CN105664860B - 基于zif-8的mof型多级孔材料及其制备方法和应用 - Google Patents
基于zif-8的mof型多级孔材料及其制备方法和应用 Download PDFInfo
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- 239000011799 hole material Substances 0.000 title claims abstract description 66
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 59
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 31
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 13
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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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
- 238000004090 dissolution Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
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- 150000002460 imidazoles Chemical class 0.000 description 1
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- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000013337 mesoporous metal-organic framework Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Chemical group 0.000 description 1
- ZJVTYKZWDWVIFD-UHFFFAOYSA-N zinc;hydrochloride Chemical group Cl.[Zn] ZJVTYKZWDWVIFD-UHFFFAOYSA-N 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
本发明涉及一种基于ZIF‑8的MOF型多级孔材料及其制备方法和应用，MOF型多级孔材料的介孔范围在2‑50nm，微孔小于2nm，其BET比表面为1300‑1850m2/g,总孔体积1.20‑2.80cm3/g，介孔孔体积为0.5‑1.90cm3/g。制备方法包括如下步骤：(1)将金属锌盐、2‑甲基咪唑、碱和有机溶剂搅拌均匀，转移至反应釜中，于80‑130℃下恒温反应2‑12小时；(2)反应完毕冷却至室温，将得到的凝胶物质于20‑50℃条件下干燥成干胶，再萃取洗涤6小时以上；(3)最后在130‑150℃、真空条件下加热12小时以上，即得本发明多级孔材料。其微孔来自于ZIF‑8结构,介孔来自于粒子间孔隙，可用于有机污染物吸附净化等。
Description
技术领域
本发明属于多孔材料合成技术领域，具体涉及一种基于ZIF-8的MOF型多级孔材料及其制备方法和应用。
背景技术
金属-有机骨架材料(Metal-Organic Frameworks，MOF)，又称为金属有机骨架化合物、金属有机配位聚合物，其是以金属离子为配位中心，通过与多齿配体配位形成的具有一定空间结构的配合物，又称为MOF孔材料，是近20多年来发展起来的一类新型无机-有机杂化孔材料。由于其对某些气体和有机分子选择性吸附作用，在世界范围内作为新型多孔吸附材料被广泛地研究和应用开发。
类沸石咪唑骨架(Zeolitic imidazolate framework,ZIF)材料是一类新型的、具有沸石拓扑结构的纳米多孔材料，它由过渡金属原子(Zn/Co)与咪唑/咪唑衍生物连接而成，属于MOF的一种，因其更高的热稳定性和化学稳定性正受到越来越多的关注。图1为配位聚合物ZIF-8即[Zn(mim)2]n的结构图。ZIF在气体储存、分离和催化方面具有广大应用。但是由于ZIF的孔道大部分是微孔(直径＜2nm)，且孔道结构单一，使得分子在其孔道内扩散受阻，对大分子吸附也受到了限制。
