技术领域technical field
本发明属于电化学催化剂领域，更具体地，涉及利用废塑料制备Fe-N-CNT催化剂的方法及产品。The invention belongs to the field of electrochemical catalysts, and more particularly, relates to a method and a product for preparing Fe-N-CNT catalysts by using waste plastics.
背景技术Background technique
自20世纪初塑料被发现以来，因其耐用、可塑、价廉等特点，被大量应用于许多行业。然而，因塑料大量使用造成了废塑料总量的快速增长，而废塑料难以处理对环境保护造成了严重的挑战。2017年全球累计产生83亿吨的废塑料，其中仅有30％左右的废塑料被回收，约30％的废塑料被填埋，剩下大量塑料制品被随意丢弃在自然环境中，如果不能及时处理废塑料的问题，不仅造成严重的环境污染，同时也造成了大量的资源浪费。Since the discovery of plastic in the early 20th century, it has been widely used in many industries because of its durability, plasticity, and low price. However, the rapid growth of the total amount of waste plastics caused by the large-scale use of plastics, and the intractability of waste plastics to deal with it has caused serious challenges to environmental protection. In 2017, a total of 8.3 billion tons of waste plastics were generated in the world, of which only about 30% of the waste plastics were recycled, about 30% of the waste plastics were landfilled, and a large number of plastic products were left in the natural environment. The problem of dealing with waste plastics not only causes serious environmental pollution, but also causes a lot of waste of resources.
而燃料电池(Fuel Cells，FC)是一种能够连续不断地将储存在燃料与氧化剂中的化学能等温地转化为电能的电化学发电装置。作为一种绿色高效的能源转化装置，FC被较普遍地认为是当今最具有潜力取代汽车传统内燃机动力源以及燃煤电厂火力发电方式的技术之一。目前，铂、钯等贵金属仍是用作燃料电池阴极ORR反应的优良电催化剂材料，但却存在着制备成本高、资源稀缺匮乏和耐久性差等缺点。因此，想要实现燃料电池大规模的产业化，必然需要在新型高效的非贵金属ORR催化剂应用技术上取得实质性突破。A fuel cell (FC) is an electrochemical power generation device that can continuously convert chemical energy stored in fuel and oxidant into electrical energy isothermally. As a green and efficient energy conversion device, FC is generally regarded as one of the technologies with the most potential to replace the traditional internal combustion engine power source of automobiles and the thermal power generation method of coal-fired power plants. At present, noble metals such as platinum and palladium are still excellent electrocatalyst materials for the ORR reaction of fuel cell cathodes, but they have disadvantages such as high preparation cost, scarcity of resources, and poor durability. Therefore, in order to realize the large-scale industrialization of fuel cells, it is necessary to make substantial breakthroughs in the application technology of new and efficient non-precious metal ORR catalysts.
近年来，金属-氮-碳类(M-N-C，M表示过渡金属元素)复合材料催化剂被学界认为是最有希望的贵金属催化剂替代品并得到广泛关注。传统的金属-氮-碳类催化剂的制备通常是将金属、氮、碳三种前驱体混合物高温煅烧，之后酸洗得到催化剂。美国阿拉莫斯实验的Zelenay课题组设计的一种典型制备方法如下：在4℃下将苯胺与金属盐混合，聚合生成聚苯胺，之后加入高比表面积的科琴黑为碳载体，将混合物高温热解，酸洗得到Fe-N-C或Co-N-C催化剂。可见目前制备过渡金属-氮-碳类催化剂的方法，存在过程复杂、反应条件较苛刻等问题，特别是前驱体中必须使用碳载体，极大的增加了催化剂制备的成本。In recent years, metal-nitrogen-carbon (M-N-C, M represents transition metal element) composite catalysts have been regarded as the most promising substitutes for noble metal catalysts by the academic community and have received extensive attention. The preparation of traditional metal-nitrogen-carbon catalysts is usually by calcining the three precursor mixtures of metal, nitrogen and carbon at high temperature, and then pickling to obtain the catalyst. A typical preparation method designed by Zelenay's research group in the Alamos experiment in the United States is as follows: aniline is mixed with metal salts at 4 °C, polymerized to form polyaniline, and then Ketjen black with high specific surface area is added as a carbon support, and the mixture is heated to high temperature. Pyrolysis, pickling to obtain Fe-N-C or Co-N-C catalyst. It can be seen that the current method for preparing transition metal-nitrogen-carbon catalysts has problems such as complicated process and harsh reaction conditions, especially the carbon support must be used in the precursor, which greatly increases the cost of catalyst preparation.
发明内容SUMMARY OF THE INVENTION
针对现有技术的上述缺点和/或改进需求，本发明提供了一种利用废塑料制备Fe-N-CNT催化剂的方法及产品，其中通过废塑料热解气在铁基催化剂表面沉积形成碳纳米管，并与含氮化合物充分混合制备Fe-N-CNT催化剂，相应的能够提高制得催化剂的性能，并减少废塑料带来的环境污染，因而尤其适用于制备氧还原反应催化剂之类的应用场合。In view of the above shortcomings and/or improvement needs of the prior art, the present invention provides a method and product for preparing Fe-N-CNT catalysts from waste plastics, wherein carbon nanometers are formed by depositing waste plastics pyrolysis gas on the surface of the iron-based catalyst. It can improve the performance of the prepared catalyst and reduce the environmental pollution caused by waste plastics, so it is especially suitable for applications such as the preparation of oxygen reduction reaction catalysts. occasion.
