Alkynyl-linked conjugated microporous polymer as well as preparation method and application thereof

Abstract

The invention relates to an alkynyl-linked conjugated microporous polymer. The molecular structure of the conjugated microporous polymer contains a structural unit as shown in the following formula (I), the alkynyl-linked conjugated microporous polymer provided by the invention consists of aryl and alkynyl, has a long-range continuous conjugated structure and is beneficial to electron conduction, and meanwhile, the alkynyl-linked conjugated microporous polymer provided by the invention has a good microporous structure and a relatively large specific surface area. The invention also provides a method for preparing the alkynyl-linked conjugated microporous polymer based on calcium carbide and application of the alkynyl-linked conjugated microporous polymer in preparation of a conjugated microporous polymer modified electrode.

Description

Technical Field

[0001] This invention belongs to the field of porous organic polymers, specifically relating to an alkyne-linked conjugated microporous polymer, its preparation method, and its application. Background Technology

[0002] Porous materials are widely used in industrial and social production due to the properties inherent in their pore structure. Covalent organic porous polymers (COPs) are a class of organic porous materials composed of light elements (carbon, hydrogen, oxygen, boron, nitrogen, etc.) linked by covalent bonds. Conjugated microporous polymers (CMPs) are a class of organic porous materials with a three-dimensional spatial framework that can connect structural units in a π-conjugated manner, characterized by high porosity, light elements, and strong covalent bonds.

[0003] The key to preparing CMPs is coupling monomers with conjugated units via conjugated covalent bonds. In 2007, Cooper et al. synthesized acetylene-linked CMPs by coupling halogenated aromatics and arylacetylenes via the Sonogashira reaction (Angew. Chem., Int. Ed. 2007, 46, 8574-8578). However, the preparation methods for arylacetylene monomers are complex and costly, limiting the large-scale synthesis and application of these CMPs. Summary of the Invention

[0004] The purpose of this invention is to provide a conjugated microporous polymer with an acetylene-linked monomer.

[0005] To achieve the above objectives, a first aspect of the present invention provides an alkynyl-linked conjugated microporous polymer, wherein the molecular structure of the conjugated microporous polymer contains structural units as shown in formula (I): .

[0006] A second aspect of the present invention provides a method for preparing an alkynyl-linked conjugated microporous polymer, the method comprising: contacting a haloaromatic monomer, calcium carbide and a catalyst to undergo a coupling reaction to obtain a reaction product.

[0007] Optionally, the molar ratio of the haloaromatic hydrocarbon to calcium carbide in the calcium carbide is 1:1-10; and the calcium carbide content in the calcium carbide is 72-82 wt%.

[0008] Optionally, the halogenated aromatic hydrocarbon is selected from one or more of chlorinated aromatic hydrocarbons, bromoaromatic hydrocarbons, and iodoaromatic hydrocarbons, preferably iodoaromatic hydrocarbons; the halogenated aromatic hydrocarbon is 1,3,5-tris(4-halogenated phenyl); preferably, the halogenated aromatic hydrocarbon is 1,3,5-tris(4-iodophenyl)benzene.

[0009] Optionally, the catalyst comprises tetra(triphenylphosphine)palladium and cuprous iodide; based on the weight of the haloaromatic hydrocarbon, the amounts of tetra(triphenylphosphine)palladium and cuprous iodide are each independently 1-5 mol%; the molar ratio of tetra(triphenylphosphine)palladium to cuprous iodide is 1:0.5-2; optionally, the coupling reaction is carried out under the action of an organic base, the organic base being selected from one or more of diethylamine, triethylamine, and N,N-diisopropylethylamine, preferably triethylamine; preferably, the molar ratio of the haloaromatic hydrocarbon to triethylamine is 1:0.02-0.1.

[0010] Optionally, the coupling reaction is carried out under oxygen-free conditions; preferably, the coupling reaction is carried out in an organic solvent; in the coupling reaction, the molar concentrations of the haloaromatic hydrocarbon and the calcium carbide in the calcium carbide are each independently 0.01-0.5 mol / L; the organic solvent is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide and dichloromethane, preferably N,N-dimethylformamide and / or dimethyl sulfoxide.

