Arsenite removal by using ZnAlFe mixed metal oxides derived from layered double hydroxides.

Luis A May Ix, Sandra Cipagauta Díaz, Francisco Tzompantzi, Raúl Pérez Hernández, Jorge M Meichtry, Emilia B Halac, Marta I Litter
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Abstract

ZnAlFe mixed metal oxides (ZnAlFe-MMOs) were synthesized from layered double hydroxides (LDHs) prepared by the coprecipitation method at pH 9 using an initial weight composition of Zn2+ = 75%, Al3+ = 15% and Fe3+ = 10%, with or without the addition of citric or oxalic acid. The solids were calcined at 400 °C to obtain the respective MMOs, which exhibited relatively high specific surface areas (165.3 - 63.8 m2 g-1) and semiconductor properties active in the visible region (bandgap values (Eg) of 2.42 - 1.77 eV). The synthesized materials were tested for the removal of trivalent arsenic by adsorption and by photocatalysis under visible light irradiation (λ ≥ 420 nm). The best removal of As(III) by adsorption (65.9%) and by photocatalysis (99.9%) was obtained with the ZnAlFe-MMOs prepared in the absence of organic acids. The XPS results indicate the coexistence of As3+ and As5+ over ZnAlFe-MMOs after the photocatalytic reaction and also confirm the formation of Fe2+ sites on the hematite surface that enhances the removal of As(III). Raman measurements confirmed that, in the photocatalytic experiments, As is largely retained as As(V) on ZnAlFe-MMOs, bound to Fe. The results of fluorescence of 7-hydroxycoumarin suggest that the photocatalyst produces HO, which can be the main species for As(III) oxidation under UV-Vis irradiation. Moreover, ZnAlFe-MMOs exhibited a good reusability after regeneration making ZnAlFe-MMOs a promising material for arsenic decontamination in polluted water.

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利用源自层状双氢氧化物的 ZnAlFe 混合金属氧化物去除亚砷酸盐。
在 pH 值为 9 的条件下,采用共沉淀法,使用 Zn2+ = 75%、Al3+ = 15%和 Fe3+ = 10%的初始重量成分,在添加或不添加柠檬酸或草酸的情况下,从层状双氢氧化物(LDHs)中合成了 ZnAlFe 混合金属氧化物(ZnAlFe-MMOs)。固体在 400 °C 煅烧后得到相应的 MMO,这些 MMO 具有相对较高的比表面积(165.3 - 63.8 m2 g-1)和在可见光区域活跃的半导体特性(带隙值 (Eg) 为 2.42 - 1.77 eV)。在可见光(λ ≥ 420 nm)照射下,对合成材料进行了吸附和光催化去除三价砷的测试。在无有机酸条件下制备的 ZnAlFe-MMOs 对 As(III)的吸附去除率(65.9%)和光催化去除率(99.9%)最好。XPS 结果表明,光催化反应后,As3+ 和 As5+ 在 ZnAlFe-MMOs 上共存,同时也证实了赤铁矿表面形成的 Fe2+ 位点增强了对 As(III) 的去除。拉曼测量证实,在光催化实验中,As 主要以 As(V) 的形式保留在 ZnAlFe-MMOs 上,并与 Fe 结合。7- 羟基香豆素的荧光结果表明,光催化剂会产生 HO-,这可能是紫外可见光照射下氧化 As(III) 的主要物质。此外,ZnAlFe-MMOs 在再生后表现出良好的可再利用性,使 ZnAlFe-MMOs 成为一种很有前途的用于污染水体砷净化的材料。
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