CN111717900A - Mechanical stripping method of functionalized boron nitride nanosheets - Google Patents
Mechanical stripping method of functionalized boron nitride nanosheets Download PDFInfo
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Abstract
The invention relates to a mechanical stripping method of a functionalized boron nitride nanosheet, which adopts boric acid and commercial block hexagonal boron nitride as raw materials and is synthesized by the following three steps: uniformly mixing boric acid and commercial hexagonal boron nitride in a mortar, and then carrying out high-temperature pretreatment, so that the commercial block hexagonal boron nitride is corroded by the dehydrated boric acid and is fixed by boron oxygen, and a solid mixture with uniform reaction is obtained; roughly grinding a solid mixture obtained after the reaction, and placing the solid mixture in a ball milling tank for mechanical ball milling treatment; dissolving and dispersing white powder obtained after ball milling in deionized water, repeatedly washing for many times to ensure that free boric acid is completely washed away, and obtaining a functionalized boron nitride nanosheet dispersion liquid product; or drying the product obtained by centrifugal washing to obtain the functionalized boron nitride nanosheet powder product. The method is simple to operate, harsh experimental conditions are not needed, the boric acid and the deionized water can be recycled, and the obtained product has high crystallinity and functionalization degree.
Description
Technical Field
The invention relates to a high-efficiency mechanical stripping method for preparing a functionalized boron nitride nanosheet with rich functionalized groups by mechanical stripping.
Background
Boron Nitride Nanosheets (BNNSs) as an important multifunctional two-dimensional material have very similar lattice constants with graphene, and the lattice difference between the two materials is only 2%. In addition, BNNSs has mechanical properties, thermal conductivity, high specific surface area, etc. comparable to graphene, and compared with graphene, BNNSs has excellent properties such as higher thermal stability, stronger oxidation resistance, better corrosion resistance, and electrical insulation. Therefore, the glass has wide application prospect in the fields of ceramics, electronics, petroleum, nuclear industry, aerospace, machinery, polymers, metals, optical glass, cosmetics and the like. The BNNSs is used as an inorganic filler and added into a polymer matrix to prepare the polymer composite material, so that the mechanical property of the composite material is greatly improved, the heat conductivity of the composite material is effectively improved, and the oxygen atom corrosion resistance and the like of the polymer can be improved. In recent years, BNNSs is applied to the positive electrode of the lithium-sulfur battery, so that the change of the electrode volume can be inhibited, and the cycle stability of the battery is improved; the modified carbon material is used for modifying the lithium-sulfur battery diaphragm, can inhibit shuttle effect and improves the overall performance of the battery. BNNSs has better biocompatibility than carbon materials, thus having good application prospect in the fields of cytotoxicity and drug delivery. Meanwhile, various pollutants such as oil, pesticides, dyes, metal ions and the like in water can be removed through adsorption. In addition, BNNSs has good application prospect in the aspects of anticorrosive materials, anticorrosive coatings, catalysis and the like.
To date, various techniques and methods for preparing boron nitride nanomaterials have been explored, and are mainly classified into two major categories, namely "bottom-up" synthesis methods and "top-down" exfoliation methods, such as: a micro-mechanical peeling method, a vortex liquid peeling method, an ultrasonic method, a solid phase synthesis reaction method, a chemical vapor deposition method, an epitaxial growth method, an ionic liquid thermal method, a chemical solvent peeling method, and the like. For example, Nag et al use boric acid and urea as raw materials, high temperature cracking is performed to obtain BNNSs with high specific surface area, but the product has low crystallinity and needs a large amount of urea, thereby causing the problems of raw material waste and environmental pollution (Angshuman Nag, et al; Graphene analytes of BN: Novel Synthesis and Properties, ACS Nano,2010,4, 1539-; lei et al successfully produced high quality BNNSs using direct ball milling of urea with commercial block h-BN, which also required large amounts of non-recoverable urea as a starting material (Weiwei Lei, et al; boronnide colloidal solutions, ultralight aerogels and free standing membrane-step elevation and functionalization, nat. com., 2015,6, 8849). Therefore, in order to prepare BNNSs with high crystallinity in an efficient and energy-saving manner, the invention takes boric acid and commercial bulk boron nitride as raw materials, the prepared BNNSs has high crystallinity, high functionalization degree, low ball milling speed and short processing time, the concentration of the obtained dispersion liquid is high, and the boric acid can be recycled as a ball milling auxiliary agent, thereby providing a new method and a new technology for the industrial application of boron nitride materials.
