聚乙二醇对羟基磷灰石除氟性能的影响

马明明; 崔淑慧; 杨家琴

doi:10.13801/j.cnki.fhclxb.20231220.001

聚乙二醇对羟基磷灰石除氟性能的影响

doi: 10.13801/j.cnki.fhclxb.20231220.001

西安工程大学　环境与化工学院，西安 710048

基金项目: 西安市科技计划项目(22NYYF051)

详细信息

通讯作者:
马明明，博士，教授，研究方向为功能材料绿色制备　E-mail: 18220593193@163.com

中图分类号: O69；TB332
计量
- 文章访问数: 204
- HTML全文浏览量: 87
- PDF下载量: 15
- 被引次数: 0
出版历程
- 收稿日期: 2023-08-30
- 修回日期: 2023-12-07
- 录用日期: 2023-12-09
- 网络出版日期: 2023-12-21
- 刊出日期: 2024-07-01

Effect of polyethylene glycol on fluoride removal performance of hydroxyapatite

College of Environmental and Chemical Engineering, Xi'an Polytechnic University, Xi'an 710048, China

Funds: Scientific Research Project Supported by Xi'an City (22NYYF051)

摘要

摘要: 为改善羟基磷灰石(HAP)合成过程易团聚导致其除氟效率不高的不足，本文应用清洁简便、绿色环保的电化学合成法，将亲水性强、分散性优异的非离子型表面活性剂聚乙二醇(PEG)加入到制备HAP的混合支持电解液中，在铜片作工作电极的表面制备出新型HAP复合材料(PEG/HAP)，并与纯HAP的晶体结构、孔径、比表面积、表面形貌、元素占比和官能团对比，以揭示PEG/HAP除氟效率高于HAP的内在机制。结果发现，PEG/HAP与HAP有相同的晶面结构特征蜂、元素和化学键，但PEG/HAP的各元素含量占比、羟基和磷酸根离子官能团的吸收峰位和吸收强度与HAP 有一定差异；PEG使HAP从短棒状的表面形貌变成有利于交换和吸附氟离子的多孔和孔隙结构，其平均孔径由16.58 nm减小到11.93 nm，比表面积从24.29 m²/g增加到29.83 m²/g；虽然PEG/ HAP与HAP的吸附类型均为IV型的H3滞后环，二者介孔分布范围一致，但PEG/ HAP的微孔和介孔数量明显高于HAP。尽管两种材料对氟离子的吸附反应均显示熵增、吸热和自发过程特征，吸附等温模型均符合Langmuir-Freundlich，但PEG/HAP的颗粒内扩散速率常数略大于HAP，PEG/HAP的吸附氟离子容量(9.56 mg/g)高于HAP (8.36 mg/g)；且去除氟离子的循环再生次数从HAP的4次增加到PEG/HAP的6次。此外，PEG的存在并没有影响制备条件参数如支持电解液pH值对HAP吸附氟离子容量的影响趋势，但却使HAP吸附氟离子容量增加。共存阴离子如Cl⁻、NO₃ ⁻、SO₄ ²⁻、CO₃ ²⁻均不干扰PEG/HAP和HAP对氟离子的吸附。
- 聚乙二醇 /
- 羟基磷灰石 /
- 电化学合成 /
- 除氟性 /
- 吸附性
Abstract: The removal efficiency of hydroxyapatite (HAP ) to fluoride was low due to its easy agglomeration during the synthesis process. Based on this, a clean, simple, green and environmentally fiendly electrochemcial synthesis method was applied to improve the fluoride removal efficiency. Polyethylene glycol (PEG), a non ionic surfactant with strong hydrophilicity and excellent dispersion, was added to the mixed support electrolyte for preparing HAP. A new type of HAP composite (PEG/HAP) was prepared on the surface of copper sheet as the working electrode. By contrast to HAP, the crystal structure, pore size, specific surface area, surface morphology, elemental proportion, and functional groups of PEG/HAP were analyzed to reveal the instrinsic mechnism of the higher fluoride removal efficiency of PEG/HAP than HAP. The results show that PEG/HAP and HAP have the same crystal plane structure characteristics, elements and chemical bonds, while the proportion of various elements as well as the absorption peaks and intensity of hydroxyl and phosphate ion functional groups in PEG/HAP have certain differences compared to HAP. PEG transformed HAP from a short rod-shaped surface morphology to a porous and porous structure that facilitated the exchange and adsorption of fluoride ions. Average pore size of PEG/HAP decreased from 16.58 nm of HAP to 11.93 nm, and its specific surface area increased from 24.29 m²/g OF HAP to 29.83 m²/g. Although the adsorption types of PEG/HAP and HAP were both IV type H3 hysteresis loop, and their mesoporous distribution ranges were consistent, the number of micropores and mesopores in PEG/HAP were significantly higher than those in HAP. Although the adsorption reactions of both materials for fluoride ions exhibited entropy increase, endothermic, and spontaneous process characteristics with the adsorption isotherm model conforming to Langmuir-Freundlich, the intra particle diffusion rate constant of PEG/HAP was slightly higher than HAP. Therefore, the maximum adsorption capacity of PEG/HAP for fluoride ions can reach 9.56 mg/g, which was higher than that of HAP of 8.36 mg/g. Compared with 4 times of recycle regeneration for removing fluoride ions of HAP, PEG/HAP can arrived at 6. In addition, the presence of PEG did not affect the change trend of preparation parameters such as electrolyte pH on the adsorption capacity of HAP for fluoride ions. However, PEG increased the adsorption capacity of HAP for fluoride ions. All coexisiting ions such as Cl⁻, NO₃ ⁻, SO₄ ²⁻, and CO₃ ²⁻ did not interfere with the adsorption of fluoride ions for PEG/HAP and HAP.
- polyethylene glycol /
- hydroxyapatite /
- electrochemical synthesis /
- defluoridation /
- adsorptivity