为实现上述目的，按照本发明的一个方面，提出了一种利用废塑料制备Fe-N-CNT催化剂的方法，该方法包括如下步骤：In order to achieve the above object, according to one aspect of the present invention, a method for preparing Fe-N-CNT catalyst by utilizing waste plastics is proposed, and the method comprises the following steps:
(a)将废塑料粉末和铁基催化剂分别置于第一加热区和第二加热区中，在惰性气氛中加热一段时间，使废塑料热解过程中产生的热解气在铁基催化剂表面沉积形成碳纳米管；(a) Put the waste plastic powder and the iron-based catalyst in the first heating zone and the second heating zone, respectively, and heat them in an inert atmosphere for a period of time, so that the pyrolysis gas generated during the pyrolysis of the waste plastic can be deposited on the surface of the iron-based catalyst. deposition to form carbon nanotubes;
(b)将所述碳纳米管酸洗后获得纯化碳纳米管，然后将该纯化碳纳米管与含氮化合物混合后充分研磨得到固体混合物；(b) acid-washing the carbon nanotubes to obtain purified carbon nanotubes, then mixing the purified carbon nanotubes with a nitrogen-containing compound and fully grinding to obtain a solid mixture;
(c)将所述固体混合物在惰性气氛下加热进行二次热解，冷却至室温后制得所述Fe-N-CNT催化剂。(c) heating the solid mixture under an inert atmosphere for secondary pyrolysis, and cooling to room temperature to obtain the Fe-N-CNT catalyst.
作为进一步优选地，所述步骤(a)中采用液氮粉碎机将废塑料进行机械粉碎，所述废塑料粉末的粒径为0.5mm～1mm。As a further preference, in the step (a), a liquid nitrogen pulverizer is used to mechanically pulverize the waste plastic, and the particle size of the waste plastic powder is 0.5 mm to 1 mm.
作为进一步优选地，所述步骤(a)中废塑料粉末和铁基催化的质量比为5:1～1:5。As a further preference, in the step (a), the mass ratio of the waste plastic powder and the iron-based catalyst is 5:1 to 1:5.
作为进一步优选地，所述步骤(a)中加热过程的升温程序为：将第二加热区以10℃/min～20℃/min的升温速率加热至750℃～900℃，升至目标温度后保温并将第一加热区以5℃/min～10℃/min的升温速率加热至500℃～600℃，然后保温5min～10min。As a further preference, the heating procedure of the heating process in the step (a) is as follows: the second heating zone is heated to 750°C to 900°C at a heating rate of 10°C/min to 20°C/min, and after rising to the target temperature Keep the temperature and heat the first heating zone to 500°C to 600°C at a heating rate of 5°C/min to 10°C/min, and then keep the temperature for 5 minutes to 10 minutes.
作为进一步优选地，所述步骤(a)和步骤(c)中惰性气氛优选为氮气或氩气，惰性气体的流量为50mL/min～100mL/min。As a further preference, in the steps (a) and (c), the inert atmosphere is preferably nitrogen or argon, and the flow rate of the inert gas is 50 mL/min˜100 mL/min.
作为进一步优选地，所述步骤(b)中酸洗的过程为：将所述碳纳米管置于浓度为30％～50％的浓硝酸中，在80℃～100℃下以600rpm～1000rpm的转速搅拌4h～6h，然后过滤获得固体产物并水洗10次～20次，最后在100℃～105℃的温度下干燥12h～24h获得纯化碳纳米管。As a further preference, the process of pickling in the step (b) is as follows: placing the carbon nanotubes in concentrated nitric acid with a concentration of 30% to 50%, at 80°C to 100°C at a temperature of 600rpm to 1000rpm Stir for 4 h to 6 h at a rotating speed, then filter to obtain a solid product and wash it with water for 10 to 20 times, and finally dry it at a temperature of 100 to 105 ° C for 12 h to 24 h to obtain purified carbon nanotubes.
作为进一步优选地，所述步骤(b)中含氮化合物为三聚氰胺或双氰胺。As a further preference, the nitrogen-containing compound in the step (b) is melamine or dicyandiamide.
作为进一步优选地，所述步骤(b)中纯化碳纳米管与含氮化合物以1:1～1:5的质量比混合，研磨时间为30min～60min。As a further preference, in the step (b), the purified carbon nanotubes are mixed with the nitrogen-containing compound in a mass ratio of 1:1 to 1:5, and the grinding time is 30 min to 60 min.
作为进一步优选地，所述步骤(c)中二次热解过程为：以5℃/min～10℃/min的升温速率加热至750℃～900℃，然后保温0.5h～2h。As a further preference, the secondary pyrolysis process in the step (c) is as follows: heating to 750°C to 900°C at a heating rate of 5°C/min to 10°C/min, and then maintaining the temperature for 0.5h to 2h.
按照本发明的另一方面，提供了一种利用上述方法制备的Fe-N-CNT催化剂。According to another aspect of the present invention, there is provided an Fe-N-CNT catalyst prepared by the above method.
