CN111662553A - Preparation method of porous ceramic microbead composite material for efficiently loading MOFs (metal-organic frameworks) - Google Patents
Preparation method of porous ceramic microbead composite material for efficiently loading MOFs (metal-organic frameworks) Download PDFInfo
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- CN111662553A CN111662553A CN202010455970.6A CN202010455970A CN111662553A CN 111662553 A CN111662553 A CN 111662553A CN 202010455970 A CN202010455970 A CN 202010455970A CN 111662553 A CN111662553 A CN 111662553A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 70
- 239000011325 microbead Substances 0.000 title claims abstract description 57
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000011068 loading method Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012700 ceramic precursor Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 10
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052863 mullite Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000013110 organic ligand Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 5
- 229960003638 dopamine Drugs 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910001570 bauxite Inorganic materials 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
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- 239000002994 raw material Substances 0.000 claims description 3
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- WGLQHUKCXBXUDV-UHFFFAOYSA-N 3-aminophthalic acid Chemical compound NC1=CC=CC(C(O)=O)=C1C(O)=O WGLQHUKCXBXUDV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
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- 239000012071 phase Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims 2
- 159000000013 aluminium salts Chemical class 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
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- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 3
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- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000002149 hierarchical pore Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002159 nanocrystal Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 3
- 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 description 3
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- 239000013118 MOF-74-type framework Substances 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004943 liquid phase epitaxy Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000013105 nano metal-organic framework Substances 0.000 description 1
- 239000013289 nano-metal-organic framework Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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Abstract
本发明涉及多孔材料领域。一种负载MOFs晶体的多孔陶瓷微珠复合材料的制备方法，首先制备多孔陶瓷微珠，（其较高比表面积的多孔结构不仅为后期MOFs晶体的负载提供充足的锚定位点，同时微球内的连通孔结构为反应物分子提供扩散传质的通道）；然后，将多孔陶瓷微珠载体上浸入反应液中，通过原位生长在陶瓷纤维、孔壁、载体表面负载的MOFs，形成具有多级孔结构的催化/吸附的复合材料。本发明制备的由多孔陶瓷微珠载体和不同的MOFs材料组成的多级孔结构催化/吸附剂可广泛应用于吸附、分离、提纯、催化等领域。
The present invention relates to the field of porous materials. A preparation method of porous ceramic microbead composites loaded with MOFs crystals. Firstly, porous ceramic microbeads are prepared. The connected pore structure provides a channel for the diffusion and mass transfer of reactant molecules); then, the porous ceramic microbead carrier is immersed in the reaction solution, and the MOFs supported on the ceramic fiber, pore wall, and carrier surface are grown in situ to form a porous ceramic microbead carrier. Catalysis/adsorption composites with hierarchical pore structure. The hierarchical porous structure catalyst/adsorber prepared by the invention, which is composed of a porous ceramic microbead carrier and different MOFs materials, can be widely used in the fields of adsorption, separation, purification, catalysis and the like.
Description
技术领域technical field
本发明涉及多孔材料领域。The present invention relates to the field of porous materials.
技术背景technical background
金属-有机骨架（MOFs），是由有机配体和无机金属离子或者金属团簇通过自组装配位连接形成的一种具有周期性网络结构的晶态多孔材料，具有较高的表面积。由于MOFs材料诸多优异结构特点，比如：高度均匀的孔径分布，高度可调的孔径，和多种官能团位点，MOFs材料在吸附分离、气体存储、化学传感器、生物医学、催化等领域有着广泛的潜在应用前景。Metal-organic frameworks (MOFs) are crystalline porous materials with periodic network structure formed by organic ligands and inorganic metal ions or metal clusters connected by self-assembly. Due to many excellent structural characteristics of MOFs, such as highly uniform pore size distribution, highly tunable pore size, and various functional group sites, MOFs have a wide range of applications in adsorption and separation, gas storage, chemical sensors, biomedicine, catalysis and other fields. Potential application prospects.
