CN113200526A - Method for preparing boron nitride nanosheet by stripping method and boron nitride nanosheet - Google Patents
Method for preparing boron nitride nanosheet by stripping method and boron nitride nanosheet Download PDFInfo
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- 229910052582 BN Inorganic materials 0.000 title claims abstract description 103
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000002135 nanosheet Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000000498 ball milling Methods 0.000 claims abstract description 53
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
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- 230000009471 action Effects 0.000 claims abstract description 8
- 238000005119 centrifugation Methods 0.000 claims abstract description 8
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- 239000013256 coordination polymer Substances 0.000 claims description 17
- 229920001795 coordination polymer Polymers 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- 239000013155 zeolitic imidazolate framework-4 Substances 0.000 claims description 4
- 239000013156 zeolitic imidazolate framework-62 Substances 0.000 claims description 4
- -1 1-ethyl Chemical group 0.000 claims description 3
- LDZYRENCLPUXAX-UHFFFAOYSA-N 2-methyl-1h-benzimidazole Chemical group C1=CC=C2NC(C)=NC2=C1 LDZYRENCLPUXAX-UHFFFAOYSA-N 0.000 claims description 3
- NKLOLMQJDLMZRE-UHFFFAOYSA-N 6-chloro-1h-benzimidazole Chemical group ClC1=CC=C2N=CNC2=C1 NKLOLMQJDLMZRE-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical class [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 3
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- REACWASHYHDPSQ-UHFFFAOYSA-N 1-butylpyridin-1-ium Chemical compound CCCC[N+]1=CC=CC=C1 REACWASHYHDPSQ-UHFFFAOYSA-N 0.000 claims description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 2
- RWXZXCZBMQPOBF-UHFFFAOYSA-N 5-methyl-1H-benzimidazole Chemical compound CC1=CC=C2N=CNC2=C1 RWXZXCZBMQPOBF-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
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- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- DIWYOVAXEJCKBW-UHFFFAOYSA-N 2-(1-butyl-2H-pyridin-6-yl)pyridine Chemical compound CCCCN1CC=CC=C1C2=CC=CC=N2 DIWYOVAXEJCKBW-UHFFFAOYSA-N 0.000 description 1
- KOHNCQSJBSTSIU-UHFFFAOYSA-N 2-(1-phenyl-2H-pyridin-6-yl)pyridine Chemical compound C1C=CC=C(C=2N=CC=CC=2)N1C1=CC=CC=C1 KOHNCQSJBSTSIU-UHFFFAOYSA-N 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
- C01B21/0648—After-treatment, e.g. grinding, purification
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
本发明提出一种剥离法制备氮化硼纳米片的方法、氮化硼纳米片，使用CPs作为球磨剂，辅助六方氮化硼h‑BN剥离成氮化硼纳米片BNNS的方法。包括：(1)将h‑BN与CPs及玛瑙小球加入到球磨罐当中，以500rpm的速度球磨2‑24h。(2)将球磨后得到的混合物分散到异丙醇中超声1h。(3)通过离心去除未剥离的h‑BN和CPs，得到氮化硼纳米片。本发明利用在球磨作用下产生的剪切力和热使CPs发生相转变，使得CPs由晶态转变为熔融液体，形成类似离子液体，以离子碎片的形式插层到h‑BN间，辅助h‑BN剥离制备BNNS。本发明所用的CPs仅包含在球磨作用下能够发生固‑液转相的体系。该方法操作简单，成本低廉，不需要复杂昂贵的设备，有利于大规模生产制备BNNS。
The invention provides a method for preparing boron nitride nanosheets by a peeling method, and a method for using CPs as a ball milling agent to assist hexagonal boron nitride h-BN peeling into boron nitride nanosheets BNNS. Including: (1) Add h-BN, CPs and agate pellets into the ball milling jar, and mill the balls at a speed of 500rpm for 2-24h. (2) Disperse the mixture obtained after ball milling into isopropanol and sonicate for 1 h. (3) The unstripped h-BN and CPs were removed by centrifugation to obtain boron nitride nanosheets. The invention utilizes the shear force and heat generated under the action of ball milling to make the CPs undergo phase transformation, so that the CPs is transformed from a crystalline state to a molten liquid to form a similar ionic liquid, which is intercalated between h-BN in the form of ionic fragments to assist h ‑BN exfoliation to prepare BNNS. The CPs used in the present invention only include systems capable of solid-liquid phase inversion under the action of ball milling. The method is simple in operation, low in cost, and does not require complicated and expensive equipment, which is favorable for large-scale production and preparation of BNNS.