总体而言，通过本发明所构思的以上技术方案与现有技术相比，主要具备以下的技术优点：In general, compared with the prior art, the above technical solutions conceived by the present invention mainly have the following technical advantages:
1.本发明不使用碳材料作为前驱体，采用废塑料作为原料，通过化学气相沉积法，将废塑料的热解气在铁催化剂表面沉积形成碳纳米管，该过程可以得到内含铁纳米颗粒的碳纳米管，形成的碳化铁是一种良好的催化活性位点，并且碳纳米管包覆铁可避免团聚、失活；1. The present invention does not use carbon materials as precursors, adopts waste plastics as raw materials, and through chemical vapor deposition method, the pyrolysis gas of waste plastics is deposited on the surface of iron catalyst to form carbon nanotubes, and this process can obtain iron-containing nanoparticles. The formed iron carbide is a good catalytically active site, and the carbon nanotube-coated iron can avoid agglomeration and deactivation;
2.同时采用本专利提供的方法一方面可以避免废塑料造成的环境污染，另一反面也达到了废塑料资源化利用的目的，极大地降低了催化剂的制备成本，并且因操作简单、工艺参数易于控制、产率较高等优势，适合进行大规模生产；2. At the same time, the method provided by this patent can avoid environmental pollution caused by waste plastics on the one hand, and achieve the purpose of resource utilization of waste plastics on the other hand, which greatly reduces the preparation cost of the catalyst. Easy to control, high yield and other advantages, suitable for large-scale production;
3.此外，本发明利用浓硝酸对制得的碳纳米管进行酸洗，不仅可以去除铁催化剂等杂质，并且能够利用浓硝酸的强氧化性引入大量含氧官能团，为二次掺氮提供有利条件，同时选取三聚氰胺或双氰胺等氮含量较高，热解过程中基本不引入碳的物质作为氮源进行二次热解，最终制得具有良好催化活性的Fe-N-CNT催化剂；3. In addition, the present invention utilizes concentrated nitric acid to pickle the obtained carbon nanotubes, which can not only remove impurities such as iron catalysts, but also can utilize the strong oxidizing property of concentrated nitric acid to introduce a large number of oxygen-containing functional groups, providing favorable conditions for secondary nitrogen doping. At the same time, materials with high nitrogen content such as melamine or dicyandiamide, which basically do not introduce carbon in the pyrolysis process, are selected as nitrogen sources for secondary pyrolysis, and finally Fe-N-CNT catalysts with good catalytic activity are obtained;
4.尤其是，本发明通过控制两次热解过程的各反应条件保证制得催化剂具有良好的催化性能，如保证惰性气体的流速在50mL/min～100mL/min的范围内，避免了过高的气流导致热解气停留时间过少，降低碳纳米管的长度及产量；同时控制第一次热解过程控制第二加热区以10℃/min～20℃/min的升温速率加热至750℃～900℃，升至目标温度后保温并将第一加热区以5℃/min～10℃/min的升温速率加热至500℃～600℃，然后保温5min～10min，从而避免温度过低导致无定型碳的大量生成，导致制成的碳纳米管过于纤细短小，同时还要避免温度过高时由于团聚作用导致碳纳米管的刚性差而产生弯曲；此外二次热解时在5℃/min～10℃/min的升温速率下加热到750℃～900℃，保证含氮化合物热解的条件下减少含氧官能团的消耗，通过控制反应过程中的各反应条件最终生成的Fe-N-CNT催化剂在碱性电解液中表现出良好的ORR催化性能，并且接近商品化Pd/C催化剂，可用于燃料电池、金属-空气电池等不同领域。4. In particular, the present invention ensures that the catalyst has good catalytic performance by controlling the reaction conditions of the two pyrolysis processes, such as ensuring that the flow rate of the inert gas is in the range of 50mL/min～100mL/min, avoiding excessively high. At the same time, the first pyrolysis process is controlled and the second heating zone is heated to 750°C at a heating rate of 10°C/min to 20°C/min. ～900℃, keep warm after rising to the target temperature, and heat the first heating zone to 500℃～600℃ at a heating rate of 5℃/min～10℃/min, and then keep the temperature for 5min～10min, so as to avoid the temperature being too low and causing no A large amount of shaped carbon is generated, resulting in too thin and short carbon nanotubes. At the same time, it is necessary to avoid bending due to poor rigidity of carbon nanotubes due to agglomeration when the temperature is too high; Heating to 750°C to 900°C at a heating rate of ~10°C/min to ensure that the consumption of oxygen-containing functional groups is reduced under the conditions of pyrolysis of nitrogen-containing compounds, and Fe-N-CNTs are finally generated by controlling the reaction conditions in the reaction process. The catalyst exhibits good ORR catalytic performance in alkaline electrolyte and is close to commercial Pd/C catalysts, which can be used in different fields such as fuel cells and metal-air batteries.