尽管MOFs材料的应用前景丰富，但我们通常制备获得的多为结晶粉体，在工业应用中粉体颗粒不宜回收，重复利用率低，，因此将需要将MOFs材料结构化，使其具有较高体密度的同时，有充足的机械强度。目前MOFs结构化的方法主要有两种。一是，直接对MOFs粉体材料进行加工，例如压制、造粒、挤出、喷雾干燥等，获得球状、棒状、块状材料，从而使其具有一定的结构和强度。但也存在许多明显的问题，挤压成型工艺中施加压力会对造成晶体内部孔结构坍塌，从而降低MOFs材料高的表面积和孔隙率；另外，成型过程中，需要加入一定量的粘结剂，会堵塞孔结构，使得MOFs材料的催化及吸附效率降低二是，主要利用原位生长，层沉积和逐步液相外延生长，在载体制备MOFs薄膜或沉积MOFs晶体，使其结构化，但是，由于载体的比表面较低，能提供给MOFs的锚定位点较小，从而导致其负载量较低Although the application prospects of MOFs materials are rich, most of the crystalline powders we usually prepare are crystalline powders. In industrial applications, the powder particles are not suitable for recycling, and the recycling rate is low. Therefore, it will be necessary to structure the MOFs materials to make them have higher At the same time of bulk density, it has sufficient mechanical strength. At present, there are two main methods for structuring MOFs. One is to directly process MOFs powder materials, such as pressing, granulation, extrusion, spray drying, etc., to obtain spherical, rod-shaped, and block-shaped materials, so that they have a certain structure and strength. However, there are also many obvious problems. The application of pressure in the extrusion molding process will cause the internal pore structure of the crystal to collapse, thereby reducing the high surface area and porosity of the MOFs material. In addition, a certain amount of binder needs to be added during the molding process. It will block the pore structure and reduce the catalysis and adsorption efficiency of MOFs materials. Second, in situ growth, layer deposition and stepwise liquid phase epitaxy are mainly used to prepare MOFs thin films on the carrier or deposit MOFs crystals to make them structured. However, due to The lower specific surface of the carrier can provide smaller anchoring sites for MOFs, resulting in a lower loading capacity
综上所述，通过高效负载实现MOFs材料结构化的关键是，寻找一种具有较高比表面积可为MOFs原位合成提供较多锚定位点的载体。同时，载体具有一定的机械强度，因此本发明提出，以具有较高比表面积的多孔莫来石陶瓷微珠和氧化铝微珠为载体，通过原位合成在其表面负载MOFs，实现其结构化，对实现MOFs材料高效重复利用具有重要意义。In summary, the key to realizing the structuring of MOFs through efficient loading is to find a carrier with a higher specific surface area that can provide more anchoring sites for MOFs in situ synthesis. At the same time, the carrier has a certain mechanical strength, so the present invention proposes to use porous mullite ceramic microbeads and alumina microbeads with high specific surface area as the carrier, and load MOFs on the surface of the carrier by in-situ synthesis to realize its structural structure. , which is of great significance to realize the efficient reuse of MOFs materials.
发明内容SUMMARY OF THE INVENTION
本发明所要解决的技术问题是：如何提供一种高效负载MOFs的多孔陶瓷微珠复合材料的制备方法。The technical problem to be solved by the present invention is: how to provide a preparation method of a porous ceramic microbead composite material loaded with MOFs with high efficiency.
本发明所采用的技术方案是：一种负载MOFs晶体的多孔陶瓷微珠复合材料的制备方法，首先制备多孔陶瓷微珠，（其较高比表面积的多孔结构不仅为后期MOFs晶体的负载提供充足的锚定位点，同时微球内的连通孔结构为反应物分子提供扩散传质的通道）；然后，将多孔陶瓷微珠载体上浸入反应液中，通过原位生长在陶瓷纤维、孔壁、载体表面负载的MOFs，形成具有多级孔结构的催化/吸附的复合材料。The technical scheme adopted in the present invention is as follows: a preparation method of a porous ceramic microbead composite material loaded with MOFs crystals, firstly, the porous ceramic microbeads are prepared, (the porous structure of the higher specific surface area not only provides sufficient support for the later MOFs crystal loading At the same time, the interconnected pore structure in the microspheres provides diffusion and mass transfer channels for reactant molecules); then, the porous ceramic microbead carrier is immersed in the reaction solution, and the ceramic fibers, pore walls, The MOFs supported on the surface of the support form a catalytic/adsorbent composite with a hierarchical pore structure.
