CN107673318B - Boron nitride nanotubes and batch preparation method thereof - Google Patents
Boron nitride nanotubes and batch preparation method thereofDownload PDFInfo
- Publication number
- CN107673318B CN107673318BCN201610619062.XACN201610619062ACN107673318BCN 107673318 BCN107673318 BCN 107673318BCN 201610619062 ACN201610619062 ACN 201610619062ACN 107673318 BCN107673318 BCN 107673318B
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- nitride nanotubes
- boron
- transition metal
- atmosphere
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PZNSFCLAULLKQX-UHFFFAOYSA-NBoron nitrideChemical compoundN#BPZNSFCLAULLKQX-UHFFFAOYSA-N0.000titleclaimsabstractdescription54
- 238000002360preparation methodMethods0.000titleclaimsabstractdescription18
- 239000012298atmosphereSubstances0.000claimsabstractdescription31
- 238000000034methodMethods0.000claimsabstractdescription25
- ZOXJGFHDIHLPTG-UHFFFAOYSA-NBoronChemical compound[B]ZOXJGFHDIHLPTG-UHFFFAOYSA-N0.000claimsabstractdescription22
- 239000003054catalystSubstances0.000claimsabstractdescription22
- 229910052796boronInorganic materials0.000claimsabstractdescription21
- QGZKDVFQNNGYKY-UHFFFAOYSA-NAmmoniaChemical compoundNQGZKDVFQNNGYKY-UHFFFAOYSA-N0.000claimsabstractdescription20
- 239000012043crude productSubstances0.000claimsabstractdescription18
- 239000002243precursorSubstances0.000claimsabstractdescription14
- 229910052582BNInorganic materials0.000claimsabstractdescription12
- BTBUEUYNUDRHOZ-UHFFFAOYSA-NBorateChemical compound[O-]B([O-])[O-]BTBUEUYNUDRHOZ-UHFFFAOYSA-N0.000claimsabstractdescription12
- 238000006243chemical reactionMethods0.000claimsabstractdescription12
- 239000002071nanotubeSubstances0.000claimsabstractdescription11
- 150000003623transition metal compoundsChemical class0.000claimsabstractdescription10
- QJGQUHMNIGDVPM-UHFFFAOYSA-Nnitrogen groupChemical group[N]QJGQUHMNIGDVPM-UHFFFAOYSA-N0.000claimsabstractdescription8
- 238000010438heat treatmentMethods0.000claimsabstractdescription6
- 230000001681protective effectEffects0.000claimsabstractdescription6
- 229910021529ammoniaInorganic materials0.000claimsabstractdescription5
- 238000004519manufacturing processMethods0.000claimsabstractdescription4
- 238000001816coolingMethods0.000claimsabstract2
- 238000004321preservationMethods0.000claimsabstract2
- IJGRMHOSHXDMSA-UHFFFAOYSA-NAtomic nitrogenChemical compoundN#NIJGRMHOSHXDMSA-UHFFFAOYSA-N0.000claimsdescription17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-NEthanolChemical compoundCCOLFQSCWFLJHTTHZ-UHFFFAOYSA-N0.000claimsdescription9
- 229910052757nitrogenInorganic materials0.000claimsdescription9
- 238000000498ball millingMethods0.000claimsdescription7
- 239000001257hydrogenSubstances0.000claimsdescription7
- 229910052739hydrogenInorganic materials0.000claimsdescription7
- 229910052723transition metalInorganic materials0.000claimsdescription7
- UFHFLCQGNIYNRP-UHFFFAOYSA-NHydrogenChemical compound[H][H]UFHFLCQGNIYNRP-UHFFFAOYSA-N0.000claimsdescription5
- 238000002156mixingMethods0.000claimsdescription5
- -1transition metal saltChemical class0.000claimsdescription5
- 238000001035dryingMethods0.000claimsdescription4
- 239000002904solventSubstances0.000claimsdescription4
- 229910000314transition metal oxideInorganic materials0.000claimsdescription4
- 239000002253acidSubstances0.000claimsdescription3
- 238000005406washingMethods0.000claimsdescription2
- 238000010923batch productionMethods0.000claims6
- 229910011131Li2B4O7Inorganic materials0.000claims1
- 229910019791Mg3B2Inorganic materials0.000claims1
- 150000001642boronic acid derivativesChemical group0.000claims1
- UFMZWBIQTDUYBN-UHFFFAOYSA-Ncobalt(II) nitrateInorganic materials[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=OUFMZWBIQTDUYBN-UHFFFAOYSA-N0.000claims1
- 238000007654immersionMethods0.000claims1
- JEIPFZHSYJVQDO-UHFFFAOYSA-Niron(III) oxideInorganic materialsO=[Fe]O[Fe]=OJEIPFZHSYJVQDO-UHFFFAOYSA-N0.000claims1
- 239000002131composite materialSubstances0.000abstractdescription2
- 239000000463materialSubstances0.000abstractdescription2
- 239000000843powderSubstances0.000description13
- NFMWFGXCDDYTEG-UHFFFAOYSA-Ntrimagnesium;diborateChemical compound[Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-]NFMWFGXCDDYTEG-UHFFFAOYSA-N0.000description10