附图说明Description of drawings
图1是本发明提供的利用废塑料制备Fe-N-CNT催化剂的工艺流程图；Fig. 1 is the process flow diagram of utilizing waste plastic to prepare Fe-N-CNT catalyst provided by the present invention;
图2是本发明实施例3中制备的碳纳米管的SEM图；Fig. 2 is the SEM image of carbon nanotubes prepared in Example 3 of the present invention;
图3是本发明实施例3中Fe-N-CNT催化剂-3的SEM图；3 is a SEM image of Fe-N-CNT catalyst-3 in Example 3 of the present invention;
图4是本发明实施例1～4中制得的Fe-N-CNT催化剂的XRD图；Fig. 4 is the XRD pattern of Fe-N-CNT catalysts prepared in Examples 1-4 of the present invention;
图5是本发明实施例1～4中制得的Fe-N-CNT催化剂的循环伏安曲线(CV)图；5 is a cyclic voltammetry (CV) diagram of Fe-N-CNT catalysts prepared in Examples 1 to 4 of the present invention;
图6是本发明实施例1～4中制得的Fe-N-CNT催化剂和商业Pd/C催化剂的线性扫描伏安曲线(LSV)图。6 is a linear sweep voltammetry (LSV) graph of Fe-N-CNT catalysts and commercial Pd/C catalysts prepared in Examples 1 to 4 of the present invention.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
按照本发明的一方面，如图1所示，提出了一种利用废塑料制备Fe-N-CNT催化剂的方法，该方法包括如下步骤：According to an aspect of the present invention, as shown in FIG. 1, a method for preparing Fe-N-CNT catalyst from waste plastics is proposed, and the method comprises the following steps:
(a)将废塑料粉末和铁基催化剂分别置于第一加热区和第二加热区中，如分别置于两段加热立式热解炉的第一加热区(上温区)和第二加热区(下温区)中，保持惰性气氛，将第二加热区以10℃/min～20℃/min的升温速率加热至750℃～900℃，升至目标温度后保温并将第一加热区以5℃/min～10℃/min的升温速率加热至500℃～600℃，然后保温5min～10min，使废塑料热解过程中产生的热解气在铁基催化剂表面沉积形成碳纳米管；(a) The waste plastic powder and the iron-based catalyst are placed in the first heating zone and the second heating zone, respectively, such as the first heating zone (upper temperature zone) and the second heating zone of the two-stage heating vertical pyrolysis furnace, respectively. In the heating zone (lower temperature zone), maintaining an inert atmosphere, the second heating zone is heated to 750°C to 900°C at a heating rate of 10°C/min to 20°C/min, and the temperature is raised to the target temperature. The zone is heated to 500℃～600℃ at a heating rate of 5℃/min～10℃/min, and then kept for 5min～10min, so that the pyrolysis gas generated during the pyrolysis of waste plastics is deposited on the surface of the iron-based catalyst to form carbon nanotubes ;
(b)将碳纳米管置于浓度为30％～50％的浓硝酸中进行钝化，在80℃～100℃下以600rpm～1000rpm的转速搅拌4h～6h，然后过滤获得固体产物并水洗10次～20次，最后在100℃～105℃的温度下干燥12h～24h获得纯化碳纳米管，将该纯化碳纳米管和含氮化合物以1:1～1:5的质量比混合，充分研磨30min～60min得到固体混合物；(b) Put the carbon nanotubes in concentrated nitric acid with a concentration of 30% to 50% for passivation, stir at a speed of 600rpm to 1000rpm at 80°C to 100°C for 4h to 6h, and then filter to obtain a solid product and wash it with water for 10 hours. 20 times to 20 times, and finally dried at a temperature of 100°C to 105°C for 12h to 24h to obtain purified carbon nanotubes. The purified carbon nanotubes and nitrogen-containing compounds are mixed in a mass ratio of 1:1 to 1:5, and fully ground. 30min～60min to obtain solid mixture;
(c)将制得的固体混合物在惰性气氛下以5℃/min～10℃/min的升温速率加热至750℃～900℃，然后保温0.5h～2h进行二次热解，冷却至室温后制得所述Fe-N-CNT催化剂。(c) The obtained solid mixture is heated to 750°C to 900°C at a heating rate of 5°C/min to 10°C/min under an inert atmosphere, then kept for 0.5h to 2h for secondary pyrolysis, and cooled to room temperature. The Fe-N-CNT catalyst was prepared.
进一步，步骤(a)中采用液氮粉碎机将废塑料进行机械粉碎，从而避免废塑料颗粒过热发生软化聚合，废塑料粉末的粒径优选为0.5mm～1mm。Further, in step (a), a liquid nitrogen pulverizer is used to mechanically pulverize the waste plastics, so as to avoid overheating and softening and polymerization of the waste plastic particles, and the particle size of the waste plastic powder is preferably 0.5 mm to 1 mm.
