技术领域technical field
本发明属于材料化学领域，尤其是涉及一种Co和Ru双金属碳纳米复合电催化材料的制备方法。The invention belongs to the field of material chemistry, and in particular relates to a preparation method of a Co and Ru bimetallic carbon nanocomposite electrocatalytic material.
背景技术Background technique
随着社会经济的快速发展，能源与环境成为人们日益关注的问题，太阳能和风能等可再生能源在人类社会总能源消费中所占的消费比例也逐步提高。但是由于这类可再生能源在转化和使用过程中电能存在一定间歇性和波动性，所以，可充电电池、电化学电容器、电解槽和燃料电池等电化学储能和转换等技术，在实现高效和可持续的能源利用方面将发挥十分关键的作用。尽管它们的工作原理不同，但这些电化学装置都是由相似的关键功能组件所构成的，而用于这些组件中的功能材料的电化学性质(例如氧化还原和催化活性)将决定装置的整体性能。因此，制备电化学性能优良的功能材料已成为电化学领域重要的研究方向。With the rapid development of social economy, energy and the environment have become increasingly concerned issues, and the proportion of renewable energy such as solar energy and wind energy in the total energy consumption of human society is also gradually increasing. However, due to the intermittent and fluctuating electrical energy in the conversion and use of such renewable energy, the electrochemical energy storage and conversion technologies such as rechargeable batteries, electrochemical capacitors, electrolyzers and fuel cells, etc. and sustainable energy use will play a key role. Despite their different working principles, these electrochemical devices are all composed of similar key functional components, and the electrochemical properties (such as redox and catalytic activity) of the functional materials used in these components will determine the overall performance of the device. performance. Therefore, the preparation of functional materials with excellent electrochemical performance has become an important research direction in the field of electrochemistry.
氢气具有高能量密度和生产环保可实现的优点，被认为是可持续能源经济的理想能源载体。水分解产氢是当代清洁能源技术的主要组成部分，然而由于水分解过程中电位过大，它实际应用是非常有限的。所以高效、低成本的水分解技术将对氢能源的应用发挥着至关重要的作用。在水分解产氢的过程中，合适的催化剂使用可以有效降低反应活化能，从而加快反应进程和产氢效率。目前，应用最广泛的催化剂主要基于Pt基纳米材料，但是地壳中含量有限自身成本较高，因此寻找低成本可替代的催化材料是当前材料研究的热点之一。With the advantages of high energy density and environmentally friendly production, hydrogen is considered as an ideal energy carrier for a sustainable energy economy. Hydrogen production from water splitting is a major component of contemporary clean energy technologies, however, its practical application is very limited due to the high potential in the water splitting process. Therefore, efficient and low-cost water splitting technology will play a vital role in the application of hydrogen energy. In the process of water splitting to produce hydrogen, the use of appropriate catalysts can effectively reduce the activation energy of the reaction, thereby accelerating the reaction process and hydrogen production efficiency. At present, the most widely used catalysts are mainly based on Pt-based nanomaterials, but the limited content in the earth's crust is expensive, so finding low-cost alternative catalytic materials is one of the hotspots of current materials research.
金属-有机骨架(MOFs)材料作为一种新型的多孔有机-无机杂化材料，具有种类繁多，功能多样、结构可调等特点。与无机材料相类似，含有氧化还原活性金属中心的MOFs也具有一定的电化学活性。MOFs具有有机分子配位的金属位点和容易调节的孔结构，这也为其性能的优化提升提供了结构基础。现在，已经有很多相关的文献报道，通过调控金属和有机组分构筑复合MOFs材料，将MOFs成功地用作充电电池和电化学电容器的电极材料，用于燃料电池的高效电催化剂，甚至用于电化学装置的电解质，但是大多数MOFs仍存在化学性质不稳定和导电性能差的缺点。近来，将MOFs材料加热转化为可利用的金属化合物和碳化物催化材料的研究已引起广泛的重视，研究表明这些MOF衍生的功能材料不仅保留了原本材料的优良特性，而且化学性质会更为稳定、导电性能更好，通常具有非常优异的催化性能，，在电化学领域具有十分重要的的开发潜力。As a new type of porous organic-inorganic hybrid materials, metal-organic frameworks (MOFs) have the characteristics of various types, various functions, and adjustable structures. Similar to inorganic materials, MOFs containing redox-active metal centers also exhibit certain electrochemical activity. MOFs have metal sites coordinated by organic molecules and easily adjustable pore structures, which also provide a structural basis for the optimization and improvement of their performance. Now, there have been a lot of relevant literature reports, and MOFs have been successfully used as electrode materials for rechargeable batteries and electrochemical capacitors, as high-efficiency electrocatalysts for fuel cells, and even as Electrolytes for electrochemical devices, but most MOFs still have the disadvantages of chemical instability and poor electrical conductivity. Recently, the research on thermally converting MOFs materials into usable metal compounds and carbide catalytic materials has attracted widespread attention. Studies have shown that these MOF-derived functional materials not only retain the excellent characteristics of the original materials, but also have more stable chemical properties. , better electrical conductivity, usually has excellent catalytic performance, and has very important development potential in the field of electrochemistry.
