电纺La2O3-CeO2纳米纤维的除氟性能

杨为森; 刘毅飞; 史丰硕; 江文龙; 陈玉煌; 胡家朋; 段改改; 简绍菊

doi:10.13801/j.cnki.fhclxb.20220809.006

电纺La₂O₃-CeO₂纳米纤维的除氟性能

doi: 10.13801/j.cnki.fhclxb.20220809.006

1.
武夷学院　生态与资源工程学院，武夷山 354300
2.
南京林业大学　材料科学与工程学院，南京 210037

基金项目: 国家自然科学基金(51903123)；福建省自然科学基金(2020J05220；2020J01419)；中央引导地方科技发展专项(2019L3021)

详细信息

作者简介:
简绍菊：杨为森，博士，副教授，研究方向为纳米复合材料，污水处理　E-mail: yangweisen@126.com

通讯作者:
胡家朋，博士，教授，硕士生导师，研究方向为环境功能材料设计　E-mail: 22402414@qq.com

中图分类号: X703
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出版历程
- 收稿日期: 2022-06-13
- 修回日期: 2022-07-09
- 录用日期: 2022-07-30
- 网络出版日期: 2022-08-11
- 刊出日期: 2023-06-15

Defluoridation performance of electrospun La₂O₃-CeO₂ nanofibers

1.
School of Ecology and Resources Engineering, Wuyi University, Wuyishan 354300, China
2.
College of Materials Science and Engineering, Nanjing Forestry University, Nanjing 210037, China

Funds: National Natural Science Foundation of China (51903123); Natural Science Foundation of Fujian Province (2020J05220; 2020J01419); Central Special Project for Fujian Local Science and Technology Development (2019L3021)

摘要

摘要: 纳米双金属氧化物作为除氟剂具有广泛的应用前景。以六水合硝酸铈和六水合硝酸镧为原料，聚丙烯腈(PAN)为模板，通过静电纺丝技术与煅烧相结合制备La₂O₃-CeO₂纳米纤维，利用TEM、SEM-EDS、BET、FTIR和XRD对La₂O₃-CeO₂纳米纤维的形貌和结构进行表征。探究了La₂O₃-CeO₂纳米纤维对氟离子吸附性能，研究了pH、吸附质(F⁻)初始浓度、吸附时间、La₂O₃-CeO₂纳米纤维投加量和共存阴离子等对除氟效率的影响。研究结果表明，La₂O₃-CeO₂纳米纤维的比表面积为31.04 m²·g⁻¹。pH为3时，La₂O₃-CeO₂纳米纤维的除氟性能最佳。La₂O₃-CeO₂的吸附效率随着F⁻初始浓度的增大而上升。准二级动力学和Langmuir等温线模型(R²>0.99)能够很好描述La₂O₃-CeO₂纳米纤维的除氟过程，最大吸附量可达111.98 mg·g⁻¹。热力学研究结果表明，La₂O₃-CeO₂纳米纤维的除氟过程是自发的(ΔG⁰<0)、熵增(ΔS⁰=56.63 J·mol⁻¹·K⁻¹)和吸热(ΔH⁰=9.90 kJ·mol⁻¹)的反应。
- CeO₂ /
- La₂O₃ /
- 氟离子 /
- 吸附 /
- 纳米纤维 /
- 纳米双金属氧化物
Abstract: Nano bimetallic oxides have broad application prospects as fluoride removal agents. La₂O₃-CeO₂ nanofibers were fabricated via electrospinning-calcination method using Ce(NO₃)₃·6H₂O and La(NO₃)₃·6H₂O as raw materials and polyacrylonitrile (PAN) as template. TEM, SEM-EDS, BET, FTIR and XRD were employed to verify the morphology and structure of La₂O₃-CeO₂ nanofibers. The defluoridation properties of La₂O₃-CeO₂ nanofibers were discussed under batch mode, and the effects of adsorbate (F⁻) initial concentration, pH, contact time, La₂O₃-CeO₂ nanofibers dose and coexisting anions on the defluoridation were explored. The results illustrate that the specific surface area of La₂O₃-CeO₂ adsorbent is 31.04 m²·g⁻¹. The La₂O₃-CeO₂ nanofibers exhibit the best defluoridation performance at pH of 3, and the adsorption capacity of La₂O₃-CeO₂ nanofibers climbs up with rise of the initial concentration of F⁻. The pseudo-second-order kinetic and Langmuir isotherm model (R²>0.99) simulate the defluoridation process of La₂O₃-CeO₂ nanofibers better, and the maximum uptake of F⁻ by La₂O₃-CeO₂ nanofibers is 111.98 mg·g⁻¹ at 45℃. Thermodynamic studies suggest that the defluoridation process of La₂O₃-CeO₂ nanofibers is a spontaneous (ΔG⁰<0), entropy increase (ΔS⁰=56.63 J·mol⁻¹·K⁻¹) and endothermic (ΔH⁰=9.90 kJ·mol⁻¹) process.
- CeO₂ /
- La₂O₃ /
- fluoride /
- adsorption /
- nanofibers /
- nano bimetallic oxides