进一步，步骤(a)中废塑料粉末和铁基催化的质量比优选为5:1～1:5。Further, in step (a), the mass ratio of waste plastic powder and iron-based catalyst is preferably 5:1 to 1:5.
进一步，步骤(a)和步骤(c)中惰性气氛优选为氮气或氩气，惰性气体的流量优选为50mL/min～100mL/min。Further, in step (a) and step (c), the inert atmosphere is preferably nitrogen or argon, and the flow rate of the inert gas is preferably 50 mL/min˜100 mL/min.
进一步，所述含氮化合物优选为三聚氰胺或双氰胺等氮含量高，热解过程基本不引入碳的物质。Further, the nitrogen-containing compound is preferably a substance with a high nitrogen content such as melamine or dicyandiamide, and substantially no carbon is introduced into the pyrolysis process.
按照本发明的另一方面，提出了一种利用上述方法制备的Fe-N-CNT催化剂。According to another aspect of the present invention, a Fe-N-CNT catalyst prepared by the above method is proposed.
如图2～图6所示，下面根据具体的利用废塑料制备Fe-N-CNT催化剂的方法及产品，对本发明作进一步说明。As shown in FIG. 2 to FIG. 6 , the present invention will be further described below according to the specific method and product for preparing Fe-N-CNT catalyst from waste plastics.
实施例1Example 1
(a)将废塑料杯、塑料盒等废塑料经过液氮粉碎机进行机械粉碎，过18目和35目的不锈钢筛得到粒径为0.5mm～1mm的塑料粉末，然后称取1g塑料粉末放入第一加热区的石英吊篮1中，称取0.5g铁基催化剂粉末放入第二加热区的石英吊篮2中，将吊篮置于石英反应器对应位置，并放入两段式立式炉中；通入流量为200mL/min的氩气30min后反应器处于惰性气氛，调整氩气流量为100mL/min并将第二加热区以20℃/min的升温速率升至800℃并保持恒温，然后将第一加热区以10℃/min的升温速率升至500℃，保温10min后自然冷却至室温，废塑料热解过程中产生的热解气在铁基催化剂表面沉积形成碳纳米管；(a) mechanically pulverize waste plastics such as waste plastic cups and plastic boxes through a liquid nitrogen pulverizer, pass through 18-mesh and 35-mesh stainless steel sieves to obtain plastic powder with a particle size of 0.5mm to 1mm, and then weigh 1g of plastic powder into the In the quartz hanging basket 1 of the first heating zone, weigh 0.5 g of iron-based catalyst powder into the quartz hanging basket 2 of the second heating zone, place the hanging basket at the corresponding position of the quartz reactor, and put it into a two-stage vertical furnace After the reactor was in an inert atmosphere after the flow rate of 200mL/min of argon was introduced for 30min, the argon flow rate was adjusted to 100mL/min and the second heating zone was raised to 800°C at a heating rate of 20°C/min and maintained at a constant temperature, Then, the first heating zone was raised to 500°C at a heating rate of 10°C/min, kept for 10 minutes, and then cooled to room temperature naturally, and the pyrolysis gas generated during the pyrolysis of waste plastics was deposited on the surface of the iron-based catalyst to form carbon nanotubes;
(b)将步骤(b)中制得的碳纳米管置于锥形瓶中，加入浓度为30％的浓硝酸，在80℃下以600rpm的转速搅拌4h，然后过滤获得固体产物并水洗10次，最后在105℃的温度下干燥12h获得纯化碳纳米管，称取0.2g纯化碳纳米管和1g三聚氰胺置于研钵中，充分研磨30min使其混合均匀得到固体混合物；(b) placing the carbon nanotubes prepared in step (b) in a conical flask, adding concentrated nitric acid with a concentration of 30%, stirring at 80° C. for 4 hours at a speed of 600 rpm, and then filtering to obtain a solid product and washing with water for 10 time, and finally dried at a temperature of 105 °C for 12 hours to obtain purified carbon nanotubes, weigh 0.2 g of purified carbon nanotubes and 1 g of melamine, put them in a mortar, and fully grind for 30 minutes to mix them uniformly to obtain a solid mixture;
(c)将固体混合物置于石英吊篮中，并将吊篮放入反应器内，首先通入流量为200mL/min的氩气使反应器处于惰性气氛中，然后调整氩气流量为100mL/min，以10℃/min的升温速率升至750℃并保温2h，二次热解后自然冷却至室温，得到Fe-N-CNT催化剂-1。(c) place the solid mixture in a quartz hanging basket, and put the hanging basket into the reactor, first feed argon with a flow rate of 200 mL/min to make the reactor in an inert atmosphere, and then adjust the argon flow rate to be 100 mL/min min, the temperature was raised to 750 °C at a heating rate of 10 °C/min and kept for 2 h. After secondary pyrolysis, it was naturally cooled to room temperature to obtain Fe-N-CNT catalyst-1.
