CN110229153B - Intercalation molecule, preparation method thereof and two-dimensional nanocomposite - Google Patents

Intercalation molecule, preparation method thereof and two-dimensional nanocomposite Download PDF

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CN110229153B
CN110229153B CN201910548012.0A CN201910548012A CN110229153B CN 110229153 B CN110229153 B CN 110229153B CN 201910548012 A CN201910548012 A CN 201910548012A CN 110229153 B CN110229153 B CN 110229153B
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李小康
蒋阳琴
李亿保
苑举君
彭光怀
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Gannan Normal University
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Abstract

The invention belongs to the technical field of two-dimensional nano materials, and particularly relates to an intercalation molecule, a preparation method thereof and a two-dimensional nano composite material. The preparation method comprises the steps of firstly grafting amino acid molecules on perylene tetracarboxylic dianhydride molecules, improving the solubility of the perylene tetracarboxylic dianhydride molecules, and obtaining intercalation molecules; the two-dimensional nanocomposite prepared by the method has a uniform lamellar structure, and is regular in structure, free of agglomeration and good in dispersibility.

Description

Intercalation molecule, preparation method thereof and two-dimensional nanocomposite
Technical Field
The invention relates to the technical field of two-dimensional nano materials, in particular to an intercalation molecule, a preparation method thereof and a two-dimensional nano composite material.
Background
The two-dimensional nanocomposite has unique electrical properties and huge specific surface area, shows wide application potential in the aspects of catalysis, energy storage, photoelectric conversion, biology and the like, and the development and design of the two-dimensional nanocomposite with novel functions become a hotspot of research more and more. The composite material generally consists of a continuous phase matrix and a dispersed phase reinforcing material, and all components can make up for each other' to show new properties which a single material does not have. Particularly, in the nano composite material, the interaction of each component is more prominent, the performance of the material is outstanding, and the application potential is huge.
Graphene oxide, molybdenum disulfide and graphite phase (g-C) 3 N 4 ) Graphene-like materials such as graphene and the like are widely applied to preparation of two-dimensional nano materials and show excellent properties and application prospects, but due to the structural characteristics of the graphene-like materials, products after successful stripping are easy to aggregate, and the electrical properties of the products are influenced. Therefore, the selection of the proper dispersant intercalation graphene-like material is important for developing the potential performance of the two-dimensional nanocomposite materialThe significance of the study.
Disclosure of Invention
The invention aims to provide an intercalation molecule, and the two-dimensional nanocomposite prepared by intercalation of the intercalation molecule has a lamellar structure, regular structure, no agglomeration and good dispersibility.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an intercalation molecule, which has a structure shown in a formula I:
Figure BDA0002104582750000011
the invention provides a preparation method of an intercalation molecule in the technical scheme, which comprises the following steps:
mixing 3,4,9, 10-perylene tetracarboxylic dianhydride, amino acid and imidazole, and grafting to obtain an intercalation molecule.
Preferably, the amino acid is L-alanine.
Preferably, the molar ratio of the 3,4,9, 10-perylene tetracarboxylic dianhydride to the amino acid is 1: 2-3.
Preferably, the using amount ratio of the 3,4,9, 10-perylene tetracarboxylic dianhydride to the imidazole is 1mmol (2-3) g.
Preferably, the grafting temperature is 120-130 ℃, and the grafting time is 5-7 h.
The invention provides a two-dimensional nano composite material, and a preparation method thereof comprises the following steps:
and mixing the intercalation molecules with a two-dimensional lamellar material, and carrying out ultrasonic treatment to obtain the two-dimensional nanocomposite.
Preferably, the two-dimensional sheet material is graphene oxide, molybdenum disulfide or graphite-phase carbon nitride.
Preferably, the mass ratio of the intercalation molecules to the two-dimensional lamellar material is 1: 1.
Preferably, the ultrasonic treatment time is 40-50 h, and the ultrasonic treatment power is 1000W.
