WO2022262154A1 - 一种富氮生物油基多孔炭及其制备方法和应用 - Google Patents

一种富氮生物油基多孔炭及其制备方法和应用 Download PDF

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WO2022262154A1
WO2022262154A1 PCT/CN2021/123436 CN2021123436W WO2022262154A1 WO 2022262154 A1 WO2022262154 A1 WO 2022262154A1 CN 2021123436 W CN2021123436 W CN 2021123436W WO 2022262154 A1 WO2022262154 A1 WO 2022262154A1
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nitrogen
oil
bio
porous carbon
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肖睿
许佳欢
刘超
薛北辰
李明
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Southeast University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/861—Porous electrodes with a gradient in the porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • Oxygen reduction reaction is the main reaction in the cathode of green energy conversion devices such as fuel cells and metal-air batteries. Its slow kinetic process leads to low overall efficiency, and cathode catalysts must be used to improve this problem.
  • platinum-carbon (Pt/C) catalysts commonly used commercially have the best catalytic activity, but noble metal catalysts have problems such as high cost, scarce resources, poor stability, and poor resistance to methanol toxicity, and their large-scale promotion and use are still facing difficulties.
  • Nitrogen-doped porous carbons exhibit excellent ORR catalytic activity, higher stability than Pt/C catalysts and resistance to methanol toxicity, and are considered to be one of the most promising metal-free catalysts.
  • Biomass is the only renewable carbon source in nature. It has a wide range of sources, low cost, and is environmentally friendly. It is often used as a raw material for carbon materials.
  • filter paper is used as a carbon source and urea as a nitrogen source, and nitrogen-containing porous carbon with micropores as the main part and a specific surface area of 689 m2g -1 can be obtained through direct carbonization, which can be used for CO2 adsorption (CN110078046A)
  • KOH or NaOH activation method is often used to increase the specific surface area of porous carbon.
  • Biomass raw materials such as protein and potatoes can be pyrolyzed and activated to obtain nitrogen-doped carbon with a specific surface area of 1274m 2 g -1 and 1134m 2 g -1 respectively.
  • Porous carbon (CN108615899A and CN09346732A) has good ORR catalytic activity.
  • Raw materials and preparation methods are the decisive factors for the properties and catalytic performance of porous carbon.
  • the nitrogen doping process often requires an external nitrogen source, and the process is more complicated.
  • the porous carbon obtained by the activation method shows the problems of non-concentrated pore size distribution and irregular structure. .
  • Bio-oil is the main product in the thermochemical conversion process of biomass. It has high carbon and oxygen content, low ash content, and is rich in aromatic products, which is very easy to polycondensate and carbonize.
  • the liquid nature of bio-oil makes it more suitable for template method than solid raw materials, resulting in porous carbon with more regular pore structure.
  • biomass tar is used as carbon source, and molecular sieve or calcined egg shell calcined calcium oxide is used as template to obtain porous carbon with high surface area, mainly micropore and mesopore, which can be used as supercapacitor electrode
  • Both materials and CO 2 adsorbents showed good performance (CN109205622 A and CN110078046 A).
  • the technical problem to be solved by the present invention is to provide a nitrogen-enriched bio-oil-based porous Carbon and its preparation method, the method uses biomass and nitrogen-containing raw materials co-pyrolysis to obtain nitrogen-rich bio-oil as carbon and nitrogen precursors, without the need for additional nitrogen sources, which simplifies the preparation process.
  • the obtained porous carbon has regular pore structure and concentrated pore size , with a high degree of graphitization, and the surface is rich in nitrogen and oxygen functional groups. It can be widely used in electrochemical catalysis of oxygen reduction reaction.
  • the technical solution provided by the present invention is: a nitrogen-rich bio-oil-based porous carbon, which is characterized in that the nitrogen-rich bio-oil obtained by co-pyrolysis of biomass and nitrogen-containing compounds is used as a precursor, and metal salts are used as a precursor. Templating agent to prepare porous carbon by one-step carbonization.
  • step (3) Preparation of nitrogen-rich bio-oil-based porous carbon: pyrolyze the mixture of step (2) under an inert gas atmosphere, keep the temperature at a constant temperature after heating up, and naturally cool to room temperature after the reaction to obtain a carbonized product;
  • step (3) Pickling the carbonized product in step (3), washing with deionized water until neutral, filtering and drying to obtain the final product.
  • the biomass in the step (1) is at least one of pine wood, rice husk, coconut shell, walnut shell, peanut shell, straw, bagasse, and the nitrogen-containing raw material is waste nylon (polyamide), urea , At least one of melamine.
