CN104611697B - Single-walled carbon nanotube vertical array-tungsten carbide nanocrystal composite material, preparation and application in electrocatalytic hydrogen evolution - Google Patents
Single-walled carbon nanotube vertical array-tungsten carbide nanocrystal composite material, preparation and application in electrocatalytic hydrogen evolution Download PDFInfo
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Abstract
一种单壁碳纳米管垂直阵列‑碳化钨纳米晶体复合材料、制备及其在电催化析氢中的应用，属于碳纳米材料技术领域。硅片上垂直生长的单壁碳纳米管阵列，垂直单壁碳纳米管阵列的顶端为碳化钨纳米晶体。先在硅片上垂直生长的单壁碳纳米管阵列，然后在单壁碳纳米管阵列蒸镀W，再生成碳化钨纳米即可。在酸碱性条件下均具有电催化析氢作用且性能稳定。
A single-walled carbon nanotube vertical array-tungsten carbide nanocrystal composite material, its preparation and its application in electrocatalytic hydrogen evolution belong to the technical field of carbon nanomaterials. A single-wall carbon nanotube array vertically grown on a silicon wafer, and the top of the vertical single-wall carbon nanotube array is a tungsten carbide nanocrystal. The single-walled carbon nanotube array is vertically grown on the silicon wafer first, and then W is evaporated on the single-walled carbon nanotube array to form tungsten carbide nanometer. It has electrocatalytic hydrogen evolution function and stable performance under both acid and alkaline conditions.
Description
技术领域technical field
本发明属于碳纳米材料技术领域，具体涉及一种制备碳纳米管垂直阵列-碳化钨复合材料的方法。The invention belongs to the technical field of carbon nanomaterials, and in particular relates to a method for preparing a carbon nanotube vertical array-tungsten carbide composite material.
背景技术Background technique
氢元素是宇宙最清洁的理想燃料。电解水是一种有效制备清洁氢能源的方法，避免了采用化石燃料，没有温室气体CO2直接排放。目前，最常用的析氢电极依然是Pt、Pd等铀系贵金属。铂系元素属于低过电位金属，对电解水析氢反应具有较高的催化活性，较好的电解稳定性，不易被氧化，但由于其价格昂贵且在地球上的储量较少，这些不利因素限制了其在工业上的生产应用。因此，寻求廉价的、低析氢过电位、高电化学稳定性以及催化活性的电极材料就显得非常重要。Hydrogen is the cleanest ideal fuel in the universe. Water electrolysis is an efficient way to produce clean hydrogen energy, avoiding the use of fossil fuels, and no direct emission of greenhouse gas CO2 . At present, the most commonly used hydrogen evolution electrodes are still uranium-series noble metals such as Pt and Pd. Platinum group elements belong to low overpotential metals, which have high catalytic activity for electrolytic water hydrogen evolution reaction, good electrolytic stability, and are not easy to be oxidized. However, due to their high price and low reserves on the earth, these unfavorable factors limit its production application in industry. Therefore, it is very important to seek cheap, low hydrogen evolution overpotential, high electrochemical stability and catalytic activity electrode materials.
碳化钨(WC)是一种具有独特物理和化学特性的材料。一方面，碳化钨具有高硬度、高耐磨性、高熔点、耐腐蚀等特点而广泛应用于切削工具、耐磨工具、精密磨具和钻头。另一方面，碳化钨具有类似Pt的催化活性，物理和化学性稳定，且价格便宜，作为催化剂在一些领域表现出独特的催化活性。随着人们对清洁能源的重视，碳化钨在催化领域，例如直接甲醇燃料电池、锂电池、催化析氢、超大电容器以及催化加氢脱氯等方面的应用引起科学家的广泛关注。在电化学领域，碳化钨作为阳极催化剂的优势在于它不仅具有催化性能可以取代Pt、Pd、Ru等贵金属，而且不易被CO毒化。因此，碳化钨催化剂可以部分或者一定程度上节省Pt、Pd、Ru等贵重金属，具有广阔的应用前景。Tungsten carbide (WC) is a material with unique physical and chemical properties. On the one hand, tungsten carbide has the characteristics of high hardness, high wear resistance, high melting point, and corrosion resistance, so it is widely used in cutting tools, wear-resistant tools, precision abrasive tools and drill bits. On the other hand, tungsten carbide has a catalytic activity similar to that of Pt, is physically and chemically stable, and is cheap. As a catalyst, it shows unique catalytic activity in some fields. With people's emphasis on clean energy, the application of tungsten carbide in the field of catalysis, such as direct methanol fuel cells, lithium batteries, catalytic hydrogen evolution, ultra-large capacitors, and catalytic hydrodechlorination, has attracted widespread attention from scientists. In the field of electrochemistry, the advantage of tungsten carbide as an anode catalyst is that it not only has catalytic performance and can replace noble metals such as Pt, Pd, and Ru, but is also not easily poisoned by CO. Therefore, tungsten carbide catalysts can partially or to a certain extent save precious metals such as Pt, Pd, Ru, etc., and have broad application prospects.
