CN106517112A - Boron nitride nanotube for hydrogen storage and synthesis method - Google Patents
Boron nitride nanotube for hydrogen storage and synthesis method Download PDFInfo
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- CN106517112A CN106517112A CN201611112194.XA CN201611112194A CN106517112A CN 106517112 A CN106517112 A CN 106517112A CN 201611112194 A CN201611112194 A CN 201611112194A CN 106517112 A CN106517112 A CN 106517112A
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- 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
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Abstract
The invention provides a boron nitride nanotube for hydrogen storage and a synthesis method. The synthesis method comprises two steps as follows: step one, synthesizing a precursor of the boron nitride nanotube from a boron trifluoride etherate solution as raw material; step two, preparing the boron nitride nanotube with high specific surface area and high adsorption activity with a low-temperature chemical vapor deposition method under conditions of protective atmosphere and carrier gas. The boron nitride nanotube synthesized with the method has high purity and large specific surface area; the synthesis method is simple, reliable, cheap and suitable for large-scale synthesis. The hydrogen adsorption capacity of the synthesized boron nitride nanotube at the room temperature is up to 0.6 g per gram, 90% of the adsorption capacity is still maintained after the boron nitride nanotube is reused 70 times, and defects of low hydrogen storage capacity, low reuse efficiency and the like of common hydrogen storage materials are overcome, therefore, the boron nitride nanotube has broad prospect in the field of hydrogen energy application.
Description
Technical field
Technical scheme is related to the hexagonal nanometer boron nitride ceramic material of tubular morphology, specifically a kind of to use
In boron nitride nano-tube and the synthetic method of hydrogen storage.
Background technology
Boron nitride is a kind of typical III-V compounds of group, as a kind of by nitrogen (N) atom and boron (B) atomic building
The layer structure material of similar graphite, with preferable processability, heat resistanceheat resistant shake anti-electricity shake, higher anti-electric field breakdown strengths, nothing
Poison ring protects, and various metals do not infiltrate, the excellent physicochemical characteristicss such as resistance to chemical attack, be widely used in cosmetics, it is high
Temperature, high frequency, high-power, photoelectron and radioprotective device, ultraviolet cosmic space, wave transparent, antifriction high performance turbine, guided missile,
The military project space industries such as carrier rocket, return formula satellite and macromolecule composite strengthening toughness reinforcing, composite ceramicses are modified and improve modeling
The fields such as material thermal conductivity.
Boron nitride nano-tube is the boron nitride nanometer material that a class is made up of tubular structure the hole being mutually communicated.Boron nitride
Nanotube integrates the advantage of boron nitride layer structure and loose structure, not only lacks with big specific surface area, abundant structure
Sunken position, and with excellent antioxygenic property, structural stability and chemical stability, thus have at aspects such as gas absorptions
Wide application prospect.
In recent years, substantial amounts of research work is devoted to the high-quality tubulose boron nitride nanostructure of control synthesis, preparation
Method has template, ball-milling method and chemical vapour deposition technique.Han et al. CNTs, B2O3And N2It is being more than as reactant
Boron nitride nano-tube (W.Q.Han, P.J.Todd, M.Strongin, Applied Physics is prepared under conditions of 1500 DEG C
Letters 2006,89,173103.)；Singhal et al. passes through ball-milling method big using pure boron powder and ammonia as reactant
Prepare under conditions of 1300 DEG C boron nitride nano-tube (S.K.Singhal, A.K.Srivastava, R.P.Pant,
S.K.Halder,B.P.Singh,A.K.Gupta,Journal of Materials Science 2008,43,5243.)；
Kuznetsov et al. is prepared more than under conditions of 3500 DEG C by arc process using hexagonal nanometer boron nitride granule as reactant
Boron nitride nano-tube (V.L.Kuznetsov, I.N.Mazov, A.I.Delidovich, E.D.Obraztsova, A.Loiseau,
Physica Status Solidi B 2007,244,4165.)；Tang et al. is using platinum as catalyst auxiliary synthesis collapse nitrogen
Change boron nanotube (C.C.Tang, Y.Bando, X.X.Ding, S.R.Qi, D.J.Golberg, J.Am.Chem.Soc.2002,
124,14550.).Zhi et al. with boron powder and metal-oxide as reactant prepare boron nitride nano-tube (C.Y.Zhi,
Y.Bando,C.C.Tan,D.Golberg,Solid State Communications 2005,135,67.).These methods are closed
Into boron nitride nano-tube yardstick it is uneven, bigger shortcoming is that building-up process needs high temperature, not only high energy consumption, and
Increased the potential safety hazard of production.Additionally, USDOE proposes solid-state hydrogen storage material in 2017 should store 5.5wt%
Hydrogen, existing preparation method cannot meet this requirement, therefore in the urgent need to a kind of preparation cost is cheap, process is simple, ring
Border pollution is little, and energy consumption is low, and the method that products obtained therefrom has high hydrogen storage ability.
