CN110314703A - A kind of preparation method of the hollow MOFs material of more shells - Google Patents
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- CN110314703A CN110314703A CN201910609898.5A CN201910609898A CN110314703A CN 110314703 A CN110314703 A CN 110314703A CN 201910609898 A CN201910609898 A CN 201910609898A CN 110314703 A CN110314703 A CN 110314703A
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 239000013110 organic ligand Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000002923 metal particle Substances 0.000 claims abstract description 5
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- -1 metals ion Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000002927 oxygen compounds Chemical class 0.000 claims description 2
- 239000011257 shell material Substances 0.000 description 31
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000005119 centrifugation Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000013148 Cu-BTC MOF Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 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 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241000143432 Daldinia concentrica Species 0.000 description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000008236 heating water Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- 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 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/397—
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of preparation methods of more shell MOFs materials.Prepare more shell-layer metal oxides first to sacrifice template, directly reacted with organic ligand, or react the more shell-layer metal oxides of carried noble metal particle under suitable conditions with the disparate metals ion of addition, organic ligand, obtain more shell hollow structures of the oxide@MOFs of oxide@MOFs or carried noble metal particle.The invention is easy to operate, has certain universality, enriches the strategy for preparing the hollow MOFs of more shells, provide mentality of designing to stablize noble metal.
Description
Technical field
The invention belongs to technical field of function materials.Specifically, the present invention relates to a kind of more hollow MOFs materials of shell
Preparation method.
Background technique
Metal organic framework (Metal Organic Frameworks, MOFs) is used as shell structurre, has both had biggish
Specific surface area, pore structure abundant, adjustable unsaturated active site, and the noble metal grain coated inside shell can be stablized
Son can effectively inhibit the reunion and loss of noble metal in reaction process.Therefore, MOFs is that the composite material of shell is being urged
There is wide potential application foreground in change field.
The preparation method of hollow MOFs Shell Materials has been reported that for example Ning Zhang et al. is with sulfonated polystyrene ball more
It constructs the bivalve hollow HKUST-1/Pd@ZIF-8(Pd nanoparticle of layer for hard template to be evenly distributed in internal HKUST-1 shell)
(small 2017,1701395).They first coat HKUST-1 in the polystyrene ball surface of sulfonation, then pass sequentially through negative
Pd nanoparticle, packet ZIF-8 are carried, polystyrene spheres are finally selectively removed.Wherein, HKUST-1 shell is conducive to expensive as skeleton
The fine dispersion of metallic, and outer layer ZIF-8 can either effectively inhibit noble metal to reunite as protective layer, and urge
Change the selectivity that reaction substrate molecular dimension is realized in reaction.Although hard template method has certain versatility, preparation process
It is cumbersome, and remove template procedure and be readily incorporated new impurity and lead to the collapsing of structure.Huo et al. passes through crystal seed and rear quarter
Erosion method successfully prepares more shell MOFs (MIL-101).The method is firstly the need of with acetic acid selective corrosion internal crystallization difference
MOFs then grows new MOF, carries out selective corrosion again, to form more shell MOFs(Angew. Chem. Int.
Ed. 2017,56,1-6).Although the method presents superiority, preparation process in more shell MOFs structure controls synthesis
Still show cumbersome, and corrosion process is easily damaged MOFs structure.How more shell MOFs are prepared using simple, general method still to deposit
It is challenging.
It sacrifices template and provides a kind of thinking for the preparation of core-shell structure.It for example, is to sacrifice template with metal oxide,
It is directly reacted with organic ligand, the MOFs advantageously formed is grown in metal oxide surface, avoids the same Xiang Chenghe of MOFs.
For example, Chen et al. is with Cu2O is to sacrifice template, is reacted using the copper ion of slow release with organic ligand, in Cu2O particle table
Face successfully coats HKUST-1 shell (ACS Appl. Mater. Interfaces 2016,8,22745-22750).I
Seminar early period with CeO2The aluminium oxide of/Pd particle surface deposition is to sacrifice template, and design is reacted with terephthalic acid (TPA), is prepared
CeO2/ Pd@MIL-53 (Al) sandwich structure (Chem. Commun. 2019,55,7651-7654).Currently, metal oxygen
Compound is to sacrifice template to focus primarily upon solid oxide.If selecting the oxide of hollow or more shell hollow structures
It to sacrifice template, or is carrier, then carried noble metal particle coats MOFs, this structure can play hollow or more shells
The advantage of hollow structure conducive to the diffusion of reaction substrate molecule, while promoting MOFs shell and oxide, your gold to a greater extent
Belong to the contact interface between particle, enhances the synergistic effect between component in catalysis reaction.The existing literature investigated according to us
And patent, not yet discovery is to sacrifice template or carrier using more shell hollow structure oxides, prepares the hollow MOFs material of more shells
The report of material.