  • the mass ratio of biomass to nitrogen-containing raw materials in the step (1) is 0.5:1-2:1.
  • the pyrolysis conditions of the step (1) are as follows: the heating rate is 1-50°C/min, the pyrolysis temperature is 500-800°C, the holding time is 1-3h, and the gas flow rate is 10-500mL/min.
  • the template agent in the step (2) is at least one of zinc chloride, magnesium acetate, magnesium hydroxide, potassium chloride, sodium chloride, and potassium carbonate.
  • the mass ratio of nitrogen-enriched bio-oil to template agent in the step (2) is 1:1-1:5.
  • the carbonization conditions of the step (3) are as follows: the heating rate is 1-20°C/min, the temperature is raised to 500-1000°C and kept at a constant temperature, the holding time is 1-3h, and the gas flow rate is 10-500mL/min.
  • the pickling conditions of the step (4) are: use 0.1-3mol/L dilute hydrochloric acid solution, the washing time is 1-12h, and the pickling temperature is 25-60°C.
  • Nitrogen-containing compounds can promote the transformation of carbonyl products into nitrogen-containing heterocyclic products. Compared with biomass pyrolysis alone, the nitrogen content in co-pyrolysis liquid products Increased from 0.8-2.1% to 8.5-12.7%, you can get low ash, high carbon content, nitrogen-rich bio-oil rich in aromatic compounds, which can be directly used as carbon and nitrogen precursors in the process of carbon production without additional Nitrogen source.
  • Nitrogen-enriched bio-oil is in a liquid state and is easy to mix evenly with metal salt templates to obtain porous carbon with regular and orderly pore structure, which is more suitable for template method than solid biomass.
  • the zinc chloride, magnesium acetate, magnesium hydroxide, potassium chloride, sodium chloride, potassium carbonate, etc. used in this method are all cheap metal salt templates.
  • the carbonized product can be made A multi-level pore structure with concentrated pore size, uniform distribution, and mesoporous dominance is produced in the medium.
  • the nitrogen-enriched bio-oil-based porous carbon produced by this method has a specific surface area of 343.26-1039.84m 2 /g, a pore volume of 0.16-1.24cm 3 /g, and a nitrogen content of 2.50-4.82wt%.
  • the total relative content of graphitic nitrogen is 30-56%, which is beneficial to generate catalytic active sites.
  • the nitrogen-enriched bio-oil-based porous carbon exhibits good catalytic activity, high stability and resistance to methanol toxicity.
  • Fig. 1 is the nitrogen adsorption-desorption curve and the pore size distribution diagram of the catalyst prepared in Example 1.
  • Fig. 2 is the X-ray photoelectron spectrogram of the catalyst prepared in Example 1.
  • Fig. 4 is the linear voltammetry curve of the catalyst prepared in Example 1 in an oxygen-saturated 0.1mol/L KOH solution.
  • a preparation method of nitrogen-rich bio-oil-based porous carbon comprising the steps of:
  • the electrochemical test conditions are as follows: In 0.1mol/L KOH solution, the electrochemical test is carried out using a three-electrode system, in which the working electrode is a glassy carbon electrode (diameter 3mm) or a rotating ring disk electrode (diameter 5.61mm), and the counter electrode is a platinum wire. Electrode, the reference electrode is Ag/AgCl electrode.
  • the catalyst was mixed with water, ethanol and The solutions were mixed to form a homogeneous suspension. Add a certain amount of suspension solution dropwise to the surface of the glassy carbon electrode or the rotating disk electrode, and let it stand and dry to obtain the working electrode to be tested. Cyclic voltammetry (CV) and linear voltammetry (LSV) were used to investigate the catalytic performance of the catalysts described in each example for the oxygen reduction reaction.
  • CV Cyclic voltammetry
  • LSV linear voltammetry
  • the test results of CV and LSV prove that NC1 has catalytic performance for oxygen reduction reaction.
  • the onset potential and half-wave potential of NC1 are 0.044V and - 0.158 V, comparable to commercial Pt/C catalysts (onset potential and half-wave potential are 0.048 V and ⁇ 0.148 V, respectively).
  • the results are shown in Figure 1.
  • the measured specific surface area is 920.58m 2 /g, and the pore volume is 0.58cm 3 /g
  • the results of elemental analysis and X-ray photoelectron spectroscopy analysis are shown in 2. It can be seen that the nitrogen content in NC1 is 3.68wt%, the total content of graphite-type and pyridine-type nitrogen in nitrogen functional groups is 56%, and the surface of NC1 is also abundant. oxygen functional group.
