新型氮化硼纳米材料的制备与表征
摘要
本论文旨在探索不同形貌氮化硼纳米材料的化学合成方法，研究其反应机理，并对产物的形貌和结构进行分析与表征。建立了简单有效的制备多种不同形貌氮化硼纳米材料的合成方法，成功地合成出了绳状、三角形片状、六边形片状、椭圆形片状、分等级纳米结构、海绵状等等多种新型氮化硼材料。具体归纳如下：
1．以硼氢化钾、氯化铵为原料，氯化钴为催化剂在600℃下制备出了绳状氮化硼纳米晶，绳状纳米晶的纯度和产率较高。
2．以六硼化钙、六硼化镧为硼源，氯化铵为氮源在600℃下成功合成了层状有序的六方氮化硼纳米晶，并对其形成机理进行了讨论。
3．以溴化锂为熔盐，在熔盐体系中低温下实现了纯的六方氮化硼晶体的生长。NaBF_4-NaNH_2-LiBr_3反应体系在650℃下和成了平均厚度约80nm，尺寸在400nm至几微米的片状氮化硼纳米晶，发现熔盐和温度对氮化硼晶体的生长产生重要的影响。
4．采用六硼化钙、六硼化镧等不同的硼源，氨基钠为氮源一步成功合成了分散性好的三角和六角片状六方氮化硼纳米微晶。
5．以三溴化硼、氯化铵、铝粉为原料在550℃下合成了比表面积大的多孔海绵状的氮化硼纳米晶。这种独特结构的氮化硼纳米材料能很好的负载贵金属纳米粒子，能作为优良的催化剂载体。
The aim of this dissertation is to explore the synthesis of different morphologies boron nitride nanomaterials by simple methods. We have established effective methods to synthesize boron nitride nanoropes, boron nitride trigons, boron nitride hexagons, boron nitride ovals, and hierarchical nanostructured boron nitride successfully. The as-prepared boron nitride materials are characterized and their growth mechanism is also investigated. The major contents can be summarized as follows:
1. We synthesized successfully rope-like boron nitride nanocrystals at 600~C for 12h using NaBH4 as boron source, NH4C1 as nitride source and COC12 as a catalyst, the BN nanorope is about 60-150nm in diameter and several micrometers in length.
2. Hierarchical nanostructured hexagonal boron nitride (hBN) was synthesized by directly nitriding cubic phase CaB6 at 500-650~C for 12-48 hours using NHaC1 as nitriding-etching reagent, the mechanism of its formation was also proposed.
3. We developed a first in-situ growth of pure boron nitride crystals at low-temperatures in molten salt flux. Adding LiBr as molten salt in the NaBFa-NaNH2 system at 650~C resulted growth of h-BN crystals having uniform thickness of about 80 nm and sizes from about 400 nm to several micrometers. We found that molten salt and temperature had strong effects on the crystal growth process.
4. Using different boron source such as CaB6 and LAB6, NaNH2 as nitride source, we synthesized the trigonal and hexagonal boron nitride nanocrystals.
5. We used BBr3, NHaCI and A1 powder as raw materials, synthesized spongy-like boron nitride nanomaterials with high surface area. This novel nanostructural material may be used as catalyst SUlport such as loading noble metals.
1．以硼氢化钾、氯化铵为原料，氯化钴为催化剂在600℃下制备出了绳状氮化硼纳米晶，绳状纳米晶的纯度和产率较高。
2．以六硼化钙、六硼化镧为硼源，氯化铵为氮源在600℃下成功合成了层状有序的六方氮化硼纳米晶，并对其形成机理进行了讨论。
3．以溴化锂为熔盐，在熔盐体系中低温下实现了纯的六方氮化硼晶体的生长。NaBF_4-NaNH_2-LiBr_3反应体系在650℃下和成了平均厚度约80nm，尺寸在400nm至几微米的片状氮化硼纳米晶，发现熔盐和温度对氮化硼晶体的生长产生重要的影响。
4．采用六硼化钙、六硼化镧等不同的硼源，氨基钠为氮源一步成功合成了分散性好的三角和六角片状六方氮化硼纳米微晶。
5．以三溴化硼、氯化铵、铝粉为原料在550℃下合成了比表面积大的多孔海绵状的氮化硼纳米晶。这种独特结构的氮化硼纳米材料能很好的负载贵金属纳米粒子，能作为优良的催化剂载体。
The aim of this dissertation is to explore the synthesis of different morphologies boron nitride nanomaterials by simple methods. We have established effective methods to synthesize boron nitride nanoropes, boron nitride trigons, boron nitride hexagons, boron nitride ovals, and hierarchical nanostructured boron nitride successfully. The as-prepared boron nitride materials are characterized and their growth mechanism is also investigated. The major contents can be summarized as follows:
1. We synthesized successfully rope-like boron nitride nanocrystals at 600~C for 12h using NaBH4 as boron source, NH4C1 as nitride source and COC12 as a catalyst, the BN nanorope is about 60-150nm in diameter and several micrometers in length.
2. Hierarchical nanostructured hexagonal boron nitride (hBN) was synthesized by directly nitriding cubic phase CaB6 at 500-650~C for 12-48 hours using NHaC1 as nitriding-etching reagent, the mechanism of its formation was also proposed.
3. We developed a first in-situ growth of pure boron nitride crystals at low-temperatures in molten salt flux. Adding LiBr as molten salt in the NaBFa-NaNH2 system at 650~C resulted growth of h-BN crystals having uniform thickness of about 80 nm and sizes from about 400 nm to several micrometers. We found that molten salt and temperature had strong effects on the crystal growth process.
4. Using different boron source such as CaB6 and LAB6, NaNH2 as nitride source, we synthesized the trigonal and hexagonal boron nitride nanocrystals.
5. We used BBr3, NHaCI and A1 powder as raw materials, synthesized spongy-like boron nitride nanomaterials with high surface area. This novel nanostructural material may be used as catalyst SUlport such as loading noble metals.
引文
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