Summary of the invention
In order to break through the limitation of the prior art, overcome the deficiencies in the prior art is more it is an object of the invention to invent one kind
The preparation method of the hollow MOFs material of shell.
To achieve the above object, the present invention adopts the following technical solutions:
The preparation method of more hollow oxide@MOFs of shell, includes the following steps:
A, the metal oxide of more shell hollow structures is prepared；
B, it disperses the step A oxide prepared in solvent；Meanwhile the solution for dissolving organic ligand is added dropwise to more shells
It in layer metal oxide dispersion, vibrates, stands, centrifugation, ethanol washing, vacuum freeze drying obtain more shell MOFs:
More shell-layer metal oxides described in above-mentioned steps A are main are as follows: the Cu of more shell hollow structures2O；
Solvent described in above-mentioned steps B: ethyl alcohol and DMA(ratio are 0.5:0.5), ethyl alcohol；
Ligand described in above-mentioned steps B: trimesic acid；Set temperature: room temperature；Reaction time: 40min.
The preparation method of the more hollow oxide of shell/noble metal@MOFs, includes the following steps:
A, the metal oxide of more shell hollow structures is prepared；
B, in metal oxide surface carried noble metal particle；
C, the oxide/noble metal for preparing step B is scattered in solvent；Meanwhile it is dissolution organic ligand and foreign peoples is golden
The solution for belonging to salt is added in more shell-layer metal oxide dispersion liquids, by obtained suspension water-bath one at a set temperature
It fixes time, is centrifuged, washs, dries, obtain oxide/noble metal@MOFs of more shells:
More shell-layer metal oxides described in above-mentioned steps B are main are as follows: more shell CeO2；Noble metal: Au；
Solvent described in above-mentioned steps C: DMF and H2O(ratio is 1:1)；
Disparate metals salt in above-mentioned steps C are as follows: Al (NO3)3·9H2O；
Ligand described in above-mentioned steps C: terephthalic acid (TPA)；Set temperature: 60 DEG C；Reaction time: 24 h.
The beneficial effects of the present invention are:
The present invention provides the preparation methods of more hollow MOFs of shell a kind of.With the Cu of more shell hollow structures2O is sacrificial mold
Plate directly reacts with organic ligand, obtains the Cu of more shells2O@Cu-MOFs structure；Or with the hollow CeO of more shells2To carry
Body, carried noble metal Au nanoparticle, is then added Al3+With terephthalic acid (TPA), the CeO of more shells is obtained2/ Au@Al-MOFs knot
Structure.The invention is easy to operate, has certain universality, the strategy for preparing the hollow MOFs of more shells is enriched, for your gold stablized
Belong to particle and provides mentality of designing.
Detailed description of the invention
Fig. 1 is the schematic diagram that embodiment is formed.
Fig. 2 is more hollow Cu of shell prepared by embodiment 12The transmission electron microscope picture of O@Cu-MOFs.
Fig. 3 is the hollow CeO of three shells prepared by embodiment 22The transmission electron microscope picture of/Au@Al-MOF.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples, these embodiments are only used for illustrating this hair
It is bright, but any restrictions are not constituted to the scope of the present invention.
Embodiment 1
(a) by CuSO4·5H2O(0.05 g) it is dissolved into 100 ml CTAB aqueous solutions (0.13 M), Vitamin C is then added
Sour (0.18 g) heats the solution to 60 DEG C after ultrasonic dissolution and keeps the temperature 20 min.By 10 ml NaOH aqueous solutions (0.2
M it) is added drop-wise in above-mentioned solution under stiring, continues to stir 10 min, centrifugation, washing, 50 DEG C of vacuum drying；
(b) by 0.5 ml trimesic acid (H3BTC ethanol solution (80 mM) and 0.5 ml DMAC N,N' dimethyl acetamide)
(DMA) with the more shell Cu of 1 ml2O(2mg ethanol solution mixing), under oscillation is several, room temperature stands 40 min, is then centrifuged for, second
Alcohol washing, freeze-drying, obtain the hollow Cu of more shells2O@Cu-MOFs material.