HTML全文

图 1 聚乙二醇(PEG)/二水磷酸二氢钙(DCPD) (a)、PEG/羟基磷灰石(HAP) (b)和标准HAP (c)的XRD图谱

Figure 1. XRD patterns of polyethylene glycol (PEG)/calcium phosphate dihydrate (DCPD) (a), PEG/hydroxyapatite (HAP) (b) and standard HAP (c)

下载: 全尺寸图片幻灯片

图 2 HAP (a) 和PEG/HAP (b)的SEM图像

Figure 2. SEM images of HAP (a) and PEG/HAP (b)

下载: 全尺寸图片幻灯片

图 3 HAP和PEG/ HAP的氮气吸附-脱附曲线

Figure 3. Nitrogen adsorption-desorption curves of HAP and PEG/HAP

STP—Standard temperature and pressure

下载: 全尺寸图片幻灯片

图 4 HAP和PEG/HAP的孔径分布曲线

Figure 4. Curves of the pore size distribution of HAP and PEG/HAP

dV/dD—Rate of change of pore diameter with pore volume

下载: 全尺寸图片幻灯片

图 5 HAP和PEG/HAP的XPS图谱

Figure 5. XPS spectra of HAP and PEG/HAP

下载: 全尺寸图片幻灯片

图 6 HAP 和PEG/HAP的红外图谱

Figure 6. FTIR spectra of HAP and PEG/HAP

下载: 全尺寸图片幻灯片

图 7 pH对PEG/HAP和HAP 吸附容量q影响

Figure 7. Effect of pH on PEG/HAP and HAP for adsorption capacity q

下载: 全尺寸图片幻灯片

图 8 温度对PEG/HAP吸附容量的影响

Figure 8. Effect of temperature on adsorption capacity of PEG/HAP

C₀—Initial concentration of F⁻

下载: 全尺寸图片幻灯片

图 9 PEG/HAP和HAP吸附F⁻的lnK_d与1/T 线性曲线(F⁻浓度：(a) 1.5 mg/L；(b) 2.0 mg/L；(c) 4.0 mg/L；(d) 6.0 mg/L；(e) 8.0mg/L；(f) 10.0 mg/L)

