CN111591990A - Activated carbon material and preparation method and application thereof - Google Patents
Activated carbon material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111591990A CN111591990A CN202010399335.0A CN202010399335A CN111591990A CN 111591990 A CN111591990 A CN 111591990A CN 202010399335 A CN202010399335 A CN 202010399335A CN 111591990 A CN111591990 A CN 111591990A
- Authority
- CN
- China
- Prior art keywords
- activated carbon
- solution
- carbon material
- pyridinium
- vinylpyridine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/372—Coating; Grafting; Microencapsulation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60H—ARRANGEMENTS OF HEATING, COOLING, VENTILATING OR OTHER AIR-TREATING DEVICES SPECIALLY ADAPTED FOR PASSENGER OR GOODS SPACES OF VEHICLES
- B60H1/00—Heating, cooling or ventilating [HVAC] devices
- B60H1/00507—Details, e.g. mounting arrangements, desaeration devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60H—ARRANGEMENTS OF HEATING, COOLING, VENTILATING OR OTHER AIR-TREATING DEVICES SPECIALLY ADAPTED FOR PASSENGER OR GOODS SPACES OF VEHICLES
- B60H3/00—Other air-treating devices
- B60H3/06—Filtering
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60H—ARRANGEMENTS OF HEATING, COOLING, VENTILATING OR OTHER AIR-TREATING DEVICES SPECIALLY ADAPTED FOR PASSENGER OR GOODS SPACES OF VEHICLES
- B60H3/00—Other air-treating devices
- B60H3/06—Filtering
- B60H2003/0691—Adsorption filters, e.g. activated carbon
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
The invention provides a method for preparing an activated carbon material, the activated carbon material prepared by the method and application of the activated carbon material in a filter. The method for preparing the activated carbon material comprises the following steps: (1) adding a pyridinium monomer into deionized water, and uniformly stirring to ensure that the molar concentration of the pyridinium monomer is 0.5-1.0 mol/L so as to obtain a solution A; (2) adding a photoinitiator into the solution A to obtain a solution B; (3) adding granular activated carbon into the solution B and uniformly stirring to obtain a mixture C; (4) filling nitrogen into the mixture C, bubbling for 10min, sealing, and starting an ultraviolet lamp in a constant-temperature water bath to perform irradiation grafting reaction; and (5) washing a product after the irradiation grafting reaction with acetone, then extracting for 24 hours, and drying at the temperature of below 60 ℃ so as to obtain the activated carbon material. The activated carbon material prepared by the method has strong adsorption performance and good antibacterial and antiseptic properties.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a method for preparing an activated carbon material, the activated carbon material prepared by the method and application of the activated carbon material in a filter.
Background
With the continuous development of economy in China, automobiles are indispensable transportation means in daily life of people. With the increase of the possession of private automobiles in cities year by year, the air pollution condition on roads is increasingly serious, the space in the automobiles is narrow, the air circulation is poor, the diffusion of pollutants is not facilitated, bacteria are easy to breed, and great harm is brought to the health of automobile owners. How to improve the quality of air in the vehicle becomes a topic which is closely concerned by the majority of vehicle owners, and an air conditioner filter with an antibacterial function is an effective means for solving the problem.
A Proton Exchange Membrane Fuel Cell (PEMFC) is a device that can directly convert chemical energy of fuel (usually hydrogen or methanol) and oxidant (oxygen or air) into electrical energy, and has the advantages of high energy conversion efficiency, no environmental pollution, simple structure, and low influence of load change on power generation efficiency, and is considered to be a type of cell with the greatest development prospect. In recent years, Fuel Cell Vehicles (FCV) and proton exchange membrane fuel cell (pem) technologies have been rapidly promoted along with the rapid development of new energy vehicles. An air filter with high efficiency and gas adsorption and antibacterial functions is required to be used in the fuel cell system, and the device is an important accessory of the fuel cell system and directly influences the service life of the fuel cell.
Therefore, it is desired to develop a material suitable for an air filter and having both adsorption and antibacterial functions.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide an activated carbon material for a vehicle air conditioner filter and a preparation method thereof, wherein the activated carbon material has antibacterial and antifungal properties on the premise of maintaining its adsorptive property, and therefore, the activated carbon material can be used in the application fields of vehicle air conditioner filters, proton exchange membrane fuel cell air filters, and the like, and can effectively improve the quality of air in vehicles and prolong the service life of fuel cells.