Description
Technical Field
The invention belongs to the technical field of two-dimensional material stripping preparation, and particularly relates to a method for preparing a boron nitride nanosheet by a stripping method and the boron nitride nanosheet, in particular to a method for preparing BNNS by utilizing CPs as a ball milling agent to assist h-BN stripping.
Background
Since 2004 when graphene was obtained from graphite exfoliation by a mechanical exfoliation method, two-dimensional materials have attracted considerable attention from researchers due to their special properties. Hexagonal boron nitride (h-BN) is a two-dimensional material with a graphene-like structure with high thermal conductivity, low density, low thermal expansion, high chemical stability and excellent electrical insulation. Compared with graphene, graphene only has covalent bonds connected by C-C bonds and has no polarity, and h-BN has partial ionic bonds in the B-N bonds in the h-BN layer due to different electronegativities of B atoms and N atoms and has certain polarity, so that van der Waals force interaction stronger than that of graphite exists between h-BN layers, and the graphene is more difficult to strip than the graphite.
Methods for preparing ultra-thin BNNS mainly include mechanical stripping (Yang G, Zhang X, Shang Y, et al. high thermal conductive synthetic polyvinyl alcohol/boron nitride nanocomposites with organic coupling orientation [ J ]. Compounds Science and Technology, 2021, 201: 108521.), liquid phase stripping (Deshk A R, Jeong J W, Lee S J, et al. ultrasonic-assisted chemical synthesis of hexagonal boron nitride synthesis [ J ]. Suitable Chemistry & Engineering, 2019, 1717 (20): 17125. chemical deposition [ 9 ] and chemical vapor deposition [ K ]. filtration Chemistry, interfacial deposition [ 31J ]. S ] 1. inorganic chemical deposition [ 5 ] N.S. J.: 1. S.S.S.S.: 1. S.S.: 1. inorganic deposition [ 1. S ] N.S.: 1. inorganic deposition, N.S.S.: 1. inorganic deposition, N.S.: 1. B.S. metals, N.S.S.: 1. B.S. A. A.
However, the conventional mechanical peeling method has a low yield; liquid phase stripping needs a large amount of solvent for long-time treatment, and common organic solvents easily cause environmental pollution; the chemical vapor deposition method has complex equipment and high manufacturing cost, and is difficult to realize large-scale preparation.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects of a method for preparing boron nitride nanosheets in a large scale in the prior art, the invention provides a method for preparing the boron nitride nanosheets by a stripping method and the boron nitride nanosheets, and particularly provides a method for promoting coordination polymers CPs to generate solid-liquid phase inversion assisted h-BN stripping by utilizing high-energy ball milling.
The technical scheme is as follows: in order to achieve the above objects, a first object of the present invention is to provide a method for peeling h-BN by CPs assisted mechanical ball milling method which is easy to generate solid-liquid phase inversion, comprising the steps of:
(1) ball milling and stripping: carrying out ball milling on hexagonal boron nitride h-BN, coordination polymer CPs and agate small balls, wherein the CPs are a system which generates solid-liquid phase inversion under the action of the ball milling;
(2) ultrasonic: dispersing the mixture obtained after ball milling in an organic solvent comprising any one of ethanol, isopropanol, N-dimethylformamide and N-methylpyrrolidone, and carrying out ultrasonic treatment;
(3) collecting: centrifuging once to obtain organic solvent dispersion liquid of the boron nitride nanosheet; and (4) centrifuging for the second time to obtain a solid phase, and drying and collecting to obtain the boron nitride nanosheet BNNS.
