MIL-53-NH-L-mal纳米晶体的制备及其在拆分1-苯乙醇中的应用

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摘要采用合成后修饰法（Post-synthetic modification，PSM）将L-苹果酸（L-mal）成功交联到金属-有机框架（MOFs）未配位的氨基上，制备得到同手性的MIL-53-NH-L-mal纳米晶体材料。采用傅里叶变换红外光谱、X射线衍射、扫描电子显微镜和热重分析等分析手段对该纳米晶体的结构与性能进行了表征。为了获得1-苯乙醇立体异构体，将所制备的MIL-53-NH-L-mal纳米晶体作为固相萃取（Solid phase extraction，SPE）柱填料，研究了1-苯乙醇的浓度与体积、固相萃取剂用量、洗脱液组成及洗脱体积等因素对拆分1-苯乙醇的影响，明确了最适宜的分离条件，同时对MIL-53-NH-L-mal纳米晶体材料的回收与再生利用性能进行了研究。结果表明：在填料量为200 mg，上样体积和浓度分别为1.0 mL和200 mg·L^-1，以及洗脱液为V（正己烷）/V（二氯甲烷）为95/5时，拆分1-苯乙醇的对映体过量值可以达到15.86%。

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	徐悦
	付宇佳
	张丽娟
	陆杰

关键词：手性拆分金属-有机框架后功能化修饰固相萃取 1-苯乙醇

Abstract： The PSM method was successfully applied to graft L-mal to the uncoordinated amino group of metal-organic frameworks (MOFs) to prepare homochiral MIL-53-NH-L-mal nanocrystals. FT-IR, PXRD, SEM and TGA were utilized to explore the structure and properties of the synthesized nanocrystals. In order to obtain the enantiomers of 1-phenylethanol, the as-prepared MIL-53-NH-L-mal nanocrystals were used as solid phase extraction (SPE) column packing. The parameters such as sample concentration and volume of 1-phenylethanol, dosage of SPE agent, eluent composition and volume for the separation of 1-phenylethanol were investigated. Meanwhile, the recovery and recycling properties of MIL-53-NH-L-mal nanocrystals were also studied. When the column packing was 200 mg, the sample volume and concentration were 1.0 mL and 200 mg·L^-1, respectively and the eluent was hexane/DCM (volume ratio 95/5), the enantiomeric excess value(ee) of separation of 1-phenylethanol can reach 15.86%.

Keywords： chiral resolution metal-organic frameworks (MOF) post-synthetic modification solid phase extraction 1-phenylethanol

Received 2022-08-15;

Fund:国家自然科学基金（21978165；22078191）。

Corresponding Authors: 陆杰,教授,E-mail:lujie@sues.edu.cn。 Email: lujie@sues.edu.cn

About author: 徐悦(1993-),女,博士,助理研究员,现从事制药分离工程方面的研究。

引用本文:

徐悦, 付宇佳, 张丽娟, 陆杰.MIL-53-NH-L-mal纳米晶体的制备及其在拆分1-苯乙醇中的应用[J]. 化学工业与工程, 2023,40(1): 104-111

XU Yue, FU Yujia, ZHANG Lijuan, LU Jie.Preparation of MIL-53-NH-L-mal nanocrystals and its application in the separation of 1-phenylethanol[J]. Chemcial Industry and Engineering, 2023,40(1): 104-111

