CN100369806C - Method for synthesizing single-morphology boron nitride nanotubes - Google Patents
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Abstract
本发明公开了一种合成单一形貌氮化硼纳米管的方法，以氨气和硼粉分别作为氮源和硼源，以Si和纳米SiO2粉末作为催化剂，在1000℃-1300℃的温度条件下，反应60-120分钟，通过控制反应过程的气氛，在同一反应体系中合成单一形貌的氮化硼纳米管。其中直接通入纯度为99.95%的NH3气，可制备出单一圆筒状形貌的氮化硼纳米管；而先通入纯度99.99%的Ar气，同时加热石英管中心热区，使温度达到1000℃-1300℃，然后关闭Ar气，再通入纯度为99.95%的NH3气，可制备出单一竹节状形貌的氮化硼纳米管。本发明合成单一形貌氮化硼纳米管的方法具有工艺简单，反应易于控制，产物纯度高等优点。The invention discloses a method for synthesizing boron nitride nanotubes with a single shape. Ammonia gas and boron powder are used as nitrogen source and boron source respectively, and Si and nano- SiO2 powder are used as catalysts. Under the conditions, the reaction takes 60-120 minutes, and the boron nitride nanotube with single shape is synthesized in the same reaction system by controlling the atmosphere in the reaction process. The NH3 gas with a purity of 99.95% can be directly introduced to prepare boron nitride nanotubes with a single cylindrical shape; while the Ar gas with a purity of 99.99% is first introduced, and the central hot zone of the quartz tube is heated at the same time to make the temperature After reaching 1000°C-1300°C, the Ar gas is turned off, and then NH 3 gas with a purity of 99.95% is introduced to prepare boron nitride nanotubes with a single bamboo-shaped shape. The method for synthesizing boron nitride nanotubes with a single shape has the advantages of simple process, easy control of reaction, high product purity and the like.
Description
技术领域technical field
本发明涉及纳米材料技术领域，具体涉及一种合成单一形貌氮化硼(BN)纳米管的方法。The invention relates to the technical field of nanomaterials, in particular to a method for synthesizing boron nitride (BN) nanotubes with a single shape.
背景技术Background technique
氮化硼纳米管的禁带宽度与纳米管的直径、螺旋性以及管壁的层数无关，这比电学性质随着纳米管的直径、螺旋性和管壁的层数等结构因素变化的碳纳米管更具有优势，并且氮化硼纳米管具有更稳定的结构，从而在纳米器件上有独特的应用前景。此外氮化硼纳米管比碳纳米管有更好的高温抗氧化性能，是良好的导热体和绝缘体。The bandgap width of boron nitride nanotubes has nothing to do with the diameter, helicity, and number of layers of the tube wall, which is better than carbon whose electrical properties change with the structural factors such as the diameter, helicity, and number of layers of the tube wall. Nanotubes have more advantages, and boron nitride nanotubes have a more stable structure, so they have unique application prospects in nanodevices. In addition, boron nitride nanotubes have better high temperature oxidation resistance than carbon nanotubes, and are good thermal conductors and insulators.
采用等离子体电弧放电的方法最先合成了氮化硼纳米管。激光烧蚀法也成功的合成了氮化硼纳米管。但这两种方法的产量、纯度不高，成本高工艺复杂，不利于工业生产。最近又发展出了碳纳米管取代反应的合成方法，其中碳纳米管起的作用是提供氮化硼纳米管生长的骨架，得到的氮化硼纳米管与碳纳米管的结构类似，但这种方法制备的氮化硼纳米管不可避免的混有碳纳米管，这影响了该方法的推广。使用金属催化剂的化学气相沉积法(CVD)可以合成氮化硼纳米管，但产物多是圆筒状和竹节状纳米管的混合物，这也在一定程度上限制了其应用。目前尚没有在同一反应体系中合成单一形貌的氮化硼纳米管的技术方法报道。Boron nitride nanotubes were first synthesized by plasma arc discharge method. Boron nitride nanotubes were also successfully synthesized by laser ablation. But the yield and purity of these two methods are not high, and the cost is high and the process is complicated, which is not conducive to industrial production. Recently, a synthesis method of carbon nanotube substitution reaction has been developed, in which the role of carbon nanotubes is to provide the framework for the growth of boron nitride nanotubes, and the obtained boron nitride nanotubes have a similar structure to carbon nanotubes, but this The boron nitride nanotubes prepared by this method are inevitably mixed with carbon nanotubes, which affects the promotion of this method. Boron nitride nanotubes can be synthesized by chemical vapor deposition (CVD) using metal catalysts, but the products are mostly a mixture of cylindrical and bamboo-shaped nanotubes, which also limits its application to a certain extent. At present, there is no report on the technical method of synthesizing boron nitride nanotubes with a single morphology in the same reaction system.
