Microfluidic Flow through Polyaniline Supported by Lamellar-Structured Graphene for Mass-Transfer-Enhanced Electrocatalytic Reduction of Hexavalent Chromium

摘要

Owing to its high efficiency and environmental compatibility, electroreduction holds great promise for the detoxification of aqueous Cr(VI). However, the typical electroreduction system often shows poor mass transfer, which results in slow reduction kinetics and hence higher energy consumption. Here, we demonstrate a flow-through electrode of polyaniline supported on lamellar-structured graphene (LGS-PANI) for electrocatalytic reduction of Cr(VI). The reaction kinetics of the LGS-PANI flow-through electrodes are 6.4 times (at acidic condition) and 17.3 times (at neutral condition) faster than traditional immersed parallel-plate electrodes. Computational fluid dynamics simulation suggests that the flowthrough mode greatly enhances the mass transfer and that the nanoscale convection induced by the PANT nanodots increases the nanoscale mass transport in the interfacial region of the electrode/solution. In situ Raman spectroscopy shows that the PANI-Cr(VI) redox reactions are dominated by the leucoemeraldine/emeraldine transition at 1.5 V cell voltage, which also remarkably contributes to the fast reaction kinetics. Using single-pass flowthrough mode, the LGS-PANI electrode reaches an average reduction efficiency of 99.8% with residual Cr(VI) concentration of 22.3 ppb (initial [Cr(VI)] = 10 ppm, flux = 20 L h(-1) m(-2)). A long-term stability test shows that the LGS-PANI maintains stable performance over 40 days of operation and achieves >98% reduction efficiency, with average current efficiency of as high as 99.1% (initial [Cr(VI)] = 10 ppm, flux = 50 L h(-1) m(-2)).