RESUMO
Heavy metals and azo dyes caused huge harm to the aqueous system and human health. A magnetic chitosan/polyethyleneimine embedded hydrophobic sodium alginate composite (MCPS) was designed and prepared to simultaneously remove aqueous same ionic type heavy metals and azo dyes. In mono-polluted system, the optimal pH for Cr(VI), MO (methyl orange), Cu(â ¡) and MB (methylene blue) were 3, 2, 6 and 12 with a saturated adsorption capacity of 87.53, 66.41, 351.03 and 286.54 mg/g, respectively. Pseudo-second-order was suitable to describe the adsorption kinetics of them and the adsorption isotherms were more consistent with the Langmuir isotherm model being a spontaneous, endothermic, and entropy-increasing process. In binary-polluted system, MCPS possessed simultaneous adsorption for Cr (â ¥)-MO and Cu(â ¡)-MB pollutants at their optimal pH, in addition, whether in anionic or cationic solution, the removal of heavy metals were promoted with the add of azo dyes but the removal of azo dyes were suppressed with the add of heavy metals. Both Cr (â ¥)-MO and Cu(â ¡)-MB pollutants could be effectively adsorbed and desorbed from MCPS by changing the pH of the aqueous solution to realize recyclability. Lastly, removal mechanism was revealed in detail by FT-IR, EDS and XPS.
Assuntos
Quitosana , Metais Pesados , Poluentes Químicos da Água , Humanos , Quitosana/química , Polietilenoimina/química , Espectroscopia de Infravermelho com Transformada de Fourier , Corantes/química , Poluentes Químicos da Água/análise , Metais Pesados/química , Água/química , Cinética , Adsorção , Compostos Azo/química , Fenômenos Magnéticos , Concentração de Íons de HidrogênioRESUMO
The adsorbents with recyclable, large adsorption capacity and selective adsorption can effectively remove the pollution and harm of heavy metal ions in water. Therefore, two magnetic composites containing sulfur (MCP-S4 and MCP-S8) on the hyper-branched surface were prepared, furthermore, their structures were characterized and adsorption performance was analyzed by FTIR, XRD, TGA, BET, SEM, TEM, VSM and ICP. The results showed that both MCP-S4 and MCP-S8 had superparamagnetism with saturation susceptibility of 22.10 and 22.26 emu/g, and owned a specific surface area of 11.394 and 11.235 m2/g, respectively. MCP-S4 and MCP-S8 could selectively adsorb Hg2+ with the exist of Fe3+, Cu2+, Co2+, Ni2+, Mn2+, and Al3+ in solution. The adsorption kinetics accorded with pseudo-second-order model and Boyd film diffusion model, and the adsorption isotherm was fitted better with Langmuir isotherm model and D-R model, furthermore, the adsorption was an entropic-increasing and endothermic process. The removal rate of Hg2+ from simulated sewage by the two materials was more than 91%, and the adsorption retention rate was more than 85% after five adsorption-desorption cycles. The adsorption mechanism was analyzed by comparing the changes of FTIR, EDS and XPS spectra before and after adsorption. It was found that functional groups (C-N, CONH, CS, SH) could form stable chelates with Hg2+, which was the main reason why MCP-S4 and MCP-S8 could adsorb Hg2+ selectively, furthermore, S atoms of CS and -SH played a leading role in the process of adsorption. In addition, DFT calculation was also used as an auxiliary means to verify the adsorption mechanism.
Assuntos
Mercúrio , Poluentes Químicos da Água , Poluentes Químicos da Água/química , Mercúrio/química , Adsorção , Enxofre , Água , Cinética , Fenômenos MagnéticosRESUMO
The development of adsorbents to remove heavy metal ions from water with recyclable, high adsorption capacity, strong selectivity, safe, and economic performances has always been the focus and challenge of current research. A hyper-branched magnetic composite material (Fe3O4@SiO2-S4) was fabricated by a method combining "grafting,", "branching," and "modification,", and the structure was characterized by FTIR, XRD, SEM, TEM, SAED, VSM, TGA, and BET. In addition, the adsorption performance and mechanism for heavy metal ions in water were studied. The as-prepared composite material had excellent selective absorbability for Hg2+, Cd2+, and Ag+ in the presence of Fe3+, Fe2+, Cu2+, Mn2+, CO2+, Zn2+, and Ni2+, and when pH = 6, T = 30 °C, t = 4 h, it reached a saturated adsorption capacity of 2.42, 2.18, and 1.94 mmol/g to Hg2+, Cd2+, and Ag+, respectively. The adsorption isotherm was consistent with the Langmuir isotherm adsorption model, and the Dubinin Redushcke (D-R) model identified that the adsorption was chemical adsorption in nature. The adsorption kinetic followed the pseudo-second-order model and Boyd film diffusion models. The adsorption capacity of as-prepared material remained about 83% after five elutions. The adsorption mechanism and selective adsorption were revealed by FTIR, EDS, XPS, and DFT calculation. N atoms and O atoms of the active functional groups complexed with metal ions to form stable 2 heptachate chelates and 1 tridentate chelate to achieve the effect of adsorption; furthermore, the adsorption was mainly governed by N atoms of Schiff base groups. This work not only explored an innovative method for the construction of adsorbing materials but also provided a promising adsorbent to selectively remove heavy metal ions in water with potential application.
Assuntos
Mercúrio , Metais Pesados , Poluentes Químicos da Água , Adsorção , Cádmio/análise , Íons , Cinética , Fenômenos Magnéticos , Metais Pesados/química , Dióxido de Silício , Água , Poluentes Químicos da Água/químicaRESUMO
A Fe3O4 hybrid material (Fe3O4@SiO2-S2) modified by Schiff-base was prepared by grafting methyl acrylate (MA), ethylenediamine (EDA), and salicylaldehyde (SA) to the prepared magnetic hybrid material (Fe3O4@SiO2-NH2) successively; what's more, the structure was characterized by FTIR, XRD, SEM, TEM, and VSM. The results showed that the Fe3O4@SiO2-S2 has an obvious core-shell structure and a saturation magnetization of 45.9 emu/g. Study on the adsorption of aqueous heavy metal ions showed that Fe3O4@SiO2-S2 posed selective adsorption for Hg2+ with the saturated adsorption capacity of 362 mg/g (1.12 mmol/g), which was superior to Fe3O4@SiO2-NH2, Fe3O4@SiO2-HO-S, and other adsorbents, at the condition of pH = 6, 45â, the adsorption capacity remained 89% after 5 cycles of adsorption-desorption; what is more, adsorption equilibrium was reached at about 300 min, and the adsorption isotherm conformed to the Langmuir isotherm adsorption model; in addition, pseudo-second-order model could be well described the adsorption kinetic process of Fe3O4@SiO2-S2 to Hg2+. The adsorption mechanism demonstrated that the N atoms of Schiff-base were mainly contributed to the adsorption of Hg2+; what is more, the N atom of tertiary amine and the O atoms of hydroxy and carbonyl also help to the adsorption of Hg2+.