Ultrasonic-responsive composite catalyst for carbon capture and preparation and application thereof
By combining carbonic anhydrase mimic enzyme, conductive polymer PEDOT:PSS, and piezoelectric linear zinc oxide in the composite catalyst, the problem of low catalytic rate of carbonic anhydrase was solved, and a highly efficient and stable CO2 capture effect was achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHINA UNIV OF PETROLEUM (BEIJING)
- Filing Date
- 2024-03-06
- Publication Date
- 2026-05-29
Smart Images
Figure CN118320863B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of carbon capture, specifically to an ultrasonically responsive composite catalyst for carbon capture and its preparation and application. Background Technology
[0002] Carbon capture, utilization, and storage (CCUS) technology refers to the use of adsorption, absorption, membrane systems, and other methods to capture and store CO2 generated in industrial and daily life activities, and then convert it into reusable industrial chemicals or fuels. It is an effective measure for CO2 emission reduction and resource utilization. Based on existing research and practice, current CO2 capture methods include physical adsorption, chemical absorption, ion-exchange membrane separation, bio-enzymatic methods, and geological process fixation. However, these technologies have been proven in actual industrial production to have high economic costs, low conversion rates, and high energy consumption. Researchers have found that compared to other physical / chemical methods, bio-enzymatic methods have advantages such as high efficiency and specificity, mild reaction conditions, low pollution, and simple post-treatment, thus gradually becoming a research hotspot in the CCUS field.
[0003] Carbonic anhydrase (CA) is a zinc-containing metalloenzyme widely found in various eukaryotes and prokaryotes. It efficiently catalyzes the reversible hydration of CO2 and is one of the highest-rate enzymes known. However, its high cost, low stability in its free form, sensitivity to organic solvents, high temperatures, and strong acid / alkali environments, difficulty in recycling, and challenges in automating and continuous operation limit its practical applications. However, carbonic anhydrase mimics, through their active site Zn, can catalyze the CO2 hydration reaction. 2+ Larger positive charge pair Through electrostatic adsorption The inability to easily dissociate from the intermediate limits the rate of CO2 hydration catalysis in the simulated CA reaction. This invention utilizes a piezoelectric material combined with a carbonic anhydrase-mimicking enzyme, and employs a conductive polymer PEDOT:PSS to transport electrons generated by the piezoelectric material to the active site Zn. 2+ Reduce Zn 2+ The positive charge increases The dissociation rate of the intermediate further enhances the ability of the carbonic anhydrase mimic enzyme to catalyze the CO2 hydration reaction.
[0004] When a piezoelectric material is subjected to an external force, a positive piezoelectric effect occurs on its surface, with the charge proportional to the magnitude of the force. Conversely, when the crystal is subjected to an electric field, an inverse piezoelectric effect occurs, with mechanical deformation proportional to the field strength. Currently, commonly studied piezoelectric materials include BiFeO3, BaTiO3, MoS2, and ZnO, which can effectively convert mechanical vibrations into electrical energy. Among these, ZnO possesses advantages such as environmental friendliness, low cost, and high piezoelectric performance. Summary of the Invention
[0005] To address at least one of the above technical problems, this invention provides a high-efficiency, low-cost, reusable, and stable composite catalyst with broad application prospects in fields such as CO2 geological sequestration, chemical liquid-phase carbon capture, and air carbon capture.
[0006] To achieve the above objectives, the present invention adopts the following technical solution:
[0007] The first aspect of the present invention provides an ultrasonically responsive composite catalyst for carbon capture, wherein the composite catalyst comprises a carbonic anhydrase mimic enzyme, a conductive polymer PEDOT:PSS, and a piezoelectric material, linear zinc oxide.
[0008] Specifically, the conductive polymer PEDOT:PSS binds carbonic anhydrase mimic enzyme and piezoelectric linear zinc oxide together via electrostatic adsorption to form the composite catalyst.
