PEO基MOFs杂化泡沫材料对四环素和Cu<sup>2+</sup>吸附性能

李微; 宁雨阳; 刘宁; 高明杰

doi:10.13205/j.hjgc.202307011

PEO基MOFs杂化泡沫材料对四环素和Cu²⁺吸附性能

doi: 10.13205/j.hjgc.202307011

李微^1, ,,
宁雨阳¹,
刘宁²,
高明杰³

1. 沈阳建筑大学市政与环境工程学院, 沈阳 110168;
2. 沈阳碧桂园房地产开发有限公司, 沈阳 110003;
3. 辽宁省城乡建设规划设计院有限责任公司, 沈阳 110001

基金项目:

沈阳市科技计划项目（22322310）；辽宁省教育厅科学研究项目（lnqn202010）；辽宁省科技厅自然科学基金（2019ZD0671）

详细信息

作者简介:
李微(1982-),女,副教授,主要研究方向为污水处理技术。liweilengjinyue@163.com

通讯作者:
李微(1982-),女,副教授,主要研究方向为污水处理技术。liweilengjinyue@163.com

计量
- 文章访问数: 49
- HTML全文浏览量: 15
- PDF下载量: 2
- 被引次数: 0
出版历程
- 收稿日期: 2023-01-19

ADSORPTION PERFORMANCE OF PEO-BASED MOFs HYBRID FOAM MATERIALS ON TETRACYCLINE AND Cu²⁺

1. College of Municipal and Environmental Engineering, Shenyang Jianzhu University, Shenyang 100168, China;
2. Shenyang Country Garden Real Estate Development Co., Ltd., Shenyang 110003, China;
3. Liaoning Urban & Rural Construction Planning Design Institute Co., Ltd., Shenyang 110001, China

摘要

摘要: 通过冰模板-冷冻干燥法合成了金属有机骨架杂化泡沫MIL-100（Fe）/PEO，利用X射线衍射、氮气吸附脱附、扫描电镜、TG-DSC技术，对杂化泡沫表面结构形态与元素组成进行表征分析，通过吸附实验分析了杂化泡沫吸附性能的影响因素及吸附动力学、吸附热力学和吸附等温线模型，利用循环再生稳定性实验研究了杂化泡沫分离再生稳定性。结果表明：MIL-100（Fe）/PEO杂化泡沫具有较强的机械强度和丰富的多孔结构，且保留了MIL-100（Fe）自身的特性；MIL-100（Fe）/PEO投加量为30 mg，吸附时间为12 h，四环素和Cu²⁺初始浓度为30 mg/L，pH为中性时，MIL-100（Fe）/PEO对TC和Cu²⁺的最大吸附量达到85.02，87.66 mg/g；材料的吸附过程符合拟二级动力学与Langmuir等温吸附模型，是一个放热、自发的过程；在循环吸附8次后，MIL-100（Fe）/PEO对TC和Cu²⁺的去除率均保持在70%左右。MIL-100（Fe）/PEO杂化泡沫是一种高效稳定的吸附剂，在废水中四环素和Cu²⁺复合污染物去除方面具有广阔的应用前景。
- MOFs杂化泡沫 /
- 四环素 /
- Cu²⁺ /
- 吸附 /
- 吸附机理
Abstract: A metal-organic backbone hybrid foam MIL-100(Fe)/PEO was prepared by the ice-template-freeze-drying method. X-ray diffraction, nitrogen adsorption-desorption, scanning electron microscopy, and TG-DSC techniques were used to characterize the structural morphology and elemental composition of the surface of the hybrid foam. The factors influencing the adsorption performance of the hybrid foam and the adsorption kinetics, adsorption thermodynamics and adsorption isotherm models were analyzed by adsorption experiments, and the stability of the hybrid foam separation and regeneration was studied using recycling stability tests. The results showed that MIL-100(Fe)/PEO hybrid foam had strong mechanical strength and rich porous structure, and retained the properties of MIL-100(Fe) itself. The maximum adsorption of tetracycline (TC) and Cu²⁺ by MIL-100(Fe)/PEO reached 85.02 mg/g and 87.66 mg/g at a MIL-100(Fe)/PEO dosing of 30 mg, an adsorption time of 12 h, an initial adsorption concentration of 20 mg/L, and neutral pH conditions. The adsorption process of the material followed the proposed secondary kinetics with the Langmuir isothermal adsorption model and was an exothermic, spontaneous process. The removal rates of both TC and Cu²⁺ by MIL-100(Fe)/PEO were maintained at about 70% after 8 cycles of adsorption. MIL-100(Fe)/PEO heterogeneous foam is an efficient and stable adsorbent and promising in application in the removal of mixed pollutants of tetracycline and Cu²⁺ from wastewater.
- MOFs heterogeneous foam /
- tetracycline /
- Cu²⁺ /
- adsorption /
- adsorption mechanism

