CN110952125A - Preparation method of octahedral zirconium-based MOF material by adopting anodic oxidation in-situ growth - Google Patents
Preparation method of octahedral zirconium-based MOF material by adopting anodic oxidation in-situ growth Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 11
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000013096 zirconium-based metal-organic framework Substances 0.000 title claims abstract description 8
- 239000013207 UiO-66 Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000012922 MOF pore Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/61—Surface area
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
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Abstract
The invention discloses a preparation method of an octahedral zirconium-based MOF material by adopting anodic oxidation in-situ growth, which comprises the steps of growing octahedral UiO-66 on a zirconium sheet in situ on an anode and a cathode simultaneously by an anodic oxidation method, respectively cleaning with DMF (dimethyl formamide) and methanol, naturally airing in the air, and drying in a vacuum drying oven to obtain the octahedral zirconium-based MOF material. Finally obtaining the UiO-66 with octahedral structure. The invention has the advantages that: firstly, the method for synthesizing the UiO-66 is green and convenient, has short synthesis time and simple synthesis conditions, and can be used for large-scale industrial production. The synthesized octahedron has diameter up to hundreds of nanometers, rich active sites during reaction and large specific surface area. Secondly, the cost of the raw materials of the experiment is low, and the experiment is convenient and easy to obtain. Finally, the octahedral solid catalyst prepared in the whole experimental process is convenient to use and beneficial to recovery, does not cause secondary pollution, and can be applied to the fields of photocatalytic hydrogen production, gas adsorption and the like.
Description
Technical Field
The invention relates to the technical field of MOF materials, in particular to a preparation method of an octahedral zirconium-based MOF material by adopting anodic oxidation in-situ growth.
Background
With the growing world population and the rapid development of the modern agricultural industry, environmental issues are becoming a focus of scientific and political attention. The treatment process of organic pollution is complex, difficult and long in time. Organic pollutants such as alkanes, alkenes, aromatics, etc. have received much attention for their persistence and toxicity. It is usually removed by various treatment methods such as electrolysis, adsorption, advanced oxidation, etc. In recent years, photocatalysis has been considered as a promising method for treating water pollution because of its low cost and high catalytic efficiency. The combination of photocatalysis with other technologies (fenton, biocatalysis, etc.) has become a research hotspot in the field of wastewater treatment. Recent advances in the field of nanotechnology have generated great interest in exploiting the uniqueness of nanomaterials for pollutant treatment and environmental remediation. The nano material has large surface area and unique optical and electrical properties, and can be used as an excellent sensor, an adsorbate and a catalyst. The photocatalytic oxidation of organic matter with nanometer material is one new kind of water treating technology, and the technology has the outstanding advantages of high efficiency, low power consumption, mild reaction condition, wide application range, etc.
The Metal Organic Framework (MOF) material is a porous crystal material formed by coordination self-assembly of metal ions or metal clusters and organic ligands, and generally has good application prospects in aspects of gas separation, luminescence, magnetism, biosensing and the like. The UiO-66 is a three-dimensional porous MOF material which is constructed by taking Zr (IV) as a metal center and terephthalic acid, oxygen atoms in Zr (IV) and carboxyl have stronger acting force, and the UiO-66 has good acid stability and water stability. At present, the synthesis of the UiO-66 material mainly adopts a solvothermal synthesis method, an ultrasonic method and a microwave method, the methods are long in time consumption, and the synthesized material is difficult to recycle. Therefore, the UiO-66 material is grown in situ in the anode and the cathode by an electrochemical method and taking a zirconium sheet as a substrate through an anodic oxidation method.
Disclosure of Invention
The invention aims to solve the problems that: the method for preparing the octahedral zirconium-based MOF material by adopting anodic oxidation in-situ growth is provided, and the prepared octahedral structure UiO-66 material has the advantages of effectively increased specific surface area, controllable appearance and size, less impurities and stable performance.
The technical scheme provided by the invention for solving the problems is as follows: a method for preparing an octahedral zirconium-based MOF material for in-situ growth by anodic oxidation, the method comprising the steps of,
cutting the purchased zirconium sheets into rectangles, respectively ultrasonically cleaning the cut zirconium sheets in acetone, ethanol solution and deionized water for 30min, removing surface impurities, and then drying the zirconium sheets by using cold air of a blower to obtain a substrate material;
step two, adding a certain amount of terephthalic acid and H into 50ml of N' N dimethylformamide solution2Ultrasonically stirring O, nitric acid and glacial acetic acid until the mixture is uniformly mixed to obtain a mixed solution; putting the pretreated zirconium sheet as a cathode and an anode into electrolyte, and oxidizing for 1 hour at the voltage of 8V to obtain a material; repeatedly washing the obtained material with DMF, methanol and deionized water for three times;
step three, drying: and (3) putting the material obtained in the second step into a vacuum drying oven for drying treatment, adjusting the temperature to 80 ℃, keeping the temperature for 10 hours, and finally naturally cooling to room temperature to obtain the dried UiO-66 octahedron with better crystal form.