[0009] In this composite catalyst, there is an electrostatic attraction between the sulfonic acid group of the carbonic anhydrase mimic enzyme, the surface hydroxyl group of zinc oxide, and the positive charge of the conductive polymer PEDOT:PSS molecule. Under ultrasonic treatment, the conductive polymer PEDOT:PSS molecule can transfer piezoelectric electrons generated inside the piezoelectric material to the carbonic anhydrase mimic enzyme, thereby improving the catalytic effect of the carbonic anhydrase mimic enzyme.
[0010] According to the composite catalyst of the present invention, preferably, the mass ratio of the carbonic anhydrase mimic enzyme, the conductive polymer PEDOT:PSS and the piezoelectric material linear zinc oxide is (1-5):(5-30):(1-10), more preferably 2:10:3.
[0011] A second aspect of the present invention provides a method for preparing the above-mentioned composite catalysts, comprising the following steps:
[0012] Linear zinc oxide piezoelectric material was dispersed in water, and carbonic anhydrase mimics, 3,4-ethylenedioxythiophene (EDOT), sodium polystyrene sulfonate (PSS), and ammonium persulfate were added. The mixture was stirred at 20–25°C for 18–24 hours.
[0013] The obtained precipitate is separated, washed, and dried to obtain the composite catalyst.
[0014] In this reaction, 3,4-ethylenedioxythiophene (EDOT) and sodium polystyrene sulfonate (PSS) are synthesized into the conductive polymer PEDOT:PSS under the action of ammonium persulfate initiator. At the same time, carbonic anhydrase mimic enzyme and zinc oxide are polymerized together through electrostatic attraction.
[0015] According to the preparation method of the present invention, preferably, the ratio of the amount of 3,4-ethylenedioxythiophene (EDOT), sodium polystyrene sulfonate (PSS) and ammonium persulfate is 10-30 μL: 5-20 μL: 50-100 mg; more preferably, it is 20 μL: 5 μL: 100 mg.
[0016] More preferably, the ratio of the piezoelectric material linear zinc oxide, carbonic anhydrase mimic enzyme, 3,4-ethylenedioxythiophene (EDOT), sodium polystyrene sulfonate (PSS), and ammonium persulfate is 20 mg: 30 mg: 20 μL: 5 μL: 100 mg.
[0017] According to the preparation method of the present invention, preferably, the washing is performed using ethanol.
[0018] According to the preparation method of the present invention, preferably, the drying is carried out by freeze drying, for example, drying in a freeze dryer for 12 to 48 hours.
[0019] According to the preparation method of the present invention, preferably, the carbonic anhydrase mimic enzyme is prepared by the following steps:
[0020] S1. Dissolve 3,4-diaminobenzenesulfonic acid and aziridine triacetic acid in HCl solution to obtain the first solution;
[0021] S2. The first solution is heated under reflux for 24-36 hours. After the reaction is completed, it is cooled to room temperature to obtain a solid precipitate (usually blue). After separation, washing and drying, an intermediate product (usually a blue-white solid) is obtained.
[0022] S3. Add the intermediate product obtained in S2 and Zn(ClO4)2·6H2O to water (dissolve it) at a mass ratio of 1:(1-1.6), and adjust the pH to 6.5-7.5 (preferably 7) using an alkaline solution; heat to 55-75°C and react for 30-90 min (preferably heat to 65°C and react for 1 hour), cool to room temperature, and add ethanol to precipitate the metal complex (generally white); after separation, washing with ethanol, and drying, obtain the carbonic anhydrase mimic enzyme.
[0023] In the preparation process of the carbonic anhydrase mimic enzyme, in step S1:
[0024] Preferably, the mass ratio of 3,4-diaminobenzenesulfonic acid to aziridine triacetic acid is (1.5-4.5):(0.5-1.2).
[0025] Preferably, the concentration of the HCl solution is 1.5 to 5 M, for example, 2 M.
[0026] In the preparation process of the carbonic anhydrase mimic enzyme, in step S2:
[0027] Preferably, the washing is performed using water.
[0028] Preferably, the drying is performed by freeze drying, for example, drying in a freeze dryer for 12 to 48 hours.
[0029] In the preparation process of the carbonic anhydrase mimic enzyme, in step S3:
[0030] Preferably, the alkaline solution is a NaOH solution.
[0031] Preferably, the drying is performed by freeze drying, for example, drying in a freeze dryer for 12 to 48 hours.