具体制备过程安如下步骤进行The specific preparation process is carried out as follows:
步骤一、制备陶瓷前体粉末，陶瓷前体粉末为多孔莫来石陶瓷前体粉末或者多孔氧化铝陶瓷前体粉末：多孔莫来石陶瓷前体粉末以高岭土、铝矾土为原料，MoO3为烧结助剂，湿混、氮烘干过筛获得；多孔氧化铝陶瓷前体粉末为α-Al2O3粉末湿混、氮烘干过筛获得；Step 1. Prepare the ceramic precursor powder. The ceramic precursor powder is a porous mullite ceramic precursor powder or a porous alumina ceramic precursor powder: the porous mullite ceramic precursor powder is made of kaolin and bauxite as raw materials, and MoO 3 It is a sintering aid, obtained by wet mixing, nitrogen drying and sieving; the porous alumina ceramic precursor powder is obtained by wet mixing, nitrogen drying and sieving of α-Al 2 O 3 powder;
步骤二、将步骤一制备的陶瓷前体粉末、聚丙烯酸、聚乙烯醇加入去离子水中获得稳定的水基陶瓷浆料；Step 2, adding the ceramic precursor powder, polyacrylic acid and polyvinyl alcohol prepared in step 1 into deionized water to obtain a stable water-based ceramic slurry;
步骤三、将稳定的水基陶瓷浆料用滴液装置滴入-15℃ ~ -40℃的油相中，形成粒径分布范围0.5-2mm的固相陶瓷微珠，30min后过滤分离，并在-20℃的乙酸乙酯中反复清洗陶瓷微珠；Step 3: The stable water-based ceramic slurry is dropped into the oil phase at -15°C ~ -40°C with a dripping device to form solid-phase ceramic microbeads with a particle size distribution range of 0.5-2mm, filtered and separated after 30 minutes, and Wash the ceramic beads repeatedly in ethyl acetate at -20°C;
步骤四、将经过乙酸乙酯反复清洗的陶瓷微珠冷冻干燥，转移至陶瓷坩埚中，进行烧结获得多孔陶瓷微珠载体；Step 4: freeze-drying the ceramic microbeads repeatedly washed with ethyl acetate, transfer to a ceramic crucible, and sinter to obtain a porous ceramic microbead carrier;
步骤五、将多孔陶瓷微珠载体先进行表面修饰处理，然后浸泡在金属盐溶液中抽真空，搅拌均匀，然后在搅拌中加入有机配体溶液，搅拌均匀，待反应完全后，过滤、洗涤、烘干获得高效负载MOFs的多孔陶瓷微珠复合材料。步骤五中，多孔陶瓷微珠载体表面修饰处理过程为，将多孔陶瓷微珠载体在APTES的乙醇溶液或者多巴胺水溶液中浸泡。Step 5. The porous ceramic microbead carrier is first subjected to surface modification treatment, then soaked in a metal salt solution to vacuumize, and stirred evenly, and then the organic ligand solution is added during stirring, stirred evenly, and after the reaction is complete, filter, wash, Porous ceramic microbead composites with high efficiency loaded MOFs were obtained by drying. In the fifth step, the surface modification treatment process of the porous ceramic microbead carrier is to soak the porous ceramic microbead carrier in an APTES ethanol solution or an aqueous dopamine solution.
APTES的乙醇溶液浓度为0.5mol/L，多巴胺水溶液浓度为0.2mol/L。The concentration of APTES in ethanol solution is 0.5mol/L, and the concentration of dopamine aqueous solution is 0.2mol/L.
金属盐和有机配体的摩尔比为1:2到2:1。The molar ratio of metal salt to organic ligand is 1:2 to 2:1.
金属盐溶液为锌盐、钴盐、铜盐、铝盐中的一种，浓度为0.0481~0.172mmol/ml，有机配体溶液为二甲基咪唑、对苯二甲酸、氨基邻苯二甲酸、均苯三甲酸中一种，浓度为0.020~0.190mmol/ml。The metal salt solution is one of zinc salt, cobalt salt, copper salt and aluminum salt, and the concentration is 0.0481~0.172mmol/ml, and the organic ligand solution is dimethylimidazole, terephthalic acid, aminophthalic acid, One of trimesic acid, the concentration is 0.020~0.190mmol/ml.