碳化钨的传统制备工艺秉承冶金工业，通过钨粉与碳粉在1500℃以上的高温反应而得。但这种方法制的碳化钨产物团聚严重、比表面积、纯度低，只能满足冶金工业需求，而不能有效的发挥其催化作用。为了适应碳化钨在催化和吸附方面的应用，科研人员开发了一些制备高比表面积碳化钨的方法。例如：气相反应物和固相金属化合物的反应，挥发性金属化合物的气相反应和气相沉积法等。通常，采用高比表面积载体和碳化钨复合对于提高碳化钨的催化活性和稳定性起到重要作用，这主要由于载体的高比表面积有利于碳化钨的高度分散。如此同时，碳纳米管具有良好的导电性、高的比表面积(单根碳纳米管具有超大的比表面积，其理论值高达)，同是具有良好的吸附能力，这些特点都为垂直碳纳米管阵列作为催化载体提供了明显的优势。因此，如何采用简单易行的方法制备出比表面积高，碳化钨颗粒小且分散均匀的碳化钨-垂直碳纳米管复合材料，对于碳化钨催化剂的开发和应用具有重要的科学意义。The traditional preparation process of tungsten carbide adheres to the metallurgical industry, and is obtained through the high temperature reaction of tungsten powder and carbon powder at a temperature above 1500 °C. However, the tungsten carbide produced by this method has serious agglomeration, low specific surface area and low purity, which can only meet the needs of the metallurgical industry, but cannot effectively play its catalytic role. In order to adapt to the application of tungsten carbide in catalysis and adsorption, researchers have developed some methods for preparing tungsten carbide with high specific surface area. For example: the reaction of gas-phase reactants and solid-phase metal compounds, the gas-phase reaction and vapor-phase deposition of volatile metal compounds, etc. Generally, the combination of high specific surface area carrier and tungsten carbide plays an important role in improving the catalytic activity and stability of tungsten carbide, mainly because the high specific surface area of the carrier is conducive to the high dispersion of tungsten carbide. At the same time, carbon nanotubes have good electrical conductivity, high specific surface area (a single carbon nanotube has a super large specific surface area, and its theoretical value is as high as), and also have good adsorption capacity. These characteristics are vertical carbon nanotubes. Arrays offer distinct advantages as catalytic supports. Therefore, how to prepare tungsten carbide-vertical carbon nanotube composites with high specific surface area, small tungsten carbide particles and uniform dispersion by a simple and feasible method has important scientific significance for the development and application of tungsten carbide catalysts.
发明内容Contents of the invention
本发明的目的在于提供一种用热丝CVD(hot filament chemical vapordeposition)的、操作简单、制备周期短、可大面积制备、高质量、可重复操作的碳纳米管垂直阵列-碳化钨复合材料制备工艺。该工艺制得碳化钨纳米晶体，尺寸较小，分布均匀，结晶质量高，无位错等晶格缺陷。垂直碳纳米管阵列-碳化钨纳米晶体复合材料具有电催化析氢活性高、过电势低，电流密度大、Tafel斜率小，在酸碱性条件下稳定等优点。The purpose of the present invention is to provide a carbon nanotube vertical array-tungsten carbide composite material prepared by hot filament CVD (hot filament chemical vapordeposition), simple operation, short preparation period, large-area preparation, high quality, and repeatable operation craft. This process produces tungsten carbide nanocrystals with small size, uniform distribution, high crystal quality, and no lattice defects such as dislocations. The vertical carbon nanotube array-tungsten carbide nanocrystal composite material has the advantages of high electrocatalytic hydrogen evolution activity, low overpotential, high current density, small Tafel slope, and stability under acidic and alkaline conditions.
其中碳纳米管垂直阵列-碳化钨复合材料：底层为硅片，硅片上为垂直生长的单壁碳纳米管阵列，垂直单壁碳纳米管阵列的顶端为碳化钨纳米晶体。碳化钨是指WC。Among them, the carbon nanotube vertical array-tungsten carbide composite material: the bottom layer is a silicon wafer, the silicon wafer is a vertically grown single-wall carbon nanotube array, and the top of the vertical single-wall carbon nanotube array is a tungsten carbide nanocrystal. Tungsten carbide refers to WC.
