低温合成UiO-66及其吸附去除水中甲基橙性能研究
收稿日期: 2025-03-05
网络出版日期: 2025-04-16
基金资助
河北省高等学校科学技术研究项目(QN2022142);青海省科技援青重点研发与转化计划(2023-QY-211)
Study on low⁃temperature synthesis of UiO-66 and its adsorption performance for removing methyl orange from water
Received date: 2025-03-05
Online published: 2025-04-16
染料废水的高效处理是亟需解决的环境问题之一。以阴离子染料甲基橙（MO）为目标污染物，系统研究UiO-66材料的吸附性能及机理。通过溶剂热法在60、80、100 ℃下制备UiO-66-M系列材料（M为合成温度），并利用XRD、SEM、FT-IR和XPS等手段表征其结构特性。结果表明：低温合成的UiO-66-60具有较高的比表面积（1 386.6 m²/g）和较大的平均孔径（1.7 nm）；同时因配体缺陷导致表面羟基密度增加，其零电荷点（pHpzc=6.8）明显高于UiO-66-80和UiO-66-100。吸附实验表明，UiO-66-60在pH=3.0、添加量为0.2 g/L时对MO的吸附量高达597.1 mg/g，优于多数文献报道的MOF基吸附剂。其吸附过程符合准二级动力学和Freundlich等温模型，表明其以多层吸附为主。机理分析表明，静电作用与π-π共轭是影响MO吸附过程的关键机制。吸附热力学分析表明，UiO-66-60对MO的吸附是自发放热过程。UiO-66-60凭借低温合成优势和高效吸附性能，可用作甲基橙染料废水处理的高效吸附剂。
刘忆贤 , 马喜龙 , 房春霞 , 谢娟 , 张志昆 , 李鹏飞 , 李正杰 , 韩继龙 . 低温合成UiO-66及其吸附去除水中甲基橙性能研究[J]. 无机盐工业, 2026 , 58(1) : 26 -36 . DOI: 10.19964/j.issn.1006-4990.2025-0108
The efficient treatment of dye wastewater is one of the urgent environmental problems that need to be addressed.Herein，the adsorption performance and mechanism of UiO-66 towards methyl orange（MO） were investigated systemically.Firstly，UiO-66-M（M represents the synthesized temperatures） were prepared by solvothermal method at 60，80 ℃，and 100 ℃，respectively.The structural and chemical properties of UiO-66-M were systematically characterized through XRD，SEM，FT-IR，and XPS measurements.Among the three UiO-66 materials，UiO-66-60 exhibited a higher specific surface area（1 386.6 m²/g） and larger average pore size（1.7 nm）.Moreover，the increased ligand defects in UiO-66-60 led to a higher surface density of the hydroxyl groups，resulting in a increased point of zero charge（pHpzc=6.8） than that of UiO-66-80 and UiO-66-100.The adsorption experiments showed that UiO-66-60 achieved an exceptional MO adsorption capacity of 597.1 mg/g under optimized conditions（pH=3.0，adsorbent dosage=0.2 g/L），which was higher than that of the most reported MOF⁃based adsorbents.The adsorption process followed the pseudo⁃second⁃order kinetic model and Freundlich isotherm model，indicating that MO molecules were adsorbed onto UiO-66-60 in multilayer manner.The electrostatic interaction and π-π stacking interaction simultaneously contributed to the MO adsorption by UiO-66-60.The thermodynamic study indicated that the MO adsorption process was spontaneous and exothermic.Owing to the low⁃temperature synthesis advantage and superior adsorption performance，UiO-66-60 could sever as an efficient adsorbent for MO removal from dye wastewater.
