Electrostatic dust collection graphene oxide nano composite material, preparation method and application
The preparation of electrostatic dust removal graphene oxide nanocomposite material with nanoarray structure by PEG-PS micelle regulation system solves the problems of conductivity attenuation, insufficient mechanical strength and agglomeration of traditional materials, and achieves high-efficiency electrostatic dust removal with a dust removal efficiency of over 98%.
Patent Information
- Application Number
- CN202511544388.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-28
- Publication Date
- 2026-01-23
AI Technical Summary
Traditional electrostatic precipitator materials, such as metal electrodes and carbon fibers, suffer from conductivity attenuation, insufficient mechanical strength, and secondary pollution during use. When graphene nanoparticles are combined with other materials, they are prone to agglomeration and poor dispersibility, which limits the development of electrostatic precipitator technology.
Using a PEG-PS micelle control system, an electrostatic dust removal graphene oxide nanocomposite material with excellent dispersibility was prepared through in-situ bonding and thermal reduction. The metal coordination polymer was uniformly dispersed and attached to the surface of graphene oxide, forming a regular nanoarray structure.
It significantly improves the conductivity, specific surface area and chemical stability of the material, enhances the electrostatic dust removal effect with a dust removal efficiency of over 98%, and the preparation process is environmentally friendly with no secondary pollution.
Smart Images
Figure CN121372671A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of nanomaterial preparation and electrostatic precipitation, and particularly relates to an electrostatic precipitation graphene oxide nanocomposite, a preparation method and application. BACKGROUND
[0002] The electrostatic precipitation technology occupies an important position in the field of industrial waste gas treatment due to its outstanding advantages of high efficiency and low energy consumption, and is widely used in many industries such as power, metallurgy and chemical industry. However, traditional electrostatic precipitation materials, such as common metal electrodes and carbon fibers, have many problems in actual application. The metal electrode is prone to conductive decay after long-term use, resulting in a decrease in dust removal efficiency. Carbon fibers have the defect of insufficient mechanical strength and are easily damaged under complex working conditions, affecting the normal operation of the equipment. In addition, these traditional materials may also produce secondary pollution during use, causing new harm to the environment and limiting the further development and application of electrostatic precipitation technology.
[0003] In recent years, nanomaterials have brought new opportunities for the innovation of electrostatic precipitation technology due to their unique physical and chemical properties. Among them, graphene and graphene oxide exhibit a series of excellent properties due to their unique two-dimensional sheet structure of a single atomic layer. Their ultra-high electrical conductivity (~10 6 S / m), huge specific surface area (2630 m 2 / g) and good chemical stability make them ideal functional substrates for preparing high-performance electrostatic precipitation materials.
[0004] Although nanographene and graphene oxide-based materials have great potential in the field of electrostatic precipitation, they still face many challenges. For example, the dust removal efficiency of single graphene material is limited. In order to further improve the performance of the material, researchers try to composite graphene and graphene oxide with other materials. However, the composite of the two materials often appears agglomeration and poor dispersion due to the different properties of the materials. SUMMARY
[0005] Based on the deficiencies of the prior art, the present application provides an electrostatic precipitation graphene oxide nanocomposite, a preparation method and application. The present application solves the problem of agglomeration of the composite material by introducing a PEG-PS micelle regulation system and combining in-situ bonding and thermal reduction method, and prepares a nanomaterial with excellent dispersion and a nanometer array structure. The dust removal efficiency of the composite material is more than 98%, which is an ideal high-efficiency nanoelectrode material for electrostatic precipitation.
[0006] To achieve the above purpose, the present application provides the following technical solutions:
[0007] An electrostatic precipitation graphene oxide nanocomposite,
[0008] The nanocomposite is prepared by in-situ bonding and thermal reduction of metal coordination polymer and graphene oxide through the introduction of a PEG-PS micelle regulation system;
[0009] The graphene oxide is a two-dimensional sheet structure and serves as a conductive and structural base of the composite material;
[0010] The metal coordination polymer is in the form of long strip nanoflower and is uniformly dispersed and attached to the surface of the graphene oxide through the steric hindrance effect of the PEG-PS micelle;
[0011] The whole forms a regular nanometer array structure and has no obvious agglomeration phenomenon.
[0012] A system composed of two-dimensional sheet structure graphene oxide and long strip nanoflower metal coordination polymer is constructed.
[0013] In addition, the nanometer array structure can provide a larger specific surface area, increase the contact area with dust, and be beneficial to the adsorption and capture of dust.
[0014] The application further provides a preparation method of the electrostatic dust removal graphene oxide nanocomposite.
