CN111056545A - Preparation method of MOFs-derived hollow porous carbon microspheres - Google Patents
Preparation method of MOFs-derived hollow porous carbon microspheres Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000004005 microsphere Substances 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 61
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000005406 washing Methods 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011258 core-shell material Substances 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
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- 239000003513 alkali Substances 0.000 claims abstract description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
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- 238000001035 drying Methods 0.000 claims description 18
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 13
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- 229910052681 coesite Inorganic materials 0.000 claims description 12
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- 238000010000 carbonizing Methods 0.000 claims description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 9
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
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- 238000002791 soaking Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- -1 carboxyl Chemical group 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims 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 claims description 3
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 2
- 239000013291 MIL-100 Substances 0.000 claims description 2
- 239000013177 MIL-101 Substances 0.000 claims description 2
- 239000013132 MOF-5 Substances 0.000 claims description 2
- 239000013118 MOF-74-type framework Substances 0.000 claims description 2
- 239000013208 UiO-67 Substances 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims 1
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- 229910052751 metal Inorganic materials 0.000 abstract description 10
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- 239000003814 drug Substances 0.000 abstract description 2
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BFQBTBHGELNZEQ-UHFFFAOYSA-N CCO.OC(=O)CS Chemical compound CCO.OC(=O)CS BFQBTBHGELNZEQ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical group C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention belongs to the technical field of inorganic nano carbon materials, and particularly relates to a preparation method of hollow porous carbon microspheres derived from metal-organic framework Materials (MOFs). The method comprises the following steps: metal Oxide (MO)x) Preparation of microspheres and surface carboxylation, MOxMOFs grows on the surface of the microsphere layer by layer to obtain a MOx @ MOFs core-shell structure composite material, and MO is addedx@ MOFs is impregnated with an organic small-molecule cross-linking agent, then cross-linking and carbonization are carried out, and finally the hollow porous carbon microsphere is prepared through acid washing or alkali washing. The invention uses MOFs shell layer as precursor to prepare hollow porous carbon microsphere, the particle size, shell layer thickness and shell layer pore channel structure of the obtained product are adjustable, the carbon shell layer can be conveniently doped with various metal or nonmetal heteroatoms (such as nitrogen and transition metal elements), the material density is low, the specific surface area is large, the strength is high, the conductivity is good,Good chemical and thermal stability, and wide application prospect in the fields of catalysis, adsorption, energy storage, drug controlled release and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic nano carbon materials, and particularly relates to a preparation method of MOFs-derived hollow porous carbon microspheres.
Background
Since Ligima discovered the carbon nanotube as a hollow nano-porous carbon material in 1991, researchers have conducted intensive research on the preparation, structure and application of the carbon nanotube, and gradually realize that the hollow carbon material has potential application values in many fields such as adsorption and energy storage. Therefore, the development and application of different types of hollow carbon materials having unique structures have attracted much attention in recent years. The hollow porous carbon microsphere is a special form of a hollow carbon material, has the characteristics of low density, large specific surface area, high strength, good conductivity and good chemical and thermal stability, and has wide application prospects in the fields of catalysis, adsorption, energy storage, drug controlled release and the like.
At present, methods for preparing the hollow porous carbon microspheres mainly comprise a chemical vapor deposition method (Chinese patent CN 104609387A), a hydrothermal method (Chinese patent CN 108203087A), a high-voltage arc discharge method (Chinese patent CNCN 101857218A) and a template method (Chinese patent CN 109824030A). The hollow carbon spheres synthesized by the chemical vapor deposition method are mostly accompanied by the generation of a large amount of byproducts, and the purity of the hollow carbon spheres is not high; the hydrothermal method has short reaction time and good water solubility of the product, but the preparation process usually needs high pressure and high equipment requirement; the product obtained by the high-voltage arc discharge method is easy to purify, but high-voltage arc discharge equipment is needed, and the production cost is high. Moreover, the above 3 methods are difficult to accurately control the size and the degree of hollowness of the carbon spheres, cannot obtain monodisperse carbon spheres, and are difficult to realize effective regulation and control of the pore structure in the carbon shell layer. The hard template method is the most widely adopted method for preparing the hollow carbon spheres at present, and the prepared hollow carbon spheres have uniform size, controllable size and good dispersibility. However, the current hard template method uses high molecular polymer as a carbonization precursor, which determines that the method is difficult to realize effective regulation and control of the inner pore structure of the shell layer of the hollow carbon sphere.
