WO2023082908A1 - Method for preparing hydrogen peroxide by means of catalytic oxygen reduction by using covalent organic framework catalyst - Google Patents

Method for preparing hydrogen peroxide by means of catalytic oxygen reduction by using covalent organic framework catalyst Download PDF

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WO2023082908A1
WO2023082908A1 PCT/CN2022/124361 CN2022124361W WO2023082908A1 WO 2023082908 A1 WO2023082908 A1 WO 2023082908A1 CN 2022124361 W CN2022124361 W CN 2022124361W WO 2023082908 A1 WO2023082908 A1 WO 2023082908A1
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organic framework
covalent organic
catalyst
framework material
hydrogen peroxide
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陆双龙
邱思杭
黄绍达
杜明亮
朱罕
段芳
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江南大学
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    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/085—Organic compound
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/30—Peroxides
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • 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

  • the invention specifically relates to a method for preparing hydrogen peroxide by using a covalent organic framework catalyst to catalyze oxygen reduction, and belongs to the technical field of electrocatalysis.
  • H2O2 is a versatile and environmentally friendly oxidizing agent. It is widely used in disinfection, pulp, textile bleaching, wastewater treatment, chemical synthesis, semiconductor cleaning, detergent and exhaust gas treatment.
  • the global demand for H2O2 is rising due to its wide range of applications. According to incomplete statistics, the global annual production of H 2 O 2 reached 5.5 million tons in 2015.
  • the industry mainly uses electrolysis and anthraquinone methods.
  • the electrolysis method has high current efficiency, short process flow and high product quality, but due to high power consumption and high production cost, it is not suitable for large-scale industrial production and has been gradually eliminated.
  • the anthraquinone method has advanced technology, high degree of automation, low product cost and low energy consumption, but the production process is complex and cumbersome. Recently, the production of hydrogen peroxide by the oxygen cathode reduction method has received widespread attention because of its low cost, low investment, and low pollution.
  • the main reaction product is H 2 O 2
  • the reaction pathway is O 2 +*+H + +e - ⁇ *OOH; *OOH+H + +e - ⁇ H 2 O 2 +*.
  • the stable *OOH intermediate state determines the selectivity of the final product.
  • *O-OH When *O-OH is broken, *O will further undergo a proton coupling reaction to generate a thermodynamically more stable water product.
  • noble metal-based materials, carbon-based materials, and single-atom catalysts (SACs) have shown excellent electrocatalytic H2O2 selectivity in the cathode part. However, these materials all face the problem of precise regulation of catalytic sites, and it is difficult to accurately adjust the active sites and content to further improve catalytic performance.
  • the covalent organic framework (COFs) material is an organic porous polymer composed of light elements such as C, H, O, N, B, etc., which is connected by covalent bonds and developed since the 21st century. Tunability, regularity and high porosity make it a potential application prospect in renewable energy.
  • covalent organic framework materials with different active centers and active quantities can be precisely regulated. For example, Yao Xiangdong et al.
  • the present invention provides a covalent organic framework material (COFs) based on a specific structure as a catalyst, and by introducing active centers into the building blocks of the covalent organic framework material, different active centers and The active quantity realizes highly efficient catalytic reduction of oxygen to hydrogen peroxide.
  • COFs material in the method of the invention has excellent oxidogen activity and stability.
  • the object of the present invention is to provide a kind of method that catalyzes oxygen reduction to prepare hydrogen peroxide, and described method is to utilize covalent organic framework material as catalyst;
  • the linear building block in described covalent organic framework material is thieno[3,2 -b] Thiophene-2,5-dicarbaldehyde (DTDA)
  • the central building block is selected from any one of the following: 4,4',4"-(1,3,5-triazine-2,4,6-tri base) triphenylamine (TTT), tris(4-aminophenyl)amine (TAPA), tris(4-aminophenyl)benzene (TAPB).
  • the present invention also provides a method for preparing hydrogen peroxide by electrocatalysis, the method is to modify the covalent organic framework material on the working electrode, and then place it in an oxygen-containing aqueous solution to carry out the electrocatalytic reaction; in the covalent organic framework material
  • the linear building unit is DTDA, and the central building unit is selected from any one of the following: TTT, TAPA, TAPB.
  • the central building block is preferably tris(4-aminophenyl)amine (TAPA).
  • TAPA tris(4-aminophenyl)amine
  • the oxygen-containing aqueous solution may be an oxygen-saturated KOH solution.
  • the concentration of the KOH solution may be 0.1M.
  • the process of modifying the working electrode with the covalent organic framework material includes:
  • the solvent is a mixed system of absolute ethanol, water and 5% Nafion 117 solution.
  • the volume ratio of absolute ethanol, water, and 5% Nafion 117 solution is 15:5:1.
  • the concentration of the COF material relative to the solvent is 6-8 mg/mL. Specifically, 7.2mg/mL is optional.
  • the electrocatalytic reaction comprises: a COF-modified working electrode, a reference electrode and a counter electrode constitute a three-electrode cell, and electrocatalyzes the reduction of oxygen into hydrogen peroxide in an oxygen-saturated KOH solution.
  • the specific process of electrocatalytic reaction comprises:
  • Modifying the working electrode Take the prepared COF material sample, mix the same proportion of carbon black acetylene black into the mixed solution of an appropriate amount of absolute ethanol, water and Nafion 117 solution, and mix evenly to obtain the catalyst ink; drop the catalyst ink Coated on a polished and clean ring-disk electrode, and dried naturally to obtain a COF-modified working electrode;
  • the carbon rod is used as the counter electrode to form a three-electrode battery.
  • oxygen-saturated 0.1M KOH solution electrocatalyzed oxygen reduction to hydrogen peroxide.
  • the preparation method of the covalent organic framework material comprises the following process:
  • the preparation method of covalent organic framework material specifically includes the following steps:
  • the organic solvent in the preparation method of the covalent organic framework material, is a mixed system of n-butanol and 1,2-dichlorobenzene. Further, the volume ratio of n-butanol and 1,2-dichlorobenzene is 1:1.
  • the catalyst in the preparation method of the covalent organic framework material, is acetic acid.
  • the concentration of the linear building units in the mixed solution is specifically 0.01-0.05 mmol/mL. Specifically, 0.04 mmol/mL is optional.
  • the concentration of the central building unit in the mixed solution is 0.01-0.05 mmol/mL. Specifically, 0.03mmol/L is optional.
  • the molar ratio of the linear building unit to the central building unit is (0.8-2):1.
  • the concentration of the acetic acid solution is 6.0 mol/L.
  • the molar ratio of acetic acid to the central building unit is 20:1.
  • the Schiff base reaction needs to be carried out under an inert atmosphere.
  • an inert atmosphere such as nitrogen gas atmosphere.
  • the reaction temperature of the Schiff base reaction is 120° C., and the time is 72 hours.
  • the preferred operation step of the solid-liquid separation is: adding absolute ethanol to the suspension, followed by centrifugation to obtain the target product.
  • washing is performed with ethanol.
  • the liquid nitrogen is used for quick freezing, and then put into a freeze dryer for drying.
  • the present invention has significant advantages:
  • the present invention uses DTDA as a linear building unit, TTT, TAPA and TAPB as a central building unit, so that the obtained COFs material has high electrical conductivity, high porosity, and abundant heteroatom catalytic active sites, and is an excellent preparation for activated carbon with oxygen reduction. Materials provide new ideas and methods.