Figure 9. Linear curves of lnK_d vs 1/T of PEG/HAP and HAP adsorption F⁻ (F⁻ concentration: (a) 1.5 mg/L; (b) 2.0 mg/L; (c) 4.0 mg/L; (d) 6.0 mg/L; (e) 8.0mg/L; (f) 10.0 mg/L)

K_d—Partition coefficient of adsorption process; T—Absolute temperature of adsorption process

下载: 全尺寸图片幻灯片

图 10 共存阴离子对PEG/HAP (a)和HAP (b)吸附容量的影响

Figure 10. Effects of coexisting ions on adsorption capacity of PEG/HAP (a) and HAP (b)

下载: 全尺寸图片幻灯片

图 11 吸附时间对PEG/HAP (a)和HAP (b)除氟效率的影响

Figure 11. Effect of adsorption time on defluoridationl efficient of PEG/HAP (a) and HAP (b)

下载: 全尺寸图片幻灯片

表 1 HAP和PEG/HAP的孔结构参数

Table 1. Pore structure parameters of HAP and PEG/HAP

Material	Parameters
Material	BET surface area/(m²·g⁻¹)	Average pore diameter/nm
HAP	24.29	16.58
PEG/HAP	29.83	11.93

下载: 导出CSV

表 2 HAP和PEG/HAP元素占比

Table 2. Atomic ratio of HAP and PEG/HAP

Material	C/at%	O/at%	P/at%	Ca/at%
HAP	14.18	59.29	12.47	14.06
PEG/HAP	17.43	56.22	11.23	15.12

下载: 导出CSV

表 3 PEG/HAP和HAP吸附F⁻的热力学参数

Table 3. Thermodynamic parameters of PEG/HAP and HAP adsorption F⁻

F⁻ initial concention/(mg·L⁻¹)	T/K	$\Delta {G}^{\ominus } $/(kJ·mol⁻¹)		$\Delta {S}^{\ominus } $/(J·K⁻¹·mol⁻¹)		$\Delta {H}^{\ominus } $/(kJ·mol⁻¹)
F⁻ initial concention/(mg·L⁻¹)	T/K	PEG/HAP	HAP	PEG/HAP	HAP	PEG/HAP	HAP
1.5	288.15	−20.6064	−20.8255	183.9473	108.6640	32.3980	10.4860
	298.15	−22.4459	−21.9122
	308.15	−24.2854	−22.9988
	318.15	−26.1248	−24.0855
	328.15	−27.9643	−25.1721
2	288.15	−20.6560	−20.8680	164.4675	112.0162	26.7353	11.4095
	298.15	−22.3007	−21.9881
	308.15	−23.9454	−23.1083
	318.15	−25.5900	−24.2285
	328.15	−27.2347	−25.3486
4	288.15	−18.1882	−17.3630	164.1350	169.6522	29.1073	31.5223
	298.15	−19.8296	−19.0595
	308.15	−21.4709	−20.7560
	318.15	−23.1123	−22.4525
	328.15	−24.7536	−24.1491
6	288.15	−16.6281	−15.7314	174.6855	167.8098	33.7075	32.6230
	298.15	−18.3750	−17.4095
	308.15	−20.1218	−19.0876
	318.15	−21.8687	−20.7657
	328.15	−23.6155	−22.4438
8	288.15	−15.8648	−14.9546	135.6928	151.0870	23.2351	28.5811
	298.15	−17.2217	−16.4655
	308.15	−18.5786	−17.9764
	318.15	−19.9356	−19.4872
	328.15	−21.2925	−20.9981
10	288.15	−15.2550	−14.6329	128.7755	129.4490	21.8517	22.6678
	298.15	−16.5427	−15.9274
	308.15	−17.8305	−17.2219
	318.15	−19.1182	−18.5164
	328.15	−20.4060	−19.8109
Notes: $\Delta {G}^{\ominus } $, $\Delta {S}^{\ominus } $ and $\Delta {H}^{\ominus } $—Standard Gibbs function change value, entropy change, and enthalpy change, respectively.