[0015] S1, PEG-PS micelle solution preparation: PEG-PS block copolymer (molecular weight 2000-10000) is prepared by using an atom transfer radical polymerization (ATRP) method, 1-3 g of the copolymer is dissolved in a mixed solvent (volume ratio 1:1, total amount 10-30 mL) of dichloromethane and tetrahydrofuran, and stirring is performed until complete clarification; 25-28% of concentrated ammonia water (6-10 mL) and anhydrous ethanol (60-100 mL) are mixed uniformly, under the condition of a 30 DEG C constant temperature water bath and continuous stirring, the PEG-PS mixed solvent solution is slowly added to the ammonia water-ethanol mixed solution at a rate of 1 mL / min; after the addition is completed, the temperature is increased to 40 DEG C and the stirring is continued for 40-80 min, the organic solvent is removed by reduced pressure distillation, and a stable PEG-PS micelle system, i.e., a micelle solution, is formed;
[0016] S2. In-situ synthesis of composite materials: Graphene oxide (50~100mg) was ultrasonically dispersed in the above micelle solution, and cyanuric chloride (concentration 2mmol / 10mL) and piperazine (molar ratio 2:3) were added sequentially and stirred vigorously for 10min; bismuth salt (0.25~0.5g) was divided into 5 equal parts, and 1 part was added to the system every 10~20min, along with FeCl3 (20~40mg). The mixture was first reacted in an ice-water mixing bath for 30min, and then transferred to an 80℃ reactor for constant temperature reaction for 12h.
[0017] Among them, the amphiphilic structure of PEG-PS micelles can facilitate the mixing of bismuth ions and Fe. 3+ Uniform distribution in the system slows down the collision rate between ions and reactants, avoids the aggregation of metal-coordinated polymers, and ensures the orderly growth of the nanoarray structure.
[0018] S3. Product separation and purification: After the reaction is completed, the mixture is placed in a centrifuge and centrifuged at 8000~12000r / min for 8~10min, and the precipitate is collected. The precipitate is washed and centrifuged with deionized water, and the process is repeated 3 times to remove residual PEG-PS micelles and unreacted raw materials. The washed precipitate is placed in a vacuum drying oven at 40~60℃ and dried for 8~12h to obtain electrostatic dust removal graphene oxide nanocomposite material.
[0019] The present invention also provides an application of electrostatic dust removal graphene oxide nanocomposite material in electrostatic dust removal, wherein the dust removal rate of the electrostatic dust removal graphene oxide nanocomposite material exceeds 98%.
[0020] Compared with the prior art, the present invention has the following significant advantages:
[0021] (1) PEG-PS block copolymers were prepared by ATRP method, which resulted in better micelle formation stability. By controlling the micelle morphology by mixing solvents, hydrophilic PEG segments formed steric hindrance, and hydrophobic PS segments optimized the system compatibility. The dual effect effectively inhibited the aggregation of metal coordination polymers and graphene oxide, significantly improving the material dispersion. Moreover, PEG-PS micelles could be completely removed by washing with the mixed solution. The nano-array structure made the charge distribution more uniform, and the dust removal efficiency exceeded 98%.
[0022] (2) This invention breaks through the limitations of traditional single materials or simple mixed materials, and constructs a system composed of two-dimensional sheet-like graphene oxide and long strip nanoflower-like metal coordination polymer. The metal coordination polymer is uniformly dispersed and attached to the surface of graphene oxide to form a nanoarray structure. This structure enables the composite material to combine the excellent conductivity, huge specific surface area and good chemical stability of graphene oxide with the characteristics of metal coordination polymer. The synergistic effect of the two greatly improves the material performance.
[0023] (3) The nano array structure of the present application can provide a larger specific surface area, increase the contact area with dust, and be beneficial to the adsorption and capture of dust; at the same time, the regular array structure is beneficial to the uniform distribution and conduction of electric charge, enhances the electrostatic dust removal effect, and has a significant advantage in dust removal efficiency compared with the disordered structure of traditional materials. The dust removal efficiency is more than 98%, and it is an ideal nano electrode material for electrostatic dust removal with high efficiency.
[0024] (4) By accurately controlling the addition amount of each raw material, it is ensured that the reaction can proceed smoothly, so that the metal coordination polymer and graphene oxide form a stable composite material through in-situ bonding. The formula avoids the problems of agglomeration and poor dispersion caused by the difference in material properties in the traditional composite process.