  • the COFs material prepared by the present invention has a clear active center and active quantity, and has diversity and excellent designability, thereby significantly improving the catalytic performance and stability of the catalyst.
  • the catalytic performance and stability of the catalyst of the present invention are excellent, especially
  • the COFs material prepared when DTDA is used as the linear building unit and TAPA as the central building unit exhibits excellent oxygen reduction catalytic performance and high hydrogen peroxide selectivity. Under alkaline conditions at 0.65V, the H 2 O 2 selectivity of TAPA-DTDA-COF reached 90%, and the oxygen reduction performance of the catalyst was still very stable after 10,000 seconds of circulation, and the obtained H 2 O 2 yield was 1.6mol g -1 catalyst h -1 . After cycling for 10000s, the catalytic activity is still very stable.
  • Fig. 1 is a transmission electron micrograph of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Examples 1-3.
  • Fig. 2 is the Fourier transform infrared spectrograms of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Examples 1-3.
  • Fig. 3 is the X-ray diffraction spectrum of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Example 1-3.
  • Fig. 4 is the oxygen reduction polarization curves of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Examples 1-3.
  • Figure 5 shows the hydrogen peroxide selectivity and the number of transferred electrons of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Example 1-3.
  • FIG. 6 shows the stability test results of the TAPA-DTDA-COF material prepared in Example 1.
  • FIG. 7 is a schematic diagram of the hydrogen peroxide selectivity and the number of electron transfers changing with voltage in Comparative Example 1.
  • a method for preparing a COFs material with tris(4-aminophenyl)amine (TAPA) as the central building block the specific steps are as follows:
  • a method for preparing a COFs material with three (4-aminophenyl) benzene (TAPB) as a central building unit the specific steps are as follows:
  • a method for preparing a COFs material with 4,4',4"-(1,3,5-triazine-2,4,6-triyl)triphenylamine (TTT) as a central building unit the specific steps are as follows:
  • FIGS a, b, c, d, e and f in Figure 1 are transmission electron microscopes of the microscopic morphology of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Examples 1-3, respectively From their transmission electron microscope photos, it can be seen that the structure of the TAPA-DTDA-COF catalyst material is a stacked structure of nanospheres in series, and the surface is uneven; the structure of the TTT-DTDA-COF catalyst material is a honeycomb-shaped carbon nanometer Rod stacked structure, and there are many pores inside the material; TAPB-DTDA-COF catalyst material is an irregular spherical structure.
  • Figure 3 is the X-ray diffraction spectrum of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF, their phase information can be obtained from their diffraction peaks, and it can be seen from the main diffraction peaks that appear It can be seen that the synthesized COFs materials have good crystallinity and order.
  • Figure 4 is the polarization curves of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF tested by the rotating disc electrode device in oxygen-saturated 0.1M KOH solution at a rotation rate of 1600rpm/min , by comparing the onset potential and half-wave potential of the three organic porous polymers TAPA-DTDA-COF, TTT-DTDA-COF, and TAPB-DTDA-COF, it can be found that TAPA-DTDA-COF has a larger onset potential and The half-wave potential, the onset potential is 0.73V, and the half-wave potential is 0.63V, showing the most excellent two-electron oxygen reduction catalytic activity. This may be because its unique structure and composition will produce some electronic effects, coordination effects, and stress effects, which can regulate the adsorption energy between the intermediate product and the catalyst, thereby greatly improving their catalytic activity for oxygen reduction.
  • Figure 5 shows the hydrogen peroxide selectivity and the number of transferred electrons calculated according to the K-L equation during the catalytic process of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF materials:
  • J is the measured current density
  • J L is the limiting current density
  • J K is the kinetic current density
  • ⁇ is the rotation rate of the working electrode
  • n is the number of transferred electrons
  • F is the Faraday constant (96485C mol- 1 )
  • C 0 is the solubility of oxygen in 0.1 mol/L KOH solution (1.2 ⁇ 10 -6 mol cm -3 )
  • D is the diffusion coefficient of oxygen in 0.1 mol/L KOH solution
  • ⁇ is the dynamic viscosity of the electrolyte ( 0.01 cm 2 ⁇ s -1 ).
  • n 4I D /(I D +N ⁇ I R );
  • I D is the disk current
  • I R is the ring current
  • N is the collection efficiency (0.37 after calibration).
  • the H 2 O 2 selectivity of TAPA-DTDA-COF was the highest, and the H 2 O 2 selectivity reached 90% at 0.65V.
  • the number of transferred electrons of TAPA-DTDA-COF is close to 2.25, which is the closest to the two-electron transfer process, so it has the best catalytic activity for oxygen reduction of hydrogen peroxide.
  • Figure 6 is the stability data of the TAPA-DTDA-COF material prepared in Example 1. The stability is evaluated by chronoamperometry and constant potential method. The TAPA-DTDA-COF material exhibited excellent stability, and the TAPA-DTDA-COF material did not attenuate after cycling for 10000s.
  • FIG. 7 is a schematic diagram of the hydrogen peroxide selectivity and electron transfer number measured in the oxygen-saturated 0.1M KOH solution of Comparative Example 1 as a function of voltage.
  • acetylene black was used as a blank control in this study.
  • Acetylene black was used as the working electrode to measure the polarization curve of the rotating disc electrode device in oxygen-saturated 0.1M KOH solution at a rotation rate of 1600rpm/min, and the hydrogen peroxide selectivity and electron transfer number were calculated by the formula.

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Abstract

Disclosed in the present invention is a method for preparing hydrogen peroxide by means of catalytic oxygen reduction by using a covalent organic framework catalyst, which belongs to the field of electrocatalysis. According to the present invention, a COF material, which is constructed by using thieno[3,2-b]thiophene-2,5-dicarbaldehyde (DTDA) as a linear construction unit, and respectively using 4,4',4''-(1,3,5-triazine-2,4,6-triyl)triphenylamine (TTT), tris(4-aminophenyl)amine (TAPA) and tris(4-aminophenyl)benzene (TAPB) as center construction units, is used as a catalyst, thereby achieving oxygen reduction preparation of hydrogen peroxide with a high oxygen reducing activity, stability and hydrogen peroxide selectivity. The operation is simple, controllability is high, and a certain universality is achieved.

Description

一种应用共价有机框架催化剂催化氧还原制备双氧水的方法A method for preparing hydrogen peroxide by catalytic oxygen reduction using covalent organic framework catalyst 技术领域technical field
本发明具体涉及一种应用共价有机框架催化剂催化氧还原制备双氧水的方法，属于电催化技术领域。The invention specifically relates to a method for preparing hydrogen peroxide by using a covalent organic framework catalyst to catalyze oxygen reduction, and belongs to the technical field of electrocatalysis.