The content of the invention
The technical problem to be solved is：There is provided a kind of boron nitride nano-tube with high-specific surface area it is low into
Originally, high yield, and the synthetic method of process is simple.Synthesized using two steps：The first step, prepares boron nitride by chemical Bubbling method and receives
Mitron presoma.Second step, with metal chloride as catalyst, by low temperature chemical vapor deposition method synthesizing high specific surface area
Boron nitride nano-tube.This synthetic method overcomes existing building-up process needs high temperature, complex technical process and raw material to hold high
Expensive shortcoming, is reactant using more cheap raw material of industry boron trifluoride ether solution, replaces expensive boron powder, greatly drops
Low production cost and energy expenditure, and products therefrom has high specific surface area.Therefore, the life of this boron nitride nano-tube
Production. art can scale production, be with a wide range of applications in new energy field.
A kind of synthetic method of the boron nitride nano-tube for hydrogen storage, its step is：
(1) 1～100 milliliter of boron trifluoride ether solution is added in the container with reflux, its backflow temperature
Spend for -4～10 DEG C, then ammonia is passed through from the bottom of container, its throughput is 10～200 ml/mins, and duration of ventilation is
1～100 minute, there is precipitate to separate out；
(2) precipitate obtained in step (1) is put in 40-80 DEG C of drying baker, is incubated 1-200 minutes；
(3) solid obtained in step (2) is placed on the inlet port of shielding gas and carrier gas, and metal chloride and its
Mol ratio is 1:0.1～1:10 amount is placed in the outlet port apart from 2～20 centimetres of boron nitride nano-tube presoma；In shielding gas
200～800 DEG C of heat treatments under atmosphere, heating rate are 500～1000 DEG C per minute, and temperature retention time is 1～3 minute；Obtain product
For boron nitride nano-tube.
Metal chloride described in previous step (3) is Sodium Chloride, potassium chloride, magnesium chloride, aluminum chloride, calcium chloride, chlorine
Change ferrum, copper chloride, manganese chloride, Chlorizate chromium, zinc chloride or cobaltous chloride.
When protective atmosphere and carrier gas in previous step (3) is neon, Krypton, argon, ammonia or nitrogen, gas flow rate is
1-200 milliliters/per minute.
Thus, the product 1. obtained by the inventive method is the boron nitride with hexagonal structure, as shown in figure 1, powder X-ray is penetrated
In ray diffraction diagram spectrum, Radix Rumiciss part (2 θ=10-90 °) diffraction maximum is clear, is staggered floor boron nitride, and does not have spreading out for other dephasigns
Peak appearance is penetrated, illustrates that gained boron nitride nano-tube purity is higher；Scanning electron microscopes of the Fig. 2 and Fig. 3 for boron nitride nano-tube
Figure and transmission electron microscope figure, it is homogeneous to respectively illustrate the nanotube pattern that this method obtains, with very big draw ratio, and
And also indicating that boron nitride nano-tube is hollow tubular structure, internal-and external diameter is basically identical, and tube wall has abundant fault of construction position；
Fig. 4 is the absorption of nitrogen and desorption isotherm in a low temperature of boron nitride nano-tube, it is shown that gained boron nitride nano-tube has height
Specific surface area.
2. present invention gained boron nitride nano-tube has the properties such as peculiar light, electricity, magnetic, heat and absorption, particularly high
The characteristics such as specific surface area, abundant fault of construction and B-N bond polarities so as to become excellent hydrogen storage material, its hydrogen storage content are high
Up to the 6wt% of mass ratio, as shown in figure 5, there is extensive prospect in hydrogen storage applications field.
3. the raw material that the present invention is adopted belongs to industrialization product for boron trifluoride ether solution, and price is relatively inexpensive to be easy to get,
Production cost can be greatly reduced.
4. synthesis used in the present invention is needed compared with low temperature, technical process simply, is suitable to scale industrial production.
Description of the drawings
Fig. 1 is boron nitride nano-tube X-ray diffraction spectrogram in example 1.
Fig. 2 is boron nitride nano-tube scanning electron microscope diagram in example 1.
Fig. 3 is boron nitride nano-tube transmission electron microscope figure in example 1.
Fig. 4 is boron nitride nano-tube low temperature nitrogen adsorption and desorption isothermal line in example 1.
Fig. 5 is boron nitride nano-tube room temperature hydrogen adsorption isothermal line in example 1.
Specific embodiment
Below in conjunction with the accompanying drawings and it is embodied as that the present invention will be further described.
Embodiment 1
(1) 1 milliliter of boron trifluoride ether solution is added in the glass container with reflux, its reflux temperature
For -4 DEG C, then ammonia is passed through from the bottom of glass container, its throughput is 10 ml/mins, and duration of ventilation is 1 minute,
There is precipitate to separate out.
