Composites for efficient removal of hexavalent chromium Cr(VI) from industrial wastewater were obtained by deposition of nano-zero-valent iron (nZVI), synthesized by environmentally friendly synthesis using oak leaf extract, on inexpensive, natural, readily available and cheap natural raw materials, sepiolite (SEP) or kaolinite/illite (KUb) clay, as support. nZVI particles were deposited from the FeCl3 solution of different concentrations, with the same volume ratio extract/FeCl3 solution (3:1), and with different masses of SEP or KUb. Physico–chemical characterization (SEM/EDS, FTIR, BET, determination of point of zero charge) of the composites and nZVI was performed. The results of SEM and BET analyses suggested more homogeneous deposition of nZVI onto SEP than onto KUb, which ensures greater availability of the nZVI surface for Cr(VI) anions. Therefore, the higher Cr(VI) removal at all investigated initial pH values (pHi) of the solution (3, 4 and 5) was achieved with the SEP composites. The adsorption results indicated that the elimination of Cr(VI) was achieved via the combined effect of reduction and adsorption. The removal of total chromium at pHi = 3 was approximately the same as that of Cr(VI) removal for the KUb composites, but lower for the SEP composites, indicating lower removal of Cr(III) compared to the reduced Cr(VI). The SEP/nZVI composite with the highest removal efficiency was applied for Cr(VI) removal from real wastewater at pHi = 3 and pHi = 5. The results demonstrated the high Cr(VI) removal capacity, validated the assumption that a good dispersion of nZVI particles is beneficial for Cr(VI) removal and showed that the produced green composites can be efficient materials for the removal of Cr(VI) from wastewater.
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