改性羟基磷灰石/混酸氧化多壁碳纳米管的制备及应用

何迎迎; 王瑞雪; 周渊; 樊林奎; 窦妍

doi:10.13801/j.cnki.fhclxb.20230825.001

改性羟基磷灰石/混酸氧化多壁碳纳米管的制备及应用

doi: 10.13801/j.cnki.fhclxb.20230825.001

何迎迎^{1, 2, 3},
王瑞雪^{1, 2, 3},
周渊^{1, 2, 3},
樊林奎^{1, 2, 3},
窦妍^{1, 2, 3, ,}

1.
长安大学　水利与环境学院，西安 710054
2.
长安大学　旱区地下水文与生态效应教育部重点实验室，西安 710054
3.
长安大学　水利部旱区生态水文与水安全重点实验室，西安 710054

基金项目: 陕西省自然科学基金(2021SF-443)

详细信息

通讯作者:
窦妍，博士，副教授，硕士生导师，研究方向为水环境污染与治理　E-mail：douyan@chd.edu.cn

中图分类号: X523；TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2023-05-30
- 修回日期: 2023-08-01
- 录用日期: 2023-08-10
- 网络出版日期: 2023-08-28
- 刊出日期: 2024-02-01

Preparation of modified hydroxyapatite/mixed acid-oxidized multi-walled carbon nanotubes and applications

HE Yingying^{1, 2, 3},
WANG Ruixue^{1, 2, 3},
ZHOU Yuan^{1, 2, 3},
FAN Linkui^{1, 2, 3},
DOU Yan^{1, 2, 3
, ,}

1.
School of Water and Environment, Chang'an University, Xi'an 710054, China
2.
Key Laboratory of Subsurface Hydrology and Ecological Effect in Arid Region of the Ministry of Education, Chang'an University, Xi'an 710054, China
3.
Key Laboratory of Eco-hydrology and Water Security in Arid and Semi-arid Regions of Ministry of Water Resources, Chang'an University, Xi'an 710054, China

Funds: Natural Science Foundation of Shaanxi Province (2021SF-443)

摘要

摘要: 开发高分散性及吸附性能良好的纳米复合材料对水体中重金属离子的去除具有重要的意义。以混酸氧化多壁碳纳米管(AO-MWCNTs)为基体，引入羟基磷灰石(HAP)，通过微波/光波组合加热辅助化学沉淀法分步制备氟碳掺杂的羟基磷灰石(FCHAP)，并将其负载到AO-MWCNTs上，合成FCH/AO-MWCNTs复合材料。将制备材料在含Mn(II)废水中进行去除效果实验，结果表明，FCH/AO-MWCNTs对Mn(II)的理论最大吸附量为317.5 mg/g，高于AO-MWCNTs及各制备中间体。结合材料的SEM-EDS、FTIR、XPS、Zeta、BET等表征结果推测，新材料FCH/AO-MWCNTs形成更丰富的孔隙结构及吸附位点，且其分散性及稳定性能表现优异，同时新材料在去除其他重金属及再生利用方面也具有一定的应用前景。
- 多壁碳纳米管 /
- 羟基磷灰石 /
- 复合纳米材料 /
- 含Mn(II)废水 /
- 吸附性能
Abstract: The development of nanocomposites with high dispersion and good adsorption properties is important for the removal of heavy metal ions from water bodies. Fluorine/carbon-doped hydroxyapatite (FCHAP) was prepared stepwise by microwave/light-wave combined heating assisted chemical precipitation using mixed-acid oxidized multi-walled carbon nanotubes (AO-MWCNTs) as the matrix and hydroxyapatite (HAP) was introduced and loaded onto AO-MWCNTs to synthesize FCH/AO-MWCNTs composites. The results show that the theoretical maximum adsorption capacity of FCH/AO-MWCNTs for Mn(II) is 317.5 mg/g, which is higher than that of AO-MWCNTs and each preparation intermediate. Combined with the characterization results of SEM-EDS, FTIR, XPS, Zeta, and BET, it is speculated that the new material FCH/AO-MWCNTs form more abundant pore structure and adsorption sites, and their dispersion and stability performance are excellent, and at the same time, the new material has broad application prospects in the removal of other heavy metals and recycling.
- multi-walled carbon nanotubes /
- hydroxyapatite /
- composite nanomaterials /
- Mn(II)-containing wastewater /
- adsorption performance

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图 1 氟碳掺杂羟基磷灰石/混酸氧化多壁碳纳米管(FCH/AO-MWCNTs)的制备

Figure 1. Schematic diagram of the preparation of fluorine/carbon-doped hydroxyapatite/mixed-acid oxidized multi-walled carbon nanotubes (FCH/AO-MWCNTs)