Key words： MOFs; UiO-66; low?temperature synthesis; methyl orange; electrostatic attraction
| [1] | 张冲，郭云，彭子芳，等.三聚氰胺功能化多孔有机聚合物的合成及其对甲基橙的吸附性能［J］.色谱，2021，39（9）：998-1005. |
| ZHANG Chong， GUO Yun， PENG Zifang，et al.Preparation of melamine?functionalized porous organic polymer and its adsorption properties for methyl orange［J］.Chinese Journal of Chromatography，2021，39（9）：998-1005. | |
| [2] | UGRASKAN V， ISIK B， YAZICI O，et al.Removal of Safranine T by a highly efficient adsorbent（Cotinus Coggygria Leaves）：Isotherms，kinetics，thermodynamics，and surface properties［J］.Surfaces and Interfaces，2022，28：101615. |
| [3] | 王萍，徐荣声，孙冬，等.氮掺杂生物炭的制备及其对亚甲基蓝的吸附性能研究［J］.无机盐工业，2024，56（9）：117-127. |
| WANG Ping， XU Rongsheng， SUN Dong，et al.Study on preparation of nitrogen?doped biochar and its adsorption properties for methylene blue［J］.Inorganic Chemicals Industry，2024，56（9）：117-127. | |
| [4] | SOLAYMAN H M， HOSSEN M A， AZIZ A ABD，et al.Performance evaluation of dye wastewater treatment technologies：A review［J］.Journal of Environmental Chemical Engineering，2023，11（3）：109610. |
| [5] | 张涵飞，申红艳，刘有智.MG复合材料的制备及其对甲基橙的吸附性能研究［J］.无机盐工业，2025，57（6）：100-107. |
| ZHANG Hanfei， SHEN Hongyan， LIU Youzhi.Study on preparation of MG composite material and its adsorption properties for methyl orange［J］.Inorganic Chemicals Industry，2025，57（6）：100-107. | |
| [6] | KAYANI K F.Bimetallic metal-organic frameworks （BMOFs） for dye removal：A review［J］.RSC Advances，2024，14（43）：31777-31796. |
| [7] | 裴秀，李亚明.共价有机框架材料的制备及对染料吸附性能的研究［J］.无机盐工业，2023，55（1）：106-111. |
| PEI Xiu， LI Yaming.Study on preparation of covalent organic framework materials and their adsorption properties for dyes［J］.Inorganic Chemicals Industry，2023，55（1）：106-111. | |
| [8] | 赵英杰，赵慧芳，王婷，等.金属-有机骨架材料用于水中痕量药物污染物的吸附脱除［J］.化工进展，2020，39（6）：2187-2205. |
| ZHAO Yingjie， ZHAO Huifang， WANG Ting，et al.Adsorption removal of trace pharmaceutical pollutants from water by metal-organic frameworks［J］.Chemical Industry and Engineering Progress，2020，39（6）：2187-2205. | |
| [9] | MANDAL W， FAJAL S， DESAI A V，et al.Metal-organic frameworks（MOFs） and related other advanced porous materials for sequestration of heavy metal?based toxic oxo?pollutants from water［J］.Coordination Chemistry Reviews，2025，524：216326. |
| [10] | 韩慧敏，袁静珂，何柏，等.UiO-66的合成、结构及应用进展［J］.精细化工，2023，40（6）：1187-1201，1238. |
| HAN Huimin， YUAN Jingke， HE Bai，et al.Progress on synthesis，structure and application of UiO-66［J］.Fine Chemicals，2023，40（6）：1187-1201，1238. | |
| [11] | 张静，刘洁.UiO系列金属有机骨架的合成方法及其吸附应用［J］.功能材料，2022，53（10）：10087-10094. |
| ZHANG Jing， LIU Jie.Synthetic methods of UiO series metal-organic frameworks and their applications in adsorption［J］.Journal of Functional Materials，2022，53（10）：10087-10094. | |
| [12] | HASAN Z， KHAN N A， JHUNG S H.Adsorptive removal of diclofenac sodium from water with Zr?based metal-organic frameworks［J］.Chemical Engineering Journal，2016，284：1406-1413. |
| [13] | WANG Chenghong， LIU Xinlei， CHEN J P，et al.Superior removal of arsenic from water with zirconium metal-organic framework UiO-66［J］.Scientific Reports，2015，5：16613. |
| [14] | AHMADIJOKANI F， MOLAVI H， REZAKAZEMI M，et al.UiO?66 metal-organic frameworks in water treatment：A critical review［J］.Progress in Materials Science，2022，125：100904. |
| [15] | ?UCZAK J， KROCZEWSKA M， BALUK M，et al.Morphology control through the synthesis of metal-organic frameworks［J］.Advances in Colloid and Interface Science，2023，314：102864. |
| [16] | ALAERTS L， SéGUIN E， POELMAN H，et al.Probing the lewis acidity and catalytic activity of the metal?organic framework［Cu3（btc）2］ （BTC=Benzene-1，3，5-tricarboxylate）［J］.Chemistry：A European Journal，2006，12（28）：7353-7363. |