HTML全文

参考文献(40)

[1]	乔娜.高铁酸钾控制水体典型抗生素与重金属复合污染的研究[D].南京:东南大学,2021.
[2]	KUMMERER K.Antibiotics in the aquatic environment:a review-Part Ⅰ[J].Chemosphere, 2009, 75(4):417-434.
[3]	于婉柔.南水北调中线干渠抗生素污染分布特征及环境行为研究[D].北京:北京交通大学, 2021.
[4]	LI N, ZHOU L, JIN X Y, et al.Simultaneous removal of tetracycline and oxytetracycline antibiotics from wastewater using a ZIF-8 metal organic-framework[J].Journal of Hazardous Materials, 2019, 366:563-572.
[5]	GUO Z Q, YANG F J, YANG R R, et al.Preparation of novel ZnO-NP@Zn-MOF-74 composites for simultaneous removal of copper and tetracycline from aqueous solution[J].Separation and Purification Technology, 2021, 274:118949.
[6]	MARTINS V V, ZANETTI M O B, PITONDO-SILVA A, et al.Aquatic environments polluted with antibiotics and heavy metals:a human health hazard[J].Environmental Science and Pollution Research, 2014, 21:5873-5878.
[7]	PHOON B L, ONG C C, SAHEED M S M, et al.Conventional and emerging technologies for removal of antibiotics from wastewater[J].Journal of Hazardous Materials, 2020, 400:122961.
[8]	唐婷.磺胺二甲基嘧啶与常见重金属的络合及其对镉在针铁矿上吸附行为的影响[D].广州:华南理工大学, 2016.
[9]	ZHU Q L, XU Q.Metal-organic framework composites[J].Chemical Society Reviews, 2014, 43(16):5468-5512.
[10]	马丽, 李莹, 衣梓硕, 等.ZIF-8@PI纤维纳米复合膜光催化剂的制备[J].化工新型材料, 2022, 50(7):95-98 ,104.
[11]	DOU Y B, ZHANG W J, KAISER A.Electrospinning of metal-organic frameworks for energy and environmental applications[J].Advanced Science, 2020, 7(3):1902590.
[12]	张琪欣.新型MIL-100(Fe)基MOFs材料的制备及其对Sr²⁺和Cs⁺的吸附[D].南京:南京航空航天大学, 2021.
[13]	DU X D,WANG C C,LIU J G,et al.Extensive and selective adsorptionof ZIF-67 towards organic dyes:performance and mechanism[J].Journal of Colloid and Interface Science, 2017, 506:437-441.
[14]	YANG Z H, CAO J, CHEN Y P, et al.Mn-doped zirconium metal-organic framework as an effective adsorbent for removal of tetracycline and Cr (Ⅵ) from aqueous solution[J].Microporous and Mesoporous Materials, 2019, 277:277-285.
[15]	曾德军.水稳定金属有机框架HKUST-1@聚合物复合材料对U(Ⅵ)的吸附行为研究[D].南昌:东华理工大学, 2021.
[16]	任龙芳, 高晓东, 张馨月, 等.UiO-66-NH₂/MoS₂@PUF的制备及其对Cr(Ⅵ)的吸附[J/OL].精细化工:1-13[2023-02-25 ].https://doi.org/10.13550/j.jxhg.20220475.
[17]	童敏曼, 赵旭东, 解丽婷, 等.金属-有机骨架材料用于废水处理[J].化学进展, 2012, 24(9):1646-1655.
[18]	ZHANG H F, DANG Q F, LIU C S, et al.Fabrication of methyl acrylate and tetraethylenepentamine grafted magnetic chitosan microparticles for capture of Cd(Ⅱ) from aqueous solutions[J].J Hazard Mater, 2019, 366:346-357.
[19]	LIU K, ZHANG S Y, HU X Y, et al.Understanding the adsorption of PFOA on MIL-101(Cr)-based anionic-exchange metal-organic frameworks:comparing DFT calculations with aqueous sorption experiments[J].Environmental Science & Technology, 2015, 49(14):8657-8665.
[20]	刘芳, 潘婷婷, 任秀蓉, 等.HCDs@MIL-100(Fe)吸附剂的制备及其苯吸附性能研究[J].化学学报, 2022, 80(7):879-887.
[21]	MA X L, WANG W L, SUN C G, et al.Adsorption performance and kinetic study of hierarchical porous Fe-based MOFs for toluene removal[J].Science of the Total Environment, 2021, 793:148622.