  • the results shown in Figure 3 show that NC1 is composed of amorphous carbon and graphite structure, and the degree of graphitization is relatively high.
  • the abundant micropores in the structure of NC1 are conducive to exposing more active sites, and the mesopores facilitate the transport and diffusion of reactants.
  • the graphitic nitrogen and pyridinic nitrogen functional groups on the surface help to generate ORR catalytic active sites on the porous carbon surface, while the oxygen functional group enhances the hydrophilicity of the catalyst surface, allowing the electrolyte to more fully infiltrate the catalyst surface.
  • its graphitized structure enhances its electrical conductivity.
  • a preparation method of nitrogen-rich bio-oil-based porous carbon comprising the steps of:
  • a preparation method of nitrogen-rich bio-oil-based porous carbon comprising the steps of:
  • NC4 has catalytic performance for oxygen reduction reaction.
  • the onset potential and half-wave potential of NC4 are 0.018V and -0.160V, respectively.
  • the measured specific surface area is 1039.84m 2 /g, and the pore volume is 1.24cm 3 /g.
  • the nitrogen content in NC4 is 2.5wt%, and the total content of graphitic and pyridinic nitrogen in nitrogen functional groups is 48%.
  • Raman spectroscopy analysis it can be seen that NC4 is mainly composed of amorphous carbon and graphitized structure, and the degree of graphitization is relatively high.
  • a preparation method of nitrogen-rich bio-oil-based porous carbon comprising the steps of:
  • NC5 has catalytic performance for oxygen reduction reaction.
  • the onset potential and half-wave potential of NC5 are -0.011V and -0.172V, respectively.
  • the measured specific surface area is 562.36m 2 /g, and the pore volume is 0.31cm 3 /g.
  • the nitrogen content in NC5 is 3.39wt%, and the total content of graphitic and pyridinic nitrogen in nitrogen functional groups is 42%.
  • Raman spectroscopy analysis it can be seen that NC5 is mainly composed of amorphous carbon and graphitized structure, and the degree of graphitization is relatively high.
  • a preparation method of nitrogen-rich bio-oil-based porous carbon comprising the steps of:
  • NC6 has catalytic performance for oxygen reduction reaction.
  • the onset potential and half-wave potential of NC6 are -0.058V and -0.181V, respectively.
  • the measured specific surface area is 343.26m 2 /g, and the pore volume is 0.22cm 3 /g.
  • the nitrogen content in NC6 is 3.07wt%, and the total content of graphitic and pyridinic nitrogen in nitrogen functional groups is 42%.
  • NC5 is mainly composed of amorphous carbon and graphitized structure, and the degree of graphitization is relatively high.
  • patents 1 and 2 in the comparison table use similar carbon precursor tar, but there is no mention of the tar preparation method, no nitrogen doping, and different application directions;
  • patent 3 uses general solid carbon sources and urea nitrogen sources (similar to the present invention), but the pore-making method is the traditional CO2 activation, the specific surface area is low, and the pore structure is different;
  • patents 4 and 5 are the preparation of nitrogen-doped porous carbon and the same oxygen reduction catalytic application as the present invention, carbon.
  • the physical and chemical properties and catalytic performance are similar to ours in the present invention, but there are two differences in the preparation method.
  • One is that the carbon source uses its own nitrogen-containing biomass, and the other is activation with alkali. Our method has stronger raw material adaptability, and the template used The agent can be recycled, which is more friendly to the environment.