本发明的有益效果是：本发明提出应用多孔陶瓷微珠（多孔莫来石微珠和多孔氧化铝微珠）为载体（陶瓷微珠粒径为1-2mm，球形度约为90%），然后通过溶液原位生长在多孔陶瓷材料的针状纤维（多孔莫来石陶瓷微珠）和孔壁上（多孔氧化铝陶瓷微珠）负载均匀的纳米MOFs晶体，获得具有一定力学性能的复合微珠材料，从而实现MOFs材料的结构化。多孔陶瓷微珠载体的孔壁，为MOFs材料晶体提供丰富的附着位点的同时，联通的大孔（5-20μm）为介质分子提供了良好的扩散传质通道；极大的提高了材料的反应效率。The beneficial effects of the present invention are as follows: the present invention proposes to use porous ceramic microbeads (porous mullite microbeads and porous alumina microbeads) as carriers (the particle size of the ceramic microbeads is 1-2 mm, and the sphericity is about 90%), Then, the nano-MOFs crystals are uniformly loaded on the needle-like fibers (porous mullite ceramic microbeads) and pore walls (porous alumina ceramic microbeads) of the porous ceramic material by solution in-situ growth to obtain composite microstructures with certain mechanical properties. bead materials, thereby realizing the structuring of MOFs materials. The pore walls of the porous ceramic microbead carrier provide abundant attachment sites for MOFs material crystals, and the interconnected macropores (5-20 μm) provide good diffusion and mass transfer channels for medium molecules; greatly improving the material’s performance. reaction efficiency.
本发明制备的由多孔陶瓷微珠载体和不同的MOFs材料组成的多级孔结构催化/吸附剂可广泛应用于吸附、分离、提纯、催化等领域。与已有的吸附/催化产品相比，具有以下优点：1)多孔陶瓷微珠载体内部连通微米级孔道可提高传质吸附效率； 2）多孔陶瓷微珠载体良好机械强度可为MOFs提供结构支撑，从而实现其回收和循环利用；3）多孔陶瓷微珠载体可负载不同的MOFs材料，拥有着特定的物理化学性能，应用范围广泛；4）多孔陶瓷微珠的毫米级球形结构可有效减小催化及吸附过程的压降。。综上所述，本发明制备的复合材料，实现了MOFs材料的结构化，对其工业应用具有重要意义。The hierarchical porous structure catalyst/adsorber prepared by the invention, which is composed of a porous ceramic microbead carrier and different MOFs materials, can be widely used in the fields of adsorption, separation, purification, catalysis and the like. Compared with the existing adsorption/catalysis products, it has the following advantages: 1) the interconnected micron-scale pores inside the porous ceramic microbead carrier can improve the mass transfer and adsorption efficiency; 2) the good mechanical strength of the porous ceramic microbead carrier can provide structural support for MOFs , so as to realize its recovery and recycling; 3) The porous ceramic microbead carrier can support different MOFs materials, has specific physical and chemical properties, and has a wide range of applications; 4) The millimeter-scale spherical structure of the porous ceramic microbeads can effectively reduce Pressure drop in catalytic and adsorption processes. . To sum up, the composite material prepared by the present invention realizes the structuring of the MOFs material, which is of great significance to its industrial application.
附图说明Description of drawings
图1是ZIF-8@多孔莫来石陶瓷微珠复合材料SEM照片。Figure 1 is the SEM image of ZIF-8@porous mullite ceramic microbead composite.
具体实施方式Detailed ways
实例1：本实施例中负载ZIF-8晶体的多孔陶瓷微珠复合材料的制备方法是按以下步骤实现的：步骤一、莫来石陶瓷：以高岭土、铝矾土为主要原料，MoO3为烧结助剂，按（3Al2O3·2SiO2）0.9（MoO3）0.1化学计量比称重混合并以无水乙醇为介质加入介质球球磨20h，烘干过筛得到均匀的混合粉末；氧化铝陶瓷：称取一定量的α-Al2O3粉末混合无水乙醇球磨20h，烘干过筛得到均匀的氧化铝粉末。步骤二、将去离子水、陶瓷粉末、聚丙烯酸（粉末质量1%）、聚乙烯醇（粉末质量1%）混和球磨24h，制备出一定固相含量20 vol%的稳定的水基陶瓷浆料。步骤三、将稳定的浆料通过气压滴液装置滴入低温煤油中（-20℃），形成不同粒径（粒径分布范围0.5mm-2mm）的固相陶瓷微珠，30min后过滤分离，并在低温（-20℃）的乙酸乙酯中反复清洗球珠。步骤四、将固相陶瓷微珠在冷冻干燥机中低压干燥12h，随后将陶瓷微珠坯体转移至陶瓷坩埚中，在马弗炉中进行烧结致密获得多孔陶瓷微珠载体，莫来石陶瓷的烧结工艺为500保温1h， 1400℃保温2h，升温速率为20℃/min；氧化铝陶瓷的烧结工艺为1400℃保温2h，升温速率为7℃/min。步骤五、首先将多孔微珠浸入APTES乙醇溶液中30min后干燥，以ZnCl2作为金属源（0.332g），溶于50ml甲醇中超声震荡处理15min，将多孔陶瓷微珠载体浸入金属溶液中抽滤5min、再缓慢搅拌2h；二甲基咪唑为有机连接体（0.816g）同样溶解于50ml甲醇中超声处理15min，缓慢加入上述溶液中，搅拌12h。