仿生FeS复合材料的制备及其对Cr(VI)的吸附性能

程爱华; 常娟

doi:10.13801/j.cnki.fhclxb.20220402.001

仿生FeS复合材料的制备及其对Cr(VI)的吸附性能

doi: 10.13801/j.cnki.fhclxb.20220402.001

程爱华^,,
常娟

西安科技大学　地质与环境学院，西安 710054

基金项目: 国家自然科学基金青年项目(51808442)National Natural Science Foundation Youth Project (51808442)

详细信息

通讯作者:
程爱华，博士，副教授，硕士生导师，研究方向为水处理技术　E-mail：cah_cheng@126.com

中图分类号: TB332；X703.1
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- 被引次数: 0
出版历程
- 收稿日期: 2022-01-12
- 修回日期: 2022-03-21
- 录用日期: 2022-03-26
- 网络出版日期: 2022-04-06
- 刊出日期: 2023-02-15

Preparation and its Cr(VI) adsorption properties of biomimetic FeS composites

CHENG Aihua^,,
CHANG Juan

College of Geology and Environment, Xi’an University of Science and Technology, Xi’an 710054, China

摘要

摘要: 纳米FeS比表面积大且还原性强，对Cr(VI)吸附性能优异，但不稳定、易团聚，为解决这一问题，本文以油菜花粉为生物模板，通过共沉淀-焙烧法制得仿生FeS复合材料(bioFeS)。通过SEM、XRD及XPS等方法对bioFeS复合材料的表面微观形态和结构进行了表征。以Cr(VI)为目标污染物，分别考察了吸附剂用量、反应时间、反应温度、初始Cr(VI)浓度和pH对bioFeS复合材料吸附Cr(VI)性能的影响，探究了反应机制。结果表明：油菜花粉生物模板成功分散了FeS，制得的bioFeS复合材料比表面积大，在反应时间为120 min、pH值为1、吸附剂投加量为0.2 g·L⁻¹、反应温度为25℃的条件下，bioFeS复合材料对Cr(VI)的吸附量可达88.95 mg·g⁻¹；该吸附过程符合准二级动力学和Langmuir等温吸附模型；共存离子NO₃⁻和SO₄²⁻会抑制Cr(VI)的去除。结合吸附动力学、热力学及XPS表面元素分析可知bioFeS复合材料除铬机制主要是吸附及化学还原作用。bioFeS复合材料处理含铬废水具有广阔的应用前景。
- FeS /
- 花粉 /
- 复合材料 /
- 吸附 /
- Cr(VI) /
- 生物模板
Abstract: Nano FeS has excellent adsorption performance for Cr(VI) because of large specific surface area and strong reducibility, but it is unstable and prone to agglomeration. In order to overcome these disadvantages, the biomimetic FeS composites (bioFeS) were prepared by co-precipitation-roasting method using rape pollen as a biological template. The surface morphology and structure of bioFeS composites were characterized by SEM, XRD and XPS. The effects of adsorbent dosage, reaction time, reaction temperature, initial Cr(VI) concentration and pH on adsorption capacity of Cr(VI) on bioFeS composites were studied to investigate the reaction mechanism using Cr(VI) as the target pollutant. The results show that rape pollen biotemplate successfully disperse FeS with a large specific surface area. The adsorption capacity of Cr(VI) on bioFeS composites can reach 88.95 mg·g⁻¹ at a reaction time of 120 min, pH of 1, adsorbent dosing of 0.2 g·L⁻¹ and a reaction temperature of 25℃. The adsorption process conforms to quasi-secondary kinetics and the Langmuir isothermal adsorption model. The coexisting ions NO₃⁻ and SO₄²⁻ will inhibit the adsorption capacity of Cr(VI). Combining with adsorption kinetics, thermodynamics and XPS surface element analysis, the mechanism of chromium removal by bioFeS composites mainly involves adsorption and chemical reduction. The method of removal of Cr(VI) in wastewater by bioFeS composites has a promising application.
- FeS /
- pollen /
- composites /
- adsorption /
- Cr(VI) /
- biotemplate

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图 1 FeS和仿生FeS(bioFeS)复合材料的SEM图像

Figure 1. SEM images of FeS and biomimetic FeS (bioFeS) composites

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图 9 bioFeS复合材料吸附Cr(VI)前后的XPS图谱：(a) C1s；(b) Fe2p；(c) S2p；(d) Cr2p

