Preparation of nickel-doped ZnFe2O4 composites and their algal removal properties
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摘要: 水体富营养化导致的有害藻华(HABs)爆发日益严重，对水环境和人类健康构成了巨大的威胁。本文采用简单的水热法制备了磁性可回收的镍掺杂 ZnFe2O4 (Ni-ZFO)吸附剂，用于去除水体中的铜绿微囊藻。通过 SEM、XRD、EDS、XPS 和振动样品磁力计(VSM)对材料进行了表征。在 30 min内，Ni-ZFO 复合材料的藻细胞去除率最高可达 99.09%，在 25℃、pH= 3~8 的条件下，去除率保持在 90.41% 以上。此外，Ni-ZFO的饱和磁化强度为67.93 emu/g，比ZnFe2O4 (ZFO)高10.74 emu/g，便于回收利用。吸附过程中藻胆蛋白含量并未增加，藻细胞在吸附过程中不会破裂，这就避免了藻毒素进入水环境而造成的二次污染。经过4次循环使用后除藻率仍保持在75%以上。本文合成的 Ni-ZFO 吸附剂对藻细胞具有较强的去除效率，且不会造成二次污染，在缓解水体富营养化的实际应用中显示出巨大的潜力，同时也充实了改性ZFO在吸附领域的应用。Abstract: Harmful algal blooms (HABs) outbreaks due to eutrophication of water bodies are becoming increasingly serious, posing a great threat to the water environment and human health. In this paper, magnetic and recoverable nickel-doped ZnFe2O4 (Ni-ZFO) adsorbents were prepared by a simple hydrothermal method for the removal of microcystis aeruginosa from water bodies. The materials were characterized by SEM, XRD, EDS, XPS and vibrating sample magnetometer (VSM). The algal cell removal of Ni-ZFO composites was up to 99.09% within 30 min and remained above 90.41% at 25℃ and pH=3-8. In addition, the saturation magnetization intensity of Ni-ZFO was 67.93 emu/g, which was 10.74 emu/g higher than that of ZnFe2O4 (ZFO), and it was easy to be recycled. The content of algal bile proteins did not increase in the adsorption process, and the algal cells would not be ruptured during the adsorption process, which avoids the secondary pollution caused by Microcystins entering the water environment. The algal removal rate remained above 75% after four times of recycling. The Ni-ZFO adsorbent synthesized in this paper has strong removal efficiency for algal cells and does not cause secondary pollution, which shows great potential in the practical application of mitigating eutrophication of water bodies, and also enriches the application of modified ZFO in the field of adsorption.
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Key words:
- microcystis aeruginosa /
- zinc ferrate /
- adsorption /
- algal removal /
- composites /
- eutrophicatio
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图 1 ZnFe2O4 (ZFO) ((a), (b))和Ni-ZFO ((c), (d))的SEM图像；((e)~(h)) 元素O、Fe、Ni、Zn的 EDS 图谱
Figure 1. SEM images of the ZnFe2O4 (ZFO) ((a), (b)) and Ni-ZFO ((c), (d)); ((e)-(h)) EDS patterns of elements O, Fe, Ni, Zn
图 4 Ni-ZFO 的XPS 图谱：(a)总谱；(b) C1s；(c) O1s；(d) Fe2p；(e) Ni2p；(f) Zn2p
sat.—Satellite peak
Figure 4. XPS spectra of Ni-ZFO: (a) Survey; (b) C1s; (c) O1s; (d) Fe2p; (e) Ni2p; (f) Zn2p
图 6 Ni-ZFO (a)、ZFO (b)的氮吸附-解吸和孔径分布
dV/dD—Pore volume per unit pore size
Figure 6. Nitrogen adsorption-desorption and pore size distribution of Ni-ZFO (a), ZFO (b)
图 7 (a) Ni-ZFO 、ZFO除藻率对比；(b) Ni-ZFO 吸附剂用量对除藻率的影响；(c) pH 对Ni-ZFO除藻率的影响；(d) 藻密度对Ni-ZFO除藻率的影响；(e) 温度对Ni-ZFO除藻率的影响；(f) 转速对Ni-ZFO除藻率的影响
C/C0—Algal density at a time/the initial algal density
Figure 7. (a) Comparison of algal removal rates of Ni-ZFO and ZFO; (b) Effect of Ni-ZFO adsorbent dosage on algae removal rate; (c) Effect of pH on the algae removal rate of Ni-ZFO; (d) Effect of algae density on the algae removal rate of Ni-ZFO; (e) Effect of temperature on the algae removal rate of Ni-ZFO; (f) Effect of speed on the algae removal rate of Ni-ZFO
图 8 除藻过程中藻细胞溶液在620 nm波长处的值
OD620—Light absorption at 620 nm
Figure 8. Value of algal cell solution at 620 nm during algae removal
图 9 Ni-ZFO吸附后藻絮体液态SEM图像
Figure 9. SEM images of the liquid state of algal flocs after Ni-ZFO adsorption
图 10 (a) Ni-ZFO的阴离子干扰实验；(b) Ni-ZFO的循环实验
Figure 10. (a) Anion interference experiment of Ni-ZFO; (b) Cycle experiment of Ni-ZFO
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