目前，电催化产氢(HER)的基础研究主要是在酸性条件下进行的，主要是因为其反应途径相对简单，这也导致该方向研究应用存在一定的局限性。近年来，逐渐开始有文献报道将掺杂Ru的材料应用于HER电催化测试研究。与Pt相比，Ru价格具有一定的优势，其价格约为Pt的十五分之一。此外，Ru具有与氢气相似的结合强度，但是，现在关于Ru作为HER催化剂的报道仍然较少。利用外来金属原子掺杂非贵金属基碳复合材料也可以优化材料催化活性。掺杂入Cu等金属离子不仅可以进一步降低Ru的含量以减低成本，还可以进一步提升材料性能。At present, the basic research of electrocatalytic hydrogen production (HER) is mainly carried out under acidic conditions, mainly because its reaction pathway is relatively simple, which also leads to certain limitations in the research and application of this direction. In recent years, there have been reports in the literature on the application of Ru-doped materials to HER electrocatalytic testing. Compared with Pt, the price of Ru has certain advantages, and its price is about one-fifteenth of that of Pt. In addition, Ru has a similar binding strength to hydrogen, however, there are still few reports on Ru as a catalyst for HER. Doping non-noble metal-based carbon composites with foreign metal atoms can also optimize the catalytic activity of materials. Doping metal ions such as Cu can not only further reduce the content of Ru to reduce the cost, but also can further improve the performance of the material.
发明内容Contents of the invention
为了克服现有技术的不足，本发明提供一种具有良好HER电催化性能的含Co和Ru双金属碳纳米复合电催化材料的制备方法。In order to overcome the deficiencies of the prior art, the invention provides a preparation method of a double-metal carbon nanocomposite electrocatalytic material containing Co and Ru with good electrocatalytic performance for HER.
本发明解决其技术问题所采用的技术方案是：一种含Co和Ru双金属碳纳米复合电催化材料的制备方法，包括以下步骤：The technical scheme adopted by the present invention to solve its technical problems is: a kind of preparation method containing Co and Ru bimetallic carbon nanocomposite electrocatalytic material, comprises the following steps:
1)将钴盐和聚乙烯吡咯烷酮溶于乙醇和去离子水的混合溶剂中，搅拌均匀，得到溶液A；1) Dissolving the cobalt salt and polyvinylpyrrolidone in a mixed solvent of ethanol and deionized water, and stirring evenly to obtain solution A;
2)将均苯三甲酸溶于乙醇和去离子水的混合溶剂中，搅拌均匀，得到溶液B；2) dissolving trimesic acid in a mixed solvent of ethanol and deionized water, and stirring evenly to obtain solution B;
3)将溶液A加入到溶液B中，搅拌直至形成沉淀，静置20-30h后，离心收集得到蓝色的沉淀物，将沉淀物使用无水乙醇洗涤后置于40-80℃的烘箱中干燥1-3h，得到Co3(BTC)2前驱体；3) Add solution A to solution B, stir until a precipitate forms, and after standing for 20-30 hours, collect the blue precipitate by centrifugation, wash the precipitate with absolute ethanol and place it in an oven at 40-80°C Dry for 1-3h to obtain Co3 (BTC)2 precursor;
4)将步骤3)中得到的Co3(BTC)2分散在去离子水和无水乙醇的混合溶剂中，混合溶剂的体积为10-40ml，加入RuCl3·xH2O搅拌反应4-24h后，离心得到沉淀物，将沉淀物使用无水乙醇洗涤后置于50-70℃的烘箱中干燥1-3h，得到含Co和Ru双金属的MOFs材料；4) Disperse the Co3 (BTC)2 obtained in step 3) in a mixed solvent of deionized water and absolute ethanol, the volume of the mixed solvent is 10-40ml, add RuCl3 ·xH2 O and stir for 4-24h Finally, centrifuge to obtain the precipitate, wash the precipitate with absolute ethanol and dry it in an oven at 50-70°C for 1-3 hours to obtain a Co and Ru bimetallic MOFs material;
5)将步骤4)中得到的MOFs材料置于管式炉里，在惰性气氛中下以1-20℃/min的升温速率将反应物升温到400-600℃并保温1-5h，冷却至室温，得到含Co和Ru双金属碳纳米复合电催化材料CoRu/C。5) Put the MOFs material obtained in step 4) in a tube furnace, raise the temperature of the reactant to 400-600°C at a rate of 1-20°C/min in an inert atmosphere, keep it warm for 1-5h, and cool to At room temperature, CoRu/C, a bimetallic carbon nanocomposite electrocatalytic material containing Co and Ru, was obtained.
进一步的，所述步骤1)中的钴盐为醋酸钴铜或硫酸钴铜或氯化钴铜，或任意两种或三种的组合。Further, the cobalt salt in step 1) is cobalt-copper acetate, cobalt-copper sulfate or cobalt-copper chloride, or any combination of two or three.
进一步的，所述步骤1)中去离子水和乙醇的体积比为1:1。Further, the volume ratio of deionized water and ethanol in the step 1) is 1:1.
进一步的，所述步骤2)中去离子水和乙醇的体积比为1:1-2。Further, the volume ratio of deionized water and ethanol in the step 2) is 1:1-2.
进一步的，所述钴盐和均苯三甲酸的物质的量比为0.5-5:1。Further, the molar ratio of the cobalt salt and trimesic acid is 0.5-5:1.
进一步的，所述步骤4)中Co3(BTC)2和RuCl3·xH2O的物质的量比为1-10:1。Further, the substance ratio of Co3 (BTC)2 and RuCl3 ·xH2 O in step 4) is 1-10:1.
进一步的，所述步骤4)中去离子水和乙醇的体积比为1:1-2，混合溶剂的体积为20ml。Further, the volume ratio of deionized water and ethanol in the step 4) is 1:1-2, and the volume of the mixed solvent is 20ml.
进一步的，所述步骤5)中惰性气氛为氮气或氩气。Further, the inert atmosphere in step 5) is nitrogen or argon.
进一步的，所述步骤5)中反应物升温到400-600℃并保温。Further, in the step 5), the temperature of the reactants is raised to 400-600° C. and kept warm.
本发明的制备方法以进一步寻找制备方法简单、成本低、催化性能优异的双金属碳纳米复合材料为研究目标，首先合成MOFs材料Co3(BTC)2，并以此为前驱体与Ru进行离子交换制备出双金属MOFs材料，最后在400-600℃下对双金属MOFs材料进行高温热解，得到石墨化程度高的双金属有机框架材料衍生的碳纳米复合材料，该材料具有大比表面积、结构规则、掺杂均匀，分布均匀的特征，是一种性能优异的电催化材料。The preparation method of the present invention aims to further find abimetallic carbon nanocomposite material with simple preparation method, low cost and excellent catalytic performance. The bimetallic MOFs material was prepared by exchange, and finally the bimetallic MOFs material was pyrolyzed at 400-600°C to obtain a carbon nanocomposite derived from a bimetallic organic framework material with a high degree of graphitization. The material has a large specific surface area, The structure is regular, the doping is uniform, and the distribution is uniform. It is an electrocatalytic material with excellent performance.
本发明以钴的盐(醋酸钴/硫酸钴/氯化钴)作为钴源，均苯三甲酸作为有机配体，合成含钴的金属框架材料(MOFs)Co3(BTC)2前驱体，再经过与RuCl3·xH2O离子交换得到含Co、Ru双金属的MOFs材料，最后通过在惰性环境中热处理碳化，得到金属有机框架衍生的双金属碳纳米复合电催化材料。该复合材料具有较好的HER性能，在1mol/L的KOH电解液中，电流密度为10mA/cm2时，其过电位为133mV。The present invention uses cobalt salt (cobalt acetate/cobalt sulfate/cobalt chloride) as the cobalt source, trimesic acid as the organic ligand, and synthesizes cobalt-containing metal framework materials (MOFs) Co3 (BTC)2 precursors, and then After ion exchange with RuCl3 ·xH2 O, the MOFs materials containing Co and Ru bimetals were obtained. Finally, the bimetallic carbon nanocomposite electrocatalytic materials derived from metal organic frameworks were obtained by heat treatment and carbonization in an inert environment. The composite material has good HER performance, and its overpotential is 133mV when the current density is 10mA/cm2 in 1mol/L KOH electrolyte.
本发明的有益效果是：使用离子交换法合成含Co和Ru双金属的MOFs材料，随后经过高温煅烧，得到具有大比表面积、结构规则、掺杂均匀的含Co和Ru双金属碳纳米复合电催化材料，是一种性能优异的电催化材料。The beneficial effect of the present invention is: use the ion exchange method to synthesize the MOFs material containing Co and Ru bimetal, and then through high-temperature calcination, obtain a Co and Ru bimetallic carbon nanocomposite electrode with large specific surface area, regular structure, and uniform doping. Catalytic material is a kind of electrocatalytic material with excellent performance.
附图说明Description of drawings
图1为本发明的实施例1中所制备的样品CoRu/C双金属碳纳米复合电催化材料的扫描电镜图片。FIG. 1 is a scanning electron microscope picture of a sample CoRu/C bimetallic carbon nanocomposite electrocatalytic material prepared in Example 1 of the present invention.
图2为本发明的实施例1所制备的含Co和Ru双金属碳纳米复合电催化材料的XRD图。Fig. 2 is the XRD pattern of the bimetallic carbon nanocomposite electrocatalytic material containing Co and Ru prepared in Example 1 of the present invention.
图3为本发明的实施例1所制备的含Co和Ru双金属碳纳米复合电催化材料的LSV曲线图。Fig. 3 is the LSV curve diagram of the bimetallic carbon nanocomposite electrocatalytic material containing Co and Ru prepared in Example 1 of the present invention.
图4为本发明的实施例1所制备的含Co和Ru双金属碳纳米复合电催化材料的Tafel图。4 is a Tafel diagram of the Co and Ru bimetallic carbon nanocomposite electrocatalytic material prepared in Example 1 of the present invention.