[22]	DENG S, ZHANG G S, CHEN S W, et al.Rapid and effective preparation of a HPEI modified MIL-100(Fe) based on cellulose fiber with a microwave irradiation method for enhanced arsenic removal in water[J].Journal of Materials Chemistry A, 2016, 4(41):15851-15860.
[23]	SUN X J, GU X L, XU W T, et al.Novel hierarchical Fe (Ⅲ)-doped Cu-MOFs with enhanced adsorption of benzene vapor[J].Frontiers in Chemistry, 2019, 7:652.
[24]	方颖.金属有机框架材料MIL-100(Fe)和ZIF-67对Cr(Ⅵ)吸附性能的研究[D].长沙:湖南大学, 2019.
[25]	LIN S H, CHEN M L.Treatment of textile wastewater by chemical methods for reuse[J].Water Research, 2019, 56(4):868-876.
[26]	HERNANDEZ R, ZAPPI M, COLUCCI J, et al.Comparing the performance of various advanced oxidation processes for treatment of acetone contaminated water[J].Journal of Hazardous Materials, 2002, 112(192):33-50.
[27]	CHEN M, ZHU M X, ZHU Y, et al.Collision of emerging and traditional methods for antibiotics removal:taking constructed wetlands and PEO as an example[J].Water Research, 2019, 178(15):100175.
[28]	冯江涛, 王桢钰, 闫炫冶, 等.吸附去除水体重金属离子的影响因素研究进展[J].西安交通大学学报, 2022, 56(2):1-16.
[29]	WANG F Y, WANG H, MA J W.Adsorption of cadmium (Ⅱ) ions from aqueous solution by a new low-cost adsorbent:bamboo charcoal[J].Journal of Hazardous Materials, 2010, 177(1/2/3):300-306.
[30]	DANTAS R F, CONTRERAS S, SANS C, et al.Sulfamethoxazole abatement by means of PEO[J].Journal of Hazardous Materials, 2018, 150(3):790-794.
[31]	王少婷, 强涛涛, 王志宏, 等.ZIF-8负载海藻酸钠/氧化石墨烯基底用于吸附盐酸四环素[J].精细化工, 2022, 39(10):2122-2131.
[32]	KONG Y, ZHUANG Y, HAN K, et al.Enhanced tetracycline adsorption using alginate-graphene-ZIF67 aerogel[J].Journal of Colloid and Interface Science, 2020, 588:124360.
[33]	LI Z Q, YANG J C, SUI K W, et al.Facile synthesis of metal-organic framework MOF-808 for arsenic removal[J].Materials Letters, 2015, 160(9):412-414.
[34]	PETROVIC M, BARCELÓ D.LC-MS for identifying photodegradation products of pharmaceuticals in the environment[J].TrAC Trends in Analytical Chemistry, 2007, 26(6):486-493.
[35]	GIOKAS D L, VLESSIDIS A G.Application of a novel chemometric approach to the determination of aqueous photolysis rates of ZIF-8 in natural waters[J].Water Research, 2007, 134(1):288-295.
[36]	李婷婷, 何帆, 蒋丹枫, 等.多金属普鲁士蓝类化合物亚铁氰化铜镍钴对铯离子的吸附[J].材料导报, 2016, 30(22):71-76.
[37]	曾辉平, 王繁烁, 于亚萍, 等.壳聚糖海藻酸钠铁锰泥吸附剂制备与除As(Ⅴ)研究[J].中国环境科学, 2020, 40(3):1146-1155.
[38]	CHEN S H, ZHANG J, ZHANG C L, et al.Equilibrium and kinetic studies of methyl orange and methyl violet adsorption on activated carbon derived from phragmites australis[J].Desalination, 2010, 252(1/2/3):149-156.
[39]	HU Q S, LIU Y L, GU X Y, et al.Adsorption behavior and mechanism of different arsenic species on mesoporous MnFe₂O₄ magnetic nanoparticles[J].Chemosphere, 2017, 181(12):328-336.
[40]	SENOSY I A, ZHANG X Z, LU Z H, et al.Magnetic metal-organic framework MIL-100(Fe)/polyethyleneimine composite as an adsorbent for the magnetic solid-phase extraction of fungicides and their determination using HPLC-UV[J].Microchimica Acta, 2021, 188(2):1-9.