(2) precipitate obtained in step (1) is put in 40 DEG C of drying bakers, is incubated 1 minute.
(3) solid obtained in step (2) is placed on the inlet port of nitrogen, and metal chloride with its mol ratio is
1:0.1 amount is placed in the outlet port apart from 2 centimetres of boron nitride nano-tube presoma；200 DEG C of heat treatments under neon protection, rise
Warm speed is 500 DEG C per minute, and temperature retention time is 1 minute.Product is obtained for boron nitride nano-tube.
By to powder product X-ray diffractogram analysis of spectrum, the diffraction maximum explanation product in Fig. 1 is with hexagonal structure
Boron nitride, and for the boron nitride of staggered floor construction, because the diffraction maximum for not having obvious other dephasigns occurs, gained boron nitride is received
Mitron purity is higher；Scanning electron microscope diagrams of the Fig. 2 for boron nitride nano-tube, it can be seen which is filamentary structure, its shape
Looks are homogeneous, with very big draw ratio, a diameter of 10～20 nanometers, a length of 20～100 microns；Jing transmission electron microscope figures
(Fig. 3) observation can be obtained, and boron nitride nano-tube is that hollow tubular structure, about 3～5 nanometers of wall thickness, and tube wall presence are abundant
Fault of construction；By absorption and the desorption isotherm of nitrogen in a low temperature of Fig. 4, gained boron nitride nano-tube specific surface can be calculated
Product is 877 square metres per gram, and pore volume is 0.97 cubic metre per gram；Again through the test to boron nitride nano-tube hydrogen storage ability
(Fig. 5), it can be deduced that conclusion, up to per gram absorption 0.6g of its absorbability to hydrogen under room temperature and 3MPa, repeats 70 times
The 90% of absorbability is remained in that, is overcome conventional hydrogen storage material hydrogen storage ability low and is reused the defects such as inefficient,
Hydrogen energy source application has extensive prospect.
Embodiment 2, example 3
The consumption of step (1) boron trifluoride ether solution in embodiment 1 is changed to into 50 milliliters, 100 milliliters, it is other every
Operation is same as Example 1, obtains product with embodiment 1.
Embodiment 4, example 5
Step (1) reflux temperature in embodiment 1 is changed to into 3 DEG C, 10 DEG C respectively, other operations with embodiment 1
It is identical, product is obtained with embodiment 1.
Embodiment 6, example 7
Step (1) ammonia flow in embodiment 1 is changed to into 100 ml/mins, 200 ml/mins respectively, it is other each
Item operation is same as Example 1, obtains product with embodiment 1.
Embodiment 8, example 9
Step (1) duration of ventilation in embodiment 1 is changed to 50 minutes, 100 minutes respectively, other operations with reality
Apply example 1 identical, product is obtained with embodiment 1.
Embodiment 10, example 11
Step (2) drying temperature in embodiment 1 is changed to into 60 DEG C, 80 DEG C respectively, other operations with embodiment 1
It is identical, product is obtained with embodiment 1.
Embodiment 12, example 13
Step (2) drying time in embodiment 1 is changed to 100 minutes, 200 minutes respectively, other operations with
Embodiment 1 is identical, obtains product with embodiment 1.
Embodiment 14, example 15
Step (3) metal chloride in embodiment 1 is changed to into 1 respectively with mol ratio:1、1:10, other operations are equal
It is same as Example 1, product is obtained with embodiment 1.
Embodiment 16, example 17
Step (3) metal chloride in embodiment 1 is placed in the length apart from boron nitride nano-tube presoma to be changed to respectively
10 centimetres, 20 centimetres, other operations are same as Example 1, obtain product with embodiment 1.
Embodiment 18, example 19
Step (3) heat treatment temperature in embodiment 1 is changed to into 400 DEG C, 800 DEG C respectively, other operations with reality
Apply example 1 identical, product is obtained with embodiment 1.
Embodiment 20, example 21
Step (3) heating rate in embodiment 1 is changed to into 750 DEG C per minute, 1000 DEG C respectively, other operations are equal
It is same as Example 1, product is obtained with embodiment 1.
Embodiment 22, example 23
Step (3) temperature retention time in embodiment 1 is changed to 2 minutes, 3 minutes respectively, other operations with enforcement
Example 1 is identical, obtains product with embodiment 1.
Embodiment 24-33
Step (3) metal chloride in embodiment 1 is changed to into potassium chloride, magnesium chloride, aluminum chloride, calcium chloride, chlorination respectively
Ferrum, copper chloride, manganese chloride, Chlorizate chromium, zinc chloride or cobaltous chloride, other operations are same as Example 1, obtain product
With embodiment 1.