具体实施方式Detailed ways
为了使本技术领域的人员更好的理解本发明方案，下面将结合本发明实施例中的附图，对发明实施例中的技术方案进行清楚、完整的描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only It is a part of embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
(1)Co3(BTC)2的制备：(1) Preparation of Co3 (BTC)2 :
(a)将0.2g Co(CH3COO)2·4H2O和1.2g聚乙烯吡咯烷酮(PVP)溶解于20mL去离子水和20mL无水乙醇混合溶液中，搅拌均匀，得到钴离子([Co2+])浓度为0.25mmol/mL的溶液A；(a) Dissolve 0.2g Co(CH3 COO)2 ·4H2 O and 1.2g polyvinylpyrrolidone (PVP) in a mixed solution of 20mL deionized water and 20mL absolute ethanol, and stir evenly to obtain cobalt ions ([Co2+ ]) concentration is the solution A of 0.25mmol/mL;
(b)将0.2g H3BTC加入到20mL去离子水和20mL无水乙醇混合溶液中，搅拌均匀，得到H3BTC的浓度为0.25mmol/mL的溶液B；(b) Add 0.2g of H3 BTC into a mixed solution of 20 mL of deionized water and 20 mL of absolute ethanol, and stir evenly to obtain a solution B with a concentration of H3 BTC of 0.25 mmol/mL;
(c)将溶液A加入到溶液B中，搅拌直至形成沉淀，然后静置24h；(c) adding solution A to solution B, stirring until a precipitate is formed, and then standing for 24 hours;
(d)将产物离心并用乙醇洗涤三次，随后在60℃下干燥2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 60° C. for 2 h;
(2)复合双金属MOFs材料的制备：(2) Preparation of composite bimetallic MOFs materials:
(a)将得到的100mg Co3(BTC)2分散于10mL去离子水和10mL无水乙醇中，加入0.571mL浓度为10mg/ml的RuCl3·xH2O搅拌24h；(a) Disperse 100 mg of Co3 (BTC)2 obtained in 10 mL of deionized water and 10 mL of absolute ethanol, add 0.571 mL of RuCl3 xH2 O with a concentration of 10 mg/ml and stir for 24 h;
(d)将产物离心并用乙醇洗涤三次，随后在60℃下干燥2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 60° C. for 2 h;
(3)CoRu/C-1材料的制备：(3) Preparation of CoRu/C-1 material:
将(2)得到的产物置于管式炉里，在惰性气体氛围下以10℃/min的速率升温至500℃，保温3h，随后冷却至室温碳纳米复合材料CoRu/C-1。The product obtained in (2) was placed in a tube furnace, and the temperature was raised to 500°C at a rate of 10°C/min under an inert gas atmosphere, kept for 3h, and then cooled to room temperature Carbon nanocomposite CoRu/C-1.
在图2中，可以看出CoRu/C-1的XRD图谱及主要特征峰均与Co晶体模拟谱图(15-0806)一致，而且其特征衍射峰也与Cu晶体特征衍射峰吻合表明样品CoRu/C-1中Co的结晶性较好。衍射图谱中没有较为尖锐的C衍射峰，这表明所获得的碳为无定形碳。In Figure 2, it can be seen that the XRD pattern and main characteristic peaks of CoRu/C-1 are consistent with the Co crystal simulation spectrum (15-0806), and its characteristic diffraction peaks are also consistent with the Cu crystal characteristic diffraction peaks, indicating that the sample CoRu The crystallinity of Co in /C-1 is better. There is no sharper C diffraction peak in the diffraction pattern, which indicates that the obtained carbon is amorphous carbon.
结合图3、4可以看出样品CoRu/C-1在电流为10mA时，过电位为133mV，Tafel斜率为147mV*dec-1，该性能与目前最好的业内电解水产氢催化剂性能相比已经很优异。这说明本发明所制备的样品具有极为优异的电催化性能，这主要依赖于该材料中Co、Ru双金属在材料整体内的高度分散和双金属协同作用，材料大比表面积，高孔隙度等特点为这一优异的电催化性能提供了结构基础。Combining Figures 3 and 4, it can be seen that when the current is 10mA, the sample CoRu/C-1 has an overpotential of 133mV and a Tafel slope of 147mV*dec-1 , which is comparable to that of the best hydrogen production catalysts for electrolysis of water in the industry. Excellent. This shows that the sample prepared by the present invention has extremely excellent electrocatalytic performance, which mainly depends on the high dispersion of Co and Ru bimetals in the material as a whole and the synergistic effect of bimetals in the material, the large specific surface area of the material, high porosity, etc. The features provide the structural basis for this excellent electrocatalytic performance.
