Effect of multi-wall carbon nanotubes on Cr(VI) reduction by citric acid: Implications for their use in soil remediation

The potential application of carbon nanotubes (CNTs) in waste water treatment and their effect on the fate of heavy metals in the environments have attracted wide attention. However, the influence of CNTs on the reduction of Cr(VI) to Cr(III) in soils remains unknown. In this study, Cr(VI) adsorption by carboxylated or hydroxylated multi-walled carbon nanotubes (MWCNT-COOH or MWCNT-OH) was investigated together with their catalytic effect on Cr(VI) reduction by citric acid. Across the initial concentration range examined (5–60 mg/L), the adsorption capacity of Cr(VI) by MWCNT-COOH and MWCNT-OH (pH 5.0) could reach to 8.09 and 7.85 mg/g, respectively. With the decrease in pH, the Cr(VI) adsorption by both MWCNTs increased, while their difference in adsorption capacity became more pronounced, evidenced by that the percentage of Cr(VI) adsorbed by MWCNT-COOH can be 1.3-fold higher than that of MWCNT-OH at a pH of 3.2. The Cr(VI) adsorption kinetics could be well described by pseudo-second-order (R² > 0.95) and intra-particle diffusion models (R² > 0.98). MWCNT-OH or MWCNT-COOH could accelerate the reduction of 0.1 mM Cr(VI) by 1.0 mM citric acid, with the first-order rate constant of 0.0325 and 0.0147 h⁻¹, respectively. This finding was explained as that the reactivity of citric acid might be enhanced with its adsorption on the MWCNT surfaces. The catalysis of the functionalized CNTs on the Cr(VI) reduction was inhibited as the pH increased. The addition of MWCNTs to an oxisol can enhance the Cr(VI) reduction because the final concentration of aqueous Cr(III), compared with that without addition of MWCNTs, increased from 20.7 to 32.6 μM. Meanwhile, re-adsorption of aqueous Cr(III) onto the solid surfaces was also observed. The results above are important for understanding on the effect of CNTs on the fate of Cr(VI) and how they can be used to remediate Cr(VI)-polluted soils.