- PNEYBMLMFCGWSK-UHFFFAOYSA-Naluminium oxideInorganic materials[O-2].[O-2].[O-2].[Al+3].[Al+3]PNEYBMLMFCGWSK-UHFFFAOYSA-N0.000description5
- 239000012300argon atmosphereSubstances0.000description5
- 238000005229chemical vapour depositionMethods0.000description4
- 238000004098selected area electron diffractionMethods0.000description4
- 229910000608Fe(NO3)3.9H2OInorganic materials0.000description3
- 239000002041carbon nanotubeSubstances0.000description3
- 239000000203mixtureSubstances0.000description3
- 239000002245particleSubstances0.000description3
- OKTJSMMVPCPJKN-UHFFFAOYSA-NCarbonChemical compound[C]OKTJSMMVPCPJKN-UHFFFAOYSA-N0.000description2
- VEXZGXHMUGYJMC-UHFFFAOYSA-NHydrochloric acidChemical compoundClVEXZGXHMUGYJMC-UHFFFAOYSA-N0.000description2
- 238000003917TEM imageMethods0.000description2
- 229910021393carbon nanotubeInorganic materials0.000description2
- 239000013078crystalSubstances0.000description2
- 230000007812deficiencyEffects0.000description2
- 150000002431hydrogenChemical class0.000description2
- 238000009413insulationMethods0.000description2
- 239000011777magnesiumSubstances0.000description2
- 239000002086nanomaterialSubstances0.000description2
- 230000003647oxidationEffects0.000description2
- 238000007254oxidation reactionMethods0.000description2
- 238000001878scanning electron micrographMethods0.000description2
- 238000001237Raman spectrumMethods0.000description1
- 230000003078antioxidant effectEffects0.000description1
- 238000001241arc-discharge methodMethods0.000description1
- 239000011247coating layerSubstances0.000description1
- 239000004020conductorSubstances0.000description1
- 238000000354decomposition reactionMethods0.000description1
- 239000008367deionised waterSubstances0.000description1
- 229910021641deionized waterInorganic materials0.000description1
- 238000010586diagramMethods0.000description1
- XLYOFNOQVPJJNP-UHFFFAOYSA-MhydroxideChemical compound[OH-]XLYOFNOQVPJJNP-UHFFFAOYSA-M0.000description1
- 238000005470impregnationMethods0.000description1
- 239000011810insulating materialSubstances0.000description1
- 238000000608laser ablationMethods0.000description1
- 238000011068loading methodMethods0.000description1
- 230000007774longtermEffects0.000description1
- 229910052751metalInorganic materials0.000description1
- 239000002184metalSubstances0.000description1
- 238000012986modificationMethods0.000description1
- 230000004048modificationEffects0.000description1
- 239000012299nitrogen atmosphereSubstances0.000description1
- 239000000047productSubstances0.000description1
- 239000002994raw materialSubstances0.000description1
- 238000013341scale-upMethods0.000description1
- 239000004065semiconductorSubstances0.000description1
- 239000007787solidSubstances0.000description1
- 239000011232storage materialSubstances0.000description1
- 239000000126substanceSubstances0.000description1
- 239000000758substrateSubstances0.000description1
- 230000002194synthesizing effectEffects0.000description1
- 238000005979thermal decomposition reactionMethods0.000description1
- 230000001988toxicityEffects0.000description1
- 231100000419toxicityToxicity0.000description1
- XLYOFNOQVPJJNP-UHFFFAOYSA-NwaterChemical compoundOXLYOFNOQVPJJNP-UHFFFAOYSA-N0.000description1
Images
Classifications
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Fibers (AREA)
Abstract
Description
Translated fromChinese技术领域technical field
本发明具体涉及一种氮化硼纳米管的批量制备方法，属于无机纳米材料技术领域。The invention specifically relates to a batch preparation method of boron nitride nanotubes, which belongs to the technical field of inorganic nanomaterials.
背景技术Background technique
氮化硼纳米管(BNNT)作为一种新型的纳米材料，其不仅与碳纳米管(CNT)有着类似的晶体结构，而且还有着与CNT相媲美的力学性能和热传导性能。除此之外，氮化硼纳米管还有优异的抗氧化性、化学稳定性和良好的绝缘性。这些独特的性能使BNNT在纳米半导体器件、储氢材料、绝缘材料、以及抗氧化包覆层等领域具有广泛的应用。As a new type of nanomaterial, boron nitride nanotubes (BNNT) not only have a similar crystal structure to carbon nanotubes (CNT), but also have mechanical properties and thermal conductivity comparable to CNTs. In addition, boron nitride nanotubes have excellent oxidation resistance, chemical stability and good insulation. These unique properties make BNNT have a wide range of applications in the fields of nano-semiconductor devices, hydrogen storage materials, insulating materials, and anti-oxidative coating layers.