[0025] (5) The solvent used in the formula is acetonitrile, which is relatively environmentally friendly compared with some toxic, harmful and strongly polluting organic solvents. The entire formula system does not introduce substances that can cause secondary pollution during preparation, in line with the concept of green chemistry. The preparation process is environmentally friendly and simple, and has good application prospects, and is different from the pollution problems that may exist in the preparation process of traditional electrostatic dust removal materials. BRIEF DESCRIPTION OF DRAWINGS
[0026] Figure 1 SEM image of graphene oxide of Example 1;
[0027] Figure 2 TEM image of the electrostatic dust removal graphene oxide nanocomposite of Example 1;
[0028] Figure 3 SEM image of the electrostatic dust removal graphene oxide nanocomposite of Example 1;
[0029] Figure 4 Dust removal efficiency graph of the electrostatic dust removal materials in Examples 1-3 and Comparative Examples 1-2 when used for electrostatic dust removal. DETAILED DESCRIPTION
[0030] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below. The following content is only an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements to the described specific implementation cases or use similar ways instead, which should all belong to the protection scope of the present application.
[0031] The above preparation method of the present application will be described below through specific examples and comparative examples.
[0032] Example 1
[0033] S1, PEG-PS micelle solution preparation: PEG-PS block copolymer (molecular weight 5000) was prepared by ATRP method, 2 g of the copolymer was dissolved in a mixed solvent of dichloromethane and tetrahydrofuran (volume ratio 1:1, total amount 20 mL) and stirred until completely clear; another concentrated ammonia (8 mL) and anhydrous ethanol (80 mL) were mixed uniformly, and the PEG-PS mixed solvent solution was slowly added to the ammonia-ethanol mixture at a rate of 1 mL / min under the condition of 30°C constant temperature water bath and continuous stirring (speed 500 r / min); after the addition was completed, the temperature was raised to 40°C and the stirring was continued for 60 min, and the organic solvent was removed by reduced pressure distillation to form a stable PEG-PS micelle system;
[0034] S2, in-situ synthesis of composite material: graphene oxide (80 mg) was ultrasonically dispersed in the above micelle solution, and cyanuric chloride (concentration 2 mmol / 10 mL, 10 mL) and piperazine (0.3 mmol) were added in turn, and stirred vigorously (speed 800 r / min) for 10 min; bismuth nitrate (0.4 g) was divided into 5 parts, and 1 part was added to the system every 15 min, and FeCl3 (30 mg) was added at the same time, first in an ice water bath for 30 min, then transferred to an 80°C oil bath reactor for constant temperature reaction for 12 h;
[0035] S3, product separation and purification: after the reaction was completed, the mixture was placed in a centrifuge and centrifuged at a speed of 10000 r / min for 9 min, and the precipitate was collected; the precipitate was washed with deionized water and centrifuged, and the operation was repeated 3 times; the washed precipitate was placed in a 50°C vacuum drying oven and dried for 10 h to obtain an electrostatically cleaned graphene oxide nanocomposite.
[0036] Example 2
[0037] S1, PEG-PS micelle solution preparation: PEG-PS block copolymer (molecular weight 5000) was prepared by ATRP method, 2 g of the copolymer was dissolved in a mixed solvent of dichloromethane and tetrahydrofuran (volume ratio 1:1, total amount 20 mL) and stirred until completely clear; another concentrated ammonia (8 mL) and anhydrous ethanol (80 mL) were mixed uniformly, and the PEG-PS mixed solvent solution was slowly added to the ammonia-ethanol mixture at a rate of 1 mL / min under the condition of 30°C constant temperature water bath and continuous stirring (speed 500 r / min); after the addition was completed, the temperature was raised to 40°C and the stirring was continued for 60 min, and the organic solvent was removed by reduced pressure distillation to form a stable PEG-PS micelle system;
[0038] S2, in-situ synthesis of composite material: graphene oxide (50 mg) was ultrasonically dispersed in the above micellar solution, and cyanuric chloride (concentration 2 mmol / 10 mL, 5 mL) and piperazine (0.15 mmol) were added in turn, and stirred vigorously (speed 700 r / min) for 10 min; bismuth chloride (0.25 g) was divided into 5 equal parts, and 1 part was added to the system every 10 min, and FeCl3 (20 mg) was added at the same time, first reacted in an ice-water mixed bath for 30 min, and then transferred to an 80°C water bath reactor for constant temperature reaction for 12 h;
[0039] S3, product separation and purification: after the reaction was completed, the mixed solution was placed in a centrifuge, and centrifuged at a speed of 8000 r / min for 8 min, and the precipitate was collected; the precipitate was washed with deionized water and centrifuged, and the operation was repeated 3 times; the washed precipitate was placed in a 40°C vacuum drying oven and dried for 8 h to obtain electrostatic dust removal graphene oxide nanocomposite.