Compared with the hollow porous carbon microspheres made of pure carbon materials, the heteroatom doping can show more excellent performance in certain aspects. For example, nitrogen atom doping can effectively improve the electron transport performance, chemical reaction activity and material stability of carbon atoms, and nitrogen-containing groups on the surface of the carbon material can improve the hydrophilicity of the material, improve the biocompatibility and the like. In recent years, a great deal of research shows that non-noble transition metals such as Fe, Co, Ni and the like are doped into the carbon material, so that the electrochemical performance of the carbon material can be effectively improved. At present, the preparation method of nitrogen-doped hollow carbon spheres can be generally divided into two methods of synchronous in-situ nitrogen doping (Chinese invention patent CN 109626355A) and post-treatment nitrogen doping (Zhu J, et al. Nanoscale, 2017, 9(35): 13257-13263). The post-treatment nitrogen doping can cause that the doping amount and the uniformity of nitrogen elements are not high enough, and chemical nitrogen rather than structural nitrogen is easier to form, and the structural nitrogen is a main factor for improving the electrochemical performance of the carbon material. However, the research on the preparation of transition metal doped hollow carbon spheres is rarely reported, and especially, the preparation of high-loading small-particle-size metal doped hollow carbon spheres is a very challenging task.
Metal-organic frameworks (MOFs) are a new class of organic-inorganic hybrid porous nanomaterials developed in the last 90 th century. MOFs have developed very rapidly since their introduction, and currently, their species have exceeded 20000. The MOFs framework structure is unique and diverse, metal is uniformly distributed in atomic scale, the pore channel structure is regular and adjustable, and the specific surface area is large, so that the MOFs framework structure has great application potential in various fields such as adsorption separation, gas storage, catalysis, electrochemistry, drug carriers and the like. The unique structure of the MOFs also enables the carbon and carbon composite material obtained by using the MOFs as a precursor to have large specific surface area, uniform and controllable pore channel structure, large metal loading capacity, small particle size and uniform distribution; the MOFs containing pyridine, pyrrole, pyridine, imidazole, pyrimidine and other nitrogen-containing rings are directly carbonized, so that N atoms can be conveniently doped in situ, and pyridine nitrogen favorable for electrocatalytic activity is more easily formed. Thus, MOFs have become the most desirable precursors for the synthesis of porous nanocarbons and composites thereof.
Disclosure of Invention
In order to solve the problems that the inner pore structure of a shell layer cannot be flexibly regulated and controlled, the load of high-load small-particle-size transition metal cannot be realized, and the in-situ doping of high-grade nitrogen is difficult to realize simply and effectively in the existing hollow carbon sphere preparation technology, the invention provides a hard template preparation method of hollow porous carbon microspheres with MOFs as a carbon source.
The invention adopts the following technical scheme:
a preparation method of MOFs-derived hollow porous carbon microspheres is to use a layer-by-layer growth method to perform MOF-derived hollow porous carbon microspheres on metal oxides MOxMOFs grows on the surface of the microsphere, and the obtained MOxAnd (2) soaking the @ MOFs core-shell structure compound in an organic small molecular cross-linking agent, washing, drying, carbonizing, and removing the metal oxide core to obtain the hollow porous carbon microsphere.
Further, the method comprises the following steps:
step 1: preparation of Metal oxide MOxMicrospheres;
step 2: carboxyl modification is carried out on the product obtained in the step 1 to obtain carboxyl-terminated MOxMicrospheres;
and step 3: MOFs grows on the outer surface of the product obtained in the step 2 to obtain MOx@ MOFs core-shell structure composite materials;
and 4, step 4: MO obtained in the step 3xThe @ MOFs core-shell structure composite material is impregnated with an organic small molecular cross-linking agent, and then is washed and dried;
and 5: crosslinking and carbonizing the product obtained in the step (4);
step 6: and (5) carrying out acid washing or alkali washing on the product obtained in the step (5) to obtain the hollow carbon sphere.