目前常用的氮化硼纳米管合成方法有电弧放电法、激光烧蚀法、机械球磨法、CVD法热分解法等。近年来，随着氮化硼纳米管的深入研究，在制备方法上取得很大的成功和进展。但现有的这些制备工艺普遍存在制备成本高或者设备工艺复杂，使用的原料具有一定的毒性、并且氮化硼纳米管产量不高等缺点。At present, the commonly used methods for synthesizing boron nitride nanotubes include arc discharge method, laser ablation method, mechanical ball milling method, CVD method and thermal decomposition method. In recent years, with the in-depth study of boron nitride nanotubes, great success and progress have been made in the preparation method. However, these existing preparation processes generally have the disadvantages of high preparation cost or complex equipment and process, the raw materials used have certain toxicity, and the yield of boron nitride nanotubes is low.
发明内容SUMMARY OF THE INVENTION
本发明的主要目的在于提供一种氮化硼纳米管及其批量制备方法，以克服现有技术中的不足。The main purpose of the present invention is to provide a boron nitride nanotube and a batch preparation method thereof, so as to overcome the deficiencies in the prior art.
为实现前述发明目的，本发明采用的技术方案包括：In order to realize the foregoing invention purpose, the technical scheme adopted in the present invention includes:
本发明实施例中提供了一种氮化硼纳米管的批量制备方法，其包括：An embodiment of the present invention provides a method for preparing boron nitride nanotubes in batches, which includes:
以硼酸盐为硼源负载催化剂而形成前驱物，所述催化剂包括过渡金属化合物；Using borate as a boron source supported catalyst to form a precursor, the catalyst includes a transition metal compound;
将所述前驱物于含氮气氛中加热至1200～1400℃，并在氨气气氛中保温反应，之后在保护气氛中降至室温，获得粗产物，The precursor is heated to 1200-1400° C. in a nitrogen-containing atmosphere, and the reaction is maintained in an ammonia gas atmosphere, and then lowered to room temperature in a protective atmosphere to obtain a crude product,
对所述粗产物进行后处理，制得所述氮化硼纳米管。The crude product is subjected to post-treatment to obtain the boron nitride nanotubes.
进一步的，所述氮化硼纳米管的管径为10～150nm，管长为20～100微米。Further, the diameter of the boron nitride nanotube is 10-150 nm, and the tube length is 20-100 microns.
与现有技术相比，本发明提供的氮化硼纳米管制备方法以廉价易得的硼酸盐为硼源，通过催化剂的设计，在前驱体(即硼源)表面直接获得氮化硼纳米管，不需要其他基底作为氮化硼纳米管的收集载体，工艺简单，条件易控，成本低廉，可批量生产，氮化硼纳米管产率高，且所获氮化硼纳米管在复合材料、导热材料等领域具有广阔应用前景。Compared with the prior art, the boron nitride nanotube preparation method provided by the present invention uses cheap and readily available borate as the boron source, and through the design of the catalyst, the boron nitride nanotubes are directly obtained on the surface of the precursor (ie the boron source). It does not need other substrates as a collection carrier for boron nitride nanotubes, the process is simple, the conditions are easy to control, the cost is low, it can be mass-produced, the yield of boron nitride nanotubes is high, and the obtained boron nitride nanotubes are in composite materials. , thermal conductive materials and other fields have broad application prospects.
附图说明Description of drawings
图1a-1b是本发明实施例1中制得的氮化硼纳米管的SEM图；1a-1b are SEM images of boron nitride nanotubes prepared in Example 1 of the present invention;
图2是本发明实施例1中制得的氮化硼纳米管的TEM图；2 is a TEM image of the boron nitride nanotubes prepared in Example 1 of the present invention;
图3是图2中单根氮化硼纳米管的选区电子衍射(SAED)图；Fig. 3 is the selected area electron diffraction (SAED) pattern of single boron nitride nanotube in Fig. 2;
图4是本发明实施例1中制得的氮化硼纳米管的Raman光谱图。4 is a Raman spectrum diagram of the boron nitride nanotubes prepared in Example 1 of the present invention.
