Fast Capture of Fluoride by Anion-Exchange Zirconium-Graphene Hybrid Adsorbent

Fluoride contamination is a severe problem affecting the safety of drinking water around the world. High-rate adsorbent materials are particularly desirable for potable water defluoridation. Current research on fluoride adsorbent materials is primarily focused on metal-based adsorbents with high capacities. However, they generally suffer from slow adsorption kinetics due to the adsorption mechanism of a sluggish exchange between coordinated hydroxyl groups and fluoride ions. Designing metal-based adsorbents to mimic the rapid ion-exchange behavior of anion-exchange resins is a promising approach to integrate fast adsorption and high capacity for fluoride removal. Herein, a ZrO(OH)_1.33Cl_0.66-reduced graphene oxide (rGO) hybrid adsorbent containing exchangeable chloride ions was synthesized with the assistance of cation-π interactions. Unlike most adsorbents requiring a high surface area, this composite has a negligible surface area (1.45 m² g^-1), but can deliver a fast fluoride capture performance (reaching equilibrium in 5 min) with high adsorption rate constants of 1.05 min^-1 and 0.171 mg g^-1 min^-1, around 10 times faster than the best result reported in the literature. Besides, ZrO(OH)_1.33Cl_0.66-rGO can also demonstrate a high fluoride uptake (44.14 mg g^-1) and high removal efficiency (94.4%) in 35 mg L^-1 fluoride solution, both among the highest performances for fluoride adsorption.