下载: 导出CSV

表 4 PEG/HAP与HAP的Langmuir-Freundlich模型拟合参数

Table 4. Fitting parameters of Langmuir-Freundlich of PEG/HAP and HAP

Model	T/K	q_m/(mg·g⁻¹)		b		n		R²
Model	T/K	PEG/HAP	HAP	PEG/HAP	HAP	PEG/HAP	HAP	PEG/HAP	HAP
Langmuir-Freundlich	288.15	4.6058	3.4550	3.0896	3.0662	1.2522	3.8708	0.9701	0.9615
	298.15	5.8948	4.3757	3.2896	27.3055	1.2079	2.8634	0.9858	0.9694
	308.15	6.8707	5.6192	2.8382	4.3399	0.8620	1.3814	0.9914	0.9818
	318.15	8.7941	7.2896	2.7633	3.3643	0.9144	1.4300	0.9757	0.9960
	328.15	10.2706	8.9194	2.9674	2.7605	0.9658	1.3416	0.9822	0.9941
Notes: b—Adsorption constant; n—Non-uniformity coefficient; R²—Correlation coefficient.

下载: 导出CSV

表 5 PEG/HAP动力学方程拟合参数

Table 5. Fitting parameters of kinetics equation for PEG/HAP

Equation	Parameters		R²
Pseudo first-order model	k₁/min⁻¹	Q_e/(mg·g⁻¹)	0.8953
Pseudo first-order model	0.0171	3.4672	0.8953
Pseudo second-order model	k₂ /(g·mg⁻¹·min⁻¹)	Q_e/(mg·g⁻¹)	0.9854
Pseudo second-order model	0.0050	4.1203	0.9854
Elovich	A/(mg·g⁻¹·min⁻¹)	B/(g·mg⁻¹)	0.9663
Elovich	0.2526	1.2902	0.9663
Morrist intraparticle diffusion model	k₃/(g·g⁻¹·min^−0.5)	C	0.9876
Morrist intraparticle diffusion model	0.1774	0.6684	0.9876
Notes: k₁—Adsorption rate constant of the quasi first order kinetic model; k₂—Adsorption rate constant of the quasi second order kinetic model; B—Desorption coefficient; A—Constant adsorption rate; k₃—Internal diffusion rate constant; C—Boundary-layer thickness; Q_e—Equilibrium adsorption capacity.

下载: 导出CSV

表 6 HAP不同动力学模型的拟合参数

Table 6. Fitting parameters of kinetics equation for HAP

Equation	Parameters		R²
Pseudo first-order model	k₁/min⁻¹	Q_e/(mg·g⁻¹)	0.9186
Pseudo first-order model	0.0136	3.1689	0.9186
Pseudo econd-order model	k₂/(g·mg⁻¹·min⁻¹)	Q_e/(mg·g⁻¹)	0.9770
Pseudo econd-order model	0.0043	3.8226	0.9770
Elovich	A/(mg·g⁻¹·min⁻¹)	B/(g·mg⁻¹)	0.9595
Elovich	0.1740	1.3443	0.9595
Morrist intraparticle diffusion model	k₃/ (g·g⁻¹·min^−0.5)	C	0.9915
Morrist intraparticle diffusion model	0.1712	0.3834	0.9915

下载: 导出CSV

表 7 HAP和PEG/HAP吸附容量

Table 7. Adsorption capacity of HAP and PEG/HAP

Material	q/(mg·g⁻¹)
Material	1st	2nd	3rd	4th	5th
HAP	2.36	2.38	2.32	2.34	2.36
PEG/HAP	2.68	2.70	2.70	2.66	2.64