[0032] According to the preparation method of the present invention, preferably, the piezoelectric linear zinc oxide material is prepared by the following steps:
[0033] A mixed solution of zinc source and urea (CO(NH2)2) was subjected to a hydrothermal reaction. The resulting precipitate was separated, washed, dried, and then calcined to obtain the piezoelectric material linear zinc oxide.
[0034] The linear zinc oxide piezoelectric material prepared by this invention has good piezoelectric properties.
[0035] In the preparation process of the piezoelectric linear zinc oxide:
[0036] Preferably, the zinc source is C4H. 10 O6Zn or ZnCl2.
[0037] Preferably, the molar ratio of the zinc source to urea is 1:(1-2), more preferably 1:1.
[0038] Preferably, the hydrothermal reaction is carried out at a temperature of 80–95°C for 4–6 hours; more preferably, the hydrothermal reaction is carried out at a temperature of 75°C for 6 hours.
[0039] Preferably, the hydrothermal reaction is carried out in a closed container, such as a sealed beaker, reaction flask, or autoclave, and preferably an autoclave lined with polytetrafluoroethylene.
[0040] Preferably, the washing is performed using a mixed solution of water and ethanol; more preferably, the volume ratio of water to ethanol is 1:(1 to 2.5), for example, 1:1.
[0041] Preferably, the drying temperature is 60-95°C in an oven for 16-32 hours; more preferably, it is 80°C in an oven for 24 hours.
[0042] Preferably, the calcination temperature is 380–480°C (more preferably 400°C), and the time is 0.5–1 hour.
[0043] Preferably, the calcination is carried out in a tube furnace or a muffle furnace; more preferably, the calcination is carried out in a muffle furnace at a temperature of 400°C for 1 hour.
[0044] In the preparation process described above in this invention, the separation can be achieved using common solid-liquid separation methods, such as filtration, vacuum filtration, and centrifugation, with centrifugation being preferred. Those skilled in the art will understand that the centrifugation and washing processes (e.g., water washing or alcohol washing) are generally repeated multiple times, for example, three times. The water used in this invention is generally deionized water, and the ethanol is generally anhydrous ethanol.
[0045] A third aspect of the present invention provides the application of the composite catalyst described above in carbon capture.
[0046] The ultrasonically responsive composite catalyst provided by this invention can significantly improve the efficiency of CO2 hydration reaction under ultrasonic excitation, thus promoting the relative CO2 capture efficiency of water. Compared with natural carbonic anhydrase, it has advantages such as low cost and availability, acid and alkali resistance, excellent thermal stability, adaptability to various complex organic and inorganic environments, and good reusability. It can efficiently catalyze the carbon dioxide hydration reaction and improve carbon capture efficiency; it has broad application prospects in CO2 geological storage, chemical liquid-phase carbon capture, and air carbon capture. It fundamentally solves the shortcomings of poor activity of natural carbonic anhydrase and addresses the practical application problems of natural carbonic anhydrase.
[0047] In experiments, the composite catalyst of this invention was used to carry out CO2 capture catalysis experiments, which can increase the CO2 capture capacity by 4 to 6 times, adapt to various environments and conditions, effectively catalyze the CO2 hydration reaction, and adapt to CO2 capture. Attached Figure Description
[0048] Figure 1 The mass spectrum of the carbonic anhydrase mimic enzyme prepared in Example 1 is shown.
[0049] Figure 2 The Fourier transform infrared spectrum of the carbonic anhydrase mimic enzyme prepared in Example 1 is shown.
[0050] Figure 3This is a comparison of the relative activities of the carbonic anhydrase mimic enzyme prepared in Example 1 and the natural carbonic anhydrase in different organic solutions.
[0051] Figure 4 The graph shows the reusability of the carbonic anhydrase mimic enzyme prepared in Example 1.
[0052] Figure 5 This is a comparison of the storage stability of the carbonic anhydrase mimic enzyme prepared in Example 1 and the natural carbonic anhydrase at 25°C.
[0053] Figure 6 The image shows a scanning electron microscope image of the zinc oxide prepared in Example 2.