Disclosure of Invention
The invention provides an efficient, safe and green synthetic method of high-crystallinity BNNSs, aiming at the problems of low crystallinity of prepared BNNSs, raw material waste, easy environmental pollution and the like. The method is simple to operate, harsh experimental conditions are not needed, the auxiliary boric acid and the deionized water for washing can be recycled, and the obtained BNNSs product has high crystallinity and functionalization degree.
In order to achieve the purpose, the invention adopts the following technical scheme:
a mechanical stripping method of a functionalized boron nitride nanosheet is characterized in that boric acid and commercial block hexagonal boron nitride are adopted as raw materials, and the method is synthesized through the following three steps: uniformly mixing boric acid and commercial hexagonal boron nitride in a mortar, and then carrying out high-temperature pretreatment, so that the commercial block hexagonal boron nitride is corroded by the dehydrated boric acid and is fixed by boron oxygen, and a uniformly reacted solid mixture is obtained; secondly, roughly grinding a solid mixture obtained after reaction, and placing the solid mixture in a ball milling tank for mechanical ball milling treatment; thirdly, dissolving and dispersing white powder obtained after ball milling in deionized water, repeatedly washing for many times to ensure that free boric acid is completely washed away, and obtaining a functionalized boron nitride nanosheet dispersion liquid product; or drying the product obtained by centrifugal washing to obtain the functionalized boron nitride nanosheet powder product.
The autoclave treatment process is a process of converting boric acid dehydration into corrosive boron oxygen, and commercial block hexagonal boron nitride is corroded by the boron oxygen and is fixed by the boron oxygen in the process; in the mechanical ball milling process in the second step, tearing and stripping the commercial block hexagonal boron nitride eroded and fixed by boron oxygen into BNNSs with high functionalization degree; more importantly, the boric acid and the deionized water used in the process can be recycled through simple evaporation, and no waste or pollution is caused. The method is simple and efficient, green and pollution-free, the obtained product has good dispersibility and stability, and the obtained BNNSs have the characteristics of uniform transverse dimension, few layers, high concentration and stability of dispersion liquid, so that the method has wider application prospect.
The method comprises the following specific steps:
step (1): uniformly mixing boric acid and commercial hexagonal boron nitride blocks in a mass ratio of 4:1-12:1, then loading the mixture into a high-pressure kettle, and carrying out heat preservation pretreatment at a temperature of not less than 200 ℃ to obtain a hard white solid A;
step (2): roughly grinding the white solid A obtained in the step (1), putting the ground white solid A into a ball milling tank, carrying out mechanical ball milling treatment at the rotating speed of not less than 200rpm, stripping commercial block hexagonal boron nitride corroded and fixed by boron oxide into sheets, and carrying out mechanical ball milling for more than 3 hours to obtain white powder B;
and (3): repeatedly washing the white powder B obtained in the step (2) with deionized water to remove free boric acid components in the white powder B, so as to obtain a high-concentration and stable BNNSs dispersion liquid product; or freezing and drying the product obtained by centrifugal washing to obtain the functionalized boron nitride nanosheet powder product.