下载: 导出CSV

表 8 HAP和PEG/HAP的氟离子去除率

Table 8. Defluoridation efficient of HAP and PEG/HAP

Material	Defluoridation efficient/%
Material	1st	2nd	3rd	4th	5th
HAP	59.0	59.5	58.0	58.5	59.0
PEG/HAP	67.0	67.5	67.5	66.5	66.0

下载: 导出CSV

表 9 HAP和PEG/HAP循环再生次数

Table 9. Recycling regeneration times of HAP and PEG/HAP

Material	C_F⁻/(mg·L⁻¹)
Material	1st	2nd	3rd	4th	5th	6th
HAP	0.65	0.75	0.86	0.94	1.12	—
PEG/HAP	0.42	0.51	0.64	0.73	0.86	0.94
Note: C_F⁻—Remain concentration of F⁻ in model waste water.

下载: 导出CSV

表 10 PEG/HAP与同类氟离子吸附剂吸附参数

Table 10. Adsorption parameters of PEG/HAP and similar fluoride ion adsorbents

Absorbents	Solution pH	Adsorption capacity/ (mg·g⁻¹)	Ref.
PEG/HAP	6.0	9.56	This work
Citric acid/HAP	8.31	2.678	[40]
Road tea-leaves	3	0.126	[41]
Polylactic acid/HAP	—	6.06	[42]

下载: 导出CSV

参考文献(42)