本发明上述的碳纳米管垂直阵列-碳化钨复合材料是通过一下方案实现的，包括以下步骤：The above-mentioned carbon nanotube vertical array-tungsten carbide composite material of the present invention is realized through the following scheme, including the following steps:
((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 Evaporator)依次在硅片表面蒸镀8-12nm厚度的Al2O3和0.7-1.2nm厚度Fe；(1) Ultrasonic cleaning of silicon wafers by methanol, acetone and isopropyl ketone respectively, drying with N 2 , and sequentially vapor-depositing Al 2 O 3 with a thickness of 8-12 nm on the surface of silicon wafers by E-Beam Evaporator And 0.7-1.2nm thickness Fe;
(2)单壁碳纳米管阵列垂直生长：设置炉温为700-800℃，总气体流量为：H2:200±10sccm、C2H2:2±0.5sccm和通过去离子水的H2为200±10sccm，总气压为25±1Torr，热丝为单根钨丝，功率为30-35W；将步骤(1)中制得的镀层的硅片置于钨丝前方0.3-0.5cm(优选0.5cm)，钨丝与硅片平行，使得气流经过热钨丝与硅片上的镀层反应，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) Vertical growth of single-walled carbon nanotube arrays: set the furnace temperature to 700-800°C, and the total gas flow is: H 2 : 200±10sccm, C 2 H 2 : 2±0.5sccm and H 2 passing through deionized water It is 200 ± 10sccm, the total air pressure is 25 ± 1Torr, and the hot wire is a single tungsten wire, and the power is 30-35W; the silicon chip of the coating made in the step (1) is placed in front of the tungsten wire 0.3-0.5cm (preferably 0.5cm), the tungsten wire is parallel to the silicon wafer, so that the air flow passes through the hot tungsten wire and the coating on the silicon wafer reacts. After 30 seconds of reaction, the power of the tungsten wire is set to 0, and the total air pressure is adjusted to 6.4Torr. After 15 minutes of reaction, the single-wall carbon Nanotube vertical array growth;
(3)通过溅射沉积(Sputter Deposition)在步骤(2)所获得的单壁垂直碳纳米管阵列上端蒸镀50-150nm厚度的W层。(3) Evaporating a W layer with a thickness of 50-150 nm on the upper end of the single-wall vertical carbon nanotube array obtained in step (2) by sputter deposition (Sputter Deposition).
(4)在950-1080℃下，总气体流量包括H2:200±10sccm、CH4:0.5sccm、通过去离子水的H2为200±10sccm，气压为25±1Torr，热丝为四根钨丝，总功率为75-80W条件下，将步骤(3)中制得含顶层为W的碳纳米管垂直阵列平行置于钨丝正下方，反应3-6h后完成碳纳米管垂直阵列-碳化钨复合材料的制备。(4) At 950-1080°C, the total gas flow rate includes H 2 : 200±10sccm, CH 4 : 0.5sccm, H 2 passing through deionized water is 200±10sccm, the air pressure is 25±1Torr, and the heating wire is four Tungsten wire, under the condition of a total power of 75-80W, place the vertical array of carbon nanotubes with a top layer of W prepared in step (3) in parallel directly under the tungsten wire, and complete the vertical array of carbon nanotubes after 3-6h of reaction- Preparation of tungsten carbide composites.
本发明所使用的CVD炉为热丝-CVD炉，所用热丝为钨丝。钨丝直径0.2-0.3mm，长度为8-12mm，可更改为一根，或四根。更改为四根时，四根钨丝水平、平行一排分开放置。上述步骤(3)的W的厚度没有具体限制，但优选为50-150nm。The CVD furnace used in the present invention is a hot wire-CVD furnace, and the used hot wire is a tungsten wire. The diameter of the tungsten wire is 0.2-0.3mm, and the length is 8-12mm, which can be changed to one or four. When changing to four, the four tungsten wires are placed horizontally and in parallel in a row. The thickness of W in the above step (3) is not particularly limited, but is preferably 50-150 nm.
本发明所得碳纳米管垂直阵列-碳化钨复合材料将碳纳米管垂直阵列-碳化钨从硅片中分离开(如刮下)后再电催化析氢中的应用。The carbon nanotube vertical array-tungsten carbide composite material obtained in the present invention is used in electrocatalyzing hydrogen evolution after the carbon nanotube vertical array-tungsten carbide is separated (for example, scraped off) from a silicon wafer.
与现有工艺相比，本发明工艺的明显优点：Compared with existing technology, the obvious advantage of the technology of the present invention:
(1)本工艺制备的WC纳米晶体直径为15-30nm，尺寸均一，无团聚，晶化程度高，缺陷较少，无杂质。(1) The WC nanocrystals prepared by this process have a diameter of 15-30nm, uniform size, no agglomeration, high degree of crystallization, less defects, and no impurities.
(2)本工艺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***、溅射沉积、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WC纳米晶体制备，工艺简化。本工艺相对于现有工艺，具有样品均匀，制备周期短，制备效率高的优点。(2) The raw material of gas in this process is common experimental gas, and the gas requirements are loose, which greatly reduces the preparation cost. The required instruments are simple, only electron beam evaporation system, sputtering deposition, and CVD furnace are needed. The preparation of WC nanocrystals can be completed only in low pressure and reducing atmosphere without special atmosphere and pressure environment, and the process is simplified. Compared with the existing technology, the process has the advantages of uniform sample, short preparation cycle and high preparation efficiency.