发明内容Contents of the invention
本发明的目的在于克服现有技术的缺点，提供一种工艺简单，反应易于控制，产物纯度高，在同一反应体系中合成单一形貌氮化硼纳米管的方法。The purpose of the present invention is to overcome the disadvantages of the prior art and provide a method for synthesizing single-morphology boron nitride nanotubes in the same reaction system with simple process, easy-to-control reaction and high product purity.
本发明的目的通过如下技术方案实现：The purpose of the present invention is achieved through the following technical solutions:
一种合成单一形貌氮化硼纳米管的方法，以氨气和硼粉分别作为氮源和硼源，以Si和纳米SiO2粉末作为催化剂，在1000℃-1300℃的温度条件下，反应60-120分钟，通过控制反应过程的气氛，在同一反应体系中合成单一形貌的氮化硼纳米管。A method for synthesizing single-morphology boron nitride nanotubes, using ammonia gas and boron powder as nitrogen source and boron source respectively, using Si and nano -SiO2 powder as catalyst, under the temperature condition of 1000°C-1300°C, the reaction For 60-120 minutes, by controlling the atmosphere in the reaction process, boron nitride nanotubes with a single shape are synthesized in the same reaction system.
为进一步实现本发明的目的，上述合成单一形貌氮化硼纳米管的方法，包括如下步骤：In order to further realize the object of the present invention, the above-mentioned method for synthesizing boron nitride nanotubes with a single shape comprises the following steps:
(1)将硼粉、Si和纳米SiO2粉末按20∶1∶1的摩尔比混合，所述的混合是在转速为150-250r/min的条件下，球磨混合4-8小时；(1) Boron powder, Si and nano-SiO 2 powders are mixed in a mol ratio of 20:1:1, and the mixing is carried out by ball milling for 4-8 hours at a rotating speed of 150-250r/min;
(2)称取0.5g步骤(1)的混合粉末放入石英舟中，置于管式炉加热的石英管中心热区；(2) Take by weighing 0.5g of the mixed powder of step (1) and put it into a quartz boat, and place it in the central heat zone of the quartz tube heated by the tube furnace;
(3)通入纯度为99.95％的NH3气，气体流量100-300ml/min，加热石英管中心热区的温度为1000℃-1300℃，反应60-120分钟，在石英舟中所得的灰白色产物，用氢氟酸除去催化剂后，即可制备出单一圆筒状形貌的氮化硼纳米管。(3) Feed NH3 gas with a purity of 99.95%, the gas flow rate is 100-300ml/min, the temperature of the hot zone in the center of the heated quartz tube is 1000°C-1300°C, and the reaction is 60-120 minutes. After removing the catalyst with hydrofluoric acid, boron nitride nanotubes with a single cylindrical shape can be prepared.