具体实施方式Detailed ways
鉴于现有技术中的不足，本案发明人经长期研究和大量实践，得以提出本发明的技术方案，其主要是采用硼酸盐为硼源，通过多种负载方式，将过渡金属盐或其氧化物或氢氧化物等催化剂负载于硼酸盐表面，然后置入化学气相沉积设备中，在含氮气氛中加热并保温反应，再经后处理得到氮化硼纳米管。如下将对该技术方案、其实施过程及原理等作进一步的解释说明。In view of the deficiencies in the prior art, after long-term research and a large amount of practice, the inventor of the present invention was able to propose the technical solution of the present invention, which mainly uses borate as the boron source, and converts the transition metal salt or its oxidation through various loading methods. Catalysts such as borate or hydroxide are loaded on the surface of borate, and then placed in chemical vapor deposition equipment, heated and kept in a nitrogen-containing atmosphere for reaction, and then post-treated to obtain boron nitride nanotubes. The technical solution, its implementation process and principle will be further explained as follows.
本发明实施例的一个方面提供了一种氮化硼纳米管的批量制备方法，其包括：One aspect of the embodiments of the present invention provides a method for preparing boron nitride nanotubes in batches, comprising:
以硼酸盐为硼源负载催化剂而形成前驱物，所述催化剂包括过渡金属化合物；Using borate as a boron source supported catalyst to form a precursor, the catalyst includes a transition metal compound;
将所述前驱物于含氮气氛中加热至1200～1400℃，并在氨气气氛中保温反应，之后在保护气氛中降至室温，获得粗产物，The precursor is heated to 1200-1400° C. in a nitrogen-containing atmosphere, and the reaction is maintained in an ammonia gas atmosphere, and then lowered to room temperature in a protective atmosphere to obtain a crude product,
对所述粗产物进行后处理，制得所述氮化硼纳米管。The crude product is subjected to post-treatment to obtain the boron nitride nanotubes.
在一些实施方案中，所述制备方法包括：至少选用球磨法、浸渍法中的任意一种方式使所述硼源负载催化剂。In some embodiments, the preparation method comprises: selecting at least any one of ball milling method and impregnation method to make the boron source support the catalyst.
在一些较为优选的实施方案中，所述制备方法包括：将所述催化剂和硼源混合并进行球磨，球磨速度为200～300r/min，时间为100～150h，获得所述前驱物。In some preferred embodiments, the preparation method includes: mixing the catalyst and the boron source and performing ball milling at a speed of 200-300 r/min and a time of 100-150 h to obtain the precursor.
进一步的，可以将硼酸盐粉体与过渡金属化合物混合置于行星球磨机中球磨100～150h，转速200～300r/min。Further, the borate powder and the transition metal compound can be mixed and placed in a planetary ball mill for ball milling for 100-150 hours at a rotational speed of 200-300 r/min.
在一些较为优选的实施方案中，所述制备方法包括：将所述催化剂和硼源于溶剂中超声混合，之后进行干燥处理，获得所述前驱物，所述溶剂包括乙醇。In some more preferred embodiments, the preparation method includes: ultrasonically mixing the catalyst and boron source in a solvent, and then drying to obtain the precursor, and the solvent includes ethanol.
进一步的，可以将硼酸盐粉体与过渡金属化合物的乙醇溶液超声混合5～10h，然后烘干。Further, the borate powder and the ethanol solution of the transition metal compound can be ultrasonically mixed for 5-10 hours, and then dried.
进一步的，所述硼酸盐包括MgB4O7、Mg2B2O5、Mg3B2O6、CaB4O7和Li2B4O7中的任意一种或两种以上的组合，优选为MgB4O7，但不限于此。Further, the borate includes any one or a combination of two or more of MgB4 O7 , Mg2 B2 O5 , Mg3 B2 O6 , CaB4 O7 and Li2 B4 O7 , preferably MgB4 O7 , but not limited thereto.
进一步的，所述过渡金属化合物包括过渡金属盐或过渡金属氧化物。Further, the transition metal compound includes transition metal salt or transition metal oxide.
例如，所述过渡金属盐包括Fe(NO3)3、Co(NO3)2和Ni(NO3)3中的任意一种或两种以上的组合。例如，所述过渡金属氧化物包括Fe2O3和CoO中的任意一种或两种的组合，但不限于此。For example, the transition metal salt includes any one or a combination of two or more of Fe(NO3 )3 , Co(NO3 )2 and Ni(NO3 )3 . For example, the transition metal oxide includes any one or a combination of two of Fe2 O3 and CoO, but is not limited thereto.
进一步的，所述过渡金属化合物优选为Fe(NO3)3。Further, the transition metal compound is preferably Fe(NO3 )3 .
较为优选的，所述硼源所含的硼元素与所述催化剂所含的过渡金属元素的摩尔比为1:0.01～0.1。More preferably, the molar ratio of the boron element contained in the boron source to the transition metal element contained in the catalyst is 1:0.01-0.1.
进一步的，所述含氮气氛包括氨气气氛或者氮气/氢气混合气氛。Further, the nitrogen-containing atmosphere includes an ammonia gas atmosphere or a nitrogen/hydrogen mixed atmosphere.
