CN106395872A - Method for synthesizing single graphite nitrogen doped carbon nanomaterial - Google Patents
Method for synthesizing single graphite nitrogen doped carbon nanomaterial Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 118
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 61
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 42
- 239000010439 graphite Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
- 239000002086 nanomaterial Substances 0.000 title abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 44
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 39
- 238000000151 deposition Methods 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 230000008021 deposition Effects 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000013341 scale-up Methods 0.000 abstract 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 14
- 239000002041 carbon nanotube Substances 0.000 description 14
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- -1 aromatic alcohols Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
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- 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
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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Abstract
本发明公开了一种合成具有单一石墨氮掺杂的纳米碳材料的方法，属于纳米碳材料的合成技术领域。该方法是采用化学气相沉积方法，以乙腈作为碳源和氮源，在沉积基体表面制备具有单一石墨氮掺杂的纳米碳材料；所述化学气相沉积的温度为750‑1000℃，沉积基体为惰性的金属氧化物或活性的FeMo/Al2O3催化剂。本发明方法具有普适性，能够在多种惰性基底纳米材料上生长出具有单一石墨氮物种掺杂的纳米碳材料，也能够在活性金属催化剂上生长出具有单一石墨氮物种掺杂的碳纳米管。此外，这种方法操作简单，能够进行批量制备，易于放大进行。The invention discloses a method for synthesizing a nano-carbon material doped with single graphite nitrogen, and belongs to the technical field of synthesis of nano-carbon materials. The method is to adopt a chemical vapor deposition method, using acetonitrile as a carbon source and a nitrogen source, to prepare a single graphite nitrogen-doped nano-carbon material on the surface of a deposition substrate; the temperature of the chemical vapor deposition is 750-1000 ° C, and the deposition substrate is Inert metal oxide or active FeMo/Al 2 O 3 catalyst. The method of the present invention is universal, and can grow nano-carbon materials doped with a single graphitic nitrogen species on a variety of inert substrate nanomaterials, and can also grow carbon nanomaterials doped with a single graphitic nitrogen species on active metal catalysts. Tube. In addition, this method is simple to operate, can be prepared in batches, and is easy to scale up.
Description
技术领域technical field
本发明涉及纳米碳材料的合成技术领域，具体涉及一种合成具有单一石墨氮掺杂的纳米碳材料的方法。The invention relates to the technical field of synthesis of nano-carbon materials, in particular to a method for synthesizing nano-carbon materials doped with a single graphite nitrogen.
背景技术Background technique
纳米碳材料由于具有比表面积高、表面化学性质可调、环境友好等特点，近年来在非金属催化领域内受到了研究人员的广泛青睐，在许多重要的催化反应如烷烃或乙苯脱氢反应、芳香醇的选择性氧化、C-H键活化等领域都表现出了相对于传统金属催化剂优异的催化性能。在纳米碳作为催化剂的催化反应中，纳米碳的微结构和表面化学性质对于催化反应有着重要的影响。比如，酮羰基或者醌基对烷烃或者乙苯脱氢反应起着关键作用，而在甲烷的活化反应中，缺陷结构又扮演着活性位的角色。除此之外，杂原子(如氮、硼、硫、磷等)掺杂可以有效调控纳米碳材料的物理化学性质和电子结构，这些对于促进纳米碳本身的催化作用有着显著的提升作用。比如，将氮原子引入到碳纳米管中，1)可以降低碳纳米管本身的HOMO-LUMO之间的带隙宽度、提高费米能级，这使得碳纳米管本身的电子更容易转移到底物分子上从而对其进行活化；2)由于氮原子的电负性大于碳原子的，这使得氮原子周围的碳原子带明显的正电荷，从而有效活化三线态的氧气分子。通常合成氮掺杂的纳米碳材料的方法有原位合成法和后处理法，前者采用含氮的有机碳源在高温条件下分解产生碳原子和氮原子并在基底上进行沉积，后者则是对已经合成后的纳米碳材料在含氮的气氛(比如氨气)下进行高温处理而得。在已经公布的报道中，大部分氮原子掺杂的纳米碳材料中氮物种的种类比较多，有吡啶氮、吡咯氮、石墨氮和氮氧化物等。这些氮物种在催化反应中或多或少的都能对催化反应产生影响，但是要区分哪一类氮物种起到最为主要的作用，目前主要采用的方法是对氮物种进行XPS分峰，将得到的各种氮物种的比例与催化活性相关联即可。这种通过XPS分峰的方法虽然常被采用，但是分峰过程带有一定的主观性，因此该方法欠妥当。为了了解到底是哪一类氮物种在发挥作用，最为有效的办法是合成出比较单一的氮物种掺杂的纳米碳材料，这对于目前的研究过程非常重要。