CN102976295B - Method for preparing two-dimensional hexagonal boron nitride nanosheet through molten caustic soda - Google Patents
Method for preparing two-dimensional hexagonal boron nitride nanosheet through molten caustic soda Download PDFInfo
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- CN102976295B CN102976295B CN201210583096.XA CN201210583096A CN102976295B CN 102976295 B CN102976295 B CN 102976295B CN 201210583096 A CN201210583096 A CN 201210583096A CN 102976295 B CN102976295 B CN 102976295B
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Abstract
The invention provides a method for preparing two-dimensional hexagonal boron nitride nanosheet through molten caustic soda. The method comprises the following steps: (1) mixing caustic soda with hexagonal boron nitride (h-BN) in the mole ratio of (1: 1)-(100: 1), and uniformly milling, then transferring the grounded material into a reaction kettle; (2) placing the reaction kettle into a heating furnace to heat at temperature ranging from the melting temperature of the caustic soda to the sum of the melting temperature and 50 DEG C for 1 to 24 hours until the caustic soda is molten, then taking out the reaction kettle, and cooling to the room temperature; and (3) washing the reaction product in the reaction kettle by water until reaching the pH (Potential of Hydrogen) of 6 to 8, and then dissolving into a solvent to separate, so as to obtain the boron nitride nanosheet. According to the method provided by the invention, the caustic soda and the hexagonal boron nitride are heated to react together, and the boron nitride is separated by the molten caustic soda, so that the boron nitride nanosheet can be prepared; the method is simple in operation and low in cost, complex and expensive instruments and equipment are not needed; and the alkali raw material is low in price and easily available, brings low toxicity to the environment, and reacts at lower temperature.
Description
Technical field
The present invention relates to a kind of molten caustic soda that utilizes and peel off boron nitride powder system for the method for boron nitride nanosheet, belong to crystalline material technical field.
Background technology
Along with the rise of Graphene research, two-dimensional material (thickness of material at 1nm between 100nm) is more and more subject to people's attention with its distinctive character.In these two-dimensional material, hexagonal boron nitride (h-BN) is because of structurally approaching with graphite, can or can not have caused concern and the interest of a lot of scientific research group: two-dimentional hexagonal boron nitride have a lot of special character as Graphene? up to now, a lot of research groups have reported many excellent properties of two-dimentional h-BN in succession in the world.But different from graphite, due to the stronger ionic linkage effect of having between layers of h-BN, the difficulty that makes to peel off boron nitride is more much bigger than the difficulty of peeling off graphite.This is also one of a lot of reasons that produce little effect when preparing hexagonal nanometer boron nitride sheet for the preparation of the method for Graphene.
From current achievement in research, can find out, the boron nitride that two dimension h-BN has a lot of other dimensional structure is (as boron nitride nano-tube, nano wire) advantage that can not compare, reports that such as people such as C.R.Dean h-BN with tens nano thickness makes the graphene device performance of substrate better; The people such as L.A.Ponomarenko can realize the transformation of Graphene from metal to isolator by the sandwich structure that h-BN nanometer sheet and Graphene are made, and (document Dean sees reference; C.R.et al.Boron nitride substrates for high-quality graphene electronics.Nature Nanotech.5; 722-726,2010; Ponomarenko, L.A.etal.Tunable metal-insulator transition in double-layer graphene heterostructures.Nature Phys.7,958-961,2011; Golberg, D.etal.Boron nitride nanotubes and nanosheets.ACS Nano.4,2979-2993,2010; Coleman, J., N.etal.Two-dimensional nanosheets produced by liquid exfoliation of layered materials.Science331,568 – 571,2011; Perim, E. & Galvao, D.S.The structure and dynamics of boron nitride nanoscrolls.Nanotechnology20,335702,2009; Y.Lin, J.W.Connell, Nanoscale.4,6908,2012).Up to the present, the method for preparing h-BN nanometer sheet has micromechanics stripping method (D.Pacile, J.C.Meyer, C.O.Girit, A.Zettl, Appl.Phys.Lett.2008,92,133107), liquid phase stripping method (C.Zhi, Y.Bando, C.Tang, H.Kuwahara, D.Golberg, Adv.Mater.2009,21,2889; K.Zhou, N.Mao, H.Wang, Y.Peng, H.Zhang, Angew.Chem.Int.Ed.2011,50,1.), vapour deposition process (L.Song, L.Ci, H.Lu, P.B.Sorokin, C.Jin, J.Ni, A.G.Kvashnin, D.G.Kvashnin, J.Lou, B.I.Yakobson, P.M.Ajayan, Nano Lett.2010,10,3209), these methods are all to use for reference the preparation method of Graphene substantially.
