Effects of Mn-Doping on Structure, Surface Properties and Selenium Adsorption of Goethite
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National Natural Science Foundation of China (No. 41561053),Hubei Key Laboratory of Biologic Resources Protection and Utilization(No.PKLHB1904) ,and the Special Funds for "Double First-Class" Construction in Hubei Province

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    Abstract:

    【Objective】Selenium (Se) is an essential micronutrient for human and animals. Ingestion of either an inadequate or excessive amount of Se tends to cause hazard to their health. Bioavailability of Se in soil depends on its forms. Iron oxide is an important component of soil and may interact with Se through desorption/adsorption. Iron and manganese oxides in soil are often cemented together forming binary metal oxides or Mn-doped iron oxides, thus significantly affecting translocation and transformation of nutrient elements and contaminants in the soil. However, so far little has been reported in-depth in the literature about effects of Mn-doped iron oxides on speciation and bioavailability of Se in soil. 【Method】Samples of pure goethite (Goe) and Mn-doped products (G-Mn0.1、G-Mn0.2、G-Mn0.3和G-Mn0.5) were prepared under set hydrothermal conditions and were characterized with the aid of X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen physical adsorption, Zeta potential analysis and potentiometric titrations. Moreover, selenite (Se(IV)) and selenate (Se(VI)) adsorption characteristics of the samples were investigated through batch adsorption experiments. 【Result】 Mn-doping at a low rate with RMn/Fe (Mn(II)/Fe(III) molar ratio being 0.1~0.2) promoted significantly formation of goethite crystals along Axis b, in the form of flat needles big in length-to-diameter ratio instead of short spindles, whereas Mn-doping at a high rate, 0.3-0.5 in RMn/Fe , which means increased Mn(II) content, inhibited significantly formation of goethite crystals along Axis b, while promoting their growth along Axis a by a certain degree and moreover making them tenuous. Additionally, a mass of Mn-doped magnetite appeared in the samples. Of Goe, G-Mn0.2 and G-Mn0.5, the specific surface area was 36.78、53.22 and 71.33 m2•g-1; the surface fractal dimension D, 2.31, 2.53 and 2.59; the mean pore diameter, 13.73, 15.59 and 6.92 nm; the isoelectric point, 7.36, 6.58 and 5.31; and the surface zeta potentials at pH=5.0 40.5, 35.3 and 4.92 mV, respectively. In terms of surface hydroxyl content, the three types of the samples followed the order of Goe < G-Mn0.2 < G-Mn0.5. At pH=5.0, the Langmuir model was found to be more suitable for use to describe isotherm adsorption data of Se(IV) and Se(VI) in the samples (R2 =0.966~0.996). The Langmuir adsorption capacity (Qmax) of Goe, G-Mn0.2 and G-Mn0.5 was 11.6, 16.8 and 20.4 mg•g-1 for Se(IV) and 7.6, 8.5 and 9.2 mg•g-1 for Se(VI), respectively. The adsorption affinity for Se(IV) slightly effect by the Mn content, which dramatically increase the adsorption affinity for Se(VI). 【Conclusion】At RMn/Fe =0.1-0.2, the formation of Goe is accelerated by Mn(II), and at RMn/Fe =0.3-0.5 Mn-doped magnetite is observed in the products. As of Goe, G-Mn0.2 and G-Mn0.5, specific surface areas and surface fractal dimension D increases in turn, while isoelectric point, surface zeta potentials at pH=5.0 and surface hydroxyl contents decreases gradually. Qmax increases with rising Mn(II) content for both Se(IV) and Se(VI), and Qmax of Se(IV) was higher than that of Se(VI), and their isotherm adsorption model is mainly kind of homogeneous surface mono-layer adsorption.

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WANG Rui, NIU Pengju, XU Haijuan, WEI Shiyong. Effects of Mn-Doping on Structure, Surface Properties and Selenium Adsorption of Goethite[J]. Acta Pedologica Sinica,2020,57(1):108-118.

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History
  • Received:May 29,2018
  • Revised:October 25,2018
  • Adopted:November 26,2018
  • Online: November 07,2019
  • Published: