技术领域technical field
本发明涉及对传统石墨电化学电极材料的改性，通过采用特殊制备方法获得高性能的石墨/金属/掺硼金刚石多层复合材料，大幅度提升石墨作为电化学电极的性能。The invention relates to the modification of traditional graphite electrochemical electrode materials. A high-performance graphite/metal/boron-doped diamond multilayer composite material is obtained by using a special preparation method, and the performance of graphite as an electrochemical electrode is greatly improved.
背景技术Background technique
随着石油化工、医药、农药和染料工业的迅速发展，工业废水中难降解有机化合物的数量与种类与日俱增，特别是其中所含的高浓度芳香族化合物，属“三致”物质，用一般的物理、化学和生物降解方法难以直接去除。电化学高级氧化法因其氧化剂来源于水分子电解的中间产物或目标物在电极表面直接氧化去除，通过调节电位而无需投加其他试剂即可完成污染物的降解，属绿色化学过程，成为废水处理技术发展的重要方向。With the rapid development of petrochemical, pharmaceutical, pesticide and dye industries, the number and types of refractory organic compounds in industrial wastewater are increasing day by day, especially the high-concentration aromatic compounds contained in them, which are "three-caused" substances. Physical, chemical and biological degradation methods are difficult to remove directly. The electrochemical advanced oxidation method is directly oxidized and removed on the surface of the electrode because the oxidant is derived from the intermediate product or target of water molecule electrolysis, and the degradation of pollutants can be completed by adjusting the potential without adding other reagents. It is a green chemical process and becomes wastewater. An important direction of technological development.
电化学高级氧化技术的关键是合适的电极材料。用于高浓度、难降解有机物的电化学高级氧化处理的电极材料应具有稳定的表面化学性质、优良的电化学催化性能、耐腐蚀性强、宽的电势窗口等。目前常用的电极材料有石墨、金属和氧化物电极，而发展最快、前景最好的则是掺硼金刚石涂层（BDD）电极。BDD电极具有最宽的电化学势窗（> 3.5 V vsNHE）、最高的析氧过电位（> 2.5 V vs NHE）、极低的背景电流（< 50 mA/cm2）、极强的化学惰性和抗污染中毒能力、非常低的表面吸附特性以及高的电催化活性等特点，理论上是最为理想的电化学水处理电极材料；而大量研究均证明在所有的实验条件下，相较于传统电极而言，金刚石电极的氧化速率和电流效率最高，具有更为优异的电极性能。The key to electrochemical advanced oxidation technology is suitable electrode material. Electrode materials for electrochemical advanced oxidation treatment of high-concentration, refractory organics should have stable surface chemical properties, excellent electrochemical catalytic performance, strong corrosion resistance, and wide potential window. At present, the commonly used electrode materials are graphite, metal and oxide electrodes, and the fastest-growing and most promising electrode is the boron-doped diamond coating (BDD) electrode. BDD electrode has the widest electrochemical potential window (> 3.5 V vs NHE), the highest oxygen evolution overpotential (> 2.5 V vs NHE), extremely low background current (< 50 mA/cm2 ), and strong chemical inertness And anti-pollution poisoning ability, very low surface adsorption characteristics and high electrocatalytic activity, it is theoretically the most ideal electrode material for electrochemical water treatment; and a large number of studies have proved that under all experimental conditions, compared with the traditional As far as electrodes are concerned, diamond electrodes have the highest oxidation rate and current efficiency, and have more excellent electrode performance.
掺硼金刚石涂层（BDD）电极目前主要使用重掺杂的硅或金属作为基体，硅作为半导体材料其电阻较大，形成硅/ BDD复合电极后电化学电解处理过程中阻抗发热量大，增加了废水处理能耗，同时还容易破坏金刚石涂层与基体的结合力，致电极整体失效；此外硅基体脆性大，机械强度不够，不利于工程应用中的安装使用。金属基体（如钨、钼、铌等）虽然有很好的机械性能和电学性能，但由于与金刚石热膨胀系数差异极大，形成的金属/ BDD复合电极结合力弱，使用过程容易出现金刚石膜脱落造成电极损坏；同时这些金属价格昂贵，使用成本高，难于工程化应用。相比而言，石墨作为BDD复合电极基体则可以全面解决上述困难：石墨价格相对低廉，加工性好，机械、电、热性能优异，尤为关键的是其热膨胀系数与金刚石极为接近，若表面镀覆金刚石涂层热应力小，对涂层结合强度影响基本可以忽略，因而石墨理论上是BDD涂层电极最理想的基体材料。Boron-doped diamond coating (BDD) electrodes currently mainly use heavily doped silicon or metal as the substrate, and silicon as a semiconductor material has a relatively high resistance. It reduces the energy consumption of wastewater treatment, and at the same time, it is easy to destroy the bonding force between the diamond coating and the substrate, causing the electrode to fail as a whole; in addition, the silicon substrate is brittle and has insufficient mechanical strength, which is not conducive to installation and use in engineering applications. Although the metal substrate (such as tungsten, molybdenum, niobium, etc.) has good mechanical and electrical properties, due to the great difference in thermal expansion coefficient with diamond, the metal/BDD composite electrode formed has weak bonding force, and the diamond film is prone to peeling off during use. Cause electrode damage; at the same time, these metals are expensive, high in use cost, and difficult to apply in engineering. In contrast, graphite as the BDD composite electrode matrix can fully solve the above difficulties: graphite is relatively cheap, has good processability, and excellent mechanical, electrical, and thermal properties. The most important thing is that its thermal expansion coefficient is very close to that of diamond. If the surface is coated with The thermal stress of the diamond-coated coating is small, and the influence on the bonding strength of the coating is basically negligible. Therefore, graphite is theoretically the most ideal substrate material for BDD coated electrodes.
尽管如此，由于化学气相沉积BDD涂层过程中必须使用氢气，以刻蚀掉金刚石生长时伴生的石墨及非晶碳，随之而来的影响就是若用石墨作为基体，金刚石生长中使用的高浓度氢同样会对石墨基体剧烈刻蚀，不仅破坏基体结构，而且使金刚石生长气氛环境失控，很难在表面形成完整的金刚石膜材，因此迄今虽然不少研究人员进行过石墨基体表面金刚石膜的生长研究，但实际应用中尚未实现石墨基体上涂覆金刚石膜的产品。而这种涂层材料的应用对电化学废水处理又是最为关键的技术环节，直接决定着电化学高级氧化技术在水处理领域应用的效果和效益。因此对于通过BDD电极使用促进电化学法在水处理中的应用而言，解决石墨基体上高质量BDD涂层的制备技术难题是极其重要的关键节点。However, because hydrogen must be used in the chemical vapor deposition BDD coating process to etch away the graphite and amorphous carbon associated with diamond growth, the ensuing impact is that if graphite is used as the substrate, the high The concentration of hydrogen will also severely etch the graphite substrate, which not only destroys the substrate structure, but also makes the diamond growth atmosphere out of control, making it difficult to form a complete diamond film on the surface. Growth research, but the product coated with diamond film on graphite substrate has not been realized in practical application. The application of this coating material is the most critical technical link for electrochemical wastewater treatment, which directly determines the effect and benefit of the application of electrochemical advanced oxidation technology in the field of water treatment. Therefore, for the application of electrochemical methods in water treatment through the use of BDD electrodes, solving the technical problems of preparing high-quality BDD coatings on graphite substrates is an extremely important key node.
理论和已有实践均证明克服上述困难的最好方法是在石墨基体上先沉积一层金属(主要是碳化物形成元素如钨、钼、钛、铌等)、再在其上生长金刚石则可以获得石墨基体上连续、完整、高质量的金刚石涂层。金属中间过渡层不仅避免石墨基体的剧烈氢刻蚀，而且可以在金刚石生长时石墨基体高温条件作用下与石墨基体及金刚石生长气氛中的碳源化合形成碳化物，不仅提高了石墨、过渡层、金刚石膜间的结合强度，而且由于金属碳化物与石墨和金刚石的热膨胀系数较为接近，可以大幅度降低生长结束后存在的热应力，最终保证金刚石涂层稳定、牢固存在于石墨基体表面。Both theory and existing practice have proved that the best way to overcome the above difficulties is to deposit a layer of metal (mainly carbide-forming elements such as tungsten, molybdenum, titanium, niobium, etc.) on the graphite substrate, and then grow diamond on it. Obtain continuous, complete, high-quality diamond coatings on graphite substrates. The metal intermediate transition layer not only avoids severe hydrogen etching of the graphite matrix, but also can combine with the carbon source in the graphite matrix and the diamond growth atmosphere to form carbides under the high temperature conditions of the graphite matrix during diamond growth, which not only improves the graphite, transition layer, The bonding strength between the diamond films, and because the thermal expansion coefficients of metal carbides and graphite and diamond are relatively close, can greatly reduce the thermal stress that exists after the growth is over, and finally ensure that the diamond coating is stable and firmly present on the surface of the graphite substrate.
但是石墨基体表面金属中间过渡层基本采用物理气相沉积技术（如溅射、离子镀、电子束蒸镀）制备，不仅需要金刚石涂层生长外的薄膜沉积设备，而且工序复杂，需在物理气相沉积系统内完成石墨基体表面金属过渡层的生长后，再取出放入化学气相沉积系统（主要是热丝化学气相沉积系统）中进行金刚石膜的制备，时间周期长，操作复杂麻烦，而且基体转移过程要暴露在大气，表面污染一定程度上还会影响后续沉积金刚石薄膜的质量。因此现有的石墨基体表面制备金刚石涂层技术存在明显弱点和缺陷，极大限制了这种新材料作为电化学电极的应用，急需改进完善。However, the metal intermediate transition layer on the surface of graphite substrate is basically prepared by physical vapor deposition technology (such as sputtering, ion plating, electron beam evaporation), which not only requires thin film deposition equipment other than diamond coating growth, but also has complex procedures, which require physical vapor deposition. After the growth of the metal transition layer on the surface of the graphite substrate is completed in the system, it is taken out and placed in a chemical vapor deposition system (mainly a hot wire chemical vapor deposition system) for the preparation of a diamond film. The time period is long, the operation is complicated and troublesome, and the substrate transfer process To be exposed to the atmosphere, surface contamination will also affect the quality of subsequent deposited diamond films to a certain extent. Therefore, there are obvious weaknesses and defects in the existing technology of preparing diamond coating on the surface of graphite substrate, which greatly limits the application of this new material as an electrochemical electrode, and urgently needs to be improved.
发明内容Contents of the invention
本发明的目的在于克服上述现有技术的不足，提供一种高效、简便、低成本、且能保证高质量的石墨/金属/金刚石涂层复合材料及其制备方法。The object of the present invention is to overcome the deficiencies of the above-mentioned prior art, and provide a graphite/metal/diamond coating composite material with high efficiency, convenience, low cost and high quality and a preparation method thereof.
本发明的解决方案是：一种石墨表面掺硼金刚石薄膜材料，其特点是在在石墨基体表面先热丝化学气相沉积一层金属钨膜作为中间过渡层，再在其上热丝化学气相沉积掺硼金刚石膜，其中金属钨层厚度为0.2 ～ 2mm，金刚石膜的厚度为0.5 ～ 10 mm。The solution of the present invention is: a boron-doped diamond film material on the surface of graphite, which is characterized in that a metal tungsten film is deposited on the surface of the graphite substrate by chemical vapor deposition of a layer of metal tungsten as an intermediate transition layer, and then chemical vapor deposition on the surface of the graphite substrate Boron-doped diamond film, wherein the metal tungsten layer has a thickness of 0.2-2 mm, and the diamond film has a thickness of 0.5-10 mm.
本发明的解决方案是：石墨表面掺硼金刚石薄膜材料的制备方法，其特点是包括以下步骤：Solution of the present invention is: the preparation method of graphite surface boron-doped diamond film material, it is characterized in that comprising the following steps:
a、将石墨基体放置于热丝等离子体化学气相沉积反应室内，将反应室抽真空至1.0 ~ 3.0 Pa；a. Place the graphite substrate in the hot wire plasma chemical vapor deposition reaction chamber, and evacuate the reaction chamber to 1.0 ~ 3.0 Pa;
b、给反应室内的热丝通电，使灯丝温度达到1200°~ 1400°C，再通入50-70°C水浴锅恒温加热气化的羰基钨蒸汽，使羰基钨蒸汽分子在石墨基体表面分解沉积出金属钨膜作为中间层；b. Power on the hot wire in the reaction chamber to make the temperature of the filament reach 1200°~1400°C, and then feed the vaporized tungsten carbonyl vapor at a constant temperature of 50-70°C into a water bath to decompose the tungsten carbonyl vapor molecules on the surface of the graphite substrate Deposit a metal tungsten film as an intermediate layer;
c、关闭羰基钨蒸汽管路进气阀，调节灯丝电源升高灯丝温度达到2100-2300°C，然后向反应室内通入甲烷、硼烷和氢气，在已沉积的钨层表面生长金刚石膜。c. Close the inlet valve of the carbonyl tungsten vapor pipeline, adjust the filament power supply to increase the temperature of the filament to 2100-2300°C, and then feed methane, borane and hydrogen into the reaction chamber to grow a diamond film on the surface of the deposited tungsten layer.
本发明的解决方案中，石墨表面掺硼金刚石薄膜材料的制备方法，其热丝化学气相沉积金刚石膜的反应气源为甲烷和氢气，掺杂源为硼烷；其中甲烷占气体总体积比例为0.5 ~ 4%，硼烷占气体总体积比例为10-1000百万分之，其余气体为氢气，总气流量为每分钟200 ~ 400毫升。In the solution of the present invention, the preparation method of boron-doped diamond film material on the surface of graphite, the reaction gas source of its hot wire chemical vapor deposition diamond film is methane and hydrogen, and the doping source is borane; wherein methane accounts for the gas total volume ratio of 0.5 ~ 4%, borane accounts for 10-1000 parts per million of the total gas volume, the rest of the gas is hydrogen, and the total gas flow is 200 ~ 400 ml per minute.
本发明的解决方案中，石墨表面掺硼金刚石薄膜材料的制备方法，其所通入的硼烷为氢稀释的硼烷。In the solution of the present invention, in the preparation method of the boron-doped diamond film material on the graphite surface, the borane introduced is hydrogen-diluted borane.
本发明的解决方案中，石墨表面掺硼金刚石薄膜材料的制备方法，其石墨基体表面制备掺硼金刚石膜的方法采用原位金属有机化合物化学气相沉积(MOCVD)技术制备，即使用同一套装置，先在石墨基体表面沉积金属钨膜作为中间层，关闭羰基钨蒸汽管路进气阀，再改变气源及工艺条件，通入甲烷、硼烷和氢气，沉积金刚石膜。In the solution of the present invention, the preparation method of the boron-doped diamond film material on the graphite surface, the method for preparing the boron-doped diamond film on the surface of the graphite substrate adopts the in-situ metal organic compound chemical vapor deposition (MOCVD) technology, that is, using the same set of equipment, Deposit a metal tungsten film on the surface of the graphite substrate as an intermediate layer, close the inlet valve of the tungsten carbonyl vapor pipeline, then change the gas source and process conditions, and inject methane, borane and hydrogen to deposit the diamond film.
本发明的优点：本发明采用热丝化学气相沉积法，在石墨基体表面先利用羰基钨热分解沉积一层金属钨作为中间过渡层，再改变气源在其上紧接原位生长掺硼金刚石膜，不像传统方法中间金属过渡层和金刚石涂层分别需要不同的装置生长，而且石墨基体也不需转移，可在同一套装置中原位连续生长，这种方法高效、简便、低成本、且能保证薄膜制备的高质量。Advantages of the present invention: the present invention adopts the hot wire chemical vapor deposition method, first uses carbonyl tungsten to thermally decompose and deposit a layer of metal tungsten as an intermediate transition layer on the surface of the graphite substrate, and then changes the gas source to grow boron-doped diamond on it in situ Unlike the traditional method, the intermediate metal transition layer and the diamond coating require different devices to grow, and the graphite substrate does not need to be transferred, and can be continuously grown in situ in the same device. This method is efficient, simple, low-cost, and It can guarantee the high quality of thin film preparation.