进一步的，所述保护气氛包括氢气、氮气或惰性气氛(例如Ar气氛)，当然也可以是其中两或三者的混合气氛。Further, the protective atmosphere includes hydrogen, nitrogen or an inert atmosphere (for example, Ar atmosphere), and of course, it can also be a mixed atmosphere of two or three of them.
在一些较为优选的实施方案中，所述制备方法包括：将所述前驱物于含氮气氛中以5～15℃/min的升温速率加热至1200～1400℃，之后在氨气气氛中保温反应。In some preferred embodiments, the preparation method comprises: heating the precursor to 1200-1400°C at a heating rate of 5-15°C/min in a nitrogen-containing atmosphere, and then maintaining the reaction in an ammonia gas atmosphere .
在一些实施方案中，所述制备方法包括：所述后处理包括：对所获粗产品依次进行酸洗、干燥处理，制得所述氮化硼纳米管。In some embodiments, the preparation method includes: the post-treatment includes: sequentially performing acid washing and drying treatment on the obtained crude product to obtain the boron nitride nanotubes.
在一些较为具体的实施方案中，所述制备方法包括：以硼酸盐为硼源负载金属催化剂或过渡金属化合物，然后将混合物放入化学气相沉积设备中，并在氨气或者氮气和氢气混合气氛中5～15℃/min的升温速率加热至1200～1400℃，之后在氨气气氛中保温反应0.5～5h，保温结束后在氮气或氩气气氛中降温至室温，得到白色粗产物，将粗产物经过酸洗、干燥获得所述氮化硼纳米管。In some specific embodiments, the preparation method includes: using borate as a boron source to support a metal catalyst or a transition metal compound, then putting the mixture into a chemical vapor deposition device, and mixing it in ammonia or nitrogen and hydrogen The heating rate of 5-15 ℃/min in the atmosphere is heated to 1200-1400 ℃, and then the reaction is kept in an ammonia gas atmosphere for 0.5-5 h. After the insulation is completed, the temperature is lowered to room temperature in a nitrogen or argon atmosphere to obtain a white crude product. The crude product is acid washed and dried to obtain the boron nitride nanotubes.
在一更为具体的实施案例中，所述制备方法包括以下步骤：In a more specific implementation case, the preparation method includes the following steps:
(1)将MgB4O7粉体负载上催化剂(例如Fe(NO3)3)后，置于高温区反应坩埚(例如高温区氧化铝舟)中，然后置入化学气相沉积设备(例如管式炉)；(1) After the MgB4 O7 powder is loaded with a catalyst (such as Fe(NO3 )3 ), it is placed in a high temperature zone reaction crucible (such as a high temperature zone alumina boat), and then placed in a chemical vapor deposition equipment (such as a tube furnace);
(2)在氨气或者氮气和氢气混合气氛中，程序升温至1100～1400℃，然后保温0.5～5h，获得所述氮化硼纳米管。(2) In an ammonia gas or a mixed atmosphere of nitrogen and hydrogen, the temperature is programmed to be 1100-1400° C., and then kept for 0.5-5 hours to obtain the boron nitride nanotubes.
其中，MgB4O7和Fe(NO3)3的摩尔比优选为1：0.01～1：0.1。Among them, the molar ratio of MgB4 O7 and Fe(NO3 )3 is preferably 1:0.01 to 1:0.1.
本发明实施例的另一个方面提供了由所述方法制备的氮化硼纳米管，其管径为10～150nm，管长为20～100微米。Another aspect of the embodiments of the present invention provides a boron nitride nanotube prepared by the method, the diameter of which is 10-150 nm and the length of which is 20-100 microns.
本发明中氮化硼纳米管的生长机制可能为：硼源来自于固态的硼酸镁。在氨气气氛中，硼元素从硼酸镁晶格中析出，溶于附着在表面的催化剂颗粒，同时来自于氨气分解的氮元素也溶于催化剂颗粒。当两种元素达到过饱和时，硼氮以一定的比例析出而形成氮化硼纳米管，并且以催化剂为位点生长于硼酸镁颗粒表面(可参阅图2所示)。The growth mechanism of the boron nitride nanotubes in the present invention may be as follows: the boron source comes from solid magnesium borate. In the ammonia gas atmosphere, the boron element is precipitated from the magnesium borate crystal lattice and dissolved in the catalyst particles attached to the surface, and the nitrogen element from the decomposition of ammonia gas is also dissolved in the catalyst particles. When the two elements are supersaturated, boron and nitrogen are precipitated in a certain proportion to form boron nitride nanotubes, which grow on the surface of magnesium borate particles using the catalyst as a site (see Figure 2).
本发明提供的氮化硼纳米管制备方法具有低成本、工艺简单、产率高、产品结晶性好等特点，且易于放大，实现大量生产，同时所获氮化硼纳米管在复合材料、导热材料等领域具有广阔应用前景。The method for preparing boron nitride nanotubes provided by the invention has the characteristics of low cost, simple process, high yield, good product crystallinity, etc., and is easy to scale up and realize mass production. Materials and other fields have broad application prospects.