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Abstract

本发明涉及一种富氮生物油基多孔炭及其制备方法与应用；其制备方法包括如下步骤：以生物质及含氮化合物为原料，通过共热解制备富氮生物油；以富氮生物油作为碳、氮前驱体，金属盐为模板剂，制成前驱体与模板剂的均匀混合物；在高温下对混合物进行炭化后得到炭化产物；对炭化产物进行酸洗，并用去离子水洗涤至中性，经抽滤和烘干后得到富氮生物油基多孔炭；本发明以富氮生物油作为前驱体，具有低灰分、高氮含量的优势，在热解过程中无需外加氮源，比固态生物质更适用于模板法，所得多孔炭具有孔结构规整、孔径集中、表面富含氮、氧官能团的特点，表现出良好的氧还原反应电催化性能。

Description

一种富氮生物油基多孔炭及其制备方法和应用 技术领域
本发明属于电化学与新能源材料制备领域，涉及一种富氮生物油基多孔炭及其制备方法和应用。
背景技术
氧还原反应(ORR)是燃料电池、金属-空气电池等绿色能源转换装置中阴极的主要反应，其缓慢的动力学过程致使整体效率低下，必须使用阴极催化剂改善这个问题。目前商业常用的铂碳(Pt/C)催化剂具有最优催化活性，但贵金属类催化剂存在成本高、资源稀缺、稳定性差、抗甲醇毒性差等问题，其大规模推广使用仍然面临困境。氮掺杂多孔炭表现出优异的ORR催化活性和高于Pt/C催化剂的稳定性和抗甲醇毒性，被认为是最具发展前景的非金属催化剂之一。
生物质是自然界中唯一的可再生碳源，其来源广泛、成本低廉、绿色环保，常被用作碳材料的原料。在现有技术中，将滤纸作为碳源、尿素作为氮源，经过直接炭化可以获得以微孔为主、比表面积为689m 2g -1的含氮多孔炭，可用于CO 2吸附(CN110078046A)；此外，常借助KOH或NaOH活化法来提高多孔炭的比表面积，蛋白质、土豆等生物质原料经热解和活化可分别得到比表面积达1274m 2g -1和1134m 2g -1的掺氮多孔炭(CN108615899A和CN09346732A)，具有较好的ORR催化活性。原料及制备方法是多孔炭性质和催化性能的决定因素，其中氮掺杂过程往往需要外加氮源，工艺较复杂，而使用活化法得到的多孔炭表现出孔径分布不集中、结构不规整的问题。
生物油是生物质热化学转化过程中的主要产物，其中碳、氧含量高，灰分少，并且富含芳香族产物，极易缩聚碳化。此外，生物油的液态性质使其比固体原料更适用于模板法，从而得到孔结构更加规整的多孔炭。在现有技术中，以生物质焦油为碳源，以分子筛或鸡蛋壳煅烧后形成的氧化钙作为模板，可得到高表面积、以微孔和介孔为主的多孔炭，在作为超级电容器电极材料和CO 2吸附剂时均表现出良好的性能(CN109205622 A和CN110078046 A)。目前，仍缺乏针对催化氧还原反应所设计的生物油基多孔炭的制备方法。
发明内容
本发明所要解决的技术问题是：针对现有技术中氮掺杂多孔炭存在的孔径分布不集中、结构不规整，电化学催化性能不佳等技术问题”提供了一种富氮生物油基多孔炭及其制备方法，该方法使用生物质与含氮原料共热解所得富氮生物油为碳、氮前驱体，无需外加氮源，简化了制备过程。所得多孔炭的孔结构规整、孔径集中，石墨化程度高，且表面富含氮、氧官能团。可以在电化学催化氧还原 反应方面广泛应用。
为解决上述技术问题，本发明提供的技术方案是：一种富氮生物油基多孔炭，其特征在于以生物质和含氮化合物共热解所得富氮生物油为前驱体，以金属盐为模板剂，通过一步炭化制备多孔炭。
进一步的，一种富氮生物油基多孔炭的制备方法，包括如下步骤：
(1)富氮生物油的制备：将生物质和含氮原料混合均匀，在惰性气体氛围下共热解得到富氮生物油；
(2)富氮生物油与模板剂混合：取步骤(1)中的富氮生物油，加入模板剂和无水乙醇后，在加热条件下搅拌均匀，待冷却至室温后得到富氮生物油与模板剂混合物；
(3)富氮生物油基多孔炭的制备：在惰性气体氛围下热解步骤(2)的混合物，待升温后保持恒温，反应结束后自然冷却至室温，得到炭化产物；
(4)对步骤(3)中的炭化产物进行酸洗处理，随后使用去离子水洗涤至中性，经过滤和干燥后得到最终产物。
