WO2021190541A1 - Polyaniline-gold composite material, and preparation and application thereof - Google Patents

Polyaniline-gold composite material, and preparation and application thereof Download PDF

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WO2021190541A1
WO2021190541A1 PCT/CN2021/082631 CN2021082631W WO2021190541A1 WO 2021190541 A1 WO2021190541 A1 WO 2021190541A1 CN 2021082631 W CN2021082631 W CN 2021082631W WO 2021190541 A1 WO2021190541 A1 WO 2021190541A1
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polyaniline
composite material
preparation
gold
acid
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PCT/CN2021/082631
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French (fr)
Chinese (zh)
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柳鹏
张亚楠
程发良
张敏
阮栋梁
王寿山
谢世磊
谢东
谭桂平
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东莞理工学院
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Publication of WO2021190541A1 publication Critical patent/WO2021190541A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J35/33—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction

Definitions

  • the invention relates to the field of composite material catalysis, in particular to a preparation method of polyaniline-gold nanoparticle composite material and its application in electrocatalytic reduction of carbon dioxide.
  • high value-added chemicals such as methane, ethylene, ethanol, propane, etc.
  • nano-carbon substrates have become the focus of research by researchers due to their unique ability to assemble carbon atoms into nanomaterials with different dimensions and structures, such as one-dimensional carbon nanotubes (CNT), carbon nanofibers (CNF) and two-dimensional Graphene.
  • CNT carbon nanotubes
  • CNF carbon nanofibers
  • Polyaniline has conductivity, stability, diversified structure, special doping mechanism, photoelectric properties, easy processing, and cheap raw materials. It has become the characteristics of conductive polymer research.
  • the polymer preparation methods are diverse, but due to the preparation process Different from the conditions, the obtained polyaniline materials have great differences in morphology and performance, which affects their application effects.
  • a method for preparing a polyaniline-gold composite material is provided.
  • the polyaniline-gold composite material obtained by the preparation method of the present invention has good electrocatalytic performance and can be applied to the field of electroreduction of CO 2 .
  • Another object of the present invention is to provide a polyaniline-gold composite material prepared by the above preparation method.
  • Another object of the present invention is to provide the application of polyaniline-gold composite material in the electro-reduction of CO 2 .
  • a preparation method of polyaniline-gold composite material includes the following steps.
  • the polyaniline template includes short-chain polyaniline.
  • a short-chain polyaniline template is prepared by cyclic voltammetry.
  • a mixed solution including aniline and acid is used as the electrolyte.
  • the acid is sulfuric acid, hydrochloric acid, or a mixture thereof.
  • the hydrophilic carbon paper is mounted on the platinum electrode holder as the working electrode.
  • the electrode and the reference electrode are not particularly limited, and those skilled in the art can make a choice based on conventional experiments and techniques.
  • the present invention uses a platinum sheet electrode as a counter electrode, and a saturated calomel electrode as a reference electrode.
  • the starting potential of the cyclic voltammetry is -0.1 ⁇ -0.4V, and the ending potential is 0.5 ⁇ 1.1V.
  • the starting potential is -0.1 ⁇ -0.2 V
  • the termination potential is 0.9 ⁇ 1.0 V.
  • the number of scan cycles is 10-40 cycles, preferably 15-30 cycles.
  • the scanning speed is 40-60 mV/s, preferably, 50 mV/s.
  • the concentration of the aniline in the mixed solution is 0.05-0.1 mol/L
  • the acid concentration is 0.05-0.1 mol/L
  • the acid is, for example, sulfuric acid
  • the molar ratio of aniline to acid is 1:1.
  • the hydrophilic carbon paper is cleaned in advance.
  • ultrasonic cleaning is performed in deionized water, ethanol, and deionized water in sequence.
  • the cleaning time is 5-20 minutes each, such as 10 minutes.
  • the gold ion solution is selected from chloroauric acid and gold trichloride solution.
  • the polyaniline obtained in step (1) is placed in a chloroauric acid solution for reaction.
  • the reaction time is 5-30 min, preferably 20-30 min.
  • the concentration of the chloroauric acid solution is 0.5-4 mmol/l, for example, 1-2 mmol/l.
  • the reaction temperature in step (2) is 2-8°C, for example 3-4°C.
  • the short-chain polyaniline synthesized by the invention is beneficial to improve the morphology of the gold particles generated in situ, so that the particle size is appropriate and uniform, and the adhesion is improved, thereby enhancing the synergistic effect of polyaniline and gold particles, and improving the catalytic performance of the composite material .
  • the synthesized network polyaniline is more, the structure is more fluffy, and the gold particles generated in situ are larger, the agglomeration is obvious, and the adhesion is reduced, which not only affects the gold loading, but also weakens the polyaniline and gold The synergistic effect of the carbon dioxide, thereby ultimately reducing the catalytic performance of the material.
  • the present invention found that the size of the gold particles also significantly affects the catalytic performance of the composite material. It is not that the smaller the particles, the better.
  • gold particles of 6-8 nm are prepared in the prior art, and the small-sized Au nanoparticles are easy to agglomerate and not easy to agglomerate. It is prepared, and its catalytic effect is far less than that of the Au nanoparticle-polyaniline composite material with a size in the range of 100-400 nm of the present invention.
  • the present invention has found through comparative research that controlling the aniline concentration and the sulfuric acid concentration in step (1) can realize the excellent compact structure of polyaniline.