孔径大于2nm、比表面积高且热稳定性好的MOF还被寄期于用在有机化合物(药物)的分离、化学催化,汽油脱硫等方面的应用。尤其是那些同时具有微孔(小于2nm)、介孔(2-50nm)的多级孔MOF更是人们梦寐以求的孔材料。由于多级孔的存在，这样的多级孔材料不仅是优良催化剂或催化剂载体，还有希望用于生物大分子的吸附、分离和生物酶的固定化,还可以用于芳香烃污染水的检测和深度净化等。
为了获得包含有微孔和介孔的多级孔MOF材料，人们试图通过使用表面活性剂为软模板的合成方法，使得某种MOF在其本来拥有微孔的基础上进一步产生介孔。虽然该方法已经能有效地应用于无机氧化物介孔(2-50nm)材料的合成，但在多级孔MOF的合成上还不尽人意。尽管目前有人用此方法已经获得包含有20nm介孔的MOF，但是其介孔孔体积很小(小于0.1cm3/g)，也就是说材料中介孔的分布仍很稀少。
中国专利CN102895953A公开了一种多级孔道ZIF-8的合成方法，该方法包括以下步骤：将阴离子表面活性剂溶于去离子水中，加入锌的无机盐，溶解后加入2-甲基咪唑混合均匀，得到溶胶状物质；对溶胶状物质进行晶化，将固体产物分离、洗涤、干燥，得到多级孔道ZIF-8粉晶；以氢氧化钠溶液和有机溶剂为萃取剂将多级孔道ZIF-8粉晶中的阴离子表面活性剂萃取出来，得到多级孔道ZIF-8。但是该专利存在以下缺点：使用了所谓用于造孔的模板剂(阴离子表面活性剂)，增加了生产成本，并且制备工艺，同时复杂表面活性剂的使用不仅不利于介孔的产生，反而因为难以全部清除而堵塞了部分粒子间孔隙。
现有技术中还有采用水溶胶的方法制备多孔MOF材料，沿袭了无机介孔分子筛的合成方法，但是得到的仍是ZIF-8纳米粒子间介孔孔隙主导的多级孔材料，由于使用了所谓模板的表面活性剂，使得这种材料的孔径分布很宽导致热稳定性不好，吸附性能较差。
发明内容
本发明的目的之一在于克服现有技术的缺陷，提供一种基于ZIF-8的MOF型多级孔材料，包含微孔和介孔，介孔可根据需要调控，可调范围在2-50nm，具有亲油疏水功能，是清除水中苯、甲苯等有机污染物良好吸附剂。
本发明的目的之二在于提供该MOF型多级孔材料的制备方法。
本发明的目的之三在于提供该MOF型多级孔材料在污水处理中有机污染物检测和吸附净化方面的应用。
本发明的技术方案为：一种基于ZIF-8的MOF型多级孔材料，包含微孔和介孔，介孔范围为2-50nm，微孔小于2nm，BET比表面为1300-1850m2/g,总孔体积1.20-2.80cm3/g，介孔孔体积为0.5-1.90cm3/g。在本发明的具体实施方式中，其微孔可视为来自于MOF“ZIF-8”结构(2-甲基咪唑锌),介孔可视为来自于小于60nm的纳米ZIF-8所形成的粒子间孔隙。
其中所述介孔孔体积优选为0.7-1.90cm3/g。
一种本发明任一基于ZIF-8的MOF型多级孔材料的制备方法，依次包括如下步骤：按比例将金属锌盐、2-甲基咪唑、碱和有机溶剂混合均匀，密闭条件下反应2-12小时，反应温度为80-130℃，反应完毕冷却得到凝胶物质。
还可以包括如下步骤：将得到的凝胶物质于20-50℃条件下干燥成干胶，之后再将其萃取洗涤6小时以上，再将洗涤后的材料脱除残留溶剂，得到MOF型多级孔材料。
上述步骤具体可以为：
步骤(1)：按比例将金属锌盐、2-甲基咪唑(Hmim)、碱和有机溶剂混合搅拌均匀，然后转移至反应釜中，密闭条件下于80-130℃下恒温反应2-12小时。
步骤(2)：反应完毕冷却至室温，将得到的凝胶物质于20-50℃条件下干燥成干胶(有机溶剂在实际生产中可以回收)，之后再将其萃取洗涤6小时以上；
步骤(3)：最后在130-150℃、真空条件下加热12小时以上，脱除残留溶剂，即得本发明多级孔材料。
所述金属锌盐可以为硝酸盐(NO3 -)、盐酸盐(Cl-)或醋酸盐(CH3COO-)；
所述碱(MOH)可以为无机碱或有机碱；
所述有机溶剂优选为不多于4个碳原子的有机溶剂，如甲醇、乙醇、丙醇或异丙醇，四氢呋喃，也可以他们的混合物。
所述金属锌盐、2－甲基咪唑、碱和有机溶剂的配比(即，Zn2+:Hmim:MOH:有机溶剂)优选为1摩尔:2-2.5摩尔:2-2.5摩尔:2.0-20升。