Further, the metal oxide in step 1 is SiO2、γ-Fe2O3Or Fe3O4Any one of them.
Further, in step 2, for MOxThe carboxylation of the microsphere, different oxide microspheres need to adopt corresponding carboxylation reagents and methods. If said MO is in step 2xThe microspheres are gamma-Fe2O3And Fe3O4When the microspheres are prepared, ethanol is used as a solvent, and thioglycollic acid is used for modification; if MO is presentxThe microspheres are SiO2When the microspheres are needed to be activated, the number of surface hydroxyl groups is increased, then 3-aminopropyl triethoxysilane (APTES) is used for surface amination, and finally, the surface amino groups are reacted with glutaric anhydride to obtain the carboxyl modified SiO2And (3) microspheres.
Further, step 3 is to grow MOFs outside the product obtained in step 2 for several times by using a Layer by Layer growth (Layer by Layer) method, wash the MOFs with anhydrous methanol, and dry the MOFs at 70 ℃ for 8 hours.
Further, the MOFs is any one of ZIF-8, MIL-101, MIL-100, MIL-88, UiO-67, MOF-5, MOF-74 or MOF-199.
Further, step 4 specifically includes: and (3) vacuumizing the product obtained in the step (3) at 140 ℃, continuously vacuumizing and cooling to room temperature after 6h, then adding the organic small-molecule cross-linking agent for impregnation, stirring at 60 ℃ for 12h, quickly washing with ethanol, and drying at 80 ℃ for 5 h.
Further, in the step 4, the organic small molecule cross-linking agent is furfuryl alcohol, phenolic resin or glycerol.
Further, step 5 is to carbonize the sample obtained in step 4 in a program-controlled tube furnace under the protection of inert gas, wherein the carbonization temperature ranges from 400 ℃ to 1300 ℃, the temperature rise rate ranges from 0.1 ℃/min to 20 ℃/min, and the heat preservation time is 0.5h to 6 h.
Further, in step 5, the inert gas is nitrogen, helium, neon, argon or xenon.
Further, in step 6, the acid is hydrofluoric acid or hydrochloric acid, and the base is sodium hydroxide or potassium hydroxide. This step is required according to MOxThe chemical property of the microsphere and the shell layer of the carbon or the metal/carbon composite are selected to be washed by acid or alkali.
The invention has the beneficial effects that:
1. according to the invention, MOFs is taken as a shell, and hollow carbon spheres are prepared through carbonization, so that the obtained product has the advantages of low density, large specific surface area, high strength, good conductivity, and good chemical and thermal stability.
2. According to the invention, MOx spherical cores with different sizes can be prepared as required, and then MOFs are wrapped on the surface of the MOx spherical cores and carbonized to obtain hollow carbon spheres with different particle sizes; in addition, the shell thickness of the finally obtained hollow carbon sphere can be simply and flexibly regulated and controlled by regulating the growth times of the MOFs.
3. According to the method, different MOFs can be selected as carbonization precursors, and different denucleation means are adopted, so that the hollow carbon spheres with different shell pore channel structures and doped with different metal and nonmetal heteroatoms are prepared. Particularly, due to the space distribution characteristics of the metal of the MOFs and the coordination relationship between the metal and the ligand, the particle size of the hollow carbon shell carbonized by the MOFs can be generally kept below 20nm when the metal loading reaches more than 50%.
Drawings
FIGS. 1a, 1b and 1c show the silica microspheres and SiO prepared in example 1, respectively2@ ZIF-8 core-shell structure composites and scanning electron microscope images (SEM) of hollow carbon microspheres.
Fig. 2 is an SEM image of the hollow carbon microsphere prepared in example 2.
Fig. 3 is an XRD diffractogram of the hollow carbon microsphere prepared in example 3.
Fig. 4a and 4b are BET and partial SEM images of the hollow copper-doped carbon microsphere prepared in example 5.
Detailed Description
The following examples are intended to better illustrate the technical solutions of the present invention, but not to limit the scope of the present invention.