背景技术Background technique
H 2O 2是一种多功能且环保的氧化剂。它在消毒，纸浆，纺织品漂白，废水处理，化学合成，半导体清洁，洗涤剂以及排气处理等领域应用广泛。由于其应用广泛，全球对H 2O 2的需求不断上升。据不完全统计，2015年全球H 2O 2的年产量达到550万吨，目前，工业上主要通过电解法和蒽醌法两种。电解法电流效率高、工艺流程短、产品质量高，但由于电耗较大，生产成本高，不适合大规模工业化生产，已逐渐被淘汰。蒽醌法技术先进，自动化程度高，产品成本和能耗较低，但是生产工艺复杂繁琐。最近，氧气阴极还原法生产双氧水因为其成本低、投资少、污染小等特点受到了广泛的关注。 H2O2 is a versatile and environmentally friendly oxidizing agent. It is widely used in disinfection, pulp, textile bleaching, wastewater treatment, chemical synthesis, semiconductor cleaning, detergent and exhaust gas treatment. The global demand for H2O2 is rising due to its wide range of applications. According to incomplete statistics, the global annual production of H 2 O 2 reached 5.5 million tons in 2015. At present, the industry mainly uses electrolysis and anthraquinone methods. The electrolysis method has high current efficiency, short process flow and high product quality, but due to high power consumption and high production cost, it is not suitable for large-scale industrial production and has been gradually eliminated. The anthraquinone method has advanced technology, high degree of automation, low product cost and low energy consumption, but the production process is complex and cumbersome. Recently, the production of hydrogen peroxide by the oxygen cathode reduction method has received widespread attention because of its low cost, low investment, and low pollution.
氧气分子在阴极部分主要发生2e -和4e -反应，对于2e -反应，反应产物主体为H 2O 2，反应途径为O 2+*+H ++e -→*OOH；*OOH+H ++e -→H 2O 2+*。稳定的*OOH中间态决定着最终产物的选择性，当*O-OH发生断裂时，*O将进一步发生质子耦合反应生成热力学更稳定的水产物。目前，贵金属基材料，碳基材料和单原子催化剂(SAC)在阴极部分表现出了优良的电催化双氧水选择性。但是，这些材料都面临催化位点的精确调控的问题，很难准确地调整活性中心以及含量来进一步提高催化性能。 Oxygen molecules mainly undergo 2e- and 4e - reactions at the cathode. For 2e - reactions, the main reaction product is H 2 O 2 , and the reaction pathway is O 2 +*+H + +e - → *OOH; *OOH+H + +e - →H 2 O 2 +*. The stable *OOH intermediate state determines the selectivity of the final product. When *O-OH is broken, *O will further undergo a proton coupling reaction to generate a thermodynamically more stable water product. Currently, noble metal-based materials, carbon-based materials, and single-atom catalysts (SACs) have shown excellent electrocatalytic H2O2 selectivity in the cathode part. However, these materials all face the problem of precise regulation of catalytic sites, and it is difficult to accurately adjust the active sites and content to further improve catalytic performance.
功能多孔材料因其优异的稳定性，多孔可调，大的比表面积，广泛应用于催化、吸附分离、可再生能源、纳米医学等领域。其中，共价有机框架(COFs)材料是21世纪以来发展的一种由共价键连接的，由C、H、O、N、B等轻质元素组成的有机多孔聚合物，由于其结构的可调性、规整性以及高孔隙，使它在可再生能源中具有潜在的应用前景。通过在构筑单元中活性中心的引入，可以精确的调控不同的活性中心和活性数量的共价有机框架材料。例如，姚向东等人近期利用2,5-噻吩二甲醛(TDC)和2,2'联硫代苯基-5,5'-二甲醛(bTDC)作为活性中心单元构筑了具有优异氧还原活性的噻吩硫基共价有机框架材料，DFT计算表明噻吩硫作为活性中心赋予了其本征结构的氧还原活性。利用COFs堆砌单元的可设计性和选择性，合理的设计具有丰富活性中心的共价有机框架材料，这为进一步理解电催化双氧水机理，提高电催化双氧水选择性具有重要意义。Functional porous materials are widely used in catalysis, adsorption separation, renewable energy, nanomedicine and other fields due to their excellent stability, adjustable porosity, and large specific surface area. Among them, the covalent organic framework (COFs) material is an organic porous polymer composed of light elements such as C, H, O, N, B, etc., which is connected by covalent bonds and developed since the 21st century. Tunability, regularity and high porosity make it a potential application prospect in renewable energy. Through the introduction of active centers in the building blocks, covalent organic framework materials with different active centers and active quantities can be precisely regulated. For example, Yao Xiangdong et al. recently used 2,5-thiophene dicarbaldehyde (TDC) and 2,2'bithiophenyl-5,5'-dicarbaldehyde (bTDC) as the active center unit to construct a compound with excellent oxygen reduction activity. Thiophene sulfur-based covalent organic framework materials, DFT calculations show that thiophene sulfur as the active center endows its intrinsic structure with oxygen reduction activity. Utilizing the designability and selectivity of COFs stacking units, rationally designing covalent organic framework materials with abundant active centers is of great significance for further understanding the mechanism of electrocatalytic hydrogen peroxide and improving the selectivity of electrocatalytic hydrogen peroxide.
发明内容Contents of the invention
【技术问题】【technical problem】
现有的共价有机框架催化剂的催化性能不理想。The catalytic performance of existing covalent organic framework catalysts is not ideal.
【技术方案】【Technical solutions】
为了解决上述问题，本发明提供了一种基于特定结构的共价有机框架材料(COFs)作为催化剂，并通过在共价有机框架材料的构筑单元中引入活性中心，精确的调控不同的活性中心和活性数量，实现高效催化氧还原成过氧化氢。本发明方法中COFs材料具有优异的氧化原活性和稳定性。In order to solve the above problems, the present invention provides a covalent organic framework material (COFs) based on a specific structure as a catalyst, and by introducing active centers into the building blocks of the covalent organic framework material, different active centers and The active quantity realizes highly efficient catalytic reduction of oxygen to hydrogen peroxide. The COFs material in the method of the invention has excellent oxidogen activity and stability.
本发明的目的是提供一种催化氧还原制备过氧化氢的方法，所述方法是利用共价有机框架材料作为催化剂；所述共价有机框架材料中的线性构筑单元为噻吩并[3,2-b]噻吩-2,5-二甲醛(DTDA)，中心构筑单元选自如下任意一种：4,4',4”-(1,3,5-三嗪-2,4,6-三基)三苯胺(TTT)、三(4-氨基苯基)胺(TAPA)、三(4-氨基苯基)苯(TAPB)。The object of the present invention is to provide a kind of method that catalyzes oxygen reduction to prepare hydrogen peroxide, and described method is to utilize covalent organic framework material as catalyst; The linear building block in described covalent organic framework material is thieno[3,2 -b] Thiophene-2,5-dicarbaldehyde (DTDA), the central building block is selected from any one of the following: 4,4',4"-(1,3,5-triazine-2,4,6-tri base) triphenylamine (TTT), tris(4-aminophenyl)amine (TAPA), tris(4-aminophenyl)benzene (TAPB).
本发明还提供了一种电催化制备双氧水的方法，所述方法是将共价有机框架材料修饰在工作电极上，然后置于含氧水溶液中进行电催化反应；所述共价有机框架材料中的线性构筑单元为DTDA，中心构筑单元选自如下任意一种：TTT、TAPA、TAPB。The present invention also provides a method for preparing hydrogen peroxide by electrocatalysis, the method is to modify the covalent organic framework material on the working electrode, and then place it in an oxygen-containing aqueous solution to carry out the electrocatalytic reaction; in the covalent organic framework material The linear building unit is DTDA, and the central building unit is selected from any one of the following: TTT, TAPA, TAPB.
在本发明的一种实施方式中，中心构筑单元优选为三(4-氨基苯基)胺(TAPA)。In one embodiment of the present invention, the central building block is preferably tris(4-aminophenyl)amine (TAPA).
在本发明的一种实施方式中，含氧水溶液可选氧气饱和的KOH溶液。In one embodiment of the present invention, the oxygen-containing aqueous solution may be an oxygen-saturated KOH solution.
