技术领域technical field
本发明属于环境保护与资源综合利用技术领域，具体涉及一种锡基复合催化剂及含该催化剂的阴极材料的制备方法。The invention belongs to the technical field of environmental protection and resource comprehensive utilization, and in particular relates to a tin-based composite catalyst and a preparation method of a cathode material containing the catalyst.
背景技术Background technique
二氧化碳是导致温室效应的重要原因之一，对二氧化碳进行转化利用，一方面可以减少温室气体的排放，另一方面可以减缓因化石燃料的大量使用而造成的资源枯竭，同时实现能量的再存储。对二氧化碳进行转化处理的方法很多，主要有生物法、辐射法、热化学法、(光)电化学法等，其中电化学还原二氧化碳法具有广泛的优势：1、电力驱动，动力来源广泛，可直接利用可再生电力或者电网废电作为电力来源；2、产物具有较高的选择性；3、操作条件温和，常温常压下即可发生反应；4、溶剂可作为质子来源，不需要通入H2等外加质子源；5、CO2可转换成为多种基础化工原料，产物可进行进一步利用，经济效益高。Carbon dioxide is one of the important causes of the greenhouse effect. The conversion and utilization of carbon dioxide can reduce greenhouse gas emissions on the one hand, slow down the depletion of resources caused by the extensive use of fossil fuels, and achieve energy restorage. There are many methods for converting carbon dioxide, mainly including biological method, radiation method, thermochemical method, (photo)electrochemical method, etc. Among them, the electrochemical reduction method of carbon dioxide has a wide range of advantages: 1. Electric drive, a wide range of power sources, can Directly use renewable electricity or power grid waste electricity as the power source; 2. The product has high selectivity; 3. The operating conditions are mild, and the reaction can occur under normal temperature and pressure; 4. The solvent can be used as a source of protons without feeding H2 and other external proton sources; 5. CO2 can be converted into a variety of basic chemical raw materials, and the products can be further utilized, with high economic benefits.
二氧化碳电化学还原其关键在于催化剂，催化剂可以直接影响反应的活性、稳定性及产物选择性。现有技术路线采用的多为金属或合金催化剂，具有活性低、稳定性差、易析氢、产物选择性差等缺点，制约了二氧化碳大规模资源化利用的发展。The key to the electrochemical reduction of carbon dioxide lies in the catalyst, which can directly affect the activity, stability and product selectivity of the reaction. Most of the existing technical routes use metal or alloy catalysts, which have disadvantages such as low activity, poor stability, easy hydrogen evolution, and poor product selectivity, which restrict the development of large-scale resource utilization of carbon dioxide.
发明内容Contents of the invention
本发明针对现有技术中的不足，其目的在于提供一种锡基复合催化剂及含该催化剂的阴极材料的制备方法。The present invention aims at the deficiencies in the prior art, and its purpose is to provide a tin-based composite catalyst and a method for preparing a cathode material containing the catalyst.
