CN107099037A - 一种多级孔UiO‑66及其衍生物的合成方法 - Google Patents
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000013207 UiO-66 Substances 0.000 claims description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000499 gel Substances 0.000 claims description 11
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 229910006213 ZrOCl2 Inorganic materials 0.000 claims description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 3
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 claims description 2
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 12
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- 230000006911 nucleation Effects 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 28
- 239000000463 material Substances 0.000 description 27
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- 238000003756 stirring Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000003643 water by type Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
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- 239000012922 MOF pore Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
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- 238000001179 sorption measurement Methods 0.000 description 4
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- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000011469 building brick Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 230000009897 systematic effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
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Abstract
本发明公开了一种多级孔UiO‑66及其衍生物的合成方法，是在常规UiO‑66的合成体系中引入适量的水，利用合成体系中水对Zr簇和配体自组装、UiO‑66成核和晶体生长等过程的影响作用来制备多级孔UiO‑66及其衍生物。本发明合成的多级孔UiO‑66及其衍生物中同时存在有微孔和介孔，其孔体积可达0.89cc/g以上，显著大于文献报道的传统UiO‑66的孔体积。
Description
技术领域
本发明属于分子筛合成技术领域，涉及一种UiO-66及其衍生物的合成方法，特别是涉及一种具有多级孔结构的UiO-66及其衍生物的合成方法。
背景技术
近年来，一种被称之为MOFs，即金属有机骨架结构(Metal-Organic Frameworks)的新材料引起了人们极大的关注。这一材料是利用有机配体与金属离子间的金属-配体间络合作用，通过自组装而形成的具有周期性网络结构的晶体。
MOFs材料具有高的空隙率、结构的多样性和可调变性等特点，在许多技术领域都表现出潜在的应用前景(Kitagawa S. Metal-organic frameworks(MOFs)[J]. ChemicalSociety Reviews, 2014, 43(16): 5415-5418.)。然而，绝大多数的MOFs材料都是微孔结构，其孔径小于2nm(Fang Q R, Makal T A, Young M D, et al. Recent advances inthe study of mesoporous metal-organic frameworks[J]. Comments on InorganicChemistry, 2010, 31(5-6): 165-195.)。尽管这种微孔结构有利于气体存储，但是减缓了气体的扩散速率，同时在催化应用中也阻碍了大分子反应物接触孔道内的反应活性位点(Jiang H L, Tatsu Y, Lu Z H, et al. Non-, micro-, and mesoporous metal-organic framework isomers: reversible transformation, fluorescence sensing,and large molecule separation[J]. Journal of the American Chemical Society,2010, 132(16): 5586-5587.)。因此，制备多级孔MOFs材料，以提高大分子在孔道内的扩散速度和MOFs微孔内活性位的可接近性，就显得十分必要。