[0011] Optionally, the coupling reaction is carried out under stirring and heating conditions; the conditions for the coupling reaction include: a reaction temperature of 60-150 ℃, preferably 70-120 ℃; and a reaction time of 12-72 h.

[0012] Optionally, the method further includes: separating the reaction product, and washing and drying the separated solid product; the drying conditions include: a drying temperature of 25-100 °C and a drying time of 12-24 h.

[0013] A third aspect of the present invention provides a conjugated microporous polymer modified electrode, the modified electrode comprising an electrode and a coating disposed on at least one side surface of the electrode, the coating comprising an alkynyl-linked conjugated microporous polymer of the first aspect of the present invention or an alkynyl-linked conjugated microporous polymer prepared by any method provided in the second aspect of the present invention.

[0014] A fourth aspect of the present invention provides a regeneration device for a complexed iron catalyst for desulfurization, the regeneration device comprising a conjugated microporous polymer-modified electrode according to a third aspect of the present invention.

[0015] Through the above technical solution, the alkynyl-linked conjugated microporous polymer provided by the present invention is composed of aryl and alkynyl groups, and has a long-range continuous conjugated structure, which is beneficial to electron conduction. At the same time, the alkynyl-linked conjugated microporous polymer provided by the present invention has a good microporous structure and a large specific surface area.

[0016] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0017] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings: Figure 1 This is the solid-state carbon NMR spectrum of the conjugated microporous polymer provided in Example 1 of this invention.

[0018] Figure 2 This is the N2 adsorption-desorption curve of the conjugated microporous polymer provided in Example 1 of the present invention.

[0019] Figure 3 This is a schematic diagram of the structure of the desulfurization complexed iron catalyst regeneration device provided by the present invention.

[0020] Figure 4 This is a linear voltage scan curve of the desulfurization complex iron catalyst regeneration device in Embodiment 8, Comparative Example 1 and Comparative Example 2 of the present invention.

[0021] Figure 5 This is a conversion rate-time curve of Fe(II)-EDTA during the electrochemical hydrogen evolution coupled with complex iron oxidation reaction in the desulfurization complex iron catalyst regeneration device of Embodiment 8, Comparative Example 1 and Comparative Example 2 of the present invention. Detailed Implementation

[0022] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0023] A first aspect of the present invention provides an alkynyl-linked conjugated microporous polymer, wherein the molecular structure of the conjugated microporous polymer contains structural units as shown in formula (I): .

[0024] The alkynyl-linked conjugated microporous polymer provided by this invention is composed of aryl and alkynyl groups and has a long-range continuous conjugated structure, which is beneficial for electron conduction. At the same time, the alkynyl-linked conjugated microporous polymer provided by this invention has a good microporous structure and a large specific surface area.

[0025] A second aspect of the present invention provides a method for preparing an alkynyl-linked conjugated microporous polymer, the method comprising: The haloaromatic monomer, calcium carbide, and catalyst are brought into contact to undergo a coupling reaction, yielding the reaction product.

[0026] The technical solution of this invention involves coupling a haloaromatic monomer and calcium carbide under the action of a catalyst, allowing the haloaromatic and calcium carbide to undergo ordered coupling polymerization. This results in haloaromatics being linked by alkyne groups, and the resulting conjugated microporous polymer not only possesses a long-range continuous conjugated structure that is conducive to electron conduction, but also has a high specific surface area and high porosity.

[0027] This invention uses calcium carbide to prepare conjugated microporous polymers, which have the advantages of low cost and wide availability compared with other terminal alkyne monomers.

[0028] In some embodiments of the present invention, the calcium carbide is commercially available calcium carbide ore, and the calcium carbide content in the calcium carbide is 72-82 wt%.

[0029] In some embodiments of the present invention, the haloaromatic hydrocarbons and calcium carbide undergo ordered coupling polymerization, and the molar ratio of the haloaromatic hydrocarbons to calcium carbide in the calcium carbide is 1:1-10. When calcium carbide is used as a raw material for coupling reaction as an alkynyl donor, the solubility of calcium carbide is poor, therefore the amount of calcium carbide used needs to be excessive.

[0030] In some embodiments of the present invention, the haloaromatic hydrocarbon is selected from one or more of chloroaromatic hydrocarbons, bromoaromatic hydrocarbons, and iodoaromatic hydrocarbons. To improve the coupling reaction efficiency, the haloaromatic hydrocarbon is preferably an iodoaromatic hydrocarbon. In the Sonogashira coupling reaction, the haloaromatic hydrocarbon is mainly sp... 2 Aryl, heteroaryl, and vinyl halogenated compounds of hybrid carbon, among which iodoaryl compounds exhibit the best activity.

[0031] In some embodiments of the present invention, the haloaromatic hydrocarbon is 1,3,5-tris(4-halophenyl)benzene. Calcium carbide reacts with 1,3,5-tris(4-halophenyl)benzene to obtain a polymer linked by alkynyl groups, and the resulting conjugated microporous polymer consists only of phenyl and alkynyl groups.

[0032] In some preferred embodiments of the present invention, the halogenated aromatic hydrocarbon is 1,3,5-tris(4-iodophenyl)benzene.

[0033] Commonly used palladium catalysts in the Sonogashira coupling reaction include Pd(PPh3)Cl2 and Pd(PPh3)4. Commonly used copper salt catalysts include cuprous iodide and cuprous bromide.

[0034] In some embodiments of the present invention, in order to improve the efficiency of the coupling reaction, the catalyst includes tetra(triphenylphosphine)palladium and cuprous iodide, and the catalyst has high catalytic activity and is easy to elute.

[0035] In some embodiments of the present invention, the amount of catalyst used is the catalytic amount, based on the weight of the haloaromatic hydrocarbon, and the amount of tetra(triphenylphosphine)palladium and the amount of cuprous iodide are each independently 1-5 mol.

[0036] In some embodiments of the present invention, the molar ratio of tetra(triphenylphosphine)palladium to cuprous iodide is 1:0.5-2. The tetra(triphenylphosphine)palladium and cuprous iodide synergistically catalyze the efficient preparation of the conjugated microporous polymer of the present invention.

[0037] In some embodiments of the present invention, the coupling reaction is carried out under the action of an organic base, wherein the organic base is selected from one or more of diethylamine, triethylamine and N,N-diisopropylethylamine, preferably triethylamine.

[0038] In some preferred embodiments of the present invention, the molar ratio of the haloaromatic hydrocarbon to the triethylamine is 1:0.02-0.1.

[0039] In some embodiments of the present invention, the coupling reaction is carried out in an organic solvent; in the coupling reaction, the molar concentrations of the haloaromatic hydrocarbon and the calcium carbide in the calcium carbide are each independently 0.01-0.5 mol / L.

[0040] In some preferred embodiments of the present invention, the organic solvent is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide and dichloromethane. In order to fully dissolve the reactant monomer and catalyst, the organic solvent is preferably N,N-dimethylformamide and / or dimethyl sulfoxide, more preferably N,N-dimethylformamide.

[0041] In some embodiments of the present invention, the coupling reaction is carried out under oxygen-isolated conditions to improve the efficiency of the catalytic reaction.

[0042] In some embodiments of the present invention, the coupling reaction is carried out under stirring and heating conditions. The conditions for the coupling reaction include a reaction temperature of 60-150 °C and a reaction time of 12-72 h. The reaction temperature can be 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, or any temperature within the aforementioned range. Coupling reaction temperatures within the above range are beneficial for promoting the ordered polymerization of haloaromatic monomers. To obtain the fully conjugated microporous polymer product of the present invention in high yield, the coupling reaction temperature is preferably 70-120 °C.

[0043] In this invention, the coupling reaction between the haloaromatic hydrocarbon and the calcium carbide in the calcium carbide can be carried out in the presence of trace amounts of water. The trace amounts of water in the reaction system can at least improve the solubility of calcium carbide, thereby improving the efficiency of the coupling reaction.