Optionally, in step (2), the CPs include, but are not limited to [ Zn (HPO) ]4)(H2PO4)]2(imH2)2、[M(1，2，4-triazole)(H2PO4)2]、ZIF-4、Zn-ZIF-62、Co-ZIF-62、ZIF-76、ZIF-76-mbim、Cu(isopropylimidazolate)、[Zn3(H2PO4)6(H2O3)]·bimH、[Zn3(H2PO4)6(H2O3)]·H(2Mebim)、[Zn2(HPO4)2(H2PO4)(5ClbimH)2](H2PO4)(MeOH)、[Cd3(SCN)2Br6(C2H9N2)2]、[Cu2(SCN)3(C2bpy)]、[Cu2(SCN)3(C4bpy)]、[Cu2(SCN)12(Phbpy)4]、[Cu2(SCN)3(3-Pybpy)]、(1-butyl-4-methylpyridinium)[Cu(SCN)2]Wherein M comprises Zn2+，Cd2+，Cr2+，Mn2+Any one of im ═ imidazole, bim ═ benzimidazole, triazole ═ triazole, 5-Clbim ═ 5-chlorobenzimidazole, 2Mebim ═ 2-methylbenzimidazole, C2bpy 1-ethyl bipyridine, C4bpy 1-butylpyridinium, Phbpy 1-phenylbyridinium, 3-Pybpy terpyridinium, isopyramidazolate isopropylimidazole, methylpyridium picolinium, mbim 5-methylbenzimidazole, 1-butyl-4-methylpyridium.
The CPs are CPs subjected to solid-liquid phase transition by ball milling, and mainly comprise the species, the melting points and the glass transition temperatures shown in the following table 1:
TABLE 1 list of CPs undergoing solid-liquid phase transition in ball milling
im ═ imidazole, bim ═ benzimidazole, 5-Clbim ═ 5-chlorobenzimidazole, 2Mebim ═ 2-methylbenzimidazole, C2bpy 1-ethyl bipyridine, C4bpy 1-butylbipyridine, Phbpy 1-phenylbipyridine, and 3-Pybpy terpyridine.
Optionally, in the step (1), the mass ratio of the hexagonal boron nitride h-BN to the coordination polymer CPs is 1: 0.1-0.5.
Optionally, in the step (1), the ball milling speed is 300 and 600rpm, and the ball milling time is 2-24 h.
Optionally, in the step (2), the mixture obtained after ball milling is dispersed in an organic solvent at a concentration of 1-10 mg/ml; the ultrasonic treatment time is 1h, and the ultrasonic treatment power is 100W.
Optionally, in the step (3), the speed of the first centrifugation is 1000-.
Optionally, in step (3), the speed of the secondary centrifugation is 9000-12000rpm, and the centrifugation time is 10-30 min.
On the other hand, the invention also provides a boron nitride nanosheet prepared according to the method.
Optionally, the lateral dimension of the boron nitride nanosheet is 3-5 μm, and 30-40% of the boron nitride nanosheets have a lateral dimension of 5 μm; the boron nitride nanosheet is thin and 1-5nm in thickness; the edge of the boron nitride nanosheet is curled, and the boron nitride nanosheet is erected.
On the other hand, the boron nitride nanosheet can be used as an inorganic filler and filled in a polymer to prepare a heat-conducting electric insulation polymer, and can be applied to various scenes such as aerospace, 5G base stations, small electronic equipment and the like.
Has the advantages that: compared with the traditional ionic liquid stripping method, the method for promoting the coordination polymer CPs to generate solid-liquid phase inversion assisted h-BN stripping by using the high-energy ball milling has the advantages that ionic fragments with different sizes are generated by phase inversion of the coordination polymer, and the intercalation and stripping effects of the multi-stage ionic fragments are better. In addition, the preparation method is simple and convenient, has high yield, abundant raw materials, low cost and low requirement on equipment, and is beneficial to large-scale production.
Drawings
Fig. 1 is a scanning electron micrograph of the boron nitride nanosheets prepared in example 1.
Detailed Description
The invention relates to a method for stripping h-BN by using CPs (continuous phase separation) auxiliary mechanical ball milling method which is easy to generate solid-liquid phase inversion, comprising the following steps:
(1) firstly, 500mg of h-BN and 50-250 mg of CPs are filled into a ball milling tank, and 50g of agate pellets with the total mass are filled into the ball milling tank and are ball milled for 2-24h at the speed of 500 rpm.
(2) The ball-milled mixture was dispersed in isopropanol at a concentration of 3mg/ml and sonicated for 1h using an ultrasonic cell disrupter (650W. times.15%, ca. 100W).
(3) The sonicated dispersion was centrifuged at 2000rpm for 15min to remove non-exfoliated boron nitride and CPs.