Embodiment 2
(a) 50 mg carbon balls are dispersed in 10 ml H2In O, Ce (NO is then added3)3 .6H2O aqueous solution (10 ml, 0.5
M), 45 min, then 45 min of ultrasound are sufficiently stirred in mixture, then 6 h of hydro-thermal process at 160 DEG C, centrifugation, washing, 80
DEG C drying is warming up to 500 DEG C with 10 DEG C/min, keeps the temperature 1 h, prepares three shell CeO2；
(b) under magnetic stirring by three shell CeO2It is dispersed in 15 ml deionized waters, ultrasound makes its dispersion, is then added
HAuCl4(500 μ l, 10 mM) solution stirs 18 h.Centrifugation, is washed with aqueous solution and is redispersed in 30 ml H2It, will be new in O
The NaBH of fresh preparation4 (500 μ l, 30 mM) is added in redisperse liquid, uses H2O washing, is dried in vacuo at 80 DEG C；
(c) by above-mentioned 10 mg, tri- shell CeO2@Au、10 mg Al(NO3)3·9H2O and 10 mg terephthalic acid (TPA) (H2BDC)
It is scattered in 4 ml N,N-dimethylformamides (DMF) and 4 ml H2In the mixed solution of O, 60 DEG C of 24 h of heating water bath.It is cooling
Three shell CeO are obtained by centrifugation, DMF and water washing, 60 DEG C of dryings to room temperature2@Au@MIL-53 material.
Embodiment 3
(a) 50 mg carbon balls are dispersed in 10 ml H2In O, Ce (NO is then added3)3 .6H2O aqueous solution (10 ml, 0.5
M), 45 min, then 45 min of ultrasound are sufficiently stirred in mixture, then 6 h of hydro-thermal process at 160 DEG C, be centrifuged, washing, 80
DEG C drying is warming up to 500 DEG C with 2 DEG C/min, keeps the temperature 1 h, preparation bivalve layer CeO2；
(b) under magnetic stirring by bivalve layer CeO2 It is dispersed in 15 ml deionized waters, ultrasound makes its dispersion, is then added
HAuCl4(500 μ l, 10 mM) solution stirs 18 h.Centrifugation, is washed with aqueous solution and is redispersed in 30ml H2It, will be fresh in O
The NaBH of preparation4 (500 μ l, 30 mM) is added in redisperse liquid, uses H2O washing, is dried in vacuo at 80 DEG C；
(c) by the bivalve above-mentioned 10 mg layer CeO2@Au、10 mg Al(NO3)3·9H2O and 10 mg terephthalic acid (TPA) (H2BDC) divide
It dissipates in 4 ml N,N-dimethylformamides (DMF) and 4 ml H2In the mixed solution of O, 60 DEG C of 24 h of heating water bath are cooled to
Room temperature obtains bivalve layer CeO by centrifugation, DMF and water washing, 60 DEG C of dryings2@Au@MIL-53 material.
Claims (3)
- The design of the MOFs material of shell more than 1., which is characterized in that the described method comprises the following steps:A, more shell-layer metal oxides of more shell-layer metal oxides or carried noble metal particle are prepared；B, it is to sacrifice template by obtained more shell-layer metal oxides, is directly reacted with organic ligand, or by more shell metallic oxygen Compound/noble metal reacts under suitable conditions with the disparate metals ion of addition, organic ligand, obtains oxide@MOFs Or oxide/noble metal@MOFs structure；With the MOFs of more shells in above structure.
- 2. the preparation method of more shell MOFs materials according to claim 1, it is characterised in that more shells in the step A Metal oxide is mainly more shell Cu2O, three shell CeO2, bivalve layer CeO2；Noble metal is mainly Au.
- 3. the preparation method of more shell MOFs materials according to claim 1, it is characterised in that ligand point in the step B It Wei not H3BTC and H2BDC, set temperature are respectively room temperature and 60 DEG C, and the reaction time is respectively 40 min and 24 h, disparate metals Salt is Al (NO3)3·9H2O。
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| CN113270595A (en) * | 2021-04-14 | 2021-08-17 | 杭州电子科技大学 | Nitrogen-doped carbon-supported non-noble metal nano catalyst prepared based on MOF |
| CN113398924A (en) * | 2021-05-28 | 2021-09-17 | 烟台大学 | Metal catalyst and preparation and application thereof |
| CN114772561A (en) * | 2022-05-07 | 2022-07-22 | 合肥工业大学 | Hollow multi-shell Sn-containing metal selenide @ carbon heterojunction and application thereof |
| CN116116463A (en) * | 2022-12-02 | 2023-05-16 | 南京医科大学 | Peroxidase-like Au/CeO 2 NR@Cu-MOFs, preparation method and application |
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