[0044] In some embodiments of the present invention, the method further includes: separating the reaction product, and washing and drying the separated solid product.

[0045] In some embodiments of the present invention, the method for washing the separated solid product is centrifugal washing, and the solvent for centrifugal washing includes dilute nitric acid, ethanol, and N,N-dimethylformamide. The concentration of the dilute nitric acid can be 0.1 mol / L.

[0046] In some preferred embodiments of the present invention, the solid product obtained by centrifugation is washed sequentially with dilute nitric acid, ethanol and N,N-dimethylformamide to fully wash away unreacted raw materials and catalysts and other impurities in the product.

[0047] In some preferred embodiments of the present invention, the drying conditions include a drying temperature of 25-100 °C and a drying time of 12-24 h. This effectively removes solvent molecules from the obtained conjugated microporous polymer product and activates the pores in the microporous material.

[0048] A third aspect of the present invention provides a conjugated microporous polymer-modified electrode, the modified electrode comprising an electrode and a coating disposed on at least one surface of the electrode, the coating comprising the aforementioned acetylene-linked conjugated microporous polymer. Preferably, the thickness of the coating is 0.1-10 μm.

[0049] The aforementioned conjugated microporous polymer-modified electrode, due to its coating which facilitates electron conduction, can be used in electrochemical hydrogen evolution oxidation reactions. Specifically, the conjugated microporous polymer-modified electrode can be used in electrochemical hydrogen evolution coupled with complexation iron oxidation reactions.

[0050] Hydrogen sulfide is an important byproduct of the oil and gas industry, with heavy crude oil typically containing more than 1.5% by weight sulfur. In refining processes, sulfur in oil products is mostly removed in the form of hydrogen sulfide. Wet hydrogen sulfide treatment technology based on complexed iron is currently relatively mature. After the oxidized complexed iron oxidizes hydrogen sulfide to elemental sulfur, oxygen can be used as an oxidant to regenerate the reduced complexed iron.

[0051] Since oxygen is produced as a byproduct of hydrogen electrolysis, the electrochemical decomposition of hydrogen can be coupled with the oxidation and regeneration of the complexed iron catalyst. The reduced state of the complexed iron catalyst is introduced into the electrolysis device, and the oxidation and regeneration of the complexed iron catalyst is achieved at the same time as hydrogen evolution at the cathode.

[0052] A fourth aspect of the present invention provides a regeneration device for a complexed iron catalyst for desulfurization, the regeneration device comprising a conjugated microporous polymer-modified electrode according to a third aspect of the present invention.

[0053] Figure 3 A schematic diagram illustrates a regeneration device for a complexed iron catalyst used in desulfurization, to... Figure 3 The electrocatalytic complex iron regeneration device shown is used as an example to introduce the method of electrochemical decomposition and hydrogen coupling for complex iron regeneration. In a preferred embodiment of the present invention, the electrocatalytic complex iron regeneration device includes an electrolytic cell and a hydrogen sulfide treatment device, wherein the hydrogen sulfide treatment device can be an existing wet hydrogen sulfide treatment device based on complex iron. For example, the hydrogen sulfide treatment device includes an absorption section and a separation section, which can be separated by a diaphragm, or other devices can be set between the absorption section and the separation section to transport the product after reaction with hydrogen sulfide in the absorption section to the separation section for separation. Fe(III)-EDTA solution is added to the absorption section of the hydrogen sulfide treatment device, and hydrogen sulfide gas is introduced into the hydrogen sulfide treatment device. Fe(III)-EDTA reacts with hydrogen sulfide to produce sulfur and Fe(II)-EDTA. Sulfur and Fe(II)-EDTA are separated in the separation section, and Fe(II)-EDTA is sent to the electrolytic cell to be oxidized to Fe(III)-EDTA by electrochemical oxidation reaction. The generated Fe(III)-EDTA is returned to the hydrogen sulfide treatment unit for recycling.

