CN105177529B - A kind of carbon nano-composite material and its preparation method and application - Google Patents
A kind of carbon nano-composite material and its preparation method and application Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 82
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 39
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 34
- 239000010432 diamond Substances 0.000 claims abstract description 34
- 239000010703 silicon Substances 0.000 claims abstract description 34
- 239000002159 nanocrystal Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000007789 gas Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000005566 electron beam evaporation Methods 0.000 claims description 16
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 239000010937 tungsten Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000002127 nanobelt Substances 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 37
- 239000002074 nanoribbon Substances 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 abstract description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 8
- 238000003491 array Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000012876 topography Methods 0.000 description 20
- 238000004050 hot filament vapor deposition Methods 0.000 description 19
- 230000010287 polarization Effects 0.000 description 17
- 235000012431 wafers Nutrition 0.000 description 15
- 238000010586 diagram Methods 0.000 description 9
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
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- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
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Abstract
本发明提供一种碳纳米复合材料及其制备方法和应用。碳纳米复合材料为石墨烯纳米带垂直阵列，且石墨烯纳米带的外壁附着有碳化硅/石墨化金刚石纳米晶体，其中碳化硅晶体包裹在石墨化金刚石晶体之中。碳纳米复合材料的制备方法，包括步骤：在硅片蒸镀Al2O3和Fe；单壁碳纳米管垂直阵列生长；在单壁碳纳米管垂直阵列蒸镀硅；在热丝CVD炉中，气体为H2、CH4，通过去离子水的H2的气氛下，处理得到碳纳米复合材料。本发明碳纳米复合材料具有电催化析氢活性高、起始电势(onset potential)低，电流密度大、Tafel斜率小、性能稳定等特点，可在电催化析氢中应用。The invention provides a carbon nanocomposite material and its preparation method and application. The carbon nanocomposite material is a vertical array of graphene nanoribbons, and the outer wall of the graphene nanoribbons is attached with silicon carbide/graphitized diamond nanocrystals, wherein the silicon carbide crystals are wrapped in the graphitized diamond crystals. The preparation method of the carbon nanocomposite material comprises the steps of: evaporating Al 2 O 3 and Fe on a silicon wafer; growing single-walled carbon nanotubes in vertical arrays; evaporating silicon in the vertical arrays of single-walled carbon nanotubes; , the gas is H 2 and CH 4 , and the carbon nanocomposite material is obtained by processing under the atmosphere of H 2 with deionized water. The carbon nanocomposite material of the present invention has the characteristics of high electrocatalytic hydrogen evolution activity, low onset potential, high current density, small Tafel slope, stable performance, etc., and can be applied in electrocatalytic hydrogen evolution.
Description
技术领域technical field
本发明涉及碳纳米材料，具体涉及一种碳纳米复合材料及其制备方法，以及该材料在电催化析氢中的应用。The invention relates to carbon nanomaterials, in particular to a carbon nanocomposite material and a preparation method thereof, as well as the application of the material in electrocatalytic hydrogen evolution.
背景技术Background technique
氢能燃烧值高，清洁无污染、资源丰富、使用范围广，开发氢能对于缓解当今社会的能源和环境问题具有重大意义。电分解水制氢是大规模获取氢能源的最主要的途径。对于析氢反应，贵金属元素(如Pt)具有优异的电催化分解水析氢活性，其析氢起始电位低，但其价格昂贵，难以大规模应用，为此寻找一种非贵金属催化剂来替代Pt是电催化析氢催化剂研究的热点。低维碳基纳米材料作为非金属电催化剂自身表现出稳定和高效的HER催化性能。特别是石墨化金刚石(graphitized nanodiamond)，这种碳基核壳纳米结构具有石墨烯的外壳和金刚石的核，具有良好的电子传导性和抗化学腐蚀性。此外，碳化硅(SiC)是第三代半导体的核心材料之一，其基本元素为Si和C，具有广泛的来源。通过酸腐蚀可制得平均晶粒尺寸小于8nm的SiC纳米晶体，具有良好的电催化析氢活性(He,C.；Wu,X.；Shen,J.；Chu,P.K.Nano Letters 2012,12,(3),1545-1548)。Hydrogen energy has a high combustion value, is clean and pollution-free, is rich in resources, and has a wide range of applications. The development of hydrogen energy is of great significance for alleviating energy and environmental problems in today's society. Hydrogen production by electrolysis of water is the most important way to obtain hydrogen energy on a large scale. For the hydrogen evolution reaction, noble metal elements (such as Pt) have excellent electrocatalytic hydrogen evolution activity in water splitting, and their hydrogen evolution onset potential is low, but they are expensive and difficult to apply on a large scale. The research hotspot of catalytic hydrogen evolution catalyst. Low-dimensional carbon-based nanomaterials exhibit stable and efficient HER catalytic performance as metal-free electrocatalysts. Especially graphitized nanodiamond, a carbon-based core-shell nanostructure with a graphene shell and a diamond core, has good electronic conductivity and chemical corrosion resistance. In addition, silicon carbide (SiC) is one of the core materials of the third-generation semiconductor, and its basic elements are Si and C, which have a wide range of sources. SiC nanocrystals with an average grain size of less than 8nm can be prepared by acid corrosion, which has good electrocatalytic hydrogen evolution activity (He, C.; Wu, X.; Shen, J.; Chu, P.K. Nano Letters 2012,12,( 3), 1545-1548).