The invention provides an intercalation molecule and a preparation method thereof, wherein the preparation method comprises the steps of firstly grafting amino acid molecules on perylene tetracarboxylic dianhydride molecules to obtain intercalation molecules; the two-dimensional nanocomposite prepared by the method has a uniform lamellar structure, and is regular in structure, free of agglomeration and good in dispersibility.
Drawings
FIG. 1 is an AFM image of a Go/NAPD two-dimensional nanocomposite material of example 1;
FIG. 2 is a TEM image of Go, NAPD and Go/NAPD two-dimensional nanocomposites of example 1;
FIG. 3 is an XRD pattern of Go, NAPD and Go/NAPD two-dimensional nanocomposite material of example 1;
FIG. 4 is a graph of the infrared spectra of the Go, NAPD and Go/NAPD two-dimensional nanocomposites of example 1;
FIG. 5 is a linear scanning polarization curve of Go, NAPD and Go/NAPD in example 1;
FIG. 6 shows MoS in example 2 2 AFM map of/NAPD two-dimensional nanocomposite;
FIG. 7 shows MoS in example 2 2 NAPD and MoS 2 TEM image of/NAPD two-dimensional nanocomposite material;
FIG. 8 shows MoS in example 2 2 NAPD and MoS 2 XRD pattern of/NAPD two-dimensional nanocomposite;
FIG. 9 shows MoS in example 2 2 NAPD and MoS 2 (iii) an infrared spectrogram of/NAPD two-dimensional nanocomposites;
FIG. 10 shows MoS in example 2 2 NAPD and MoS 2 Linear scan polarization curve of/NAPD;
FIG. 11 shows g-C in example 3 3 N 4 AFM map of/NAPD two-dimensional nanocomposite;
FIG. 12 shows g-C in example 3 3 N 4 NAPD and g-C 3 N 4 TEM image of/NAPD two-dimensional nanocomposite material;
FIG. 13 shows g-C in example 3 3 N 4 NAPD and g-C 3 N 4 XRD of/NAPD two-dimensional nanocompositesDrawing;
FIG. 14 shows g-C in example 3 3 N 4 NAPD and g-C 3 N 4 (iii) an infrared spectrogram of/NAPD two-dimensional nanocomposites;
FIG. 15 shows g-C in example 3 3 N 4 /, NAPD and g-C 3 N 4 Linear scan polarization curve of/NAPD.
Detailed Description
The invention provides an intercalation molecule, which has a structure shown in a formula I:
Figure 1
the invention provides a preparation method of intercalation molecules in the technical scheme, which comprises the following steps:
mixing 3,4,9, 10-perylene tetracarboxylic dianhydride, amino acid and imidazole, and grafting to obtain an intercalation molecule.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The invention mixes 3,4,9, 10-perylene tetracarboxylic dianhydride, amino acid and imidazole for grafting to obtain intercalation molecules. In the present invention, the amino acid is preferably L-alanine. In the present invention, the molar ratio of the 3,4,9, 10-perylenetetracarboxylic dianhydride to the amino acid is preferably 1: 2. In the invention, the using amount ratio of the 3,4,9, 10-perylenetetracarboxylic dianhydride to the imidazole is preferably 1mmol (2-3) g, and more preferably 1mmol:2 g. The present invention utilizes imidazole as a solvent. The mixing process is not particularly limited in the present invention, and the raw materials can be uniformly mixed by using a method known to those skilled in the art.
In the present invention, it is preferable to further include, before the grafting: the system obtained by mixing 3,4,9, 10-perylenetetracarboxylic dianhydride, amino acid and imidazole is melted. In the invention, the melting temperature is preferably 90-120 ℃, more preferably 100-110 ℃, and the melting time is preferably 1-3 h, more preferably 2 h. The melting is preferably carried out in a nitrogen protective atmosphere, and the oxygen-free environment is ensured by the nitrogen atmosphere.
After the melting is finished, the temperature of the obtained system is preferably raised to 120-130 ℃ for grafting. In the invention, the grafting time is preferably 4-7 h, and more preferably 5-6 h. In the present invention, the rate of temperature rise is preferably 20 ℃/min.