[0054] In some specific embodiments of the present invention, the cathode chamber and the anode chamber in the electrolytic cell can be separated by a proton exchange membrane. Na₂SO₄ aqueous solution is added to the cathode chamber and the anode chamber respectively, and Fe(II)-EDTA is added to the anode chamber. The cathode and anode are connected to an external constant voltage power supply via wires. After applying voltage, a large number of bubbles are generated on the cathode in the cathode chamber, and the Fe(II)-EDTA in the anode chamber is oxidized to Fe(III)-EDTA.

[0055] The alkyne-linked conjugated microporous polymer material provided by this invention has a long-range continuous conjugated structure that is conducive to electron conduction, which is beneficial to the adsorption and enrichment of complexed iron in the electrolyte, thereby helping to reduce the overpotential of the anodic reaction and improving the efficiency of the complexed iron oxidation reaction.

[0056] The present invention will be further described in detail below through embodiments, but these embodiments are not intended to limit the invention. All raw materials used in the embodiments are commercially available.

[0057] The calcium carbide was purchased from Acros, and its calcium carbide content was 72-82 wt%. A 5 wt% Nafion solution containing 5 wt% Nafion, including 45 wt% water.

[0058] Example 1 This embodiment illustrates the preparation method of the acetylene-linked conjugated microporous polymer of the present invention, including the following steps: S1. 8.95 mmol of 1,3,5-tris(4-iodophenyl)benzene and 1.7 g of calcium carbide (calcium carbide amount 19.13-21.78 mmol) were dispersed in 100 mL of N,N-dimethylformamide to obtain a first mixture; 0.1 mmol of tetrakis(triphenylphosphine)palladium, 0.1 mmol of cuprous iodide and 0.5 mmol of triethylamine were added to the first mixture to obtain a second mixture; S2. The second mixture is subjected to gas replacement, and a coupling reaction is carried out by heating the second mixture under a nitrogen atmosphere at a reaction temperature of 80 °C for 48 h to obtain a reaction mixture; S3. The reaction mixture was subjected to solid-liquid separation. The obtained solid product was centrifuged and washed successively with 0.1 mol / L dilute nitric acid, ethanol (99.5 wt%), and N,N-dimethylformamide. The washed product was dried at 80 °C for 24 h. The resulting conjugated microporous polymer was designated CMP-1. The yield of CMP-1 was 84.2%.

[0059] The structure of CMP-1 was analyzed using nuclear magnetic resonance spectroscopy. Figure 1 Solid-state NMR for CMP-1 13 C-spectrum, as Figure 1 As shown, the peaks at 142 ppm and 128 ppm are attributed to carbon atoms on the benzene ring, and the peak at 93 ppm is attributed to carbon atoms on the alkynyl group.

[0060] The N2 adsorption-desorption test (BET method) was performed on CMP-1. Figure 2 The N2 adsorption-desorption curve and pore size distribution curve of CMP-1 are shown. The test results show that the specific surface area of ​​CMP-1 is 325.5 m². 2 / g, pore volume is 0.651 cm³ 3 / g, micropore volume is 0.089 cm³ 3 / g indicates that CMP-1 has microporous properties.

[0061] Example 2 The method for preparing the alkynyl-linked conjugated microporous polymer in this embodiment is basically similar to that in Example 1, except that the reaction temperature in step S2 is 60 °C and the reaction time is 72 h. The resulting conjugated microporous polymer is designated CMP-2, with a yield of 41.2%.

[0062] Example 3 The method for preparing the alkynyl-linked conjugated microporous polymer in this embodiment is basically similar to that in Example 1, except that the reaction temperature in step S2 is 120 °C and the reaction time is 36 h. The resulting conjugated microporous polymer is designated CMP-3, with a yield of 82.1%.

[0063] Example 4 The method for preparing the alkynyl-linked conjugated microporous polymer in this embodiment is basically similar to that in Example 1, except that the reaction temperature in step S2 is 150 °C and the reaction time is 12 h. The resulting conjugated microporous polymer is designated CMP-4, with a yield of 55.6%.

[0064] Example 5 The method for preparing the alkynyl-linked conjugated microporous polymer in this embodiment is basically similar to that in Example 1, except that the reaction solvent in step S1 is dimethyl sulfoxide. The resulting conjugated microporous polymer is designated CMP-5, with a yield of 83.6%.

