Kinetics of Direct Reaction of Vanadate, Chromate, and Permanganate with Graphene Nanoplatelets for Use in Water Purification

Abstract

Oxometalates of vanadium(V), chromium(VI), and manganese(VII) have negative impacts on water resources due to their toxicity. To remove them, the kinetics of 0.04 mM oxometalates in natural and synthetic water were studied using graphene nanoplatelets (GNP). The GNP were dispersible in water and formed aggregates >15 µm that could be easily separated. Within 30 min, the GNP were covered with ~0.4 mg/g vanadium and ~1.0 mg/g chromium as Cr(OH)3. The reaction of 0.04 mM permanganate with 50 mg of GNP resulted in a coverage of 10 mg/g in 5 min, while the maximum value was 300 mg/g manganese as Mn2O3/MnO. TEM showed a random metal distribution on the surfaces; no clusters or nanoparticles were detected. The rate of disappearance in aerated water followed a pseudo second-order adsorption kinetics (PSO) for V(V), a pseudo second-order reaction for Cr(VI), and a pseudo first-order reaction for Mn(VII). For Cr(VI) and Mn(VII), the rate constants were found to depend on the GNP mass. Oxygen sorption occurred with PSO kinetics as a parallel slow process upon contact of GNP with air-saturated water. For thermally regenerated GNP, the rate constant decreased for V(V) but increased for Cr(VI), while no effect was observed for Mn(VII). GNP capacity was enhanced through regeneration for V(V) and Cr(VI); no effect was observed for Mn(VII). The reactions are well-suited for use in water purification processes and the reaction products, GNP, decorated with single metal atoms, are of great interest for the construction of sensors, electronic devices, and for application in single-atom catalysis (SAC).