[0054] Figure 7 The image shows a transmission electron microscope image of the zinc oxide prepared in Example 2.
[0055] Figure 8 The image shows the piezoelectric properties of the zinc oxide prepared in Example 2.
[0056] Figure 9 This is a comparison graph showing the catalytic performance of the composite catalyst in Test Example 1 under ultrasonic and non-ultrasonic conditions.
[0057] Figure 10 The graph shows the pH change over time in CO2 capture using the composite catalyst in Test Example 2.
[0058] Figure 11 This is a comparison chart of CO2 capture capacity of the composite catalyst in Test Example 2. Detailed Implementation
[0059] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments, further clarifies the invention. Those skilled in the art should understand that the specific descriptions below are illustrative rather than restrictive, and should not be construed as limiting the scope of protection of the present invention.
[0060] All numerical specifications in this invention (e.g., temperature, time, concentration, and weight, including ranges for each) are generally approximate values that can be changed in increments of 0.1 or 1.0 (+) or (-). All numerical specifications are to be understood as being preceded by the term "about". Unless otherwise specified, all raw materials used are available from publicly available commercial sources, and all reagents used are of analytical grade purity unless otherwise specified.
[0061] Example 1
[0062] This embodiment prepares a carbonic anhydrase mimic enzyme, including the following steps:
[0063] S1. Weigh 3g of 3,4-diaminobenzenesulfonic acid and 1g of nitrotriacetic acid, and dissolve them in 40mL of 2M HCl.
[0064] S2. Reflux the liquid from S1 in an oil bath for 24 hours. Cool the sapphire blue solution to room temperature to obtain a blue solid precipitate. Centrifuge the blue solid precipitate at 10,000 rpm for 10 minutes, wash with water, centrifuge again, and repeat the above process three times. Dry the resulting blue-white solid overnight in a freeze dryer.
[0065] S3. The blue-white solid obtained in S2 and Zn(ClO4)2·6H2O were dissolved in water at a mass ratio of approximately 1:1.5, and the pH was adjusted to 7 using NaOH solution. The mixture was heated to 65°C and reacted for 1 hour, then allowed to cool naturally to room temperature. Anhydrous ethanol was added to precipitate the white metal complex. The precipitate was centrifuged at 10,000 rpm for 10 minutes, washed with anhydrous ethanol, and centrifuged again. This process was repeated three times. The resulting white solid was then freeze-dried for 24 hours. The carbonic anhydrase mimic enzyme was finally obtained.
[0066] Figure 1 The mass spectrum of the carbonic anhydrase mimic enzyme prepared in Example 1 is shown. Figure 2 The Fourier transform infrared spectrum is shown for the carbonic anhydrase mimic enzyme prepared in Example 1. Based on the analysis in Example 1, the target product, the carbonic anhydrase mimic enzyme, was synthesized.
[0067] Figure 3 This is a comparison of the relative activities of the carbonic anhydrase mimic enzyme prepared in Example 1 and the natural carbonic anhydrase in different organic solutions. The specific testing process is as follows:
[0068] Enzyme activity was determined using the esterase method: Carbonic anhydrase mimics can rapidly catalyze the hydrolysis of the optimal substrate p-nitrophenyl acetate (p-NPA) to p-nitrophenol (p-NP). The enzyme activity was obtained by measuring the concentration of p-NP generated from the hydrolysis of p-NPA by carbonic anhydrase or its mimics using a microplate reader. Full-wavelength scanning tests of p-NP at different concentration gradients showed that the absorbance of p-NP reached its peak at a wavelength of 400 nm. The specific method for determining enzyme activity is as follows:
[0069] Assay for carbonic anhydrase mimic enzyme activity: 6.8 mL of deionized water was pipetted into 3 mL of carbonic anhydrase mimic enzyme solution (1 mg / mL) and 0.2 mL of p-NPA (3 mM) (p-NPA dissolved in acetonitrile). The mixture was reacted at room temperature for 30 min. 200 μL of the mixture was then pipetted into a 96-well plate. Parallel assays were performed, and the absorbance of the mixture at 400 nm was measured using a microplate reader. The experiment was repeated three times, with a blank sample consisting only of deionized water and an equal volume of p-NPA.
