Ce改性金属有机骨架材料对氟的吸附

武鑫霞; 曹占平; 苏婷; 李岚

doi:10.13801/j.cnki.fhclxb.20200225.003

Ce改性金属有机骨架材料对氟的吸附

doi: 10.13801/j.cnki.fhclxb.20200225.003

武鑫霞^1,,
曹占平^1, ,,
苏婷^2,,
李岚^1,

1.
天津工业大学　环境科学与工程学院，天津 300387
2.
福建工程学院　生态环境与城市建设学院，福州 350100

基金项目: 国家自然科学基金(21872104)

详细信息

通讯作者:
曹占平，博士，副教授，硕士生导师，研究方向为环境功能材料与水处理　E-mail：caozhanping2012@126.com

中图分类号: TB333
计量
- 文章访问数: 1168
- HTML全文浏览量: 359
- PDF下载量: 83
- 被引次数: 0
出版历程
- 收稿日期: 2019-11-06
- 录用日期: 2020-01-09
- 网络出版日期: 2020-02-26
- 刊出日期: 2020-10-15

Adsorption of Ce modified metal organic framework to fluorine

WU Xinxia^1
,,
CAO Zhanping^{1
, ,},
SU Ting^2
,,
LI Lan^1
,

1.
School of Environmental Science and Engineering, Tiangong University, Tianjin 300387, China
2.
College of Ecological Environment and Urban Construction, Fujian University of Engineering, Fuzhou 350100, China

摘要

摘要: 利用水热合成法，将金属Ce与合成金属有机骨架材料(MOFs)所需的反应前体混合，通过“一锅法”和“两步法”分别合成性能不同的Ce/MOF-5材料。采用SEM、XRD、BET等对合成材料进行表征。结果表明：不同的方法合成的Ce/MOF-5形貌有较大差异，对氟吸附性能也不同。并测定了初始浓度、pH值、吸附时间对F⁻吸附效果的影响。实验表明，通过“一锅法”合成的Ce/MOF-5材料对F⁻的吸附在pH=7、吸附时间为60 min左右即可达到吸附平衡，吸附量为109.6 mg·g⁻¹，符合准二级动力学模型和Freundlich等温吸附模型。
- 氟 /
- 吸附 /
- MOF-5 /
- 一锅法合成 /
- 吸附热力学 /
- 吸附动力学
Abstract: The Ce/MOF-5 materials with different properties were synthesized by means of hydrothermal synthesis method by mixing Ce with the reaction precursors required for the synthesis of metal organic framework materials (MOFs). The synthetic materials were characterized by SEM, XRD and BET, etc. The results show that the Ce/MOF-5 synthesized by different methods shows significant differences in morphology and fluorine adsorption performance. The effect of the initial concentration, pH value and adsorption time on the adsorption effect of F⁻ was also determined. The experiments show that the adsorption of F⁻ by Ce/MOF-5 material synthesized by the "one-pot method" obtains an adsorption balance of 109.6 mg·g⁻¹ at pH=7, with a adsorption time of about 60 min. It conforms to the quasi-second order kinetic model and Freundlich isothermal adsorption model.
- fluoride /
- adsorption /
- MOF-5 /
- one-pot synthesis /
- adsorption thermodynamics /
- adsorption kinetics

HTML全文

图 1 Ce/MOF-5 Ⅰ、Ce/MOF-5 Ⅱ和MOF-5的XRD图谱

Figure 1. XRD patters of Ce/MOF-5 Ⅰ, Ce/MOF-5 Ⅱ and MOF-5

下载: 全尺寸图片幻灯片

图 2 MOF-5、Ce/MOF-5Ⅰ和Ce/MOF-5Ⅱ材料的SEM图像和EDS图谱

Figure 2. SEM images and EDS spectra of MOF-5, Ce/MOF-5 Ⅰ and Ce/MOF-5 Ⅱ

下载: 全尺寸图片幻灯片

图 3 MOF-5、Ce/MOF-5Ⅰ和Ce/MOF-5Ⅱ材料的FTIR图谱

Figure 3. FTIR spectra of MOF-5、Ce/MOF-5Ⅰand Ce/MOF-5Ⅱ

下载: 全尺寸图片幻灯片

图 4 Ce/MOF-5Ⅰ和Ce/MOF-5Ⅱ的N₂吸附-解吸等温线

Figure 4. N₂ adsorption-desorption isotherms of Ce/MOF-5Ⅰand Ce/MOF-5Ⅱ

下载: 全尺寸图片幻灯片

图 5 不同F^-初始浓度C_e下Ce/MOF-5的吸附量q_e

Figure 5. Adsorption quantity q_e of F^- by Ce/MOF-5 at different initial concentrations C_e