The white solid powder B is dissolved and dispersed in deionized water by stirring, and after the free boron oxygen is completely dissolved, the washing treatment is repeated for a plurality of times until the pH value of the supernatant is not changed (about 9.2), which indicates that the free boric acid in the dispersion liquid system is completely washed away. And then, drying the sample after the washing treatment is finished, and finally obtaining a BNNSs powder product with high quality and high functionalization degree. Dispersing the powder product in different solvents, such as ethanol, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), chloroform, acetone, tetrahydrofuran, etc., to obtain high and stable dispersion, wherein the dispersion concentration of the powder product in water can reach 100 mg/mL.
And (4): and (4) carrying out a simple evaporation process on the supernatant obtained by centrifugal washing in the step (3) to respectively obtain reusable raw materials, namely auxiliary boric acid and detergent deionized water.
The pretreatment temperature is 200-.
The raw material recovery comprises rotary evaporation treatment, oven evaporation treatment, sunlight natural evaporation treatment or freeze drying treatment and the like.
Compared with the prior art, the invention has the beneficial effects that:
1 commercial block hexagonal boron nitride used in the present invention undergoes significant changes in powder X-ray diffraction pattern (XRD) after autoclave heat treatment and mechanical ball milling. As shown in fig. 1, the (0002) plane diffraction peak intensity of the BO-h-BN sample obtained after the autoclave heat treatment is significantly reduced, and the half-peak width is significantly broadened, which indicates that in the autoclave heat treatment process, boric acid loses water to form a boroxy glass phase and simultaneously generates a significant corrosion effect on commercial block hexagonal boron nitride, so that the thickness of the original hexagonal boron nitride sample is reduced; and then ball milling and stripping are carried out to obtain a final boron nitride nanosheet product, the intensity of the (0002) crystal face diffraction peak is more obviously weakened, the half-peak width is wider, and the reduction of the layer number can be qualitatively analyzed according to a Scherrer formula (D is K lambda/Bcos theta), so that the purpose of obviously stripping BO-h-BN in the ball milling process is achieved. SEM micrographic observations of the samples also revealed this change, as shown in FIGS. 2-4, for commercial Bulk hexagonal boron nitride (Bulk h-BN) having a lateral dimension of about 10 μm and a thickness of about 1 μm; the BO-h-BN sample obtained after the autoclave heat treatment shows obvious corrosion stripping marks, the transverse size is approximately distributed at 2-8 mu m, and the thickness is approximately 1 mu m; and BNNSs samples obtained after ball milling and stripping,the stripping degree is higher, the particle size is more uniform, the transverse dimension is hundreds of nanometers, and the thickness reaches the level of several nanometers. The TEM photograph of the BNNSs sample is shown in fig. 5, the stripped BNNSs sample has uniform size distribution, the low contrast of the image indicates that the product has very few layer number structure, the high magnification TEM picture shows that the BNNSs sample (2.01nm) with 6 layer structure in the sample has the calculated interlayer distance of 0.335nm, which indicates that the BNNSs sample obtained after autoclave heat treatment and mechanical ball milling treatment has high crystallinity and retains the intrinsic property of h-BN. The enhancement of the degree of functionalization is expressed in the variation of the dispersion of each sample in water (FIG. 6) and the amount of the functionalized groups in each sample (FIG. 7). FIG. 6 shows the dispersion of each sample in water, with commercial bulk hexagonal boron nitride having excellent hydrophobic properties, floating on the water surface; most of BO-h-BN sample is settled at the water bottom, and a small amount of BO-h-BN sample is suspended in water, which shows that the boron nitride sample is partially functionalized and has certain hydrophilicity after being subjected to autoclave heat treatment; the BNNSs sample after ball milling and stripping can be completely dispersed in deionized water, and the concentration of the dispersion liquid in example 1 reaches 25.5mg/mL, which shows that the product has higher functionalization degree. As shown in FIG. 7, the BO-h-BN sample after the autoclave heat treatment appeared at 1200cm in the range of 900--1The B-O bond absorption peak between the two shows that the bulk hexagonal boron nitride sample is effectively functionalized; the B-O bond absorption strength of the BNNSs sample obtained after ball milling treatment is enhanced, which fully explains the further enhancement of the functionalization degree. Therefore, the invention simultaneously realizes the purposes of functionalizing and stripping the block hexagonal boron nitride and obtaining the high-quality boron nitride nanosheet.