[0070] The experiment primarily evaluated carbonic anhydrase and its mimics through relative enzyme activity. Relative enzyme activity refers to the ratio of the enzyme activity under specific experimental conditions to the maximum enzyme activity in that experimental environment.
[0071] Figure 4 The graph shows the reusability of the carbonic anhydrase mimic enzyme prepared in Example 1.
[0072] Carbonic anhydrase cannot be repeatedly recycled and reused, but carbonic anhydrase mimics can be reused multiple times. To test the reusability of carbonic anhydrase mimics, pipette 6.8 mL of deionized water, add 3 mL of carbonic anhydrase mimic solution (1 mg / mL) and 0.2 mL of p-NPA (3 mM) (p-NPA is dissolved in acetonitrile), react for 30 min, pipette 200 μL of the mixture into a 96-well plate, and perform parallel testing. Measure the absorbance of the mixture at 400 nm using a microplate reader. After measurement, wash with anhydrous ethanol by centrifugation, dry at room temperature, and test again. Repeat this process 10 times to test the reusability of the carbonic anhydrase mimics.
[0073] Figure 5 This is a comparison of the storage stability of the carbonic anhydrase mimic enzyme (MCA) prepared in Example 1 and natural carbonic anhydrase (CA) at 25°C. Samples were taken every 3 days to determine their enzyme activity using the above testing methods. The initial activity of carbonic anhydrase or carbonic anhydrase mimic enzyme was defined as 100%, and the enzyme activity under other conditions was calculated as a relative enzyme activity.
[0074] like Figure 3 , Figure 4 and Figure 5 As shown, the artificial carbonic anhydrase mimic enzyme in this embodiment has better stability and storage stability than natural carbonic anhydrase, can adapt to various complex organic environments, and can be recycled and reused, thus achieving the effects of saving costs and reducing usage.
[0075] Example 2
[0076] This embodiment prepares a piezoelectric linear zinc oxide material, including the following steps:
[0077] S4. Add 25 mL of 0.2 M C4H2O solution to a stirring vessel at a stirring speed of 500 rpm / min. 10 A solution of O6Zn was added to 25 mL of a 0.2 M aqueous solution of CO(NH2)2 to obtain a mixed solution.
[0078] S5. Seal the resulting mixture in an autoclave and heat it at 75°C for 6 hours, then allow it to cool naturally to room temperature.
[0079] S6. Centrifuge the obtained precipitate at 10,000 rpm / min for 10 minutes, wash with water and anhydrous ethanol (volume ratio 1:1), centrifuge again, repeat the above process three times, and dry the obtained white solid in an oven at 80°C for 24 hours.
[0080] S7. Finally, the white solid powder is calcined in a tube furnace at 400°C for 0.5 hours to obtain the piezoelectric material zinc oxide.
[0081] Figure 6 The image shows a scanning electron microscope (SEM) image of the zinc oxide prepared in Example 2.
[0082] Figure 7 The image shows a transmission electron microscope (TEM) image of the zinc oxide prepared in Example 2.
[0083] like Figure 6 and Figure 7 As shown, the piezoelectric zinc oxide material prepared in this embodiment has a distinct linear structure and a complete structure.
[0084] Figure 8 The image shows the piezoelectric properties of the zinc oxide prepared in Example 2.
[0085] The piezoelectric catalytic performance of ZnO nanomaterials was evaluated using an ultrasonic therapy device with a frequency of 1 MHz, a duty cycle of 50%, a relative frequency of 100 Hz, and a power of 1.5 W / cm². 2 The organic dye in methylene blue solution was degraded under ultrasonic vibration. Zinc oxide was used to degrade methylene blue dye under ultrasonic conditions. The absorbance curve of the degradation shows that the higher the degradation efficiency of methylene blue, the stronger the piezoelectric properties.
[0086] Example 3
[0087] This embodiment prepares a composite catalyst, including the following steps:
[0088] S8. Disperse the ZnO (20 mg) prepared in Example 2 in 20 mL of water, add the carbonic anhydrase mimic enzyme (30 mg) prepared in Example 1, and finally add EDOT (20 μL), PSS (5 μL) and ammonium persulfate (100 mg). Stir continuously at 25°C for 24 hours.