The following examples illustrate examples of hollow carbon spheres prepared by using different metal oxide microspheres as cores, different MOFs packages, different carbonization conditions and different methods for removing cores.
Example 1
Step 1: preparing the silicon dioxide microspheres: 0.017 g of potassium chloride is dissolved in 6.75 mL of distilled water, then 9mL of ammonia water and 65 mL of absolute ethyl alcohol are added, and then the mixture is stirred for 5min at the temperature of 30 ℃ in a heat collection type magnetic stirrer to obtain a mixed solution I.
Weighing 3.95 g of tetraethyl silicate, dissolving the tetraethyl silicate in 33.3 mL of absolute ethanol, then dropwise adding the tetraethyl silicate into the mixed solution I at the speed of 40 mu L each time by transferring every 12 s until the dropwise adding is finished (the dropwise adding process is not interrupted), and stirring for reacting for 3 h at the stirring speed of 900 r/min. The samples were then washed 3 times by centrifugation with absolute ethanol for 3 min each. The solution was then vacuum dried on a rotary evaporator at 30 ℃.
Step 2: activating the silica microspheres: 18 mL of distilled water was added to the vacuum-dried sample, and the mixture was ultrasonically shaken for 30 min (the temperature was kept at about 25 ℃ during the ultrasonic treatment). After the sonication, 22 mL of concentrated HCl was added to the sample, and the mixture was stirred under reflux at 110 ℃ for 6 hours. And after the reaction is finished, centrifugally washing the reaction product for 4-5 times by using distilled water, washing the sample to be neutral, centrifugally washing the sample for 3 times by using absolute ethyl alcohol, and drying the sample for 12 hours in vacuum at the temperature of 70 ℃.
And step 3: amino modification: after the vacuum drying is finished, a sample is taken out, 81.2 mL of absolute ethyl alcohol is added, and the ultrasonic treatment is carried out for 30 min. Then stirred under reflux at 85 ℃ for 5min, after which 21 mL of APTES was added rapidly and stirred under reflux for 24 h. Then washing with absolute ethyl alcohol for 10 times, and then vacuumizing and rotary evaporating to dryness at 40 ℃ in a rotary evaporator.
And 4, step 4: carboxyl modification: adding 21.56 mL of DMF into the amino modified sample, carrying out ultrasonic treatment for 30 min, and then stirring for 5min at 80 ℃ to obtain a mixed solution II.
Weighing 0.4 g of glutaric anhydride and 0.375 g of triethylamine, adding the mixture into 21.56 mL of DMF, uniformly mixing, dropwise adding the mixture into the second mixed solution, and stirring the mixture for reaction for 24 hours under the protection of argon. After the reaction is finished, DMF is used for centrifugal washing for 3 times, 0.1M hydrochloric acid is used for centrifugal washing for 5 times, distilled water is used for centrifugal washing for 5 times, anhydrous methanol is used for centrifugal washing for 8 times, and vacuum pumping and rotary evaporation are carried out at 40 ℃ to dryness to obtain the carboxyl-terminated silicon spheres.
And 5: growing MOFs: 0.2075 g of dimethylimidazole is dissolved in 5mL of anhydrous methanol solution and then added to the carboxyl-terminated silicon spheres, then 0.075 g of zinc nitrate is dissolved in 5mL of anhydrous methanol and added to the carboxyl-terminated silicon spheres, the mixture is subjected to ultrasonic oscillation for 30 min, then the reaction is stirred for 10 min at the temperature of 70 ℃, and the anhydrous methanol is centrifugally washed for 8 times. MOFs grows twice according to the steps, and the SiO is obtained after drying for 8 hours at 70 DEG C2@ ZIF-8 core-shell structure complex.
Step 6: crosslinking agent impregnated SiO2@ ZIF-8: mixing SiO2@ ZIF-8 core-shell structure was heated at 90 deg.C for 4 h under vacuum. Immediately after the vacuum extraction, furfuryl alcohol was added for impregnation (the amount of furfuryl alcohol added just before the sample) and stirred at 60 ℃ for 12 h. Washing with ethanol by centrifugation for 2 times, and drying at 80 deg.C for 5 hr.