为了实现上述目的，本发明采取的技术方案如下：In order to achieve the above object, the technical scheme that the present invention takes is as follows:
一种锡基复合催化剂的制备方法，其特征在于，所述制备方法包括以下步骤：A kind of preparation method of tin-based composite catalyst, is characterized in that, described preparation method comprises the following steps:
(1)将碳纳米管加至体积比为1:x的乙醇与去离子水的混合液中，超声分散3h以上，得到溶液A；(1) adding carbon nanotubes to a mixed solution of ethanol and deionized water with a volume ratio of 1:x, and ultrasonically dispersing for more than 3 hours to obtain solution A;
所述x的取值范围为：0.1<x<100；The value range of x is: 0.1<x<100;
(2)将锡盐与柠檬酸盐混合后加到去离子水中形成混合溶液，混合溶液中的柠檬酸根过量使锡离子能够完全被络合；将混合溶液在室温下超声分散至其稳定，得到溶液B；(2) After mixing tin salt and citrate, add it to deionized water to form a mixed solution. The excess citrate in the mixed solution can completely complex the tin ions; the mixed solution is ultrasonically dispersed at room temperature until it is stable to obtain Solution B;
(3)将溶液A与溶液B混合，超声至碳纳米管分散均匀，得到溶液C；其中，溶液C中1g碳纳米管对应0.001-0.1mol金属锡离子；(3) Mix solution A with solution B, and ultrasonically disperse the carbon nanotubes evenly to obtain solution C; wherein, 1 g of carbon nanotubes in solution C corresponds to 0.001-0.1 mol of metal tin ions;
(4)在持续超声条件下，向溶液C中加入过量硼氢化盐粉末或硼氢化盐水溶液对锡离子进行还原，至溶液中无气泡产生，得到溶液D；或向溶液C中加入过量强碱后，将其置于聚四氟乙烯容器中，在100℃-180℃下加热5小时以上，得到溶液E；(4) Under continuous ultrasonic conditions, add excess borohydride salt powder or borohydride salt solution to solution C to reduce tin ions until no bubbles are generated in the solution to obtain solution D; or add excess strong base to solution C Finally, place it in a polytetrafluoroethylene container and heat it at 100°C-180°C for more than 5 hours to obtain solution E;
(5)将溶液D或E用去离子水抽滤、清洗，获得的固体置于烘箱中于40℃-80℃干燥，所得的黑色粉末即为锡基复合催化剂。(5) The solution D or E was filtered and washed with deionized water, and the obtained solid was dried in an oven at 40°C-80°C, and the obtained black powder was the tin-based composite catalyst.
由所述溶液D获得的锡基复合催化剂为锡氧化物/锡/碳纳米管复合材料。The tin-based composite catalyst obtained from the solution D is a tin oxide/tin/carbon nanotube composite material.
由所述溶液E获得的锡基复合催化剂为二氧化锡/碳纳米管复合材料。The tin-based composite catalyst obtained from the solution E is a tin dioxide/carbon nanotube composite material.
步骤(1)中所述的碳纳米管为单壁、双壁或多壁碳纳米管；通过化学气相沉积法、石墨电弧法或模板法合成。The carbon nanotubes described in step (1) are single-wall, double-wall or multi-wall carbon nanotubes; they are synthesized by chemical vapor deposition, graphite arc method or template method.
步骤(1)中所述的碳纳米管表面经酸洗或氧化处理后，其表面接枝有羧基或羟基亲水集团，在去离子水中的分散度提高。After the surface of the carbon nanotubes described in step (1) is pickled or oxidized, the surface is grafted with carboxyl or hydroxyl hydrophilic groups, and the dispersion degree in deionized water is improved.
步骤(2)所述的锡盐为二价锡盐或四价锡盐；所述的柠檬酸盐为柠檬酸钠或柠檬酸钾。The tin salt described in step (2) is divalent tin salt or tetravalent tin salt; and the described citrate is sodium citrate or potassium citrate.
步骤(4)中所述的硼氢化盐为NaBH4或KBH4；强碱为NaOH或KOH；BH4-或OH-与锡离子的摩尔比大于10。The borohydride salt described in step (4) is NaBH4 or KBH4 ; the strong base is NaOH or KOH; the molar ratio of BH4- or OH- to tin ions is greater than 10.
一种含锡基复合催化剂的阴极材料的制备方法，所述制备方法包含以下步骤：A preparation method of a cathode material containing a tin-based composite catalyst, the preparation method comprising the following steps:
(1)将锡基复合催化剂、导电性碳材料和粘结剂按照8:1:0.5-4的比例在易挥发醇中进行混合，搅拌至易挥发醇全部挥发，形成粘稠固体；(1) Mix the tin-based composite catalyst, the conductive carbon material and the binder in the volatile alcohol according to the ratio of 8:1:0.5-4, and stir until the volatile alcohol is all volatilized to form a viscous solid;
所述的易挥发醇为乙醇或异丙醇；Described volatile alcohol is ethanol or Virahol;
(2)将粘稠固体通过压制法压制于150-400目的钢丝网上，在室温下晾干即可。(2) The viscous solid is pressed onto a 150-400 mesh steel wire mesh by a pressing method, and then dried at room temperature.