After the grafting is finished, the invention preferably cools a product system obtained by grafting to room temperature, then adds absolute ethyl alcohol to remove redundant solvent, and carries out reflux after the temperature is reduced to 90 ℃; then cooling and standing the system obtained by refluxing in sequence; and sequentially carrying out first suction filtration, dissolution, acidification, second suction filtration, ultrasound treatment and drying on the solid obtained by standing to obtain the intercalated molecule. In the invention, the refluxing time is preferably 1-3 h, and more preferably 2 h. The specific conditions for cooling and standing are not particularly limited in the present invention, and those well known to those skilled in the art may be selected. In the present invention, the first suction filtration is preferably vacuum filtration, and the conditions for the vacuum filtration are not particularly limited, and those well known to those skilled in the art may be selected. In the present invention, the solid obtained by the first suction filtration is preferably dissolved in distilled water, and the amount of the distilled water used in the present invention is not particularly limited, and the solid obtained by the first suction filtration can be dissolved. The invention preferably uses hydrochloric acid for acidification, the concentration of the hydrochloric acid is preferably 1mol/L, and the invention is favorable for obtaining product molecules through acidification. In the invention, the solid obtained by acidification is preferably subjected to second suction filtration, and the mode of the second suction filtration is preferably reduced pressure suction filtration. The solid obtained by the second suction filtration is preferably added with distilled water for ultrasonic treatment (H removal) + ) (ii) a The power of the ultrasonic wave is preferably 1000W, and the time of the ultrasonic wave is preferably 1-2 h. In the present invention, the drying method is preferably suction filtration drying.
In the present invention, the synthesis route of the intercalation molecule is as follows:
Figure BDA0002104582750000041
wherein R is CH 3 The name of the intercalation molecule is N, N' -dipropionic acid-3, 4,9, 10-perylenetetracarboxylic acid diimide (NAPD).
The invention provides a two-dimensional nano composite material, and a preparation method thereof comprises the following steps:
and mixing the intercalation molecules with a two-dimensional lamellar material, and carrying out ultrasonic treatment to obtain the two-dimensional nanocomposite.
In the invention, the two-dimensional sheet material is preferably graphene oxide, molybdenum disulfide or graphite-phase carbon nitride; the source of the two-dimensional sheet material is not particularly limited in the present invention, and the two-dimensional sheet material from a source known to those skilled in the art or the two-dimensional sheet material prepared by a conventional preparation method in the art can be selected. In the present invention, the mass ratio of the intercalation molecules to the two-dimensional lamellar material is preferably 1: 1.
The present invention preferably performs the mixing at room temperature. In the present invention, the mixing is preferably performed by mixing the intercalation molecules with the two-dimensional lamellar material, then mixing the resulting mixture with deionized water, and then subjecting the resulting mixture to ultrasonic treatment. In the invention, the time of ultrasonic treatment is preferably 40-50 h, more preferably 42-48 h, and the power of ultrasonic treatment is preferably 1000W. In the ultrasonic process, intercalation molecules and the two-dimensional lamellar material are combined by virtue of pi-pi interaction and hydrogen bond interaction, so that the intercalation molecules are intercalated into the two-dimensional lamellar material.
After the ultrasonic treatment is finished, the invention preferably carries out centrifugation and drying on the dispersion liquid obtained by ultrasonic in sequence to obtain the two-dimensional nano composite material. The centrifugation method is not particularly limited in the present invention, and the centrifugation method may be selected from methods known to those skilled in the art. In the present invention, the drying temperature is preferably 60 ℃ and the drying time is preferably 24 hours.