Due to the characteristics of high specific surface area, adjustable surface chemical properties, and environmental friendliness, nanocarbon materials have been widely favored by researchers in the field of non-metallic catalysis in recent years. They are used in many important catalytic reactions such as alkane or ethylbenzene dehydrogenation , the selective oxidation of aromatic alcohols, and the activation of C-H bonds have shown excellent catalytic performance compared to traditional metal catalysts. In the catalytic reaction of nanocarbon as a catalyst, the microstructure and surface chemical properties of nanocarbon have an important influence on the catalytic reaction. For example, the ketone carbonyl or quinone group plays a key role in the dehydrogenation reaction of alkanes or ethylbenzene, and in the activation reaction of methane, the defect structure plays the role of the active site. In addition, heteroatom (such as nitrogen, boron, sulfur, phosphorus, etc.) doping can effectively regulate the physical and chemical properties and electronic structure of nano-carbon materials, which can significantly improve the catalytic effect of nano-carbon itself. For example, introducing nitrogen atoms into carbon nanotubes, 1) can reduce the bandgap width between the HOMO-LUMO of carbon nanotubes and increase the Fermi level, which makes it easier for the electrons of carbon nanotubes to transfer to the substrate 2) Since the electronegativity of the nitrogen atom is greater than that of the carbon atom, the carbon atoms around the nitrogen atom are obviously positively charged, thereby effectively activating the triplet oxygen molecule. Generally, the methods for synthesizing nitrogen-doped nano-carbon materials include in-situ synthesis and post-treatment. The former uses nitrogen-containing organic carbon sources to decompose under high temperature conditions to produce carbon atoms and nitrogen atoms and deposit them on the substrate, while the latter uses It is obtained by treating the synthesized nano-carbon material under a nitrogen-containing atmosphere (such as ammonia gas) at high temperature. In the published reports, there are many types of nitrogen species in most nitrogen-doped carbon nanomaterials, including pyridine nitrogen, pyrrole nitrogen, graphitic nitrogen, and nitrogen oxides. These nitrogen species can more or less affect the catalytic reaction in the catalytic reaction, but to distinguish which type of nitrogen species plays the most important role, the main method currently used is to perform XPS peak splitting on nitrogen species, and The ratio of the various nitrogen species obtained can be correlated with the catalytic activity. Although this method of peak splitting by XPS is often used, the peak splitting process is somewhat subjective, so this method is not appropriate. In order to understand which type of nitrogen species is playing a role, the most effective way is to synthesize nano-carbon materials doped with a relatively single nitrogen species, which is very important for the current research process.
发明内容Contents of the invention
为了解决目前合成氮掺杂纳米碳材料中所存在的氮物种种类繁多，难以单一化的问题，本发明提供一种合成具有单一石墨氮掺杂的纳米碳材料的方法。In order to solve the problem that there are many types of nitrogen species in the synthesis of nitrogen-doped nano-carbon materials and it is difficult to single them out, the present invention provides a method for synthesizing nano-carbon materials with single graphite nitrogen doping.
本发明技术方案如下：Technical scheme of the present invention is as follows:
一种合成具有单一石墨氮掺杂的纳米碳材料的方法，该方法是采用化学气相沉积方法，以乙腈作为碳源和氮源，在沉积基体表面制备具有单一石墨氮掺杂的纳米碳材料。A method for synthesizing a single graphite nitrogen-doped nano-carbon material. The method is to prepare a single graphite-nitrogen-doped nano-carbon material on the surface of a deposition substrate by using acetonitrile as a carbon source and a nitrogen source by chemical vapor deposition.
所述化学气相沉积的温度为750-1000℃。The temperature of the chemical vapor deposition is 750-1000°C.
所述化学气相沉积过程中，沉积基体为惰性的金属氧化物或活性的FeMo/Al2O3催化剂。In the chemical vapor deposition process, the deposition substrate is an inert metal oxide or an active FeMo/Al 2 O 3 catalyst.