(3)应用本工艺所制备的碳纳米管垂直阵列-碳化钨复合材料操作简单，只需在制备垂直碳纳米管阵列和制备WC纳米晶体前调节好气体流量、气压。WC纳米晶体制备过程中不调节任何参数。(3) The carbon nanotube vertical array-tungsten carbide composite material prepared by this process is easy to operate, only need to adjust the gas flow and air pressure before preparing the vertical carbon nanotube array and WC nanocrystal. No parameters were adjusted during the preparation of WC nanocrystals.
(4)本工艺相对于现有工艺，只需将含W的垂直单壁碳纳米管阵列经过950-1080℃一次处理，制备时间短，温度相对较低低，大大降低能耗。(4) Compared with the existing process, this process only needs to process the W-containing vertical single-walled carbon nanotube array once at 950-1080°C. The preparation time is short, the temperature is relatively low, and the energy consumption is greatly reduced.
(5)本工艺制备垂直碳纳米管阵列-碳化钨纳米晶体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，在酸碱性条件下均具有电催化析氢作用且性能稳定。(5) The vertical carbon nanotube array-tungsten carbide nanocrystal composite material prepared by this process has high electrocatalytic hydrogen evolution activity, low onset potential, high current density, and small Tafel slope. Electrocatalytic hydrogen evolution and stable performance.
附图说明Description of drawings
图1a,b是实施例1单壁碳纳米管垂直阵列-碳化钨纳米晶体复合材料TEM图；Fig. 1a, b are the TEM pictures of embodiment 1 single-walled carbon nanotube vertical array-tungsten carbide nanocrystal composite material;
图1c是实施例1制备单壁碳纳米管垂直阵列-碳化钨纳米晶体复合材料XRD图；Fig. 1c is the XRD pattern of the single-walled carbon nanotube vertical array-tungsten carbide nanocrystal composite material prepared in Example 1;
图2a,b是实施例2制备垂直单壁碳纳米管垂直阵列-碳化钨纳米晶体复合材料SEM图；Fig. 2a, b are the SEM pictures of the vertical single-walled carbon nanotube vertical array-tungsten carbide nanocrystal composite material prepared in embodiment 2;
图2c-e是实施例2制备垂直单壁碳纳米管垂直阵列-碳化钨纳米晶体复合材料TEM图Figure 2c-e is the TEM image of the vertical single-walled carbon nanotube vertical array-tungsten carbide nanocrystal composite material prepared in Example 2
图2f,g分别为实施例2提供的催化剂在0.5M/L H2SO4溶液(PH＝1)中的极化曲线及其Tafel曲线，扫描速率为5mV/s；Figure 2f and g are the polarization curve and Tafel curve of the catalyst provided in Example 2 in 0.5M/ LH2SO4 solution (PH=1), respectively, and the scan rate is 5mV/s;
图2h,i分别为实施例2提供的催化剂在0.1M/L KOH溶液(PH＝13)中的极化曲线及其Tafel曲线，扫描速率为5mV/s；Figure 2h, i are the polarization curve and Tafel curve of the catalyst provided in Example 2 in 0.1M/L KOH solution (PH=13), respectively, and the scan rate is 5mV/s;
图2j,k分别为实施例2提供的催化剂在0.5M/L H2SO4溶液(PH＝1)和0.1M/L KOH溶液(PH＝13)中稳定性测试；Fig. 2j, k are respectively the stability test of the catalyst provided in Example 2 in 0.5M/LH 2 SO 4 solution (PH=1) and 0.1M/L KOH solution (PH=13);
图3a是实施例3制备垂直单壁碳纳米管垂直阵列-碳化钨纳米晶体复合材料Raman图；Fig. 3 a is that embodiment 3 prepares the Raman figure of vertical single-walled carbon nanotube vertical array-tungsten carbide nanocrystal composite material;
图3b,c分别是实施例3提供的负载催化剂在0.5M/L H2SO4溶液(PH＝1)中的极化曲线及其Tafel曲线，扫描速率为5mV/s；Figure 3b and c are the polarization curve and Tafel curve of the supported catalyst provided in Example 3 in 0.5M/ LH2SO4 solution (PH=1), respectively, and the scan rate is 5mV/s;
图3d,e分别为实施例3提供的负载催化剂在0.1M/L KOH溶液(PH＝13)中的极化曲线及其Tafel曲线，扫描速率为5mV/s；Figure 3d and e are the polarization curve and Tafel curve of the supported catalyst provided in Example 3 in 0.1M/L KOH solution (PH=13), respectively, and the scan rate is 5mV/s;
图4a是实施例4制备垂直单壁碳纳米管垂直阵列-碳化钨纳米晶体复合材料Raman图；Fig. 4 a is the Raman graph of embodiment 4 preparing vertical single-walled carbon nanotube vertical array-tungsten carbide nanocrystal composite material;
图4b,c分别是实施例4提供的负载催化剂在0.5M/L H2SO4溶液(PH＝1)中的极化曲线及其Tafel曲线，扫描速率为5mV/s；Figure 4b and c are the polarization curve and Tafel curve of the supported catalyst provided in Example 4 in 0.5M/ LH2SO4 solution (PH=1), respectively, and the scan rate is 5mV/s;
图4d分别为实施例4提供的负载催化剂在0.1M/L KOH溶液(PH＝13)中的极化曲线，扫描速率为5mV/s；Figure 4d is the polarization curve of the supported catalyst provided in Example 4 in 0.1M/L KOH solution (PH=13), and the scan rate is 5mV/s;