实施例2Example 2
(1)Co3(BTC)2的制备：(1) Preparation of Co3 (BTC)2 :
(a)将0.2g Co(CH3COO)2·4H2O和1.2g PVP溶解于20mL去离子水和20mL无水乙醇混合溶液中，搅拌均匀，得到钴离子([Co2+])浓度为0.25mmol/mL的溶液A；(a) Dissolve 0.2g Co(CH3 COO)2 4H2 O and 1.2g PVP in a mixed solution of 20mL deionized water and 20mL absolute ethanol, stir well to obtain the concentration of cobalt ion ([Co2+ ]) Solution A of 0.25mmol/mL;
(b)将0.18g H3BTC加入到20mL去离子水和40mL无水乙醇混合溶液中，搅拌均匀，得到H3BTC的浓度为0.25mmol/mL的溶液B；(b) Add 0.18g of H3 BTC into a mixed solution of 20 mL of deionized water and 40 mL of absolute ethanol, and stir evenly to obtain a solution B with a concentration of H3 BTC of 0.25 mmol/mL;
(c)将溶液A加入到溶液B中，搅拌直至形成沉淀，然后静置30h；(c) adding solution A to solution B, stirring until a precipitate is formed, and then standing for 30 hours;
(d)将产物离心并用乙醇洗涤三次，随后在80℃下干燥3h；(d) The product was centrifuged and washed three times with ethanol, then dried at 80° C. for 3 h;
(2)复合双金属MOFs材料的制备：(2) Preparation of composite bimetallic MOFs materials:
(a)将得到的100mg Co3(BTC)2分散于10mL去离子水和10mL无水乙醇中，加入1.142mL浓度为10mg/ml的RuCl3·xH2O搅拌20h；(a) Disperse 100 mg of Co3 (BTC)2 obtained in 10 mL of deionized water and 10 mL of absolute ethanol, add 1.142 mL of RuCl3 xH2 O with a concentration of 10 mg/ml and stir for 20 h;
(d)将产物离心并用乙醇洗涤三次，随后在60℃下干燥3h；(d) The product was centrifuged and washed three times with ethanol, then dried at 60° C. for 3 h;
(3)CoRu/C-2材料的制备：(3) Preparation of CoRu/C-2 material:
将(2)得到的产物置于管式炉里，在惰性气体氛围下以1℃/min的速率升温至400℃，保温3h，随后冷却至室温碳纳米复合材料CoRu/C-2。The product obtained in (2) was placed in a tube furnace, and the temperature was raised to 400°C at a rate of 1°C/min under an inert gas atmosphere, kept for 3h, and then cooled to room temperature Carbon nanocomposite CoRu/C-2.
实施例3Example 3
(1)Co3(BTC)2的制备：(1) Preparation of Co3 (BTC)2 :
(a)将0.2g Co(CH3COO)2·4H2O和1.2gPVP溶解于20mL去离子水和20mL无水乙醇混合溶液中，搅拌均匀，得到钴离子([Co2+])浓度为0.25mmol/mL的溶液A；(a) Dissolve 0.2g Co(CH3 COO)2 ·4H2 O and 1.2g PVP in a mixed solution of 20mL deionized water and 20mL absolute ethanol, and stir evenly to obtain a cobalt ion ([Co2+ ]) concentration of 0.25mmol/mL solution A;
(b)将0.18g H3BTC加入到20mL去离子水和40mL无水乙醇混合溶液中，搅拌均匀，得到H3BTC的浓度为0.25mmol/mL的溶液B；(b) Add 0.18g of H3 BTC into a mixed solution of 20 mL of deionized water and 40 mL of absolute ethanol, and stir evenly to obtain a solution B with a concentration of H3 BTC of 0.25 mmol/mL;
(c)将溶液A加入到溶液B中，搅拌直至形成沉淀，然后静置20h；(c) adding solution A to solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d)将产物离心并用乙醇洗涤三次，随后在40℃下干燥3h；(d) The product was centrifuged and washed three times with ethanol, then dried at 40° C. for 3 h;
(2)复合双金属MOFs材料的制备：(2) Preparation of composite bimetallic MOFs materials:
(a)将得到的100mg Co3(BTC)2分散于10mL去离子水和10mL无水乙醇中，加入0.285mL浓度为10mg/ml的RuCl3·xH2O搅拌24h；(a) Disperse 100 mg of Co3 (BTC)2 obtained in 10 mL of deionized water and 10 mL of absolute ethanol, add 0.285 mL of RuCl3 xH2 O with a concentration of 10 mg/ml and stir for 24 h;
(d)将产物离心并用乙醇洗涤三次，随后在60℃下干燥2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 60° C. for 2 h;
(3)CoRu/C-3材料的制备：(3) Preparation of CoRu/C-3 material:
将(2)得到的产物置于管式炉里，在惰性气体氛围下以15℃/min的速率升温至600℃，保温4h，随后冷却至室温碳纳米复合材料CoRu/C-3。The product obtained in (2) was placed in a tube furnace, and the temperature was raised to 600°C at a rate of 15°C/min under an inert gas atmosphere, kept for 4h, and then cooled to room temperature Carbon nanocomposite CoRu/C-3.