(4) And centrifuging the supernatant at 9000rpm for 15min, pouring off isopropanol, and drying overnight to collect the boron nitride nanosheet.
The CPs used in the present invention comprise only systems capable of undergoing solid-liquid phase inversion under the action of ball milling. The CPs are subjected to phase transformation by utilizing shearing force and heat generated under the action of ball milling, so that the CPs are transformed into molten liquid from a crystalline state to form similar ionic liquid, and the similar ionic liquid is intercalated among h-BN in the form of ionic fragments to assist h-BN in stripping to prepare BNNS. The method is simple to operate, low in cost, free of complex and expensive equipment and beneficial to large-scale production and preparation of BNNS.
The following examples, which are used to illustrate and explain the technical solution of the present invention by using different CPs to assist the mechanical ball milling method to strip h-BN, can be better understood according to the following examples. However, those skilled in the art will readily appreciate that the specific material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims. The compounds in the foregoing table 1 are all the CPs substances in which the CPs are phase-transformed by the shearing force and heat generated by the ball milling, and thus, the principle of the embodiment of the present invention is also satisfied.
Example 1
Preparation of phase transition CPs:
[Zn(HPO4)(H2PO4)2](imH2)2the preparation of (1): zinc oxide (81mg, 1mmol), imidazole (136mg, 2mmol), ethanol (500. mu.L), phosphoric acid (205. mu.L, 3mmol) were ground in a mortar for 10 minutes. The powder obtained was washed three times with ethanol centrifugation (8000rpm 5min) and transferred to vacuum drying at 100 ℃ overnight to obtain a dry pure phase.
Preparing boron nitride nanosheets:
500mg of h-BN and 100mg of [ Zn (HPO) ] are initially taken4)(H2PO4)2](imH2)2Loading into ball milling jar, and mixing with 1.2 cm-diameter Marma3 agate pellets, 15 agate pellets of 1cm, 10 agate pellets of 8mm and 50 agate pellets of 6mm (the total mass of all the agate pellets is about 50g) are put into a ball milling tank and ball milled for 24h at the speed of 500rpm,
the ball-milled mixture was dispersed in isopropanol at a concentration of 3mg/mL and sonicated using an ultrasonic cell disruptor at 100W for 1 h.
And centrifuging the ultrasonic dispersion liquid at 2000rpm for 15min to remove the non-peeled boron nitride nanosheets. And centrifuging the supernatant at 9000rpm for 15min, and drying overnight to obtain the boron nitride nanosheet with the yield of 34.1%.
FIG. 1 is a scanning electron micrograph of the boron nitride nanosheets prepared in this example, from which it can be seen that large, thin boron nitride nanosheets having a lateral dimension of 3-5 μm, with 30-40% of the boron nitride nanosheets having a lateral dimension of 5 μm, are obtained. The edge of the boron nitride nanosheet is curled, and the boron nitride nanosheet is erected and has the thickness of 2-5 nm. The size and thickness of the boron nitride nanosheet obtained by stripping are important indexes for evaluating the boron nitride nanosheet, and the boron nitride nanosheet obtained by the embodiment is large in size and thin in thickness, and is a high-quality boron nitride nanosheet. In the embodiment, the CPs are converted from large scale to small scale under the action of ball milling, and are used for assisting the stripping of boron nitride, so that the boron nitride nanosheet with large size and thin thickness can be obtained.
Example 2
Preparation of phase transition CPs:
[Zn(1，2，4-triazole)2(H2PO4)2]the preparation of (1): zinc oxide (81mg, 1mmol), 1, 2, 4-triazole (138mg, 2mmol) and phosphoric acid (85%, 134. mu.L, 2mmol) were placed in a ball mill. The mixture was milled for 60 minutes at 500 rpm. The resulting powder was washed with methanol and transferred to drying at 100 ℃ overnight to give a dry pure phase.
Preparing boron nitride nanosheets:
500mg of h-BN and 100mg of [ Zn (1, 2, 4-triazole) are initially taken2(H2PO4)2]Placing into a ball milling jar, and placing 3 agate pellets with diameter of 1.2cm and diameter of 1cm into the jarCharging 15 small balls, 10 small balls of 8mm agate and 50 small balls of 6mm agate (the total mass of all the agate small balls is about 50g) into a ball milling tank, ball milling at 500rpm for 24h,
the ball-milled mixture was dispersed in 30mL of isopropanol at a concentration of 3mg/mL by sonication with an ultrasonic cell disruptor at a power of 100W for 1 h.