Because hexagonal boron nitride monocrystalline up to now does not still have commercialization, so preparing boron nitride nanosheet, micromechanics stripping method is just restricted; In addition, the method productive rate is very low.Liquid phase stripping method need to be selected suitable solvent, and these solvents are often expensive, and boiling point is high, needs special processing while testing in addition.Vapour deposition process is prepared h-BN nanometer sheet often needs temperature very high, and normally 1000 ℃, and also raw material is poisonous, and experimentation is difficult to control.
Summary of the invention
For the existing deficiency of preparing the existence of hexagonal boron nitride (h-BN) nanometer sheet technology of preparing, the present invention proposes a kind of molten caustic soda that utilizes simple to operate, that cost is low and prepares the method for two-dimentional hexagonal nanometer boron nitride sheet.
The present invention utilizes molten caustic soda to prepare the method for two-dimentional hexagonal nanometer boron nitride sheet, comprises the following steps:
(1) by alkali (as lithium hydroxide, sodium hydroxide, potassium hydroxide etc.) and hexagonal boron nitride (h-BN) in molar ratio the ratio of 1:1-100:1 mix and grind evenly, and transfer in reactor;
(2) reactor is placed in to process furnace and carries out reacting by heating, the melting temperature that Heating temperature is alkali, to more than fusing point between 50 ℃, makes alkali fusion, and the reaction times is 1-24 hour, takes out reactor, is cooled to room temperature;
(3) reaction product in reactor is washed to pH value 6-8, then is dissolved in separation in solvent, can obtain boron nitride nanosheet.
Described alkali is a kind of alkali, or the mixture of two kinds of alkali arbitrary proportions.While adopting the mixture of two kinds of alkali, described in step (2), the fusing point of alkali is the eutectic point of two kinds of alkali, need to be according to the ratio-dependent of two kinds of alkali.
Described solvent is that toluene, ethanol, methyl alcohol, Virahol, water or other can make the solvent of boron nitride nanosheet separation.
The present invention, by alkali reacting by heating together with hexagonal boron nitride, utilizes the alkali after melting to peel off boron nitride, with this, prepares boron nitride nanosheet, simple to operate, cost is low, does not need the plant and instrument of complex and expensive, and alkali raw material used is cheap and easy to get, little to environmental toxicity, and react temperature required lower
Accompanying drawing explanation
Fig. 1 is the photo that boron nitride nanosheet prepared by the present invention is dissolved in respectively the Tyndall phenomenon that in toluene, ethanol, isopropyl alcohol and water, (from left to right) produces under laser radiation.
Fig. 2 is the stereoscan photograph of the boron nitride nanosheet prepared of the present invention.
Fig. 3 is the transmission electron microscope photo (100nm is length scales) of the boron nitride nanosheet prepared of the present invention.
Fig. 4 has provided the atomic force microscopy of boron nitride nanosheet and the thickness of nanometer sheet size prepared by the present invention.Left side figure is the shape appearance figure of nanometer sheet, and the right figure is the gauge of nanometer sheet different positions.
Embodiment
Embodiment 1
(1) weighing sodium hydroxide 2.060g, potassium hydroxide 2.716g and h-BN(hexagonal boron nitride) mol ratio of 0.2482g(sodium hydroxide and potassium hydroxide is 51.5:48.5, the mixture of two kinds of alkali and the mol ratio of h-BN are 10:1), mix and be placed in the mortar of glass material, grind and (mesh-of-grind is not required for 10 minutes, the object of grinding is in order to mix), transfer in teflon-lined stainless steel cauldron.