[0089] S9. Centrifuge the obtained precipitate at 10,000 rpm / min for 10 minutes, wash with anhydrous ethanol, centrifuge again, repeat the above process three times, and dry the obtained yellow solid in a freeze dryer for 24 hours.
[0090] Example 4
[0091] This embodiment prepares a composite catalyst, including the following steps:
[0092] S8. Disperse the ZnO (20 mg) prepared in Example 2 in 10 mL of water, add the carbonic anhydrase mimic enzyme (30 mg) prepared in Example 1, and finally add EDOT (10 μL), PSS (0 μL) and ammonium persulfate (50 mg) respectively. Stir continuously at 20°C for 24 hours.
[0093] S9. Centrifuge the obtained precipitate at 10,000 rpm / min for 10 minutes, wash with anhydrous ethanol, centrifuge again, repeat the above process three times, and dry the obtained yellow solid in a freeze dryer for 24 hours.
[0094] In this embodiment, since no polymerizable monomer PSS was added, characterization revealed that no polymerization occurred and no conductive polymer was formed.
[0095] Example 5
[0096] This embodiment prepares a composite catalyst, including the following steps:
[0097] S8. Disperse the ZnO (20 mg) prepared in Example 2 in 30 mL of water, add the carbonic anhydrase mimic enzyme (30 mg) prepared in Example 1, and finally add EDOT (30 μL), PSS (10 μL) and ammonium persulfate (150 mg) respectively. Stir continuously at 30°C for 24 hours.
[0098] S9. Centrifuge the obtained precipitate at 10,000 rpm / min for 10 minutes, wash with anhydrous ethanol, centrifuge again, repeat the above process three times, and dry the obtained yellow solid in a freeze dryer for 24 hours.
[0099] In this embodiment, due to the excessive amount of ammonium persulfate, the conductive polymer formed by polymerization is too large, occupying the catalytic sites and thus having no performance effect.
[0100] Test Example 1
[0101] The composite catalyst prepared in Example 3 of this invention was used to test the performance of CO2 catalytic hydration reaction. Carbonic anhydrase mimic enzyme can catalyze the CO2 hydration reaction, and the test was conducted to test the activity of carbonic anhydrase mimic enzyme.
[0102] The specific steps are as follows:
[0103] (1) Accurately weigh 0.02g of composite catalyst, dissolve it in 40mL of deionized water, and stir to dissolve it completely.
[0104] (2) Accurately weigh 54.34 mg of p-nitrophenol acetate and dissolve it in 100 mL of deionized water to obtain a 3 mmol / L solution.
[0105] (3) Take 3 mL of the solution from step (2) and add it to the solution from step (1). Use an ultrasonic physiotherapy device (parameters: 1.0 MHz, 50% duty cycle, 1.0 W / cm²) -2 ), take 200 μL of the solution at 0, 5, 10, 15, 20, 25, and 30 minutes to measure the absorbance at 400 nm, and plot the curve. For example... Figure 9 The composite catalyst shown can improve catalytic performance by 2 to 3 times compared with the blank experiment (without ultrasound), demonstrating good catalytic performance.
[0106] The conductive polymer PEDOT:PSS, as a highly efficient electronic conductor and polymer, can firstly couple the sulfonic acid groups of the carbonic anhydrase mimic enzyme with the positive charge of the PEDOT molecule through electrostatic attraction. Secondly, the efficient electron transport of PEDOT:PSS can transfer piezoelectric electrons generated inside zinc oxide under ultrasonic conditions to the catalytic site of the carbonic anhydrase mimic enzyme, Zn. 2+ This enhances the catalytic performance of the complex enzyme.
[0107] Test Example 2
[0108] The composite catalyst prepared in Example 3 of this invention was used to test its performance in capturing CO2 during hydration. The specific steps are as follows:
[0109] (1) Accurately weigh 0 mg, 1 mg, 2 mg, 3 mg and 4 mg of composite catalyst, dissolve them in 200 mL of deionized water, and stir to dissolve them completely.