[0040] Example 3
[0041] S1, preparation of PEG-PS micellar solution: PEG-PS block copolymer (molecular weight 10000) was prepared by ATRP method, 3 g of the copolymer was dissolved in a mixed solvent of dichloromethane and tetrahydrofuran (volume ratio 1:1, total amount 30 mL), and stirred until completely clear; another concentrated ammonia water (10 mL) and anhydrous ethanol (100 mL) were mixed uniformly, and the PEG-PS mixed solvent solution was slowly added to the ammonia water-ethanol mixture at a rate of 1 mL / min in a 30°C constant temperature water bath with continuous stirring (speed 600 r / min); after the addition was completed, the temperature was raised to 40°C and the stirring was continued for 80 min, and the organic solvent was removed by reduced pressure distillation to form a stable PEG-PS micellar system;
[0042] S2, in-situ synthesis of composite material: graphene oxide (100 mg) was ultrasonically dispersed in the above micellar solution, and cyanuric chloride (concentration 2 mmol / 10 mL, 15 mL) and piperazine (0.45 mmol) were added in turn, and stirred vigorously (speed 900 r / min) for 10 min; bismuth sulfate (0.5 g) was divided into 5 equal parts, and 1 part was added to the system every 20 min, and FeCl3 (40 mg) was added at the same time, first reacted in an ice-water mixed bath for 30 min, and then transferred to an 80°C high pressure reactor for constant temperature reaction for 12 h;
[0043] S3, product separation and purification: after the reaction was completed, the mixed solution was placed in a centrifuge, and centrifuged at a speed of 12000 r / min for 10 min, and the precipitate was collected; the precipitate was washed with deionized water and centrifuged, and the operation was repeated 3 times; the washed precipitate was placed in a 60°C vacuum drying oven and dried for 12 h to obtain electrostatic dust removal graphene oxide nanocomposite.
[0044] Comparative Example 1
[0045] S1, ultrasonic dispersion of graphene oxide (80 mg) in ammonia-ethanol mixture (8 mL of concentrated ammonia + 80 mL of anhydrous ethanol);
[0046] S2, add cyanuric chloride (concentration 2 mmol / 10 mL, 10 mL) and piperazine (0.3 mmol) in turn, and stir vigorously (speed 800 r / min) for 10 min; divide bismuth nitrate (0.4 g) into 5 equal parts, add 1 part to the system every 15 min, and add FeCl3(30 mg) at the same time, first react in an ice-water mixed bath for 30 min, then transfer to an 80°C oil bath reactor for constant temperature reaction for 12 h;
[0047] S3, the subsequent separation and purification steps are consistent with Example 1, and the composite material is obtained.
[0048] Comparative Example 2
[0049] Directly place graphene oxide (80 mg) in a 50°C vacuum drying oven and dry for 10 h as a comparative sample.
[0050] Figure 1 SEM image of graphene oxide of Example 1; the results show that the graphene oxide has a two-dimensional sheet structure, the sheet surface is smooth and has a certain wrinkle, and this morphology provides sufficient attachment sites for subsequent loading of metal coordination polymers. The high aspect ratio characteristic of the two-dimensional sheet structure is the core basis for the construction of the conductive network of the composite material.
[0051] Figure 2 TEM image of the electrostatic precipitator graphene oxide nanocomposite material of Example 1; the microstructure of the composite material is intuitively presented: the long strip nanoflower-shaped metal coordination polymer is uniformly dispersed and attached to the surface of the graphene oxide sheet layer by in-situ bonding, without obvious agglomeration, forming a regular nanometer array structure. The principle lies in the amphiphilic regulation of PEG-PS micelles: the hydrophilic PEG segment forms a steric hindrance on the particle surface, and the hydrophobic PS segment optimizes the compatibility of metal ions and graphene oxide, inhibits agglomeration and guides the ordered growth of metal coordination polymers, verifying the core design of the invention "micelle regulation system solves the agglomeration problem".
[0052] Figure 3SEM image of the electrostatic precipitation graphene oxide nanocomposite of Example 1; further confirms the macrodispersibility and array structure integrity of the composite: the graphene oxide sheet does not stack, and the long strip nanoflower structure of the metal coordination polymer is uniformly distributed, forming a three-dimensional through array system. This structure not only retains the high specific surface area advantage of graphene oxide, but also builds an efficient charge conduction channel through array design, providing structural support for dust adsorption and charge transfer in subsequent electrostatic precipitation processes, and is consistent with the principle of "nanometer array structure enhancing dust removal performance" in the invention.