所述沉积基体为惰性的金属氧化物(SBA-15、氧化镁、氧化铝或二氧化钛)时，沉积得到单一石墨氮掺杂的卷曲石墨层；单一石墨氮掺杂的卷曲石墨层中的氮含量为0.5～10at.％，其中以石墨氮形式存在的氮所占比例≥90％。When the deposition substrate is an inert metal oxide (SBA-15, magnesia, aluminum oxide or titania), deposition obtains a single graphite nitrogen-doped curled graphite layer; the nitrogen content in the single graphite nitrogen-doped curled graphite layer It is 0.5-10 at.%, wherein the proportion of nitrogen existing in the form of graphitic nitrogen is ≥90%.
所述沉积基体为活性的FeMo/Al2O3催化剂时，沉积得到单一石墨氮掺杂的碳纳米管；单一石墨氮掺杂的碳纳米管中的氮含量为0.5～10at.％，其中以石墨氮形式存在的氮所占比例≥70。When the deposition substrate is an active FeMo/Al 2 O 3 catalyst, a single graphite nitrogen-doped carbon nanotube is deposited; the nitrogen content in the single graphite nitrogen-doped carbon nanotube is 0.5 to 10 at.%, wherein The proportion of nitrogen existing in the form of graphitic nitrogen is ≥70.
本发明优点如下：The advantages of the present invention are as follows:
1、本发明使用乙腈作为碳源和氮源，其沸点低，容易得到气化产物，并且在较低的温度下易分解。1. The present invention uses acetonitrile as a carbon source and a nitrogen source, which has a low boiling point, is easy to obtain gasification products, and is easy to decompose at a relatively low temperature.
2、本发明使用的前驱体乙腈，具有普适性，能够在多种惰性的金属氧化物上分解得到石墨氮掺杂的纳米碳基复合材料。2. The precursor acetonitrile used in the present invention has universal applicability, and can be decomposed on various inert metal oxides to obtain graphite-nitrogen-doped nano-carbon-based composite materials.
3、本发明使用的前驱体乙腈，具有普适性，能够在活性的FeMo/Al2O3催化剂上生长出具有单一石墨氮结构的碳纳米管。3. The precursor acetonitrile used in the present invention is universal, and can grow carbon nanotubes with a single graphitic nitrogen structure on the active FeMo/Al 2 O 3 catalyst.
4、本发明的合成过程简单，易于操作，可大规模生产。4. The synthesis process of the present invention is simple, easy to operate, and can be produced on a large scale.
附图说明Description of drawings
图1为本发明具有单一石墨氮掺杂的纳米碳材料合成过程示意图。Fig. 1 is a schematic diagram of the synthesis process of the nano-carbon material with single graphite nitrogen doping in the present invention.
图2为实施例1中Al2O3基底上石墨氮掺杂的纳米碳材料(Al2O3@CNx)的XPS图谱。FIG. 2 is an XPS spectrum of graphitic nitrogen-doped nano-carbon material (Al 2 O 3 @CNx) on an Al 2 O 3 substrate in Example 1. FIG.
图3为实施例2中TiO2基底上石墨氮掺杂的纳米碳材料(TiO2@CNx)的XPS图谱。3 is the XPS spectrum of the graphitic nitrogen-doped nano-carbon material (TiO 2 @CNx) on the TiO 2 substrate in Example 2.
图4为实施例4中SBA-15基底上石墨氮掺杂的纳米碳材料(SBA-15@CNx)的XPS图谱。Fig. 4 is the XPS spectrum of the nano-carbon material (SBA-15@CNx) doped with graphite nitrogen on the SBA-15 substrate in Example 4.
图5为实施例5和对比例1中采用不同前驱体(咪唑，乙腈)在FeMo/Al2O3表面生长的掺氮的碳纳米管表面的氮物种的XPS图谱。5 is an XPS spectrum of nitrogen species on the surface of nitrogen-doped carbon nanotubes grown on the surface of FeMo/Al 2 O 3 using different precursors (imidazole, acetonitrile) in Example 5 and Comparative Example 1. FIG.
具体实施方式detailed description
以下结合附图和实施例详述本发明。The present invention is described in detail below in conjunction with accompanying drawing and embodiment.
以下各实施例中所用的碳源和氮源前驱体均为乙腈液体，通过化学气相沉积方法，以不同的惰性氧化物为基底得到石墨氮掺杂的卷曲层状石墨，或者在活性的FeMo/Al2O3上生长出石墨氮掺杂的碳纳米管。实施例中沉积温度选择为800℃。作为参照，对比例中以咪唑作为碳源和氮源合成了氮物种较多的氮掺杂的碳纳米管。The carbon source and nitrogen source precursors used in the following examples are all acetonitrile liquids. By chemical vapor deposition, different inert oxides are used as substrates to obtain graphitic nitrogen-doped curled layered graphite, or in active FeMo/ Graphite nitrogen-doped carbon nanotubes grown on Al 2 O 3 . In the embodiment, the deposition temperature is selected as 800°C. As a reference, in the comparative example, nitrogen-doped carbon nanotubes with more nitrogen species were synthesized by using imidazole as a carbon source and a nitrogen source.