实施例4Example 4
(1)Co3(BTC)2的制备：(1) Preparation of Co3 (BTC)2 :
(a)将0.1g Co(CH3COO)2·4H2O和1.2g聚乙烯吡咯烷酮(PVP)溶解于20mL去离子水和20mL无水乙醇混合溶液中，搅拌均匀，得到钴离子([Co2+])浓度为0.125mmol/mL的溶液A；(a) Dissolve 0.1g Co(CH3 COO)2 4H2 O and 1.2g polyvinylpyrrolidone (PVP) in a mixed solution of 20mL deionized water and 20mL absolute ethanol, and stir evenly to obtain cobalt ions ([Co2+ ]) solution A whose concentration is 0.125mmol/mL;
(b)将0.2g H3BTC加入到20mL去离子水和20mL无水乙醇混合溶液中，搅拌均匀，得到H3BTC的浓度为0.25mmol/mL的溶液B；(b) Add 0.2g of H3 BTC into a mixed solution of 20 mL of deionized water and 20 mL of absolute ethanol, and stir evenly to obtain a solution B with a concentration of H3 BTC of 0.25 mmol/mL;
(c)将溶液A加入到溶液B中，搅拌直至形成沉淀，然后静置28h；(c) adding solution A to solution B, stirring until a precipitate is formed, and then standing for 28 hours;
(d)将产物离心并用乙醇洗涤三次，随后在70℃下干燥2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 70° C. for 2 h;
(2)复合双金属MOFs材料的制备：(2) Preparation of composite bimetallic MOFs materials:
(a)将得到的100mg Co3(BTC)2分散于10mL去离子水和10mL无水乙醇中，加入0.571mL浓度为10mg/ml的RuCl3·xH2O搅拌24h；(a) Disperse 100 mg of Co3 (BTC)2 obtained in 10 mL of deionized water and 10 mL of absolute ethanol, add 0.571 mL of RuCl3 xH2 O with a concentration of 10 mg/ml and stir for 24 h;
(d)将产物离心并用乙醇洗涤三次，随后在60℃下干燥2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 60° C. for 2 h;
(3)CoRu/C-4材料的制备：(3) Preparation of CoRu/C-4 material:
将(2)得到的产物置于管式炉里，在惰性气体氛围下以10℃/min的速率升温至600℃，保温4h，随后冷却至室温碳纳米复合材料CoRu/C-4。The product obtained in (2) was placed in a tube furnace, and the temperature was raised to 600°C at a rate of 10°C/min under an inert gas atmosphere, kept for 4h, and then cooled to room temperature Carbon nanocomposite CoRu/C-4.
实施例5Example 5
(1)Co3(BTC)2的制备：(1) Preparation of Co3 (BTC)2 :
(a)将0.1g Co(CH3COO)2·4H2O和1.2g聚乙烯吡咯烷酮(PVP)溶解于20mL去离子水和20mL无水乙醇混合溶液中，搅拌均匀，得到钴离子([Co2+])浓度为0.125mmol/mL的溶液A；(a) Dissolve 0.1g Co(CH3 COO)2 4H2 O and 1.2g polyvinylpyrrolidone (PVP) in a mixed solution of 20mL deionized water and 20mL absolute ethanol, and stir evenly to obtain cobalt ions ([Co2+ ]) solution A whose concentration is 0.125mmol/mL;
(b)将0.2g H3BTC加入到20mL去离子水和20mL无水乙醇混合溶液中，搅拌均匀，得到H3BTC的浓度为0.25mmol/mL的溶液B；(b) Add 0.2g of H3 BTC into a mixed solution of 20 mL of deionized water and 20 mL of absolute ethanol, and stir evenly to obtain a solution B with a concentration of H3 BTC of 0.25 mmol/mL;
(c)将溶液A加入到溶液B中，搅拌直至形成沉淀，然后静置20h；(c) adding solution A to solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d)将产物离心并用乙醇洗涤三次，随后在65℃下干燥2.5h；(d) The product was centrifuged and washed three times with ethanol, then dried at 65° C. for 2.5 h;
(2)复合双金属MOFs材料的制备：(2) Preparation of composite bimetallic MOFs materials:
(a)将得到的100mg Co3(BTC)2分散于5mL去离子水和5mL无水乙醇中，加入0.571mL浓度为10mg/ml的RuCl3·xH2O搅拌4h；(a) Disperse 100 mg of Co3 (BTC)2 obtained in 5 mL of deionized water and 5 mL of absolute ethanol, add 0.571 mL of RuCl3 xH2 O with a concentration of 10 mg/ml and stir for 4 h;
(d)将产物离心并用乙醇洗涤三次，随后在55℃下干燥3h；(d) The product was centrifuged and washed three times with ethanol, then dried at 55° C. for 3 h;
(3)CoRu/C-5材料的制备：(3) Preparation of CoRu/C-5 material:
将(2)得到的产物置于管式炉里，在惰性气体氛围下以18℃/min的速率升温至550℃，保温1h，随后冷却至室温碳纳米复合材料CoRu/C-5。The product obtained in (2) was placed in a tube furnace, and the temperature was raised to 550°C at a rate of 18°C/min under an inert gas atmosphere, kept for 1h, and then cooled to room temperature Carbon nanocomposite CoRu/C-5.
