CN111471189A - Three-dimensional frame material constructed by connecting molybdenum disulfide through two-connection ligand and preparation method - Google Patents
Three-dimensional frame material constructed by connecting molybdenum disulfide through two-connection ligand and preparation method Download PDFInfo
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Abstract
The invention discloses a three-dimensional frame material constructed by connecting molybdenum disulfide with a secondary connecting ligand and a preparation method thereof, belonging to the field of material preparation. The molybdenum disulfide layers are connected through Van der Waals force and are difficult to pull apart, in the preparation method process, solvent molecules N 'N-dimethylacetamide is firstly inserted between the layers, the distance between the layers is increased preliminarily, the resistance of an organic ligand inserted between the layers is reduced, and then the solvent molecules N' N-dimethylacetamide is replaced by ligands p-phenylenediamine and biphenyldiamine through a replacement method to form an ordered three-dimensional structure. The three-dimensional framework structure shows excellent electrocatalytic performance when used as an electrode material for electrocatalytic hydrogen evolution. The material synthesis method is simple and easy to implement, green and environment-friendly, and has universality. The three-dimensional frame structure material obtained by the method can simultaneously have the performances of a two-dimensional material in the aspects of light, electricity, sound and the like, and also has the performances of a three-dimensional material in the aspects of a net structure and the like.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a three-dimensional frame material constructed by connecting molybdenum disulfide with a secondary connecting ligand and a preparation method thereof.
Background
In the past decades, the construction of metal-organic framework structures by coordination bonds linking inorganic clusters to organic molecules has been an important development in the field of chemistry. The introduction of organic molecules creates enough space to interact precisely with guest molecules and maximize exposure of functional units. Another key to the metal-organic framework structureThe assembly is a two-level construction unit for controlling topology, the two-level construction unit is usually zero-dimensional or one-dimensional, the two-dimensional construction unit is very rare, in recent years, scientists have made some progress on the research of two-dimensional layered metal organic framework materials, but the performances of the two-dimensional construction unit in the aspects of electricity, magnetism and optics cannot be mentioned with the latest two-dimensional inorganic materials, the connection of a two-dimensional semiconductor and an organic molecule can combine the inherent physical properties and the structural advantages of a network structure, at present, a large number of researches on constructing a three-dimensional framework structure by using graphene or hydrotalcite as a construction unit are made, for example, in 2010, yildimum topic group studies on the construction of a graphene framework material, since the surface of graphene contains abundant hydroxide functional groups, dehydration condensation is easy to carry out with hydroxyl groups on boric acid, the experiment synthesizes a three-dimensional framework material by using graphene as a construction unit by dehydrating graphene and p-diboronic acid under the hydrothermal condition of 80 ℃, the three-dimensional framework material modified by adjusting the proportions of graphene and p-diboronic acid (Jagreen and boron peroxide, calcium phosphate]Inserted between ZnAl-L DH and MgAl-L DH layers and the interlayer spacing was enlarged to 1.51nm (SCD-ZnAl-L DH) and 1.61nm (SCD-MgAl-L DH) (Xue X Y, Gu Q Y, Pan G H, L iang J, Huang G L, Sun G B, Ma S L and Yang XJ. organic chemistry.2014,53,1521-1,BD2,BD3Inserting the graphene oxide layers to prepare a series of intercalation products rGO-BD with adjustable and controllable pore sizes1，rGO-BD2,rGO-BD3(Lee K,Yoon Y,Cho Y H,Sae Mi Lee S M,Shin Y H,Lee H Land Lee H Y.ACS Nano.,2016,10,6799-6807)。