进一步的，所述步骤(1)中的生物质为松木、稻壳、椰壳、核桃壳、花生壳、秸秆、甘蔗渣中的至少一种，含氮原料为废弃尼龙(聚酰胺)、尿素、三聚氰胺中的至少一种。
进一步的，所述步骤(1)中生物质与含氮原料质量比为0.5:1-2:1。
进一步的，所述步骤(1)热解条件为：升温速率为1-50℃/min，热解温度为500-800℃，保温时间为1-3h，气体流速为10-500mL/min。
进一步的，所述步骤(2)中模板剂为氯化锌、乙酸镁、氢氧化镁、氯化钾、氯化钠、碳酸钾中的至少一种。
进一步的，所述步骤(2)中富氮生物油与模板剂质量比为1:1-1:5。
进一步的，所述步骤(3)炭化条件为：升温速率为1-20℃/min，升温至500-1000℃并保持恒温，保温时间为1-3h，气体流速为10-500mL/min。
进一步的，所述步骤(4)的酸洗条件为：使用0.1-3mol/L稀盐酸溶液，洗涤时间为1-12h，酸洗温度为25-60℃。
与现有技术相比，本发明的有益效果：
1.生物质与含氮原料共热解过程中存在协同效应，含氮化合物可促使羰基类产物向含氮杂环产物转化，相比生物质单独热解，共热解液体产物中的氮含量由0.8-2.1％增加至8.5-12.7％，即可得到低灰分、高碳含量、富含芳香族化合物的富氮生物油，在制炭过程中可直接作为碳、氮前驱体，而无需外加氮源。
2.富氮生物油呈液态，易与金属盐模板剂均匀混合，从而得到具备孔结构 规整有序的多孔炭，比固态生物质更适用于模板法。
3.本方法使用的氯化锌、乙酸镁、氢氧化镁、氯化钾、氯化钠、碳酸钾等均为廉价金属盐模板剂，经热解和酸洗脱除后，可使炭化产物中产生孔径集中、分布均匀、以介孔为主的多级孔结构。
4.利用本方法制作的富氮生物油基多孔炭，比表面积可达343.26-1039.84m 2/g，孔容达0.16-1.24cm 3/g，氮含量为2.50-4.82wt％，其中吡啶型氮和石墨型氮的总相对含量为30-56％，利于产生催化活性位点。作为氧还原反应的电催化剂，该富氮生物油基多孔炭呈现出良好的催化活性、高稳定性和抗甲醇毒性。
附图说明
图1是实施例1制备催化剂的氮气吸脱附曲线及孔径分布图。
图2是实施例1制备催化剂的X光电子能谱图。
图3是实施例1制备催化剂的拉曼光谱图。
图4是实施例1制备催化剂在氧气饱和的0.1mol/LKOH溶液中的线性伏安曲线。
具体实施方式
为了更清楚地说明本发明的技术方案，下面结合实施例及附图对本发明中进行进一步详细的叙述，但本发明的实施方式不限于此。对未注明的参数工艺，可按照常规技术进行。
实施例1
一种富氮生物油基多孔炭的制备方法，包括如下步骤：
1)富氮生物油的制备：称取150g干燥松木成型颗粒和150g聚酰胺，混合均匀后在氮气氛围下进行热解，升温速率为10℃/min,热解温度为600℃，保温1h，氮气流速为500mL/min，得到富氮生物油，记为A1。
2)富氮生物油与模板剂混合物的制备：称取10gA1和10g氯化锌，向其中加入乙醇后，在85℃下搅拌均匀，冷却至室温后得到富氮生物油与模板剂的混合物，记为B1。
3)富氮生物油基多孔炭的制备：称取8g B1，在氩气氛围中进行热解，升温速率10℃/min,热解温度为800℃，保温2h，氮气流速为100mL/min。待反应结束后冷却至室温，取出炭化产物。在研钵中将产物研磨至粉末状，使用2mol/L盐酸溶液在常温下酸洗12h，随后对酸洗溶液进行抽滤，并用去离子水将产物洗涤至中性。最后，在105℃烘箱中干燥12h得到用于催化氧还原反应的富氮生物油基多孔炭，记为NC1。
电化学测试条件如下：在0.1mol/LKOH溶液中，采用三电极体系进行电化学测试，其中工作电极为玻碳电极(直径3mm)或旋转环盘电极(直径5.61mm)，对电极为铂丝电极，参比电极为Ag/AgCl电极。将催化剂与水、无水乙醇和
Figure PCTCN2021123436-appb-000001
溶液混合，制成均匀的悬浊液。将一定量悬浊液滴加到玻碳电极或旋转圆盘电极表面，静置干燥后得到待测试工作电极。采用循环伏安法(CV)和线性伏安扫描法(LSV)考察各实施例所述催化剂的氧还原反应催化性能。
