Reduction Removal of Cr(VI) Using Oxalic Acid With MOF‐525(Fe) as Catalyst: Performance and Mechanism

Abstract

ABSTRACTHexavalent chromium (Cr(VI)) has attracted great considerations due to their high toxicity, teratogenicity, and carcinogenicity. In this study, four Zr‐MOFs were synthesized and used to comparative study their catalytic performances of oxalic acid (OA) for Cr(VI) removal. Results showed that the removal efficiency for Cr(VI) was reached 65.91%, 78.64%, 53.58%, and 96.32% by MOF‐525, MOF‐525(Co), MOF‐525(Zn), and MOF‐525(Fe) in the presence of OA when the initial Cr(VI) concentration was 100 mg·L−1, respectively. The single‐factor experiments for further improving the Cr(VI) removal by MOF‐525(Fe)/OA demonstrated that the optimal conditions were OA dosage of 790 mg·L−1, and MOF‐525(Fe) dosage of 500 mg·L−1 and pH of 2.0, and the MOF‐525(Fe)/OA system could be used to treat Cr(VI)‐containing wastewater at concentrations below 50 mg·L−1. Ionic strength studies indicated that Na+, K+, Mg2+, Cl−, and SO42− had little effect on the catalytic reduction of Cr(VI), while high concentrations of Ca2+ (0.10 and 0.25 mol·L−1), NO3− (0.25 mol·L−1), and PO43− (0.25 mol·L−1) had significant inhibition effects. The reusability experiments showed that the stability of MOF‐525(Fe) was excellent, and it could be used for potential applications. Based on the results of Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), and Electron Paramagnetic Resonance spectrometer (EPR), the possible reduction mechanism of Cr(VI) by MOF‐525(Fe)/OA system was proposed as follows: The complexation of OA with Fe3+ was first complexed to produce Fe2+ and CO2•−, then Cr(VI) was combined with Zr–O and Fe–O clusters in MOF‐525(Fe) to obtain activation energy, and the reduction ability was enhanced at the same time; finally, Cr(VI) obtained electrons from CO2•− and was sequentially reduced as Cr(V) and Cr(III).