所述金属锌盐、2－甲基咪唑、碱和有机溶剂的配比进一步优选为1摩尔:2-2.5摩尔:2-2.5摩尔:3-7升，有机溶剂用量过大，降低生产效率，增加了生产成本。
所述反应釜优选为配有聚四氟乙烯内衬的不锈钢反应釜。
本发明可以通过下列方式调整介孔的大小：
(i)改变反应混合物中使用单一溶剂(或混合溶剂)的比例；(ii)改变反应温度来调控MOF纳米粒子的大小及堆积密度，从而改变其介孔的大小。其原理在于：纳米ZIF-8与所述有机溶剂形成凝胶，如果纳米ZIF-8粒子数目少，有利于形成较大的粒子间孔隙，反之亦反；反应时间和温度变化可调控ZIF-8粒子的大小，同样导致介孔大小的改变；不同溶剂其表面张力不同，当溶剂挥发干时对纳米粒子产生的凝聚力就不同，表面张力大的溶剂有利于形成粒子间更小孔隙的MOF材料。
本发明通过改变有机溶剂的用量和/或反应温度来调控ZIF-8纳米粒子在MOF型多级孔材料单片体中的堆积密度，从而调控其介孔大小，获得同时具有有序微孔(来自于ZIF-8结构)和介孔(产生于纳米ZIF-8粒子间孔隙)的基于ZIF-8的多级孔MOF材料。根据申请人的若干次实验，采用上述方式，介孔孔径的可调范围至少2-60nm之间，本领域技术人员可以在具体的原料和工艺条件下，通过实验获得所需孔径的介孔。
本发明的有益效果如下：本发明MOF型多级孔材料同时具有微孔和介孔，且介孔孔体积较大，具备良好的热稳定性，真空条件下，150℃经历12小时结构无任何变化，其结构都具有优良的微孔(ZIF-8孔结构)和良好的亲油疏水性。
本发明MOF型多级孔材料可用于芳香族化合物污染水的深度净化应用，具体使用方法如下：
将本发明MOF型多级孔材料颗粒制成固定床，让被处理的污染水通过床体；或者将本发明MOF型多级孔材料颗粒投入被处理污水中搅拌至少5分钟，然后将本发明MOF型多级孔材料颗粒与水体分离。
另外，鉴于本发明MOF型多级孔材料，这种材料也可以用于其他用途的吸附剂，例如，对水的净化处理，对空气中有机污染物VOC等的吸附等，用于吸附气体或液体中的杂质。
附图说明
图1为配位聚合物ZIF-8的结构图。
图2为实施例1合成的MOF型多级孔材料和常规ZIF-8的X射线衍射图。
图3为实施例1合成的MOF型多级孔材料的扫描电镜(SEM)图片。
图4为实施例1合成的MOF型多级孔材料的氮气吸附等温线和孔径分布图。
图5为实施例1合成的MOF型多级孔材料在室温下对甲苯水溶液的吸附等温线。
具体实施方式
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限定本发明的范围。
实施例1
将1.188克(4mmol)Zn(NO3)2·6H2O和0.656克(8mmol)Hmim于18mL无水乙醇中，加入8mmol氢氧化钠于室温搅拌均匀后，转移至20毫升容量的聚四氟乙烯反应釜中密闭于100℃反应6小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇萃取洗涤7小时。150℃真空(0.2mmHg)脱去残留乙醇即得本发明MOF型多级孔材料，收率96％(以Hmim计),图2为合成的MOF型多级孔材料的X射线衍射图，纳米粒子粒度小于60nm，图3为合成的MOF型多级孔材料的扫描电镜(SEM)图片，微孔(1.1nm)和介孔(35nm),BET比表面1320M2/g,总孔体积2.12cm3/g，介孔体积1.7cm3/g，图4为合成的MOF型多级孔材料的氮气吸附等温线和孔径分布图，其中IPD-mesoMOF-12-i、IPD-mesoMOF-12-ii和IPD-mesoMOF-12-iii分别表示用于实验的多个IPD-mesoMOF-12样品。
将所制备的MOF型多级孔材料颗粒制成固定床，让被处理的污染水通过床体，在室温下测试对甲苯水溶液的吸附效果，以甲苯为例:
实验表明，本发明MOF型多级孔材料对甲苯的吸附可在5分钟达到平衡；每公斤本发明MOF型多级孔材料可从甲苯污染的水中吸附220克甲苯(具体见图5)；甲苯含量为0.7mg/L(饮用水甲苯含量的国家标准)，经过处理后其含量可降低到0.14mg/L。
实施例2