将样品过滤，用去离子水和甲醇反复冲洗，放入60℃烘箱中干燥过夜，获得ZIF-8@多孔陶瓷微珠复合材料样品。Example 1: The preparation method of the porous ceramic microbead composite material loaded with ZIF-8 crystals in this example is realized according to the following steps: Step 1 , mullite ceramics: take kaolin and bauxite as the main raw materials, and MoO as Sintering aid, weighed and mixed according to the stoichiometric ratio of (3Al 2 O 3 · 2SiO 2 ) 0.9 (MoO 3 ) 0.1 , and was added to the medium by anhydrous ethanol for ball milling for 20h, dried and sieved to obtain a uniform mixed powder; oxidation Aluminum ceramics: Weigh a certain amount of α-Al 2 O 3 powder and mix it with anhydrous ethanol for ball milling for 20 hours, then dry and sieve to obtain uniform alumina powder. Step 2: Mix deionized water, ceramic powder, polyacrylic acid (1% by mass of powder), and polyvinyl alcohol (1% by mass of powder) and ball-milled for 24 hours to prepare a stable water-based ceramic slurry with a certain solid content of 20 vol% . Step 3. The stable slurry is dropped into low temperature kerosene (-20°C) through the air pressure dripping device to form solid-phase ceramic microbeads with different particle sizes (particle size distribution range 0.5mm-2mm), and filter and separate after 30 minutes. The beads were washed repeatedly in low temperature (-20°C) ethyl acetate. Step 4: Dry the solid-phase ceramic microbeads in a freeze dryer at low pressure for 12 hours, then transfer the ceramic microbeads to a ceramic crucible, and sinter and densify them in a muffle furnace to obtain porous ceramic microbead carriers, mullite ceramics The sintering process of alumina ceramics is 500 °C for 1 h, 1400 °C for 2 h, and the heating rate is 20 °C/min; the sintering process of alumina ceramics is 1400 °C for 2 h, and the heating rate is 7 °C/min. Step 5. First, the porous microbeads were immersed in APTES ethanol solution for 30min and then dried. Using ZnCl 2 as the metal source (0.332g), it was dissolved in 50ml methanol and subjected to ultrasonic vibration for 15min, and the porous ceramic microbead carrier was immersed in the metal solution for suction filtration. 5min, and then slowly stirred for 2h; dimethylimidazole as an organic linker (0.816g) was also dissolved in 50ml of methanol for 15min ultrasonic treatment, slowly added to the above solution, and stirred for 12h. The samples were filtered, rinsed repeatedly with deionized water and methanol, and dried in an oven at 60 °C overnight to obtain ZIF-8@porous ceramic microbead composite samples.
实例2：负载NH2-UiO-66纳米晶体的多孔陶瓷微球复合材料的制备步骤与实例1不同的是步骤五），以ZrCl4为金属源（0.466g），溶于50mlDMF和HCl的混合溶液（体积比为5：1），将载体浸泡其中预处理即抽滤、缓慢搅拌2h；NH2-BDC作为有机连接体（0.181g）溶解于50ml的DMF中，将其缓慢加入上述溶液中，并将混合液转移至反应釜中，在80℃下晶化反应12h，过滤、反复洗涤、干燥。Example 2: Preparation of porous ceramic microsphere composites loaded with NH 2 -UiO-66 nanocrystals The step is different from Example 1 in step 5), with ZrCl 4 as the metal source (0.466g), dissolved in a mixture of 50ml DMF and HCl solution (volume ratio of 5:1), soak the carrier in it for pretreatment, namely suction filtration and slow stirring for 2h; NH 2 -BDC as an organic linker (0.181g) was dissolved in 50ml of DMF, and slowly added to the above solution , and the mixture was transferred to the reaction kettle, crystallized at 80 °C for 12 h, filtered, washed repeatedly and dried.