| [17] | JAJKO G， GUTIéRREZ-SEVILLANO J J， S?AWEK A，et al.Water adsorption in ideal and defective UiO-66 structures［J］.Microporous and Mesoporous Materials，2022，330：111555. |
| [18] | DESTEFANO M R， ISLAMOGLU T， GARIBAY S J，et al.Room?temperature synthesis of UiO-66 and thermal modulation of densities of defect sites［J］.Chemistry of Materials，2017，29（3）：1357-1361. |
| [19] | JAJKO G， GRYTA P， KOZYRA P，et al.Effect of synthesis temperature on water adsorption in UiO-66 derivatives：Experiment，DFT+D modeling，and Monte Carlo simulations［J］.The Journal of Physical Chemistry C，2022，126（21）：9185-9194. |
| [20] | KIM J Y， KANG J，CHA S，et al.Stability of Zr?based UiO-66 metal-organic frameworks in basic solutions［J］.Nanomaterials，2024，14（1）：110. |
| [21] | AHMADIJOKANI F， MOHAMMADKHANI R， AHMADIPOUYA S，et al.Superior chemical stability of UiO-66 metal-organic fra?meworks（MOFs） for selective dye adsorption［J］.Chemical Engineering Journal，2020，399：125346. |
| [22] | WAN Dongjin， CHENG Xiaofan， SHI Yahui，et al.Insights into lead removal in water using a novel carbonized material derived from the by?product of oil refining：Action mechanism and performance optimization［J］.Journal of Chemical Technology & Biotechnology，2021，96（11）：3224-3236. |
| [23] | LAFI R， HAFIANE A.Removal of methyl orange （MO） from aqueous solution using cationic surfactants modified coffee waste（MCWs）［J］.Journal of the Taiwan Institute of Chemical Engineers，2016，58：424-433. |
| [24] | 熊波，黎泰华，周武平，等.一步热聚合法制备Cu2O/CuO-g-C3N4吸附剂及其对甲基橙吸附的性能［J］.应用化学，2023，40（3）：420-429. |
| XIONG Bo， LI Taihua， ZHOU Wuping，et al.Preparation of Cu2O/CuO-g-C3N4 adsorbent by one?step thermal polymerization and adsorption properties for methyl orange［J］.Chinese Journal of Applied Chemistry，2023，40（3）：420-429. | |
| [25] | NAGA A O ABO EL， SHABAN S A， KADY F Y A EL.Metal organic framework?derived nitrogen?doped nanoporous carbon as an efficient adsorbent for methyl orange removal from aqueous solution［J］.Journal of the Taiwan Institute of Chemical Engineers，2018，93：363-373. |
| [26] | BAO Shuangyou， LI Kai， NING Ping，et al.Synthesis of amino?functionalization magnetic multi?metal organic framework（Fe3O4/MIL-101（Al0.9Fe0.1）/NH2） for efficient removal of methyl orange from aqueous solution［J］.Journal of the Taiwan Institute of Chemical Engineers，2018，87：64-72. |
| [27] | EDIATI R， AULIA W， NIKMATIN B A，et al.Chitosan/UiO-66 composites as high?performance adsorbents for the removal of methyl orange in aqueous solution［J］.Materials Today Chemistry，2021，21：100533. |
| [28] | LV Shiwen， LIU Jingmin， MA Hui，et al.Simultaneous adsorption of methyl orange and methylene blue from aqueous solution using amino functionalized Zr?based MOFs［J］.Microporous and Mesoporous Materials，2019，282：179-187. |
| [29] | WU Shichuan， YOU Xia， YANG Cao，et al.Adsorption behavior of methyl orange onto an aluminum?based metal organic framework，MIL-68（Al）［J］.Water Science and Technology，2017，75（12）：2800-2810. |
| [30] | YANG Jimin， YING Rongjian， HAN Chunxiang，et al.Adsorptive removal of organic dyes from aqueous solution by a Zr?based metal?organic framework：Effects of Ce（Ⅲ） doping［J］.Dalton Transactions，2018，47（11）：3913-3920. |
| [31] | WANG Chao， FENG Xuezhen， SHANG Shibin，et al.Adsorption of methyl orange from aqueous solution with lignin?modified metal-organic frameworks：Selective adsorption and high adsorption capacity［J］.Bioresource Technology，2023，388：129781. |
| [32] | 王伟涛，陈香李，杨百勤.固体在液相中吸附热力学参数计算介绍［J］.大学化学，2021，36（2）：233-240. |
| WANG Weitao， CHEN Xiangli， YANG Baiqin.Calculation of adsorption thermodynamics parameters for adsorption on the solid?liquid interface［J］.University Chemistry，2021，36（2）：233-240. |
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