纳米颗粒由于其尺寸较小，结构和性质都相当复杂，其表面态和缺陷态都对它的电催化性能有很大的影响，这使得对3C-SiC纳米颗粒的电催化性能很难控制，在应用上就有很大困难。碳纳米管垂直阵列具有高比表面积、良好的导电性、物理、化学稳定性，而在析氢催化中作为载体广泛使用。垂直石墨烯纳米带阵列是将单根碳纳米管展开，其依然保持碳纳米管垂直阵列的取向性。这种结构既能支撑其他纳米晶体生长，同时具有良好的导电性，物理和化学稳定性。热丝CVD(hot filament CVD)法常见于制备高熔点的碳纳米材料如：金刚石、SiC等。热丝CVD属于一种低温CVD法，其热丝温度高于2000℃，而炉体温度可以维持在相对较低的温度。目前，还没有热丝CVD法制备碳化硅/石墨化金刚石纳米材料的报道，更没有一种方法能够制备碳化硅/石墨化金刚石-石墨烯纳米带复合材料，也无碳化硅/石墨化金刚石-石墨烯纳米带作为析氢催化剂的报道。Due to the small size of nanoparticles, the structure and properties are quite complex, and their surface states and defect states have a great influence on its electrocatalytic performance, which makes it difficult to control the electrocatalytic performance of 3C-SiC nanoparticles. There are great difficulties in application. The vertical array of carbon nanotubes has high specific surface area, good electrical conductivity, physical and chemical stability, and is widely used as a carrier in hydrogen evolution catalysis. The vertical graphene nanoribbon array is to expand a single carbon nanotube, which still maintains the orientation of the vertical array of carbon nanotubes. This structure can not only support the growth of other nanocrystals, but also has good electrical conductivity, physical and chemical stability. The hot filament CVD (hot filament CVD) method is commonly used in the preparation of high-melting carbon nanomaterials such as diamond and SiC. Hot wire CVD is a low temperature CVD method, the temperature of the hot wire is higher than 2000°C, and the temperature of the furnace body can be maintained at a relatively low temperature. At present, there is no report on the preparation of silicon carbide/graphitized diamond nanomaterials by hot wire CVD, and there is no method that can prepare silicon carbide/graphitized diamond-graphene nanoribbon composite materials, and there is no silicon carbide/graphitized diamond- Graphene nanoribbons reported as hydrogen evolution catalysts.
发明内容Contents of the invention
本发明的目的在于提供一种纳米晶体颗粒均匀、高质量的碳纳米复合材料；本发明的另一目的在于提供碳纳米复合材料的制备方法，该方法应采用热丝CVD、操作简单、制备周期短、可重复操作；本发明第三个目的在于提供碳纳米复合材料在电催化析氢中的应用。The purpose of the present invention is to provide a kind of carbon nanocomposite material with uniform nanocrystal particle and high quality; Another purpose of the present invention is to provide the preparation method of carbon nanocomposite material, this method should adopt hot wire CVD, simple operation, short preparation period Short, repeatable operation; the third purpose of the present invention is to provide the application of carbon nanocomposite materials in electrocatalytic hydrogen evolution.
本发明是通过以下方案实现的：The present invention is achieved through the following schemes:
一种碳纳米复合材料，其为石墨烯纳米带垂直阵列，且石墨烯纳米带的外壁附着有碳化硅/石墨化金刚石纳米晶体，其中碳化硅晶体包裹在石墨化金刚石晶体之中。A carbon nanocomposite material, which is a vertical array of graphene nanoribbons, and the outer wall of the graphene nanoribbons is attached with silicon carbide/graphitized diamond nanocrystals, wherein the silicon carbide crystals are wrapped in the graphitized diamond crystals.
一种碳纳米复合材料的制备方法，包括以下步骤：A method for preparing carbon nanocomposites, comprising the steps of:
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗，N2吹干；通过电子束蒸发***(E-Beam Evaporation)依次蒸镀8-12nm Al2O3，0.7-1.2nm Fe；(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone, and dried with N 2 ; 8-12nm Al 2 O 3 and 0.7-1.2nm Fe were sequentially evaporated by E-Beam Evaporation;
(2)在热丝CVD炉温700-800℃下，气体流量分别为H2:200±10sccm，C2H2:2±0.5sccm，通过去离子水的H2为200±10sccm，总气压为25±1Torr，热丝为单根钨丝或单根钽丝，功率为30-35W条件下，将步骤(1)中制得的硅片置于钨丝或钽丝前方0.2～0.5cm处，反应30～60s将钨丝或钽丝功率设置为0，总气压调节为6.4±0.5Torr，反应15min后完成单壁碳纳米管垂直阵列生长；(2) At a hot wire CVD furnace temperature of 700-800°C, the gas flow rates are H 2 : 200±10sccm, C 2 H 2 : 2±0.5sccm, the H 2 passing through deionized water is 200±10sccm, the total gas pressure 25±1Torr, the heating wire is a single tungsten wire or a single tantalum wire, and the power is 30-35W, place the silicon wafer prepared in step (1) 0.2-0.5cm in front of the tungsten wire or tantalum wire , set the power of tungsten wire or tantalum wire to 0, and adjust the total air pressure to 6.4±0.5Torr after 30-60 seconds of reaction, and complete the vertical array growth of single-walled carbon nanotubes after 15 minutes of reaction;
(3)通过电子束蒸发***在步骤(2)所获得的单壁碳纳米管垂直阵列蒸镀1-5nm的硅，蒸镀速率为0.01nm/min；(3) evaporating 1-5nm silicon on the vertical array of single-walled carbon nanotubes obtained in step (2) by the electron beam evaporation system, and the evaporation rate is 0.01nm/min;
(4)在热丝CVD炉温950-1050℃下，气体流量分别为H2:125-175sccm，CH4:0.3-0.6sccm，通过去离子水的H2为5-25sccm，总气压为25-30Torr，热丝为四根钨丝或四根钽丝，功率为75-85W条件下，将经步骤(3)处理的单壁碳纳米管垂直阵列置于钨丝或钽丝正下方，反应1-4h即得碳纳米复合材料(碳化硅/石墨化金刚石-石墨烯纳米带复合材料)。(4) At a hot wire CVD furnace temperature of 950-1050°C, the gas flow rates are H 2 : 125-175 sccm, CH 4 : 0.3-0.6 sccm, the H 2 passing through deionized water is 5-25 sccm, and the total air pressure is 25 -30Torr, the heating wire is four tungsten wires or four tantalum wires, and under the condition of 75-85W power, the vertical array of single-walled carbon nanotubes treated in step (3) is placed directly under the tungsten wire or tantalum wire, and the reaction The carbon nanocomposite material (silicon carbide/graphitized diamond-graphene nanoribbon composite material) is obtained in 1-4h.