图5a是实施例5制备垂直单壁碳纳米管垂直阵列-碳化钨纳米晶体复合材料Raman图；Fig. 5 a is the Raman diagram of the vertical single-walled carbon nanotube vertical array-tungsten carbide nanocrystal composite material prepared in embodiment 5;
图5b,c分别是实施例5提供的负载催化剂在0.5M/L H2SO4溶液(PH＝1)中的极化曲线及其Tafel曲线，扫描速率为5mV/s；Figure 5b and c are the polarization curve and Tafel curve of the supported catalyst provided in Example 5 in 0.5M/ LH2SO4 solution (PH=1), respectively, and the scan rate is 5mV/s;
图5d,e分别为实施例5提供的负载催化剂在0.1M/L KOH溶液(PH＝13)中的极化曲线及其Tafel曲线，扫描速率为5mV/s。Figure 5d and e are the polarization curve and Tafel curve of the supported catalyst provided in Example 5 in 0.1M/L KOH solution (PH=13), 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：本发明所使用的CVD炉为热丝-CVD炉。Embodiment 1: The CVD furnace used in the present invention is a hot wire-CVD furnace.
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗15分钟，N2吹干。通过电子束蒸发***(E-Beam Evaporation)依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone for 15 minutes, and then blown dry with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system (E-Beam Evaporation).
(2)在炉温720℃下，气体流量分别为H2:200sccm，C2H2:2.2sccm，通过去离子水的H2为200sccm，总气压为25.5Torr，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0.3cm，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 furnace temperature of 720°C, the gas flow rates are H 2 : 200 sccm, C 2 H 2 : 2.2 sccm, the H 2 passing through deionized water is 200 sccm, the total air pressure is 25.5 Torr, and the heating wire is a single tungsten wire , under the condition of 30W power, place the silicon wafer made in (1) 0.3cm 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 single-walled carbon nanometer after 15 minutes of reaction. Tubes are grown in vertical arrays.
(3)通过蒸发溅射(Sputter Deposition)在(2)所获得的单壁垂直碳纳米管蒸镀50nm W。(3) 50 nm W was deposited on the single-walled vertical carbon nanotubes obtained in (2) by sputtering (Sputter Deposition).
(4)在950℃下，气体流量分别为H2:200sccm，CH4:0.5sccm，通过去离子水的H2为210sccm，总气压为25.5Torr，热丝为四根钨丝，总功率为75W条件下，将(3)中制得含碳纳米管垂直阵列和W的硅片置于钨丝正下方，反应6h后完成碳纳米管垂直阵列-碳化钨复合材料的制备。(4) At 950°C, the gas flow rates are H 2 : 200 sccm, CH 4 : 0.5 sccm, the H 2 passing through deionized water is 210 sccm, the total pressure is 25.5 Torr, the heating wires are four tungsten wires, and the total power is Under the condition of 75W, place the silicon wafer containing the vertical array of carbon nanotubes and W obtained in (3) directly under the tungsten wire, and complete the preparation of the vertical array of carbon nanotubes-tungsten carbide composite material after 6 hours of reaction.
从图1：TEM形貌图可以看出，所制得WC纳米颗粒尺寸较小，结晶质量良好。XRD图谱表明，所制备碳纳米管垂直阵列-碳化钨复合材料除了碳纳米管和WC纳米晶体外不含其它杂相。From Figure 1: TEM topography, it can be seen that the prepared WC nanoparticles have a small size and good crystal quality. The XRD pattern shows that the prepared carbon nanotube vertical array-tungsten carbide composite material does not contain other impurity phases except carbon nanotubes and WC nanocrystals.
实施例2：本发明所使用的CVD炉为热丝-CVD炉。Embodiment 2: The CVD furnace used in the present invention is a hot wire-CVD furnace.
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗15分钟，N2吹干。通过电子束蒸发***(E-Beam Evaporation)依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone for 15 minutes, and then blown dry with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system (E-Beam Evaporation).
(2)在炉温750℃下，气体流量分别为H2:200sccm，C2H2:2.2sccm，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 furnace temperature of 750°C, the gas flow rates are H 2 : 200 sccm, C 2 H 2 : 2.2 sccm, the H 2 passing through deionized water is 200 sccm, the total air pressure is 25 Torr, and the heating wire is a single tungsten wire. With a power of 30W, 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 6.4Torr, and complete the single-walled carbon nanotube after 15 minutes of reaction Vertical array growth.