下载: 全尺寸图片幻灯片

图 6 溶液pH值对Ce/MOF-5吸附F^-吸附率η的影响

Figure 6. Effect of pH value on adsorption ratio η of F^- by Ce/MOF-5

下载: 全尺寸图片幻灯片

图 7 温度对Ce/MOF-5吸附F^-性能的影响

Figure 7. Effect of temperature on Ce/MOF-5 adsorption of F^-

下载: 全尺寸图片幻灯片

图 8 吸附时间对Ce/MOF-5吸附F⁻性能的影响

Figure 8. Effect of adsorption time on adsorption of F⁻by Ce/MOF-5

下载: 全尺寸图片幻灯片

图 9 Ce/MOF-5对F^-的吸附等温模型拟合

Figure 9. Adsorption isotherm model fitting of Ce/MOF-5 for F^-

下载: 全尺寸图片幻灯片

图 10 Ce/MOF-5对F^-的吸附动力学模型拟合

Figure 10. Adsorption kinetic model fitting of Ce/MOF-5 for F^-

下载: 全尺寸图片幻灯片

图 11 Ce/MOF-5对F^-的颗粒内扩散模型拟合

Figure 11. Particle diffusion model fitting of Ce/MOF-5 for F^-

下载: 全尺寸图片幻灯片

表 1 Ce/MOF-5对F⁻的吸附等温线拟合参数

Table 1. Adsorption isotherm fitting parameters of Ce/MOF-5 to F⁻

	Langmuir model			Freundlich model
	q_m	K_L	R²	n	K_F	R²
Ce/MOF-5Ⅰ	158.22	0.074	0.984	1.859	16.75	0.994
Ce/MOF-5Ⅱ	136.43	0.034	0.977	1.358	6.68	0.967
Notes：q_m—Saturated adsorption capacity(mg·g⁻¹); K_L—Adsorption correlation constant(L·mg⁻¹); K_F, n—Adsorption correlation constants.

下载: 导出CSV

表 2 Ce/MOF-5对F^-的吸附动力学拟合参数

Table 2. Adsorption kinetics fitting parameters of Ce/MOF-5 for F^-

	Quasi-first-order			Quasi-second-order			Elovich equation
	Q_c	K₁	R²	Q_c	K₂	R²	α	β	R²
Ce/MOF-5Ⅰ	79.42	0.064	0.933	110	0.01	0.999	526.02	0.0885	0.991
Ce/MOF-5Ⅱ	68.44	0.053	0.895	66.7	0.02	0.973	182.79	0.1044	0.950
Note: Q_c—Theoretical calculated adsorption amount(mg·g⁻¹); α, β—Elovich constants, which represent the initial adsorption rate g/(mg·min) and desorption constant (g·mg^-1); K₁—Pseudo first-order adsorption rate constant (min^-1); K₂—Pseudo second-order adsorption rate constant g/(mg·min).

下载: 导出CSV

表 3 Ce/MOF-5对F^-的吸附和脱附效率

Table 3. Adsorption and desorption efficiency of Ce/MOF-5 for F^-

	Recycling 1	Recycling 2	Recycling 3
Adsorption rate of Ce/MOF-5 Ⅰ/%	98	95	93
Desorption rate of Ce/MOF-5 Ⅰ/%	96	92	89
Adsorption rate of Ce/MOF-5 Ⅱ/%	97	93	90
Desorption rate of Ce/MOF-5 Ⅱ/%	95	91	87

下载: 导出CSV

表 4 不同吸附剂对F^-吸附性能的比较

Table 4. Comparison of F^- adsorption properties by different adsorbents

Material	MOF-5	Ce/MOF-5Ⅰ	MIL-53(Fe)	ZIF-8	ZIF-9	UIO-66(Zr)	Cu-MOF^[5]
Adsorption capacity	0	109.6	16.96	0.90	1.70	40.09	0.2

下载: 导出CSV

参考文献(20)