实施例6Example 6
(1)Co3(BTC)2的制备：(1) Preparation of Co3 (BTC)2 :
(a)将0.1g Co(CH3COO)2·4H2O和0.6g聚乙烯吡咯烷酮(PVP)溶解于20mL去离子水和20mL无水乙醇混合溶液中，搅拌均匀，得到钴离子([Co2+])浓度为0.125mmol/mL的溶液A；(a) Dissolve 0.1g Co(CH3 COO)2 4H2 O and 0.6g polyvinylpyrrolidone (PVP) in a mixed solution of 20mL deionized water and 20mL absolute ethanol, and stir evenly to obtain cobalt ions ([Co2+ ]) concentration is the solution A of 0.125mmol/mL;
(b)将0.2g H3BTC加入到20mL去离子水和10mL无水乙醇混合溶液中，搅拌均匀，得到H3BTC的浓度为0.25mmol/mL的溶液B；(b) Add 0.2g of H3 BTC into a mixed solution of 20 mL of deionized water and 10 mL of absolute ethanol, and stir evenly to obtain a solution B with a concentration of H3 BTC of 0.25 mmol/mL;
(c)将溶液A加入到溶液B中，搅拌直至形成沉淀，然后静置20h；(c) adding solution A to solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d)将产物离心并用乙醇洗涤三次，随后在70℃下干燥1.2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 70° C. for 1.2 h;
(2)复合双金属MOFs材料的制备：(2) Preparation of composite bimetallic MOFs materials:
(a)将得到的100mg Co3(BTC)2分散于5mL去离子水和5mL无水乙醇中，加入0.571mL浓度为10mg/ml的RuCl3·xH2O搅拌24h；(a) Disperse 100 mg of Co3 (BTC)2 obtained in 5 mL of deionized water and 5 mL of absolute ethanol, add 0.571 mL of RuCl3 xH2 O with a concentration of 10 mg/ml and stir for 24 h;
(d)将产物离心并用乙醇洗涤三次，随后在60℃下干燥2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 60° C. for 2 h;
(3)CoRu/C-6材料的制备：(3) Preparation of CoRu/C-6 material:
将(2)得到的产物置于管式炉里，在惰性气体氛围下以12℃/min的速率升温至600℃，保温5h，随后冷却至室温碳纳米复合材料CoRu/C-6。The product obtained in (2) was placed in a tube furnace, and the temperature was raised to 600°C at a rate of 12°C/min under an inert gas atmosphere, kept for 5h, and then cooled to room temperature Carbon nanocomposite CoRu/C-6.
实施例7Example 7
(1)Co3(BTC)2的制备：(1) Preparation of Co3 (BTC)2 :
(a)将0.1g Co(CH3COO)2·4H2O和0.6g聚乙烯吡咯烷酮(PVP)溶解于20mL去离子水和20mL无水乙醇混合溶液中，搅拌均匀，得到钴离子([Co2+])浓度为0.125mmol/mL的溶液A；(a) Dissolve 0.1g Co(CH3 COO)2 4H2 O and 0.6g polyvinylpyrrolidone (PVP) in a mixed solution of 20mL deionized water and 20mL absolute ethanol, and stir evenly to obtain cobalt ions ([Co2+ ]) concentration is the solution A of 0.125mmol/mL;
(b)将0.2g H3BTC加入到20mL去离子水和10mL无水乙醇混合溶液中，搅拌均匀，得到H3BTC的浓度为0.25mmol/mL的溶液B；(b) Add 0.2g of H3 BTC into a mixed solution of 20 mL of deionized water and 10 mL of absolute ethanol, and stir evenly to obtain a solution B with a concentration of H3 BTC of 0.25 mmol/mL;
(c)将溶液A加入到溶液B中，搅拌直至形成沉淀，然后静置20h；(c) adding solution A to solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d)将产物离心并用乙醇洗涤三次，随后在60℃下干燥2.8h；(d) The product was centrifuged and washed three times with ethanol, then dried at 60° C. for 2.8 h;
(2)复合双金属MOFs材料的制备：(2) Preparation of composite bimetallic MOFs materials:
(a)将得到的100mg Co3(BTC)2分散于5mL去离子水和5mL无水乙醇中，加入0.571mL浓度为10mg/ml的RuCl3·xH2O搅拌14h；(a) Disperse 100 mg of Co3 (BTC)2 obtained in 5 mL of deionized water and 5 mL of absolute ethanol, add 0.571 mL of RuCl3 xH2 O with a concentration of 10 mg/ml and stir for 14 h;
(d)将产物离心并用乙醇洗涤三次，随后在58℃下干燥2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 58° C. for 2 h;
(3)CoRu/C-7材料的制备：(3) Preparation of CoRu/C-7 material:
将(2)得到的产物置于管式炉里，在惰性气体氛围下以18℃/min的速率升温至500℃，保温3h，随后冷却至室温碳纳米复合材料CoRu/C-7。The product obtained in (2) was placed in a tube furnace, and the temperature was raised to 500°C at a rate of 18°C/min under an inert gas atmosphere, kept for 3h, and then cooled to room temperature Carbon nanocomposite CoRu/C-7.