附图说明Description of drawings
图1是本发明使用的制备系统结构图；Fig. 1 is the preparation system structural diagram that the present invention uses;
图2是依据实施例1和实施例2制备出的石墨基体表面掺硼金刚石涂层的Raman光谱。Figure 2 is the Raman spectrum of the boron-doped diamond coating on the surface of the graphite substrate prepared according to Example 1 and Example 2.
图中，1为水浴锅（内装盛羰基钨容器），2为甲烷容器，3为氢气容器，4为硼烷容器，5为热丝电源，6为进气口，7为热丝，8为石墨基体，9为水冷样品台，10为沉积室，11为真空抽气口。In the figure, 1 is a water bath (with a tungsten carbonyl container inside), 2 is a methane container, 3 is a hydrogen container, 4 is a borane container, 5 is a heating wire power supply, 6 is an air inlet, 7 is a heating wire, 8 is Graphite substrate, 9 is a water-cooled sample stage, 10 is a deposition chamber, and 11 is a vacuum exhaust port.
具体实施方式detailed description
本发明实施例1：Embodiment 1 of the present invention:
预先打开加热羰基钨恒温水浴锅电源，调节水浴锅温度至50°C恒温；将石墨基体固定于热丝化学气相沉积系统的水冷样品台上，抽沉积室的真空至真空度为2.0 Pa，并打开样品台冷却水；启动热丝电源，升高电源功率至热丝温度达1200°；打开羰基钨气路上的调节针阀三分之一圈，往真空室内通入针阀开度控制量的羰基钨蒸汽；上述条件维持1.5小时时间，完成钨中间层生长。关闭羰基钨气路上的针阀，增大热丝电源功率至热丝温度达2200°，通入200 SCCM氢气、20SCCM甲烷、20SCCM氢稀释的硼烷（即硼烷和氢气混合气体，硼烷体积浓度为万分之一），持续沉积3小时，最后逐渐降低热丝功率缓慢冷却关机。其中金属钨薄膜厚度为1 mm，掺硼金刚石薄膜的厚度为1.5mm，硼含量为50ppm。Turn on the power supply of the heated tungsten carbonyl constant temperature water bath in advance, adjust the temperature of the water bath to a constant temperature of 50°C; fix the graphite substrate on the water-cooled sample stage of the hot wire chemical vapor deposition system, pump the vacuum of the deposition chamber to a vacuum degree of 2.0 Pa, and Turn on the cooling water of the sample stage; start the hot wire power supply, increase the power of the power supply until the temperature of the hot wire reaches 1200°; open the adjusting needle valve on the tungsten carbonyl gas circuit for one-third of a turn, and pass the needle valve opening control amount into the vacuum chamber Carbonyl tungsten vapor; the above conditions are maintained for 1.5 hours to complete the growth of the tungsten intermediate layer. Close the needle valve on the tungsten carbonyl gas circuit, increase the power supply of the hot wire until the temperature of the hot wire reaches 2200°, and feed 200 SCCM hydrogen, 20 SCCM methane, and 20 SCCM hydrogen-diluted borane (that is, the mixed gas of borane and hydrogen, the volume of borane Concentration is 1/10,000), continue to deposit for 3 hours, and finally gradually reduce the power of the hot wire to cool down and shut down. The thickness of the metal tungsten film is 1 mm, the thickness of the boron-doped diamond film is 1.5 mm, and the boron content is 50 ppm.