[0053] Figure 4 Dust removal efficiency diagram of the electrostatic precipitation materials in Examples 1-3 and Comparative Examples 1-2 when used for electrostatic precipitation; it can be clearly seen that the electrostatic precipitation effect of Examples 1-3 is better, and can reach 98%. The dust removal efficiency of Comparative Example 1 and Comparative Example 2 is 89% and 85%, respectively.
[0054] The composite material of Comparative Example 1 (without micelles) is agglomerated due to the metal coordination polymer, while the PEG-PS micelles prepared by ATRP method in the present application significantly improve the dispersibility of the composite material through the dual effects of steric hindrance and compatibility optimization, and the dust removal efficiency breaks through 98%.
[0055] Comparative Example 2 single graphene oxide, due to the lack of synergistic effect of metal coordination polymer, the adsorption site and charge conduction efficiency are limited. The "two-dimensional graphene oxide + long strip nanoflower metal coordination polymer" array structure constructed by the present application has high specific surface area and efficient charge conduction characteristics, which improves the dust removal efficiency.
Claims
1. An electrostatically precipitated graphene oxide nanocomposite, characterized by, The nanocomposite is prepared by in-situ bonding and thermal reduction of metal coordination polymer and graphene oxide, and the graphene oxide is a two-dimensional sheet structure and serves as a conductive and structural base of the nanocomposite; the metal coordination polymer is in the form of long strip nanoflower and is uniformly dispersed on the surface of the graphene oxide by steric hindrance of the PEG-PS micelles, and the whole forms a regular nanometer array structure without obvious agglomeration.
2. A method of preparing the electrostatically dedusting graphene oxide nanocomposite of claim 1, characterized by, The method comprises the following steps: S1, PEG-PS micelle solution preparation: a PEG-PS block copolymer with a molecular weight of 2000-10000 is prepared by an atom transfer radical polymerization (ATRP) method, 1-3 g of the copolymer is dissolved in a mixed solvent of dichloromethane and tetrahydrofuran, and stirring is performed until the solution is completely clear; 6-10 mL of 25-28% concentrated ammonia water and 60-100 mL of anhydrous ethanol are mixed uniformly, and the mixed solvent solution of the PEG-PS is slowly added to the ammonia-ethanol mixed solution at a rate of 1 mL / min under the condition of a 30°C constant-temperature water bath and continuous stirring; after the addition is completed, the temperature is increased to 40°C and the stirring is continued for 40-80 min, and the organic solvent is removed by reduced-pressure distillation to form a stable PEG-PS micelle system, i.e., a micelle solution; S2, in-situ synthesis of the nanocomposite: 50-100 mg of graphene oxide is ultrasonically dispersed in the above micelle solution, and cyanuric chloride and piperazine are added in sequence, and the molar ratio of the two is 2:3, and the stirring is performed at a high speed for 10 min; 0.25-0.5 g of bismuth salt is divided into 5 equal parts, and 1 part is added to the system every 10-20 min, and 20-40 mg of FeCl3 is added at the same time, and the reaction is first performed in an ice-water mixed bath for 30 min, and then the reaction system is transferred to a 80°C reactor for constant-temperature reaction for 12 h; S3, product separation and purification: after the reaction is completed, the mixed solution is placed in a centrifuge and centrifuged at a speed of 8000-12000 r / min for 8-10 min, and the precipitate is collected; the precipitate is washed with deionized water and centrifuged, and the operation is repeated for 3 times to remove the residual PEG-PS micelles and unreacted raw materials; The washed precipitate is placed in a 40-60°C vacuum drying oven and dried for 8-12 h to obtain an electrostatically dedusted graphene oxide nanocomposite.
3. The preparation method according to claim 2, characterized in that, In step S1, the volume ratio of dichloromethane to tetrahydrofuran is 1:1, and the total amount of the mixed solvent is 10-30 mL.
4. The production method according to claim 2, characterized by, In step S2, the concentration of cyanuric chloride is 2 mmol / 10 mL.
5. The preparation method according to claim 2, characterized in that, In step S2, the stirring speed is 700-900 r / min.
6. The preparation method according to claim 2, characterized in that, The bismuth salt is one or more of bismuth nitrate, bismuth chloride or bismuth sulfate.
7. Use of the electrostatic precipitator graphene oxide nanocomposite according to claim 1 in an electrostatic precipitator, characterized in that, The dedusting rate of the nanocomposite is more than 98%.