Due to the two-dimensional semiconductor material MoS2The interlayer has strong acting force and is difficult to strip and intercalate, so the research on constructing an ordered three-dimensional frame structure by connecting molybdenum disulfide with organic molecules is not available at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the problem that the two-linking ligand with different lengths, p-phenylenediamine and biphenyldiamine are inserted between layers of semiconductor material molybdenum disulfide, thereby constructing an ordered three-dimensional framework structure material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides an ordered three-dimensional framework material constructed by connecting molybdenum disulfide with a secondary connecting ligand, which is characterized in that: the ordered three-dimensional framework material comprises PPDA-MoS2And BPDA-MoS2(ii) a The ordered three-dimensional framework material is prepared by a method of constructing an ordered three-dimensional structure by connecting a two-connection ligand and a two-dimensional semiconductor material through a coordination bond; the secondary connecting ligand comprises p-phenylenediamine (PPDA) and Biphenyldiamine (BPDA); the two-dimensional semiconductor material is molybdenum disulfide (MoS)2。
In a second aspect, the present invention provides a method for preparing the ordered three-dimensional framework material constructed by connecting the molybdenum disulfide with the two connecting ligands, which is characterized in that: the method comprises the following steps:
(1) 352mg (NH)4)6Mo7O24·4H2O，960mg Na2S·9H2O，10mLH2O, DMA of 1m L and N of 2m L2H4·H2O is put into a Teflon-liner high-pressure reaction kettle with the thickness of 25m L after being stirred evenly, heated for 24 hours at the temperature of 230 ℃, taken out of the reaction kettle, cooled and collected at the bottom of the container as black crystals DMA-MoS2Washing the synthesized sample with deionized water and ethanol for three times respectively, and then activating with supercritical carbon dioxide;
(2) 30mg PPDA and 90mg DMA-MoS2Grinding in a glove box filled with argon to obtain a fine mixture, sealing the mixture in a Pyrex tube, and heating at 120 deg.C for 24 hr, by meltingInfiltration of PPDA into DMA-MoS by melt diffusion2To produce PPDA-MoS2(ii) a Cooling to room temperature, washing the primary product with solvent for several times until the color of the washing solution is transparent, and obtaining pure PPDA-MoS2A product; alternatively, the first and second electrodes may be,
30mg of BPDA was mixed with 90mg of DMA-MoS2Grinding in a glove box filled with argon to obtain a fine mixture, sealing the mixture in a Pyrex tube, heating at 120 deg.C for 24 hours, and infiltrating BPDA into DMA-MoS by melt diffusion2To produce BPDA-MoS2(ii) a Cooling to room temperature, washing the primary product with solvent for several times until the color of the washing solution is transparent, and obtaining pure BPDA-MoS2And (3) obtaining the product.
Preferably, the activation in step (1) is carried out by first placing the ethanol-containing sample in a sample chamber, then completely exchanging with supercritical carbon dioxide, heating the sample chamber filled with carbon dioxide to 40 ℃ after the exchange, keeping the sample chamber in a carbon dioxide state for 1h, and then slowly releasing the carbon dioxide to obtain a dried sample.
Further, repeatedly washing the primary product cooled to room temperature in the step (2) by using an ethanol reagent, dissolving out unreacted ligand PPDA or BPDA until the washing liquid is a colorless transparent liquid, and obtaining pure PPDA-MoS2Or BPDA-MoS2And (3) obtaining the product.
Further, PPDA and DMA-MoS in the step (2)2Mixture of (A), BPDA and DMA-MoS2The mixture of (a) is mixed and ground in a glove box to sufficiently isolate air and oxygen and prevent the production of by-products.
According to the invention, solvent molecules N, N' -Dimethylacetamide (DMA) are firstly inserted between layers of molybdenum disulfide, the interlayer spacing is initially increased, the barrier of two connecting ligands inserted between the layers is reduced, then a replacement method is utilized, the solvent molecules between the layers are replaced by PPDA and BPDA, PPDA and BPDA are connected with molybdenum disulfide through coordination bonds, and an ordered three-dimensional framework structure material is constructed.