The following examples are provided to illustrate the intercalation molecule, its preparation method and the two-dimensional nanocomposite material provided by the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding L-alanine and (2 mmo) into 50mL round bottoml), 3,4,9, 10-perylenetetracarboxylic dianhydride (1mmol) and 2g of imidazole are melted under the protection of nitrogen at the temperature of 90 ℃, and then the temperature is raised to 120 ℃ for grafting for 6 hours; cooling the system obtained by grafting to room temperature at room temperature, adding 25mL of absolute ethyl alcohol, and refluxing for 2h after the oil bath temperature is reduced to 90 ℃; closing the reaction, cooling the obtained system, and standing; carrying out vacuum filtration on the solid obtained by standing, transferring the solid obtained by vacuum filtration into a 250mL beaker, and adding distilled water for dissolving; then, acidifying the obtained dissolved substance by using 1mol/L hydrochloric acid, and filtering the solid obtained by acidification; transferring the solid obtained by suction filtration into a beaker, adding distilled water, performing ultrasonic treatment for 2 hours under the condition of 1000W, and performing suction filtration and drying on a system obtained by ultrasonic treatment; obtaining N, N' -dipropionic acid-3, 4,9, 10-perylenetetracarboxylic acid diimide intercalation molecule (NAPD, IR (KBr, cm) -1 ):1255.4,1401.6,1590.2, 1365.5,1436.5(-CH 3 ),1655.3,1696.7,1742.3(C＝O),2940.5(C-H),3443.3 (O-H)； 1 H NMR(DMSO,400MHz,ppm):8.01-8.03(d,8H),5.52-5.56(m,2H), 1.66-1.68(d,6H)；MALDI-TOF-MS:calcd for C 30 H 18 N 2 O 8 ,534.0.)；
70mL of concentrated H was taken 2 SO 4 Placing in 500mL beaker, stirring at 8 deg.C in ice bath for 30min while adding 3g graphite and 1.5g NaNO 3 9g of KMnO were added at 18 ℃ 4 Then reacting for 30min, transferring the obtained reaction solution to a 40 ℃ oil bath for reaction for 2h, then dropwise adding 138mL of deionized water by using a funnel, and transferring the obtained system to a 98 ℃ oil bath for reaction for 15min after the addition is finished; after the reaction is finished, cooling the obtained product system in water bath for 10min, taking out the obtained solid, adding 420mL of water, and adding H into the obtained mixed system 2 O 2 (30%) until the solution is bright yellow, standing and washing, washing the obtained precipitate for 2 times by using 10% HCl, then washing by using deionized water until the pH value of washing liquor is 6, drying the obtained washing product at 60 ℃, adding the obtained dried product into water, sequentially performing ultrasonic treatment and centrifugation, and then drying the supernatant at 60 ℃ to obtain graphene oxide Go;
and (3) placing 25mg of graphene oxide and 25mg of NAPD in a 100mL conical flask, dispersing the obtained mixture in 50mL deionized water at room temperature, placing the obtained solution in a numerical control ultrasonic cleaner for ultrasonic treatment for 48h under the condition of 1000W, centrifuging the obtained dispersion, taking the supernatant, and drying at 60 ℃ for 24h to obtain the Go/NAPD two-dimensional nanocomposite.
FIG. 1 is an AFM image of a Go/NAPD two-dimensional nanocomposite material of example 1; as can be seen from the figure, the method of the invention produces the Go/NAPD two-dimensional nanocomposite material with a lamellar structure and a regular structure, and the synthesized Go/NAPD nanocomposite material can be considered to be formed by compounding N, N' -dipropionic acid-3, 4,9, 10-perylenetetracarboxylic acid diimide on graphene oxide (with the thickness of 1.588nm and about 5 layers).
FIG. 2 is a TEM image of Go, NAPD and Go/NAPD two-dimensional nanocomposites of example 1; wherein a is a TEM image of Go, and the graphene oxide is in a lamellar structure and is tightly connected among layers; b is a TEM image of NAPD, and NAPD can be seen to be a substance with a blocky structure with uniform appearance and nonuniform size; c is an SEM photograph of Go/NAPD, and it can be clearly seen that the two-dimensional nanocomposite prepared in example 1 is a bulk structure in which lamellar structures are stacked. It can also be seen from the figure that the Go/NAPD two-dimensional nanocomposite material is completely different from graphene oxide and NAPD in structure, the Go/NAPD two-dimensional nanocomposite material is larger in volume, the thickness of the nanosheet is thickened, and the Go/NAPD nanosheet is compounded by Go and NAPD, so the thickness is increased.