HTML全文

图 1 La(NO₃)₃/Ce(NO₃)₃/PAN纤维 (a) 与La₂O₃-CeO₂纳米纤维 (b) 的SEM图像，La₂O₃-CeO₂纳米纤维的TEM图像 (c) 和EDS能谱 (d)

Figure 1. SEM images of La(NO₃)₃/Ce(NO₃)₃/PAN (a) and La₂O₃-CeO₂ nanofibers (b), TEM image (c) and EDS spectrum of La₂O₃-CeO₂ nanofibers (d)

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图 2 La₂O₃-CeO₂纳米纤维的N₂吸附-解吸附等温线 (a) 和孔径分布图 (b)

Figure 2. N₂ adsorption-desorption isotherms of La₂O₃-CeO₂ nanofibers (a) and its corresponding BJH pore size distribution (b)

dV/dD—Pore area

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图 3 pH值对La₂O₃-CeO₂纳米纤维除氟性能的影响(a) 和pH_pzc(b)

Figure 3. Effect of pH on the adsorption of F⁻ by La₂O₃-CeO₂ nanofibers (a) and pH_pzc (b)

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图 4 投加量对La₂O₃-CeO₂纳米纤维除氟性能的影响

Figure 4. Effect of dosage on the adsorption of F⁻ by La₂O₃-CeO₂ nanofibers

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图 5 不同初始浓度时La₂O₃-CeO₂纳米纤维的吸附动力学曲线及动力学模型拟合曲线

Figure 5. Adsorption dynamic curves and kinetic models fitting of La₂O₃-CeO₂ nanofibers at various concentrations

Q_t—Adsorption capacity at time t

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图 6 初始浓度对La₂O₃-CeO₂纳米纤维吸附F⁻性能的影响及吸附等温线模型

Figure 6. Effect of initial concentration on the adsorption of F⁻ by La₂O₃-CeO₂ nanofibers and adsorption isotherm

C_e—Solution F⁻ concentration after adsorption

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图 7 La₂O₃-CeO₂纳米纤维除氟的lnK_D(平衡常数)与10³/T的关系

Figure 7. Relationship between ln K_D(equilibrium constant) and 10³/T for removal of fluoride by La₂O₃-CeO₂ nanofibers

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图 8 共存阴离子对La₂O₃-CeO₂纳米纤维除氟性能的影响

Figure 8. Effect of coexisting anions on fluoride removal by La₂O₃-CeO₂ nanofibers

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图 9 La₂O₃-CeO₂纳米纤维的循环使用性能

Figure 9. Recyclability of La₂O₃-CeO₂ nanofibers

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图 10 La₂O₃-CeO₂纳米纤维吸附前后的XRD图谱 (a) 和FTIR图谱(b)