如1所示为以下实施例中合成过程示意图，炉A和炉B通过气体管道相连接，其中炉A中对应的管道内坩埚中放置乙腈，乙腈在900℃条件下蒸发为气体产物，气体产物随氩气进入炉B中对应管道，并在炉B中管道内分解并在基底上沉积；氩气作为保护气体和载气。As shown in 1, it is a schematic diagram of the synthesis process in the following examples. Furnace A and furnace B are connected by a gas pipeline, wherein acetonitrile is placed in a crucible in the corresponding pipeline in furnace A, and acetonitrile is evaporated at 900 ° C to a gas product, the gas product Argon enters the corresponding pipeline in furnace B, and decomposes in the pipeline in furnace B and deposits on the substrate; argon is used as a protective gas and a carrier gas.
实施例1Example 1
称取100mg氧化铝粉末装入炉B坩埚中，量取2ml乙腈放入炉A坩埚中，当炉B温度升至800℃后，将炉A温度升至90℃，保温10min后降温。在基底上得到了石墨氮掺杂的纳米碳材料(层状卷曲石墨)，该石墨氮掺杂的纳米碳材料中氮含量为1.5at.％，其中以石墨氮形式存在的氮占为95％(图2)。该石墨氮掺杂的纳米碳材料包覆在氧化铝表面形成复合材料。Weigh 100mg of alumina powder into the crucible of furnace B, measure 2ml of acetonitrile into the crucible of furnace A, when the temperature of furnace B rises to 800°C, raise the temperature of furnace A to 90°C, keep it for 10 minutes and then cool down. Obtained graphite nitrogen-doped nano-carbon material (layered curly graphite) on the substrate, nitrogen content is 1.5at.% in this graphite nitrogen-doped nano-carbon material, wherein the nitrogen that exists in the form of graphite nitrogen accounts for 95% (figure 2). The graphitic nitrogen-doped nano-carbon material is coated on the surface of aluminum oxide to form a composite material.
实施例2Example 2
称取100mg二氧化钛粉末装入炉B坩埚中，量取2ml乙腈放入炉A坩埚中，当炉B温度升至800℃后，将炉A温度升至90℃，保温10min后降温。在基底上得到了石墨氮掺杂的纳米碳材料(层状卷曲石墨)。该石墨氮掺杂的纳米碳材料中氮含量为4.8at.％，其中以石墨氮形式存在的氮占92％(图3)。该石墨氮掺杂的纳米碳材料包覆在二氧化钛表面形成复合材料。Weigh 100mg of titanium dioxide powder into the crucible of furnace B, measure 2ml of acetonitrile into the crucible of furnace A, when the temperature of furnace B rises to 800°C, raise the temperature of furnace A to 90°C, hold for 10 minutes and then cool down. Graphite nitrogen-doped nano-carbon materials (layered curly graphite) were obtained on the substrate. The nitrogen content in the graphitic nitrogen-doped nano-carbon material is 4.8 at.%, wherein the nitrogen in the form of graphitic nitrogen accounts for 92% (FIG. 3). The graphite nitrogen-doped nano-carbon material is coated on the surface of titanium dioxide to form a composite material.
实施例3Example 3
称取100mg氧化镁装入炉B坩埚中，量取2ml乙腈放入炉A坩埚中，当炉B温度升至800℃后，将炉A温度升至90℃，保温10min后降温。在基底上得到了石墨氮掺杂的纳米碳材料(层状卷曲石墨)。该石墨氮掺杂的纳米碳材料中氮含量为2at.％，其中以石墨氮形式存在的氮占为90％。该石墨氮掺杂的纳米碳材料包覆在氧化镁表面形成复合材料。Weigh 100mg of magnesia into the crucible of furnace B, measure 2ml of acetonitrile into the crucible of furnace A, when the temperature of furnace B rises to 800°C, raise the temperature of furnace A to 90°C, hold for 10min and then cool down. Graphite nitrogen-doped nano-carbon materials (layered curly graphite) were obtained on the substrate. The nitrogen content in the graphitic nitrogen-doped nano-carbon material is 2 at.%, and the nitrogen existing in the form of graphitic nitrogen accounts for 90%. The graphitic nitrogen-doped nano-carbon material is coated on the surface of magnesium oxide to form a composite material.