FIG. 3 is an XRD pattern of the two-dimensional nanocomposites of Go, NAPD and Go/NAPD in example 1 with scan angles ranging from 10 to 70. As can be seen from the figure, the synthesized Go has a strong diffraction peak around 2 θ ═ 12 °, indicating that the synthesized substance has a good lamellar structure, and a group of weak diffraction peaks around 43 °. The synthesized NAPD showed strong diffraction peaks around 12.5 °, 17 °, 26.5 ° and 27 °. As can be seen from the figure, the prepared Go/NAPD two-dimensional nanocomposite has characteristic diffraction peaks of graphene oxide and NAPD, and the diffraction peak intensity is large, the peak is sharp, the half-peak width is small, but the position of the peak is slightly shifted, which indicates that NAPD can be successfully intercalated into graphene oxide, NAPD intercalated graphene oxide is formed, the Go/NAPD two-dimensional nanocomposite is good in crystallinity, and no miscellaneous peak exists, and the product purity is high.
FIG. 4 is a graph of the infrared spectra of the Go, NAPD and Go/NAPD two-dimensional nanocomposites of example 1. As can be seen from the figure, graphene oxide is 3450cm -1 The nearby absorption peak is wider and stronger and belongs to the stretching vibration peak of-OH; 1750cm -1 The absorption peak at (A) is a telescopic vibration peak of 1630cm, which is C ═ O in carbonyl and carboxyl groups in graphene oxide -1 Corresponding to the C-OH bending vibration peak of the Go, 1107cm -1 The absorption peak is the vibration peak of C-O-C, which indicates that the prepared graphene oxide has at least four functional groups. Perylene tetracarboxylic dianhydride-alanine is in 1350cm -1 ～1750cm -1 There are many characteristic absorption peaks, which are characteristic peaks of the naphthalene nucleus. The Go/NAPD two-dimensional nano material formed by NAPD intercalated graphene oxide has obvious Go and NAPD characteristic peaks, and the sizes and the positions of the peaks are shifted, so that the crystal structure of a raw material is changed by intercalation.
FIG. 5 is a linear scanning polarization curve of Go, NAPD and Go/NAPD in example 1; as can be seen from the figure, the lowest initial overpotential of graphene oxide is nearly-0.35 mV; NAPD is an organic matter, has a peak at-0.15 mV, and has an initial overpotential close to-0.36 mV; the initial overpotential of the synthesized Go/NAPD nanoplates was slightly smaller.
Example 2
Adding L-alanine, (2mmol), 3,4,9, 10-perylene tetracarboxylic dianhydride (1mmol) and 2g of imidazole into a 50mL round bottom, melting under the protection of nitrogen and at the temperature of 90 ℃, and then raising the temperature to 120 ℃ for grafting for 6 hours; cooling the system obtained by grafting to room temperature, adding 25mL of absolute ethyl alcohol, and refluxing for 2h after the oil bath temperature is reduced to 90 ℃; closing the reaction, cooling the obtained system, and standing; carrying out vacuum filtration on the solid obtained by standing, transferring the solid obtained by vacuum filtration into a 250mL beaker, and adding distilled water for dissolving; then, acidifying the obtained dissolved substance by using 1mol/L hydrochloric acid, and filtering the solid obtained by acidification; transferring the solid obtained by suction filtration into a beaker, adding distilled water, performing ultrasonic treatment for 2 hours under the condition of 1000W, and performing suction filtration and drying on a system obtained by ultrasonic treatment; obtaining N, N' -dipropionic acid-3, 4,9, 10-perylenetetracarboxylic acid diimide (NAPD) intercalation molecules;
25mg of molybdenum disulfide MoS is taken 2 And 25mg of NAPD in a 100mL Erlenmeyer flask, dispersing the obtained mixture in 50mL deionized water at room temperature, placing the obtained solution in a numerical control ultrasonic cleaner for ultrasonic treatment under the condition of 1000W for 48h, centrifuging the obtained dispersion, taking the supernatant, and drying at 60 ℃ for 24h to obtain MoS 2 NAPD two-dimensional nanocomposites.