采用旋转圆盘电极装置对制得的Fe-N-CNT催化剂-1进行氧化还原性能测试，称取10mg的Fe-N-CNT催化剂-1并依次加入100μL无水乙醇和40μL Nafion溶液，经过30min的超声分散后获得混合溶液，取2μL的混合溶液均匀地涂到工作电极玻碳电极上，此外对电极为Pt丝电极，饱和甘汞电极为参比电极；在室温并且氧气饱和的0.1mol/LKOH溶液中进行电化学测试，循环伏安曲线(CV)具体测试参数为：扫描电压范围-0.8～0.2V(vs SCE，0.2～1.2Vvs RHE)，扫描速率10mV/s；线性扫描伏安曲线(LSV)具体测试参数为：扫描电压为-1～0V(vs SCE,0～1V vs RHE)，扫描速率5mV/s，圆盘电极转速为1600rpm；The redox performance of Fe-N-CNT catalyst-1 was tested by rotating disk electrode device, 10 mg of Fe-N-CNT catalyst-1 was weighed and 100 μL of absolute ethanol and 40 μL of Nafion solution were added in turn, after 30 min The mixed solution was obtained after the ultrasonic dispersion of 2 μL, and 2 μL of the mixed solution was uniformly applied to the glassy carbon electrode of the working electrode. In addition, the counter electrode was a Pt wire electrode, and the saturated calomel electrode was the reference electrode; Electrochemical test was carried out in LKOH solution, and the specific test parameters of cyclic voltammetry curve (CV) were: scanning voltage range -0.8~0.2V (vs SCE, 0.2~1.2Vvs RHE), scanning rate 10mV/s; linear scanning voltammetry curve (LSV) The specific test parameters are: the scanning voltage is -1~0V (vs SCE, 0~1V vs RHE), the scanning rate is 5mV/s, and the rotating speed of the disk electrode is 1600rpm;
Fe-N-CNT催化剂-1的起始电位为0.887V(vs RHE)，半波电位0.714V(vs RHE)。The onset potential of Fe-N-CNT catalyst-1 was 0.887 V (vs RHE) and the half-wave potential was 0.714 V (vs RHE).
实施例2Example 2
(a)将废塑料杯、塑料盒等废塑料经过液氮粉碎机进行机械粉碎，过18目和35目的不锈钢筛得到粒径为0.5mm～1mm的塑料粉末，然后称取2.5g塑料粉末放入第一加热区的石英吊篮1中，称取0.5g铁基催化剂粉末放入第二加热区的石英吊篮2中，将吊篮置于石英反应器对应位置，并放入两段式立式炉中；通入流量为200mL/min的氩气30min后反应器处于惰性气氛，调整氩气流量为50mL/min并将第二加热区以10℃/min的升温速率升至750℃并保持恒温，然后将第一加热区以5℃/min的升温速率升至550℃，保温8min后自然冷却至室温，废塑料热解过程中产生的热解气在铁基催化剂表面沉积形成碳纳米管；(a) mechanically pulverize waste plastics such as waste plastic cups and plastic boxes through a liquid nitrogen pulverizer, pass through 18-mesh and 35-mesh stainless steel sieves to obtain plastic powder with a particle size of 0.5mm to 1mm, and then weigh 2.5g of plastic powder and put it in Put into the quartz hanging basket 1 of the first heating zone, weigh 0.5 g of iron-based catalyst powder and put it into the quartz hanging basket 2 of the second heating zone, place the hanging basket in the corresponding position of the quartz reactor, and put it into a two-stage vertical In the furnace; the reactor was in an inert atmosphere after the flow rate of 200mL/min of argon was introduced for 30min, the argon flow rate was adjusted to 50mL/min, and the second heating zone was raised to 750°C at a heating rate of 10°C/min and maintained at a constant temperature , then the first heating zone was raised to 550°C at a heating rate of 5°C/min, kept for 8 minutes and then cooled to room temperature naturally, and the pyrolysis gas generated during the pyrolysis of waste plastics was deposited on the surface of the iron-based catalyst to form carbon nanotubes;
(b)将步骤(b)中制得的碳纳米管置于锥形瓶中，加入浓度为40％的浓硝酸，在100℃下以800rpm的转速搅拌6h，然后过滤获得固体产物并水洗20次，最后在100℃的温度下干燥24h获得纯化碳纳米管，称取0.5g纯化碳纳米管和0.5g三聚氰胺置于研钵中，充分研磨40min使其混合均匀得到固体混合物；(b) placing the carbon nanotubes prepared in step (b) in a conical flask, adding concentrated nitric acid with a concentration of 40%, stirring at 800 rpm for 6 h at 100° C., and then filtering to obtain a solid product and washing with water for 20 second, and finally dried at a temperature of 100 °C for 24 hours to obtain purified carbon nanotubes, weigh 0.5 g of purified carbon nanotubes and 0.5 g of melamine, put them in a mortar, and fully grind for 40 minutes to mix them uniformly to obtain a solid mixture;
(c)将固体混合物置于石英吊篮中，并将吊篮放入反应器内，首先通入流量为200mL/min的氩气使反应器处于惰性气氛中，然后调整氩气流量为50mL/min，以8℃/min的升温速率升至800℃并保温1.5h，二次热解后自然冷却至室温，得到Fe-N-CNT催化剂-2。(c) the solid mixture is placed in a quartz hanging basket, and the hanging basket is placed in the reactor. First, the argon gas with a flow rate of 200 mL/min is introduced to make the reactor in an inert atmosphere, and then the argon gas flow is adjusted to be 50 mL/min. min, the temperature was raised to 800 °C at a heating rate of 8 °C/min and kept for 1.5 h. After secondary pyrolysis, it was naturally cooled to room temperature to obtain Fe-N-CNT catalyst-2.