本发明所使用的热丝为钨丝或钽丝，其直径0.25mm，长度约为8mm。钨丝或钽丝单根时水平放置，四根时水平放置平行排列。The heating wire used in the present invention is a tungsten wire or a tantalum wire with a diameter of 0.25 mm and a length of about 8 mm. A single tungsten wire or tantalum wire should be placed horizontally, and four wires should be placed horizontally and arranged in parallel.
本发明碳纳米复合材料具有电催化析氢活性高、起始电势(onset potential)低，电流密度大、Tafel斜率小、性能稳定等特点，可在电催化析氢中应用。The carbon nanocomposite material of the present invention has the characteristics of high electrocatalytic hydrogen evolution activity, low onset potential, high current density, small Tafel slope, stable performance, etc., and can be applied in electrocatalytic hydrogen evolution.
与现有工艺相比，本发明的优点：Compared with existing technology, the advantages of the present invention:
1)本发明制备的碳纳米复合材料，石墨烯纳米带保持垂直形态，缺陷较少，无杂质。扫描电镜(SEM)形貌图和透射电子显微镜(TEM)形貌图表明，石墨化金刚石包裹碳化硅纳米晶体，尺寸细小，分布均匀，晶化程度高，无表面缺陷。碳化硅/石墨化金刚石纳米晶体均匀附着于石墨烯纳米带。1) In the carbon nanocomposite material prepared by the present invention, the graphene nanobelt maintains a vertical shape, has fewer defects, and has no impurities. Scanning electron microscope (SEM) topography and transmission electron microscope (TEM) topography show that graphitized diamond wraps silicon carbide nanocrystals with small size, uniform distribution, high degree of crystallization, and no surface defects. SiC/graphitized diamond nanocrystals are uniformly attached to graphene nanoribbons.
2)本发明气体原料为普通实验气体，对气体要求宽松，大大降低制备成本。所需仪器简单，仅需要电子束蒸发***和热丝CVD炉。不需要特殊气氛、压强环境，只需在低压、还原气氛即可完成碳化硅/石墨化金刚石-石墨烯纳米带复合材料制备。本发明相对于现有技术，只需将含硅的单壁碳纳米管垂直阵列经过950-1050℃一次处理，制备时间短，工艺简化，温度低，制备效率高，大大降低能耗。2) The gas raw material of the present invention is an ordinary experimental gas, and the requirements for the gas are relaxed, which greatly reduces the preparation cost. The required instruments are simple, only an electron beam evaporation system and a hot wire CVD furnace are needed. No special atmosphere or pressure environment is required, and the silicon carbide/graphitized diamond-graphene nanoribbon composite material can be prepared only in a low pressure and reducing atmosphere. Compared with the prior art, the present invention only needs to process the silicon-containing single-walled carbon nanotube vertical array once at 950-1050°C, and has short preparation time, simplified process, low temperature, high preparation efficiency and greatly reduced energy consumption.
3)应用本发明方法所制备的碳纳米复合材料，其中石墨化金刚石和碳化硅纳米晶体结晶质量高。石墨化金刚石外层包裹有1-3层石墨烯，石墨化金刚石包裹碳化硅纳米晶体。石墨化金刚石纳米晶体尺寸可调，而碳化硅纳米晶体尺寸可保持不变。石墨化金刚石与外层石墨烯，石墨化金刚石与碳化硅之间均有化学键的键-键连接。3) The carbon nanocomposite material prepared by the method of the present invention has high crystallization quality of graphitized diamond and silicon carbide nanocrystals. The outer layer of graphitized diamond is wrapped with 1-3 layers of graphene, and the graphitized diamond is wrapped with silicon carbide nanocrystals. The size of graphitized diamond nanocrystals can be tuned, while that of silicon carbide nanocrystals can remain constant. There are bond-bond connections between the graphitized diamond and the outer graphene, and between the graphitized diamond and silicon carbide.
4)碳纳米复合材料具有电催化析氢活性高、起始电势低，电流密度大、Tafel斜率小、性能稳定等优点。4) Carbon nanocomposites have the advantages of high electrocatalytic hydrogen evolution activity, low initial potential, high current density, small Tafel slope, and stable performance.
附图说明Description of drawings
图1是实施例1制备碳纳米复合材料的SEM形貌图、TEM形貌图、极化曲线及其Tafel曲线；其中a是碳纳米复合材料SEM形貌图，b、c分别是碳纳米复合材料的TEM暗场像图和TEM明场像图；d、e分别是碳纳米复合材料在0.5M H2SO4溶液中的极化曲线及其Tafel曲线，扫描速率为5mV/s。Fig. 1 is the SEM topography diagram, TEM topography diagram, polarization curve and its Tafel curve of the carbon nanocomposite material prepared in Example 1; wherein a is the SEM topography diagram of the carbon nanocomposite material, and b and c are respectively the carbon nanocomposite TEM dark-field image and TEM bright-field image of the material; d and e are the polarization curve and Tafel curve of the carbon nanocomposite in 0.5MH 2 SO 4 solution, respectively, and the scan rate is 5mV/s.