FIG. 6 shows MoS in example 2 2 AFM map of/NAPD two-dimensional nanocomposite; it is evident from the figure that NAPD was successfully inserted into molybdenum disulfide, NAPD-intercalated molybdenum disulfide two-dimensional nanocomposite was prepared, and the synthesized MoS 2 the/NAPD composite nano material has a sheet-shaped layered structure (with the thickness of 1.819nm and about 2-3 layers), NAPD is compounded on molybdenum disulfide, and points on the sheet-shaped structure can be molybdenum disulfide or NAPD.
FIG. 7 shows MoS in example 2 2 NAPD and MoS 2 TEM image of/NAPD two-dimensional nanocomposite material; and a is a scanning electron microscope image of NAPD, which shows that NAPD is a substance with a block structure with uniform appearance and uneven size, and also shows that NAPD is a block structure formed by stacking sheet structures. b is pure MoS 2 In a scanning electron microscope image, MoS can be seen from the image 2 The nano-sheet is formed by stacking a lamellar structure into a three-dimensional material, and the nano-sheet can be obtained by ultrasonic stripping. c is MoS 2 SEM image of/NAPD two-dimensional nanocomposite from which the MoS produced can be clearly seen 2 the/NAPD two-dimensional nano composite material is a block structure formed by stacking sheet structures. Furthermore, compared to molybdenum disulfide and NAPD, MoS 2 the/NAPD two-dimensional nanocomposites are more bulky and thicker due to MoS 2 the/NAPD two-dimensional nano composite material is composed of MoS 2 And NAPD, the thickness is increased.
FIG. 8 shows MoS in example 2 2 NAPD and MoS 2 XRD pattern of/NAPD two-dimensional nanocomposite; the scanning angle is 10-70 degrees. As can be seen from the figure, MoS 2 The monomer is derived at 2 theta ═ 14.4 DEGThe emission peak is strong and the half-peak width is small, and the emission peak is MoS with a crystal face of (002) 2 Characteristic peak of (D), description of MoS 2 Very distinct lamellar structure with 2H-MoS 2 The matching degree of a standard card (JCPDS card number 65-0160) is extremely high, and the crystal faces corresponding to 33.6 degrees, 40 degrees and 49.8 degrees are respectively (100), (103) and (110). Furthermore, the MoS is intercalated by NAPD 2 Prepared MoS 2 The diffraction peak of the NAPD two-dimensional nanocomposite still has extremely high matching with a standard card number (JCPDS card number 65-0160) map, the diffraction peak is sharp, but the position of the peak is shifted, and a plurality of peaks are reduced, thereby indicating that NAPD is successfully inserted into MoS 2 In (1). MoS 2 the/NAPD two-dimensional nano composite material has characteristic diffraction peaks of NAPD and MoS 2 But the peak position is shifted due to insertion of the NAPD into the MoS 2 In (1), the MoS is destroyed 2 A crystal structure.
FIG. 9 shows MoS in example 2 2 NAPD and MoS 2 An infrared spectrum of the/NAPD two-dimensional nanocomposite; as can be seen from the figure, the molybdenum disulfide is at 3436cm -1 The nearby absorption peak is broad and strong, belonging to the stretching vibration peak of-OH, which is probably due to the sample containing water. In addition 1150cm -1 And 1370cm -1 A strong absorption peak appears nearby. NAPD at 1350cm -1 ～1750cm -1 There are many characteristic absorption peaks, which are characteristic peaks of naphthalene nucleus. MoS formed in NAPD intercalated molybdenum disulfide 2 Significant MoS in/NAPD two-dimensional nanocomposites 2 And NAPD characteristic peaks, with shifts in peak size and position due to intercalation changing the crystal structure of the starting material.
FIG. 10 shows MoS in example 2 2 NAPD and MoS 2 Linear scan polarization curve of NAPD; as can be seen from the figure, the lowest initial overpotential for molybdenum disulfide is approximately-0.39 mV; NAPD has a peak at-0.15 mV, and its initial overpotential is close to-0.36 mV; MoS 2 The initial overpotential of the/NAPD two-dimensional nanocomposite material is close to that of molybdenum disulfide.