在本发明的一种实施方式中，KOH溶液的浓度可为0.1M。In one embodiment of the present invention, the concentration of the KOH solution may be 0.1M.
在本发明的一种实施方式中，所述共价有机框架材料修饰在工作电极的过程包括：In one embodiment of the present invention, the process of modifying the working electrode with the covalent organic framework material includes:
将COF材料、炭黑乙炔黑分散到溶剂中，混匀，然后滴涂在工作电极上，干燥后，获得COF修饰的工作电极。Disperse the COF material and carbon black acetylene black into a solvent, mix them evenly, and then drop-coat them on the working electrode. After drying, a COF-modified working electrode is obtained.
在本发明的一种实施方式中，所述溶剂为无水乙醇、水和5％Nafion 117溶液的混合体系。其中，无水乙醇、水、5％Nafion 117溶液的体积比为15：5：1。In one embodiment of the present invention, the solvent is a mixed system of absolute ethanol, water and 5% Nafion 117 solution. Among them, the volume ratio of absolute ethanol, water, and 5% Nafion 117 solution is 15:5:1.
在本发明的一种实施方式中，COF材料相对溶剂的浓度为6-8mg/mL。具体可选7.2mg/mL。In one embodiment of the present invention, the concentration of the COF material relative to the solvent is 6-8 mg/mL. Specifically, 7.2mg/mL is optional.
在本发明的一种实施方式中，所述电催化反应包括：将COF修饰的工作电极与参比电极和对电极构成三电极电池，在氧气饱和的KOH溶液中，电催化氧还原成双氧水。In one embodiment of the present invention, the electrocatalytic reaction comprises: a COF-modified working electrode, a reference electrode and a counter electrode constitute a three-electrode cell, and electrocatalyzes the reduction of oxygen into hydrogen peroxide in an oxygen-saturated KOH solution.
在本发明的一种实施方式中，电催化反应的具体过程包括：In one embodiment of the present invention, the specific process of electrocatalytic reaction comprises:
(1)修饰工作电极：取制备的COF材料样品，同等比例的炭黑乙炔黑混合加入到适量无水乙醇、水和Nafion 117溶液的混合溶液中，混合均匀，得到催化剂墨水；将催化剂墨水滴涂在抛光洁净的环盘电极上，自然风干后，获得COF修饰的工作电极；(1) Modifying the working electrode: Take the prepared COF material sample, mix the same proportion of carbon black acetylene black into the mixed solution of an appropriate amount of absolute ethanol, water and Nafion 117 solution, and mix evenly to obtain the catalyst ink; drop the catalyst ink Coated on a polished and clean ring-disk electrode, and dried naturally to obtain a COF-modified working electrode;
(2)将COF修饰的工作电极与饱和甘汞电极为参比电极、对电极构成三电极电池，在氧气饱和的0.1M KOH溶液中，电催化氧还原成双氧水。(2) The COF-modified working electrode and the saturated calomel electrode were used as the reference electrode, and the counter electrode constituted a three-electrode cell. In an oxygen-saturated 0.1M KOH solution, the electrocatalyzed reduction of oxygen into hydrogen peroxide was performed.
在本发明的一种实施方式中，电催化反应在美国pine公司生产制造一体化旋转圆盘电极装置和上海辰华电化学工作站(型号为CHI660E)上进行，负载催化剂的旋转圆盘电极为工作电极，饱和甘汞电极为参比电极(文中所涉及的电势都归一位标准氢电极E(RHE)＝E(SCE)+0.244+0.0591*pH)，碳棒作为对电极构成三电极电池，在氧气饱和的0.1M KOH溶液中，电催化氧还原成双氧水。In one embodiment of the present invention, the electrocatalytic reaction is carried out on an integrated rotating disk electrode device manufactured by American Pine Company and Shanghai Chenhua Electrochemical Workstation (model CHI660E), and the rotating disk electrode loaded with catalyst is the working electrode , the saturated calomel electrode is the reference electrode (the potentials involved in the paper are normalized to one standard hydrogen electrode E(RHE)=E(SCE)+0.244+0.0591*pH), and the carbon rod is used as the counter electrode to form a three-electrode battery. In oxygen-saturated 0.1M KOH solution, electrocatalyzed oxygen reduction to hydrogen peroxide.
在本发明的一种实施方式中，所述共价有机框架材料的制备方法包括如下过程：In one embodiment of the present invention, the preparation method of the covalent organic framework material comprises the following process:
将线性构筑单元和中心构筑单元为单体分散在有机溶剂中，在催化剂的作用下发生席夫碱反应，反应结束后，固液分离、收集固体，洗涤、干燥，即得共价有机框架材料。Disperse the linear building unit and the central building unit as monomers in an organic solvent, and undergo a Schiff base reaction under the action of a catalyst. After the reaction, separate the solid from the liquid, collect the solid, wash, and dry to obtain the covalent organic framework material .
在本发明的一种实施方式中，共价有机框架材料的制备方法具体包括如下步骤：In one embodiment of the present invention, the preparation method of covalent organic framework material specifically includes the following steps:
1)将线性构筑单元、中心构筑单元加入到有机溶剂中，超声得到均匀的混合溶液；1) adding the linear building unit and the central building unit into the organic solvent, and ultrasonically obtaining a uniform mixed solution;
2)将醋酸溶液加入混合溶液中获得最终溶液，将溶液转移至派克管内，用液氮快速冰冻，将其内压抽至真空，然后密封；恢复室温解冻后，反复抽真空三次；将抽真空后的溶液放至100-150℃下进行反应；2) Add acetic acid solution to the mixed solution to obtain the final solution, transfer the solution to the Parker tube, freeze it quickly with liquid nitrogen, evacuate its internal pressure to a vacuum, and then seal it; after returning to room temperature and thawing, repeatedly evacuate three times; The final solution is placed at 100-150°C for reaction;
3)反应结束后冷却至室温，固液分离、收集固体，洗涤、干燥，得到COFs催化剂材料。3) Cool to room temperature after the reaction, separate the solid from the liquid, collect the solid, wash, and dry to obtain the COFs catalyst material.
在本发明的一种实施方式中，共价有机框架材料的制备方法中，所述有机溶剂为正丁醇和1,2-二氯苯混合体系。进一步的，正丁醇和1,2-二氯苯的体积比为1:1。In one embodiment of the present invention, in the preparation method of the covalent organic framework material, the organic solvent is a mixed system of n-butanol and 1,2-dichlorobenzene. Further, the volume ratio of n-butanol and 1,2-dichlorobenzene is 1:1.
在本发明的一种实施方式中，共价有机框架材料的制备方法中，所述催化剂为醋酸。In one embodiment of the present invention, in the preparation method of the covalent organic framework material, the catalyst is acetic acid.
在本发明的一种实施方式中，混合溶液中，线性构筑单元的浓度具体为0.01-0.05mmol/mL。具体可选0.04mmol/mL。In one embodiment of the present invention, the concentration of the linear building units in the mixed solution is specifically 0.01-0.05 mmol/mL. Specifically, 0.04 mmol/mL is optional.
为在本发明的一种实施方式中，混合溶液中，中心构筑单元的浓度为0.01-0.05mmol/mL。具体可选0.03mmol/L。In one embodiment of the present invention, the concentration of the central building unit in the mixed solution is 0.01-0.05 mmol/mL. Specifically, 0.03mmol/L is optional.
在本发明的一种实施方式中，混合溶液中，线性构筑单元与中心构筑单元的摩尔比为(0.8-2)：1。In one embodiment of the present invention, in the mixed solution, the molar ratio of the linear building unit to the central building unit is (0.8-2):1.