[1]	YU Z, XU C, YUAN K, et al. Characterization and adsorption mechanism of ZrO₂ mesoporous fibers for health-hazardous fluoride removal[J]. Journal of Hazardous Materials,2017,346:82-92.
[2]	RAGHAV S, KUMAR D. Comparative kinetics and thermodynamic studies of fluoride adsorption by two novel synthesized biopolymer composites[J]. Carbohydrate Polymers,2019,203:430-440. doi: 10.1016/j.carbpol.2018.09.054
[3]	LU G K, LI S, GUO Z, et al. Imparting functionality to a metal–organic framework material by controlled nanoparticle encapsulation[J]. Nature Chemistry,2012,4(4):310-316. doi: 10.1038/nchem.1272
[4]	ZHAO X, LIU D, HUANG H, et al. The stability and defluoridation performance of MOFs in fluoride solutions[J]. Microporous and Mesoporous Materials,2014,185:72-78. doi: 10.1016/j.micromeso.2013.11.002
[5]	郭云龙. ZIF-8和NH_2-MIL-101(Al)吸附水中磷和氟的研究[D]. 昆明: 云南大学, 2015. GUO Yunlong. Adsorption of phosphorus and fluorine in water by zif-8 and nh_2-mil-101 (Al)[D]. Kunming: Yunnan University, 2015(in Chinese).
[6]	张楠通. 金属有机骨架材料MIL-96的可控制备及其在除氟和储氢上的研究[D]. 合肥: 中国科学技术大学, 2014. ZHANG Nantong. Controlled preparation of metal-organic framework material mil-96 and its research on fluorine removal and hydrogen storage[D]. Hefei: University of Science and Technology of China, 2014(in Chinese).
[7]	DENG H, YU X. Adsorption of fluoride, arsenate and phosphate in aqueous solution by cerium impregnated fibrous protein[J]. Chemical Engineering Journal,2012,184:205-212. doi: 10.1016/j.cej.2012.01.031
[8]	QI Z, JOSHI T P, LIU R, et al. Synthesis of Ce(III)-doped Fe3O4 magnetic particles for efficient removal of antimony from aqueous solution[J]. Journal of Hazardous Materials,2017,329:193-204. doi: 10.1016/j.jhazmat.2017.01.007
[9]	BISERCIC M S, MARJANOVIC B, VASILJEVIC B N, et al. The quest for optimal water quantity in the synthesis of metal-organic framework MOF-5[J]. Microporous and Mesoporous Materials,2019,278:23-29. doi: 10.1016/j.micromeso.2018.11.005
[10]	HE L, LIU Y, LIU J, et al. Core-shell noble-metal@metal-organic-framework nanoparticles with highly selective sensing property[J]. Angewandte Chemie,2013,52(13):3741-3745. doi: 10.1002/anie.201209903
[11]	LI Y, TANG J, HE L, et al. Core-shell upconversion nanoparticle@metal-organic framework nanoprobes for luminescent/magnetic dual-mode targeted imaging[J]. Advanced Materials,2015,27(27):4075-4080. doi: 10.1002/adma.201501779
[12]	BURGAZ E, ERCIYES A, ANDAC M, et al. Synthesis and characterization of nano-sized metal organic framework-5 (MOF-5) by using consecutive combination of ultrasound and microwave irradiation methods[J]. Inorganica Chimica Acta,2019,485:118-124. doi: 10.1016/j.ica.2018.10.014
[13]	KANG D, YU X, GE M, et al. Morphology-dependent properties and adsorption performance of CeO2 for fluoride removal[J]. Chemical Engineering Journal,2017,330:36-43. doi: 10.1016/j.cej.2017.07.140
[14]	DHILLON A, SONI S K, KUMAR D, et al. Enhanced fluoride removal performance by Ce-Zn binary metal oxide: Adsorption characteristics and mechanism[J]. Journal of Fluorine Chemistry,2017,199:67-76.
[15]	OZEN H A, OZTURK B. Gas separation characteristic of mixed matrix membrane prepared by MOF-5 including different metals[J]. Separation and Purification Technology,2019,211:514-521. doi: 10.1016/j.seppur.2018.09.052
[16]	SUN X, WU T, YAN Z, et al. Novel MOF-5 derived porous carbons as excellent adsorption materials for n-hexane[J]. Journal of Solid State Chemistry,2019,271:354-360. doi: 10.1016/j.jssc.2019.01.002
[17]	ZUNIGAMURO N M, BONILLAPETRICIOLET A, MENDOZACASTIL D I, et al. Fluoride adsorption properties of cerium-containing bone char[J]. Journal of Fluorine Chemistry,2017,197:63-73. doi: 10.1016/j.jfluchem.2017.03.004
[18]	BANERJEE S, SHARMA Y C. Synthesis and application of Zn/Ce bimetallic oxides for the decontamination of arsenite (As-III) ions from aqueous solutions[J]. Journal of Environmental Management,2019,233:151-164.
[19]	王磊, 白成玲, 朱振亚. 氧化石墨烯/海藻酸钠复合膜对Pb(II)的吸附性能和机制[J]. 复合材料学报, 2020, 37(3):681-689. WANG Lei, BAI Chengling, ZHU Zhenya. Adsorption properties and mechanism of Pb(II) on GO/sodium alginate composite membranes[J]. Acta Materiae Composites Sinica,2020,37(3):681-689(in Chinese).
[20]	刘德坤, 刘航, 杨柳, 等. 镧、铈改性介孔氧化铝对氟离子的吸附[J]. 材料导报, 2019, 33(4):590-594. doi: 10.11896/cldb.201904005 LIU Dekun, LIU Hang, YANG Liu, et al. Adsorption of fluoride ions by modified mesoporous alumina with lanthanum and cerium[J]. Materials Guide,2019,33(4):590-594(in Chinese). doi: 10.11896/cldb.201904005