(2) reactor is placed in to 180 ℃ of process furnace and reacts 2 hours, take out reactor, be cooled to room temperature.Sodium hydroxide and the potassium hydroxide in molar ratio temperature of the mixed eutectic point of 51.5:48.5 are 165 ℃, and temperature of reaction can be arranged on 180 ℃.
(3) reaction product in reactor is dissolved in to 300ml deionized water, by Büchner funnel, filters, clean to filtrate pH value 6-8.Be dissolved in toluene, ethanol, Virahol or water, standing separation or centrifugation, can obtain boron nitride nanosheet again.
Fig. 1 is the photo that boron nitride nanosheet prepared by the present invention is dissolved in respectively the Tyndall phenomenon that in toluene, ethanol, isopropyl alcohol and water, (from left to right) produces under laser radiation.
Fig. 2 has provided the stereoscan photograph of boron nitride nanosheet prepared by the present embodiment.
Fig. 3 has provided the transmission electron microscope photo of boron nitride nanosheet prepared by the present embodiment.
Fig. 4 has provided the atomic force microscopy of boron nitride nanosheet and the thickness of nanometer sheet size prepared by the present embodiment.
Embodiment 2
As described in Example 1, difference is: middle sodium hydroxide 4.120g, potassium hydroxide 5.432g and the h-BN(hexagonal boron nitride of weighing of step (1)) mol ratio of 0.2482g(sodium hydroxide and potassium hydroxide is 51.5:48.5, and the mixture of two kinds of alkali and the mol ratio of h-BN are 10:1).The mixed temperature of eutectic point of sodium hydroxide and potassium hydroxide is 160 ℃, and temperature of reaction is 160 ℃.Reaction times is 15 hours
Embodiment 3
As described in Example 1, difference is: middle lithium hydroxide 3.473g, sodium hydroxide 14.2g and the h-BN(hexagonal boron nitride of weighing of step (1)) mol ratio of 0.2482g(lithium hydroxide and sodium hydroxide is 29:71, the mixture of two kinds of alkali and the mol ratio of h-BN are 50:1), the temperature of eutectic point of lithium hydroxide and sodium hydroxide mixture is 220 ℃, temperature of reaction is set to 225 ℃, and the reaction times is 6 hours.Product in reactor is dissolved in toluene.
Embodiment 4
As described in Example 1, difference is: middle lithium hydroxide 7.425g, potassium hydroxide 38.713g and the h-BN(hexagonal boron nitride of weighing of step (1)) mol ratio of 0.2482g(lithium hydroxide and potassium hydroxide is 31:69, the mixture of two kinds of alkali and the mol ratio of h-BN are 100:1), the temperature of the eutectic point of lithium hydroxide and potassium hydroxide mixture is 225 ℃, temperature of reaction is set to 235 ℃, and the reaction times is 20 hours.Product in reactor is soluble in water.
Embodiment 5
The mol ratio that takes lithium hydroxide 0.2395g and h-BN powder 0.24g(lithium hydroxide and h-BN is 1:1), after ground and mixed is even, be transferred to reactor, reactor is placed in to 480 ℃ of process furnace and reacts 24 hours, take out reactor, be cooled to room temperature.Be washed to filtrate pH value 6-8.Product in reactor is dissolved in toluene.The fusing point of lithium hydroxide is 471 ℃, and temperature of reaction is set to 480 ℃.
Embodiment 6
The mol ratio of weighing sodium hydroxide 8g and h-BN powder 0.24g(sodium hydroxide and h-BN is 20:1), after ground and mixed is even, be transferred to reactor, reactor is placed in to 330 ℃ of process furnace and reacts 6 hours, take out reactor, be cooled to room temperature.Be washed to filtrate pH value 6-8.Product in reactor is dissolved in methyl alcohol.The fusing point of lithium hydroxide is 318 ℃, and temperature of reaction is set to 330 ℃.