And 7: carbonizing a sample: carbonizing in a program control tube furnace after drying is finished, wherein the program in the program control tube furnace is as follows: heating to 250 deg.C for 360 min at 30 deg.C for 44 min, heating to 600 deg.C for 60 min at 250 deg.C for 350 min, and cooling to 30 deg.C at 600 deg.C for 114 min. The protective gas during carbonization is argon.
And 8: removing cores of carbonized samples: and (3) after carbonization is finished, cooling to about 30 ℃, taking out the sample, soaking the sample in 1% hydrofluoric acid for 12h, then centrifugally washing the sample for 5 times by using absolute ethyl alcohol, and drying the sample in a drying oven at 80 ℃ for 5h to obtain the hollow nitrogen-doped carbon sphere. Sphericity: 85%, hollowness: 100%, spherical diameter: 1.5 μm, specific surface area: 601.6m2/g。
FIG. 1a is a schematic diagram of silica microspheres prepared in this example. It can be seen from the figure that the silica microspheres have uniform particle size of about 1.5 μm. FIG. 1b shows SiO obtained after ZIF-8 grows on the surface of a silica microsphere2The @ ZIF-8 composite material shows that MOFs on the surface of the silica microsphere is uniformly coated on the surface of the silica microsphere. FIG. 1c is SiO2@ ZIF-8 is carbonized and acid-washed to obtain a hollow final productPorous carbon microspheres. As can be seen from fig. 1c, hollow nitrogen-doped carbon microspheres can be successfully obtained from the preparation steps of example 1.
Example 2
This example is the same as example 1 and will not be repeated except that SiO is impregnated with furfuryl alcohol2After the @ ZIF-8 microspheres are dried, the carbonization procedure is as follows: heating to 250 deg.C for 44 min at 30 deg.C for 360 min, heating to 950 deg.C for 700 min at 250 deg.C for 120 min, and cooling to 30 deg.C at 950 deg.C for 174 min. The protective gas during carbonization is nitrogen.
The hollow nitrogen-doped carbon microsphere prepared in this example is shown in fig. 2. Sphericity: 80%, hollowness: 100%, spherical diameter: 1.5 μm, specific surface area: 548.3 m2/g。
Example 3
This example is the same as example 1 in the steps of preparing, activating and carboxylating silica microspheres, and will not be described again, except that,
growing MOFs: dissolving 0.25 mol of trimesic acid in 5mL of absolute ethanol solution, then adding the solution into carboxyl terminated silicon spheres, dissolving 0.25 mol of ferric trichloride hexahydrate in 5mL of absolute ethanol, adding the solution into the carboxyl terminated silicon spheres, then stirring and reacting for 30 min at 70 ℃, and centrifugally washing for 8 times by the absolute ethanol. MOFs grows twice according to the steps, and the SiO is obtained after drying for 8 hours at 70 DEG C2@ MIL-100 (Fe) core-shell structure complex.
Crosslinking agent impregnated SiO2@ MIL-100 (Fe): mixing SiO2The @ MIL-100 (Fe) core-shell structure is vacuumized and heated for 4 h at the temperature of 90 ℃. Immediately after the vacuum pumping is finished, adding phenolic resin for impregnation (the adding amount of the phenolic resin just exceeds the sample), and stirring for 12h at the temperature of 60 ℃. Washing with ethanol by centrifugation for 2 times, and drying at 80 deg.C for 5 hr.
Removing cores of carbonized samples: and soaking the carbonized sample in a sodium hydroxide solution for 12h, then centrifugally washing the sample for 5 times by using absolute ethyl alcohol, and drying the sample in a drying oven at 80 ℃ for 5h to obtain the hollow iron atom doped carbon spheres. Sphericity: 85%, hollowness: 100%, spherical diameter: 1.5 μm, specific surface area: 288.6 m2Per g, iron content: 53 percent. The hollow iron atom prepared in this exampleThe XRD diffraction pattern of the doped carbon microsphere is shown in figure 3. Comparing with the standard spectrum, several obvious diffraction peaks in the XRD diffraction spectrum respectively represent the (110), (200) and (211) crystal faces of the metal simple substance iron, which shows that the hollow microsphere formed by the Fe/C composite material is obtained after carbonization. In addition, the average particle size of the metal particles is calculated to be 15 nm by an XRD spectrogram and a Sherrer formula.