Embodiment 34-37
Step (3) protective atmosphere in embodiment 1 is changed to into Krypton, argon, ammonia or nitrogen, other operations respectively
It is same as Example 1, product is obtained with embodiment 1.
Claims (8)
1. a kind of synthetic method of the boron nitride nano-tube for hydrogen storage, it is characterised in that its step is：
(1) 1～100 milliliter of boron trifluoride ether solution is added in the glass container with reflux, its backflow temperature
Spend for -4～10 DEG C, then ammonia is passed through from the bottom of glass container, its throughput is 10～200 ml/mins, during ventilation
Between be 1～100 minute, have precipitate to separate out；
(2) precipitate obtained in step (1) is put in 40-80 DEG C of drying baker, is incubated 1-200 minutes；
(3) solid obtained in step (2) is placed on the inlet port of shielding gas, and metal chloride is 1 with its mol ratio:
0.1～1:10 amount is placed in the outlet port apart from 2～20 centimetres of boron nitride nano-tube presoma；200 under protective atmosphere～
800 DEG C of heat treatments, heating rate are 500～1000 DEG C per minute, and temperature retention time is 1～3 minute, obtains product and receives for boron nitride
Mitron.
2. it is according to claim 1 it is a kind of for hydrogen storage boron nitride nano-tube synthetic method, it is characterised in that：
Metal chloride described in step (3) be Sodium Chloride, potassium chloride, magnesium chloride, aluminum chloride, calcium chloride, iron chloride, copper chloride,
Manganese chloride, Chlorizate chromium, zinc chloride or cobaltous chloride.
3. it is according to claim 1 it is a kind of for hydrogen storage boron nitride nano-tube synthetic method, it is characterised in that：
Protective atmosphere in step (3) is neon, Krypton, argon, ammonia or nitrogen, and gas flow rate is 1-200 milliliters/per minute.
4. the boron nitride nano-tube being fabricated to according to claim 1 synthetic method, it is characterised in that：Boron nitride nano-tube is six sides
The boron nitride of structure, and be staggered floor construction.
5. the boron nitride nano-tube being fabricated to according to claim 4 synthetic method, it is characterised in that：Boron nitride nano-tube is hollow
Tubular structure, internal-and external diameter is consistent, and tube wall has abundant fault of construction position.
6. the boron nitride nano-tube being fabricated to according to claim 4 synthetic method, it is characterised in that：Boron nitride nano-tube has height
Specific surface area.
7. the boron nitride nano-tube being fabricated to according to claim 4 synthetic method, it is characterised in that：Gained boron nitride nanometer pipe
There are B-N bond polarity characteristics.
8. the boron nitride nano-tube being fabricated to according to claim 4 synthetic method, it is characterised in that：Boron nitride nano-tube has
Light, electricity, magnetic, heat and adsorption property.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107262128A (en) * | 2017-05-23 | 2017-10-20 | 湖北第二师范学院 | Visible-light response type nitride porous boryl composite photocatalyst material and preparation method |
| CN111268688A (en) * | 2020-03-23 | 2020-06-12 | 河北工业大学 | Method for low-temperature synthesis of boron nitride and ammonium fluoroborate |
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| CN1539729A (en) * | 2003-10-27 | 2004-10-27 | 北京科技大学 | Method for synthesizing boron nitride from aether boron trifluoride and lithium nitride |
| CN101633498A (en) * | 2009-09-01 | 2010-01-27 | 北京工业大学 | Preparation method of boron nitride nano tube with controllable dimension |
| CN104860273A (en) * | 2015-03-25 | 2015-08-26 | 孙旭阳 | Method for preparing two-dimensional hexagonal boron nitride by using molten state reaction bed |
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Patent Citations (3)
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| CN1539729A (en) * | 2003-10-27 | 2004-10-27 | 北京科技大学 | Method for synthesizing boron nitride from aether boron trifluoride and lithium nitride |
| CN101633498A (en) * | 2009-09-01 | 2010-01-27 | 北京工业大学 | Preparation method of boron nitride nano tube with controllable dimension |
| CN104860273A (en) * | 2015-03-25 | 2015-08-26 | 孙旭阳 | Method for preparing two-dimensional hexagonal boron nitride by using molten state reaction bed |
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| CHENGCHUN TANG ET AL.: "Fluorination and Electrical Conductivity of BN Nanotubes", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107262128A (en) * | 2017-05-23 | 2017-10-20 | 湖北第二师范学院 | Visible-light response type nitride porous boryl composite photocatalyst material and preparation method |
| CN107262128B (en) * | 2017-05-23 | 2020-12-15 | 湖北第二师范学院 | Visible light response type porous boron nitride-based composite photocatalytic material and preparation method thereof |
| CN111268688A (en) * | 2020-03-23 | 2020-06-12 | 河北工业大学 | Method for low-temperature synthesis of boron nitride and ammonium fluoroborate |
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