图2是实施例2制备碳纳米复合材料的SEM形貌图、TEM形貌图；其中a、b是碳纳米复合材料的SEM形貌图；c、d和e、f分别是碳纳米复合材料的TEM明场像图和TEM暗场像图。Fig. 2 is the SEM topography figure, TEM topography figure of carbon nanocomposite material prepared in embodiment 2; Wherein a, b are the SEM topography figure of carbon nanocomposite material; C, d and e, f are carbon nanocomposite material respectively TEM bright field image and TEM dark field image.
图3是实施例3制备碳纳米复合材料的TEM形貌图、极化曲线和计时电流曲线；其中a、c和b、d分别是碳纳米复合材料的TEM暗场像图和TEM明场像图；e是碳纳米复合材料在0.5M H2SO4溶液中的初始极化曲线及经过1000次循环之后的极化曲线；f是碳纳米复合材料在0.5M H2SO4溶液中在电势分别为-155、-173和-185mV时的计时电流曲线。Fig. 3 is the TEM topography figure, polarization curve and chronocurrent curve of carbon nanocomposite material prepared in embodiment 3; Wherein a, c and b, d are TEM dark field image figure and TEM bright field image of carbon nanocomposite material respectively Figure; e is the initial polarization curve of carbon nanocomposite in 0.5MH 2 SO 4 solution and the polarization curve after 1000 cycles; f is the potential of carbon nanocomposite in 0.5MH 2 SO 4 solution at Chronoamperometry curves at -155, -173 and -185mV.
图4是实施例4制备碳纳米复合材料的TEM形貌图、极化曲线及其Tafel曲线；其中a、b和c、d分别是碳纳米复合材料的TEM暗场像图和TEM明场像图；e、f分别是碳纳米复合材料在0.5M H2SO4溶液中的极化曲线及其Tafel曲线，扫描速率为5mV/s。Fig. 4 is the TEM topography figure, polarization curve and Tafel curve thereof of carbon nanocomposite material prepared in embodiment 4; Wherein a, b and c, d are TEM dark field image figure and TEM bright field image of carbon nanocomposite material respectively Figures; e and f are the polarization curves and Tafel curves of carbon nanocomposites in 0.5MH 2 SO 4 solution, respectively, and the scan rate is 5mV/s.
图5是实施例5制备碳纳米复合材料的SEM形貌图、TEM形貌图、极化曲线及其Tafel曲线；其中a是碳纳米复合材料SEM形貌图；b、c分别是碳纳米复合材料的TEM暗场像图和明场像图；d、e分别是碳纳米复合材料在0.5M H2SO4溶液中的极化曲线及其Tafel曲线，扫描速率为5mV/s。Fig. 5 is the SEM topography diagram, TEM topography diagram, polarization curve and its Tafel curve of carbon nanocomposite material prepared in embodiment 5; Wherein a is carbon nanocomposite material SEM topography diagram; B, c are respectively carbon nanocomposite TEM dark-field image and bright-field image of the material; d and e are the polarization curve and Tafel curve of the carbon nanocomposite in 0.5MH 2 SO 4 solution, respectively, and the scan rate is 5mV/s.
图6是实施例6制备碳纳米复合材料的SEM形貌图、TEM形貌图、极化曲线及其Tafel曲线；其中a是碳纳米复合材料的SEM形貌图；b、c分别是碳纳米复合材料的TEM暗场像图和TEM明场像图；d、e分别是碳纳米复合材料在0.5M H2SO4溶液中的极化曲线及其Tafel曲线，扫描速率为5mV/s。Fig. 6 is the SEM topography diagram, TEM topography diagram, polarization curve and its Tafel curve of carbon nanocomposite material prepared in embodiment 6; Wherein a is the SEM topography diagram of carbon nanocomposite material; B, c are respectively carbon nanometer TEM dark-field image and TEM bright-field image of the composite; d and e are the polarization curve and Tafel curve of the carbon nanocomposite in 0.5MH 2 SO 4 solution, respectively, and the scan rate is 5mV/s.
具体实施方式detailed description
下面结合附图对本发明的具体实施方式做进一步详细描述。The specific implementation manners of the present invention will be further described in detail below in conjunction with the accompanying drawings.
实施例1：Example 1:
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗，N2吹干。通过电子束蒸发***依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone, and dried with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system.
(2)在热丝CVD炉温750℃下，气体流量分别为H2:190sccm，C2H2:2.2sccm，通过去离子水的H2为190sccm，总气压为25.5Torr，热丝为单根钨丝，功率为30W条件下，将步骤(1)中制的硅片置于钨丝前方0.5cm，反应30s后将钨丝功率设置为0，总气压调节为6.4Torr，反应15min后完成单壁碳纳米管垂直阵列生长。(2) At a hot wire CVD furnace temperature of 750°C, the gas flow rates are H 2 : 190 sccm, C 2 H 2 : 2.2 sccm, the H 2 passing through deionized water is 190 sccm, the total air pressure is 25.5 Torr, and the hot wire is single A tungsten wire, under the condition of 30W power, place the silicon chip made in step (1) 0.5cm in front of the tungsten wire, set the power of the tungsten wire to 0 after 30s of reaction, adjust the total air pressure to 6.4Torr, and complete the reaction after 15 minutes Vertical array growth of single-walled carbon nanotubes.
(3)通过电子束蒸发***在(2)所获得的单壁碳纳米管垂直阵列蒸镀1nm的硅。(3) Evaporate 1 nm of silicon on the vertical array of single-walled carbon nanotubes obtained in (2) by an electron beam evaporation system.