为了制备多级孔MOFs材料，人们在合成方法上进行了多方面的探索。
传统的多级孔MOFs材料合成方法之一是增加有机配体的长度(Eddaoudi M, KimJ, Rosi N, et al. Systematic design of pore size and functionality inisoreticular MOFs and their application in methane storage[J]. Science, 2002,295(5554): 469-472.)，然而该方法降低了MOFs材料的稳定性和孔结构的连通性。
另一方法是利用模板剂与络合剂的协同作用，以达到制备多级孔MOFs材料的目的(Sun L B, Li J R, Park J, et al. Cooperative template-directed assembly ofmesoporous metal-organic frameworks[J]. Journal of the American ChemicalSociety, 2011, 134(1): 126-129.)，然而该方法中的络合剂会嵌入到MOFs材料的晶体结构中，后续消除络合剂的操作常常会对MOFs材料的物理性质造成影响(McNamara N D,Hicks J C. Chelating Agent-Free, Vapor-Assisted Crystallization Method toSynthesize Hierarchical Microporous/Mesoporous MIL-125(Ti)[J]. ACS appliedmaterials & interfaces, 2015, 7(9): 5338-5346.)。
此外，软/硬模板法(Gu Z Y, Park J, Raiff A, et al. Metal-organicframeworks as biomimetic catalysts[J]. ChemCatChem, 2014, 6(1): 67-75.)、分步配体交换法(stepwise ligand exchange) (Li T, Kozlowski M T, Doud E A, et al.Stepwise ligand exchange for the preparation of a family of mesoporous MOFs[J]. Journal of the American Chemical Society, 2013, 135(32): 11688-11691.)、金属-配体-碎片共组装法(metal-ligand-fragment co-assembly) (Park J, Wang Z U,Sun L B, et al. Introduction of functionalized mesopores to metal-organicframeworks via metal-ligand-fragment coassembly[J]. Journal of the AmericanChemical Society, 2012, 134(49): 20110-20116.)等方法也被用来合成多级孔MOFs材料。然而这些方法的适用范围有限，且目前能合成出的MOFs材料的稳定性能差。
UiO-66是一种新型锆基MOFs的典型代表。同其它MOFs材料相比，其除了具有较高的比表面积之外，还具有良好的热和化学稳定性，特别是对水和有机溶剂的稳定性(CavkaJ H, Jakobsen S, Olsbye U, et al. A new zirconium inorganic building brickforming metal organic frameworks with exceptional stability, J. Am. Chem.Soc., 2008, 130(42): 13850-13851.)。另外，UiO-66还具有Lewis Acid的特性，这使得其在很多酸催化反应中能够展现出较好的催化性能(Zhou F, Lu N, Fan B, et al.Zirconium-containing UiO-66 as an efficient and reusable catalyst fortransesterification of triglyceride with methanol[J]. Journal of EnergyChemistry, 2016, 25(5): 874-879.)。
但是，UiO-66的孔径分别为0.8nm和1.1nm，孔口尺寸仅为0.6nm，其微孔的特性使其在催化和吸附应用中存在较大的扩散阻力。因此，探索一种简单易行的制备多级孔UiO-66的方法，对于改善UiO-66的催化和吸附性能，扩展其应用前景具有重要意义。
发明内容
本发明的目的是克服现有UiO-66及其衍生物存在的不足，提供一种简单易行的多级孔UiO-66及其衍生物的合成方法。
