption for treating actual groundwater using scaled-up equipment is impressively low at approximately 0.2 kWh/m3. The high affinity of CNT-CeO2 towards fluoride is attributed to the intercalation Faraday capacitance initiated by the reaction between F− with CeO2, as verified by the electrochemical quartz crystal microbalance (EQCM). Moreover, EQCM results show a substantial increase in both mass and current as the potential increased beyond 0.8 V vs Ag/AgCl, implying that the current surge is not a result of water splitting but rather the adsorption of F− onto the CNT-CeO2 electrode. The addition of CNTs substantially increases the conductivity of CeO2 electrodes and restricts the aggregation of CeO2, thereby accelerating ion diffusion and promoting selective adsorption characteristics. Importantly, our electro-driven approach demonstrates excellent adsorption–desorption over 20 cycles. This comprehensive study advances the technological development of selective CDI, while providing new insights for fluoride removal in groundwater.