为进一步实现本发明的目的，上述合成单一形貌氮化硼纳米管的方法，还可以是包括如下步骤：In order to further realize the purpose of the present invention, the method for synthesizing single-morphology boron nitride nanotubes may also include the following steps:
(1)将硼粉、Si和纳米SiO2粉末按20∶1∶1的摩尔比混合，所述的混合是在转速为150-250r/min的条件下，球磨混合4-8小时；(1) Boron powder, Si and nano-SiO 2 powders are mixed in a mol ratio of 20:1:1, and the mixing is carried out by ball milling for 4-8 hours at a rotating speed of 150-250r/min;
(2)称取0.5g步骤(1)的混合粉末放入石英舟中，置于管式炉加热的石英管中心热区；(2) Take by weighing 0.5g of the mixed powder of step (1) and put it into a quartz boat, and place it in the central heat zone of the quartz tube heated by the tube furnace;
(3)先通入流量为100-300ml/min纯度99.99％的Ar气，同时加热石英管中心热区，使温度达到1000℃-1300℃，然后关闭Ar气，再通入纯度为99.95％的NH3气，气体流量100-300ml/min，反应60-120分钟，在石英舟中所得的灰白色产物，用氢氟酸除去催化剂后，即可制备出单一竹节状形貌的氮化硼纳米管。(3) First feed Ar gas with a flow rate of 100-300ml/min and a purity of 99.99%, and heat the central hot zone of the quartz tube at the same time to make the temperature reach 1000°C-1300°C, then close the Ar gas, and then feed Ar gas with a purity of 99.95% NH 3 gas, gas flow rate 100-300ml/min, reaction 60-120 minutes, the off-white product obtained in the quartz boat, after removing the catalyst with hydrofluoric acid, a boron nitride nanometer with a single bamboo-shaped shape can be prepared. Tube.
本发明制备的氮化硼纳米管，分别具有单一的圆筒状或竹节状的形貌。二者在物理性质上有所不同，从结构上讲，竹节状氮化硼纳米管直径更粗，相对容易同其他物质结合制备纳米复合材料；而圆筒状氮化硼纳米管的结构更稳定，在纳米电子学上用于绝缘保护是一类很好的材料。The boron nitride nanotubes prepared by the invention respectively have a single cylindrical or bamboo-shaped shape. The two are different in physical properties. In terms of structure, bamboo-shaped boron nitride nanotubes have a thicker diameter and are relatively easy to combine with other substances to prepare nanocomposites; while cylindrical boron nitride nanotubes have a more structured structure. Stable, it is a good material for insulation protection in nanoelectronics.
本发明的原理：(1)通过预先的球磨混合，使硼粉与催化剂充分混合。由此催化剂与反应物之间接触良好，有利于生长高质量的氮化硼纳米管。(2)采用两种过程进行反应，通过控制反应过程的气氛达到制备不同形貌氮化硼纳米管的目的。(3)纳米管的生长机理在两个反应过程中是不同的。在直接通入NH3的反应中，当温度到达900℃时，NH3就可以与B在B颗粒的表面反应生成BN，通常情况下，形成完整六方BN晶体的温度在1300℃以上，因此反应生成的主要是乱层结构的BN(t-BN)。在温度达到可以使纳米Si颗粒熔化的时候，就没有足够的B和B2O2溶解到Si颗粒中，而且生成的BN会包覆在Si颗粒的表面，这也会阻止B与B2O2溶解到颗粒中，因此不会出现SLS和VLS的生长机理，而表现出一种氧化物辅助生长的机理。实验中使用的SiO2与B反应生成了B2O2，由于B2O2的蒸汽压较B2O3和B高很多，在气相中很容易扩散到t-BN表面的形核位置，接着同NH3反应生长出BN纳米管。从而产物是圆筒状氮化硼纳米管。(4)先在Ar气中加热到反应温度的条件下，加热过程不会直接生成BN，达到设定温度后，B和反应生成的气体B2O2可以溶解到Si颗粒中，通入NH3后，SLS和VLS生长机理主导了竹节状BN纳米管的生长，生长出竹节状BN纳米管。(5)本发明制备的圆筒状纳米管的直径(10～50nm)要小于竹节状纳米管的直径(30～100nm)。Principles of the present invention: (1) Boron powder and catalyst are fully mixed through ball milling in advance. Therefore, the contact between the catalyst and the reactant is good, which is conducive to the growth of high-quality boron nitride nanotubes. (2) Two processes are used for the reaction, and the purpose of preparing boron nitride nanotubes with different shapes is achieved by controlling the atmosphere of the reaction process. (3) The growth mechanism of nanotubes is different in the two reaction