实施例2：Example 2:
预先打开加热羰基钨恒温水浴锅电源，调剂水浴锅温度至50°C恒温；将石墨阴极固定于热丝化学气相沉积系统的水冷样品台上，抽沉积室的真空至真空度为2.0 Pa，并打开样品台冷却水；启动热丝电源，升高电源功率至热丝温度达1200°；打开羰基钨气路上的调节针阀三分之一圈，往真空室内通入针阀开度控制量的羰基钨蒸汽；上述条件维持2小时时间，完成钨中间层生长。关闭羰基钨气路上的针阀，增大热丝电源功率至热丝温度达2200°，通入300 SCCM氢气、40SCCM甲烷、50SCCM氢稀释的硼烷（即硼烷和氢气混合气体，硼烷体积浓度为万分之一），持续沉积5小时，最后逐渐降低热丝功率缓慢冷却关机。其中金属钨薄膜厚度为1.5 mm，掺硼金刚石薄膜的厚度为2.5mm，硼含量为150ppm。Turn on the power supply of the heating tungsten carbonyl constant temperature water bath in advance, adjust the temperature of the water bath to a constant temperature of 50°C; fix the graphite cathode on the water-cooled sample stage of the hot wire chemical vapor deposition system, pump the vacuum of the deposition chamber to a vacuum degree of 2.0 Pa, and Turn on the cooling water of the sample stage; start the hot wire power supply, increase the power of the power supply until the temperature of the hot wire reaches 1200°; open the adjusting needle valve on the tungsten carbonyl gas circuit for one-third of a turn, and pass the needle valve opening control amount into the vacuum chamber Carbonyl tungsten vapor; the above conditions are maintained for 2 hours to complete the growth of the tungsten intermediate layer. Close the needle valve on the tungsten carbonyl gas circuit, increase the power supply of the hot wire until the temperature of the hot wire reaches 2200 °, and feed 300 SCCM hydrogen, 40 SCCM methane, and 50 SCCM hydrogen-diluted borane (that is, the mixed gas of borane and hydrogen, the volume of borane Concentration is 1/10,000), continue to deposit for 5 hours, and finally gradually reduce the power of the hot wire to cool down and shut down. Among them, the thickness of the metal tungsten film is 1.5 mm, the thickness of the boron-doped diamond film is 2.5 mm, and the boron content is 150 ppm.
图2为制备出的石墨基体表面掺硼金刚石涂层的Raman光谱。其中1＃为实施例1的Raman光谱，2＃为实施例2 的Raman光谱。图中在约1332 cm-1处均出现一个尖锐的sp3-C相的一阶Raman共振峰，而在1350 cm-1和1580 cm-1处无明显的D峰和G峰，表明二者均为较为纯洁的金刚石膜，几乎没有石墨和非晶碳杂相。同时谱图上在约1240 ~ 1218 cm-1附近均出现弱的Raman共振峰，该峰是由于硼掺入金刚石晶格后B-C键增多而引起的晶体无序状态增多所表现出的特征峰，且随着反应气源中B/C比的增加，该Raman峰的强度逐渐增强，表明随着B/C比的增加，金刚石膜中B的含量随之增大，即实施例2所得金刚石膜中硼含量高于实施例1。Figure 2 is the Raman spectrum of the prepared boron-doped diamond coating on the surface of the graphite substrate. Wherein 1# is the Raman spectrum of embodiment 1, and 2# is the Raman spectrum of embodiment 2. In the figure, there is a sharp first-order Raman resonance peak of sp3 -C phase at about 1332 cm-1 , but there are no obvious D peaks and G peaks at 1350 cm-1 and 1580 cm-1 , indicating that the two Both are relatively pure diamond films, with almost no graphite and amorphous carbon impurities. At the same time, there are weak Raman resonance peaks around 1240 ~ 1218 cm-1 in the spectrum, which is a characteristic peak due to the increase in crystal disorder caused by the increase of BC bonds after boron is doped into the diamond lattice. And along with the increase of B/C ratio in the reaction gas source, the intensity of this Raman peak strengthens gradually, shows that along with the increase of B/C ratio, the content of B in the diamond film increases thereupon, namely the obtained diamond film of embodiment 2 Middle boron content is higher than embodiment 1.
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