步骤(1)中所述的导电性碳为石墨或导电炭黑；粘结剂为萘酚溶液或聚四氟乙烯溶液。The conductive carbon described in step (1) is graphite or conductive carbon black; the binder is naphthol solution or polytetrafluoroethylene solution.
步骤(2)中所述的压制为单面压制或双面压制，通过辊压机、压面条机或压片机实现。The pressing described in step (2) is single-sided pressing or double-sided pressing, and is realized by a roller press, noodle press or tablet press.
所述双面压制的另一侧物质为等量的粘稠固体或等量的导电性物质；The substance on the other side of the double-sided pressing is an equal amount of viscous solid or an equal amount of conductive substance;
所述的导电物质为石墨、导电炭黑、碳纳米管或石墨烯。The conductive substance is graphite, conductive carbon black, carbon nanotube or graphene.
锡基复合催化剂或含锡基复合催化剂的阴极材料在CO2电化学转化中的应用。Application of tin-based composite catalysts or cathode materials containing tin-based composite catalysts inCO2 electrochemical conversion.
所述CO2电化学转化法的拉第效率大于60％。The Raday efficiency of theCO2 electrochemical conversion method is greater than 60%.
本发明的有益效果为：使用该发明制备的锡基复合催化剂及阴极材料，可有效对CO2进行电化学转化，催化反应的法拉第效率可超过60％，反应可得到较高活性、较好稳定性及相对单一的CO、甲酸等小分子有机物产物，所得阴极材料催化寿命长，具有较好的稳定性。The beneficial effects of the present invention are: using the tin-based composite catalyst and cathode material prepared by the present invention can effectively electrochemically convertCO2 , the Faraday efficiency of the catalytic reaction can exceed 60%, and the reaction can obtain higher activity and better stability properties and relatively single small molecule organic products such as CO and formic acid, the obtained cathode material has a long catalytic life and good stability.
具体实施方式Detailed ways
本发明提供了一种锡基复合催化剂及含该催化剂的阴极材料的制备方法，下面结合具体实施方式对本发明做进一步说明，但本发明的保护范围并不限于此。The present invention provides a tin-based composite catalyst and a method for preparing a cathode material containing the catalyst. The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.
实施例1：锡基复合催化剂(锡氧化物/锡/碳纳米管复合材料)的制备。Example 1: Preparation of tin-based composite catalyst (tin oxide/tin/carbon nanotube composite material).
将0.02mol SnCl2与0.05mol柠檬酸钠加入100mL去离子水中，超声至其完全溶解，制备得到0.2M的SnCl2-柠檬酸钠水溶液，即溶液A。Add 0.02 mol SnCl2 and 0.05 mol sodium citrate into 100 mL of deionized water, sonicate until they are completely dissolved, and prepare a 0.2 M SnCl2 -sodium citrate aqueous solution, namely solution A.
取0.1g碳纳米管，加入至25mL去离子水/25mL乙醇的混合溶液中，室温下超声3小时以上使碳纳米管分散均匀，获得溶液B。Take 0.1 g of carbon nanotubes, add them to a mixed solution of 25 mL of deionized water/25 mL of ethanol, and ultrasonically disperse the carbon nanotubes at room temperature for more than 3 hours to obtain solution B.
取10mL溶液A与50mL溶液B混合，在室温条件下超声1.5h以上，获得溶液C。在持续超声条件下，向溶液C中缓慢加入2.78g KBH4进行还原，还原过程至少保持2h，直至溶液中无气泡冒出，获得溶液D。Mix 10 mL of solution A with 50 mL of solution B, and sonicate at room temperature for more than 1.5 h to obtain solution C. Under continuous ultrasonic conditions, slowly add 2.78g KBH4 to solution C for reduction, and keep the reduction process for at least 2h until no bubbles emerge in the solution, and solution D is obtained.
将溶液D用去离子水抽滤清洗，获得的固体置于60℃烘箱中干燥，所得的黑色粉末即为锡基复合催化剂，此催化剂核心为金属锡，表面为一层自然形成的锡氧化物。The solution D was filtered and washed with deionized water, and the obtained solid was dried in an oven at 60°C. The obtained black powder was a tin-based composite catalyst. The core of the catalyst was metallic tin, and the surface was a layer of naturally formed tin oxide. .