According to one aspect of the present invention, there is provided a method of preparing an activated carbon material, the method comprising:
(1) adding a pyridinium monomer into deionized water, and uniformly stirring to ensure that the molar concentration of the pyridinium monomer is 0.5-1.0 mol/L so as to obtain a solution A;
(2) adding a photoinitiator into the solution A to ensure that the mass percentage concentration of the photoinitiator is 0.1-0.5% so as to obtain a solution B;
(3) adding granular activated carbon into the solution B, and uniformly stirring to ensure that the mass ratio of the granular activated carbon to the solution B is 1: 6-1: 20 so as to obtain a mixture C;
(4) filling nitrogen into the mixture C, bubbling for 10min, sealing, and starting an ultraviolet lamp in a constant-temperature water bath to perform irradiation grafting reaction; and
(5) and washing the product after the irradiation grafting reaction with acetone, extracting for 24 hours, and drying at the temperature of below 60 ℃ to obtain the activated carbon material.
Therefore, the method for preparing the activated carbon material can be used for preparing the activated carbon material with both the adsorption performance and the antibacterial and mildewproof performance, the preparation method is simple and easy to implement, and the pyridinium can be effectively grafted on the surface of the granular activated carbon, so that the activated carbon has good antibacterial and mildewproof performance, and the application range of the activated carbon is expanded. Therefore, the activated carbon product prepared by the method can be used for an air filter in an automobile and an air filter in a fuel cell system, so that the quality of air in the automobile can be effectively improved, and the service life of the fuel cell can be effectively prolonged.
In addition, the method for preparing the activated carbon material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the pyridinium salt monomer is at least one selected from the group consisting of 4-vinylpyridine-alkylammonium bromide, 4-vinylpyridine-alkoxyammonium bromide, 4-vinylpyridine-alkylammonium bromide containing an aromatic ring, and 4-vinylpyridine-alkoxyammonium bromide containing an aromatic ring.
In some embodiments of the invention, the 4-vinylpyridine-alkylammonium bromide is 4-vinylpyridine-octylammonium bromide.
In some embodiments of the invention, the photoinitiator is Esacure TZT.
In some embodiments of the invention, the granular activated carbon is a natural plant-based char material.
In some embodiments of the present invention, the natural plant charcoal material is at least one selected from bamboo charcoal, coconut shell charcoal, rice hull charcoal and wheat straw charcoal.
In some embodiments of the invention, the irradiation intensity of the irradiation grafting reaction is 2-4W/m2。
In some embodiments of the present invention, the reaction temperature of the irradiation grafting reaction is 30 to 60 ℃, and the reaction time is 30 to 60 min.
According to another aspect of the present invention, the present invention also provides an activated carbon material prepared by the method of the previous embodiment, and according to an embodiment of the present invention, the activated carbon material comprises: the particle activated carbon comprises a particle activated carbon matrix and a pyridinium monomer layer, wherein the pyridinium monomer layer is formed on the surface of the particle activated carbon matrix through ultraviolet irradiation grafting.
According to a further aspect of the invention, the invention further provides the use of the activated carbon material according to the previous embodiment in a filter, which is an air conditioning filter for a vehicle or a filter for a fuel cell.
Drawings
FIG. 1 is a schematic diagram of a grafting reaction in preparing an activated carbon material according to one embodiment of the present invention.
Fig. 2 is an EDS elemental map of an activated carbon material prepared in example 3 of the present invention, and the presence of N, O and Br indicates that 4-vinylpyridine-octylammonium bromide pyridinium salt monomer has been grafted to the surface of the activated carbon material.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
According to one aspect of the present invention, there is provided a method of preparing an activated carbon material, the method comprising:
(1) adding a pyridinium monomer into deionized water, and uniformly stirring to ensure that the molar concentration of the pyridinium monomer is 0.5-1.0 mol/L so as to obtain a solution A;
(2) adding a photoinitiator into the solution A to ensure that the mass percentage concentration of the photoinitiator is 0.1-0.5% so as to obtain a solution B;
(3) adding granular activated carbon into the solution B, and uniformly stirring to ensure that the mass ratio of the granular activated carbon to the solution B is 1: 6-1: 20 so as to obtain a mixture C;
(4) filling nitrogen into the mixture C, bubbling for 10min, sealing, and starting an ultraviolet lamp in a constant-temperature water bath to perform irradiation grafting reaction; and
(5) and washing the product after the irradiation grafting reaction with acetone, extracting for 24 hours, and drying at the temperature of below 60 ℃ to obtain the activated carbon material.