processes. In the reaction of directly feeding NH 3 , when the temperature reaches 900°C, NH 3 can react with B on the surface of B particles to form BN. Usually, the temperature for forming a complete hexagonal BN crystal is above 1300°C, so the reaction What is generated is mainly a BN (t-BN) with a turbostratic structure. When the temperature reaches the temperature that can melt the nano-Si particles, there will not be enough B and B 2 O 2 to dissolve into the Si particles, and the generated BN will coat the surface of the Si particles, which will also prevent the formation of B and B 2 O 2 dissolves into the particles, so instead of the growth mechanism of SLS and VLS, it exhibits an oxide-assisted growth mechanism. The SiO 2 used in the experiment reacted with B to form B 2 O 2 . Since the vapor pressure of B 2 O 2 is much higher than that of B 2 O 3 and B, it is easy to diffuse to the nucleation site on the surface of t-BN in the gas phase. Then react with NH 3 to grow BN nanotubes. The product is thus cylindrical boron nitride nanotubes. (4) Under the condition of heating to the reaction temperature in Ar gas first, BN will not be directly generated during the heating process. After reaching the set temperature, B and the gas B 2 O 2 generated by the reaction can be dissolved into Si particles, and NH After 3 , the SLS and VLS growth mechanisms dominated the growth of bamboo-shaped BN nanotubes, and bamboo-shaped BN nanotubes were grown. (5) The diameter (10-50nm) of the cylindrical nanotube prepared by the present invention is smaller than the diameter (30-100nm) of the bamboo-shaped nanotube.
相对于现有技术，本发明合成单一形貌氮化硼纳米管的方法工艺简单，反应易于控制，产物纯度高。Compared with the prior art, the method for synthesizing boron nitride nanotubes with a single shape has simple process, easy control of reaction and high product purity.
附图说明Description of drawings
附图1实例1所得氮化硼纳米管的透射电子显微镜照片(放大6万倍)。Accompanying drawing 1 example 1 gained the transmission electron micrograph (magnification 60,000 times) of boron nitride nanotube.
附图2实例2所得氮化硼纳米管的透射电子显微镜照片(放大3万倍)。Accompanying drawing 2 Example 2 obtained transmission electron micrographs of boron nitride nanotubes (magnified 30,000 times).
附图3实例3所得氮化硼纳米管的扫描电子显微镜照片(放大5万倍)。Accompanying drawing 3 Example 3 obtained scanning electron micrographs of the boron nitride nanotube (magnified 50,000 times).
附图4实例4所得氮化硼纳米管的扫描电子显微镜照片(放大2万倍)。Accompanying drawing 4 Example 4 obtained scanning electron micrographs of the boron nitride nanotube (enlarged 20,000 times).
附图5实例5所得氮化硼纳米管的扫描电子显微镜照片(放大6.5万倍)。Accompanying drawing 5 Example 5 obtained scanning electron micrographs of the boron nitride nanotube (magnification 65,000 times).
附图6实例6所得氮化硼纳米管的X射线衍射图谱。Accompanying drawing 6 example 6 obtained boron nitride nanotubes X-ray diffraction pattern.
具体实施方式Detailed ways
下面结合附图和实施例对本发明作进一步的说明，但本发明要求保护的范围并不局限于实施例表示的范围。The present invention will be further described below in conjunction with the accompanying drawings and examples, but the protection scope of the present invention is not limited to the range indicated by the examples.