[1]	GEORGE S, MEHTA D, SAHARAN V K. Application of hydroxyapatite and its modified forms as adsorbents for water defluoridation: An insight into process synthesis[J]. Reviews in Chemical Engineering, 2018, 36(3): 369-400.
[2]	GONG L Y, FENG L. Preparation and defluorination mechanism of a novel copolymerized hydroxyapatite-aluminium chloride material[J]. RSC Advances, 2015, 5(115): 95334-95343. doi: 10.1039/C5RA20372D
[3]	SAHU H, MOHANTY K. Al grafted natural hydroxyapatite for neem oil transesterification: Kinetic study at optimal point[J]. Chemical Engineering Journal, 2015, 280: 564-574. doi: 10.1016/j.cej.2015.06.040
[4]	MONDALl P, MEHTA D, GEORGE S. Defluoridation studies with synthesized magnesium-incorporated hydroxyapatite and parameter optimization using response surface methodology[J]. Desalination and Water Treatment, 2016, 57(56): 27294-27313. doi: 10.1080/19443994.2016.1167628
[5]	赵瑨云, 胡家朋, 林皓, 等. Ag⁺改性羟基磷灰石制备及其除氟抑菌特性研究[J]. 硅酸盐通报, 2020, 39(12): 3977-3984. ZHAO Jinyun, HU Jiapeng, LIN Hao, et al. Fabrication of hydroxyapatite-modified Ag⁺ and its property for defluorination and bacteriostasis activity[J]. Bulltin of the Chinese Ceramic Society, 2020, 39(12): 3977-3984(in Chinese).
[6]	CHEN Z, LIU Y, MAO L, et al. Effect of cation doping on the structure of hydroxyapatite and the mechanism of defluoridation[J]. Ceramics International, 2017, 44(6): 6002-6009.
[7]	GAO S, SUN R, WEI Z, et al. Size-dependent defluoridation properties of synthetic hydroxyapatite[J]. Journal of Fluorine Chemistry, 2009, 130(6): 550-556. doi: 10.1016/j.jfluchem.2009.03.007
[8]	干成果, 冯莉. 负载羟基磷灰石活性炭的制备及除氟性能[J]. 功能材料, 2013, 44(22): 3243-3246. GAN Chengguo, FENG Li. Preparation of activated carbon supported hydroxyapatite and the removal performance of fluorine ion[J]. Journal of Functional Materials, 2013, 44(22): 3243-3246(in Chinese).
[9]	SANI T, GṌMEZ-HORTIGŰELA L, MAYORAL Á, et al. Controlled growth of nano-hydroxyapatite on stilbite: Defluoridation performance[J]. Microporous & Mesoporous Materials, 2017, 254: 86-95.
[10]	GERGELY G, WéBER F, LUKÁCS I, et al. Preparation and characterization of hydroxyapatite from eggshell[J]. Ceramics International, 2010, 36(2): 803-806. doi: 10.1016/j.ceramint.2009.09.020
[11]	WORKENEH K, ZEREFFA E A, SEGNE T A, et al. Eggshell-derived nanohydroxyapatite adsorbent for defluoridation of drinking water from bofo of ethiopia[J]. Journal of Nanomaterials, 2019, 2: 1-12.
[12]	SAMANT A, NAYAK B, MISRA P K. Kinetics and mechanistic interpretation of fluoride removal by nanocrystalline hydroxyapatite derived from Limacine artica shells[J]. Journal of Environmental Chemical Engineering, 2017, 5(6): 5429-5438. doi: 10.1016/j.jece.2017.09.058
[13]	XU F, JIANG C, LI D. Defluoridation of wastewaters using HAP-coated-limestone[J]. Separation Science & Technology, 2018, 54(14): 2304-2313.
[14]	YU X, TONG S, GE M, et al. Removal of fluoride from drinking water by cellulose@hydroxyapatite nano-composites[J]. Carbohydrate Polymers, 2013, 92(1): 269-275. doi: 10.1016/j.carbpol.2012.09.045
[15]	胡家朋. 羟基磷灰石复合改性材料的制备及其除氟性能研究[D]. 南昌: 南昌大学, 2016 HU Jiapeng. Preparation and defluoridation properties of hydroxyapatite modified composites[D]. Nanchang: Nanchang Univercity, 2016(in Chinese).