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图 2 辅助方法对HAP吸附性能的影响

Figure 2. Influence of auxiliary methods on the adsorption performance of HAP

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图 3 AO-MWCNTs、HAP、氟碳掺杂的羟基磷灰石(FCHAP)、FCH/AO-MWCNTs的EDS结果

Figure 3. EDS results of AO-MWCNTs, HAP, fluorine/carbon-doped hydroxyapatite (FCHAP), FCH/AO-MWCNTs

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图 4 HAP ((a), (b))、FCHAP ((c), (d))及FCH/AO-MWCNTs ((e), (f))的SEM图像

Figure 4. SEM images of HAP ((a), (b)), FCHAP ((c), (d)) and FCH/AO-MWCNTs ((e), (f))

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图 5 HAP、FCHAP和FCH/AO-MWCNTs的FTIR图谱

Figure 5. FTIR spectra of HAP, FCHAP and FCH/AO-MWCNTs

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图 6 HAP、FCHAP和FCH/AO-MWCNTs的XPS全谱

Figure 6. XPS full spectra of HAP, FCHAP and FCH/AO-MWCNTs

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图 7 HAP、FCHAP和FCH/AO-MWCNTs的XRD图谱

Figure 7. XRD patterns of HAP, FCHAP and FCH/AO-MWCNTs

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图 8 HAP、FCHAP和FCH/AO-MWCNTs的Zeta电位

Figure 8. Zeta potential test results of HAP, FCHAP and FCH/AO-MWCNTs

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图 9 HAP (a)、FCHAP (b)、FCH/AO-MWCNTs (c)的粒径测试结果

Figure 9. Particle size test results of HAP (a), FCHAP (b), FCH/AO-MWCNTs (c)

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图 10 HAP、FCHAP和FCH/AO-MWCNTs的N₂吸附-脱附等温线及孔径分布图

STP—Standard temperature and pressure

Figure 10. N₂ adsorption-desorption isotherms and pore size distributions of HAP, FCHAP, and FCH/AO-MWCNTs

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图 11 FCH/AO-MWCNTs吸附Mn(II)的热力学模型拟合结果

C_e—Concentration of adsorbent at adsorption equilibrium; q_e—Equilibrium adsorption capacity; K_d—Equilibrium constant; R²—Correlation coefficient of model fit; T—Temperature

Figure 11. Thermodynamic model fitting results for the adsorption of Mn(II) by FCH/AO-MWCNTs

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图 12 多离子共存情况下FCH/AO-MWCNTs的去除效率

Figure 12. Removal efficiency of FCH/AO-MWCNTs in case of multiple ion coexistence

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图 13 FCH/AO-MWCNTs的再生循环实验

Figure 13. Regeneration cycle experiment of FCH/AO-MWCNTs

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图 14 MWCNTs、AO-MWCNTs、HAP、FCHAP、FCH/AO-MWCNTs的Langmuir模型拟合

Figure 14. Langmuir model fitting for MWCNTs, AO-MWCNTs, HAP, FCHAP, FCH/AO-MWCNTs

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图 15 吸附Mn(II)前后的FCH/AO-MWCNTs的表征结果：(a) FTIR图谱；(b) XPS全谱

Figure 15. Characterization results of FCH/AO-MWCNTs before and after adsorption of Mn(II): (a) FTIR spectra; (b) XPS full spectra

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图 16 FCH/AO-MWCNTs对Mn(II)的吸附原理图

Figure 16. Schematic diagram of adsorption of Mn(II) by FCH/AO-MWCNTs

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表 1 羟基磷灰石(HAP)的合成方法及名称

Table 1. Synthesis methods and names of hydroxyapatite (HAP)

Name	HAP synthesis method
HAP-1	Microwave/light-wave combined heating
HAP-2	Microwave
HAP-3	Heating
HAP-4	Traditional chemical precipitation
HAP-5	Ultrasouic

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表 2 不同质量比AO-MWCNTs制备的FCH/AO-MWCNTs对Mn(II)的吸附率

Table 2. Adsorption rates of Mn(II) on FCH/AO-MWCNTs prepared with different mass ratios of AO-MWCNTs

AO-MWCNTs/wt%	Mn(II) adsorption rate/%
0	95.3778
0.25	94.9556
0.5	96.7556
1	95.7333
2	95.6676
5	94.0667
Note: Initial concentration of Mn(II) is 30 mg/L.