以下结合附图和若干实施例对本发明的技术方案作进一步的解释说明。The technical solutions of the present invention will be further explained below with reference to the accompanying drawings and several embodiments.
实施例1：称取0.0404gFe(NO3)3.9H2O和1.8gMgB4O7粉体溶于5ml无水乙醇中超声2h后在60℃条件下烘干，得到淡黄色硼酸镁粉体，之后将硼酸镁粉体放入氧化铝舟中并置于CVD炉中，用Ar排除炉腔中的空气，再通入200sccm的NH3，程序升温到1300℃并保温180min,反应结束后关闭氨气，在氩气气氛中降温到室温，制得白色粗产物。请参见图1a-1b为制得的粗产物中氮化硼纳米管的SEM图，表明有大量的氮化硼纳米管生成，并且氮化硼纳米管生长于硼酸镁表面。前述粗产物经过浓度为1mol/L～5mol/L的盐酸酸洗，超声10～12，过滤后再用去离子水清洗数次，然后60℃干燥12h，即可以得到纯净的氮化硼。请参见图2和图3分别为制得的氮化硼纳米管的TEM图和选区电子衍射(SAED)图，表明氮化硼纳米管有良好结晶性。Example 1: Weigh 0.0404g Fe(NO3 )3 .9H2 O and 1.8g MgB4 O7 powder, dissolve it in 5ml absolute ethanol, ultrasonicate for 2 hours, and dry it at 60°C to obtain light yellow magnesium borate powder , then put the magnesium borate powder into an alumina boat and place it in a CVD furnace, use Ar to remove the air in the furnace cavity, and then introduce 200sccm of NH3 , program the temperature to 1300 ° C and keep it for 180 min, and shut down after the reaction is completed. Ammonia, cooled to room temperature in an argon atmosphere to obtain a white crude product. 1a-1b are SEM images of boron nitride nanotubes in the obtained crude product, which show that a large number of boron nitride nanotubes are generated, and the boron nitride nanotubes grow on the surface of magnesium borate. The aforesaid crude product is pickled with hydrochloric acid with a concentration of 1 mol/L to 5 mol/L, ultrasonicated for 10 to 12 hours, filtered and then washed with deionized water for several times, and then dried at 60°C for 12 hours to obtain pure boron nitride. Please refer to FIG. 2 and FIG. 3 for the TEM images and the selected area electron diffraction (SAED) images of the boron nitride nanotubes, respectively, which show that the boron nitride nanotubes have good crystallinity.
实施例2：称取MgB4O7粉体、Fe(NO3)3以摩尔比1:0.1混合，之后置于行星球磨机中设定转速200～300r/min并球磨150h，再取出混合物1g放入氧化铝舟中置于CVD炉中，用Ar排除炉腔中的空气，通入100标准毫升/分钟(sccm)的N2和100sccm的H2，程序升温到1300℃。然后关闭N2和H2，通入氮气200sccm，保温180min,反应结束关闭氨气，在氩气气氛中降温到室温。取出样品，得到白色粗产物，表征其为氮化硼纳米管。Example 2: Weigh MgB4 O7 powder and Fe(NO3 )3 and mix them at a molar ratio of 1:0.1, then place them in a planetary ball mill at a speed of 200-300 r/min and mill them for 150 hours, then take out 1 g of the mixture and put it in a planetary ball mill. Put it in an alumina boat and place it in a CVD furnace, use Ar to remove the air in the furnace cavity, pass 100 standard milliliters/minute (sccm) of N2 and 100 sccm of H2 , and program the temperature to 1300°C. Then, N2 and H2 were turned off, 200 sccm of nitrogen was introduced, and the temperature was maintained for 180 min. After the reaction was completed, the ammonia gas was turned off, and the temperature was lowered to room temperature in an argon atmosphere. A sample was taken out to obtain a white crude product, which was characterized as boron nitride nanotubes.
实施例3：称取0.0404gFe(NO3)3.9H2O和1.8gMgB4O7粉体溶于5ml无水乙醇中超声2h后在60℃条件下烘干，得到淡黄色硼酸镁粉体，之后将硼酸镁粉体放入氧化铝舟中并置于CVD炉中，用Ar排除炉腔中的空气，再通入通入100标准毫升/分钟(sccm)的N2和100sccm的H2，程序升温到1300℃并保温180min,反应结束后关闭N2和H2，在氩气气氛中降温到室温，制得白色粗产物氮化硼纳米管。Example 3: Weigh 0.0404g Fe(NO3 )3 .9H2 O and 1.8g MgB4 O7 powder, dissolve it in 5ml absolute ethanol, ultrasonicate for 2 hours, and dry it at 60°C to obtain light yellow magnesium borate powder , and then put the magnesium borate powder into the alumina boat and place it in the CVD furnace, use Ar to remove the air in the furnace cavity, and then pass in 100 standard milliliters/min (sccm) of N2 and 100 sccm of H2 , program the temperature to 1300°C and keep the temperature for 180min. After the reaction, turn off N2 and H2 , cool down to room temperature in an argon atmosphere, and obtain a white crude product of boron nitride nanotubes.