在本发明的一种实施方式中，醋酸溶液的浓度为6.0mol/L。In one embodiment of the present invention, the concentration of the acetic acid solution is 6.0 mol/L.
在本发明的一种实施方式中，醋酸与中心构筑单元的摩尔比为20:1。In one embodiment of the present invention, the molar ratio of acetic acid to the central building unit is 20:1.
在本发明的一种实施方式中，共价有机框架材料的制备方法中，所述席夫碱反应还需在惰性气氛下进行。比如氮气气体氛围。In one embodiment of the present invention, in the preparation method of the covalent organic framework material, the Schiff base reaction needs to be carried out under an inert atmosphere. Such as nitrogen gas atmosphere.
在本发明的一种实施方式中，所述席夫碱反应的反应温度为120℃，时间为72h。In one embodiment of the present invention, the reaction temperature of the Schiff base reaction is 120° C., and the time is 72 hours.
在本发明的一种实施方式中，所述固液分离优选的操作步骤为：在悬浮液中添加无水乙 醇，之后离心分离即可获得目标产物。In one embodiment of the present invention, the preferred operation step of the solid-liquid separation is: adding absolute ethanol to the suspension, followed by centrifugation to obtain the target product.
在本发明的一种实施方式中，用乙醇进行洗涤。In one embodiment of the invention, washing is performed with ethanol.
在本发明的一种实施方式中，洗涤后，利用液氮速冻，然后放入冷冻干燥机中进行干燥。In one embodiment of the present invention, after washing, the liquid nitrogen is used for quick freezing, and then put into a freeze dryer for drying.
本发明与现有技术相比，具有显著优点：Compared with the prior art, the present invention has significant advantages:
本发明以DTDA为线性构筑单元，TTT、TAPA以及TAPB为中心构筑单元，使得到的COFs材料的具有高电导率，高孔隙率，丰富的杂原子催化活性点，为制备具有优异氧还原活性碳材料提供新的思路及方法。The present invention uses DTDA as a linear building unit, TTT, TAPA and TAPB as a central building unit, so that the obtained COFs material has high electrical conductivity, high porosity, and abundant heteroatom catalytic active sites, and is an excellent preparation for activated carbon with oxygen reduction. Materials provide new ideas and methods.
本发明制备得到的COFs材料具有明确的活性中心和活性数量，具有多样性和优异的可设计性，从而显著提高了催化剂的催化性能和稳定性，本发明催化剂的催化性能和稳定性能优异，尤其是当以DTDA为线性构筑单元，TAPA为中心构筑单元时制备得到的COFs材料表现出优异的氧还原催化性能，具有较高的双氧水选择性。在碱性条件下在0.65V时，TAPA-DTDA-COF的H 2O 2选择性达到了90％，循环了10000s催化剂氧还原性能仍十分稳定，得到的H 2O 2产率为1.6mol g -1 catalysth -1。循环10000s后，催化活性仍然十分稳定。 The COFs material prepared by the present invention has a clear active center and active quantity, and has diversity and excellent designability, thereby significantly improving the catalytic performance and stability of the catalyst. The catalytic performance and stability of the catalyst of the present invention are excellent, especially The COFs material prepared when DTDA is used as the linear building unit and TAPA as the central building unit exhibits excellent oxygen reduction catalytic performance and high hydrogen peroxide selectivity. Under alkaline conditions at 0.65V, the H 2 O 2 selectivity of TAPA-DTDA-COF reached 90%, and the oxygen reduction performance of the catalyst was still very stable after 10,000 seconds of circulation, and the obtained H 2 O 2 yield was 1.6mol g -1 catalyst h -1 . After cycling for 10000s, the catalytic activity is still very stable.
附图说明Description of drawings
图1为实施例1-3制备得到的TAPA-DTDA-COF、TAPB-DTDA-COF和TTT-DTDA-COF的透射电镜照片。Fig. 1 is a transmission electron micrograph of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Examples 1-3.
图2为实施例1-3制备得到的TAPA-DTDA-COF、TAPB-DTDA-COF和TTT-DTDA-COF的傅立叶变换红外光谱图。Fig. 2 is the Fourier transform infrared spectrograms of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Examples 1-3.
图3为实施例1-3制备得到的TAPA-DTDA-COF、TAPB-DTDA-COF和TTT-DTDA-COF的X射线衍射谱图。Fig. 3 is the X-ray diffraction spectrum of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Example 1-3.
图4为实施例1-3制备得到的TAPA-DTDA-COF、TAPB-DTDA-COF和TTT-DTDA-COF的氧还原极化曲线。Fig. 4 is the oxygen reduction polarization curves of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Examples 1-3.
图5为实施例1-3制备得到的TAPA-DTDA-COF、TAPB-DTDA-COF和TTT-DTDA-COF的双氧水选择性和转移电子数。Figure 5 shows the hydrogen peroxide selectivity and the number of transferred electrons of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Example 1-3.
图6为实施例1制备得到的TAPA-DTDA-COF材料的稳定性测试结果。FIG. 6 shows the stability test results of the TAPA-DTDA-COF material prepared in Example 1.
图7为对比例1的双氧水选择性和电子转移数随电压变化的示意图。FIG. 7 is a schematic diagram of the hydrogen peroxide selectivity and the number of electron transfers changing with voltage in Comparative Example 1.
具体实施方式Detailed ways
为了更好的理解本发明，下面结合实例进一步阐明本发明的内容，但本发明的内容不局限于下面所给出的实例In order to better understand the present invention, below in conjunction with example further clarifies content of the present invention, but content of the present invention is not limited to the example given below
实施例1Example 1
一种以三(4-氨基苯基)胺(TAPA)为中心构筑单元的COFs材料的制备方法，具体步骤如下：A method for preparing a COFs material with tris(4-aminophenyl)amine (TAPA) as the central building block, the specific steps are as follows:
(1)分别称取DTDA 7.30mg(0.04mmol)和TAPA 8.80mg(0.03mmol)加入到5mL玻璃管中，然后加入正丁醇500μL和1,2-二氯苯500μL于上述玻璃瓶中，超声30分钟得到均匀的混合溶液，取100μL的6mol/L醋酸溶液加入其混合溶液中超声10分钟获得最终溶液。(1) Weigh 7.30mg (0.04mmol) of DTDA and 8.80mg (0.03mmol) of TAPA into a 5mL glass tube, then add 500μL of n-butanol and 500μL of 1,2-dichlorobenzene into the above glass bottle, and ultrasonically After 30 minutes to obtain a uniform mixed solution, take 100 μL of 6 mol/L acetic acid solution and add it to the mixed solution and sonicate for 10 minutes to obtain the final solution.
(2)将玻璃瓶内混合均匀的溶液转移至派克管内，用液氮快速冰冻，将其内压抽至真空，然后密封。恢复室温解冻后，反复抽真空三次。将抽真空后的溶液放至120℃烘箱中，反应三天，反应结束后冷却至室温。将反应得到的产物用乙醇进行洗涤，直到洗出的乙醇无色为止。洗涤后的产物加适量环己烷以降低溶剂冰点，液氮速冻后放入冷冻干燥机。24h后得到干燥的COFs催化剂材料，命名为TAPA-DTDA-COF。(2) Transfer the uniformly mixed solution in the glass bottle to the Parker tube, freeze it quickly with liquid nitrogen, evacuate the internal pressure to a vacuum, and then seal it. After returning to room temperature and thawing, vacuumize repeatedly three times. Put the vacuumized solution in an oven at 120°C, react for three days, and cool to room temperature after the reaction. The product obtained by the reaction was washed with ethanol until the ethanol washed out was colorless. Add appropriate amount of cyclohexane to the washed product to lower the freezing point of the solvent, freeze it in liquid nitrogen and put it into a freeze dryer. After 24h, the dried COFs catalyst material was obtained, which was named TAPA-DTDA-COF.