And centrifuging the ultrasonic dispersion liquid at 2000rpm for 15min to remove the non-peeled boron nitride nanosheets. And centrifuging the supernatant at 9000rpm for 15min, and drying overnight to obtain the boron nitride nanosheet with the yield of 28.1%.
The results of the boron nitride nanosheets obtained in this example were the same as in example 1, with lateral dimensions of 3-5 μm, and approximately 30-40% of the boron nitride nanosheets had lateral dimensions of 5 μm. The edge of the boron nitride nanosheet is curled, and the boron nitride nanosheet is erected and has the thickness of 1-3 nm.
Example 3
Preparation of phase transition CPs:
preparation of ZIF-4: 1.2g of zinc nitrate hexahydrate, 0.9g of imidazole and 90ml of N, N-dimethylformamide are put into a 100ml reaction kettle and react for 72 hours at 100 ℃, after natural cooling, the mixture is washed three times by N, N-dimethylformamide and dichloromethane respectively, and is transferred to be dried at 100 ℃ overnight, so as to obtain a dry pure phase.
Preparing boron nitride nanosheets:
firstly, 500mg of h-BN and 100mg of ZIF-4 are taken to be filled into a ball milling tank, 3 agate small balls with the diameter of 1.2cm, 15 agate small balls with the diameter of 1cm, 10 agate small balls with the diameter of 8mm and 50 agate small balls with the diameter of 6mm (the total mass of all the agate small balls is about 50g) are filled into the ball milling tank, ball milling is carried out for 24h at the speed of 500rpm,
the ball-milled mixture was dispersed in 30mL of isopropanol at a concentration of 3mg/mL by sonication with an ultrasonic cell disruptor at a power of 100W for 1 h.
And centrifuging the ultrasonic dispersion liquid at 2000rpm for 15min to remove the non-peeled boron nitride nanosheets. And centrifuging the supernatant at 9000rpm for 15min, and drying overnight to obtain the boron nitride nanosheet with the yield of 12.1%.
The results of the boron nitride nanosheets obtained in this example were the same as in example 1, with lateral dimensions of 3-5 μm, and approximately 30-40% of the boron nitride nanosheets had lateral dimensions of 5 μm. The edge of the boron nitride nanosheet is curled, and the boron nitride nanosheet is erected and has a thickness of about 2-5 nm.
Comparative example 1
Preparing boron nitride nanosheets:
firstly, 500mg of h-BN and 100mg of urea are filled into a ball milling tank, 3 agate small balls with the diameter of 1.2cm, 15 agate small balls with the diameter of 1cm, 10 agate small balls with the diameter of 8mm and 50 agate small balls with the diameter of 6mm (the total mass of all the agate small balls is about 50g) are filled into the ball milling tank, the ball milling is carried out for 24 hours at the speed of 500rpm,
the ball-milled mixture was dispersed in 30mL of isopropanol at a concentration of 3mg/mL by sonication with an ultrasonic cell disruptor at a power of 100W for 1 h.
And centrifuging the ultrasonic dispersion liquid at 2000rpm for 15min to remove the non-peeled boron nitride nanosheets. And centrifuging the supernatant at 9000rpm for 15min, and drying overnight to obtain the boron nitride nanosheet with the yield of 11.3%.
As a result of the boron nitride nanosheets obtained in this comparative example, the lateral dimensions were 3-5 μm, and about 20-30% of the boron nitride nanosheets had a lateral dimension of 5 μm. The edge of the boron nitride nanosheet is curled, and the boron nitride nanosheet is erected and has a thickness of 5-10 nm.
Comparative example 2
Preparing boron nitride nanosheets:
100mg of h-BN and 30ml of isopropanol were taken and placed in a centrifuge tube and sonicated for 1h using an ultrasonic cell disruptor at a power of 100W.
And centrifuging the ultrasonic dispersion liquid at 2000rpm for 15min to remove the non-peeled boron nitride nanosheets. And centrifuging the supernatant at 9000rpm for 15min, and drying overnight to obtain the boron nitride nanosheet with the yield of 0.2%.