2 the invention creatively carries out autoclave pretreatment on boric acid and commercial block hexagonal boron nitride, so that the final product has uniform appearance characteristics and high functionalization degree, the mechanical ball milling time is greatly shortened, and the energy is saved.
3 the boric acid and the deionized water for washing which are used as raw materials can be respectively recycled from the washed liquid through simple evaporation, so that the experimental raw materials are saved, the environment is protected, and the practicability of the technology is improved.
4 the raw materials used by the method are boric acid and commercial block hexagonal boron nitride, which belong to common chemical raw materials which are industrially produced, are cheap and easily obtained, and are nontoxic and harmless, so that the production cost is further reduced, and a foundation is laid for the practical industrial application of the boric acid and the commercial block hexagonal boron nitride.
Drawings
The invention is further described with reference to the following figures and specific examples.
FIG. 1 is an XRD spectrum of Bulk h-BN, BO-h-BN and BNNSs samples of example 1.
FIG. 2 is an SEM picture of a Bulk h-BN sample from example 1.
FIG. 3 is an SEM picture of a BO-h-BN sample in example 1.
FIG. 4 is an SEM picture of the BNNSs product of example 1.
FIG. 5 is a TEM image of the BNNSs product of example 1.
FIG. 6 is a photograph of the dispersion in water of Bulk h-BN, BO-h-BN and BNNSs samples from example 1.
FIG. 7 is an FTIR spectrum of Bulk h-BN, BO-h-BN and BNNSs samples from example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples and accompanying drawings, which are illustrative only and are not intended to limit the embodiments of the present invention
Example 1
Step (1): after uniformly milling 80g of boric acid and 10g of commercial hexagonal boron nitride block (Bulk h-BN), the mixture was charged to an autoclave and treated at 220 c for 12 hours to give a hard white solid a. And repeatedly washing the sample A by deionized water to remove free boric acid to obtain a BO-h-BN intermediate product for detecting the performance of the pretreated sample.
Step (2): and (3) putting the product A obtained in the step (1) into a ball milling tank, and treating for 6 hours at the rotating speed of 580rpm to obtain a product B.
And (3): washing the product B obtained in the step (2) with deionized water to remove free boric acid in the liquid, so as to obtain a high-concentration and stable BNNSs dispersion liquid product; or freezing and drying the wet product obtained by centrifugal cleaning to obtain the powder product of the functionalized BNNSs.
And (4): and (4) carrying out rotary evaporation treatment on the supernatant obtained by centrifugal washing in the step (3) to respectively obtain reusable auxiliary boric acid and detergent deionized water.