  • gold particles with strong adhesion, appropriate size, and uniform particles without agglomeration will be obtained.
  • a short-chain polyaniline structure suitable for in-situ generation of gold particles is prepared by cyclic voltammetry.
  • the polyaniline and gold ion solution undergo redox reaction.
  • the polyaniline structure can improve the adhesion of gold on the surface of polyaniline. Focus on obtaining gold particles with excellent morphology.
  • the invention utilizes the good electrocatalytic CO2 performance of Au metal, plus the unique conductivity, reducibility, ease of synthesis and low cost of polyaniline (PANI), and prepares the PANI/Au nanometers with controllable size by in-situ reduction method.
  • the composite material can be used in the field of electro-reduction CO2, due to its suitable gold loading, uniform particles, no large agglomeration, and good synergy between gold and polyaniline, so the catalytic effect is excellent.
  • the method provided by the invention is carried out under low temperature and normal pressure, and the preparation method is simple and convenient.
  • FIG. 1 is an SEM image of the polyaniline template prepared in Example 1.
  • Example 2 is a SEM image of the polyaniline-gold composite material prepared in Example 1.
  • FIG. 3 is a linear scan (LSV) graph of electrochemical reduction of carbon dioxide of the polyaniline-gold composite material prepared in Example 1.
  • LSV linear scan
  • FIG. 4 is a graph showing the Faraday efficiency (FE) of the electrochemical reduction of carbon dioxide line of the polyaniline-gold composite material prepared in Example 1.
  • Example 5 is an SEM image of the polyaniline-gold composite material prepared in Example 2.
  • FIG. 6 is a graph showing the Faraday efficiency (FE) of the electrochemical reduction of carbon dioxide line of the polyaniline-gold composite material prepared in Example 2.
  • Embodiment 1 A preparation method of polyaniline-gold composite material, including the following steps.
  • the hydrophilic carbon paper with a thickness of 0.2mm was washed in deionized water, ethanol, and deionized water in order, each for 10 minutes.
  • the cleaned hydrophilic carbon paper was installed on the platinum electrode holder as the working electrode, and the geometric size of the working electrode was 1 cm ⁇ 1 cm.
  • a platinum sheet is used as the counter electrode, with a geometric size of 1 cm ⁇ 1 cm.
  • the saturated calomel electrode (SCE) serves as the reference electrode and is placed in the electrolytic cell.
  • step (3) After taking out the polyaniline-gold material prepared in step (3), rinse it with deionized water to obtain a polyaniline-gold composite material.
  • Figure 1 is an SEM image of the polyaniline template prepared in this example. It can be seen from Figure 1 that the generated polyaniline particles are evenly spread on the surface of the carbon paper, and part of the short-chain polyaniline protrusions are formed. Increase the contact area of the catalytic reaction.
  • Figure 2 is an SEM image of the prepared polyaniline-gold material. It can be seen from Figure 2 that the produced gold particles are uniform with a size of about 160 nm.
  • Figure 3 is a linear scan (LSV) graph of electrochemical reduction of carbon dioxide for polyaniline oxygen-gold composites. It can be seen from Figure 3 that the wave potential of the polyaniline-gold composite material in nitrogen is -0.4 V (vs. RHE), and the wave potential in CO2 is higher than its potential in argon atmosphere, which is- 0.3 V (vs. RHE). Potential from -0.3 ⁇ -0.9V, the current density of polyaniline-gold composite material in CO2 is higher than its current density in nitrogen atmosphere, carbon dioxide reduction reaction is dominant, -0.9 ⁇ -1.1V, polyaniline-gold composite material is in CO2 Its current density is lower than its current density in a nitrogen atmosphere, and the hydrogen evolution reaction is dominant. The figure shows that the prepared polyaniline-gold composite material has good CO2 reduction performance.
  • Figure 4 shows the Faraday efficiency (FE) graph of electrochemical reduction of polyaniline oxygen-gold composite material. It can be seen from Figure 4 that the electrocatalytic reduction of carbon dioxide by this material only produces H2 and CO. From -0.5 to -0.7 V (vs. RHE), the CO production of materials gradually increases, and the highest CO production at -0.7 V (vs. RHE) is about 99%. After that, the CO Faraday efficiency gradually decreases and the hydrogen production gradually increases.
  • FE Faraday efficiency
  • Embodiment 2 A preparation method of polyaniline-gold composite material, including the following steps.
  • the hydrophilic carbon paper with a thickness of 0.2 mm was ultrasonically cleaned in deionized water, ethanol, and deionized water for 10 minutes each.
  • the cleaned hydrophilic carbon paper is installed on the platinum electrode holder as the working electrode. Put the platinum mesh as the counter electrode and the saturated calomel electrode (SCE) as the reference electrode in the electrolytic cell.
  • SCE saturated calomel electrode
  • step (3) After taking out the polyaniline-gold material obtained in step (3), rinse it with deionized water to obtain a polyaniline-gold composite material.
  • Figure 5 is the SEM image of the prepared polyaniline-gold material. It can be seen that the gold particles generated are slightly aggregated, with a size of about 330 nm, and the short-chain polyaniline also becomes a network structure and the content increases.
  • Figure 6 is a graph showing the Faraday efficiency (FE) of electrochemical reduction of the polyaniline oxygen-gold composite material of the polyaniline oxygen-gold composite material. It can be seen from this that the only products of electrocatalytic reduction of carbon dioxide by this material are H2 and CO. From -0.5 to -0.7 V (vs. RHE), the CO production of materials gradually increased. At -0.7 V (vs. RHE), the CO production of materials was the highest, about 24%. After that, the CO Faraday efficiency gradually decreased and the hydrogen production gradually increased.