[16]	赵瑨云, 刘瑞来, 徐婕, 等. 原位合成羟基磷灰石/壳聚糖复合吸附剂及除氟特性研究[J]. 高分子通报, 2021(2): 54-62. ZHAO Jinyun, LIU Ruilai, XU Jie, et al. In situ fabracation of hydroxyapatite/chitosan composite adsorbent and its property for defluorination[J]. Polymer Bulletin, 2021(2): 54-62(in Chinese).
[17]	叶建东, 肖锋, 王秀鹏, 等. 十二烷基硫酸钠在化学沉淀法合成羟基磷灰石粉体中的防团聚作用[J]. 功能材料, 2005(10): 120-122. YE Jiandong, XIAO Feng, WANG Xiupeng, et al. Role of sodium dodecyl sulfate in de-agglomeration of hydroxyapatite powder synthesized by chemical precipitation method[J]. Journal of Functional Materials, 2005(10): 120-122(in Chinese).
[18]	MUKHERJEE S, KNDU B, CHANDA A, et al. Effect of functionalisation of CNT in the preparation of HAP-CNT biocomposites[J]. Ceramics International, 2015, 41(3): 3766-3774. doi: 10.1016/j.ceramint.2014.11.052
[19]	章萍, 杨陈凯, 马若男, 等. 碳纳米管/羟基磷灰石复合材料对水体F⁻的去除研究[J]. 中国环境科学, 2019, 39(1): 179-187. ZHANG Ping, YANG Chenkai, MA Ruonan, et al. Effective removal of fluoride by carbon nanotubes/hydroxyapatite composite[J]. China Environmental Science, 2019, 39(1): 179-187(in Chinese).
[20]	PRABHU S M, ELANCHEZHIYAN S S D, LEE G, et al. Assembly of nano-sized hydroxyapatite onto graphene oxide sheets via in-situ fabrication method and its prospective application for defluoridation studies[J]. Chemical Engineering Journal, 2016, 300: 334-342. doi: 10.1016/j.cej.2016.04.111
[21]	贾晓林, 钟香崇. 聚乙二醇在MgAl₂O₄前驱体表面的吸附及改性作用[J]. 中国粉体技术, 2004(5): 12-15. JIA Xiaolin, ZHONG Xiangchong. Effect of PEG on absorption state and surface modification of MgAlO₄ precursor[J]. China Powder Science and Technology, 2004(5): 12-15(in Chinese ).
[22]	逯英英, 陈肖平, 马枭, 等. 聚乙二醇改性酚醛树脂基球形炭吸附脱硫脱氮性能研究[J]. 石油与天然气化工, 2017, 46(4): 6-10. LU Yingying, CHEN Xiaoping, MA Xiao, et al. Performance study on adsorption removal of sulfur and nitrogen compounds of carbon spheres derived from phenolic resin with polyethylene glycol[J]. Chemical Engineering of Oil & Gas, 2017, 46(4): 6-10(in Chinese).
[23]	李金鑫, 龚巧迪, 杨金燕. 改性羟基磷灰石对水体中五价钒的吸附[J]. 硅酸盐通报, 2018, 37(4): 1355-1362, 1386. LI Jinxin, GONG Qiaodi, YANG Jinyan. Adsorption of vanavandium(V) in aqueous solution by modified hydroxyapatite[J]. Bulltin of the Chinese Ceramic Society, 2018: 37(4): 1355-1362, 1386(in Chinese).
[24]	朱丹琛, 刘秀秀, 陈彰旭, 等. 羟基磷灰石微球的仿生合成及除氟性能[J]. 化学研究与应用, 2019, 31(3): 570-575. ZHU Danchen, LIU Xiuxiu, CHEN Zhangxu, et al. Biomimetic synthesis of hydroxyapatite microspheres and its defluoridation properties[J]. Chemical Research and Application, 2019, 31(3): 570-575(in Chinese).
[25]	RIVERA E M, ARAIZA M, BROSTOW W, et al. Synthesis of hydroxyapatite from eggshells[J]. Materials Letters, 1999, 41(3): 128-134. doi: 10.1016/S0167-577X(99)00118-4
[26]	JIE W, LI Y. Tissue engineering scaffold material of nano-apatite crystals and polyamide composite[J]. European Polymer Journal, 2004, 40(3): 509-515. doi: 10.1016/j.eurpolymj.2003.10.028
[27]	周婷婷. 磁性导电聚合物材料的合成及其对水中 Cr(VI)的吸附研究[D]. 广州: 华南理工大学, 2020. ZHOU Tingting. Preparation of magnetic conductive polymers materials and their performance in removing Cr(VI) in water[J]. Guangzhou: South China University of Technology, 2020(in Chinese).
[28]	BAUTISTA L F, PINILLA J, ARACIL J, et al. Adsorption isotherms of aspartame on commercial and chemically modified divinylbenzene styrene resins at different temperatures[J]. Journal of Chemical and Engineering Data, 2002, 47(3): 620-627. doi: 10.1021/je010325a