实施例2Example 2
一种以三(4-氨基苯基)苯(TAPB)为中心构筑单元的COFs材料的制备方法，具体步骤如下：A method for preparing a COFs material with three (4-aminophenyl) benzene (TAPB) as a central building unit, the specific steps are as follows:
(1)分别称取DTDA 7.30mg(0.04mmol)和TAPA 10.50mg(0.03mmol)加入到5mL玻璃管中，然后加入正丁醇500μL和1,2-二氯苯500μL于上述玻璃瓶中，超声30分钟得到均匀的混合溶液，取100μL的6mol/L醋酸溶液加入其混合溶液中超声10分钟获得最终溶液。(1) Weigh 7.30mg (0.04mmol) of DTDA and 10.50mg (0.03mmol) of TAPA into a 5mL glass tube, then add 500μL of n-butanol and 500μL of 1,2-dichlorobenzene into the above glass bottle, and ultrasonically After 30 minutes to obtain a uniform mixed solution, take 100 μL of 6 mol/L acetic acid solution and add it to the mixed solution and sonicate for 10 minutes to obtain the final solution.
(2)将玻璃瓶内混合均匀的溶液转移至派克管内，用液氮快速冰冻，将其内压抽至真空，然后密封。恢复室温解冻后，反复抽真空三次。将抽真空后的溶液放至120℃烘箱中，反应三天，反应结束后冷却至室温。将反应得到的产物用乙醇进行洗涤，直到洗出的乙醇无色为止。洗涤后的产物加适量环己烷以降低溶剂冰点，液氮速冻后放入冷冻干燥机。24h后得到干燥的COFs催化剂材料，命名为TAPB-DTDA-COF。(2) Transfer the uniformly mixed solution in the glass bottle to the Parker tube, freeze it quickly with liquid nitrogen, evacuate the internal pressure to a vacuum, and then seal it. After returning to room temperature and thawing, vacuumize repeatedly three times. Put the vacuumized solution in an oven at 120°C, react for three days, and cool to room temperature after the reaction. The product obtained by the reaction was washed with ethanol until the ethanol washed out was colorless. Add appropriate amount of cyclohexane to the washed product to lower the freezing point of the solvent, freeze it in liquid nitrogen and put it into a freeze dryer. After 24h, the dried COFs catalyst material was obtained, which was named TAPB-DTDA-COF.
实施例3Example 3
一种以4,4',4”-(1,3,5-三嗪-2,4,6-三基)三苯胺(TTT)为中心构筑单元的COFs材料的制备方法，具体步骤如下：A method for preparing a COFs material with 4,4',4"-(1,3,5-triazine-2,4,6-triyl)triphenylamine (TTT) as a central building unit, the specific steps are as follows:
(1)分别称取DTDA 7.30mg(0.04mmol)和TTT 10.50mg(0.03mmol)加入到5mL玻璃管中，然后加入正丁醇500μL和1,2-二氯苯500μL于上述玻璃瓶中，超声30分钟得到均匀的混合溶液，取100μL的6mol/L醋酸溶液加入其混合溶液中超声10分钟获得最终溶液。(1) Weigh 7.30mg (0.04mmol) of DTDA and 10.50mg (0.03mmol) of TTT into a 5mL glass tube, then add 500μL of n-butanol and 500μL of 1,2-dichlorobenzene into the above glass bottle, and ultrasonically After 30 minutes to obtain a uniform mixed solution, take 100 μL of 6 mol/L acetic acid solution and add it to the mixed solution and sonicate for 10 minutes to obtain the final solution.
(2)将玻璃瓶内混合均匀的溶液转移至派克管内，用液氮快速冰冻，将其内压抽至真空，然后密封。恢复室温解冻后，反复抽真空三次。将抽真空后的溶液放至120℃烘箱中，反应三天，反应结束后冷却至室温。将反应得到的产物用乙醇进行洗涤，直到洗出的乙醇无色为 止。洗涤后的产物加适量环己烷以降低溶剂冰点，液氮速冻后放入冷冻干燥机。24h后得到干燥的COFs催化剂材料，命名为TTT-DTDA-COF。(2) Transfer the uniformly mixed solution in the glass bottle to the Parker tube, freeze it quickly with liquid nitrogen, evacuate the internal pressure to a vacuum, and then seal it. After returning to room temperature and thawing, vacuumize repeatedly three times. Put the vacuumized solution in an oven at 120°C, react for three days, and cool to room temperature after the reaction. The product obtained by the reaction was washed with ethanol until the ethanol washed out was colorless. Add appropriate amount of cyclohexane to the washed product to lower the freezing point of the solvent, freeze it in liquid nitrogen and put it into a freeze dryer. After 24h, the dried COFs catalyst material was obtained, which was named TTT-DTDA-COF.
图1中的a、b、c、d、e和f图分别为实施例1-3制备得到的TAPA-DTDA-COF、TAPB-DTDA-COF和TTT-DTDA-COF的微观形貌的透射电镜照片，从它们的透射电镜照片中可以看出，TAPA-DTDA-COF催化剂材料的结构为串联的纳米球堆积结构，且表面凹凸不平；TTT-DTDA-COF催化剂材料的结构为蜂巢状的碳纳米棒堆积结构，且材料内部具有很多孔隙；TAPB-DTDA-COF催化剂材料为不规则的球状结构。Figures a, b, c, d, e and f in Figure 1 are transmission electron microscopes of the microscopic morphology of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF prepared in Examples 1-3, respectively From their transmission electron microscope photos, it can be seen that the structure of the TAPA-DTDA-COF catalyst material is a stacked structure of nanospheres in series, and the surface is uneven; the structure of the TTT-DTDA-COF catalyst material is a honeycomb-shaped carbon nanometer Rod stacked structure, and there are many pores inside the material; TAPB-DTDA-COF catalyst material is an irregular spherical structure.
图2是TAPA-DTDA-COF、TAPB-DTDA-COF和TTT-DTDA-COF的傅立叶变换红外光谱图，从(a)，(b)和(c)图中可以发现，合成的COF材料的红外光谱图中在1582cm -1处出现明显的伸缩振动峰，这归结为-C＝N键的伸缩振动，同时并没有发现合成单体中的醛基(1645cm -1)和氨基(3450cm -1)的伸缩振动峰。这些结果表明醛基和氨基在该反应条件下成功的转化为-C＝N基团。 Figure 2 is the Fourier transform infrared spectrum of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF, from (a), (b) and (c) can be found that the infrared spectrum of the synthesized COF material There is an obvious stretching vibration peak at 1582cm -1 in the spectrum, which is attributed to the stretching vibration of the -C=N bond. At the same time, no aldehyde group (1645cm -1 ) and amino group (3450cm -1 ) in the synthesized monomer were found stretching vibration peak. These results indicated that aldehyde and amino groups were successfully converted to -C=N groups under the reaction conditions.