实施例2：含锡基复合催化剂(锡氧化物/锡/碳纳米管复合材料)的阴极材料的制备及电化学还原CO2的实验。Example 2: Preparation of cathode material containing tin-based composite catalyst (tin oxide/tin/carbon nanotube composite material) and experiment of electrochemically reducing CO2 .
取80mg锡基复合催化剂(锡氧化物/锡/碳纳米管复合材料)，10mg C45炭黑，20mgPTFE乳液(60％含量)，加入适量乙醇，在称量瓶中搅拌至乙醇全部挥发，获得粘稠固体；将粘稠固体通过压面条机压制于300目钢丝网上，压制后形成的阴极材料上锡基复合催化剂的负载量为20mg/cm2。Get 80mg of tin-based composite catalyst (tin oxide/tin/carbon nanotube composite material), 10mg of C45 carbon black, 20mg of PTFE emulsion (60% content), add appropriate amount of ethanol, stir until ethanol is all volatilized in weighing bottle, obtain viscous Viscous solid: the viscous solid is pressed on a 300-mesh steel wire mesh by a pasta machine, and the loading capacity of the tin-based composite catalyst on the cathode material formed after pressing is 20 mg/cm2 .
在H型电解池中进行CO2的还原实验，反应体系为三电极，对电极为Pt丝电极，参比电极为饱和甘汞(SCE)，工作电极为上述阴极材料，阴极与对电极腔体之间通过Nafion质子交换膜隔开。反应体系为0.1M碳酸氢钾水溶液，反应过程中持续通入CO2气体。The reduction experiment ofCO2 was carried out in an H-type electrolytic cell, the reaction system was three electrodes, the counter electrode was a Pt wire electrode, the reference electrode was saturated calomel (SCE), the working electrode was the above-mentioned cathode material, the cathode and the counter electrode cavity separated by a Nafion proton exchange membrane. The reaction system is a 0.1M potassium bicarbonate aqueous solution, andCO gas is continuously introduced during the reaction.
反应前在N2饱和的0.1M KHCO3溶液中先进行30分钟、-2.0V vs SCE的预电解实验，以避免在CO2电化学还原过程中锡氧化物被还原。预电解后，在-0.6V～-2.0V区间内对体系进行线性伏安扫描，没有出现锡氧化物的还原峰。Before the reaction, a 30-min pre-electrolysis experiment at -2.0V vs SCE was performed inN2 -saturated 0.1MKHCO3 solution to avoid the reduction of tin oxide during the electrochemical reduction ofCO2 . After pre-electrolysis, linear voltammetry scanning was performed on the system in the range of -0.6V to -2.0V, and no reduction peak of tin oxide appeared.
CO2电化学还原反应的电压范围为-0.8V～-1.8V vs SCE，以0.2V为间隔，时间为1小时。实验发现，在1h的反应时间内，电解电流保持稳定，没有出现明显衰减。从-1.0V开始有甲酸产生，随着施加电压的降低(过电位的增加)，产生甲酸的量呈现增加的趋势，法拉第效率随着电压的增加先升高后降低，-1.4V时法拉第效率最高，约为65％。The voltage range of theCO2 electrochemical reduction reaction was -0.8V～-1.8V vs SCE, with 0.2V as the interval, and the time was 1 hour. The experiment found that within the reaction time of 1 h, the electrolysis current remained stable without significant attenuation. From -1.0V, formic acid is produced. As the applied voltage decreases (increase of overpotential), the amount of formic acid produced shows an increasing trend. The Faraday efficiency increases first and then decreases with the increase of voltage. The Faraday efficiency at -1.4V The highest, about 65%.
实施例3：锡基复合催化剂(二氧化锡/碳纳米管复合材料)的制备。Example 3: Preparation of tin-based composite catalyst (tin dioxide/carbon nanotube composite material).
将0.02mol SnCl2与0.05mol柠檬酸钠加入100mL去离子水中，超声至完全溶解，制备得到0.2M的SnCl2-柠檬酸钠水溶液，即溶液A。Add 0.02 mol SnCl2 and 0.05 mol sodium citrate into 100 mL of deionized water, sonicate until completely dissolved, and prepare a 0.2 M SnCl2 -sodium citrate aqueous solution, namely solution A.