实施例1Example 1
分别称取1.08g B，0.14g Si，0.3g SiO2，在氩气保护下在行星式球磨机上混合，转速为200r/min，时间6h。称取0.5g混合粉末放入石英舟中，置于管式炉加热的石英管中心热区。直接通入NH3气(纯度99.95％)，气体流量150ml/min，反应温度为1200℃，反应时间为90分钟。产物为灰白色粉末，用氢氟酸除去Si后，产物用无水乙醇分散后在透射电子显微镜下观察。如图1所示，可以发现大量单一圆筒状形貌氮化硼纳米管，纳米管的直径范围在10-40nm，长度可以达到10-30微米。Weigh 1.08g of B, 0.14g of Si, and 0.3g of SiO 2 respectively, and mix them on a planetary ball mill under the protection of argon at a speed of 200r/min for 6h. Weigh 0.5g of the mixed powder into a quartz boat and place it in the central hot zone of the quartz tube heated by a tube furnace. Directly feed NH 3 gas (purity 99.95%), the gas flow rate is 150ml/min, the reaction temperature is 1200°C, and the reaction time is 90 minutes. The product is an off-white powder, and after removing Si with hydrofluoric acid, the product is dispersed with absolute ethanol and observed under a transmission electron microscope. As shown in Figure 1, a large number of boron nitride nanotubes with a single cylindrical shape can be found. The diameter of the nanotubes ranges from 10-40 nm and the length can reach 10-30 microns.
实施例2Example 2
分别称取1.08g B，0.14g Si，0.3g SiO2，在氩气保护下在行星式球磨机上混合，转速为150r/min，时间8h。称取0.5g混合粉末放入石英舟中，置于管式炉加热的石英管中心热区。直接通入NH3气(纯度99.95％)，气体流量300ml/min，反应温度为1000℃，反应时间为120分钟。产物为灰白色粉末，用氢氟酸除去Si后，产物用无水乙醇分散后在透射电子显微镜下观察。如图2所示，可以发现大量单一圆筒状形貌氮化硼纳米管。Weigh 1.08g of B, 0.14g of Si, and 0.3g of SiO 2 respectively, and mix them on a planetary ball mill under the protection of argon at a speed of 150r/min for 8h. Weigh 0.5g of the mixed powder into a quartz boat and place it in the central hot zone of the quartz tube heated by a tube furnace. Directly feed NH 3 gas (purity 99.95%), the gas flow rate is 300ml/min, the reaction temperature is 1000°C, and the reaction time is 120 minutes. The product is an off-white powder, and after removing Si with hydrofluoric acid, the product is dispersed with absolute ethanol and observed under a transmission electron microscope. As shown in Figure 2, a large number of boron nitride nanotubes with single cylindrical morphology can be found.
实施例3Example 3
分别称取1.08g B，0.14g Si，0.3g SiO2，在氩气保护下在行星式球磨机上混合，转速为250r/min，时间4h。称取0.5g混合粉末放入石英舟中，置于管式炉加热的石英管中心热区。直接通入NH3气(纯度99.95％)，气体流量100ml/min，反应温度为1300℃，反应时间为60分钟。产物为灰白色粉末，用扫描电镜观察。如图3所示，可以发现大量单一圆筒状形貌氮化硼纳米管。Weigh 1.08g B, 0.14g Si, and 0.3g SiO 2 , respectively, and mix them on a planetary ball mill under the protection of argon at a speed of 250r/min for 4h. Weigh 0.5g of the mixed powder into a quartz boat and place it in the central hot zone of the quartz tube heated by a tube furnace. Directly feed NH 3 gas (purity 99.95%), the gas flow rate is 100ml/min, the reaction temperature is 1300°C, and the reaction time is 60 minutes. The product is an off-white powder, observed with a scanning electron microscope. As shown in Figure 3, a large number of boron nitride nanotubes with single cylindrical morphology can be found.