Compared with the prior art, the invention has the advantages that: the preparation method has the advantages of simple process and convenient operation; the prepared octahedral-structure UiO-66 material has the advantages of effectively increased specific surface area, controllable appearance and size, less impurities and stable performance. The UiO-66 material prepared by the method can be widely applied to the field of photocatalysis; the diameter of the UiO-66 octahedron prepared by the invention is hundreds of nanometers, the structure can provide more active sites and adsorption sites for photocatalysis, and the intermediate gap can also reduce the diffusion resistance of reactant molecules and product molecules in the catalyst and improve the catalytic reaction performance.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is an SEM image of UiO-66 octahedra of an anode made according to the present invention;
FIG. 2 is an SEM image of UiO-66 octahedra of a cathode prepared according to the present invention;
FIG. 3 is a TEM image of a UiO-66 octahedron prepared by the present invention;
Detailed Description
The following detailed description of the embodiments of the present invention will be provided with reference to the accompanying drawings and examples, so that how to implement the embodiments of the present invention by using technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
The first method is an early preparation stage of the reaction, cutting the mixture into a fixed size of 1cm x 4cm to facilitate uniform growth of UiO-66, and respectively ultrasonically cleaning the mixture for 30min by using acetone, ethanol and deionized water so as to remove surface impurities. Finally, the clean pure substrate material is obtained by blowing the substrate material by cold air of a blower.
The method is a preparation method of the in-situ growth UiO-66 octahedral structure material, and is specifically carried out according to the following steps:
adding a certain amount of terephthalic acid, H2Adding nitric acid into 50ml N' N Dimethylformamide (DMF) solution to make terephthalic acid and H2And (3) ultrasonically stirring the mixture until the mixture is uniformly mixed to obtain a mixed solution, wherein the molar ratio of the O to the nitric acid is 1:4: 2. And adding a certain amount of glacial acetic acid to regulate the morphology. And (3) putting the pretreated zirconium sheet serving as a cathode and an anode into electrolyte, keeping the voltage at 8V, and oxidizing for 1 hour to obtain the UiO-66 octahedron with better appearance. The material was then washed repeatedly three times with DMF, methanol, deionized water.
And (3) drying the obtained material in a vacuum drying oven at 80 ℃ for 10h, and finally naturally cooling to room temperature to obtain the dried UiO-66 octahedron with better crystal form.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the independent claims are intended to be embraced therein.
Claims (1)
1. A preparation method of octahedral zirconium-based MOF materials by adopting anodic oxidation in-situ growth is characterized by comprising the following steps: the method comprises the following steps of,
cutting the purchased zirconium sheets into rectangles, respectively ultrasonically cleaning the cut zirconium sheets in acetone, ethanol solution and deionized water for 30min, removing surface impurities, and then drying the zirconium sheets by using cold air of a blower to obtain a substrate material;
step two, adding a certain amount of terephthalic acid and H into 50ml of N' N dimethylformamide solution2Ultrasonically stirring O, nitric acid and glacial acetic acid until the mixture is uniformly mixed to obtain a mixed solution; putting the pretreated zirconium sheet as a cathode and an anode into electrolyte, and oxidizing for 1 hour at the voltage of 8V to obtain a material; repeatedly washing the obtained material with DMF, methanol and deionized water for three times;
step three, drying: and (3) putting the material obtained in the second step into a vacuum drying oven for drying treatment, adjusting the temperature to 80 ℃, keeping the temperature for 10 hours, and finally naturally cooling to room temperature to obtain the dried UiO-66 octahedron with better crystal form.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023138283A1 (en) * | 2022-01-24 | 2023-07-27 | 中国科学院深圳先进技术研究院 | Environmentally friendly and rapid preparation method for metal-organic framework compound thin film plating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS535758A (en) * | 1976-07-06 | 1978-01-19 | Inoue Japax Res | Method of manufacturing electrolytic capacitor |
| CN101994144A (en) * | 2010-12-08 | 2011-03-30 | 西安优耐特容器制造有限公司 | Processing method for anodic oxidation of zirconium surface |
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2019
- 2019-12-11 CN CN201911264281.0A patent/CN110952125A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS535758A (en) * | 1976-07-06 | 1978-01-19 | Inoue Japax Res | Method of manufacturing electrolytic capacitor |
| CN101994144A (en) * | 2010-12-08 | 2011-03-30 | 西安优耐特容器制造有限公司 | Processing method for anodic oxidation of zirconium surface |
Non-Patent Citations (1)
| Title |
|---|
| IVO STASSEN ET AL: "Electrochemical Film Deposition of the Zirconium Metal−Organic Framework UiO-66 and Application in a Miniaturized Sorbent Trap", 《CHEM. MATER.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023138283A1 (en) * | 2022-01-24 | 2023-07-27 | 中国科学院深圳先进技术研究院 | Environmentally friendly and rapid preparation method for metal-organic framework compound thin film plating |
| CN116516433A (en) * | 2022-01-24 | 2023-08-01 | 中国科学院深圳先进技术研究院 | Green rapid preparation method of metal organic framework compound film coating |
| CN116516433B (en) * | 2022-01-24 | 2024-04-26 | 中国科学院深圳先进技术研究院 | Green rapid preparation method of metal organic framework compound film coating |
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