实施例4：称取0.0404gFe(NO3)3.9H2O和1.8gMgB4O7粉体溶于5ml无水乙醇中超声2h后在60℃条件下烘干，得到淡黄色硼酸镁粉体，之后将硼酸镁粉体放入氧化铝舟中并置于CVD炉中，用Ar排除炉腔中的空气，再通入200sccm的NH3，程序升温到1200℃并保温180min,反应结束后关闭氨气，在氩气气氛中降温到室温，制得白色粗产物氮化硼纳米管。Example 4: Weigh 0.0404g Fe(NO3 )3 .9H2 O and 1.8g MgB4 O7 powder, dissolve it in 5ml absolute ethanol, ultrasonicate for 2 hours, and dry it at 60°C to obtain light yellow magnesium borate powder , then put the magnesium borate powder into an alumina boat and place it in a CVD furnace, use Ar to remove the air in the furnace cavity, and then introduce 200sccm of NH3 , program the temperature to 1200 ° C and keep it for 180 min, and shut down after the reaction is completed. Ammonia, cooled to room temperature in an argon atmosphere to obtain a white crude product of boron nitride nanotubes.
应当理解，上述实施例仅为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。It should be understood that the above-mentioned embodiments are only intended to illustrate the technical concept and characteristics of the present invention, and the purpose thereof is to enable those who are familiar with the art to understand the content of the present invention and implement it accordingly, and cannot limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included within the protection scope of the present invention.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610619062.XACN107673318B (en) | 2016-08-01 | 2016-08-01 | Boron nitride nanotubes and batch preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610619062.XACN107673318B (en) | 2016-08-01 | 2016-08-01 | Boron nitride nanotubes and batch preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107673318A CN107673318A (en) | 2018-02-09 |
| CN107673318Btrue CN107673318B (en) | 2020-11-27 |
Family
ID=61133770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610619062.XAActiveCN107673318B (en) | 2016-08-01 | 2016-08-01 | Boron nitride nanotubes and batch preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107673318B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111204720A (en)* | 2020-02-10 | 2020-05-29 | 浙江硼矩新材料科技有限公司 | Batch preparation method of boron nitride nanotubes |
| KR102494639B1 (en)* | 2020-08-19 | 2023-02-02 | 내일테크놀로지 주식회사 | Method for preparing nano-materials and apparatus thereof |
| CN113901183A (en)* | 2021-08-20 | 2022-01-07 | 苏州景鹊机器人智能科技有限公司 | Method, device and system for extracting relation words between entities in medical text |
| CN113788464B (en)* | 2021-08-20 | 2022-12-27 | 武汉工程大学 | Method for preparing boron nitride nanotube by using double transition metal oxide as catalyst |
| CN114852976B (en)* | 2022-06-09 | 2023-06-23 | 桂林理工大学 | A hollow boron nitride short rod and its preparation method |
| CN116143083B (en)* | 2023-02-02 | 2024-07-05 | 浙江硼矩新材料科技有限公司 | Floating catalytic preparation method of boron nitride nanotube |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424254A (en)* | 2003-01-03 | 2003-06-18 | 浙江大学 | Preparation of boron nitride nano tube |
| CN1789115A (en)* | 2005-12-20 | 2006-06-21 | 山东大学 | Method for preparing boron nitride nanometer ring and tube |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101513995B (en)* | 2009-04-01 | 2010-12-29 | 武汉工程大学 | Method for preparing boron nitride nano-tube |
| CN101580236B (en)* | 2009-06-16 | 2011-03-23 | 武汉工程大学 | Method for preparing boron nitride nanotubes by annealing of inorganic boracic precursor |
| CN101633498A (en)* | 2009-09-01 | 2010-01-27 | 北京工业大学 | Preparation method of boron nitride nano tube with controllable dimension |
| CN102849694A (en)* | 2012-10-20 | 2013-01-02 | 景德镇陶瓷学院 | Preparation method of batch preparation of boron nitride nanotube |
| US10343908B2 (en)* | 2013-11-01 | 2019-07-09 | Bnnt, Llc | Induction-coupled plasma synthesis of boron nitrade nanotubes |
- 2016
- 2016-08-01CNCN201610619062.XApatent/CN107673318B/enactiveActive
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424254A (en)* | 2003-01-03 | 2003-06-18 | 浙江大学 | Preparation of boron nitride nano tube |
| CN1789115A (en)* | 2005-12-20 | 2006-06-21 | 山东大学 | Method for preparing boron nitride nanometer ring and tube |
Non-Patent Citations (3)
| Title |
|---|
| Formation and structure of boron nitride nanotubes;Jiang ZHANG et al.;《J. Mater. Sci. Technol.》;20051231;第21卷(第1期);全文* |