[1] 慕洋洋. 新型生物印迹脂肪酶及其在1-苯乙醇拆分中的应用[D]. 天津:天津大学, 2014 MU Yangyang. The improved bio-imprinted lipase and its application in the resolution of 1-phenylethanol[D]. Tianjin:Tianjin University, 2014 (in Chinese)
[2] XU Z, LIU L, ZHANG J. Synthesis of metal-organic zeolites with homochirality and high porosity for enantioselective separation[J]. Inorganic Chemistry, 2016, 55(13):6355-6357
[3] 赵慧玲. 纤维素的手性分离特性研究[D]. 昆明:云南师范大学, 2016 ZHAO Huiling. Study on chiral separation characteristics of cellulose[D]. Kunming:Yunnan Normal University, 2016 (in Chinese)
[4] YE F, ZHANG Z, ZHAO W, et al. Two methods for the preparation of sitagliptin phosphate via chemical resolution and asymmetric hydrogenation[J]. RSC Advances, 2021, 11(8):4805-4809
[5] 刘亚茹. 天冬氨酸的结晶行为与手性分离[D]. 广州:华南理工大学, 2019 LIU Yaru. Study on the crystallization and chiral resolution of aspartic acid[D]. Guangzhou:South China University of Technology, 2019 (in Chinese)
[6] GHOSH S, BADRUDDOZA A Z M, UDDIN M S, et al. Adsorption of chiral aromatic amino acids onto carboxymethyl-β-cyclodextrin bonded Fe₃O₄/SiO₂ core-shell nanoparticles[J]. Journal of Colloid and Interface Science, 2011, 354(2):483-492
[7] 梁谦, 王恒山. 手性表面活性剂在手性合成、识别及拆分中的应用[J]. 广东化工, 2009, 36(9):67-68 LIANG Qian, WANG Hengshan. The applications of chiral surfactants in chiral synthesis, recognition and separation[J]. Guangdong Chemical Industry, 2009, 36(9):67-68(in Chinese)
[8] ZHAO J, LI H, HAN Y, et al. Chirality from substitution:Enantiomer separation via a modified metal-organic framework[J]. Journal of Materials Chemistry A, 2015, 3(23):12145-12148
[9] SUTTIPAT D, BUTCHA S, ASSAVAPANUMAT S, et al. Chiral macroporous MOF surfaces for electroassisted enantioselective adsorption and separation[J]. ACS Applied Materials & Interfaces, 2020, 12(32):36548-36557
[10] CONNOLLY B M, MADDEN D G, WHEATLEY A E H, et al. Shaping the future of fuel:Monolithic metal-organic frameworks for high-density gas storage[J]. Journal of the American Chemical Society, 2020, 142(19):8541-8549
[11] KOU W, YANG C, YAN X. Post-synthetic modification of metal-organic frameworks for chiral gas chromatography[J]. Journal of Materials Chemistry A, 2018, 6(37):17861-17866
[12] LU Y, ZHANG H, CHAN J, et al. Homochiral MOF-polymer mixed matrix membranes for efficient separation of chiral molecules[J]. Angewandte Chemie (International Ed in English), 2019, 58(47):16928-16935
[13] 张新. 后功能化修饰金属-有机框架材料的制备及其荧光传感性能[D]. 杭州:浙江大学, 2019 ZHANG Xin. Preparation and fluorescence sensing properties of post-functionalization modified metal-organic frameworks[D]. Hangzhou:Zhejiang University, 2019 (in Chinese)
[14] HU X, HUANG G, ZHANG S, et al. An easy and low-cost method of embedding chiral molecules in metal-organic frameworks for enantioseparation[J]. Chemical Communications (Cambridge, England), 2020, 56(54):7459-7462
[15] 魏凯凯. 手性金属-有机骨架材料应用于固相萃取手性分析研究[D]. 昆明:云南师范大学, 2018 WEI Kaikai. Chiral analysis by solid phase extraction with chiral metal-organic frameworks[D]. Kunming:Yunnan Normal University, 2018 (in Chinese)
[16] GASCON J, AKTAY U, HERNANDEZ-ALONSO M D, et al. Amino-based metal-organic frameworks as stable, highly active basic catalysts[J]. Journal of Catalysis, 2009, 261(1):75-87
[17] BEHBAHANI M, MOHABATKAR H, NOSRATI M. Analysis and comparison of lignin peroxidases between fungi and bacteria using three different modes of Chou's general pseudo amino acid composition[J]. Journal of Theoretical Biology, 2016, 411:1-5
[18] LI J, WU Y, LI Z, et al. Characteristics of arsenate removal from water by metal-organic frameworks (MOFs)[J]. Water Science and Technology:A Journal of the International Association on Water Pollution Research, 2014, 70(8):1391-1397
[19] COUCK S, DENAYER J F M, BARON G V, et al. An amine-functionalized MIL-53 metal-organic framework with large separation power for CO₂ and CH₄[J]. Journal of the American Chemical Society, 2009, 131(18):6326-6327
[20] CHENG X, ZHANG A, HOU K, et al. Size- and morphology-controlled NH₂-MIL-53(Al) prepared in DMF-water mixed solvents[J]. Dalton Transactions (Cambridge, England:2003), 2013, 42(37):13698-13705
[21] ALQADAMI A A, KHAN M A, SIDDIQUI M R, et al. Development of citric anhydride anchored mesoporous MOF through post synthesis modification to sequester potentially toxic lead (Ⅱ) from water[J]. Microporous and Mesoporous Materials, 2018, 261:198-206
[22] DA SILVA M R, MAURO LANÇAS F. Evaluation of ionic liquids supported on silica as a sorbent for fully automated online solid-phase extraction with LC-MS determination of sulfonamides in bovine milk samples[J]. Journal of Separation Science, 2018, 41(10):2237-2244
[23] 刘敏. 固定化离子液体拆分氨氯地平对映体研究[D]. 杭州:浙江大学, 2020 LIU Min. Study on enantioseparation of amlodipine by immobilized chiral ionic liquids[D]. Hangzhou:Zhejiang University, 2020 (in Chinese)