Example 4
Step 1: preparing ferroferric oxide microspheres: 2.7 g FeCl3∙6H2O was dissolved in 50 ml of ethylene glycol. Stirring for 0.5h gave a yellow clear solution. After 5.75 g of sodium acetate was added to the above solution and stirring was continued for 0.5 hour, the resulting solution was transferred to a polytetrafluoroethylene liner having a capacity of 80 ml and placed in a stainless steel autoclave. 473K was heated at high temperature for 8 hours and cooled to room temperature. Collecting black magnetic microspheres, washing with ethanol for three times, and vacuum drying at 70 deg.C for 12 h.
Step 2: carboxyl modification: 0.25 g of Fe3O4Adding 50 mL of mercaptoacetic acid ethanol solution (0.29 mM), mechanically stirring for 24 h, recovering with an external magnetic field, washing with distilled water and anhydrous methanol for 5 times, and centrifuging to dry.
And step 3: growing MOFs: 0.2075 g of dimethylimidazole and 0.075 g of zinc nitrate are respectively dissolved in two 5mL anhydrous methanol solutions, then the two solutions are respectively and sequentially added into carboxyl-terminated silicon spheres, ultrasonic oscillation is carried out for 30 min, mechanical stirring reaction is carried out for 10 min at the temperature of 70 ℃, and the anhydrous methanol is centrifugally washed for 8 times. MOFs grows twice according to the steps, and is dried for 8 hours at 70 ℃ to obtain Fe3O4@ ZIF-8 core-shell structure complex.
And 4, step 4: crosslinking agent impregnated Fe3O4@ ZIF-8: mixing Fe3O4@ ZIF-8 core-shell structure was heated at 90 deg.C for 4 h under vacuum. Immediately after the evacuation, glycerol was added for impregnation (the amount of glycerol added just before the sample), and the mixture was stirred at 60 ℃ for 12 hours.
And 5: carbonizing a sample: washing with ethanol by centrifugation for 2 times, and drying at 80 deg.C for 5 hr. Carbonizing in a program control tube furnace after drying is finished, wherein the program in the program control tube furnace is as follows: heating to 250 deg.C for 360 min at 30 deg.C for 44 min, heating to 600 deg.C for 60 min at 250 deg.C for 350 min, and cooling to 30 deg.C at 600 deg.C for 114 min. The protective gas during carbonization is helium.
And 5: removing cores of carbonized samples: and after carbonization is finished, taking out the sample, soaking the sample in 1% hydrofluoric acid for 12h, then centrifugally washing the sample for 5 times by using absolute ethyl alcohol, and drying the sample in a drying oven at 80 ℃ for 5h to obtain the hollow nitrogen-doped carbon sphere. Sphericity: 85%, hollowness: 100%, spherical diameter: 1.5 μm, specific surface area: 576.8 m2/g。
Example 5
The steps of this embodiment are substantially the same as those of embodiment 3, and the description of the same parts is omitted. The difference is that the temperature of the water tank is controlled,
growing MOFs: 0.182 g of copper nitrate trihydrate and 0.0875 g of trimesic acid were weighed, and 5mL of anhydrous methanol was added thereto, respectively, and dissolved by ultrasonic waves to prepare a solution. Subjecting the obtained carboxylated SiO2Microsphere addition of Cu (NO)3)2Soaking the mixture in methanol solution at 25 deg.c for 15min, adding trimesic acid solution, stirring for several seconds, and standing at 25 deg.c for 15 min. The mixture was magnetically separated and then washed 3 times with methanol. The growth is circulated for 3 times to obtain SiO2@ CuBTC core-shell structure composite material.
The obtained copper atom-doped hollow carbon microsphere has the following sphericity: 85%, hollowness: 100%, spherical diameter: 1.5 μm, copper content: 53%, specific surface area: 302.6 m2(ii) in terms of/g. As can be seen from the combination of FIG. 4a (SEM image of sample) and FIG. 4b (pore size distribution diagram), the average diameter of the copper particles is about 30nm, and the pore size of the hollow carbon microsphere is relatively uniform and mainly concentrated at 0.5 nm.