采用旋转圆盘电极装置对制得的Fe-N-CNT催化剂-2进行氧化还原性能测试，称取10mg的Fe-N-CNT催化剂-2并依次加入100μL无水乙醇和40μL Nafion溶液，经过30min的超声分散后获得混合溶液，取2μL的混合溶液均匀地涂到工作电极玻碳电极上，此外对电极为Pt丝电极，饱和甘汞电极为参比电极；在室温并且氧气饱和的0.1mol/LKOH溶液中进行电化学测试，循环伏安曲线(CV)具体测试参数为：扫描电压范围-0.8～0.2V(vs SCE，0.2～1.2Vvs RHE)，扫描速率10mV/s；线性扫描伏安曲线(LSV)具体测试参数为：扫描电压为-1～0V(vs SCE,0～1V vs RHE)，扫描速率5mV/s，圆盘电极转速为1600rpm；The redox performance of Fe-N-CNT catalyst-2 was tested by rotating disk electrode device, 10 mg of Fe-N-CNT catalyst-2 was weighed and 100 μL of absolute ethanol and 40 μL of Nafion solution were added in sequence, after 30 min The mixed solution was obtained after the ultrasonic dispersion of 2 μL, and 2 μL of the mixed solution was uniformly applied to the glassy carbon electrode of the working electrode. In addition, the counter electrode was a Pt wire electrode, and the saturated calomel electrode was the reference electrode; Electrochemical test was carried out in LKOH solution, and the specific test parameters of cyclic voltammetry curve (CV) were: scanning voltage range -0.8~0.2V (vs SCE, 0.2~1.2Vvs RHE), scanning rate 10mV/s; linear scanning voltammetry curve (LSV) The specific test parameters are: the scanning voltage is -1~0V (vs SCE, 0~1V vs RHE), the scanning rate is 5mV/s, and the rotating speed of the disk electrode is 1600rpm;
Fe-N-CNT催化剂-2的起始电位为0.893V(vs RHE)，半波电位0.707V(vs RHE)。The onset potential of Fe-N-CNT catalyst-2 was 0.893 V (vs RHE) and the half-wave potential was 0.707 V (vs RHE).
实施例3Example 3
(a)将废塑料杯、塑料盒等废塑料经过液氮粉碎机进行机械粉碎，过18目和35目的不锈钢筛得到粒径为0.5mm～1mm的塑料粉末，然后称取0.5g塑料粉末放入第一加热区的石英吊篮1中，称取2.5g铁基催化剂粉末放入第二加热区的石英吊篮2中，将吊篮置于石英反应器对应位置，并放入两段式立式炉中；通入流量为200mL/min的氩气30min后反应器处于惰性气氛，调整氩气流量为80mL/min并将第二加热区以15℃/min的升温速率升至900℃并保持恒温，然后将第一加热区以8℃/min的升温速率升至600℃，保温5min后自然冷却至室温，废塑料热解过程中产生的热解气在铁基催化剂表面沉积形成碳纳米管，图2是制得的碳纳米管的SEM图，铁基催化剂表面沉积出的黑色块状物质即为碳纳米管；(a) mechanically pulverize waste plastics such as waste plastic cups and plastic boxes through a liquid nitrogen pulverizer, pass through 18-mesh and 35-mesh stainless steel sieves to obtain plastic powder with a particle size of 0.5mm to 1mm, and then weigh 0.5g of plastic powder and put it in Put into the quartz hanging basket 1 of the first heating zone, weigh 2.5 g of iron-based catalyst powder and put it into the quartz hanging basket 2 of the second heating zone, place the hanging basket in the corresponding position of the quartz reactor, and put it into a two-stage vertical In the furnace; the reactor was in an inert atmosphere after the flow rate of 200mL/min of argon was introduced for 30min, the argon flow rate was adjusted to 80mL/min, and the second heating zone was raised to 900°C at a heating rate of 15°C/min and maintained at a constant temperature , and then the first heating zone was raised to 600°C at a heating rate of 8°C/min, kept for 5 minutes and then cooled to room temperature naturally. The pyrolysis gas generated during the pyrolysis of waste plastics was deposited on the surface of the iron-based catalyst to form carbon nanotubes. Fig. 2 is a SEM image of the prepared carbon nanotubes, and the black lumps deposited on the surface of the iron-based catalyst are carbon nanotubes;
(b)将步骤(b)中制得的碳纳米管置于锥形瓶中，加入浓度为50％的浓硝酸，在90℃下以1000rpm的转速搅拌5h，然后过滤获得固体产物并水洗15次，最后在105℃的温度下干燥18h获得纯化碳纳米管，称取0.5g纯化碳纳米管和1.5g三聚氰胺置于研钵中，充分研磨60min使其混合均匀得到固体混合物；(b) placing the carbon nanotubes prepared in step (b) in a conical flask, adding concentrated nitric acid with a concentration of 50%, stirring at 1000 rpm at 90° C. for 5 h, then filtering to obtain a solid product and washing with water for 15 hours second, and finally dried at a temperature of 105°C for 18 hours to obtain purified carbon nanotubes, weigh 0.5 g of purified carbon nanotubes and 1.5 g of melamine, put them in a mortar, and fully grind for 60 minutes to mix them uniformly to obtain a solid mixture;
(c)将固体混合物置于石英吊篮中，并将吊篮放入反应器内，首先通入流量为200mL/min的氩气使反应器处于惰性气氛中，然后调整氩气流量为80mL/min，以5℃/min的升温速率升至850℃并保温0.5h，二次热解后自然冷却至室温，得到Fe-N-CNT催化剂-3，图3是制得的Fe-N-CNT催化剂-3的SEM图，其中碳纳米管外径大约为20nm～50nm，长度可达数个微米。(c) the solid mixture is placed in a quartz hanging basket, and the hanging basket is placed in the reactor. First, the argon gas with a flow rate of 200 mL/min is introduced to make the reactor in an inert atmosphere, and then the argon gas flow is adjusted to be 80 mL/min. min, the temperature was raised to 850 °C at a heating rate of 5 °C/min and kept for 0.5 h. After secondary pyrolysis, it was naturally cooled to room temperature to obtain Fe-N-CNT catalyst-3. Figure 3 shows the prepared Fe-N-CNT. SEM image of catalyst-3, wherein the outer diameter of carbon nanotubes is about 20nm-50nm, and the length can reach several microns.
采用旋转圆盘电极装置对制得的Fe-N-CNT催化剂-3进行氧化还原性能测试，称取10mg的Fe-N-CNT催化剂-3并依次加入100μL无水乙醇和40μL Nafion溶液，经过30min的超声分散后获得混合溶液，取2μL的混合溶液均匀地涂到工作电极玻碳电极上，此外对电极为Pt丝电极，饱和甘汞电极为参比电极；在室温并且氧气饱和的0.1mol/LKOH溶液中进行电化学测试，循环伏安曲线(CV)具体测试参数为：扫描电压范围-0.8～0.2V(vs SCE，0.2～1.2Vvs RHE)，扫描速率10mV/s；线性扫描伏安曲线(LSV)具体测试参数为：扫描电压为-1～0V(vs SCE,0～1V vs RHE)，扫描速率5mV/s，圆盘电极转速为1600rpm；The redox performance of Fe-N-CNT catalyst-3 prepared was tested by rotating disk electrode device, 10 mg of Fe-N-CNT catalyst-3 was weighed and 100 μL of absolute ethanol and 40 μL of Nafion solution were added in turn, after 30 min The mixed solution was obtained after the ultrasonic dispersion of 2 μL, and 2 μL of the mixed solution was uniformly applied to the glassy carbon electrode of the working electrode. In addition, the counter electrode was a Pt wire electrode, and the saturated calomel electrode was the reference electrode; Electrochemical test was carried out in LKOH solution, and the specific test parameters of cyclic voltammetry curve (CV) were: scanning voltage range -0.8~0.2V (vs SCE, 0.2~1.2Vvs RHE), scanning rate 10mV/s; linear scanning voltammetry curve (LSV) The specific test parameters are: the scanning voltage is -1~0V (vs SCE, 0~1V vs RHE), the scanning rate is 5mV/s, and the rotating speed of the disk electrode is 1600rpm;
Fe-N-CNT催化剂-3的起始电位为0.932V(vs RHE)，半波电位0.773V(vs RHE)。The onset potential of Fe-N-CNT catalyst-3 was 0.932 V (vs RHE) and the half-wave potential was 0.773 V (vs RHE).
