The removal efficiency and mechanism of Cr(VI) removal from aqueous solution on semi-decomposed maize straw biochars pyrolyzed at 300 to 600 °C were investigated. The removal of Cr(VI) by the biochars decreased with pyrolysis temperature increasing from 300 to 600 °C, and the maximum removal capacity of Cr(VI) for maize straw biochar pyrolyzed at 300 °C was 91 mg/g at pH 2.0. The percentage removal of Cr(VI) rapidly decreased with pH increasing from 2.0 to 8.0, with the maximum (>99.9%) at pH 2.0. The variation of Cr(VI) and Cr(III) concentrations in the solution after reaction showed that Cr(VI) concentration decreased while Cr(III) increased and the equilibrium was reached after 48 h, while the redox potential after reaction decreased due to Cr(VI) reduction. X-ray photoelectron spectroscopy (XPS) semi-quantitative analysis showed that Cr(III) accounted for 75.7% of the total Cr bound to maize straw biochar, which indicated reductive adsorption was responsible for Cr(VI) removal by the biochars. Cr(VI) was firstly adsorbed onto the positively charged biochar surface and reduced to Cr(III) by electrons provided by oxygen-containing functional groups (e.g., C=O), and subsequently part of the converted Cr(III) remained on the biochar surface and the rest released into solution. Fourier transform infrared (FTIR) data indicated the participation of C=O, Si–O, –CH2 and –CH3 groups in Cr(VI) removal by the biochars. This study showed that maize straw biochar pyrolyzed at 300 °C for 2 h was one low-cost and efficient adsorbent for Cr(VI) removal from aqueous solution.
The influence of pyrolysis temperature on cadmium (Cd) removal capacity and mechanisms by maize straw biochars (MSB) and Platanus leaves biochars (PLB) pyrolyzed at 300, 400, 500 and 600 °C was investigated. The results showed that the biochars pyrolyzed at 500 °C had the highest adsorption capacity for Cd, and the maximum adsorption at pH 5.0 was 35.46 mg/g and 25.45 mg/g for MSB and PLB, respectively. The increase in adsorption efficiency with increasing temperature indicated that the adsorption of Cd onto the biochars was endothermic. Based on the balance analysis between cations (Ca2+ and Mg2+) released and Cd adsorbed onto biochar in combination with SEM-EDX, FTIR, and XRD analysis, it was concluded that cation exchange, complexation with surface functional groups, precipitation with minerals (CdCO3), and coordination with π electrons were the dominant mechanisms responsible for Cd adsorption by MSB. With the pyrolysis temperature increasing from 300 to 600 °C, the contribution of cation exchange (Ca2+ and Mg2+) on Cd removal by MSB decreased from 37.4% to 11.7%, while the contribution of precipitation with Otavite (CdCO3) and Cd2+-π electrons interaction increased. For PLB, the insoluble Cd minerals were not detected by XRD, and the contribution of cation exchange had no significant difference for PLB pyrolyzed at 300, 400, 500 and 600 °C.
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