[0110] (2) Pass CO2 with a purity of 99.9% into the solution of step (1) at a flow rate of 40 mL / min, measure its pH value every 30 seconds, and plot the curve.
[0111] like Figure 10 As shown, after the addition of the composite catalyst, the pH showed a significant decreasing trend within 0–1 min, mainly because CO2 underwent a rapid hydration reaction under the catalysis of the catalyst. Figure 11 As shown, compared with the blank experiment, the CO2 capture capacity increased by 8.6 times when only 1 mg of composite catalyst was added. The CO2 capture capacity increased significantly with the increase of composite catalyst dosage.
[0112] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. It is impossible to exhaustively list all the implementation methods here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.
Claims
1. An ultrasonically responsive composite catalyst for carbon capture, wherein, The composite catalyst comprises a carbonic anhydrase mimic enzyme, a conductive polymer PEDOT:PSS, and a piezoelectric material, linear zinc oxide. The composite catalyst was obtained by dispersing linear zinc oxide piezoelectric material in water, adding carbonic anhydrase mimic enzyme, 3,4-ethylenedioxythiophene, sodium polystyrene sulfonate and ammonium persulfate, and stirring at 20-25°C for 18-24 hours.
2. The composite catalyst according to claim 1, wherein, The mass ratio of the carbonic anhydrase mimic enzyme, the conductive polymer PEDOT:PSS, and the piezoelectric material linear zinc oxide is (1~5):(5~30):(1~10).
3. A method for preparing the composite catalyst according to claim 1 or 2, wherein, The piezoelectric material linear zinc oxide was dispersed in water, and carbonic anhydrase mimic enzyme, 3,4-ethylenedioxythiophene, sodium polystyrene sulfonate and ammonium persulfate were added. The mixture was stirred at 20-25°C for 18-24 hours. The obtained precipitate is separated, washed, and dried to obtain the composite catalyst.
4. The preparation method according to claim 3, wherein, The ratio of 3,4-ethylenedioxythiophene, sodium polystyrene sulfonate, and ammonium persulfate is 10-30 μL: 5-20 μL: 50-100 mg.
5. The preparation method according to claim 3, wherein, The carbonic anhydrase mimic enzyme is prepared through the following steps: S1. Dissolve 3,4-diaminobenzenesulfonic acid and aziridine triacetic acid in HCl solution to obtain the first solution; S2. The first solution is heated under reflux for 24-36 hours. After the reaction is completed, it is cooled to room temperature to obtain a solid precipitate. After separation, washing and drying, the intermediate product is obtained. S3. Add the intermediate product obtained in S2 and Zn(ClO4)2·6H2O to water at a mass ratio of 1:(1~1.6), and adjust the pH to 6.5~7.5 with alkaline solution; heat to 55~75℃ and react for 30~90 min, cool to room temperature and add ethanol to precipitate the metal complex; after separation, washing with ethanol and drying, the carbonic anhydrase mimic enzyme is obtained.
6. The preparation method according to claim 5, wherein, In step S1, the mass ratio of 3,4-diaminobenzenesulfonic acid to azirmonotriacetic acid is (1.5~4.5):(0.5~1.2).
7. The preparation method according to claim 5, wherein, In step S3, the alkaline solution is a NaOH solution.
8. The preparation method according to claim 3, wherein, The piezoelectric linear zinc oxide material is prepared by the following steps: A mixed solution of zinc source and urea is subjected to a hydrothermal reaction. The resulting precipitate is separated, washed, dried, and then calcined to obtain the piezoelectric material linear zinc oxide.
9. The preparation method according to claim 8, wherein, The zinc source is C4H. 10 O6Zn or ZnCl2.
10. The preparation method according to claim 8, wherein, The molar ratio of the zinc source to urea is 1:(1~2).
11. The preparation method according to claim 8, wherein, The hydrothermal reaction is carried out at a temperature of 80-95°C for 4-6 hours.
12. The preparation method according to claim 8, wherein, The calcination temperature is 380~480℃, and the time is 0.5~1 hour.
13. The application of the composite catalyst according to claim 1 or 2 in carbon capture.