The above embodiments are merely preferred embodiments of the present invention, and not intended to limit the scope of the invention, so that equivalent changes or modifications made based on the structure, characteristics and principles of the invention should be included in the claims of the present invention.
Claims (10)
1. A preparation method of MOFs-derived hollow porous carbon microspheres is characterized in that a layer-by-layer growth method is utilized to perform MOF-derived hollow porous carbon microspheres on metal oxide MOxGrowing MOFs on the surface of the microsphere, and growing the MOFs on the surface of the microsphereThe obtained MOxAnd (2) soaking the @ MOFs core-shell structure compound in an organic small molecular cross-linking agent, washing, drying, carbonizing, and removing the metal oxide core to obtain the hollow porous carbon microsphere.
2. The method for preparing MOFs-derived hollow porous carbon microspheres according to claim 1, comprising the steps of:
step 1: preparation of Metal oxide MOxMicrospheres;
step 2: carboxyl modification is carried out on the product obtained in the step 1 to obtain carboxyl-terminated MOxMicrospheres;
and step 3: MOFs grows on the outer surface of the product obtained in the step 2 to obtain MOx@ MOFs core-shell structure composite materials;
and 4, step 4: MO obtained in the step 3xThe @ MOFs core-shell structure composite material is impregnated with an organic small molecular cross-linking agent, and then is washed and dried;
and 5: crosslinking and carbonizing the product obtained in the step 4;
step 6: and (5) carrying out acid washing or alkali washing on the product obtained in the step (5) to finally obtain the hollow carbon sphere.
3. The method for preparing MOFs-derived hollow porous carbon microspheres according to claim 2, wherein said metal oxide in step 1 is SiO2、γ-Fe2O3Or Fe3O4Any one of them.
4. The process according to claim 3, wherein MO is a compound selected from the group consisting of Mo, in, MoxThe microspheres are gamma-Fe2O3Or Fe3O4When microspherical, MOxThe microspheres adopt ethanol as a solvent and are modified by thioglycollic acid; MO (metal oxide semiconductor)xThe microspheres are SiO2When, MOxThe microspheres are activated, then surface amination is carried out by using 3-aminopropyl triethoxysilane, and finally the surface amino reacts with glutaric anhydride to obtain the SiO modified by carboxyl2And (3) microspheres.
5. The method for preparing hollow porous carbon microspheres derived from MOFs according to claim 2, wherein the step 3 is to grow MOFs outside the product obtained in the step 2 by a layer-by-layer growth method for a plurality of times, wash the MOFs with anhydrous methanol, and dry the MOFs at 70 ℃ for 8 hours.
6. The method for preparing hollow porous carbon microspheres derived from MOFs according to claim 2, wherein said MOFs is any one of ZIF-8, MIL-101, MIL-100, MIL-88, UiO-67, MOF-5, MOF-74 or MOF-199.
7. The method for preparing MOFs-derived hollow porous carbon microspheres according to claim 2, wherein the step 4 specifically comprises: vacuumizing the product obtained in the step (3) at 140 ℃, continuously vacuumizing and cooling to room temperature after 6 hours, then adding the organic small-molecule cross-linking agent for impregnation, stirring at 60 ℃ for 12 hours, quickly washing with ethanol, and drying at 80 ℃ for 5 hours; and 5, specifically, carbonizing the sample obtained in the step 4 in a program-controlled tube furnace under the protection of inert gas, wherein the carbonization temperature ranges from 400 ℃ to 1300 ℃, the temperature rise rate ranges from 0.1 ℃/min to 20 ℃/min, and the heat preservation time is 0.5h to 6 h.
8. The method for preparing MOFs-derived hollow porous carbon microspheres according to claim 2, wherein said organic small molecule cross-linking agent in step 4 is furfuryl alcohol, phenolic resin or glycerol.
9. The method according to claim 7, wherein the inert gas is nitrogen, helium, neon, argon or xenon.
10. The method according to claim 2, wherein in step 6, the acid is hydrofluoric acid or hydrochloric acid, and the base is sodium hydroxide or potassium hydroxide.
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Application publication date: 20200424 |