(3)通过蒸发溅射(Sputter Deposition)在(2)所获得的单壁垂直碳纳米管蒸镀100nm W。(4)在1050℃下，气体流量分别为H2:200sccm，CH4:0.5sccm，通过去离子水的H2为200sccm，总气压为25Torr，热丝为四根钨丝，总功率为78W条件下，将(3)中制得含碳纳米管垂直阵列和W的硅片置于钨丝正下方，反应6h后完成碳纳米管垂直阵列-碳化钨复合材料的制备。(3) 100 nm W was evaporated on the single-walled vertical carbon nanotubes obtained in (2) by sputtering (Sputter Deposition). (4) At 1050°C, the gas flow rate is H 2 : 200 sccm, CH 4 : 0.5 sccm, the H 2 passing through deionized water is 200 sccm, the total pressure is 25 Torr, the heating wire is four tungsten wires, and the total power is 78W Under the conditions, place the silicon wafer containing the vertical array of carbon nanotubes and W prepared in (3) directly under the tungsten wire, and complete the preparation of the vertical array of carbon nanotubes-tungsten carbide composite material after 6 hours of reaction.
图2a,b为SEM形貌图，可以看出碳纳米管垂直阵列-碳化钨复合材料中碳纳米管保持垂直形态，WC纳米颗粒位于碳纳米管垂直阵列顶端；图2c,e为TEM形貌图，可以看出，WC纳米晶体颗粒较小，分布均匀，直径约为25nm。由高分辨TEM形貌图(图2c)可以看出，WC纳米晶体不含位错等晶格缺陷；图2f,g分别是实施例2提供的催化剂在0.5M/L H2SO4溶液(PH＝1)中的极化曲线及其Tafel曲线，可以看出电流密度大，起始电势(onset potential)低，Tafel斜率为72mV dec-1，催化剂在酸性条件下表现出良好的析氢催化活性；图2h,i分别为实施例2提供的催化剂在0.1M/L KOH溶液(PH＝13)中的极化曲线及其Tafel曲线，可以看出电流密度大，起始电势(onset potential)低，Tafel斜率为106mV dec-1，催化剂在碱性条件下表现出良好的析氢催化活性。图2j,k分别为实施例2提供的催化剂在0.5M/L H2SO4溶液(PH＝1)和0.1M/L KOH溶液(PH＝13)中的稳定性测试，可以看出经过30000s的循环，催化剂依然在酸碱条件下保持良好的稳定性。Figure 2a and b are SEM images, it can be seen that the carbon nanotubes in the carbon nanotube vertical array-tungsten carbide composite maintain a vertical shape, and the WC nanoparticles are located at the top of the vertical array of carbon nanotubes; Figure 2c, e are the TEM images From the figure, it can be seen that the WC nanocrystal particles are small and evenly distributed, with a diameter of about 25 nm. It can be seen from the high - resolution TEM topography (Figure 2c) that WC nanocrystals do not contain lattice defects such as dislocations ; =1) Polarization curve and its Tafel curve, it can be seen that the current density is high, the onset potential (onset potential) is low, the Tafel slope is 72mV dec -1 , and the catalyst shows good hydrogen evolution catalytic activity under acidic conditions; Figure 2h and i are the polarization curve and Tafel curve of the catalyst provided in Example 2 in 0.1M/L KOH solution (PH=13) respectively, it can be seen that the current density is large and the onset potential (onset potential) is low, The Tafel slope is 106mV dec -1 , and the catalyst shows good hydrogen evolution catalytic activity under alkaline conditions. Figure 2j, k are respectively the stability test of the catalyst provided in Example 2 in 0.5M/LH 2 SO 4 solution (PH=1) and 0.1M/L KOH solution (PH=13), it can be seen that after 30000s Cycle, the catalyst still maintains good stability under acid-base conditions.
实施例3：本发明所使用的CVD炉为热丝-CVD炉。Embodiment 3: The CVD furnace used in the present invention is a hot wire-CVD furnace.
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗15分钟，N2吹干。通过电子束蒸发***(E-Beam Evaporation)依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone for 15 minutes, and then blown dry with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system (E-Beam Evaporation).
(2)在炉温780℃下，气体流量分别为H2:210sccm，C2H2:2.5sccm，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 furnace temperature of 780°C, the gas flow rates are H 2 : 210 sccm, C 2 H 2 : 2.5 sccm, the H 2 passing through deionized water is 200 sccm, the total air pressure is 25 Torr, and the heating wire is a single tungsten wire. With a power of 30W, 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 6.4Torr, and complete the single-walled carbon nanotube after 15 minutes of reaction Vertical array growth.
(3)通过蒸发溅射(Sputter Deposition)在(2)所获得的单壁垂直碳纳米管蒸镀100nm W。(3) 100 nm W was evaporated on the single-walled vertical carbon nanotubes obtained in (2) by sputtering (Sputter Deposition).