| Synthesis of boron nitride nanostructures from borates of alkali and alkaline earth metals;Andrei T. Matveev et al.;《Journal of Materials Chemistry A》;20150904;第3卷;第20756页左栏第2段，图6* |
| Synthesis of boron nitride nanotubes and their applications;Beilstein J. Nanotechnol et al.;《Beilstein J. Nanotechnol.》;20150108;第6卷;全文* |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107673318A (en) | 2018-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107673318B (en) | Boron nitride nanotubes and batch preparation method thereof | |
| Portehault et al. | A general solution route toward metal boride nanocrystals | |
| CN108545708B (en) | A kind of preparation method of coral-like hexagonal boron nitride micro-nano tube sheet composite structure | |
| CN107634224B (en) | A kind of preparation method of outer wall fluorinated multi-wall carbon nanotube containing iron fluoride intercalation | |
| CN109956463A (en) | A kind of carbon nanotube and preparation method thereof | |
| CN101348242A (en) | Method for preparing boron nitride nanotubes by magnesia thermal reduction | |
| CN110451465B (en) | Sea urchin-shaped boron nitride nanosphere-nanotube hierarchical structure and preparation method thereof | |
| CN101302006A (en) | Preparation method of carbon nanotubes with controllable wall layers | |
| CN101850972B (en) | Method for preparing silicon carbide nano wires | |
| CN103449403A (en) | Method for manufacturing nitrogen-doped multi-wall carbon nano tube | |
| CN105645375A (en) | Method for direct growth of porous carbon nanotubes on nano-porous copper | |
| CN101633498A (en) | Preparation method of boron nitride nano tube with controllable dimension | |
| CN107032326A (en) | A kind of method that solid catalysis prepares spiral carbon nano pipe | |
| CN107161960B (en) | A kind of high pressure vapor prepares the method and apparatus of boron nitride spherical powder | |
| CN110577209A (en) | Preparation method of in-situ synthesis of carbon nanotube surface-supported copper oxide nanoparticles | |
| CN113353899B (en) | A kind of preparation method of boron nitride nanotube, boron nitride nanotube and application thereof | |
| CN108046327B (en) | A kind of preparation method of tungsten disulfide nanotube | |
| CN106702347A (en) | Method for preparing rare-earth hexaboride nano material taking carbon cloth as base | |
| CN115353094A (en) | Solid phase purification method of carbon nano tube | |
| CN108928822B (en) | Method for preparing molybdenum carbide by gaseous reduction of molybdenum oxide | |
| CN102849694A (en) | Preparation method of batch preparation of boron nitride nanotube | |
| CN106882772B (en) | A kind of preparation method for the boron nitride nano-tube that caliber is controllable | |
| CN105129786A (en) | Preparing method for massive single-layer graphene | |
| CN105800628A (en) | Method for preparing quasi-one-dimensional rare earth hexaboride nanowire | |
| CN105290414A (en) | Method for synthesizing nano copper particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right | Effective date of registration:20201204 Address after:No. 6-2, No. 2 and No. 3, Huayuan Ginza, hi tech Zone, Ningbo City, Zhejiang Province, 315000 Patentee after:Ningbo haiwozi Environmental Protection Technology Co.,Ltd. Address before:215123, Suzhou, Jiangsu province Suzhou Industrial Park alone villa lake high Parish, if the waterway 398 Patentee before:SUZHOU INSTITUTE OF NANO-TECH AND NANO-BIONICS (SINANO), CHINESE ACADEMY OF SCIENCES | |
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right | Effective date of registration:20220902 Address after:315000 Room 202, building 2, No. 55, Longtanshan Road, Daqi street, Beilun District, Ningbo City, Zhejiang Province Patentee after:Zhejiang Boju New Material Technology Co.,Ltd. Address before:No. 6-2, No. 2 and No. 3, Huayuan Ginza, hi tech Zone, Ningbo City, Zhejiang Province, 315000 Patentee before:Ningbo haiwozi Environmental Protection Technology Co.,Ltd. | |
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right | Effective date of registration:20230321 Address after:201900 Building 13, No. 3938, Yunchuan Road, Baoshan District, Shanghai Patentee after:Shanghai boron moment New Material Technology Co.,Ltd. Address before:315000 Room 202, building 2, No. 55, Longtanshan Road, Daqi street, Beilun District, Ningbo City, Zhejiang Province Patentee before:Zhejiang Boju New Material Technology Co.,Ltd. |