将1.188克(4mmol)Zn(NO3)2·6H2O和10mmol Hmim于18mL无水乙醇中，加入10mmol氢氧化钠于室温搅拌均匀后，转移至20毫升容量的聚四氟乙烯反应釜中密闭于120℃反应6小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇萃取洗涤7小时。150℃真空(0.2mmHg)脱去残留乙醇即得本发明MOF型多级孔材料，收率97％(以Hmim计),纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(35nm),BET比表面1670M2/g,总孔体积1.54cm3/g，介孔体积1.03cm3/g。
实施例3
将1.188克(4mmol)Zn(NO3)2·6H2O和0.656克(8mmol)Hmim于15mL无水乙醇中，加入8mmol氢氧化钠于室温搅拌均匀后，转移至20毫升容量的聚四氟乙烯反应釜中密闭于120℃反应6小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇萃取洗涤7小时。150℃真空(0.2mmHg)脱去残留乙醇即得本发明MOF型多级孔材料，收率97％(以Hmim计),纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(35nm),BET比表面1660M2/g,总孔体积1.47cm3/g，介孔体积0.97cm3/g。
实施例4
将1.188克(4mmol)Zn(NO3)2·6H2O和0.656克(8mmol)Hmim于20mL无水乙醇中，加入8mmol氢氧化钠于室温搅拌均匀后，转移至25毫升容量的聚四氟乙烯反应釜中密闭于130℃反应6小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇萃取洗涤7小时。150℃真空(0.2mmHg)脱去残留乙醇即得本发明MOF型多级孔材料，收率98％(以Hmim计),纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(35nm),BET比表面1740M2/g,总孔体积1.34cm3/g，介孔体积0.77cm3/g。
实施例5
将1.188克(4mmol)Zn(NO3)2·6H2O和0.656克(8mmol)Hmim于20mL无水乙醇中，加入8mmol氢氧化钠于室温搅拌均匀后，转移至20毫升容量的聚四氟乙烯反应釜中密闭于130℃反应2小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水甲醇萃取洗涤6小时以上。150℃真空(0.2mmHg)脱去残留乙醇即得MOF型多级孔材料，收率96％(以Hmim计)。纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(36nm),BET比表面1730M2/g,总孔体积1.36cm3/g，介孔体积0.80cm3/g。
实施例6
将1.188克(4mmol)Zn(NO3)2·6H2O和0.656克(8mmol)Hmim于20mL无水乙醇中，加入8mmol氢氧化钠于室温搅拌均匀后，转移至25毫升容量的聚四氟乙烯反应釜中密闭于130℃反应4小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水甲醇萃取洗涤6小时以上。150℃真空(0.2mmHg)脱去残留乙醇即得MOF型多级孔材料，收率96％(以Hmim计)。纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(34nm),BET比表面1700M2/g,总孔体积1.35cm3/g，介孔体积0.80cm3/g。
实施例7
将1.188克(4mmol)Zn(NO3)2·6H2O和0.656克(8mmol)Hmim于9mL无水乙醇和9mL四氢呋喃混合溶剂中，加入8mmol氢氧化钠于室温搅拌均匀后，转移至20毫升容量的聚四氟乙烯反应釜中密闭于100℃反应12小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水甲醇萃取洗涤6小时以上。150℃真空(0.2mmHg)脱去残留乙醇即得MOF型多级孔材料，收率96％(以Hmim计)。纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(36nm),BET比表面1850m2/g,总孔体积1.49cm3/g，介孔体积0.91cm3/g。