Figure 10. XRD patterns (a) and FTIR spectra (b) of La₂O₃-CeO₂ nanofibers before and after adsorption

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表 1 La₂O₃-CeO₂纳米纤维的吸附动力学拟合参数(T=25℃)

Table 1. Adsorption kinetics fitting parameters of La₂O₃-CeO₂ nanofibers (T=25℃)

Model	parameters	C₀/(mg·L⁻¹)
Model	parameters	20	50
Pseudo-first-order	k₁×10²	1.626	1.640
	Q_e	12.33	33.06
	R²	0.8888	0.8268
Pseudo-second-order	k₂×10²	0.532	0.147
	Q_e	64.98	114.42
	R²	0.9999	0.9999
Weber-Morris model	k_id1	11.812	29.903
	R²	0.8463	0.9844
	k_id2	2.6920	4.0108
	R²	0.6032	0.9652
	k_id3	0.5101	0.9792
	R²	0.1105	0.1113
Notes: k₁―Pseudo-first-order kinetic constant; k₂―Pseudo-second-order kinetic constant; k_id―Intra-particle diffusion rate constant; R²—Fit coefficient; C₀—Solution F⁻ concentration before adsorption.

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表 2 La₂O₃-CeO₂纳米纤维的吸附等温线拟合参数

Table 2. Adsorption isotherm fitting parameters of La₂O₃-CeO₂ nanofibers

T/℃	Langmuir			Freundlich
T/℃	b/(L·mg⁻¹)	Q_m/(mg·g⁻¹)	R²	k_F/(L^1/n·mg^1−1/n·g⁻¹)	n	R²
25	0.3944	93.02	0.9999	48.37	0.2218	0.7012
35	0.6636	101.32	0.9966	53.37	0.2187	0.6953
45	0.6439	111.98	0.9990	62.84	0.2018	0.5756
Notes: Q_m―Maximum adsorption capacity; b, k_F and n―Isotherm constants.

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表 3 La₂O₃-CeO₂纳米纤维与其他相关吸附剂除氟性能的比较

Table 3. Comparison of defluoridation performance of other related adsorbents with La₂O₃-CeO₂ nanofibers

Adsorbents	pH	Q_m/(mg·g⁻¹)	Ref.
Lanthanum modified mesoporous alumina (La/MA)	6	26.45	[25]
Cerium modified mesoporous alumina (Ce/MA)	6	13.06	[25]
La-Ce-Fe₃O₄	3	19.78(45℃)	[26]
La₂O₃-CeO₂/laterite	−	58.02(RT)	[15]
Bx-Ce-La@500	3	88.13(25℃)	[27]
Ce-AlOOH	3	62.77(30℃)	[28]
ZCPC films	7	12.88(30℃)	[29]
ZLPC films	7	11.57(30℃)	[29]
La-Al-Fe trioxide composite	8.25	28.06(25℃)	[30]
CeO₂ micro-nanofibers	3	21.45(35℃)	[14]
La₂O₃-CeO₂ nanofibers	3	111.98(45℃)	This sthdy
Note: RT—Room temperature; ZCPC—Zirconium-cerium; ZLPC—Zirconium-lanthanum.

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表 4 La₂O₃-CeO₂纳米纤维吸附F⁻的热力学常数

Table 4. Thermodynamic parameters of defluoridation by La₂O₃-CeO₂ nanofibers

T/℃	lnK_D	ΔG⁰ /(kJ·mol⁻¹)	ΔH⁰ /(kJ·mol⁻¹)	ΔS⁰ /(J·mol⁻¹·K⁻¹)
15	4.77	−11.43	9.90	56.63
25	5.22	−12.94
35	5.59	−14.32
45	6.23	−16.49
Note: ΔG⁰, ΔH⁰ and ΔS⁰—Gibbs free energy change, the enthalpy change and the entropy change, respectively.

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