Drawings
FIG. 1: the structure schematic diagram of the three-dimensional frame structure material obtained in the embodiment 1 of the invention;
FIG. 2: a schematic structural diagram of the three-dimensional frame structural material obtained in embodiment 2 of the present invention;
FIG. 3: a scanning electron microscope image of the three-dimensional frame structure material obtained in embodiment 1 of the present invention;
FIG. 4: a scanning electron microscope image of the three-dimensional frame structure material obtained in embodiment 2 of the present invention;
FIG. 5: the X-ray powder diffraction pattern of the three-dimensional frame structure material obtained in the embodiment 1 of the invention; (the results of the figure demonstrate the success of the synthesis of the novel materials)
FIG. 6: the X-ray powder diffraction pattern of the three-dimensional frame structure material obtained in the embodiment 2 of the invention; (the results of the figure demonstrate the success of the synthesis of the novel materials)
FIG. 7: a transmission electron microscope image of the three-dimensional frame structure material obtained in example 1 of the present invention; (the interlayer spacing increases from 0.62nm to 1.28nm after insertion of the organic ligand)
FIG. 8: a transmission electron microscope image of the three-dimensional frame structure material obtained in example 2 of the present invention; (the interlayer spacing increases from 0.62nm to 1.61nm after insertion of the organic ligand)
FIG. 9: the method of the invention is a schematic flow chart.
Detailed Description
The invention will be further illustrated with reference to the attached drawings and specific examples, which are intended to facilitate a better understanding of the contents of the invention, but these specific embodiments do not in any way limit the scope of the invention.
Example 1
p-Phenylenediamine-MoS2(abbreviated as PPDA-MoS)2) The synthesis preparation comprises the following specific steps: 352mg of (NH)4)6Mo7O24·4H2O, 960mg of Na2S·9H2O, H of 10m L2O, DMA of 1m L and N of 2m L2H4·H2Placing O into a Teflon-liner high-pressure reaction kettle with the thickness of 25m L, uniformly stirring, heating at 230 ℃ for 24 hours, taking out the reaction kettle, cooling, and collecting black crystals DMA-MoS at the bottom of a container2The freshly synthesized samples were washed three times with deionized water and ethanol eachAnd then activated with supercritical carbon dioxide.
30mg of p-phenylenediamine and 90mg of DMA-MoS2Ground together to give a fine mixture in a glove box filled with argon to prevent the activated sample from absorbing water. The mixture was sealed in a Pyrex tube and heated at 120 ℃ for 24 hours, and p-phenylenediamine (90mg) was infiltrated into DMA-MoS by melt diffusion2To produce PPDA-MoS2. Cooling to room temperature, washing the product with ethanol for several times until the color of the washing solution becomes transparent to obtain pure PPDA-MOS2And (3) obtaining the product.
Example 2
Biphenyl diamine-MoS2(abbreviated as BPDA-MoS)2) The synthesis preparation comprises the following specific steps:
352mg of (NH)4)6Mo7O24·4H2O, 960mg of Na2S·9H2O, H of 10m L2O, DMA of 1m L and N of 2m L2H4·H2Placing O into a Teflon-liner high-pressure reaction kettle with the thickness of 25m L, uniformly stirring, heating at 230 ℃ for 24 hours, taking out the reaction kettle, cooling, and collecting black crystals DMA-MoS at the bottom of a container2The as-synthesized samples were washed three times with deionized water and ethanol, respectively, and then activated with supercritical carbon dioxide.
30mg of biphenyldiamine and 90mg of DMA-MoS2Ground together to give a fine mixture in a glove box filled with argon to prevent the activated sample from absorbing water. The mixture was sealed in a Pyrex tube and heated at 120 ℃ for 24 hours, and biphenyldiamine (90mg) was infiltrated into DMA-MoS by a melt diffusion method2To produce BPDA-MoS2. Cooling to room temperature, washing the product with ethanol for several times until the color of the washing solution becomes transparent, and obtaining pure BPDA-MoS2And (3) obtaining the product.