  • FE Faraday efficiency
  • Embodiment 3 A preparation method of polyaniline-gold composite material, including the following steps.
  • the hydrophilic carbon paper with a thickness of 0.2 mm was ultrasonically cleaned in deionized water, ethanol, and deionized water for 10 minutes each.
  • the cleaned hydrophilic carbon paper is installed on the platinum electrode holder as the working electrode.
  • the platinum wire is used as the counter electrode and the saturated calomel electrode (SCE) is used as the reference electrode, placed in the electrolytic cell.
  • SCE saturated calomel electrode
  • step (3) After taking out the polyaniline-gold material obtained in step (3), rinse it with deionized water to obtain a polyaniline-gold composite material.

Abstract

A preparation method for a polyaniline-gold composite material. The method comprises the following steps: (1) preparing a short-chain polyaniline template; and (2) reacting the short-chain polyaniline template with gold ions to obtain the polyaniline-gold composite material. According to the present invention, the size-controllable PANI/Au nanometer composite material is prepared by means of an in-situ reduction method, the composite material can be applied to the field of electroreduction of CO2, and the catalytic effect of the composite material is excellent due to the fact that a gold loading amount is proper, particles are uniform, no large agglomeration exists and a good synergistic effect exists between the composite material and polyaniline.

Description

聚苯胺-金复合材料、制备及其用途Polyaniline-gold composite material, preparation and use thereof
相关申请的交叉引用。Cross-references to related applications.
本申请要求于2020年3月26日提交中国专利局，申请号为202010225323.6，发明名称为“聚苯胺-金复合材料、制备及其用途”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of a Chinese patent application filed with the Chinese Patent Office on March 26, 2020, the application number is 202010225323.6, and the invention title is "polyaniline-gold composite material, preparation and use", the entire content of which is incorporated by reference In this application.
技术领域Technical field
本发明涉及复合材料催化领域，特别涉及聚苯胺-金纳米粒子复合材料的制备方法及其在电催化还原二氧化碳中的应用。The invention relates to the field of composite material catalysis, in particular to a preparation method of polyaniline-gold nanoparticle composite material and its application in electrocatalytic reduction of carbon dioxide.
背景技术Background technique
二氧化碳电催化——以二氧化碳为原料，通过电催化还原二氧化碳得到高附加值的甲烷、乙烯、乙醇、丙烷等化学品，这些物质可以直接用作汽车、飞机等交通工具的燃料，使得碳循环变得更为容易，一定程度上降低CO2的释放，缓解温室效应。Carbon dioxide electrocatalysis-using carbon dioxide as a raw material, through electrocatalytic reduction of carbon dioxide to obtain high value-added chemicals such as methane, ethylene, ethanol, propane, etc., these substances can be directly used as fuel for vehicles such as cars and airplanes, making the carbon cycle change It’s easier to get it, to a certain extent, to reduce the release of CO2 and alleviate the greenhouse effect.
在电化学还原CO2的研究中，主要采用金属催化剂。相对于金属的高价格和低储量，非金属，尤其是碳材料，来源更广，价格也低廉得多，且对环境友好，因此许多研究者正在尝试将金属负载于非金属基底上来电化学催化还原CO2。目前，纳米碳基底由于其将碳原子组装成具有不同维度和结构的纳米材料的独特能力而成为研究者重点研究的对象，如一维碳纳米管（CNT）、碳纳米纤维（CNF）和二维石墨烯。In the study of electrochemical reduction of CO2, metal catalysts are mainly used. Compared with the high price and low reserves of metals, non-metals, especially carbon materials, have wider sources, much lower prices, and are environmentally friendly. Therefore, many researchers are trying to load metals on non-metal substrates for electrochemical catalysis. Reduce CO2. At present, nano-carbon substrates have become the focus of research by researchers due to their unique ability to assemble carbon atoms into nanomaterials with different dimensions and structures, such as one-dimensional carbon nanotubes (CNT), carbon nanofibers (CNF) and two-dimensional Graphene.
技术问题technical problem
聚苯胺具有导电性、稳定性，结构多样化，特殊的掺杂机制，光电性质、易加工和原料廉价易得，已成为导电聚合物研究的特点，该聚合物制备方法多样，但因制备工艺和条件不同，得到的聚苯胺材料在形态和性能等方面都有较大的差异，从而影响其应用效果。Polyaniline has conductivity, stability, diversified structure, special doping mechanism, photoelectric properties, easy processing, and cheap raw materials. It has become the characteristics of conductive polymer research. The polymer preparation methods are diverse, but due to the preparation process Different from the conditions, the obtained polyaniline materials have great differences in morphology and performance, which affects their application effects.
技术解决方案Technical solutions
根据本申请的各种实施例，提供一种聚苯胺-金复合材料的制备方法，本发明的制备方法得到的聚苯胺-金复合材料具有良好的电催化性能，可应用于电还原CO 2领域。本发明的另一目的在于提供上述制备方法制备得到的聚苯胺-金复合材料。本发明的另一目的在于提供聚苯胺-金复合材料在电还原CO 2中的应用。 According to various embodiments of the present application, a method for preparing a polyaniline-gold composite material is provided. The polyaniline-gold composite material obtained by the preparation method of the present invention has good electrocatalytic performance and can be applied to the field of electroreduction of CO 2 . Another object of the present invention is to provide a polyaniline-gold composite material prepared by the above preparation method. Another object of the present invention is to provide the application of polyaniline-gold composite material in the electro-reduction of CO 2 .