图3是TAPA-DTDA-COF、TAPB-DTDA-COF和TTT-DTDA-COF的X射线衍射谱图，从它们的衍射峰中可以得到它们的物相信息，从出现的主要衍射峰中可以看出，合成了的COFs材料具有较好的结晶性和有序性。Figure 3 is the X-ray diffraction spectrum of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF, their phase information can be obtained from their diffraction peaks, and it can be seen from the main diffraction peaks that appear It can be seen that the synthesized COFs materials have good crystallinity and order.
实施例4应用共价有机框架催化剂催化氧还原成双氧水Example 4 Application of Covalent Organic Framework Catalyst to Catalyze Oxygen Reduction into Hydrogen Peroxide
(1)取1.5mg制备的COF材料样品，同等质量的炭黑或乙炔黑混合加入到150μL的无水乙醇、50μL的水和10μL 5％Nafion 117溶液的混合溶液中，将其混合溶液超声30min制备混合均匀的催化剂墨水，取10μL配制的催化剂墨水滴涂在抛光洁净的环盘电极上，自然风干后，作为工作电极备用。(1) Take 1.5 mg of the prepared COF material sample, mix the same mass of carbon black or acetylene black into a mixed solution of 150 μL of absolute ethanol, 50 μL of water and 10 μL of 5% Nafion 117 solution, and ultrasonicate the mixed solution for 30 minutes Prepare evenly mixed catalyst ink, take 10 μL of the prepared catalyst ink and drop-coat it on a polished and clean ring-disk electrode, and let it dry naturally, then use it as a working electrode for later use.
(2)电催化过程在美国pine公司生产制造一体化旋转圆盘电极装置和上海辰华电化学工作站(型号为CHI660E)上进行，负载催化剂的旋转圆盘电极为工作电极，饱和甘汞电极为参比电极(文中所涉及的电势都归一位标准氢电极E(RHE)＝E(SCE)+0.244+0.0591*pH)，碳棒作为对电极构成三电极电池，在氧气饱和的0.1M KOH溶液中，电催化氧还原成双氧水。(2) The electrocatalytic process was carried out on an integrated rotating disk electrode device manufactured by American Pine Company and Shanghai Chenhua Electrochemical Workstation (model CHI660E). The rotating disk electrode loaded with catalyst was used as the working electrode, and the saturated calomel electrode was used as the reference. The specific electrode (the potentials involved in this article are all normalized to a standard hydrogen electrode E(RHE)=E(SCE)+0.244+0.0591*pH), and the carbon rod is used as the counter electrode to form a three-electrode battery. In an oxygen-saturated 0.1M KOH solution , the electrocatalytic reduction of oxygen to hydrogen peroxide.
图4是在氧气饱和的0.1M KOH溶液中通过旋转圆盘电极装置在旋转速率为1600rpm/min时所测试的TAPA-DTDA-COF、TAPB-DTDA-COF和TTT-DTDA-COF的极化曲线，通过比较TAPA-DTDA-COF、TTT-DTDA-COF、TAPB-DTDA-COF三种有机多孔聚合物的起始电位和半波电位，可以发现TAPA-DTDA-COF具有更大的起始电位和半波电位，起始电位为0.73V，半波电位为0.63V，表现出最优异的二电子氧还原催化活性。这可能是因为它独特的结构和组成成分会产生一些电子效应、配位效应以及应力效应，能够调控中间产物与催化剂之间的吸附能，从而大大的提高它们的氧还原催化活性。Figure 4 is the polarization curves of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF tested by the rotating disc electrode device in oxygen-saturated 0.1M KOH solution at a rotation rate of 1600rpm/min , by comparing the onset potential and half-wave potential of the three organic porous polymers TAPA-DTDA-COF, TTT-DTDA-COF, and TAPB-DTDA-COF, it can be found that TAPA-DTDA-COF has a larger onset potential and The half-wave potential, the onset potential is 0.73V, and the half-wave potential is 0.63V, showing the most excellent two-electron oxygen reduction catalytic activity. This may be because its unique structure and composition will produce some electronic effects, coordination effects, and stress effects, which can regulate the adsorption energy between the intermediate product and the catalyst, thereby greatly improving their catalytic activity for oxygen reduction.
图5是TAPA-DTDA-COF、TAPB-DTDA-COF和TTT-DTDA-COF材料在催化过程中根据K-L方程所计算出来的双氧水选择性和转移电子数：Figure 5 shows the hydrogen peroxide selectivity and the number of transferred electrons calculated according to the K-L equation during the catalytic process of TAPA-DTDA-COF, TAPB-DTDA-COF and TTT-DTDA-COF materials:
K-L方程为：
Figure PCTCN2022124361-appb-000001
The KL equation is:
Figure PCTCN2022124361-appb-000001
其中，
Figure PCTCN2022124361-appb-000002
J为所测量的电流密度，J L为极限电流密度，J K为动力学电流密度，ω为工作电极的旋转速率，n为转移电子数，F为法拉第常数(96485C·mol- 1)，C 0为氧气在0.1mol/L的KOH溶液的溶度(1.2×10 -6mol·cm -3)，D为氧气在0.1mol/L的KOH溶液的扩散系数，γ为电解质的动力学粘度(0.01cm 2·s -1)。 in,
Figure PCTCN2022124361-appb-000002
J is the measured current density, J L is the limiting current density, J K is the kinetic current density, ω is the rotation rate of the working electrode, n is the number of transferred electrons, F is the Faraday constant (96485C mol- 1 ), C 0 is the solubility of oxygen in 0.1 mol/L KOH solution (1.2×10 -6 mol cm -3 ), D is the diffusion coefficient of oxygen in 0.1 mol/L KOH solution, γ is the dynamic viscosity of the electrolyte ( 0.01 cm 2 ·s -1 ).
通过测量RRDE电极中的圆盘电极的氧气分子的还原电流和Pt环上对产物双氧水的氧化电流，可以定量的分析生成H 2O 2的选择性和转移的电子数(n)： By measuring the reduction current of the oxygen molecule of the disc electrode in the RRDE electrode and the oxidation current of the product hydrogen peroxide on the Pt ring, the selectivity of H 2 O 2 and the number of transferred electrons (n) can be quantitatively analyzed:
H 2O 2的选择性(％)＝200×I R/(N×I D+I R)； Selectivity (%) of H 2 O 2 = 200×I R /(N×I D +I R );
n＝4I D/(I D+N×I R)； n=4I D /(I D +N×I R );
其中I D是盘电流，I R是环电流，N是收集效率(校准后为0.37)。 where I D is the disk current, I R is the ring current, and N is the collection efficiency (0.37 after calibration).
在电压范围为0.20～0.65V内，TAPA-DTDA-COF的H 2O 2选择性最高，且在0.65V时H 2O 2选择性达到了90％。TAPA-DTDA-COF的转移电子数接近于2.25左右，最接近于两电子转移过程，因此具有最佳的氧还原双氧水催化活性。 In the voltage range of 0.20～0.65V, the H 2 O 2 selectivity of TAPA-DTDA-COF was the highest, and the H 2 O 2 selectivity reached 90% at 0.65V. The number of transferred electrons of TAPA-DTDA-COF is close to 2.25, which is the closest to the two-electron transfer process, so it has the best catalytic activity for oxygen reduction of hydrogen peroxide.
图6为实施例1制备得到的TAPA-DTDA-COF材料的稳定性数据，利用计时电流法和恒电位法来评价稳定性，可以发现，本发明制备得到的具有最佳氧还原双氧水催化活性的TAPA-DTDA-COF材料表现出优异的稳定性，TAPA-DTDA-COF材料在循环了10000s后仍未出现衰减的现象。Figure 6 is the stability data of the TAPA-DTDA-COF material prepared in Example 1. The stability is evaluated by chronoamperometry and constant potential method. The TAPA-DTDA-COF material exhibited excellent stability, and the TAPA-DTDA-COF material did not attenuate after cycling for 10000s.