实施例4Example 4
分别称取1.08g B，0.14g Si，0.3g纳米SiO2，在氩气保护下在行星式球磨机上混合，转速为200r/min，时间5h。称取0.5g混合粉末放入石英舟中，置于管式炉加热的石英管中心热区。先通入流量为300ml/min的Ar气(纯度99.99％)，同时加热到1200℃，然后关闭Ar气，再通入流量为200ml/min的NH3气(纯度99.95％)，反应90分钟。产物为灰白色粉末，用氢氟酸除去Si后，产物用无水乙醇分散后在透射电子显微镜下观察。如图4所示，可以发现大量的单一竹节状形貌氮化硼纳米管，纳米管的直径范围在30-100nm，长为10-50微米。Weigh 1.08g B, 0.14g Si, and 0.3g nano-SiO 2 respectively, and mix them on a planetary ball mill under the protection of argon at a speed of 200r/min for 5h. Weigh 0.5g of the mixed powder into a quartz boat and place it in the central hot zone of the quartz tube heated by a tube furnace. First feed the Ar gas (purity 99.99%) with a flow rate of 300ml/min, while heating to 1200°C, then close the Ar gas, then feed the NH gas (purity 99.95%) with a flow rate of 200ml/min, and react for 90 minutes. The product is an off-white powder, and after removing Si with hydrofluoric acid, the product is dispersed with absolute ethanol and observed under a transmission electron microscope. As shown in FIG. 4 , a large number of boron nitride nanotubes with a single bamboo-shaped morphology can be found. The diameter of the nanotubes ranges from 30-100 nm and the length is 10-50 microns.
实施例5Example 5
分别称取1.08g B，0.14g Si，0.3g纳米SiO2，在氩气保护下在行星式球磨机上混合，转速为150r/min，时间8h。称取0.5g混合粉末放入石英舟中，置于管式炉加热的石英管中心热区。先通入流量为100ml/min的Ar气(纯度99.99％)，同时加热到1000℃，然后关闭Ar气，再通入流量为300ml/min的NH3气(纯度99.95％)，反应120分钟。产物为灰白色粉末，用氢氟酸除去Si后，产物用无水乙醇分散后在透射电子显微镜下观察。如图5所示，可以发现明显的单一竹节状形貌氮化硼纳米管，纳米管的直径为100nm。Weigh 1.08g B, 0.14g Si, and 0.3g nano-SiO 2 respectively, and mix them on a planetary ball mill under the protection of argon at a speed of 150r/min for 8h. Weigh 0.5g of the mixed powder into a quartz boat and place it in the central hot zone of the quartz tube heated by a tube furnace. First feed the Ar gas (purity 99.99%) with a flow rate of 100ml/min, while heating to 1000°C, then close the Ar gas, then feed the NH gas (purity 99.95%) with a flow rate of 300ml/min, and react for 120 minutes. The product is an off-white powder, and after removing Si with hydrofluoric acid, the product is dispersed with absolute ethanol and observed under a transmission electron microscope. As shown in Figure 5, a single bamboo-shaped boron nitride nanotube can be found, and the diameter of the nanotube is 100 nm.
实施例6Example 6
分别称取1.08g B，0.14g Si，0.3g纳米SiO2，在氩气保护下在行星式球磨机上混合，转速为250r/min，时间4h。称取0.5g混合粉末放入石英舟中，置于管式炉加热的石英管中心热区。先通入流量为200ml/min的Ar气(纯度99.99％)，同时加热到1300℃，然后关闭Ar气，再通入流量为100ml/min的NH3气(纯度99.95％)，反应60分钟。产物为灰白色粉末，用X射线衍射测定，如图6所示，其中主要成分是六方BN、菱面体BN以及Si。用氢氟酸除去Si后，产物用无水乙醇分散后在透射电子显微镜下观察。同样可以发现大量单一竹节状形貌氮化硼纳米管。Weigh 1.08g B, 0.14g Si, and 0.3g nano-SiO 2 respectively, and mix them on a planetary ball mill under the protection of argon at a speed of 250r/min for 4h. Weigh 0.5g of the mixed powder into a quartz boat and place it in the central hot zone of the quartz tube heated by a tube furnace. First feed the Ar gas (purity 99.99%) with a flow rate of 200ml/min, while heating to 1300°C, then close the Ar gas, and then feed the NH gas (purity 99.95%) with a flow rate of 100ml/min, and react for 60 minutes. The product is off-white powder, determined by X-ray diffraction, as shown in Figure 6, wherein the main components are hexagonal BN, rhombohedral BN and Si. After removing Si with hydrofluoric acid, the product was dispersed with absolute ethanol and observed under a transmission electron microscope. A large number of boron nitride nanotubes with single bamboo-shaped morphology can also be found.
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