一种聚苯胺-金复合材料的制备方法，所述方法包括如下步骤。A preparation method of polyaniline-gold composite material, the method includes the following steps.
（1）制备短链状聚苯胺模版。(1) Prepare short-chain polyaniline templates.
（2）短链状聚苯胺模版与金离子反应，得到聚苯胺-金复合材料。(2) The short-chain polyaniline template reacts with gold ions to obtain a polyaniline-gold composite material.
其中，聚苯胺模板包括短链聚苯胺。Among them, the polyaniline template includes short-chain polyaniline.
在其中一个实施例中，所述步骤（1）中，以循环伏安法制备得到短链状聚苯胺模板。优选的，以包括苯胺和酸的混合溶液为电解液。优选的，所述酸是硫酸，盐酸，或其混合物。In one of the embodiments, in the step (1), a short-chain polyaniline template is prepared by cyclic voltammetry. Preferably, a mixed solution including aniline and acid is used as the electrolyte. Preferably, the acid is sulfuric acid, hydrochloric acid, or a mixture thereof.
在其中一个实施例中，所述步骤（1）中，将亲水碳纸装于铂电极夹上作为工作电极。In one of the embodiments, in the step (1), the hydrophilic carbon paper is mounted on the platinum electrode holder as the working electrode.
在其中一个实施例中，所述步骤（1）中，对电极和参比电极不做特别限定，本领域技术人员基于常规实验和技术可以做出选择。示例性的，本发明以铂片电极为对电极，饱和甘汞电极为参比电极。In one of the embodiments, in the step (1), the electrode and the reference electrode are not particularly limited, and those skilled in the art can make a choice based on conventional experiments and techniques. Exemplarily, the present invention uses a platinum sheet electrode as a counter electrode, and a saturated calomel electrode as a reference electrode.
在其中一个实施例中， 所述循环伏安法的起始电位为-0.1～-0.4 V，终止电位为0.5～1.1 V。优选的，起始电位为-0.1～-0.2 V，终止电位为0.9～1.0 V。在其中一个实施例中，所述循环伏安法中，扫描圈数为10～40圈，优选的，15-30圈。扫描速度是40-60 mV/s，优选的，50 mV/s。In one of the embodiments, the starting potential of the cyclic voltammetry is -0.1~-0.4V, and the ending potential is 0.5~1.1V. Preferably, the starting potential is -0.1～-0.2 V, the termination potential is 0.9 ~ 1.0 V. In one of the embodiments, in the cyclic voltammetry, the number of scan cycles is 10-40 cycles, preferably 15-30 cycles. The scanning speed is 40-60 mV/s, preferably, 50 mV/s.
在其中一个实施例中，所述苯胺在混合溶液中的浓度为0.05 -0.1 mol/L，酸浓度为0.05-0.1 mol/L。优选的，所述酸例如是硫酸，苯胺与酸的摩尔比为1：1。In one of the embodiments, the concentration of the aniline in the mixed solution is 0.05-0.1 mol/L, and the acid concentration is 0.05-0.1 mol/L. Preferably, the acid is, for example, sulfuric acid, and the molar ratio of aniline to acid is 1:1.
在其中一个实施例中，步骤（1）中，所述亲水碳纸预先清洗处理。例如依次在去离子水、乙醇、去离子水中分别超声清洗。优选的，清洗时间各5-20分钟，例如10分钟。In one of the embodiments, in step (1), the hydrophilic carbon paper is cleaned in advance. For example, ultrasonic cleaning is performed in deionized water, ethanol, and deionized water in sequence. Preferably, the cleaning time is 5-20 minutes each, such as 10 minutes.
在其中一个实施例中，步骤（2）中，所述金离子溶液选自氯金酸、三氯化金溶液。优选的，将步骤（1）制得的聚苯胺置于氯金酸溶液中反应。In one of the embodiments, in step (2), the gold ion solution is selected from chloroauric acid and gold trichloride solution. Preferably, the polyaniline obtained in step (1) is placed in a chloroauric acid solution for reaction.
在其中一个实施例中，步骤（2）中，所述反应时间为5~30 min，优选为20-30min。In one of the embodiments, in step (2), the reaction time is 5-30 min, preferably 20-30 min.
在其中一个实施例中，步骤（2）中，所述氯金酸溶液的浓度为0.5-4mmol/l，例如1-2mmol/l。In one of the embodiments, in step (2), the concentration of the chloroauric acid solution is 0.5-4 mmol/l, for example, 1-2 mmol/l.
在其中一个实施例中，步骤（2）的反应温度为2-8℃，例如3-4℃。In one of the embodiments, the reaction temperature in step (2) is 2-8°C, for example 3-4°C.