(4)在热丝CVD炉温950℃下，气体流量分别为H2:125sccm，CH4:0.3sccm，通过去离子水的H2为7.5sccm，总气压为25Torr，热丝为四根钨丝，功率为75W条件下，将步骤(3)中制得含单壁碳纳米管垂直阵列和硅族元素的硅片置于钨丝正下方，反应1h后完成碳纳米复合材料的制备。(4) At a hot wire CVD furnace temperature of 950°C, the gas flow rates are H 2 : 125 sccm, CH 4 : 0.3 sccm, the H 2 passing through deionized water is 7.5 sccm, the total pressure is 25 Torr, and the hot wire is four tungsten Wire, under the condition of 75W power, place the silicon chip containing the vertical array of single-walled carbon nanotubes and silicon group elements prepared in step (3) directly under the tungsten wire, and complete the preparation of carbon nanocomposite material after reacting for 1 hour.
图1中a为碳纳米复合材料SEM形貌图。从SEM图可以看出石墨烯纳米带保持垂直形态，石墨化金刚石包裹碳化硅纳米晶***于石墨烯纳米带顶端；图1中b,c分别为碳纳米复合材料TEM暗场像和明场像形貌图，可以看出单壁碳管已剖开形成石墨烯纳米带，石墨化金刚石包裹碳化硅纳米晶体尺寸均一，无团聚，结晶质量良好，碳化硅纳米晶体被石墨化金刚石包裹；图1中d,e分别是碳纳米复合材料在0.5M H2SO4溶液中的极化曲线及其Tafel曲线。可以看出碳纳米复合材料具有较低的起始电势(onset potential)，约为85mV。在电压为0.3V相对于标准氢电极时，电流密度为36.8mA cm-2，较低的Tafel斜率约为168mV dec-1。In Fig. 1, a is the SEM image of the carbon nanocomposite material. It can be seen from the SEM image that the graphene nanoribbon maintains a vertical shape, and the graphene diamond-wrapped silicon carbide nanocrystal is located on the top of the graphene nanoribbon; b and c in Figure 1 are the TEM dark field image and bright field image of the carbon nanocomposite material, respectively From the picture, it can be seen that the single-walled carbon tube has been cut to form a graphene nanoribbon, and the graphitized diamond-wrapped silicon carbide nanocrystal has uniform size, no agglomeration, and the crystal quality is good. The silicon carbide nanocrystal is wrapped by graphitized diamond; in Figure 1 d, e are the polarization curves and Tafel curves of carbon nanocomposites in 0.5MH 2 SO 4 solution, respectively. It can be seen that the carbon nanocomposite material has a relatively low onset potential, about 85mV. When the voltage is 0.3V relative to the standard hydrogen electrode, the current density is 36.8mA cm -2 , and the lower Tafel slope is about 168mV dec -1 .
实施例2：Example 2:
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗，N2吹干。通过电子束蒸发***依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone, and dried with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system.
(2)在热丝CVD炉温750℃下，气体流量分别为H2:200sccm，C2H2:2.3sccm，通过去离子水的H2为210sccm，总气压为25Torr，热丝为单根钨丝，功率为30W条件下，将(1)中制的硅片置于钨丝前方0.3cm，反应45s后将钨丝功率设置为0，总气压调节为6.4Torr，反应15min后完成单壁碳纳米管垂直阵列生长。(2) At the temperature of the hot wire CVD furnace at 750°C, the gas flow rates are H 2 : 200 sccm, C 2 H 2 : 2.3 sccm, the H 2 passing through the deionized water is 210 sccm, the total air pressure is 25 Torr, and the hot wire is a single Tungsten wire, under the condition of 30W power, place the silicon chip made in (1) 0.3cm in front of the tungsten wire, set the power of the tungsten wire to 0 after 45s of reaction, adjust the total air pressure to 6.4Torr, and complete the single wall after 15 minutes of reaction Vertical array growth of carbon nanotubes.
(3)通过电子束蒸发***在(2)所获得的单壁碳纳米管垂直阵列蒸镀2nm的硅。(3) Evaporate 2 nm of silicon on the vertical array of single-walled carbon nanotubes obtained in (2) by an electron beam evaporation system.
(4)在热丝CVD炉温950℃下，气体流量分别为H2:150sccm，CH4:0.5sccm，通过去离子水的H2为10sccm，总气压为25Torr，热丝为四根钨丝，功率为80W条件下，将(3)中制得含单壁碳纳米管垂直阵列和硅的硅片置于钨丝正下方，反应1h后完成碳纳米复合材料的制备。(4) At a hot wire CVD furnace temperature of 950°C, the gas flow rates are H 2 : 150 sccm, CH 4 : 0.5 sccm, the H 2 passing through deionized water is 10 sccm, the total pressure is 25 Torr, and the hot wire is four tungsten wires , under the condition of a power of 80W, the silicon wafer containing the vertical array of single-walled carbon nanotubes and silicon prepared in (3) was placed directly under the tungsten wire, and the preparation of the carbon nanocomposite was completed after 1 hour of reaction.
图2中a,b为碳纳米复合材料的SEM形貌图，可以看出石墨烯纳米带保持垂直形态，石墨化金刚石包裹碳化硅纳米晶***于石墨烯纳米带顶端；图2中c,d和e,f分别为碳纳米复合材料的TEM的明场像图和暗场像图。TEM形貌图表明，单壁碳管已剖开形成石墨烯纳米带，碳化硅纳米晶体尺寸均一，无团聚，结晶质量良好，碳化硅纳米晶体平均直径约为2.0nm，碳化硅纳米晶体被石墨化金刚石包裹。石墨化金刚石外层包裹有2-3层石墨烯，石墨化金刚石包裹碳化硅纳米晶体附着于石墨烯纳米带。In Figure 2, a and b are SEM topography images of carbon nanocomposites. It can be seen that the graphene nanoribbon maintains a vertical shape, and graphene diamond-wrapped silicon carbide nanocrystals are located at the top of the graphene nanoribbon; in Figure 2, c, d and e, f are TEM bright-field images and dark-field images of carbon nanocomposites, respectively. The TEM topography shows that the single-walled carbon tubes have been cut open to form graphene nanoribbons, the silicon carbide nanocrystals have uniform size, no agglomeration, and the crystallization quality is good. Chemicalized diamond wrap. The outer layer of graphitized diamond is wrapped with 2-3 layers of graphene, and the graphitized diamond is wrapped with silicon carbide nanocrystals attached to graphene nanoribbons.