Description of the drawings:
FIG. 1 is an XRD spectrum of Bulk h-BN, BO-h-BN and BNNSs samples, and the diffraction intensity of the crystal face of the sample (0002) is gradually weakened and the half-peak width is gradually widened along with the steps of autoclave heat treatment and mechanical ball milling, which shows that the process has excellent stripping effect. FIGS. 2-4 are SEM pictures of Bulk h-BN, BO-h-BN and BNNSs samples, respectively, also showing the superior effect of the stripping process; figure 5 is a TEM picture of a BNNSs product, with lower contrast indicating a lower number of layers in the product and an interplanar spacing of 0.335nm indicating excellent crystallinity of the product (the total thickness of the 6-layer boron nitride nanoplates in figure 5d is about 2.01 nm). FIG. 6 shows the dispersion of three samples in water, with Bulk h-BN possessing outstanding hydrophobic properties; the BO-h-BN sample shows hydrophilic property and has certain dispersibility, which indicates that the sample has certain functionalization degree and larger particles; the BNNSs product shows excellent dispersion effect and dispersion stability, which shows that the product obtains sufficient stripping and higher functionalization degree, the boron nitride material is hydrophobic, and can have better dispersion in water only by grafting a certain number of functional groups on the boron nitride material, so that the powder product obtained by the method has higher dispersion concentration in water compared with the existing product; similarly, the functional group can also ensure that the functional group can be stably dispersed in other solvents, has excellent dispersibility compared with the existing products, and has different dispersion concentrations and stabilities in other solvents. FIG. 7 FTIR spectra of Bulk h-BN, BO-h-BN and BNNSs samples at 900--1The absorption peak of the B-O bond of (A) gradually increased, confirming the difference in dispersibility for each sample in FIG. 6. The characteristics fully show that the method can simultaneously and efficiently strip and functionalize the boron nitride nanosheet, and provides high-quality boron nitride material for application in actual production and lifeRaw materials.
Examples 2, 3, 4 and 5
The amounts of boric acid and commercial hexagonal boron nitride used in step (1) of example 1 were changed to 72g and 18g, respectively; 75g and 12.5 g; 80g and 8 g; 84g and 7g (the mass ratio of the boric acid to the boron nitride is respectively changed to 4:1, 6:1, 10:1 and 12: 1). Other operations were performed as in example 1 to produce a high crystallinity, functionalized BNNSs dispersion or powder product. Further increasing the amount of added boric acid also produces high quality functionalized BNNSs product, but with reduced relative yield.
Examples 6, 7, 8, 9, 10, 11, 12, 13, 14, 15
The autoclave treatment temperature in the step (1) in examples 1 to 5 was changed to 200 ℃ and 240 ℃ respectively. The other operations are the same as those in example 1, and a high-crystallinity functionalized BNNSs dispersion liquid product or powder product can be prepared, and the purposes of converting boric acid dehydration into corrosive boron oxygen, eroding and fixing commercial block hexagonal boron nitride can be realized at the temperature of more than 200 ℃.
Examples 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35
The autoclave soak treatment times in step (1) in examples 6 to 15 were changed to 12 hours and 24 hours, respectively. The other operations were the same as in example 1, and a high crystallinity, functionalized BNNSs dispersion product or powder product was prepared.
Examples 36, 37, 38, 39 and 40
The ball milling rotation speed in step (2) in examples 1 to 5 was changed to 200 rpm. The other operations are the same as those in example 1, a high-crystallinity functionalized BNNSs dispersion liquid product or powder product can be prepared, and the mixed powder after the reaction can be ground in the ball milling process, so that the purpose of stripping boron nitride can be achieved.
Examples 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55
The ball milling time in step (2) in examples 1 to 5 was changed to 12h, 18h, 24 h. The other operations were the same as in example 1, and a high crystallinity, functionalized BNNSs dispersion product or powder product was prepared. With the increase of the ball milling time, the product size is gradually reduced, and the functionalization degree is gradually enhanced, but is relatively time-consuming.
Examples 56, 57, 58, 59, 60, 61, 62, 63, 64, 65
The rotary evaporation treatment process in the embodiments 1 to 5 is changed into an oven evaporation treatment process and a sunlight natural evaporation treatment process, so that the aim of recovering boric acid and deionized water can be achieved, the mass of the auxiliary agent boric acid in the recovery process can be increased relative to that of the boric acid added before, a feasible method support is provided for the reutilization of raw materials, and the rotary evaporation treatment process is lower in cost and more environment-friendly.
Nothing in this specification is said to apply to the prior art.