(4)在1080℃下，气体流量分别为H2:190sccm，CH4:0.5sccm，通过去离子水的H2为200sccm，总气压为25.8Torr，热丝为四根钨丝，总功率为80W条件下，将(3)中制得含碳纳米管垂直阵列和W的硅片置于钨丝正下方，反应6h后完成碳纳米管垂直阵列-碳化钨复合材料的制备。(4) At 1080°C, the gas flow rates are H 2 : 190 sccm, CH 4 : 0.5 sccm, the H 2 passing through deionized water is 200 sccm, the total air pressure is 25.8 Torr, the heating wires are four tungsten wires, and the total power is Under the condition of 80W, place the silicon wafer containing the vertical array of carbon nanotubes and W obtained in (3) directly under the tungsten wire, and complete the preparation of the vertical array of carbon nanotubes-tungsten carbide composite material after 6 hours of reaction.
图3a为Raman光谱，可以看出制备的碳纳米管垂直阵列-碳化钨复合材料缺陷较低，不含氧化物，即步骤(3)中蒸镀的W，已完全转化为WC。图3b,c分别是实施例3提供的催化剂在0.5M/L H2SO4溶液(PH＝1)中的极化曲线及其Tafel曲线，可以看出电流密度大，起始电势(onset potential)低，Tafel斜率为85mV dec-1，催化剂在酸性条件下表现出良好的析氢催化活性；图3d,e分别为实施例3提供的催化剂在0.1M/L KOH溶液(PH＝13)中的极化曲线及其Tafel曲线，可以看出电流密度大，起始电势(onset potential)低，Tafel斜率为121mVdec-1，催化剂在碱性条件下表现出良好的析氢催化活性。Figure 3a is the Raman spectrum. It can be seen that the prepared carbon nanotube vertical array-tungsten carbide composite material has low defects and does not contain oxides, that is, the W evaporated in step (3) has been completely converted into WC. Figure 3b and c are the polarization curve and Tafel curve of the catalyst provided in Example 3 in 0.5M/LH 2 SO 4 solution (PH=1), respectively. It can be seen that the current density is large, and the onset potential (onset potential) low, the Tafel slope is 85mV dec -1 , and the catalyst exhibits good catalytic activity for hydrogen evolution under acidic conditions; Fig. From the chemical reaction curve and its Tafel curve, it can be seen that the current density is high, the onset potential is low, and the Tafel slope is 121mVdec -1 . The catalyst exhibits good catalytic activity for hydrogen evolution under alkaline conditions.
实施例4：本发明所使用的CVD炉为热丝-CVD炉。Embodiment 4: The CVD furnace used in the present invention is a hot wire-CVD furnace.
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗15分钟，N2吹干。通过电子束蒸发***(E-Beam Evaporation)依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone for 15 minutes, and then blown dry with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system (E-Beam Evaporation).
(2)在炉温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0.5cm，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 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 air pressure is 25 Torr, and the heating wire is a single tungsten wire. With a power of 30W, 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 6.4Torr, and complete the single-walled carbon nanotube after 15 minutes of reaction Vertical array growth.
(3)通过蒸发溅射(Sputter Deposition)在(2)所获得的单壁垂直碳纳米管蒸镀75nm W。(3) 75nm W was evaporated on the single-walled vertical carbon nanotubes obtained in (2) by sputtering (Sputter Deposition).
(4)在1050℃下，气体流量分别为H2:200sccm，CH4:0.5sccm，通过去离子水的H2为200sccm，总气压为25Torr，热丝为四根钨丝，总功率为78W条件下，将(3)中制得含垂直碳纳米管阵列和W的硅片置于钨丝正下方，反应6h后完成碳纳米管垂直阵列-碳化钨复合材料的制备。(4) At 1050°C, the gas flow rate is H 2 : 200 sccm, CH 4 : 0.5 sccm, the H 2 passing through deionized water is 200 sccm, the total pressure is 25 Torr, the heating wire is four tungsten wires, and the total power is 78W Under the conditions, place the silicon wafer containing vertical carbon nanotube arrays and W prepared in (3) directly under the tungsten wire, and complete the preparation of the carbon nanotube vertical array-tungsten carbide composite material after 6 hours of reaction.