如图4所示，CV和LSV的测试结果证明NC1具有对氧还原反应的催化性能，在0.1mol/LKOH溶液中的LSV测试中，NC1的起始电位和半波电位分别为0.044V和-0.158V，与商业Pt/C催化剂相当(起始电位和半波电位分别为0.048V和-0.148V)。通过氮气吸脱附测试分析，结果如图1所示，NC1中存在发达的孔隙，以微孔和小尺寸介孔为主，测得比表面积为920.58m 2/g，孔容为0.58cm 3/g，元素分析与X射线光电子能谱分析结果如2所示，可知NC1中氮含量为3.68wt％，氮官能团中石墨型与吡啶型氮的总含量为56％，NC1表面还有丰富的氧官能团。通过拉曼光谱分析，结果如图3可知NC1由无定型碳和石墨结构组成，石墨化程度较高。作为ORR催化剂，NC1结构中丰富的微孔有利于暴露更多活性位点，介孔有助于反应物质的传输与扩散。其表面石墨型氮和吡啶型氮官能团有助于多孔炭表面产生ORR催化活性位点，而氧官能团增强了催化剂表面亲水性，使电解液更充分地浸润催化剂表面。另外，其石墨化结构增强了本身导电性。
实施例2
一种富氮生物油基多孔炭的制备方法，包括如下步骤：
1)富氮生物油的制备：称取150g干燥松木颗粒和150g尿素，混合均匀后在氮气氛围下进行热解，升温速率为1℃/min,热解温度为500℃，保温3h，氮气流速为10mL/min，得到富氮生物油，记为A2。
2)富氮生物油与模板剂混合物的制备：称取10gA2和20g氢氧化镁，向其中加入乙醇后，在85℃下搅拌均匀，冷却至室温后得到富氮生物油与模板剂的混合物，记为B2。
3)富氮生物油基多孔炭的制备：称取8g B2，在氩气氛围中进行热解，升温速率1℃/min,热解温度为500℃，保温3h，氮气流速为10mL/min。待反应结束后冷却至室温，取出炭化产物。在研钵中将产物研磨至粉末状，使用3mol/L盐酸溶液在60℃下酸洗6h，随后对酸洗溶液进行抽滤，并用去离子水将产物洗涤至中性。最后，在105℃烘箱中干燥12h得到用于催化氧还原反应的富氮生物油基多孔炭，记为NC2。
CV和LSV的测试结果证明NC2具有对氧还原反应的催化性能，在0.1mol/L KOH溶液中的LSV测试中，NC2的起始电位和半波电位分别为0.035V和-0.160V。NC3中存在发达的孔隙，以介孔为主，兼有少量微孔，测得比表面积为573.99m 2/g，孔容为0.39cm 3/g。NC2中氮含量为4.82wt％，氮官能团中石墨型与吡啶型氮的总含量为30％。通过拉曼光谱分析可知NC2主要由无定型碳和少量石墨化结构组成。
实施例3
一种富氮生物油基多孔炭的制备方法，包括如下步骤：
1)富氮生物油的制备：称取300g干燥花生壳和150g三聚氰胺，混合均匀后在氮气氛围下进行热解，升温速率为50℃/min,热解温度为800℃，保温2h，氮气流速为200mL/min，得到富氮生物油，记为A3。
2)富氮生物油与模板剂混合物的制备：称取10gA3和5g乙酸镁，向其中加入乙醇后，在85℃下搅拌均匀，冷却至室温后得到富氮生物油与模板剂的混合物，记为B3。
3)富氮生物油基多孔炭的制备：称取8g B3，在氩气氛围中进行热解，升温速率20℃/min,热解温度为1000℃，保温1h，氮气流速为200mL/min。待反应结束后冷却至室温，取出炭化产物。在研钵中将产物研磨至粉末状，使用0.1mol/L盐酸溶液在60℃下酸洗12h，随后对酸洗溶液进行抽滤，并用去离子水将产物洗涤至中性。最后，在105℃烘箱中干燥12h得到用于催化氧还原反应的富氮生物油基多孔炭，记为NC3。
CV和LSV的测试结果证明NC3具有对氧还原反应的催化性能，在0.1mol/L KOH溶液中的LSV测试中，NC3的起始电位和半波电位分别为0.021V和-0.166V。NC3中存在发达的孔隙，以介孔为主，兼有少量微孔，测得比表面积为1066.81m 2/g，孔容为0.72cm 3/g。NC3中氮含量为3.11wt％，氮官能团中石墨型与吡啶型氮的总含量为52％。通过拉曼光谱分析可知NC3主要由无定型碳和石墨化结构组成，石墨化程度较高。
实施例4