取0.1g碳纳米管，加入至25mL去离子水/25mL乙醇的混合溶液中，室温下超声3小时以上使碳纳米管混合均匀，获得溶液B。Take 0.1 g of carbon nanotubes, add them to a mixed solution of 25 mL of deionized water/25 mL of ethanol, and sonicate at room temperature for more than 3 hours to mix the carbon nanotubes evenly, and obtain solution B.
取10mL溶液A与50mL溶液B混合，在室温条件下超声1.5h以上，获得溶液C。在持续超声条件下，向溶液C中加入0.02mol KOH，然后将其置于聚四氟乙烯容器中，在150℃下进行水热反应，反应时间为10h，获得溶液E。Mix 10 mL of solution A with 50 mL of solution B, and sonicate at room temperature for more than 1.5 h to obtain solution C. Under continuous ultrasonic conditions, 0.02mol KOH was added to solution C, and then it was placed in a polytetrafluoroethylene container for hydrothermal reaction at 150°C for 10 hours to obtain solution E.
将溶液E用去离子水抽滤清洗，获得的固体置于60℃烘箱中干燥，获得锡基复合催化剂，此催化剂为二氧化锡/碳纳米管复合材料。经电镜表征可知，该催化剂中1-3nm的二氧化锡纳米片自组装成30-40nm的纳米球，此纳米二氧化锡球沉积于单根碳纳米管纤维或多根碳纳米管组成的管束上。The solution E was filtered and washed with deionized water, and the obtained solid was dried in an oven at 60° C. to obtain a tin-based composite catalyst, which was a tin dioxide/carbon nanotube composite material. Electron microscope characterization shows that the 1-3nm tin dioxide nanosheets in the catalyst self-assemble into 30-40nm nanospheres, and the nano-tin dioxide balls are deposited on a single carbon nanotube fiber or a tube bundle composed of multiple carbon nanotubes superior.
实施例4：含锡基复合催化剂(二氧化锡/碳纳米管复合材料)的阴极材料的制备及电化学还原CO2的实验。Example 4: Preparation of cathode material containing tin-based composite catalyst (tin dioxide/carbon nanotube composite material) and experiment of electrochemically reducing CO2 .
取80mg锡基复合催化剂(二氧化锡/碳纳米管复合材料)催化剂，10mg C45炭黑，20mg PTFE乳液(60％含量)，加入适量乙醇，在称量瓶中搅拌至乙醇挥发完全，获得粘稠固体。将粘稠固体通过压面条机压制于300目钢丝网上，压制后形成的阴极材料上锡基复合催化剂的负载量为20mg/cm2。Get 80mg tin-based composite catalyst (tin dioxide/carbon nanotube composite material) catalyst, 10mg C45 carbon black, 20mg PTFE emulsion (60% content), add appropriate amount of ethanol, stir until ethanol volatilizes completely in weighing bottle, obtain viscous Thick solid. The viscous solid was pressed onto a 300-mesh steel wire mesh by a pasta machine, and the loading amount of the tin-based composite catalyst on the cathode material formed after pressing was 20 mg/cm2 .
在H型电解池中进行CO2的还原实验，反应体系为三电极，对电极为Pt丝电极，参比电极为饱和甘汞(SCE)，工作电极为上述阴极材料，阴极与对电极腔体之间通过Nafion质子交换膜隔开。反应体系为0.1M碳酸氢钾水溶液，反应过程中持续通入CO2气体。The reduction experiment ofCO2 was carried out in an H-type electrolytic cell, the reaction system was three electrodes, the counter electrode was a Pt wire electrode, the reference electrode was saturated calomel (SCE), the working electrode was the above-mentioned cathode material, the cathode and the counter electrode cavity separated by a Nafion proton exchange membrane. The reaction system is a 0.1M potassium bicarbonate aqueous solution, andCO gas is continuously introduced during the reaction.