实施例4Example 4
(a)将废塑料杯、塑料盒等废塑料经过液氮粉碎机进行机械粉碎，过18目和35目的不锈钢筛得到粒径为0.5mm～1mm的塑料粉末，然后称取1g塑料粉末放入第一加热区的石英吊篮1中，称取1g铁基催化剂粉末放入第二加热区的石英吊篮2中，将吊篮置于石英反应器对应位置，并放入两段式立式炉中；通入流量为200mL/min的氩气30min后反应器处于惰性气氛，调整氩气流量为100mL/min并将第二加热区以18℃/min的升温速率升至850℃并保持恒温，然后将第一加热区以6℃/min的升温速率升至530℃，保温10min后自然冷却至室温，废塑料热解过程中产生的热解气在铁基催化剂表面沉积形成碳纳米管；(a) mechanically pulverize waste plastics such as waste plastic cups and plastic boxes through a liquid nitrogen pulverizer, pass through 18-mesh and 35-mesh stainless steel sieves to obtain plastic powder with a particle size of 0.5mm to 1mm, and then weigh 1g of plastic powder into the In the quartz hanging basket 1 of the first heating zone, weigh 1 g of iron-based catalyst powder into the quartz hanging basket 2 of the second heating zone, place the hanging basket at the corresponding position of the quartz reactor, and put it into a two-stage vertical furnace ; The reactor was in an inert atmosphere after 30min of argon with a flow rate of 200mL/min, adjusted the argon flow rate to 100mL/min and the second heating zone was raised to 850°C at a heating rate of 18°C/min and maintained at a constant temperature, then The first heating zone was raised to 530°C at a heating rate of 6°C/min, kept for 10 minutes, and then cooled to room temperature naturally, and the pyrolysis gas generated during the pyrolysis of waste plastics was deposited on the surface of the iron-based catalyst to form carbon nanotubes;
(b)将步骤(b)中制得的碳纳米管置于锥形瓶中，加入浓度为30％的浓硝酸，在100℃下以1000rpm的转速搅拌4h，然后过滤获得固体产物并水洗20次，最后在100℃的温度下干燥24h获得纯化碳纳米管，称取0.5g纯化碳纳米管和1g双氰胺置于研钵中，充分研磨30min使其混合均匀得到固体混合物；(b) placing the carbon nanotubes prepared in step (b) in a conical flask, adding concentrated nitric acid with a concentration of 30%, stirring at 100° C. for 4 hours at a speed of 1000 rpm, and then filtering to obtain a solid product and washing with water for 20 time, and finally dried at a temperature of 100 °C for 24 hours to obtain purified carbon nanotubes, weigh 0.5 g of purified carbon nanotubes and 1 g of dicyandiamide, put them in a mortar, and fully grind for 30 minutes to mix them uniformly to obtain a solid mixture;
(c)将固体混合物置于石英吊篮中，并将吊篮放入反应器内，首先通入流量为200mL/min的氩气使反应器处于惰性气氛中，然后调整氩气流量为50mL/min，以7℃/min的升温速率升至900℃并保温1h，二次热解后自然冷却至室温，得到Fe-N-CNT催化剂-4。(c) the solid mixture is placed in a quartz hanging basket, and the hanging basket is placed in the reactor. First, the argon gas with a flow rate of 200 mL/min is introduced to make the reactor in an inert atmosphere, and then the argon gas flow is adjusted to be 50 mL/min. min, the temperature was raised to 900 °C at a heating rate of 7 °C/min and kept for 1 h. After secondary pyrolysis, it was naturally cooled to room temperature to obtain Fe-N-CNT catalyst-4.
采用旋转圆盘电极装置对制得的Fe-N-CNT催化剂-4进行氧化还原性能测试，称取10mg的Fe-N-CNT催化剂-4并依次加入100μL无水乙醇和40μL Nafion溶液，经过30min的超声分散后获得混合溶液，取2μL的混合溶液均匀地涂到工作电极玻碳电极上，此外对电极为Pt丝电极，饱和甘汞电极为参比电极；在室温并且氧气饱和的0.1mol/LKOH溶液中进行电化学测试，循环伏安曲线(CV)具体测试参数为：扫描电压范围-0.8～0.2V(vs SCE，0.2～1.2Vvs RHE)，扫描速率10mV/s；线性扫描伏安曲线(LSV)具体测试参数为：扫描电压为-1～0V(vs SCE,0～1V vs RHE)，扫描速率5mV/s，圆盘电极转速为1600rpm；The redox performance of the prepared Fe-N-CNT catalyst-4 was tested by using a rotating disk electrode device. 10 mg of Fe-N-CNT catalyst-4 was weighed and 100 μL of absolute ethanol and 40 μL of Nafion solution were added in turn. After 30 min The mixed solution was obtained after the ultrasonic dispersion of 2 μL, and 2 μL of the mixed solution was uniformly applied to the glassy carbon electrode of the working electrode. In addition, the counter electrode was a Pt wire electrode, and the saturated calomel electrode was the reference electrode; Electrochemical test was carried out in LKOH solution, and the specific test parameters of cyclic voltammetry curve (CV) were: scanning voltage range -0.8~0.2V (vs SCE, 0.2~1.2Vvs RHE), scanning rate 10mV/s; linear scanning voltammetry curve (LSV) The specific test parameters are: the scanning voltage is -1~0V (vs SCE, 0~1V vs RHE), the scanning rate is 5mV/s, and the rotating speed of the disk electrode is 1600rpm;
Fe-N-CNT催化剂-4的起始电位为0.910V(vs RHE)，半波电位0.773V(vs RHE)。Fe-N-CNT catalyst-4 has an onset potential of 0.910 V (vs RHE) and a half-wave potential of 0.773 V (vs RHE).
图4是实施例1～4中制备的Fe-N-CNT催化剂的XRD谱图，制得的Fe-N-CNT催化剂中均含有Fe、Fe3C等对氧还原催化过程有促进作用的成分；Figure 4 is the XRD patterns of the Fe-N-CNT catalysts prepared in Examples 1 to 4. The prepared Fe-N-CNT catalysts all contain components such as Fe and Fe3 C that can promote the catalytic process of oxygen reduction. ;
图5是实施例1～4中制备的Fe-N-CNT催化剂的循环伏安曲线图，制得的Fe-N-CNT催化剂均在0.7V左右出现明显的氧气还原峰，说明该催化剂催化氧还原反应过程较明显；Fig. 5 is the cyclic voltammetry diagram of the Fe-N-CNT catalysts prepared in Examples 1-4. The Fe-N-CNT catalysts prepared all show an obvious oxygen reduction peak at about 0.7V, indicating that the catalyst catalyzes oxygen The reduction reaction process is obvious;
图6是实施例1～4中制备的Fe-N-CNT催化剂与商用Pd/C催化剂的线性扫描伏安曲线图，Fe-N-CNT催化剂-3具有更正的起始电位和半波电位，且性能接近商用Pd/C催化剂。Fig. 6 is the linear sweep voltammogram of Fe-N-CNT catalyst prepared in Examples 1-4 and commercial Pd/C catalyst, Fe-N-CNT catalyst-3 has more positive onset potential and half-wave potential, And the performance is close to that of commercial Pd/C catalysts.
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。Those skilled in the art can easily understand that the above are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, etc., All should be included within the protection scope of the present invention.
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