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表 3 HAP、FCHAP和FCH/AO-MWCNTs的比表面积、孔容及孔径

Table 3. BET surface area, pore volume and pore size of HAP, FCHAP and FCH/AO-MWCNTs

Material	Surface area/ (m²·g⁻¹)	Pore volume/ (cm³·g⁻¹)	Pore size/ nm
HAP	101.20	0.6179	24.4186
FCHAP	54.44	0.3841	28.2206
FCH/AO-MWCNTs	57.33	0.2445	17.0544

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表 4 FCH/AO-MWCNTs吸附Mn(II)的准一级和准二级动力学模型参数

Table 4. Pseudo-first-order and pseudo-second-order kinetic parameters for the adsorption of Mn(II) by FCH/AO-MWCNTs

Model	Parameter	FCH/AO-MWCNTs
Pseudo first-order model	q_e.cal/(mg·g⁻¹)	3.75
	k₁/min⁻¹	0.0138
	R²	0.9309
Pseudo second-order model	q_e.cal/(mg·g⁻¹)	29.8
	k₂/(min⁻¹)	0.0041
	R²	0.9989
	q_e.exp/(mg·g⁻¹)	29.40
Notes: q_e.cal—Calculated equilibrium adsorption capacity; k₁—Adsorption rate constant of the Pseudo first-order kinetic equation; R²—Correlation coefficient of model fit; k₂—Adsorption rate constant of the Pseudo second-order kinetic equation; q_e.exp—Experimental equilibrium adsorption capacity.

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表 5 FCH/AO-MWCNTs吸附Mn(II)的热力学模型参数

Table 5. Thermodynamic model parameters for the adsorption of Mn(II) by FCH/AO-MWCNTs

T/K	$ {{\Delta }{S}} $/ (J·K⁻¹·mol⁻¹)	$ {{\Delta }{H}} $/ (kJ·mol⁻¹)	$ {{\Delta }{G}} $/ (kJ·mol⁻¹)	R²
293	34.85	−7.989	−1.821	0.9930
303			−1.856	0.9981
313			−1.891	0.9987
323			−1.923	0.9930
Notes: ΔS—Entropy change under standard conditions; ΔH—Standard enthalpy change under standard conditions; ΔG—Gibbs free energy change under standard conditions at different temperatures.

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表 6 FCH/AO-MWCNTs吸附Mn(II)的等温吸附模型参数

Table 6. Isothermal adsorption model parameters for Mn(II) adsorption by FCH/AO-MWCNTs

Model	Parameter	FCH/AO-MWCNTs
Langmuir isotherm	q_max1/(mg·g⁻¹)	317.5
	K_L/(L·mg⁻¹)	0.292
	R²	0.9977
Freundlich isotherm	K_F/(mg·g⁻¹·(L·mg⁻¹)^1/n)	72.53
	1/n	0.541
	R²	0.9553
Dubinin- Radushkevich	q_max2/(mol·g⁻¹)	466.1
	K/(mol²·kJ⁻²)	0.00084
	E/(kJ·mol⁻¹)	24.37
	R²	0.9964
Notes: q_max1—Maximum adsorption capacity calculated by Langmuir isotherm model; K_L—Langmuir constant; K_F—Freundlich constant; 1/n—Ion exchange strength constant; q_max2—Maximum adsorption capacity calculated by Dubinin-Radushkevich isotherm model; K—Dubinin-Radushkevich constant; E—Average free energy of adsorption.

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表 7 材料的理论最大Mn(II)吸附量计算结果

Table 7. Calculation of the theoretical maximum Mn(II) adsorption amount of the material

Materials	K_L/ (L·mg⁻¹)	R²	q_max/ (mg·g⁻¹)	Surface area/ (m²·g⁻¹)	Number of adsorbed metal atoms per unit surface area/(atoms·nm⁻²)
MWCNTs	0.249	0.9887	0.58	91.45	0.069
AO-MWCNTs	1.192	0.9995	5.77	91.44	0.690
HAP	0.063	0.9954	36.34	101.20	3.940
FCHAP	0.179	0.9800	273.97	54.44	55.140
FCH/AO-MWCNTs	0.292	0.9977	317.50	57.33	60.680
Notes: The adsorption data of MWCNTs and AO-MWCNTs materials were obtained from the literature [28]; q_max—Maximum adsorption capacity calculated by Langmuir isotherm model.

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表 8 FCH/AO-MWCNTs与其他材料锰吸附性能对比

Table 8. Comparison of Mn(II) adsorption performance of FCH/AO-MWCNTs and other materials

Material	q_max/(mg·g⁻¹)
FCH/AO-MWCNTs	317.5
Banana stalk biochar^[38]	109.1
N-acetylcysteine on multi-walled Carbon nanotubes^[39]	146.7
Magnetic hydroxyapatite^[40]	0.7
Cellulose^[41]	52.9

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