本发明所述的多级孔UiO-66及其衍生物的合成方法是通过在常规UiO-66的合成体系中引入适量的水，利用合成体系中的水对Zr簇和配体的自组装、UiO-66成核和晶体生长等过程的影响作用，来制备多级孔的UiO-66及其衍生物。
具体地，本发明所述的多级孔UiO-66及其衍生物的合成方法是将可溶性锆盐溶解在N’N-二甲基甲酰胺(DMF)中，加入对苯二甲酸或其衍生物，并添加一定量的水，以上述混合溶液进行水热晶化反应制备多级孔UiO-66及其衍生物。
其中，本发明上述合成方法中，加入的水量与DMF用量的摩尔比为0.4～1.5∶1。
进一步地，本发明上述合成方法中所使用的可溶性锆盐可以是ZrCl4或ZrOCl2·8H2O。
所述的对苯二甲酸衍生物包括2-氨基对苯二甲酸、2-硝基对苯二甲酸或2-溴对苯二甲酸。
具体地，本发明上述合成方法中，所述水热晶化反应是在100～150℃的反应温度下水热晶化反应20～30h。
本发明上述合成方法中，还可以在所述可溶性锆盐的DMF溶液中加入无机酸。所述无机酸优选使用盐酸。
进而，本发明是将上述水热晶化反应得到的产物离心得到白色凝胶状产物，再分别以DMF和甲醇洗涤后，干燥得到所合成的多级孔UiO-66材料。
本发明提供了一种不需要使用任何模板剂、络合剂来制备多级孔UiO-66的简单易行的合成方法。该方法通过在常规UiO-66合成体系中引入适量的水，利用合成体系中的水加速Zr簇(Zr6(μ3-O)4(μ3-OH)4(CO2)12)的形成，从而影响配体的自组装过程，使得UiO-66晶体中的有机配体缺失，最终制备得到了多级孔的UiO-66材料。
本发明提供的多级孔UiO-66及其衍生物的合成方法绿色温和、简单易行，合成的多级孔UiO-66及其衍生物同时存在有微孔和介孔，从孔径分布图中可以看出在样品中存在有3～15nm范围内的介孔。本发明合成的多级孔UiO-66及其衍生物孔体积可达0.89cc/g以上，大于文献报道的传统UiO-66的孔体积0.44cc/g(Wu H, Yong S C, Krungleviciute V,et al. Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption[J].Journal of the American Chemical Society, 2013, 135(28):10525-32.)1倍以上，且微孔与介孔孔体积之比不小于1∶2.0。
附图说明
图1是实施例1合成的多级孔UiO-66的XRD图。
图2是实施例1合成的多级孔UiO-66的N2吸附-脱附等温线和孔径分布图。
具体实施方式
下述实施例仅为本发明的优选技术方案，并不用于对本发明进行任何限制。对于本领域技术人员而言，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
实施例1。
将5mmol ZrCl4、5mmol对苯二甲酸、5mmol浓HCl依次加入到30ml DMF溶液中，搅拌2h，再向上述溶液中加入5ml去离子水，搅拌均匀，装入带有聚四氟乙烯内衬的不锈钢反应釜中，置于120℃恒温烘箱中，水热晶化反应24h。取出反应釜，冷却至室温，将反应产物离心得到白色凝胶状产物，分别以DMF和甲醇充分洗涤，干燥，得多级孔UiO-66材料。
图1为上述合成多级孔UiO-66的XRD图。从图中可以看出，所合成样品显示出了与文献报道UiO-66(Cavka J H, Jakobsen S, Olsbye U, et al. A new zirconiuminorganic building brick forming metal organic frameworks with exceptionalstability.[J]. Journal of the American Chemical Society, 2008, 130(42):13850-1.)相一致的特征衍射峰，表明本实施例合成的多级孔UiO-66仍然保持了UiO-66原有的晶体结构。
图2是本实施例合成的多级孔UiO-66的N2吸附-脱附等温线和孔径分布图。图中的吸附等温线显示出了Ⅰ型和Ⅳ型吸附等温线的特点，表明在样品中同时存在有微孔和介孔。经BJH模型计算，可以得出样品的微孔和介孔孔体积之比达到1∶3，并从孔径分布图可以看出样品中存在有3～15nm范围内的介孔。同时，多级孔UiO-66的孔体积达到1.1cc/g。
实施例2。
将5mmol ZrCl4、5mmol对苯二甲酸依次加入到30ml DMF溶液中，搅拌2h，再向上述溶液中加入5ml去离子水，搅拌均匀，装入带有聚四氟乙烯内衬的不锈钢反应釜中，置于120℃恒温烘箱中，水热晶化反应24h。取出反应釜，冷却至室温，将反应产物离心得到白色凝胶状产物，分别以DMF和甲醇充分洗涤，干燥，得多级孔UiO-66材料。
本实施例所合成样品的孔体积为0.93cc/g，样品中存在3～10nm范围的介孔，且微孔与介孔的孔体积比达到1∶2.6。
实施例3。
将5mmol ZrOCl2·8H2O、5mmol对苯二甲酸、10mmol浓HCl依次加入到25ml DMF溶液中，搅拌2h，再向上述溶液中加入4ml去离子水，搅拌均匀，装入带有聚四氟乙烯内衬的不锈钢反应釜中，置于150℃恒温烘箱中，水热晶化反应24h。取出反应釜，冷却至室温，将反应产物离心得到白色凝胶状产物，分别以DMF和甲醇充分洗涤，干燥，得多级孔UiO-66材料。
本实施例所合成样品的孔体积为0.96cc/g，样品中存在3～11nm范围的介孔，且微孔与介孔的孔体积比达到1∶2.7。
实施例4。