Example 3
Adding L-alanine, (2mmol), 3,4,9, 10-perylenetetracarboxylic dianhydride (1mmol) and 2g of imidazole into a 50mL round bottom, melting under the protection of nitrogen and at the temperature of 90 ℃, and then raising the temperature to 120 ℃ for grafting for 6 hours; cooling the system obtained by grafting to room temperature, adding 25mL of absolute ethyl alcohol, and refluxing for 2h after the oil bath temperature is reduced to 90 ℃; closing the reaction, cooling the obtained system, and standing; carrying out vacuum filtration on the solid obtained by standing, transferring the solid obtained by vacuum filtration into a 250mL beaker, and adding distilled water for dissolving; then, acidifying the obtained dissolved substance by using 1mol/L hydrochloric acid, and filtering the solid obtained by acidification; transferring the solid obtained by suction filtration into a beaker, adding distilled water, performing ultrasonic treatment for 2 hours under the condition of 1000W, and performing suction filtration and drying on a system obtained by ultrasonic treatment; obtaining N, N' -dipropionic acid-3, 4,9, 10-perylenetetracarboxylic acid diimide (NAPD) intercalation molecules;
weighing 2g of melamine, placing the melamine in a ceramic crucible, then placing the crucible in a tube furnace, heating to 550 ℃ at a speed of 15 ℃/min, and carrying out heat preservation reaction for 2 hours; after the reaction is finished, naturally cooling the obtained product system to room temperature, and grinding the product system to powder to obtain graphite-phase carbon nitride g-C 3 N 4 ；
25mg of g-C are taken 3 N 4 And 25mg of NAPD in a 100mL conical flask, dispersing the obtained mixture in 50mL of deionized water at room temperature, placing the obtained solution in a numerical control ultrasonic cleaner for ultrasonic treatment under the condition of 1000W for 48h, centrifuging the obtained dispersion, taking the supernatant, and drying at 60 ℃ for 24h to obtain g-C 3 N 4 NAPD two-dimensional nanocomposites.
FIG. 11 shows g-C in example 3 3 N 4 AFM map of/NAPD two-dimensional nanocomposite; it is evident from the figure that NAPD is successfully inserted into g-C 3 N 4 In the preparation of NAPD intercalated g-C 3 N 4 Two-dimensional nanocomposite material, g-C 3 N 4 NAPD nanocomposites; furthermore, it can be clearly seen that there are many nanosheets (2.512 nm thick, about 7 layers) with many nanoparticles, perhaps g-C, on each nanosheet 3 N 4 NAPDs are compounded on the nano-chip or g-C is compounded on the NAPDs 3 N 4 Successfully prepare g-C 3 N 4 NAPD two-dimensional nanocomposites.
FIG. 12 shows g-C in example 3 3 N 4 NAPD and g-C 3 N 4 TEM image of/NAPD two-dimensional nanocomposite material; a is g-C 3 N 4 The scanning electron micrograph of (a) shows g-C 3 N 4 Is a lamellar structure, some lamellae have holes therein, which may be too thoroughly calcined during preparation. b is a scanning electron micrograph of NAPD, from which it can be seen that NAPD is a substance having a uniform morphology and a blocky structure of uneven size, and that NAPD is a blocky structure stacked from a lamellar structure. C is g-C 3 N 4 SEM image of/NAPD two-dimensional nanocomposite material, from which g-C can be clearly seen 3 N 4 the/NAPD two-dimensional nano composite material is a block structure formed by stacking a lamellar structure. Furthermore, it can be seen that g-C 3 N 4 NAPD two-dimensional nanocomposite material and g-C 3 N 4 Totally different from the structure of NAPD, g-C 3 N 4 NAPD two-dimensional nanocomposites are larger in volume, thicker in thickness, more tightly packed layer-to-layer, possibly with strong forces between layers, and g-C 3 N 4 the/NAPD nano-sheet is composed of g-C 3 N 4 And NAPD, the thickness is increased.
