CN111471189B - 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 component of the metal organic framework structure is a two-dimensional building unit for topology control, which is usually zero-dimensional or one-dimensional, and the two-dimensional building unit is very rare, and in recent years, although some progress has been made in the research of two-dimensional layered metal organic framework materials, scientists still cannot compare the performances of the two-dimensional layered metal organic framework structure with the performances of the latest two-dimensional inorganic material. The combination of two-dimensional semiconductors with organic molecules combines these inherent physical properties with the structural advantages of networks. At present, a great deal of researches for constructing a three-dimensional framework structure by using graphene or hydrotalcite as a construction unit are carried out, for example: in 2010, the Yildirim T topic group studied about grapheneIn the construction of the framework material, the surface of graphene contains abundant hydroxyl functional groups, and the graphene and the hydroxyl groups on boric acid are easy to perform dehydration condensation, so that the experiment synthesizes the three-dimensional framework material with the graphene as a construction unit by dehydrating the graphene and the p-phenylboronic acid under the hydrothermal condition of 80 ℃, and the three-dimensional framework materials with different intercalation ratios are obtained by adjusting the ratio of the graphene to the p-phenylboronic acid (W.Burress J, Gadipelli S, Ford J, M.Simmons J, Zhou W and Yildirim T.Angew.chem.int.Ed.,2010,49, 8902-8904). In 2012, the Loh KP group modified pyridine group on the surface of graphene oxide, and reacted with iron-containing porphyrin to obtain a metal-organic framework material with high porosity (Jahan M, Ba Q L and Loh K p.j.am.chem.soc.,2012,134, 6707-. In 2014, the Xiaojing Yang project group cyclodextrin [ (beta-cyclodextrin) SCD]Intercalated between ZnAl-LDH and MgAl-LDH layers, and the interlayer spacing is expanded to 1.51nm (SCD-ZnAl-LDH) and 1.61nm (SCD-MgAl-LDH), respectively (Xue X Y, Gu Q Y, Pan G H, Liang J, Huang G L, Sun G B, Ma S L and Yang X J. organic chemistry.2014,53, 1521-. In 2016, the Hyoyoung Lee topic group will use organic ligands BD of varying lengths1,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 L and 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, theThe invention provides an ordered three-dimensional frame 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, 1mL of DMA and 2mL of N2H4·H2Stirring O uniformly, putting the mixture into a 25mL Teflon-liner high-pressure reaction kettle, heating the mixture for 24 hours at 230 ℃, taking the reaction kettle out, cooling the reaction kettle, and collecting black crystals DMA-MoS at the bottom of a container2Washing 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 the productPure 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, 10mL of H2O, 1mL of DMA and 2mL of N2H4·H2Placing O into a Teflon-liner high-pressure reaction kettle of 25mL, uniformly stirring, heating at 230 ℃ for 24 hours, taking out the reaction kettle, cooling, and collecting black crystals DMA-MoS at the bottom of the container2The as-synthesized samples were washed three times with deionized water and ethanol, respectively, and 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, 10mL of H2O, 1mL of DMA and 2mL of N2H4·H2Placing O into a Teflon-liner high-pressure reaction kettle of 25mL, uniformly stirring, heating at 230 ℃ for 24 hours, taking out the reaction kettle, cooling, and collecting black crystals DMA-MoS at the bottom of the 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 (5)
1. A preparation method of an ordered three-dimensional frame material constructed by connecting a two-connection ligand with molybdenum disulfide is characterized by comprising the following steps of: the ordered three-dimensional framework material is PPDA-MoS2Or 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 is p-phenylenediamine (PPDA) or Biphenyldiamine (BPDA); the two-dimensional semiconductor material is molybdenum disulfide (MoS)2(ii) a The method comprises the following steps:
(1) 352mg (NH)4)6Mo7O24·4H2O，960mg Na2S·9H2O，10mLH2O, 1mL of DMA which is N, N' -dimethylacetamide, and 2mL of N2H4·H2O is put into a Teflon-liner with the volume of 25mL after being stirred evenly and is subjected to high-pressure reactionHeating at 230 deg.C for 24 hr, taking out, cooling, and collecting black crystal DMA-MoS at the bottom of the container2Washing 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.
2. The method for preparing the ordered three-dimensional framework material constructed by connecting the two-connecting ligand with the molybdenum disulfide as claimed in claim 1, 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.
3. 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 1 or 2, 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.
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 1 or 2, 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.
5. 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 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.
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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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