Efficient Sequestration of Hexavalent Chromium by Graphene-Based Nanoscale Zero-Valent Iron Composite Coupled with Ultrasonic Pretreatment

Nanoscale zero-valent iron (nZVI) has attracted considerable attention for its potential to sequestrate and immobilize heavy metals such as Cr(VI) from an aqueous solution. However, nZVI can be easily oxidized and agglomerate, which strongly affects the removal efficiency. In this study, graphene-based nZVI (nZVI/rGO) composites coupled with ultrasonic (US) pretreatment were studied to solve the above problems and conduct the experiments of Cr(VI) removal from an aqueous solution. SEM-EDS, BET, XRD, and XPS were performed to analyze the morphology and structures of the composites. The findings showed that the removal efficiency of Cr(VI) in 30 min was increased from 45.84% on nZVI to 78.01% on nZVI/rGO and the removal process performed coupled with ultrasonic pretreatment could greatly shorten the reaction time to 15 min. Influencing factors such as the initial pH, temperature, initial Cr(VI) concentration, and co-existing anions were studied. The results showed that the initial pH was a principal factor. The presence of HPO(4)(2−), NO(3)(−), and Cl(−) had a strong inhibitory effect on this process, while the presence of SO(4)(2−) promoted the reactivity of nZVI/rGO. Combined with the above results, the process of Cr(VI) removal in US-nZVI/rGO system consisted of two phases: (1) The initial stage is dominated by solution reaction. Cr(VI) was reduced in the solution by Fe(2+) caused by ultrasonic cavitation. (2) In the following processes, adsorption, reduction, and coprecipitation coexisted. The addition of rGO enhanced electron transportability weakened the influence of passivation layers and improved the dispersion of nZVI particles. Ultrasonic cavitation caused pores and corrosion at the passivation layers and fresh Fe(0) core was exposed, which improved the reactivity of the composites.