实施例4Example 4
称取300mg SBA-15装入炉B坩埚中，量取6ml乙腈放入炉A坩埚中，当炉B温度升至800℃后，将炉A温度升至90℃，保温20min后降温。在基底上得到了石墨氮掺杂的纳米碳材料(层状卷曲石墨)。该石墨氮掺杂的纳米碳材料中氮含量为5at.％，其中以石墨氮形式存在的氮占94％(图4)。该石墨氮掺杂的纳米碳材料包覆在SBA-15表面形成复合材料。Weigh 300mg of SBA-15 into the crucible of furnace B, measure 6ml of acetonitrile into the crucible of furnace A, when the temperature of furnace B rises to 800°C, raise the temperature of furnace A to 90°C, hold for 20min and then cool down. Graphite nitrogen-doped nano-carbon materials (layered curly graphite) were obtained on the substrate. The nitrogen content in the graphitic nitrogen-doped nano-carbon material is 5 at.%, wherein nitrogen in the form of graphitic nitrogen accounts for 94% (FIG. 4). The graphitic nitrogen-doped nano-carbon material is coated on the surface of SBA-15 to form a composite material.
实施例5Example 5
称取100mg FeMo/Al2O3装入炉B坩埚中，量取6ml乙腈放入炉A坩埚中，当炉B温度升至800℃后，将炉A温度升至90℃，保温40min后降温。在基底上得到了石墨氮掺杂的纳米碳材料(碳纳米管)。所得石墨氮掺杂的碳纳米管中氮含量为5at.％，其中以石墨氮形式存在的氮占70％(图5)。该石墨氮掺杂的纳米碳材料包覆在FeMo/Al2O3表面形成复合材料。Weigh 100mg of FeMo/Al 2 O 3 into the crucible of furnace B, measure 6ml of acetonitrile into the crucible of furnace A, when the temperature of furnace B rises to 800°C, raise the temperature of furnace A to 90°C, keep it warm for 40min and then cool down . Graphite nitrogen-doped nano-carbon materials (carbon nanotubes) were obtained on the substrate. The nitrogen content in the obtained graphitic nitrogen-doped carbon nanotubes was 5 at.%, and the nitrogen existing in the form of graphitic nitrogen accounted for 70% (FIG. 5). The graphitic nitrogen-doped nano-carbon material is coated on the surface of FeMo/Al 2 O 3 to form a composite material.
对比例1Comparative example 1
称取100mg FeMo/Al2O3装入炉B坩埚中，量取2g咪唑放入炉A坩埚中，当炉B温度升至800℃后，将炉A温度升至250℃，保温20min后降温。在基底上得到了氮掺杂的碳纳米管。所得氮掺杂的碳纳米管中氮含量为4at.％，其中以石墨氮形式存在的氮占40％，以吡啶氮形式存在的氮占20％，以吡咯氮形式存在的氮占10％(图5)。Weigh 100mg FeMo/Al 2 O 3 into the crucible of furnace B, measure 2g of imidazole into the crucible of furnace A, when the temperature of furnace B rises to 800°C, raise the temperature of furnace A to 250°C, keep it warm for 20min and then cool down . Nitrogen-doped carbon nanotubes were obtained on the substrate. The nitrogen content in the obtained nitrogen-doped carbon nanotubes is 4 at.%, wherein the nitrogen existing in the form of graphitic nitrogen accounts for 40%, the nitrogen existing in the form of pyridine nitrogen accounts for 20%, and the nitrogen existing in the form of pyrrole nitrogen accounts for 10% ( Figure 5).
显然，本发明中采用的乙腈前驱体是一种有效的碳源和氮源，能够在CVD过程中分解得到石墨氮掺杂的纳米碳材料。相对于咪唑作为碳源和氮源，乙腈作为前驱体的得到的氮掺杂的碳纳米管具有更高比例的石墨氮。Obviously, the acetonitrile precursor used in the present invention is an effective carbon source and nitrogen source, which can be decomposed in the CVD process to obtain graphitic nitrogen-doped nano-carbon materials. The resulting nitrogen-doped carbon nanotubes with acetonitrile as a precursor have a higher proportion of graphitic nitrogen relative to imidazole as a carbon and nitrogen source.
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