Embodiment 7
The mol ratio that takes potassium hydroxide 28.053g and h-BN powder 0.24g(potassium hydroxide and h-BN is 50:1), after ground and mixed is even, be transferred to reactor, reactor is placed in to 410 ℃ of process furnace and reacts 1 hour, take out reactor, be cooled to room temperature.Be washed to filtrate pH value 6-8.Product in reactor is dissolved in Virahol.The fusing point of lithium hydroxide is 360 ℃, and temperature of reaction is set to 410 ℃.
Claims (1)
1. utilize molten caustic soda to prepare a method for two-dimentional hexagonal nanometer boron nitride sheet, it is characterized in that, comprise the following steps:
(1) by alkali and hexagonal boron nitride in molar ratio the ratio of 1:1-100:1 mix and grind evenly, and transfer in reactor, described alkali is the mixture of a kind of or two kinds of arbitrary proportions in lithium hydroxide, sodium hydroxide and three kinds of alkali of potassium hydroxide;
(2) reactor is placed in to process furnace and carries out reacting by heating, the melting temperature that Heating temperature is alkali, to more than fusing point between 50 ℃, makes alkali fusion, and the reaction times is 1-24 hour, takes out reactor, is cooled to room temperature;
(3) reaction product in reactor is washed to pH value 6-8, then is dissolved in separation in solvent, obtain boron nitride nanosheet.
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| WO2015076375A1 (en) * | 2013-11-25 | 2015-05-28 | 独立行政法人物質・材料研究機構 | Oxygen reduction electrode catalyst, electrode catalyst for hydrogen generation reaction, and electrode |
| CN105253862B (en) * | 2014-07-15 | 2019-03-12 | 中国科学院过程工程研究所 | A kind of method of high-temperature liquid-phase removing large scale preparation class graphene boron nitride nanosheet |
| CN106082147B (en) * | 2016-05-31 | 2018-06-05 | 山东大学 | The method that a kind of liquid phase chemical stripping of stabilization prepares boron nitride nanosheet |
| CN108529573B (en) * | 2017-03-06 | 2021-12-07 | 中国科学院宁波材料技术与工程研究所 | Method for preparing hexagonal boron nitride nanosheets by using molten alkali and ultrasonic stripping technology |
| CN107337185A (en) * | 2017-06-27 | 2017-11-10 | 华南农业大学 | A kind of hydrophily boron nitride nanosheet and its preparation method and application |
| CN108190959B (en) * | 2018-01-23 | 2020-05-08 | 福州大学 | Method for preparing single-layer molybdenum sulfide based on molten alkali metal liquid insertion stripping |
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| CN110484206B (en) * | 2019-08-23 | 2021-08-20 | 河南富莱格超硬材料有限公司 | Cubic boron nitride abrasive surface treatment method |
| CN114031078B (en) * | 2021-11-19 | 2024-04-12 | 徐州纳烯新材料研究院有限公司 | Preparation method of fluorine-free MXene two-dimensional nanosheets |
| CN116178642B (en) * | 2023-04-24 | 2023-07-25 | 山东鹏程陶瓷新材料科技有限公司 | Surface grafting modified hexagonal boron nitride and preparation method thereof |
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| CN101244812A (en) * | 2008-02-26 | 2008-08-20 | 武汉理工大学 | Method for manufacturing flying saucer shaped nano-hexagonal boron nitride powder |
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| WO2012115348A2 (en) * | 2011-02-23 | 2012-08-30 | 한국과학기술원 | High-quality hexagonal boron-nitride nanosheet using a multi-component low eutectic temperature system |
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| CN101244812A (en) * | 2008-02-26 | 2008-08-20 | 武汉理工大学 | Method for manufacturing flying saucer shaped nano-hexagonal boron nitride powder |
| CN101913576A (en) * | 2010-08-12 | 2010-12-15 | 山东大学 | Preparation method of ultrathin boron nitride nanosheet with high specific surface area |
| WO2012115348A2 (en) * | 2011-02-23 | 2012-08-30 | 한국과학기술원 | High-quality hexagonal boron-nitride nanosheet using a multi-component low eutectic temperature system |
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