实例3：负载MOF-5纳米晶体的多孔陶瓷微珠复合材料的制备。与实施例2不同之处在于：步骤五中ZnCl2作为金属源（0.410g），BDC作为有机连接体（0.166g），分别溶解于50ml的DMF中，与载体混和在120℃下反应20h。Example 3: Preparation of porous ceramic microbead composites loaded with MOF-5 nanocrystals. The difference from Example 2 is that in step 5, ZnCl 2 was used as the metal source (0.410g), and BDC was used as the organic linker (0.166g), which were respectively dissolved in 50ml of DMF, mixed with the carrier and reacted at 120°C for 20h.
实例4：负载HKUST-1纳米晶体的多孔陶瓷微珠的制备。与实施例2不同之处在于步骤五中Cu(NO3)2·3H2O 作为金属源（2.077g），H3BTC作为有机连接体（1.0g），分别溶解于50ml的DMF中，与载体混和在85℃下反应20h。Example 4: Preparation of porous ceramic microbeads loaded with HKUST-1 nanocrystals. The difference from Example 2 is that in step 5, Cu(NO 3 ) 2 ·3H 2 O was used as the metal source (2.077g), and H 3 BTC was used as the organic linker (1.0g), which were respectively dissolved in 50ml of DMF and mixed with The carrier was mixed and reacted at 85°C for 20h.
实例5：负载ZIF-67纳米晶体的多孔陶瓷微珠的制备。与实施例1不同之处在于步骤五中Co(NO3)2·6H2O作为金属源（0.7g），二甲基咪唑作为有机连接体（1.65g），分别溶解于30ml甲醇中，室温下与载体混合反应12h。Example 5: Preparation of ZIF-67 nanocrystal loaded porous ceramic microbeads. The difference from Example 1 is that in step 5, Co(NO 3 ) 2 ·6H 2 O was used as the metal source (0.7g) and dimethylimidazole was used as the organic linker (1.65g), which were respectively dissolved in 30ml methanol at room temperature. The mixture was mixed with the carrier for 12h.
实例6：负载Mg-MOF-74纳米晶体的多孔陶瓷微珠的制备。与实施例2不同之处在于步骤五中Mg(NO3)2·6H2O 作为金属源（0.95g），2,5-二羟基对苯二甲酸作为有机连接体（0.224g），分别溶解于50ml的DMF中，与载体混和在125℃下反应20h。Example 6: Preparation of porous ceramic microbeads loaded with Mg-MOF-74 nanocrystals. The difference from Example 2 is that in step 5, Mg(NO 3 ) 2 ·6H2O was used as the metal source (0.95g) and 2,5-dihydroxyterephthalic acid was used as the organic linker (0.224g), which were dissolved in 50ml respectively. in DMF, mixed with the carrier and reacted at 125°C for 20h.
实例7：负载MOF-808纳米晶体的多孔陶瓷微珠的制备。与实施例2不同之处在于步骤五中，ZrOCl2·8H2O为金属源（0.97g），H3BTC为有机连接体（0.21g），分别溶解于50ml的甲酸和50ml的DMF中，与载体混和在130℃下反应24h。Example 7: Preparation of porous ceramic microbeads loaded with MOF-808 nanocrystals. The difference from Example 2 is that in step 5, ZrOCl 2 ·8H 2 O is the metal source (0.97g), and H 3 BTC is the organic linker (0.21g), which are respectively dissolved in 50ml of formic acid and 50ml of DMF, Mixed with carrier and reacted at 130°C for 24h.
实例8: 与实施例1、2、3、4、5、6、7、8不同之处在于步骤五中，首先将多孔微珠载体浸入多巴胺水溶液中进行预处理；Example 8: The difference from Examples 1, 2, 3, 4, 5, 6, 7, and 8 is that in step 5, the porous microbead carrier is first immersed in an aqueous dopamine solution for pretreatment;
实例9: 与实施例1、2、3、4、5、6、7、8、9不同之处在于步骤五中，在恒容条件下，金属盐溶液和有机配体的摩尔比不同，分别为：1:2； 1:1 和 2:1。Example 9: The difference from Examples 1, 2, 3, 4, 5, 6, 7, 8, and 9 is that in step 5, under constant volume conditions, the mol ratios of the metal salt solution and the organic ligand are different, respectively. As: 1:2; 1:1 and 2:1.
Claims (5)
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