实施例3：Example 3:
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗，N2吹干。通过电子束蒸发***依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone, and dried with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system.
(2)在热丝CVD炉温750℃下，气体流量分别为H2:200sccm，C2H2:1.9sccm，通过去离子水的H2为190sccm，总气压为25Torr，热丝为单根钽丝，功率为30W条件下，将(1)中制的硅片置于钽丝前方0.4cm，反应60s后将钽丝功率设置为0，总气压调节为6.0Torr，反应15min后完成单壁碳纳米管垂直阵列生长。(2) At the temperature of the hot wire CVD furnace at 750°C, the gas flow rates are H 2 : 200 sccm, C 2 H 2 : 1.9 sccm, the H 2 passing through the deionized water is 190 sccm, the total air pressure is 25 Torr, and the hot wire is a single For tantalum wire, under the condition of 30W power, place the silicon wafer made in (1) 0.4cm in front of the tantalum wire, set the power of tantalum wire to 0 after 60s of reaction, adjust the total air pressure to 6.0Torr, and complete the single wall after 15 minutes of reaction Vertical array growth of carbon nanotubes.
(3)通过电子束蒸发***在(2)所获得的单壁碳纳米管垂直阵列蒸镀3nm的硅。(3) Evaporate 3nm silicon on the vertical array of single-walled carbon nanotubes obtained in (2) by an electron beam evaporation system.
(4)在热丝CVD炉温1000℃下，气体流量分别为H2:140sccm，CH4:0.5sccm，通过去离子水的H2为10sccm，总气压为30Torr，热丝为四根钽丝，功率为80W条件下，将(3)中制得含单壁碳纳米管垂直阵列和硅族元素的硅片置于钽丝正下方，反应2h后完成碳纳米复合材料的制备。(4) At a hot wire CVD furnace temperature of 1000°C, the gas flow rates are H 2 : 140 sccm, CH 4 : 0.5 sccm, the H 2 passing through deionized water is 10 sccm, the total pressure is 30 Torr, and the hot wire is four tantalum wires , under the condition of a power of 80W, the silicon wafer containing vertical arrays of single-walled carbon nanotubes and silicon group elements prepared in (3) was placed directly under the tantalum wire, and the carbon nanocomposite material was prepared after 2 hours of reaction.
图3中a,c和b,d分别为碳纳米复合材料的TEM暗场像图和TEM明场像图。从图3中a,b可以看出石墨化金刚石包裹碳化硅纳米晶体尺寸均一，无团聚，结晶质量良好，碳化硅纳米晶体被石墨化金刚石包裹，石墨化金刚石外层包裹有2层石墨烯。从图3中c,d可以看出石墨化金刚石与外层石墨烯，石墨化金刚石与碳化硅纳米晶体之间均有化学键与化学键的连接。图3中e为碳纳米复合材料在0.5M H2SO4溶液中的极化曲线和循环1000次后的极化曲线。可以看出曲线变化不大，表明所制得碳纳米复合材料具有良好的电催化析氢稳定性。图3中f为碳纳米复合材料在-155，-173和-185mV下在0.5M H2SO4溶液中的计时电流曲线，可以看出在不同电压下经过30000s循环后，碳纳米复合材料电流密度几乎维持不变。In Fig. 3, a, c, b, and d are TEM dark field images and TEM bright field images of carbon nanocomposites, respectively. From Figure 3a and b, it can be seen that the graphitized diamond-wrapped silicon carbide nanocrystals have uniform size, no agglomeration, and good crystal quality. The silicon carbide nanocrystals are wrapped by graphitized diamond, and the outer layer of graphitized diamond is wrapped with two layers of graphene. It can be seen from c and d in Figure 3 that there are chemical bonds and chemical bonds between the graphitized diamond and the outer graphene, and between the graphitized diamond and the silicon carbide nanocrystal. Figure 3 e is the polarization curve of the carbon nanocomposite in 0.5MH 2 SO 4 solution and the polarization curve after 1000 cycles. It can be seen that the curve does not change much, indicating that the prepared carbon nanocomposite has good electrocatalytic hydrogen evolution stability. In Figure 3, f is the chronoamperometric curve of carbon nanocomposites in 0.5MH 2 SO 4 solution at -155, -173 and -185mV. It can be seen that after 30000s cycle at different voltages, the current density of carbon nanocomposites almost unchanged.
实施例4：Example 4:
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗，N2吹干。通过电子束蒸发***依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone, and dried with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system.
(2)在热丝CVD炉温750℃下，气体流量分别为H2:200sccm，C2H2:2.5sccm，通过去离子水的H2为200sccm，总气压为24.5Torr，热丝为单根钽丝，功率为30W条件下，将(1)中制的硅片置于钽丝前方0.4cm，反应50s后将钽丝功率设置为0，总气压调节为6.6Torr，反应15min后完成单壁碳纳米管垂直阵列生长。(2) At a hot wire CVD furnace temperature of 750°C, the gas flow rates are H 2 : 200 sccm, C 2 H 2 : 2.5 sccm, the H 2 passing through deionized water is 200 sccm, the total pressure is 24.5 Torr, and the hot wire is single A tantalum wire, under the condition of 30W power, place the silicon chip made in (1) 0.4cm in front of the tantalum wire, set the power of the tantalum wire to 0 after 50s of reaction, adjust the total air pressure to 6.6Torr, and complete the single operation after 15 minutes of reaction. Vertical array growth of walled carbon nanotubes.