实施例8
将0.22克(1mmol)Zn(CH3COO)2·6H2O和0.164克(2mmol)Hmim于18mL乙醇中，加入2mmol三丁基胺于室温搅拌均匀后，密闭于125℃反应5小时。胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇或甲醇萃取洗涤6小时以上。150℃真空(0.2mmHg)脱去残留乙醇即得多级孔材料IPD-mesoMOF-12，收率95％(以Hmim计)。纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(36nm),BET比表面1710M2/g,总孔体积2.11cm3/g，介孔体积1.70cm3/g。
实施例9
将0.22克(1mmol)Zn(CH3COO)2·6H2O和0.164克(2mmol)Hmim于18mL乙醇中，加入2mmol氢氧化钠,于室温搅拌均匀后，密闭于125℃反应5小时。胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇或甲醇萃取洗涤6小时以上。150℃真空(0.2mmHg)脱去残留乙醇即得多级孔材料，收率95％(以Hmim计)。纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(33nm),BET比表面1610M2/g,总孔体积2.01cm3/g，介孔体积1.50cm3/g。
实施例10
将0.22克(1mmol)Zn(CH3COO)2·6H2O和0.164克(2mmol)Hmim于18mL乙醇中，加入2mmol LiOH于室温搅拌均匀后，密闭于125℃反应5小时。胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇或甲醇萃取洗涤6小时以上。150℃真空(0.2mmHg)脱去残留乙醇即得多级孔材料IPD-mesoMOF-12，收率95％(以Hmim计)。纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(36nm),BET比表面1710M2/g,总孔体积1.50cm3/g，介孔体积0.78cm3/g。
实施例11
将0.22克(1mmol)Zn(CH3COO)2·6H2O和0.164克(2mmol)Hmim于25mL乙醇中，加入2mmol LiOH于室温搅拌均匀后，密闭于125℃反应5小时。胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇或甲醇萃取洗涤6小时以上。150℃真空(0.2mmHg)脱去残留乙醇即得多级孔材料IPD-mesoMOF-12，收率90％(以Hmim计)。纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(36nm),BET比表面1670M2/g,总孔体积1.45cm3/g，介孔体积0.70cm3/g。
实施例12
将1.188克(4mmol)Zn(NO3)2·6H2O和10mmol Hmim于18mL无水乙醇中，加入10mmol氢氧化钠于室温搅拌均匀后，转移至20毫升容量的聚四氟乙烯反应釜中密闭于110℃反应6小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇萃取洗涤7小时。150℃真空(0.2mmHg)脱去残留乙醇即得本发明MOF型多级孔材料，收率97％(以Hmim计),纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(30nm),BET比表面1620M2/g,总孔体积1.52cm3/g，介孔体积1.01cm3/g。
实施例13
将1.188克(4mmol)Zn(NO3)2·6H2O和8mmol Hmim于12mL无水乙醇中，加入8mmol氢氧化钠于室温搅拌均匀后，转移至20毫升容量的聚四氟乙烯反应釜中密闭于100℃反应2小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇萃取洗涤7小时。150℃真空(0.2mmHg)脱去残留乙醇即得本发明MOF型多级孔材料，收率97％(以Hmim计),纳米粒子粒度小于60nm，微孔(1.1nm)和介孔(25nm),BET比表面1670M2/g,总孔体积1.24cm3/g，介孔体积0.54cm3/g。