图4a为Raman光谱，可以看出制备的碳纳米管垂直阵列-碳化钨复合材料缺陷较低，不含氧化物，即步骤(3)中蒸镀的W，已完全转化为WC。图4b,c分别是实施例4提供的催化剂在0.5M/L H2SO4溶液(PH＝1)中的极化曲线及其Tafel曲线，可以看出电流密度大，起始电势(onset potential)低，Tafel斜率为85mV dec-1，催化剂在酸性条件下表现出良好的析氢催化活性。图4d为实施例4提供的催化剂在0.1M/L KOH溶液(PH＝13)中的极化曲线，可以看出电流密度大，起始电势(onset potential)低，催化剂在碱性条件下表现出良好的析氢催化活性。Figure 4a is the Raman spectrum. It can be seen that the prepared carbon nanotube vertical array-tungsten carbide composite material has low defects and does not contain oxides, that is, the W evaporated in step (3) has been completely converted into WC. Figure 4b and c are the polarization curve and Tafel curve of the catalyst provided in Example 4 in 0.5M/LH 2 SO 4 solution (PH=1), respectively. It can be seen that the current density is large and the onset potential (onset potential) Low, the Tafel slope is 85mV dec -1 , and the catalyst shows good hydrogen evolution catalytic activity under acidic conditions. Figure 4d is the polarization curve of the catalyst provided in Example 4 in 0.1M/L KOH solution (PH=13), it can be seen that the current density is large, the onset potential (onset potential) is low, and the catalyst behaves under alkaline conditions good catalytic activity for hydrogen evolution.
实施例5：本发明所使用的CVD炉为热丝-CVD炉。Embodiment 5: The CVD furnace used in the present invention is a hot wire-CVD furnace.
(1)将硅片分别经过甲醇、丙酮和异丙酮超声清洗15分钟，N2吹干。通过电子束蒸发***(E-Beam Evaporation)依次蒸镀10nm Al2O3，0.8nm Fe。(1) Silicon wafers were ultrasonically cleaned with methanol, acetone and isopropanone for 15 minutes, and then blown dry with N 2 . 10nm Al 2 O 3 and 0.8nm Fe were sequentially evaporated by an electron beam evaporation system (E-Beam Evaporation).
(2)在炉温725℃下，气体流量分别为H2:210sccm，C2H2:2.2sccm，通过去离子水的H2为190sccm，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0.5cm，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 furnace temperature of 725°C, the gas flow rates are H 2 : 210 sccm, C 2 H 2 : 2.2 sccm, the H 2 passing through deionized water is 190 sccm, the total air pressure is 25 Torr, and the heating wire is a single tungsten wire. With a power of 30W, 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 6.4Torr, and complete the single-walled carbon nanotube after 15 minutes of reaction Vertical array growth.
(3)通过蒸发溅射(Sputter Deposition)在(2)所获得的单壁垂直碳纳米管蒸镀150nm W。(3) 150 nm W was evaporated on the single-walled vertical carbon nanotubes obtained in (2) by sputtering (Sputter Deposition).
(4)在1050℃下，气体流量分别为H2:210sccm，CH4:0.5sccm，通过去离子水的H2为210sccm，总气压为25Torr，热丝为四根钨丝，总功率为80W条件下，将(3)中制得含碳纳米管垂直阵列和W的硅片置于钨丝正下方，反应6h后完成碳纳米管垂直阵列-碳化钨复合材料的制备。(4) At 1050°C, the gas flow rate is H 2 : 210 sccm, CH 4 : 0.5 sccm, the H 2 passing through deionized water is 210 sccm, the total pressure is 25 Torr, the heating wire is four tungsten wires, and the total power is 80W Under the conditions, place the silicon wafer containing the vertical array of carbon nanotubes and W prepared in (3) directly under the tungsten wire, and complete the preparation of the vertical array of carbon nanotubes-tungsten carbide composite material after 6 hours of reaction.
图5a为Raman光谱，可以看出制备的碳纳米管垂直阵列-碳化钨复合材料缺陷较低，不含氧化物，即步骤(3)中蒸镀的W，已完全转化为WC。图5b,c分别是实施例5提供的催化剂在0.5M/L H2SO4溶液(PH＝1)中的极化曲线及其Tafel曲线，可以看出电流密度大，起始电势(onset potential)低，Tafel斜率为80mV dec-1，催化剂在酸性条件下表现出良好的析氢催化活性；图5d,e分别为实施例5提供的催化剂在0.1M/L KOH溶液(PH＝13)中的极化曲线及其Tafel曲线，可以看出电流密度大，起始电势(onset potential)低，Tafel斜率为107mVdec-1，催化剂在碱性条件下表现出良好的析氢催化活性。Figure 5a is the Raman spectrum. It can be seen that the prepared carbon nanotube vertical array-tungsten carbide composite material has low defects and does not contain oxides, that is, the W evaporated in step (3) has been completely converted into WC. Figure 5b and c are the polarization curve and Tafel curve of the catalyst provided in Example 5 in 0.5M/LH 2 SO 4 solution (PH=1), respectively. It can be seen that the current density is large and the onset potential (onset potential) low, the Tafel slope is 80mV dec -1 , and the catalyst exhibits good catalytic activity for hydrogen evolution under acidic conditions; Fig. From the chemical reaction curve and its Tafel curve, it can be seen that the current density is high, the onset potential is low, and the Tafel slope is 107mVdec -1 . The catalyst exhibits good catalytic activity for hydrogen evolution under alkaline conditions.
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