Figure 9. XPS spectra of bioFeS composites before and after adsorption of Cr(VI): (a) C1s; (b) Fe2p; (c) S2p; (d) Cr2p

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图 2 bioFeS复合材料的XRD图谱

Figure 2. XRD patterns of bioFeS composites

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图 3 FeS和bioFeS复合材料的孔径分布

Figure 3. Pore size distribution of FeS and bioFeS composites

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图 4 初始pH对bioFeS复合材料吸附Cr(VI)溶液Zeta电位及平衡pH的影响

Figure 4. Effect of initial pH on Zeta potential and equilibrium pH of adsorption Cr(VI) on bioFeS composites

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图 5 初始pH对bioFeS复合材料吸附Cr(VI)效果及铁离子浸出浓度的影响

Figure 5. Effect of initial pH on adsorption capacity of Cr(VI) on bioFeS composites and change of iron ion leaching concentration

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图 6 共存离子对bioFeS复合材料吸附Cr(VI)效果的影响

Figure 6. Effect of coexisting ions adsorption capacity of Cr(VI) on bioFeS composites

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图 7 不同吸附剂对Cr(VI)的吸附动力学

Figure 7. Adsorption kinetic of various adsorbents for Cr(VI)

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图 8 bioFeS复合材料的再生性

Figure 8. Regeneration property of bioFeS composites

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表 1 bioFeS复合材料BET比表面积和孔隙性质

Table 1. BET surface areas and pore properties of bioFeS composites

Sample	S_BET/ (m²·g⁻¹)	Pore volume/ (cm³·g⁻¹)	Pore size/ nm
FeS	15.59	0.038	11.87
bioFeS composites	173.51	0.122	5.78
Note: S_BET—BET surface area.

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表 2 不同吸附剂吸附Cr(VI)的动力学参数

Table 2. Kinetic parameters of Cr(VI) adsorption by various adsorbents

Adsorbent	Pseudo-first order model			Pseudo-second order model
Adsorbent	k₁/min⁻¹	R²	q_e/(mg·g⁻¹)	k₂/(g·mg⁻¹·min⁻¹)	R²	q_e/(mg·g⁻¹)
bioFeS composites	0.0481	0.991	37.728	0.012	0.998	88.574
Roasting FeS	0.0396	0.914	31.325	0.007	0.978	69.686
FeS	0.0430	0.900	29.964	0.004	0.987	65.726
Roasting pollen	0.0329	0.923	33.016	0.001	0.633	44.952
Notes: q_e—Amount of adsorption at equilibrium; k₁—Quasi-first-order kinetic model constant; k₂—Quasi-second-order kinetic model constant; R—Correlation coefficient.

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表 3 bioFeS复合材料吸附Cr(VI)的Langmuir和Freundlich吸附等温线参数

Table 3. Langmuir and Freundlich adsorption isotherm parameters of Cr(VI) adsorption by bioFeS composites

Adsorbent	Langmuir model			Freundlich model
Adsorbent	b	R²	Q₀/(mg·g⁻¹)	K_F	R²	n
bioFeS composites	0.013	0.997	94.967	8.692	0.990	1.454
Notes: Q₀—Maximum adsorption capacity; b—Adsorption equilibrium constant of Langmuir model; K_F—Adsorption equilibrium constant of Freundlich model; n—Adsorption strength constant in the Freundlich model.

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表 4 bioFeS复合材料吸附Cr(VI)的热力学参数

Table 4. Thermodynamic parameters of Cr(VI) adsorption by bioFeS composites

C₀/(mg·L⁻¹)	ΔG/(kJ·mol⁻¹)			ΔH/(kJ·mol⁻¹)	ΔS/(kJ·mol⁻¹·K⁻¹)
C₀/(mg·L⁻¹)	293 K	298 K	303 K	ΔH/(kJ·mol⁻¹)	ΔS/(kJ·mol⁻¹·K⁻¹)
10	−21.082	−22.687	−23.270	43.211	0.220
20	−20.021	−21.016	−22.532	53.490	0.251
30	−19.103	−20.644	−21.734	58.052	0.264
50	−18.194	−20.237	−21.076	66.467	0.290
100	−17.186	−19.986	−20.786	88.616	0.362
150	−16.903	−19.308	−20.342	84.109	0.346
Notes: C₀—Initial concentration of the solution; ΔH—Enthalpy; ΔS—Entropy; ΔG—Gibbs free energy.

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