一种富氮生物油基多孔炭的制备方法，包括如下步骤：
1)富氮生物油的制备：称取150g干燥秸秆和300g尿素，混合均匀后在氮气氛围下进行热解，升温速率为50℃/min,热解温度为800℃，保温2h，氮气流速为200mL/min，得到富氮生物油，记为A4。
2)富氮生物油与模板剂混合物的制备：称取10gA4和10g乙酸镁，向其中加入乙醇后，在85℃下搅拌均匀，冷却至室温后得到富氮生物油与模板剂的 混合物，记为B4。
3)富氮生物油基多孔炭的制备：称取8g B4，在氩气氛围中进行热解，升温速率10℃/min,热解温度为800℃，保温2h，氮气流速为100mL/min。待反应结束后冷却至室温，取出炭化产物。在研钵中将产物研磨至粉末状，使用2mol/L盐酸溶液在60℃下酸洗12h，随后对酸洗溶液进行抽滤，并用去离子水将产物洗涤至中性。最后，在105℃烘箱中干燥12h得到用于催化氧还原反应的富氮生物油基多孔炭，记为NC4。
CV和LSV的测试结果证明NC4具有对氧还原反应的催化性能，在0.1mol/L KOH溶液中的LSV测试中，NC4的起始电位和半波电位分别为0.018V和-0.160V。NC4中存在发达的孔隙，以介孔为主，兼有少量微孔，测得比表面积为1039.84m 2/g，孔容为1.24cm 3/g。NC4中氮含量为2.5wt％，氮官能团中石墨型与吡啶型氮的总含量为48％。通过拉曼光谱分析可知NC4主要由无定型碳和石墨化结构组成，石墨化程度较高。
实施例5
一种富氮生物油基多孔炭的制备方法，包括如下步骤：
1)富氮生物油的制备：称取150g干燥核桃壳和150g尿素，混合均匀后在氮气氛围下进行热解，升温速率为50℃/min,热解温度为800℃，保温2h，氮气流速为200mL/min，得到富氮生物油，记为A5。
2)富氮生物油与模板剂混合物的制备：称取10gA5和15g碳酸镁，向其中加入乙醇后，在85℃下搅拌均匀，冷却至室温后得到富氮生物油与模板剂的混合物，记为B5。
3)富氮生物油基多孔炭的制备：称取8g B5，在氩气氛围中进行热解，升温速率10℃/min,热解温度为900℃，保温2h，氮气流速为500mL/min。待反应结束后冷却至室温，取出炭化产物。在研钵中将产物研磨至粉末状，使用2mol/L盐酸溶液在60℃下酸洗12h，随后对酸洗溶液进行抽滤，并用去离子水将产物洗涤至中性。最后，在105℃烘箱中干燥12h得到用于催化氧还原反应的富氮生物油基多孔炭，记为NC5。
CV和LSV的测试结果证明NC5具有对氧还原反应的催化性能，在0.1mol/L KOH溶液中的LSV测试中，NC5的起始电位和半波电位分别为-0.011V和-0.172V。NC5中存在发达的孔隙，以介孔为主，兼有少量微孔，测得比表面积为562.36m 2/g，孔容为0.31cm 3/g。NC5中氮含量为3.39wt％，氮官能团中石墨型与吡啶型氮的总含量为42％。通过拉曼光谱分析可知NC5主要由无定型碳和石墨化结构组成，石墨化程度较高。
实施例6
一种富氮生物油基多孔炭的制备方法，包括如下步骤：
1)富氮生物油的制备：称取150g干燥稻壳和150g聚酰胺，混合均匀后在氮气氛围下进行热解，升温速率为10℃/min,热解温度为600℃，保温2h，氮气流速为200mL/min，得到富氮生物油，记为A6。
2)富氮生物油与模板剂混合物的制备：称取10gA6和40g氯化钾，向其中加入乙醇后，在85℃下搅拌均匀，冷却至室温后得到富氮生物油与模板剂的混合物，记为B6。
3)富氮生物油基多孔炭的制备：称取8g B6，在氩气氛围中进行热解，升温速率10℃/min,热解温度为800℃，保温2h，氮气流速为100mL/min。待反应结束后冷却至室温，取出炭化产物。在研钵中将产物研磨至粉末状，使用2mol/L盐酸溶液在60℃下酸洗12h，随后对酸洗溶液进行抽滤，并用去离子水将产物洗涤至中性。最后，在105℃烘箱中干燥12h得到用于催化氧还原反应的富氮生物油基多孔炭，记为NC6。