The result of the boron nitride nanosheet obtained in the comparative example is not different from that of the original boron nitride, the transverse dimension of the boron nitride nanosheet is 30-50 mu m, and the boron nitride nanosheet is very thick and 1-2 mu m in thickness.
Comparative example 3
Preparing boron nitride nanosheets:
100mg of h-BN and 30ml of isopropanol are taken and loaded into a centrifuge tube, and the cell is sonicated for 24h by an ultrasonic cell disruptor at a power of 100W.
And centrifuging the ultrasonic dispersion liquid at 2000rpm for 15min to remove the non-peeled boron nitride nanosheets. And centrifuging the supernatant at 9000rpm for 15min, and drying overnight to obtain the boron nitride nanosheet with the yield of 16.3%.
As a result of the boron nitride nanosheets obtained in this comparative example, the lateral dimensions were 1-3 μm, and about 20-30% of the boron nitride nanosheets had 3 μm lateral dimensions. The edge of the boron nitride nanosheet is curled, and the boron nitride nanosheet is erected and has the thickness of 1-10 nm.
Examples results and analysis
TABLE 2 comparison of the yield and CPs melting points of boron nitride nanosheets obtained in examples and comparative examples
Combining the experimental results of examples 1-3 and comparative examples 1-3, it can be seen that the use of CPs to assist the h-BN stripping also provides a higher yield than the use of isopropanol ultrasound and urea ball milling stripping, especially a much higher effect than the use of pure isopropanol ultrasound, and the results of comparative example 3 demonstrate that pure isopropanol ultrasound can only be obtained at the lowest level of the examples of the present invention after 24 hours, which undoubtedly greatly reduces the time and improves the production yield. Compared with the method of comparative example 1, in which urea ball milling is used, in examples 1 to 3 of the method of the present invention, the stripping yield and the effect are improved, especially in [ Zn (HPO) used in examples 1 and 24)(H2PO4)2](imH2)2And [ Zn (1, 2, 4-triazole)2(H2PO4)2]Compared with comparative example 1, the efficiency is improved by nearly 3 times.
The yield comparison result fully shows that CPs is used for assisting h-BN stripping, so that the method is more favorable for h-BN stripping compared with the conventional isopropanol ultrasonic and urea ball milling, and the boron nitride nanosheet with higher yield is obtained;
meanwhile, by comparing the efficiency of CPs assisting h-BN stripping with different melting points Tm, the efficiency of CPs assisting h-BN stripping becomes lower as the melting point is increased, and lower melting point [ Zn (HPO) is used4)(H2PO4)2](imH2)2The stripping obtained is most efficient. It is shown that when low melting point CPs are used for assisting h-BN stripping, the stripping yield is greatly improved.
This is caused by the fact that the energy generated during ball milling is not enough to convert the CPs with high melting point into ion fragments, while the CPs with low melting point can be converted into a large amount of ion fragments under the action of ball milling to assist h-BN stripping, thereby obtaining higher yield.
In addition, the product obtained by the method is a large and thin boron nitride nanosheet, an excellent h-BN stripping effect is obtained, and particularly, the method makes more obvious progress in the aspects of size distribution breadth and multi-stage ion fragment intercalation compared with isopropanol ultrasonic and urea ball milling stripping. Significant progress has been made, both in terms of lateral dimensions and thickness, in particular with lateral dimensions of 3-5 μm, and approximately 30-40% of the boron nitride nanoplates have a lateral dimension of 5 μm; the edge of the boron nitride nanosheet is curled, and the boron nitride nanosheet is erected and has a thickness of about 2-5 nm. It can be seen that the boron nitride nanosheet prepared by the method of the present invention obtains a larger proportion of a product with a large transverse size and has a thinner thickness.