[0065] Example 6 The method for preparing the alkynyl-linked conjugated microporous polymer in this embodiment is basically similar to that in Example 1, except that the amount of calcium carbide used in step S1 is 0.85 g. The resulting conjugated microporous polymer is designated CMP-6, with a yield of 43.8%.

[0066] Example 7 This embodiment illustrates the preparation method of the conjugated microporous polymer-modified electrode of the present invention, including: Weigh 2 mg of the conjugated microporous polymer CMP-1 prepared in Example 1, and ultrasonically disperse CMP-1 in a mixed solution of 0.2 mL of ethanol and Nafion to obtain a CMP-1 dispersion. Take 0.1 mL of the CMP-1 dispersion and drop it onto the surface of the pretreated bare glassy carbon electrode, and dry it at 80 °C to obtain the modified electrode CMP-1 / GCE. The thickness of the conjugated microporous polymer coating on the glassy carbon electrode is approximately 8 μm.

[0067] The mixed solution includes equal volumes of anhydrous ethanol (99.5 wt%) and Nafion solution (5 wt%).

[0068] Example 8 This embodiment illustrates a method for electrolytic hydrogen-coupled complexed iron oxidation regeneration, including: use Figure 3 Electrolytic hydrogen-coupled complex iron oxidation regeneration experiments were conducted using the H-type electrolytic cell shown. The electrolyte in the cathode chamber was a 0.1 mol / L Na₂SO₄ solution with pH=5; Fe(II)-EDTA was added to the electrolyte in the anode chamber, resulting in a Fe(II)-EDTA concentration of 1 mmol / L and a Na₂SO₄ concentration of 0.1 mol / L. Using a Pt sheet electrode as the cathode and the modified electrode CMP-1 / GCE prepared in Example 7 as the anode (with a Nafion 117 proton exchange membrane separating the cathode and anode chambers), the electrolytic hydrogen-coupled complex iron oxidation regeneration experiments were performed.

[0069] Linear voltage scan tests were performed on an electrolytic device consisting of the modified CMP-1 / GCE as the anode, and the results are as follows: Figure 4 As shown.

[0070] An electrolytic device consisting of the modified electrode CMP-1 / GCE as the anode was used at 1.5 V to perform an electrochemical hydrogen evolution coupled complex iron oxidation reaction. The concentration C of Fe(II)-EDTA in the electrolyte in the anode chamber was measured at 10 min, 25 min, 50 min, 75 min, and 100 min after the start of the reaction. C0 was taken as the initial concentration of Fe(II)-EDTA in the anode chamber before the electrochemical reaction, and the C / C0 ratio was calculated. The results are shown in Table 1 and... Figure 5 As shown.

[0071] Comparative Example 1 The method for electrolytic hydrogen-coupled complex iron oxidation regeneration in this comparative example is similar to that in Example 8, except that the anode is a Pt sheet.

[0072] Linear voltage scan tests were performed using an electrolytic device with Pt anodes, and the results are as follows: Figure 4 As shown.

[0073] An electrolytic device with Pt anodes was used to conduct an electrochemical hydrogen evolution coupled with complex iron oxidation reaction. The ratio of Fe(II)-EDTA concentration in the electrolyte to the initial concentration (C / C0) is shown in Table 1. Figure 5 As shown.

[0074] Comparative Example 2 The method for electrolytic hydrogen-coupled complexation iron oxidation regeneration in this comparative example is similar to that in Example 8, except that the anode is a glassy carbon electrode.

[0075] Linear voltage scan tests were performed using an electrolytic device with glassy carbon electrodes as the anode. The results are as follows: Figure 4 As shown.

[0076] An electrolytic device with a glassy carbon electrode as the anode was used to perform an electrochemical hydrogen evolution coupled with complex iron oxidation reaction. The ratio of Fe(II)-EDTA concentration in the electrolyte to the initial concentration, C / C0, is shown in Table 1. Figure 5 As shown.