有益效果Beneficial effect
本发明合成的短链聚苯胺有利于提高原位生成的金颗粒的形貌，使其颗粒尺寸合适且均匀，附着力提高，从而增强聚苯胺与金颗粒的协同作用，提高复合材料的催化性能。相反的，若合成的网状聚苯胺越多，结构越蓬松，其原位生成的金颗粒则更大，团聚明显，附着力降低，不仅影响了金的负载量，也减弱了聚苯胺与金的协同作用，从而最终降低材料的催化性能。此外，本发明发现，金颗粒的尺寸大小也明显影响复合材料的催化性能，并非颗粒越小越好，如现有技术制备有6-8nm的金颗粒，该小尺寸Au纳米颗粒易团聚且不易制备，而其催化效果远没有本发明尺寸在100-400nm范围内的Au纳米颗粒-聚苯胺复合材料好。本发明经对比研究发现，控制步骤（1）的苯胺浓度和硫酸浓度，能实现聚苯胺优良的致密性结构。此外将步骤（2）的反应时间和金离子溶液的浓度调控在特定反应温度下的范围内，会得到附着力强、尺寸大小适当、且颗粒均匀无团聚的金粒子。The short-chain polyaniline synthesized by the invention is beneficial to improve the morphology of the gold particles generated in situ, so that the particle size is appropriate and uniform, and the adhesion is improved, thereby enhancing the synergistic effect of polyaniline and gold particles, and improving the catalytic performance of the composite material . On the contrary, if the synthesized network polyaniline is more, the structure is more fluffy, and the gold particles generated in situ are larger, the agglomeration is obvious, and the adhesion is reduced, which not only affects the gold loading, but also weakens the polyaniline and gold The synergistic effect of the carbon dioxide, thereby ultimately reducing the catalytic performance of the material. In addition, the present invention found that the size of the gold particles also significantly affects the catalytic performance of the composite material. It is not that the smaller the particles, the better. For example, gold particles of 6-8 nm are prepared in the prior art, and the small-sized Au nanoparticles are easy to agglomerate and not easy to agglomerate. It is prepared, and its catalytic effect is far less than that of the Au nanoparticle-polyaniline composite material with a size in the range of 100-400 nm of the present invention. The present invention has found through comparative research that controlling the aniline concentration and the sulfuric acid concentration in step (1) can realize the excellent compact structure of polyaniline. In addition, by adjusting the reaction time of step (2) and the concentration of the gold ion solution within a specific reaction temperature range, gold particles with strong adhesion, appropriate size, and uniform particles without agglomeration will be obtained.
本发明通过循环伏安法制备得到了适于原位生成金颗粒的短链聚苯胺结构，通过聚苯胺与金离子溶液进行氧化还原反应，所述聚苯胺结构能够提高金在聚苯胺表面的附着力，得到形貌优良的金粒子。本发明利用Au金属良好的电催化CO2性能，加上聚苯胺（PANI）独特的导电性、还原性、易于合成及成本低廉等特性，通过原位还原法制备了尺寸可控的PANI/Au纳米复合材料，该复合材料可应用于电还原CO2 领域，由于其金负载量适宜且颗粒均匀，无大块团聚，金与聚苯胺之间存在良好的协同作用，故催化效果优良。本发明提供的方法在低温常压下进行，制备方法简便。In the present invention, a short-chain polyaniline structure suitable for in-situ generation of gold particles is prepared by cyclic voltammetry. The polyaniline and gold ion solution undergo redox reaction. The polyaniline structure can improve the adhesion of gold on the surface of polyaniline. Focus on obtaining gold particles with excellent morphology. The invention utilizes the good electrocatalytic CO2 performance of Au metal, plus the unique conductivity, reducibility, ease of synthesis and low cost of polyaniline (PANI), and prepares the PANI/Au nanometers with controllable size by in-situ reduction method. Composite material, the composite material can be used in the field of electro-reduction CO2, due to its suitable gold loading, uniform particles, no large agglomeration, and good synergy between gold and polyaniline, so the catalytic effect is excellent. The method provided by the invention is carried out under low temperature and normal pressure, and the preparation method is simple and convenient.
附图说明Description of the drawings
为了更好地描述和说明这里公开的那些发明的实施例和/或示例，可以参考一幅或多幅附图。用于描述附图的附加细节或示例不应当被认为是对所公开的发明、目前描述的实施例和/或示例以及目前理解的这些发明的最佳模式中的任何一者的范围的限制。In order to better describe and illustrate the embodiments and/or examples of the inventions disclosed herein, one or more drawings may be referred to. The additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed inventions, the currently described embodiments and/or examples, and the best mode of these inventions currently understood.
图1为实施例1制备得到的聚苯胺模板的SEM图。FIG. 1 is an SEM image of the polyaniline template prepared in Example 1.
图2为实施例1制备得到的聚苯胺-金复合材料SEM图。2 is a SEM image of the polyaniline-gold composite material prepared in Example 1.
图3为实施例1制备得到的聚苯胺-金复合材料的电化学还原二氧化碳线性扫描（LSV）图。FIG. 3 is a linear scan (LSV) graph of electrochemical reduction of carbon dioxide of the polyaniline-gold composite material prepared in Example 1. FIG.
图4为实施例1制备得到的聚苯胺-金复合材料的电化学还原二氧化碳线法拉第效率（FE）图。4 is a graph showing the Faraday efficiency (FE) of the electrochemical reduction of carbon dioxide line of the polyaniline-gold composite material prepared in Example 1.
图5为实施例2制备得到的聚苯胺-金复合材料的SEM图。5 is an SEM image of the polyaniline-gold composite material prepared in Example 2.
图6为实施例2制备得到的聚苯胺-金复合材料的电化学还原二氧化碳线法拉第效率（FE）图。6 is a graph showing the Faraday efficiency (FE) of the electrochemical reduction of carbon dioxide line of the polyaniline-gold composite material prepared in Example 2.