CV和LSV的测试结果证明NC6具有对氧还原反应的催化性能，在0.1mol/L KOH溶液中的LSV测试中，NC6的起始电位和半波电位分别为-0.058V和-0.181V。NC6中存在发达的孔隙，以微孔为主，兼有少部分介孔，测得比表面积为343.26m 2/g，孔容为0.22cm 3/g。NC6中氮含量为3.07wt％，氮官能团中石墨型与吡啶型氮的总含量为42％。通过拉曼光谱分析可知NC5主要由无定型碳和石墨化结构组成，石墨化程度较高。
实施例7 一种富氮生物油基多孔炭的制备方法与现有技术的对比
Figure PCTCN2021123436-appb-000002
Figure PCTCN2021123436-appb-000003
与本发明相比，对比表中专利1和2采用相似的碳前驱体焦油，但未提及焦油制备方式，也未掺氮，应用方向也不同；专利3采用一般固体碳源、尿素氮源(与本发明相似)，但造孔方式为传统CO 2活化，比表面积低、孔结构不同；专利4和5均为掺氮多孔炭的制备及与本发明相同的氧还原催化应用、炭的理化性质及催化性能与本发明我们相近，然而制备方法有两点不同，一是碳源采用了自身含氮的生物质，二是用碱活化，我们的方法原料适应性更强，采用的模板剂可回收利用，对环境更加友好。
上述的对实施例的描述是为了便于该技术领域的普通技术人员对本发明的理解和使用。熟悉本领域技术的人员显然可以对这些实施例做出各种修改，并把在此说明的一般原理应用于其他实验中而不必经过创造性的劳动。因此，本发明不限于上述实施例，在不脱离本发明精神和范围的前提下所做出的改进和修改都应该在本发明的保护范围之内。

Claims (10)

  1. 一种富氮生物油基多孔炭，其特征在于所述多孔碳以生物质和含氮化合物共热解所得富氮生物油为前驱体，以金属盐为模板剂，通过一步炭化制备多孔炭。
  2. 根据权利要求1所述的一种富氮生物油基多孔炭的制备方法，其特征在于，包括如下步骤：
    (1)富氮生物油的制备：将生物质和含氮原料混合均匀，在惰性气体氛围下共热解得到富氮生物油；
    (2)富氮生物油与模板剂混合：取步骤(1)中的富氮生物油，加入模板剂和无水乙醇后，在加热条件下搅拌均匀，待冷却至室温后得到富氮生物油与模板剂混合物；
    (3)富氮生物油基多孔炭的制备：在惰性气体氛围下炭化步骤(2)的混合物，待升温后保持恒温，反应结束后自然冷却至室温，得到炭化产物；
    (4)对步骤(3)中的炭化产物进行酸洗处理，随后使用去离子水洗涤至中性，经过滤和干燥后得到最终产物。
  3. 根据权利要求2所述的一种富氮生物油基多孔炭的制备方法，其特征在于：所述步骤(1)中的生物质为松木、稻壳、椰壳、核桃壳、花生壳、秸秆、甘蔗渣中的至少一种，含氮原料为废弃尼龙(聚酰胺)、尿素、三聚氰胺中的至少一种。
  4. 根据权利要求2所述的一种富氮生物油基多孔炭的制备方法，其特征在于：所述步骤(1)中生物质与含氮原料质量比为0.5:1～2:1。
  5. 根据权利要求2所述的一种富氮生物油基多孔炭的制备方法，其特征在于：所述步骤(1)热解的条件为：升温速率为1-50℃/min，热解温度为500-800℃，保温时间为1-3h，气体流速为10-500mL/min。
  6. 根据权利要求2所述的一种富氮生物油基多孔炭的制备方法，其特征在于：所述步骤(2)中模板剂为氯化锌、乙酸镁、氢氧化镁、碳酸镁、氯化钾、碳酸钾中的至少一种。
  7. 根据权利要求2所述的一种富氮生物油基多孔炭的制备方法，其特征在于：所述步骤(2)中富氮生物油与模板剂质量比为1:1-1:5。
  8. 根据权利要求2所述的一种富氮生物油基多孔炭的制备方法，其特征在于：所述步骤(3)炭化的条件为：升温速率为1-20℃/min，升温至500-1000℃并保持恒温，保温时间为1-3h，气体流速为10-500mL/min。
  9. 根据权利要求2所述的一种富氮生物油基多孔炭的制备方法，其特征在于：所述步骤(4)的酸洗条件为：使用0.1-3mol/L稀盐酸溶液，洗涤时间为1-12 h，酸洗温度为25-60℃。
  10. 根据权利要求1-9所述的一种富氮生物油基多孔炭在电化学催化氧还原反应上的应用。
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