实施例8Example 8
(1)Co3(BTC)2的制备：(1) Preparation of Co3 (BTC)2 :
(a)将0.1g Co(CH3COO)2·4H2O和0.6g聚乙烯吡咯烷酮(PVP)溶解于10mL去离子水和10mL无水乙醇混合溶液中，搅拌均匀，得到钴离子([Co2+])浓度为0.25mmol/mL的溶液A；(a) Dissolve 0.1g Co(CH3 COO)2 ·4H2 O and 0.6g polyvinylpyrrolidone (PVP) in a mixed solution of 10mL deionized water and 10mL absolute ethanol, and stir evenly to obtain cobalt ions ([Co2+ ]) concentration is the solution A of 0.25mmol/mL;
(b)将0.2g H3BTC加入到20mL去离子水和10mL无水乙醇混合溶液中，搅拌均匀，得到H3BTC的浓度为0.25mmol/mL的溶液B；(b) Add 0.2g of H3 BTC into a mixed solution of 20 mL of deionized water and 10 mL of absolute ethanol, and stir evenly to obtain a solution B with a concentration of H3 BTC of 0.25 mmol/mL;
(c)将溶液A加入到溶液B中，搅拌直至形成沉淀，然后静置20h；(c) adding solution A to solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d)将产物离心并用乙醇洗涤三次，随后在60℃下干燥2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 60° C. for 2 h;
(2)复合双金属MOFs材料的制备：(2) Preparation of composite bimetallic MOFs materials:
(a)将得到的100mg Co3(BTC)2分散于5mL去离子水和10mL无水乙醇中，加入0.571mL浓度为10mg/ml的RuCl3·xH2O搅拌14h；(a) Disperse 100 mg of Co3 (BTC)2 obtained in 5 mL of deionized water and 10 mL of absolute ethanol, add 0.571 mL of RuCl3 xH2 O with a concentration of 10 mg/ml and stir for 14 h;
(d)将产物离心并用乙醇洗涤三次，随后在68℃下干燥2.2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 68° C. for 2.2 h;
(3)CoRu/C-8材料的制备：(3) Preparation of CoRu/C-8 material:
将(2)得到的产物置于管式炉里，在惰性气体氛围下以8℃/min的速率升温至550℃，保温4h，随后冷却至室温碳纳米复合材料CoRu/C-8。The product obtained in (2) was placed in a tube furnace, and the temperature was raised to 550°C at a rate of 8°C/min under an inert gas atmosphere, kept for 4h, and then cooled to room temperature Carbon nanocomposite CoRu/C-8.
实施例9Example 9
(1)Co3(BTC)2的制备：(1) Preparation of Co3 (BTC)2 :
(a)将0.1g Co(CH3COO)2·4H2O和0.6g聚乙烯吡咯烷酮(PVP)溶解于10mL去离子水和10mL无水乙醇混合溶液中，搅拌均匀，得到钴离子([Co2+])浓度为0.25mmol/mL的溶液A；(a) Dissolve 0.1g Co(CH3 COO)2 ·4H2 O and 0.6g polyvinylpyrrolidone (PVP) in a mixed solution of 10mL deionized water and 10mL absolute ethanol, and stir evenly to obtain cobalt ions ([Co2+ ]) concentration is the solution A of 0.25mmol/mL;
(b)将0.2g H3BTC加入到20mL去离子水和10mL无水乙醇混合溶液中，搅拌均匀，得到H3BTC的浓度为0.25mmol/mL的溶液B；(b) Add 0.2g of H3 BTC into a mixed solution of 20 mL of deionized water and 10 mL of absolute ethanol, and stir evenly to obtain a solution B with a concentration of H3 BTC of 0.25 mmol/mL;
(c)将溶液A加入到溶液B中，搅拌直至形成沉淀，然后静置20h；(c) adding solution A to solution B, stirring until a precipitate is formed, and then standing for 20 hours;
(d)将产物离心并用乙醇洗涤三次，随后在60℃下干燥2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 60° C. for 2 h;
(2)复合双金属MOFs材料的制备：(2) Preparation of composite bimetallic MOFs materials:
(a)将得到的100mg Co3(BTC)2分散于5mL去离子水和10mL无水乙醇中，加入0.571mL浓度为10mg/ml的RuCl3·xH2O搅拌14h；(a) Disperse 100 mg of Co3 (BTC)2 obtained in 5 mL of deionized water and 10 mL of absolute ethanol, add 0.571 mL of RuCl3 xH2 O with a concentration of 10 mg/ml and stir for 14 h;
(d)将产物离心并用乙醇洗涤三次，随后在60℃下干燥2h；(d) The product was centrifuged and washed three times with ethanol, then dried at 60° C. for 2 h;
(3)CoRu/C-9材料的制备：(3) Preparation of CoRu/C-9 material:
将(2)得到的产物置于管式炉里，在惰性气体氛围下以20℃/min的速率升温至500℃，保温5h，随后冷却至室温碳纳米复合材料CoRu/C-9。The product obtained in (2) was placed in a tube furnace, and the temperature was raised to 500°C at a rate of 20°C/min under an inert gas atmosphere, kept for 5h, and then cooled to room temperature Carbon nanocomposite CoRu/C-9.
上述具体实施方式用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明作出的任何修改和改变，都落入本发明的保护范围。The above specific embodiments are used to explain the present invention, rather than to limit the present invention. Within the spirit of the present invention and the protection scope of the claims, any modification and change made to the present invention will fall into the protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
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| CN201810525921.8ACN108754531B (en) | 2018-05-29 | 2018-05-29 | A kind of preparation method of bimetallic carbon nanocomposite electrocatalytic material containing Co and Ru |
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| CN201810525921.8ACN108754531B (en) | 2018-05-29 | 2018-05-29 | A kind of preparation method of bimetallic carbon nanocomposite electrocatalytic material containing Co and Ru |
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| CN201810525921.8AExpired - Fee RelatedCN108754531B (en) | 2018-05-29 | 2018-05-29 | A kind of preparation method of bimetallic carbon nanocomposite electrocatalytic material containing Co and Ru |
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