Claims (6)
1. The ordered three-dimensional frame material constructed by connecting molybdenum disulfide with two connecting ligands is characterized in that: the ordered three-dimensional framework material comprises PPDA-MoS2And BPDA-MoS2(ii) a The above-mentionedThe ordered three-dimensional framework material is prepared by a method of constructing an ordered three-dimensional structure by connecting a two-connection ligand and a two-dimensional semiconductor material through a coordination bond; the secondary connecting ligand comprises p-phenylenediamine (PPDA) and Biphenyldiamine (BPDA); the two-dimensional semiconductor material is molybdenum disulfide (MoS)2。
2. A method of making an ordered three-dimensional framework material constructed from a bis-linked ligand linked molybdenum disulfide as defined in claim 1, comprising: the method comprises the following steps:
(1) 352mg (NH)4)6Mo7O24·4H2O，960mg Na2S·9H2O，10mLH2O, DMA of 1m L and N of 2m L2H4·H2O is put into a Teflon-liner high-pressure reaction kettle with the thickness of 25m L after being stirred evenly, heated for 24 hours at the temperature of 230 ℃, taken out of the reaction kettle, cooled and collected at the bottom of the container as black crystals DMA-MoS2Washing the synthesized sample with deionized water and ethanol for three times respectively, and then activating with supercritical carbon dioxide;
(2) 30mg PPDA and 90mg DMA-MoS2Grinding in a glove box filled with argon to obtain a fine mixture, sealing the mixture in a Pyrex tube, heating at 120 deg.C for 24 hr, and infiltrating PPDA into DMA-MoS by melt diffusion2To produce PPDA-MoS2(ii) a Cooling to room temperature, washing the primary product with solvent for several times until the color of the washing solution is transparent, and obtaining pure PPDA-MoS2A product; alternatively, the first and second electrodes may be,
30mg of BPDA was mixed with 90mg of DMA-MoS2Grinding in a glove box filled with argon to obtain a fine mixture, sealing the mixture in a Pyrex tube, heating at 120 deg.C for 24 hours, and infiltrating BPDA into DMA-MoS by melt diffusion2To produce BPDA-MoS2(ii) a Cooling to room temperature, washing the primary product with solvent for several times until the color of the washing solution is transparent, and obtaining pure BPDA-MoS2And (3) obtaining the product.
3. The method for preparing the ordered three-dimensional framework material constructed by connecting the two-linking ligand with the molybdenum disulfide as claimed in claim 2, wherein: in the activation in the step (1), firstly, the ethanol-containing sample is placed in a sample chamber, then the ethanol-containing sample is completely exchanged with supercritical carbon dioxide, after the exchange, the sample chamber filled with carbon dioxide is heated to 40 ℃ and is kept in a carbon dioxide state for 1h, and then the carbon dioxide is slowly released, so that a dry sample can be obtained.
4. The method for preparing the ordered three-dimensional framework material constructed by connecting the double-connecting ligand with the molybdenum disulfide as claimed in claim 2 or 3, wherein: repeatedly cleaning the primary product cooled to room temperature in the step (2) by using an ethanol reagent, dissolving out unreacted ligand PPDA or BPDA until the washing liquid is colorless transparent liquid, and obtaining pure PPDA-MoS2Or BPDA-MoS2And (3) obtaining the product.
5. The method for preparing the ordered three-dimensional framework material constructed by connecting the double-connecting ligand with the molybdenum disulfide as claimed in claim 2 or 3, wherein: PPDA and DMA-MoS in the step (2)2Mixture of (A), BPDA and DMA-MoS2The mixture of (a) is mixed and ground in a glove box to sufficiently isolate air and oxygen and prevent the production of by-products.
6. The method for preparing the ordered three-dimensional framework material constructed by connecting the two-linking ligand with the molybdenum disulfide as claimed in claim 4, wherein: PPDA and DMA-MoS in the step (2)2Mixture of (A), BPDA and DMA-MoS2The mixture of (a) is mixed and ground in a glove box to sufficiently isolate air and oxygen and prevent the production of by-products.
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| US20190039028A1 (en) * | 2017-07-24 | 2019-02-07 | Northeastern University | Porous Membranes Comprising Nanosheets and Fabrication Thereof |
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| CN105797753A (en) * | 2016-04-19 | 2016-07-27 | 武汉大学 | MoS2/TiO2 two-dimensional composite nanometer photocatalyst and preparation method and application thereof |
| CN106477631A (en) * | 2016-10-11 | 2017-03-08 | 郑州大学 | A kind of method realizing molybdenum bisuphide 2H to 1T phase in version |
| KR20180097166A (en) * | 2017-02-22 | 2018-08-30 | 가천대학교 산학협력단 | Transtion metaldichalcogenide-carbon nanocomposites and method for manufacturing the same |
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