[29]	GAUTHAM P J, PRABHAKAR T C. A modified Langmuir-Freundlich isotherm model for simulating pH-dependent adsorption effects[J]. Journal of Contaminant Hydrology, 2012, 129-130: 46-53. doi: 10.1016/j.jconhyd.2011.12.001
[30]	LI H, XIAO D L, HE H, et al. Adsorption behavior and adsorption mechanism of Cu(II) ions on amino-functionalized magnetic nanoparticles[J]. Transactions of Nonferrous Metals Society of China, 2013, 23(9): 2657-2665. doi: 10.1016/S1003-6326(13)62782-X
[31]	TOFIGHY M A, MOHAMMADI T. Adsorption of divalent heavy metal ions from water using carbon nanotube sheets[J]. Journal of Hazardous Materials, 2011, 185(1): 140-147. doi: 10.1016/j.jhazmat.2010.09.008
[32]	周亚平, 周理. 超临界氢在活性炭上的吸附等温线研究[J]. 物理化学学报, 1997, 13(2): 119-127. doi: 10.3866/PKU.WHXB19970205 ZHOU Yaping, ZHOU Li. Study on the adsorption isotherms of supercritical hydrogen on activated carbon[J]. Acta Physical Chemisry, 1997, 13(2): 119-127(in Chinese ). doi: 10.3866/PKU.WHXB19970205
[33]	GREGORIO M. BET adsorption reaction model based on the pseudo steady-state hypothesis for describing the kinetics of adsorption in liquid phase[J]. Journal of Colloid and Interface Science, 2016, 467: 170-179. doi: 10.1016/j.jcis.2016.01.016
[34]	蔡金水, 康得军, 杨天学, 等. 铁改性杭锦土吸附剂对水中砷的去除研究[J]. 环境科学研究, 2021, 34(2): 346-355. CHAI Jinshui, KANG Dejun, YANG Tianxue, et al. Removal of arsenic from water by iron modified Hangjin clay adsorbent[J]. Research of Environmental Sciences, 2021, 34(2): 346-355(in Chinese).
[35]	HOSLETT J, GHAZAL H, KATSOU E, et al. The removal of tetracycline from water using biochar produced from agricultural discarded material[J]. Science of the Total Environment, 2021, 751: 141755. doi: 10.1016/j.scitotenv.2020.141755
[36]	ZHANG C J, HU M, KE Q F, et al. Nacre-inspired hydroxyapatite/chitosan layered composites effectively remove lead ions in continuous-flow wastewater[J]. Journal of Hazardous Materials, 2020, 386: 121999. doi: 10.1016/j.jhazmat.2019.121999
[37]	TIAN Y, LI J B, TODD W W, et al. Application of oily sludge-derived char for lead and cadmium removal from aqueous solution[J]. Chemical Engineering Journal, 2020, 384: 123386. doi: 10.1016/j.cej.2019.123386
[38]	KIM Y S, KIM J H. Isotherm, kinetic and thermodynamic studies on the adsorption of paclitaxel onto sylopute[J]. The Journal of Chemical Thermodynamics, 2019, 130: 104-113. doi: 10.1016/j.jct.2018.10.005
[39]	CRINI G, PEINDY N, GIMBERT F. Removal of C.I. basic green 4 (malachite green) from aqueous solutions by absorption using cyclodextrinbased adsorbent: Kinetic and equilibrium studies[J]. Separation Purification Technology, 2007, 53(1): 97-110. doi: 10.1016/j.seppur.2006.06.018
[40]	赵佳昕, 李文博 , 王吉坤. 柠檬酸优化水热合成羟基磷灰石及矿井水除氟性能[J]. 洁净煤技术, 2022, 28(2): 175-185. ZHAO Jiaxin, LI Wenbo, WANG Jikun. Optimization of hydrothermal synthesis of hydroxyapatite with citric acid and its fluorine removal[J]. Clean Coal Technology, 2022, 28(2): 175-185(in Chinese).
[41]	张强英, 陶金帅, 李伟, 等. 废弃茶叶吸附剂去除水中的氟离子[J]. 环境化学, 2022, 41(4): 1303-1311. ZHANG Qiangying, TAO Jinshuai, LI Wei, et al. Removal of fluoride ions from water using discarded tea adsorbent[J]. Environmental Chemistry, 2022, 41(4): 1303-1311(in Chinese) .
[42]	刘瑞来. 聚乳酸 /羟基磷灰石复合纤维膜制备及其对水中氟离子的吸附[J]. 科学技术与工程, 2018, 18(31): 50-57. LIU Ruilai. Preparation of polylactic acid/hydroxyapatite composite fiber membrane and its adsorption of fluoride ions[J]. Science Technology and Engineering, 2018, 18(31): 50-57(in Chinese).