本发明的实施方式Embodiments of the present invention
为了便于理解本发明，下面将对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。In order to facilitate the understanding of the present invention, the present invention will be described more fully below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments, and are not intended to limit the present invention.
实施例1：一种聚苯胺-金复合材料的制备方法，包括如下步骤。Embodiment 1: A preparation method of polyaniline-gold composite material, including the following steps.
（1）将取0.2mm厚度的亲水碳纸依次在去离子水、乙醇、去离子水中分别超声清洗，各清洗10分钟。将经过清洗的亲水碳纸装于铂电极夹上当作工作电极、工作电极的几何尺寸为1 cm×1 cm。以铂片当对电极，几何尺寸为1 cm×1 cm。饱和甘汞电极（SCE）当参比电极，置于电解池中。(1) The hydrophilic carbon paper with a thickness of 0.2mm was washed in deionized water, ethanol, and deionized water in order, each for 10 minutes. The cleaned hydrophilic carbon paper was installed on the platinum electrode holder as the working electrode, and the geometric size of the working electrode was 1 cm×1 cm. A platinum sheet is used as the counter electrode, with a geometric size of 1 cm×1 cm. The saturated calomel electrode (SCE) serves as the reference electrode and is placed in the electrolytic cell.
（2）配制苯胺与硫酸的混合溶液，其中苯胺浓度为0.05 mol/L，硫酸浓度为0.05 mol/L。将配制的苯胺与酸的混合溶液加入到步骤（1）中的电解池中，以循环伏安法（CV）进行氧化还原制备聚苯胺模板，循环伏安法的起始电位为-0.1 V，终止电位为0.9 V，扫描圈数为15圈，扫描速度50 mV/s。(2) Prepare a mixed solution of aniline and sulfuric acid, where the concentration of aniline is 0.05 mol/L and the concentration of sulfuric acid is 0.05 mol/L. The prepared mixed solution of aniline and acid is added to the electrolytic cell in step (1), and the polyaniline template is prepared by redox by cyclic voltammetry (CV). The initial potential of the cyclic voltammetry is -0.1 V, The termination potential is 0.9 V, the number of scan circles is 15 circles, and the scan speed is 50 mV/s.
（3）配制氯金酸溶液，其浓度为1 mmol/L。将（2）制备的聚苯胺材料置于氯金酸溶液中，在4 ℃条件下浸渍，制备得到大量金颗粒。其中，反应时间为30 min。(3) Prepare a chloroauric acid solution with a concentration of 1 mmol/L. The polyaniline material prepared in (2) is placed in a chloroauric acid solution and immersed at 4°C to prepare a large number of gold particles. Among them, the reaction time is 30 min.
（4）将步骤（3）中制备得到的聚苯胺-金材料取出后，用去离子水冲洗干净，即得到聚苯胺-金复合材料。(4) After taking out the polyaniline-gold material prepared in step (3), rinse it with deionized water to obtain a polyaniline-gold composite material.
图1为本实施例制备得到的聚苯胺模板的SEM图，从图1中可以看出，生成的聚苯胺颗粒均匀铺在碳纸表面，一部分形成了短链状的聚苯胺凸起，其结构增加了催化反应的接触面积。Figure 1 is an SEM image of the polyaniline template prepared in this example. It can be seen from Figure 1 that the generated polyaniline particles are evenly spread on the surface of the carbon paper, and part of the short-chain polyaniline protrusions are formed. Increase the contact area of the catalytic reaction.
图2为制备得到的聚苯胺-金材料SEM图，从图2中可以看出，生成的金颗粒均匀，尺寸大小约为160 nm。Figure 2 is an SEM image of the prepared polyaniline-gold material. It can be seen from Figure 2 that the produced gold particles are uniform with a size of about 160 nm.
图3为聚苯胺氧-金复合材料的电化学还原二氧化碳线性扫描（LSV）图。从图3可以看出，聚苯胺-金复合材料在氮气中的起波电位为-0.4 V（vs. RHE），在CO2中的起波电位高于其在氩气氛围中的电位，为-0.3 V（vs. RHE）。电位从-0.3 ~ -0.9V，聚苯胺-金复合材料在CO2中的电流密度高于其在氮气氛围中的电流密度，二氧化碳还原反应占优势，-0.9 ~ -1.1V，聚苯胺-金复合材料在CO2中的电流密度低于其在氮气氛围中的电流密度，析氢反应占优势。该图表明制备的聚苯胺-金复合材料具有良好的还原CO2 性能。Figure 3 is a linear scan (LSV) graph of electrochemical reduction of carbon dioxide for polyaniline oxygen-gold composites. It can be seen from Figure 3 that the wave potential of the polyaniline-gold composite material in nitrogen is -0.4 V (vs. RHE), and the wave potential in CO2 is higher than its potential in argon atmosphere, which is- 0.3 V (vs. RHE). Potential from -0.3 ~ -0.9V, the current density of polyaniline-gold composite material in CO2 is higher than its current density in nitrogen atmosphere, carbon dioxide reduction reaction is dominant, -0.9 ~ -1.1V, polyaniline-gold composite material is in CO2 Its current density is lower than its current density in a nitrogen atmosphere, and the hydrogen evolution reaction is dominant. The figure shows that the prepared polyaniline-gold composite material has good CO2 reduction performance.