(3)通过电子束蒸发***在(2)所获得的单壁碳纳米管垂直阵列蒸镀4nm的硅。(3) Evaporate 4nm silicon on the vertical array of single-walled carbon nanotubes obtained in (2) by an electron beam evaporation system.
(4)在热丝CVD炉温950℃下，气体流量分别为H2:150sccm，CH4:0.75sccm，通过去离子水的H2为15sccm，总气压为27.5Torr，热丝为四根钽丝，功率为85W条件下，将(3)中制得含单壁碳纳米管垂直阵列和硅族元素的硅片置于钽丝正下方，反应3h后完成碳纳米复合材料的制备。(4) At a hot wire CVD furnace temperature of 950°C, the gas flow rates are H 2 : 150 sccm, CH 4 : 0.75 sccm, the H 2 passing through deionized water is 15 sccm, the total air pressure is 27.5 Torr, and the hot wire is four tantalum Wire, under the condition of power of 85W, place the silicon chip containing the vertical array of single-walled carbon nanotubes and silicon group elements prepared in (3) directly under the tantalum wire, and complete the preparation of carbon nanocomposite after reacting for 3 hours.
图4中a,b和c,d分别为碳纳米复合材料的TEM暗场像图和TEM明场像图。从图中可以看出石墨化金刚石包裹碳化硅纳米晶体尺寸均一，无团聚，结晶质量良好，碳化硅纳米晶体被石墨化金刚石包裹，石墨化金刚石外层包裹有1-2层石墨烯。碳化硅纳米晶体尺寸均一，无团聚，结晶质量良好，平均直径约为2.0nm；图4中e,f分别是碳纳米复合材料在0.5MH2SO4溶液中的极化曲线及其Tafel曲线。可以看出碳纳米复合材料具有较低的起始电势约为30mV。在电压为0.3V相对于标准氢电极时，电流密度为95.7mA cm-2，较低的Tafel斜率约为139mV dec-1。In Fig. 4, a, b and c, d are TEM dark-field images and TEM bright-field images of carbon nanocomposites, respectively. It can be seen from the figure that the graphitized diamond-wrapped silicon carbide nanocrystals have uniform size, no agglomeration, and good crystal quality. The silicon carbide nanocrystals are wrapped by graphitized diamond, and the outer layer of graphitized diamond is wrapped with 1-2 layers of graphene. The silicon carbide nanocrystals have uniform size, no agglomeration, good crystal quality, and an average diameter of about 2.0nm; e and f in Figure 4 are the polarization curve and Tafel curve of the carbon nanocomposite in 0.5MH 2 SO 4 solution, respectively. It can be seen that the carbon nanocomposite has a lower onset potential of about 30 mV. When the voltage is 0.3V relative to the standard hydrogen electrode, the current density is 95.7mA cm -2 , and the lower Tafel slope is about 139mV dec -1 .
实施例5：Example 5:
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗，N2吹干。通过电子束蒸发***依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone, and dried with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system.
(2)在热丝CVD炉温750℃下，气体流量分别为H2:200sccm，C2H2:2sccm，通过去离子水的H2为200sccm，总气压为25Torr，热丝为单根钨丝，功率为30W条件下，将(1)中制的硅片置于钽丝前方0.5cm，反应30s后将钽丝功率设置为0，总气压调节为6.4Torr，反应15min后完成单壁碳纳米管垂直阵列生长。(2) At a hot wire CVD furnace temperature of 750°C, the gas flow rates are H 2 : 200 sccm, C 2 H 2 : 2 sccm, the H 2 passing through deionized water is 200 sccm, the total pressure is 25 Torr, and the hot wire is a single tungsten Wire, under the condition of 30W power, place the silicon wafer made in (1) 0.5cm in front of the tantalum wire, set the power of the tantalum wire to 0 after 30s of reaction, adjust the total air pressure to 6.4Torr, and complete the single-walled carbon after 15 minutes of reaction. Nanotubes are grown in vertical arrays.
(3)通过电子束蒸发***在(2)所获得的单壁碳纳米管垂直阵列蒸镀4nm的硅。(3) Evaporate 4nm silicon on the vertical array of single-walled carbon nanotubes obtained in (2) by an electron beam evaporation system.
(4)在热丝CVD炉温1000℃下，气体流量分别为H2:175sccm，CH4:0.5sccm，通过去离子水的H2为20sccm，总气压为30Torr，热丝为四根钽丝，功率为80W条件下，将(3)中制得含单壁碳纳米管垂直阵列和硅族元素的硅片置于钽丝正下方，反应3h后完成碳纳米复合材料的制备。(4) At a hot wire CVD furnace temperature of 1000°C, the gas flow rates are H 2 : 175 sccm, CH 4 : 0.5 sccm, the H 2 passing through deionized water is 20 sccm, the total air pressure is 30 Torr, and the hot wire is four tantalum wires , under the condition of power of 80W, the silicon wafer containing the vertical array of single-walled carbon nanotubes and silicon group elements prepared in (3) was placed directly under the tantalum wire, and the carbon nanocomposite material was prepared after 3 hours of reaction.