Claims (8)
1. A mechanical stripping method of a functionalized boron nitride nanosheet is characterized in that boric acid and commercial block hexagonal boron nitride are adopted as raw materials, and the method is synthesized through the following three steps: firstly, uniformly mixing boric acid and commercial hexagonal boron nitride in a mortar, and then carrying out high-temperature pretreatment, so that the commercial block hexagonal boron nitride is corroded by dehydrated boric acid and is fixed by boron oxygen, and a solid mixture which is uniformly reacted is obtained; secondly, roughly grinding a solid mixture obtained after reaction, and placing the solid mixture in a ball milling tank for mechanical ball milling treatment; thirdly, dissolving and dispersing white powder obtained after ball milling in deionized water, repeatedly washing for many times to ensure that free boric acid is completely washed away, and obtaining a functionalized boron nitride nanosheet dispersion liquid product; or drying the product obtained by centrifugal washing to obtain the functionalized boron nitride nanosheet powder product.
2. A mechanical stripping method of functionalized boron nitride nanosheets is characterized by comprising the following specific steps:
step (1): uniformly mixing boric acid and commercial hexagonal boron nitride blocks in a mass ratio of 4:1-12:1, putting the mixture into a high-pressure kettle, and pretreating at a temperature of not less than 200 ℃ to obtain a hard white solid A;
step (2): roughly grinding the white solid A obtained in the step (1), putting the ground white solid A into a ball milling tank, carrying out mechanical ball milling treatment at a rotating speed of not less than 200rpm, and stripping commercial block hexagonal boron nitride corroded and fixed by boron oxide into sheets to obtain white powder B;
and (3): repeatedly washing the white powder B obtained in the step (2) with deionized water to remove free boric acid components in the white powder B, and obtaining a stable BNNSs dispersion liquid product; or freezing and drying the product obtained by centrifugal washing to obtain the functionalized boron nitride nanosheet powder product.
3. The peeling method according to claim 1 or 2, wherein the powder product is dispersible in different solvents such as water, ethanol, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP), chloroform, acetone, tetrahydrofuran, or the like, to obtain a highly concentrated and stable dispersion.
4. The peeling method as claimed in claim 3, wherein the dispersion concentration of the powdery product in water is 100 mg/mL.
5. The peeling method as claimed in claim 1 or 2, further comprising a raw material recovery process, namely evaporating the supernatant obtained by the centrifugal washing in the step (3) to respectively obtain the reusable auxiliary boric acid and the detergent deionized water.
6. The peeling method according to claim 5, wherein the recovery process of the raw material is a rotary evaporation treatment, an oven evaporation treatment, a natural solar evaporation treatment or a freeze-drying treatment.
7. The exfoliation method of claim 1 or 2, wherein the boron nitride nanoplates have lateral dimensions of several hundred nanometers and a thickness of several nanometers after mechanical ball milling.
8. The stripping method as claimed in claim 1, wherein the high temperature is 200-.
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| CN112225186A (en) * | 2020-10-21 | 2021-01-15 | 江西联锴科技有限公司 | Preparation method of spherical boron nitride |
| CN112919431A (en) * | 2021-02-07 | 2021-06-08 | 辽东学院 | High-yield and high-crystallinity hexagonal boron nitride nanosheet and preparation method thereof |
| CN113264778A (en) * | 2021-05-17 | 2021-08-17 | 厦门理工学院 | Boron nitride composite ceramic and preparation method and application thereof |
| CN113264778B (en) * | 2021-05-17 | 2022-10-14 | 厦门理工学院 | Boron nitride composite ceramic and preparation method and application thereof |
| CN114005989A (en) * | 2021-11-01 | 2022-02-01 | 南京大学 | Porous carrier for lithium-sulfur battery and preparation method thereof |
| CN114653371A (en) * | 2022-04-08 | 2022-06-24 | 江西师范大学 | Preparation method of high-defect boron nitride supported atomic-level dispersed metal catalyst |
| CN114653371B (en) * | 2022-04-08 | 2023-05-05 | 江西师范大学 | Preparation method of atomic-level dispersed metal catalyst supported by high-defect boron nitride |
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