实施例14
将1.188克(4mmol)Zn(NO3)2·6H2O和0.656克(8mmol)Hmim于18mL无水乙醇中，加入8mmol氢氧化钠于室温搅拌均匀后，混入8mmol氯化钠纳米粒子(粒度60nm),混匀，之后迅速转移至20毫升容量的聚四氟乙烯反应釜中密闭于100℃反应6小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇萃取洗涤7小时。150℃真空(0.2mmHg)脱去残留乙醇即得MOF型多级孔材料，收率96％(以Hmim计)。纳米粒子粒度小于60nm，微孔(1.2nm)和介孔(45nm),BET比表面1720M2/g,总孔体积2.19cm3/g，介孔体积1.9cm3/g。
实施例15
将1.188克(4mmol)Zn(NO3)2·6H2O和0.656克(8mmol)Hmim于18mL无水乙醇中，加入8mmol氢氧化钠于室温搅拌均匀后，混入12mmol氯化钠纳米粒子(粒度60nm),混匀，之后迅速转移至20毫升容量的聚四氟乙烯反应釜中密闭于100℃反应6小时。冷至室温后，胶状物质于室温干燥成干胶，之后再将其用索氏提取器以无水乙醇萃取洗涤7小时。150℃真空(0.2mmHg)脱去残留乙醇即得MOF型多级孔材料，收率96％(以Hmim计)。纳米粒子粒度小于60nm，微孔(1.2nm)和介孔(47nm),BET比表面1750M2/g,总孔体积2.19cm3/g，介孔体积1.93cm3/g。
将实施例14和实施例15制备的MOF型多级孔材料与实施例1做甲苯吸附的平行试验，吸附效果比实施例1又提高20％以上，平衡时间为3分钟。
对于上述采用硝酸锌的实施例，分别以盐酸锌和醋酸锌替代硝酸锌，获得的结果基本相同。
根据反应机理以及大量实验，以其他不多于碳原子的有机溶剂替代上述实施例中的无水乙醇，同样可以制得IPD-mesoMOF-12。
本发明制备的IPD-mesoMOF-12，外观呈白色固态干胶(研磨后呈粉末)。
Claims (6)
1.一种基于ZIF-8的MOF型多级孔材料，包含微孔和介孔，其特征在于同时具有来自于ZIF-8结构的有序微孔和产生于纳米ZIF-8粒子间孔隙的介孔，介孔范围为2-50nm，微孔小于2nm，BET比表面为1300-1850m2/g,总孔体积1.20-2.80cm3/g，介孔孔体积为0.5-1.90cm3/g。
2.根据权利要求1所述的MOF型多级孔材料，其特征在于介孔孔体积为0.7-1.90cm3/g。
3.根据权利要求1所述的基于ZIF-8的MOF型多级孔材料的制备方法，其特征在于依次包括如下步骤：
按比例将金属锌盐、2-甲基咪唑、碱和有机溶剂混合均匀，密闭条件下反应2-12小时，反应温度为80-130℃，反应完毕冷却得到凝胶物质，具体为：
步骤(1)：按比例将金属锌盐、2-甲基咪唑、碱和有机溶剂混合搅拌均匀，然后转移至反应釜中，密闭条件下于80-130℃下恒温反应2-12小时；
步骤(2)：反应完毕冷却至室温，将得到的凝胶物质于20-50℃条件下干燥成干胶，之后再将其萃取洗涤6小时以上；
步骤(3)：最后在130-150℃、真空条件下加热12小时以上，脱除残留溶剂，即得多级孔材料，
所述金属锌盐为硝酸盐、盐酸盐或醋酸盐；
所述碱为无机碱或有机碱；
所述有机溶剂为不多于4个碳原子的有机溶剂；
所述金属锌盐、2-甲基咪唑、碱和有机溶剂的配比为1摩尔:2-2.5摩尔:2-2.5摩尔:2.0-20升。
4.根据权利要求3所述MOF型多级孔材料的制备方法，其特征在于步骤(1)中金属锌盐、2-甲基咪唑、碱和有机溶剂的配比为1摩尔:2-2.5摩尔:2-2.5摩尔:3-7升。
5.根据权利要求1或2所述的基于ZIF-8的MOF型多级孔材料或者根据权利要求3或4所述的方法制备的基于ZIF-8的MOF型多级孔材料用作吸附剂的应用。
6.根据权利要求1或2所述的基于ZIF-8的MOF型多级孔材料或者根据权利要求3或4所述的方法制备的基于ZIF-8的MOF型多级孔材料在芳香族化合物污染水深度净化中的应用，其特征在于用作吸附剂。
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