图7为对比例1在氧气饱和的0.1M KOH溶液中测得的双氧水选择性和电子转移数随电压变化的示意图。7 is a schematic diagram of the hydrogen peroxide selectivity and electron transfer number measured in the oxygen-saturated 0.1M KOH solution of Comparative Example 1 as a function of voltage.
对比例1Comparative example 1
为了排除载体乙炔黑所产生的双氧水对催化剂的干扰，在本研究中将乙炔黑作为空白对照。将乙炔黑作为工作电极，测量在氧气饱和的0.1M KOH溶液中通过旋转圆盘电极装置在旋转速率为1600rpm/min时的极化曲线，并通过公式计算得到双氧水选择性和电子转移数。In order to exclude the interference of hydrogen peroxide produced by the carrier acetylene black on the catalyst, acetylene black was used as a blank control in this study. Acetylene black was used as the working electrode to measure the polarization curve of the rotating disc electrode device in oxygen-saturated 0.1M KOH solution at a rotation rate of 1600rpm/min, and the hydrogen peroxide selectivity and electron transfer number were calculated by the formula.
结果发现，载体乙炔黑在同等条件下几乎不产生双氧水，可以排除对催化剂的干扰。It was found that the carrier acetylene black hardly produces hydrogen peroxide under the same conditions, which can eliminate the interference on the catalyst.
以上所述的实施案例只是本发明的一种较佳的方案，并非对本发明作任何形式上的限制，在不超出权利要求所记载的技术方案的前提下还有其它的变体和改型。The above-mentioned implementation case is only a preferred solution of the present invention, and does not limit the present invention in any form, and there are other variations and modifications on the premise of not exceeding the technical solution described in the claims.

Claims (10)

  1. 一种催化氧还原制备过氧化氢的方法，其特征在于，所述方法是利用共价有机框架材料作为催化剂；所述共价有机框架材料中的线性构筑单元为噻吩并[3,2-b]噻吩-2,5-二甲醛，中心构筑单元选自如下任意一种：4,4',4”-(1,3,5-三嗪-2,4,6-三基)三苯胺、三(4-氨基苯基)胺、三(4-氨基苯基)苯。A method for preparing hydrogen peroxide by catalytic oxygen reduction, characterized in that the method utilizes a covalent organic framework material as a catalyst; the linear building block in the covalent organic framework material is thieno[3,2-b ]thiophene-2,5-dicarbaldehyde, the central building block is selected from any one of the following: 4,4',4"-(1,3,5-triazine-2,4,6-triyl) triphenylamine, Tris(4-aminophenyl)amine, tris(4-aminophenyl)benzene.
  2. 一种电催化制备双氧水的方法，其特征在于，所述方法是将共价有机框架材料修饰在工作电极上，然后置于含氧水溶液中进行电催化反应；所述共价有机框架材料中的线性构筑单元为噻吩并[3,2-b]噻吩-2,5-二甲醛，中心构筑单元选自如下任意一种：4,4',4”-(1,3,5-三嗪-2,4,6-三基)三苯胺、三(4-氨基苯基)胺、三(4-氨基苯基)苯。A method for preparing hydrogen peroxide by electrocatalysis, characterized in that the method is to modify a covalent organic framework material on a working electrode, and then place it in an oxygen-containing aqueous solution to carry out an electrocatalytic reaction; in the covalent organic framework material The linear building block is thieno[3,2-b]thiophene-2,5-dicarbaldehyde, and the central building block is selected from any one of the following: 4,4',4"-(1,3,5-triazine- 2,4,6-triyl)triphenylamine, tris(4-aminophenyl)amine, tris(4-aminophenyl)benzene.
  3. 根据权利要求1或2所述的方法，其特征在于，共价有机框架材料的制备方法包括如下过程：The method according to claim 1 or 2, wherein the preparation method of covalent organic framework material comprises the following process:
    将线性构筑单元和中心构筑单元为单体分散在有机溶剂中，在催化剂的作用下发生席夫碱反应，反应结束后，固液分离、收集固体，洗涤、干燥，即得共价有机框架材料。Disperse the linear building unit and the central building unit as monomers in an organic solvent, and undergo a Schiff base reaction under the action of a catalyst. After the reaction, separate the solid from the liquid, collect the solid, wash, and dry to obtain the covalent organic framework material .
  4. 根据权利要求3所述的方法，其特征在于，共价有机框架材料的制备方法中，所述有机溶剂为正丁醇和1,2-二氯苯混合体系。The method according to claim 3, characterized in that, in the preparation method of the covalent organic framework material, the organic solvent is a mixed system of n-butanol and 1,2-dichlorobenzene.
  5. 根据权利要求3所述的方法，其特征在于，共价有机框架材料的制备方法中，所述催化剂为醋酸。The method according to claim 3, characterized in that, in the preparation method of covalent organic framework material, the catalyst is acetic acid.
  6. 根据权利要求3所述的方法，其特征在于，催化剂与中心构筑单元的摩尔比为20:1。The method according to claim 3, characterized in that the molar ratio of the catalyst to the central building unit is 20:1.
  7. 根据权利要求3-6任一项所述的方法，其特征在于，混合溶液中，线性构筑单元与中心构筑单元的摩尔比为(0.8-2)：1。The method according to any one of claims 3-6, characterized in that, in the mixed solution, the molar ratio of the linear building unit to the central building unit is (0.8-2):1.
  8. 根据权利要求1或2所述的方法，其特征在于，共价有机框架材料的制备方法具体包括如下步骤：The method according to claim 1 or 2, wherein the preparation method of the covalent organic framework material specifically comprises the following steps:
    1)将线性构筑单元、中心构筑单元加入到有机溶剂中，超声得到均匀的混合溶液；1) adding the linear building unit and the central building unit into the organic solvent, and ultrasonically obtaining a uniform mixed solution;
    2)将醋酸溶液加入混合溶液中获得最终溶液，将溶液转移至派克管内，用液氮快速冰冻，将其内压抽至真空，然后密封；恢复室温解冻后，反复抽真空三次；将抽真空后的溶液放至100-150℃下进行反应；2) Add acetic acid solution to the mixed solution to obtain the final solution, transfer the solution to the Parker tube, freeze it quickly with liquid nitrogen, evacuate its internal pressure to a vacuum, and then seal it; after returning to room temperature and thawing, repeatedly evacuate three times; The final solution is placed at 100-150°C for reaction;
    3)反应结束后冷却至室温，固液分离、收集固体，洗涤、干燥，得到COFs催化剂材料。3) Cool to room temperature after the reaction, separate the solid from the liquid, collect the solid, wash, and dry to obtain the COFs catalyst material.
  9. 根据权利要求8所述的方法，其特征在于，混合溶液中，线性构筑单元的浓度为0.01-0.05mmol/mL。The method according to claim 8, characterized in that, in the mixed solution, the concentration of the linear building units is 0.01-0.05mmol/mL.
  10. 根据权利要求8所述的方法，其特征在于，混合溶液中，中心构筑单元的浓度为0.01-0.05mmol/mL。The method according to claim 8, characterized in that, in the mixed solution, the concentration of the central building unit is 0.01-0.05mmol/mL.
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