将5mmol ZrCl4、5mmol对苯二甲酸、5mmol浓HCl依次加入到30ml DMF溶液中，搅拌2h，再向上述溶液中加入3ml去离子水，搅拌均匀，装入带有聚四氟乙烯内衬的不锈钢反应釜中，置于120℃恒温烘箱中，水热晶化反应24h。取出反应釜，冷却至室温，将反应产物离心得到白色凝胶状产物，分别以DMF和甲醇充分洗涤，干燥，得多级孔UiO-66材料。
本实施例所合成样品的孔体积为0.91cc/g，样品中存在3～10nm范围的介孔，且微孔与介孔的孔体积比达到1∶2.5。
实施例5。
将5mmol ZrCl4、5mmol对苯二甲酸、5mmol浓HCl依次加入到30ml DMF溶液中，搅拌2h，再向上述溶液中加入10ml去离子水，搅拌均匀，装入带有聚四氟乙烯内衬的不锈钢反应釜中，置于120℃恒温烘箱中，水热晶化反应24h。取出反应釜，冷却至室温，将反应产物离心得到白色凝胶状产物，分别以DMF和甲醇充分洗涤，干燥，得多级孔UiO-66材料。
本实施例所合成样品的孔体积为0.76cc/g，样品中存在3～7nm范围的介孔，且微孔与介孔的孔体积比达到1∶2.0。
实施例6。
将5mmol ZrCl4、5mmol 2-氨基对苯二甲酸依次加入到30ml DMF溶液中，搅拌2h，再向上述溶液中加入5ml去离子水，搅拌均匀，装入带有聚四氟乙烯内衬的不锈钢反应釜中，置于120℃恒温烘箱中，水热晶化反应30h。取出反应釜，冷却至室温，将反应产物离心得到白色凝胶状产物，分别以DMF和甲醇充分洗涤，干燥，得多级孔UiO-66-NH2材料。
本实施例所合成样品的孔体积为0.98cc/g，样品中存在3～12nm范围的介孔，且微孔与介孔的孔体积比达到1∶2.7。
实施例7。
将5mmol ZrCl4、5mmol 2-硝基对苯二甲酸，5mmol浓HCl依次加入到30ml DMF溶液中，搅拌2h，再向上述溶液中加入5ml去离子水，搅拌均匀，装入带有聚四氟乙烯内衬的不锈钢反应釜中，置于100℃恒温烘箱中，水热晶化反应30h。取出反应釜，冷却至室温，将反应产物离心得到白色凝胶状产物，分别以DMF和甲醇充分洗涤，干燥，得多级孔UiO-66-NO2材料。
本实施例所合成样品的孔体积为0.81cc/g，样品中存在3～8nm范围的介孔，且微孔与介孔的孔体积比达到1∶2.3。
实施例8。
将5mmol ZrCl4、5mmol 2-硝基对苯二甲酸依次加入到30ml DMF溶液中，搅拌2h，再向上述溶液中加入5ml去离子水，搅拌均匀，装入带有聚四氟乙烯内衬的不锈钢反应釜中，置于100℃恒温烘箱中，水热晶化反应30h。取出反应釜，冷却至室温，将反应产物离心得到白色凝胶状产物，分别以DMF和甲醇充分洗涤，干燥，得多级孔UiO-66-NO2材料。
本实施例所合成样品的孔体积为0.89cc/g，样品中存在3～10nm范围的介孔，且微孔与介孔的孔体积比达到1∶2.5。
实施例9。
将5mmol ZrCl4、5mmol 2-溴对苯二甲酸依次加入到30ml DMF溶液中，搅拌2h，再向上述溶液中加入5ml去离子水，搅拌均匀，装入带有聚四氟乙烯内衬的不锈钢反应釜中，置于120℃恒温烘箱中，水热晶化反应20h。取出反应釜，冷却至室温，将反应产物离心得到白色凝胶状产物，分别以DMF和甲醇充分洗涤，干燥，得多级孔UiO-66-Br材料。
本实施例所合成样品的孔体积为0.93cc/g，样品中存在3～11nm范围的介孔，且微孔与介孔的孔体积比达到1∶2.6。
Claims (8)
1.一种多级孔UiO-66及其衍生物的合成方法，是将可溶性锆盐溶解在DMF中，加入对苯二甲酸或其衍生物，以上述混合溶液进行水热晶化反应制备多级孔UiO-66及其衍生物，其特征是在所述混合溶液中添加一定量的水。
2.根据权利要求1所述的合成方法，其特征是加入的水量与DMF用量的摩尔比为0.4～1.5∶1。
3.根据权利要求1或2所述的合成方法，其特征是所述的可溶性锆盐为ZrCl4或ZrOCl2·8H2O。
4.根据权利要求1或2所述的合成方法，其特征是所述的对苯二甲酸衍生物为2-氨基对苯二甲酸、2-硝基对苯二甲酸或2-溴对苯二甲酸。
5.根据权利要求1或2所述的合成方法，其特征是所述水热晶化反应是在100～150℃的反应温度下水热晶化反应20～30h。
6.根据权利要求1或2所述的合成方法，其特征是在所述可溶性锆盐的DMF溶液中加入无机酸。
7.根据权利要求6所述的合成方法，其特征是所述无机酸为盐酸。
8.根据权利要求1或2所述的合成方法，其特征是将所述水热晶化反应得到的产物离心得到白色凝胶状产物，以DMF和甲醇洗涤，干燥得到多级孔UiO-66及其衍生物。
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| CN111634985A (zh) * | 2020-06-12 | 2020-09-08 | 东北大学 | 基于UiO-66的CDI极板及脱磷酸盐的装置和方法 |
| CN111821960A (zh) * | 2020-07-24 | 2020-10-27 | 北京工商大学 | 基于金属有机骨架复合材料的液相色谱固定相及制备方法 |
| CN112642488A (zh) * | 2020-12-16 | 2021-04-13 | 福州大学 | 一种蛋黄-蛋壳mof/cof复合材料及其无模板制备方法和催化应用 |
| CN113209967A (zh) * | 2021-04-23 | 2021-08-06 | 东北石油大学 | 磁性催化剂及其制备方法、应用 |
| CN113209967B (zh) * | 2021-04-23 | 2022-01-25 | 东北石油大学 | 磁性催化剂及其制备方法、应用 |
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