In conclusion, the invention discloses a method for preparing boron nitride nanosheets by a stripping method, wherein a ball milling mode is adopted to strip layered boron nitride, a coordination polymer is added as a ball milling agent, the selected coordination polymer can generate phase transformation in the ball milling process, the phase transformation of the coordination polymer from crystals to liquid is promoted by the shearing and friction heat of the ball milling, the coordination polymer plays a role similar to that of ionic liquid to strip two-dimensional materials, but the coordination polymer is converted into a solid after the ball milling is stopped. Compared with the traditional ionic liquid stripping, the ionic fragments with different sizes are generated by phase transformation of the coordination polymer, and the intercalation and stripping effects of the multi-stage ionic fragments are better.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. A method for preparing boron nitride nanosheets by a stripping method is characterized by comprising the following steps:
(1) ball milling and stripping: ball-milling hexagonal boron nitride h-BN and coordination polymers CPs, wherein the CPs are a system which generates solid-liquid phase inversion under the ball-milling action;
(2) ultrasonic: dispersing the mixture obtained after ball milling in an organic solvent, and carrying out ultrasonic treatment;
(3) collecting: centrifuging once to obtain organic solvent dispersion liquid of the boron nitride nanosheet; and (4) centrifuging for the second time to obtain a solid phase, and drying and collecting to obtain the boron nitride nanosheet BNNS.
2. The method for preparing boron nitride nanosheets by the lift-off process of claim 1, wherein in step (2), the CPs include, but are not limited to, [ Zn (HPO)4)(H2PO4)]2(imH2)2、[M(1，2，4-triazole)(H2PO4)2]、ZIF-4、Zn-ZIF-62、Co-ZIF-62、ZIF-76、ZIF-76-mbim、Cu(isopropylimidazolate)、[Zn3(H2PO4)6(H2O3)]·bimH、[Zn3(H2PO4)6(H2O3)]·H(2Mebim)、[Zn2(HPO4)2(H2PO4)(5ClbimH)2](H2PO4)(MeOH)、[Cd3(SCN)2Bt6(C2H9N2)2]、[Cu2(SCN)3(C2bpy)]、[Cu2(SCN)3(C4bpy)]、[Cu2(SCN)12(Phbpy)4]、[Cu2(SCN)3(3-Pybpy)]、(1-butyl-4-methylpyridinium)[Cu(SCN)2]Wherein M comprises Zn2+，Cd2+，Cr2+，Mn2+Any one of im ═ imidazole, bim ═ benzimidazole, triazole ═ triazole, 5-Clbim ═ 5-chlorobenzimidazole, 2Mebim ═ 2-methylbenzimidazole, C2bpy 1-ethyl bipyridine, C4bpy 1-butylpyridinium, Phbpy 1-phenylbyridinium, 3-Pybpy terpyridinium, isopyramidazolate isopropylimidazole, methylpyridium picolinium, mbim 5-methylbenzimidazole, 1-butyl-4-methylpyridium.
3. The method for preparing boron nitride nanosheets by the exfoliation method according to claim 1, wherein in step (1), the mass ratio of the hexagonal boron nitride h-BN to the coordination polymer CPs is 1: 0.1-0.5.
4. The method for preparing boron nitride nanosheets by the exfoliation method as recited in claim 1, wherein in step (1), the ball milling speed is 300-600rpm, and the ball milling time is 2-24 h.
5. The method for preparing boron nitride nanosheets by the exfoliation method according to claim 1, wherein in step (2), the mixture obtained after ball milling is dispersed in an organic solvent at a concentration of 1 to 10mg/ml, the organic solvent comprising any one of ethanol, isopropanol, N-dimethylformamide, and N-methylpyrrolidone; the ultrasonic treatment time is 1h, and the ultrasonic treatment power is 100W.
6. The method for preparing boron nitride nanosheets by the exfoliation method as recited in claim 1, wherein in step (3), the speed of the primary centrifugation is 1000-3000rpm, and the centrifugation time is 10-30 min.
7. The method for preparing boron nitride nanosheets by the lift-off method as defined in claim 1, wherein in step (3), the speed of the secondary centrifugation is 9000-.
8. Boron nitride nanoplates produced according to the method of any of claims 1-7.
9. Boron nitride nanoplatelets according to claim 8 wherein the boron nitride nanoplatelets have a lateral dimension of 3-5 μ ι η and 30-40% of the boron nitride nanoplatelets have a lateral dimension of 5 μ ι η; the edge of the boron nitride nanosheet is curled, and the thickness of the boron nitride nanosheet is 1-5 nm.
10. Use of boron nitride nanoplates according to claims 8 or 9 as inorganic filler to prepare thermally conductive, electrically insulating polymers, including but not limited to applications in the fields of aerospace, 5G base stations, small electronic devices.
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