图4为聚苯胺氧-金复合材料的电化学还原法拉第效率（FE）图。从图4可以看出，该材料电催化还原二氧化碳产物只有H2和CO。从-0.5 ~ -0.7 V（vs. RHE），材料产CO逐渐升高，在-0.7 V（vs. RHE）时材料产CO最高，约99%，之后CO法拉第效率逐渐降低，氢气产量逐渐升高。Figure 4 shows the Faraday efficiency (FE) graph of electrochemical reduction of polyaniline oxygen-gold composite material. It can be seen from Figure 4 that the electrocatalytic reduction of carbon dioxide by this material only produces H2 and CO. From -0.5 to -0.7 V (vs. RHE), the CO production of materials gradually increases, and the highest CO production at -0.7 V (vs. RHE) is about 99%. After that, the CO Faraday efficiency gradually decreases and the hydrogen production gradually increases.
实施例2：一种聚苯胺-金复合材料的制备方法，包括如下步骤。Embodiment 2: A preparation method of polyaniline-gold composite material, including the following steps.
（1）将取0.2 mm厚度的亲水碳纸依次在去离子水、乙醇、去离子水中分别超声清洗，各清洗10分钟。将经过清洗的亲水碳纸装于铂电极夹上当作工作电极。以铂网当对电极、饱和甘汞电极（SCE）当参比电极，置于电解池中。(1) The hydrophilic carbon paper with a thickness of 0.2 mm was ultrasonically cleaned in deionized water, ethanol, and deionized water for 10 minutes each. The cleaned hydrophilic carbon paper is installed on the platinum electrode holder as the working electrode. Put the platinum mesh as the counter electrode and the saturated calomel electrode (SCE) as the reference electrode in the electrolytic cell.
（2）配制苯胺与硫酸的混合溶液，其中苯胺浓度为0.05 mol/L，硫酸浓度为0.1 mol/L。将配制的苯胺与硫酸的混合溶液加入到步骤（1）中的电解池中，以循环伏安法（CV）进行氧化还原制备聚苯胺模板。循环伏安法的起始电位为-0.2 V，终止电位为0.9 V，扫描圈数为30圈，扫描速度50 mV/s。(2) Prepare a mixed solution of aniline and sulfuric acid, where the concentration of aniline is 0.05 mol/L and the concentration of sulfuric acid is 0.1 mol/L. The prepared mixed solution of aniline and sulfuric acid is added to the electrolytic cell in step (1), and the polyaniline template is prepared by cyclic voltammetry (CV) for redox. The starting potential of cyclic voltammetry is -0.2 V, the ending potential is 0.9 V, the number of scanning cycles is 30, and the scanning speed is 50 mV/s.
（3）配制氯金酸溶液，其浓度为1 mmol/L。将（2）制备的聚苯胺材料置于氯金酸溶液中，在4 ℃条件下浸渍，制备大量金颗粒。其中，反应时间为20 min。(3) Prepare a chloroauric acid solution with a concentration of 1 mmol/L. The polyaniline material prepared in (2) is placed in a chloroauric acid solution and immersed at 4 ℃ to prepare a large number of gold particles. Among them, the reaction time is 20 min.
（4）将步骤（3）中得到的聚苯胺-金材料取出后，用去离子水冲洗干净，即得到聚苯胺-金复合材料。(4) After taking out the polyaniline-gold material obtained in step (3), rinse it with deionized water to obtain a polyaniline-gold composite material.
图5为制备得到的聚苯胺-金材料SEM图，从中可以看出，生成的金颗粒稍有聚集，尺寸大小约为330 nm，短链状的聚苯胺也变为网状结构且含量增加。Figure 5 is the SEM image of the prepared polyaniline-gold material. It can be seen that the gold particles generated are slightly aggregated, with a size of about 330 nm, and the short-chain polyaniline also becomes a network structure and the content increases.
图6为聚苯胺氧-金复合材料的聚苯胺氧-金复合材料的电化学还原法拉第效率（FE）图。从中可以看出，该材料电催化还原二氧化碳产物只有H2和CO。从-0.5~-0.7 V（vs. RHE），材料产CO逐渐升高，在-0.7 V（vs. RHE）时材料产CO最高，约24%，之后CO法拉第效率逐渐降低，氢气产量逐渐升高。Figure 6 is a graph showing the Faraday efficiency (FE) of electrochemical reduction of the polyaniline oxygen-gold composite material of the polyaniline oxygen-gold composite material. It can be seen from this that the only products of electrocatalytic reduction of carbon dioxide by this material are H2 and CO. From -0.5 to -0.7 V (vs. RHE), the CO production of materials gradually increased. At -0.7 V (vs. RHE), the CO production of materials was the highest, about 24%. After that, the CO Faraday efficiency gradually decreased and the hydrogen production gradually increased.
实施例3：一种聚苯胺-金复合材料的制备方法，包括如下步骤。Embodiment 3: A preparation method of polyaniline-gold composite material, including the following steps.
（1）将取0.2 mm厚度的亲水碳纸依次在去离子水、乙醇、去离子水中分别超声清洗，各清洗10分钟。将经过清洗的亲水碳纸装于铂电极夹上当作工作电极。以铂丝当对电极、饱和甘汞电极（SCE）当参比电极，置于电解池中。(1) The hydrophilic carbon paper with a thickness of 0.2 mm was ultrasonically cleaned in deionized water, ethanol, and deionized water for 10 minutes each. The cleaned hydrophilic carbon paper is installed on the platinum electrode holder as the working electrode. The platinum wire is used as the counter electrode and the saturated calomel electrode (SCE) is used as the reference electrode, placed in the electrolytic cell.