反应前在N2饱和的0.1M KHCO3溶液中先进行30分钟、-2.0V vs SCE的预电解实验，以避免在CO2电化学还原过程中锡氧化物被还原。预电解后，在-0.6V～-2.0V区间内对体系进行线性伏安扫描，没有出现二氧化锡的还原峰。CO2电化学还原反应的电压范围为-0.8V～-1.8V vs SCE，以0.2V为间隔，时间为1小时。实验发现，在1h的反应时间内，电解电流保持稳定，没有出现明显衰减。从-1.0V开始有甲酸产生，随着施加电压的降低(过电位的增加)，产生甲酸的量呈现增加的趋势，法拉第效率随着电压的增加先升高后降低，-1.4V时法拉第效率最高，约为40％。Before the reaction, a 30-min pre-electrolysis experiment at -2.0V vs SCE was performed inN2 -saturated 0.1MKHCO3 solution to avoid the reduction of tin oxide during the electrochemical reduction ofCO2 . After pre-electrolysis, linear voltammetry scanning was performed on the system in the range of -0.6V to -2.0V, and no reduction peak of tin dioxide appeared. The voltage range of theCO2 electrochemical reduction reaction was -0.8V～-1.8V vs SCE, with 0.2V as the interval, and the time was 1 hour. The experiment found that within the reaction time of 1 h, the electrolysis current remained stable without significant attenuation. From -1.0V, formic acid is produced. As the applied voltage decreases (increase of overpotential), the amount of formic acid produced shows an increasing trend. The Faraday efficiency increases first and then decreases with the increase of voltage. The Faraday efficiency at -1.4V Highest, about 40%.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510958892.0ACN105435771B (en) | 2015-12-18 | 2015-12-18 | A kind of preparation method of tinbase composite catalyst and the cathode material containing the catalyst |
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| CN201510958892.0ACN105435771B (en) | 2015-12-18 | 2015-12-18 | A kind of preparation method of tinbase composite catalyst and the cathode material containing the catalyst |
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| CN105435771Btrue CN105435771B (en) | 2018-04-17 |
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| CN201510958892.0AActiveCN105435771B (en) | 2015-12-18 | 2015-12-18 | A kind of preparation method of tinbase composite catalyst and the cathode material containing the catalyst |
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|---|---|
| CN (1) | CN105435771B (en) |
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| CN108441878A (en)* | 2018-03-01 | 2018-08-24 | 浙江大学 | A kind of electrochemically reducing carbon dioxide reaction nanometer tin-based catalyst and the preparation method and application thereof |
| CN108889291B (en)* | 2018-06-13 | 2020-10-23 | 中国科学院化学研究所 | SnO2Modified fullerene composite material with micro-nano structure and preparation method and application thereof |
| CN112768650A (en)* | 2020-12-31 | 2021-05-07 | 上海今海新材料科技有限公司 | Sodium-ion battery negative electrode material and preparation method thereof |
| CN114836778A (en)* | 2022-03-16 | 2022-08-02 | 杭州师范大学 | TiO supported by PdCu alloy particles 2 Preparation method of metal nanosheet material electrocatalyst |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1418725A (en)* | 2002-12-12 | 2003-05-21 | 北方交通大学 | Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube |
| US20130029557A1 (en)* | 2010-03-31 | 2013-01-31 | Qi Cai | Method for making cathode slurry |
| CN103715436A (en)* | 2013-12-19 | 2014-04-09 | 东华大学 | Carbon dioxide electrochemical reduction catalyst as well as preparation method and application thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418725A (en)* | 2002-12-12 | 2003-05-21 | 北方交通大学 | Method for prepn. of electrode catalyst with function of anti-CD and contg. platinum and ruthenium series carried on carbon nanometer tube |
| US20130029557A1 (en)* | 2010-03-31 | 2013-01-31 | Qi Cai | Method for making cathode slurry |
| CN103715436A (en)* | 2013-12-19 | 2014-04-09 | 东华大学 | Carbon dioxide electrochemical reduction catalyst as well as preparation method and application thereof |
| Title |
|---|
| "SnO2/碳纳米管纳米复合材料的制备及表征";刘红梅;《长春工业大学学报（自然科学版）》;20090228;第30卷(第1期);第9-11页* |
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| CN105435771A (en) | 2016-03-30 |
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