FIG. 13 shows g-C in example 3 3 N 4 NAPD and g-C 3 N 4 XRD pattern of/NAPD two-dimensional nanocomposite; the scanning angle is 10-70 degrees. As can be seen from the figure, g-C 3 N 4 The monomer has a strong diffraction peak near 2 theta (27.3 degrees) and a small half-value width, and is g-C having a crystal face of (002) 3 N 4 Characteristic peak of (A), indicating g-C produced 3 N 4 A significant layer structure with g-C 3 N 4 The standard card (JCPDS card number 50-1250) of (A) is consistent, and has a tiny diffraction peak near 13 degrees. Also, it can be seen from the figure that g-C is intercalated by NAPD 3 N 4 g-C prepared 3 N 4 g-C in structure of/NAPD two-dimensional nanomaterial 3 N 4 The diffraction peak is reduced, even around 13 DEGThe diffraction peak of (A) completely disappeared, indicating that NAPD was successfully inserted into g-C 3 N 4 In (1). g-C 3 N 4 the/NAPD two-dimensional material has characteristic diffraction peaks of NAPD and g-C 3 N 4 But the peak position is shifted due to NAPD insertion g-C 3 N 4 In (C), g-C is destroyed 3 N 4 A crystal structure.
FIG. 14 shows g-C in example 3 3 N 4 NAPD and g-C 3 N 4 An infrared spectrum of the/NAPD two-dimensional nanocomposite; the wave number range is 4000-700 cm -1 . As can be seen from the figure, g-C 3 N 4 At 3436cm -1 The nearby absorption peak is wider and stronger and belongs to the stretching vibration peak of N-H; 1200-1700cm -1 Is C-N (-C) -C and C-NH-C telescopic vibration, 810cm -1 It is similar to benzene ring stretching vibration. NAPD at 1350cm -1 ～1750cm -1 There are many characteristic absorption peaks, which are characteristic peaks of the naphthalene nucleus. g-C intercalated at NAPD 3 N 4 Formed g-C 3 N 4 The g-C is obvious in the/NAPD two-dimensional nano material 3 N 4 And NAPD characteristic peaks, with shifts in peak size and position due to intercalation changing the crystal structure of the starting material.
FIG. 15 shows g-C in example 3 3 N 4 /, NAPD and g-C 3 N 4 Linear scan polarization curve of NAPD; as can be seen from the figure, g-C 3 N 4 The lowest initial overpotential of (a) is approximately-0.4 mV; NAPD has a peak at-0.15 mV, and its initial overpotential is close to-0.36 mV; synthetic g-C 3 N 4 Initial overpotential of-0.39 mV for/NAPD two-dimensional nanocomposites between g-C 3 N 4 And NAPD, indicating the g-C of NAPD intercalation 3 N 4 The two-dimensional nano composite material can improve the catalytic hydrogen evolution activity. This may be due to the NAPD complexing to g-C 3 N 4 The ultrathin nano-sheet formed after neutralization leads more active sites to be exposed, so that the g-C is improved 3 N 4 Catalytic hydrogen evolution activity of/NAPD nanocomposites.
According to the embodiment, the amino acid molecules are firstly connected to the perylene tetracarboxylic dianhydride molecules to improve the solubility of the perylene tetracarboxylic dianhydride molecules, and then the intercalation molecule molecules are used as the disperse phase intercalation two-dimensional lamellar material to prepare the two-dimensional nanocomposite.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.

Claims (1)

1. A two-dimensional nanocomposite material, characterized in that the preparation method comprises the following steps:
mixing the intercalation molecules with the two-dimensional lamellar material, and performing ultrasonic treatment to obtain a two-dimensional nanocomposite;
the intercalated molecule has a structure shown in formula I:
Figure FDF0000011083760000011
the two-dimensional sheet material is molybdenum disulfide or graphite-phase carbon nitride;
the mass ratio of the intercalation molecules to the two-dimensional lamellar material is 1: 1-1: 2;
the ultrasonic treatment time is 40-50 h, and the ultrasonic treatment power is 1000W.
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