图5中a为碳纳米复合材料的SEM形貌图，可以看出石墨烯纳米带保持垂直形态，石墨化金刚石包裹碳化硅位于石墨烯纳米带顶端。图5中b、c分别为碳纳米复合材料的TEM暗场像图和TEM明场像图。从图中可以看出碳化硅/石墨化金刚石纳米晶体尺寸均一，无团聚，结晶质量良好，碳化硅纳米晶体被石墨化金刚石包裹，石墨化金刚石外层包裹有2层石墨烯。石墨化金刚石纳米晶体尺寸较大，无团聚，结晶质量良好。而碳化硅纳米晶体平均直径约为2.0nm；图5中d,e分别是碳纳米复合材料在0.5M H2SO4溶液中的极化曲线及其Tafel曲线。可以看出碳纳米复合材料具有较低的起始电势，约为59mV。在电压为0.3V相对于标准氢电极时，电流密度为70.3mA cm-2，Tafel斜率约为124mV dec-1。Figure 5a is the SEM topography of the carbon nanocomposite material. It can be seen that the graphene nanoribbon maintains a vertical shape, and the graphene diamond-wrapped silicon carbide is located at the top of the graphene nanoribbon. b and c in Fig. 5 are the TEM dark-field image and TEM bright-field image of the carbon nanocomposite, respectively. It can be seen from the figure that the silicon carbide/graphitized diamond nanocrystals have uniform size, no agglomeration, and good crystallization quality. The silicon carbide nanocrystals are wrapped by graphitized diamond, and the outer layer of graphitized diamond is wrapped with two layers of graphene. The graphitized diamond nanocrystals have large size, no agglomeration, and good crystal quality. The average diameter of silicon carbide nanocrystals is about 2.0nm; d and e in Figure 5 are the polarization curve and Tafel curve of the carbon nanocomposite in 0.5MH 2 SO 4 solution, respectively. It can be seen that the carbon nanocomposite material has a lower onset potential of about 59mV. When the voltage is 0.3V relative to the standard hydrogen electrode, the current density is 70.3mA cm -2 , and the Tafel slope is about 124mV dec -1 .
实施例6：Embodiment 6:
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗，N2吹干。通过电子束蒸发***依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone, and dried with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system.
(2)在热丝CVD炉温750℃下，气体流量分别为H2:205sccm，C2H2:1.8sccm，通过去离子水的H2为210sccm，总气压为24.5Torr，热丝为单根钨丝，功率为30W条件下，将(1)中制的硅片置于钨丝前方0.5cm，反应30s后将钨丝功率设置为0，总气压调节为6.8Torr，反应15min后完成单壁碳纳米管垂直阵列生长。(2) At a hot wire CVD furnace temperature of 750°C, the gas flow rates are H 2 : 205 sccm, C 2 H 2 : 1.8 sccm, the H 2 passing through deionized water is 210 sccm, the total pressure is 24.5 Torr, and the hot wire is single A tungsten wire, under the condition of 30W power, place the silicon wafer made in (1) 0.5cm in front of the tungsten wire, set the power of the tungsten wire to 0 after 30s of reaction, adjust the total air pressure to 6.8Torr, and complete the single Vertical array growth of walled carbon nanotubes.
(3)通过电子束蒸发***在(2)所获得的单壁碳纳米管垂直阵列蒸镀3nm的硅。(3) Evaporate 3nm silicon on the vertical array of single-walled carbon nanotubes obtained in (2) by an electron beam evaporation system.
(4)在热丝CVD炉温1050℃下，气体流量分别为H2:150sccm，CH4:0.5sccm，通过去离子水的H2为25sccm，总气压为30Torr，热丝为四根钨丝，功率为85W条件下，将(3)中制得含单壁碳纳米管垂直阵列和硅族元素的硅片置于钨丝正下方，反应4h后完成碳纳米复合材料的制备。(4) At a hot wire CVD furnace temperature of 1050°C, the gas flow rates are H 2 : 150 sccm, CH 4 : 0.5 sccm, the H 2 passing through deionized water is 25 sccm, the total pressure is 30 Torr, and the hot wire is four tungsten wires , under the condition of a power of 85W, the silicon wafer containing vertical arrays of single-walled carbon nanotubes and silicon group elements prepared in (3) was placed directly under the tungsten wire, and the carbon nanocomposite material was prepared after 4 hours of reaction.
图6中a为碳纳米复合材料的SEM形貌图，可以看出石墨烯纳米带保持垂直形态，石墨化金刚石包裹碳化硅位于石墨烯纳米带顶端。图6中b、c分别为碳纳米复合材料的TEM暗场像图和TEM明场像图。从图中可以看出碳化硅纳米晶体尺寸均一，平均尺寸约为2nm，无团聚，结晶质量良好，碳化硅纳米晶体被石墨化金刚石包裹。石墨化金刚石晶粒尺寸约为10nm，石墨化金刚石外层包裹有2-3层石墨烯。图6中d、e分别是碳纳米复合材料在0.5MH2SO4溶液中的极化曲线及其Tafel曲线。可以看出碳纳米复合材料具有较低的起始电势，约为78mV。在电压为0.3V相对于标准氢电极时，电流密度为26.0mA cm-2，较低的Tafel斜率约为162mV dec-1。Figure 6a is the SEM topography of the carbon nanocomposite material. It can be seen that the graphene nanoribbon maintains a vertical shape, and the graphene diamond-wrapped silicon carbide is located at the top of the graphene nanoribbon. b and c in Fig. 6 are the TEM dark-field image and TEM bright-field image of the carbon nanocomposite, respectively. It can be seen from the figure that the silicon carbide nanocrystals are uniform in size, the average size is about 2nm, there is no agglomeration, the crystal quality is good, and the silicon carbide nanocrystals are wrapped by graphitized diamond. The grain size of graphitized diamond is about 10nm, and the outer layer of graphitized diamond is wrapped with 2-3 layers of graphene. In Figure 6, d and e are the polarization curve and Tafel curve of the carbon nanocomposite in 0.5M H 2 SO 4 solution, respectively. It can be seen that the carbon nanocomposite material has a lower onset potential of about 78mV. When the voltage is 0.3V relative to the standard hydrogen electrode, the current density is 26.0mA cm -2 , and the lower Tafel slope is about 162mV dec -1 .
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