（2）配制苯胺与硫酸的混合溶液，其中苯胺浓度为0.08 mol/L，硫酸浓度为0.05 mol/L。将配制的苯胺与硫酸的混合溶液加入到步骤（1）中的电解池中，以循环伏安法（CV）进行氧化还原制备聚苯胺模板。循环伏安法的起始电位为-0.2 V，终止电位为1.0 V，扫描圈数为20圈，扫描速度50 mV/s。(2) Prepare a mixed solution of aniline and sulfuric acid, where the concentration of aniline is 0.08 mol/L and the concentration of sulfuric acid is 0.05 mol/L. The prepared mixed solution of aniline and sulfuric acid is added to the electrolytic cell in step (1), and the polyaniline template is prepared by cyclic voltammetry (CV) for redox. The starting potential of cyclic voltammetry is -0.2 V, the ending potential is 1.0 V, the number of scan circles is 20, and the scan speed is 50 mV/s.
（3）配制氯金酸溶液，其浓度为1 mmol/L。将（2）制备的聚苯胺材料置于氯金酸溶液中，在4 ℃条件下浸渍，制备大量金颗粒。其中，反应时间为10 min。(3) Prepare a chloroauric acid solution with a concentration of 1 mmol/L. The polyaniline material prepared in (2) is placed in a chloroauric acid solution and immersed at 4 ℃ to prepare a large number of gold particles. Among them, the reaction time is 10 min.
（4）将步骤（3）中得到的聚苯胺-金材料取出后，用去离子水冲洗干净，即得到聚苯胺-金复合材料。(4) After taking out the polyaniline-gold material obtained in step (3), rinse it with deionized water to obtain a polyaniline-gold composite material.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and their description is relatively specific and detailed, but they should not be understood as a limitation on the patent scope of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all fall within the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (9)

  1. 一种聚苯胺-金复合材料的制备方法，所述方法包括如下步骤。A preparation method of polyaniline-gold composite material, the method includes the following steps.
    （1）制备短链状聚苯胺模版。(1) Prepare short-chain polyaniline templates.
    （2）短链状聚苯胺模版与金离子反应，得到聚苯胺-金复合材料。(2) The short-chain polyaniline template reacts with gold ions to obtain a polyaniline-gold composite material.
    其中，聚苯胺模板包括短链聚苯胺。Among them, the polyaniline template includes short-chain polyaniline.
  2. 根据权利要求1的制备方法，所述步骤（1）中，以循环伏安法制备得到短链状聚苯胺模板。优选的，以包括苯胺和酸的混合溶液为电解液。优选的，所述酸是硫酸，盐酸，或其混合物。The preparation method according to claim 1, wherein in the step (1), a short-chain polyaniline template is prepared by cyclic voltammetry. Preferably, a mixed solution including aniline and acid is used as the electrolyte. Preferably, the acid is sulfuric acid, hydrochloric acid, or a mixture thereof.
  3. 根据权利要求1的制备方法， 所述循环伏安法的起始电位为-0.1～-0.4 V，终止电位为0.5～1.1 V。优选的，起始电位为-0.1～-0.2 V，终止电位为0.9～1.0 V。根据本发明的制备方法，所述循环伏安法中，扫描圈数为10～40圈，优选的，15-30圈。扫描速度是40-60 mV/s，优选的，50 mV/s。The preparation method according to claim 1, wherein the initial potential of the cyclic voltammetry is -0.1~-0.4V, and the termination potential is 0.5~1.1V. Preferably, the starting potential is -0.1 to -0.2 V, and the ending potential is 0.9 to 1.0 V. According to the preparation method of the present invention, in the cyclic voltammetry, the number of scanning cycles is 10-40 cycles, preferably 15-30 cycles. The scanning speed is 40-60 mV/s, preferably, 50 mV/s.
  4. 根据权利要求1的制备方法，所述苯胺在混合溶液中的浓度为0.05-0.1 mol/L，酸浓度为0.05-0.1 mol/L。优选的，所述酸例如是硫酸，苯胺与酸的摩尔比为1：1。According to the preparation method of claim 1, the concentration of the aniline in the mixed solution is 0.05-0.1 mol/L, and the acid concentration is 0.05-0.1 mol/L. Preferably, the acid is, for example, sulfuric acid, and the molar ratio of aniline to acid is 1:1.
  5. 根据权利要求1的制备方法，步骤（2）中，所述反应时间为5-30 min，优选为20-30min。The preparation method according to claim 1, in step (2), the reaction time is 5-30 min, preferably 20-30 min.
  6. 根据权利要求1的制备方法，步骤（2）中，所述氯金酸溶液的浓度为0.5-4mmol/l，例如1-2mmol/l。According to the preparation method of claim 1, in step (2), the concentration of the chloroauric acid solution is 0.5-4 mmol/l, for example, 1-2 mmol/l.
  7. 根据权利要求1的制备方法，步骤（2）的反应温度为2-8℃，例如3-4℃。According to the preparation method of claim 1, the reaction temperature in step (2) is 2-8°C, for example 3-4°C.
  8. 由权利要求1-7任一项的制备方法制备得到的聚苯胺-金复合材料。A polyaniline-gold composite material prepared by the preparation method of any one of claims 1-7.
  9. 权利要求8的聚苯胺-金复合材料在电还原CO2中的应用。Use of the polyaniline-gold composite material of claim 8 in the electro-reduction of CO2.
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