[0077] Table 1

[0078] according to Figure 4 The results show that, compared with Pt sheet and glassy carbon electrode as anode, the conjugated microporous polymer modified electrode CMP-1 / GCE (represented by CMP-1 in the figure) provided by the present invention has the lowest starting voltage when used for electrolytic hydrogen coupling iron oxide regeneration, indicating that the modified electrode CMP-1 / GCE as anode material is beneficial to reducing the voltage of the electrolytic reaction.

[0079] According to Table 1 and Figure 5 The results show that, compared with Pt sheet and glassy carbon electrode as anode, the conjugate microporous polymer modified electrode CMP-1 / GCE (represented by CMP-1 in the figure) provided by the present invention has the highest Fe(II)-EDTA conversion efficiency in the electrolyte when used for electrolytic hydrogen-coupled iron oxide regeneration, thus improving the conversion reaction rate of Fe(II)-EDTA.

[0080] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0081] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0082] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. An alkynyl-linked conjugated microporous polymer, characterized in that, The conjugated microporous polymer comprises structural units of formula (I) in the molecular structure thereof: 。 2. A method of making an alkinyl-linked conjugated microporous polymer, characterized by, The method comprises: The halogenated aromatic hydrocarbon monomer, calcium carbide and a catalyst are contacted to carry out a coupling reaction to obtain a reaction product.

3. The method of claim 2, wherein, The molar ratio of the halogenated aromatic hydrocarbon to the calcium carbide in the calcium carbide is 1:1-10; The content of the calcium carbide in the calcium carbide is 72-82 wt%.

4. The method of claim 2, wherein, The halogenated aromatic hydrocarbon is selected from one or more of chlorinated aromatic hydrocarbons, brominated aromatic hydrocarbons and iodinated aromatic hydrocarbons, and is preferably iodinated aromatic hydrocarbons; The halogenated aromatic hydrocarbon is 1,3,5-tris(4-halogenated phenyl)benzene. Preferably, the halogenated aromatic hydrocarbon is 1,3,5-tris(4-iodophenyl)benzene.

5. The method of claim 2, wherein, The catalyst comprises tetrakis(triphenylphosphine)palladium and cuprous iodide. The amount of the tetrakis(triphenylphosphine)palladium and the cuprous iodide is each independently 1-5 mol% based on the weight of the halogenated aromatic hydrocarbon. The molar ratio of the tetrakis(triphenylphosphine)palladium to the cuprous iodide is 1:0.5-2. Optionally, the coupling reaction is carried out in the presence of an organic base selected from one or more of diethylamine, triethylamine and N,N-diisopropylethylamine, and is preferably triethylamine; preferably, the molar ratio of the halogenated aromatic hydrocarbon to the triethylamine is 1:0.02-0.

1.

6. The method of claim 2, wherein, The coupling reaction is carried out in an oxygen-free environment. Preferably, the coupling reaction is carried out in an organic solvent; in the coupling reaction, the substance amount concentration of the halogenated aromatic hydrocarbon and the calcium carbide in the calcium carbide is each independently 0.01-0.5 mol / L; the organic solvent is selected from one or more of N,N-dimethylformamide, dimethyl sulfoxide and dichloromethane, and is preferably N,N-dimethylformamide and / or dimethyl sulfoxide.

7. The method of claim 2, wherein, The coupling reaction is carried out under stirring and heating; the conditions of the coupling reaction include that the reaction temperature is 60-150 ℃, and is preferably 70-120 ℃; the reaction time is 12-72 h.

8. The method of claim 2, wherein, The method further comprises: The reaction product is separated, and the separated solid product is washed and dried; The drying conditions include that the drying temperature is 25-100 ℃, and the drying time is 12-24 h.

9. A conjugated microporous polymer modified electrode characterized in that, The modified electrode comprises an electrode and a coating layer arranged on at least one side surface of the electrode, and the coating layer comprises the alkynyl-attached conjugated microporous polymer of claim 1 or the alkynyl-attached conjugated microporous polymer prepared by the method of any one of claims 2-8.

10. A regeneration apparatus of a complex iron catalyst for desulfurization, characterized by comprising: The regeneration device comprises the conjugated microporous polymer modified electrode of claim 9.

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