Therefore, the method for preparing the activated carbon material can be used for preparing the activated carbon material with both the adsorption performance and the antibacterial and mildewproof performance, the preparation method is simple and easy to implement, and the pyridinium can be effectively grafted on the surface of the granular activated carbon, so that the activated carbon has good antibacterial and mildewproof performance, and the application range of the activated carbon is expanded. Therefore, the activated carbon product prepared by the method can be used for an air filter in an automobile and an air filter in a fuel cell system, so that the quality of air in the automobile can be effectively improved, and the service life of the fuel cell can be effectively prolonged.
The method for preparing the activated carbon material according to the above embodiment of the present invention will be described in detail.
(1) Firstly, adding a pyridinium monomer into deionized water and uniformly stirring to ensure that the molar concentration of the pyridinium monomer is 0.5-1.0 mol/L so as to obtain a solution A. Thereby preparing a pyridinium salt monomer solution.
According to an embodiment of the present invention, the pyridinium salt monomer may be at least one selected from the group consisting of 4-vinylpyridine-alkylammonium bromide, 4-vinylpyridine-alkoxyammonium bromide, 4-vinylpyridine-alkylammonium bromide having an aromatic ring and 4-vinylpyridine-alkoxyammonium bromide having an aromatic ring. Thus, the above pyridinium salt monomer can be effectively grafted to the surface of the activated carbon. In addition, the inventor finds that the adoption of the plurality of pyridinium monomers can obviously improve the grafting rate and further can endow the activated carbon with stronger antibacterial and mildewproof properties.
According to a specific embodiment of the present invention, the above pyridinium salt monomer is preferably 4-vinylpyridine-alkylammonium bromide, and 4-vinylpyridine-octylammonium bromide is most preferable among the 4-vinylpyridine-alkylammonium bromides. Because, the inventors found that by grafting activated carbon using 4-vinylpyridine-octylammonium bromide as a pyridinium monomer, the specific surface area of activated carbon was hardly affected and 95% or more of the original specific surface area could be maintained, and thus it could be judged that the adsorption performance of activated carbon was hardly lowered. In addition, 4-vinylpyridine-octylammonium bromide is used as a pyridinium monomer to graft the activated carbon, and antibacterial performance evaluation is performed on the activated carbon, so that evaluation results of escherichia coli and staphylococcus aureus are good, and the antibacterial effect is shown. The antibacterial and mildewproof grade can reach 0 grade by testing, which shows that the mildewproof effect is good. Therefore, the inventor thinks that the best choice is 4-vinylpyridine-octylammonium bromide as a pyridinium monomer aiming at the granular activated carbon material, and the two can not only exert respective performances, but also do not influence the performances of the other, thereby further improving the adsorbability and the mildew-proof antibacterial performance of the prepared activated carbon material to the maximum extent.
In addition, the inventor analyzes the antibacterial mechanism of the pyridine antibacterial agent, and the antibacterial effect of the pyridine antibacterial agent is based on sterilization rather than merely bacteriostasis and is divided into two steps of adsorption and killing. Macromolecular chains (such as bromo-n-octane, dodecane, hexadecane, octadecane and the like) on the pyridinium can improve the density of antibacterial groups and enhance the killing capability, thereby improving the antibacterial performance; however, the inventors found that, as the molecular weight of the polymer chain is increased, the gas permeation step is hindered, and the adsorption capacity of the grafted activated carbon is lowered, resulting in a decrease in antibacterial performance. Therefore, the adopted 4-vinylpyridine-octylammonium bromide with moderate polymer chain length has better antibacterial effect compared with dodecane, hexadecane, octadecane and the like. On the other hand, the high molecular chain is easy to degrade and open under the action of high temperature, illumination and oxygen to form harmful gases such as acetaldehyde and formaldehyde and influence the air quality in the whole vehicle, so that the 4-vinylpyridine-bromo-n-octane with moderate molecular weight is more suitable for the vehicle air conditioner filter and the fuel cell filter.
The molar concentration of the pyridinium monomer in the solution A prepared as described above is 0.5mol/L to 1.0 mol/L. Therefore, the method can ensure that the concentration of the pyridinium monomer is enough to improve the grafting rate, and further obtain enough mildew-proof antibacterial performance, and in addition, the concentration is not easy to be too high, so that the adsorption performance of the activated carbon is prevented from being influenced by grafting too much pyridinium monomer. Specifically, the molar concentration of the pyridinium salt monomer in the solution A can be 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L or 1.0 mol/L. And then the active carbon material with good adsorptivity, antibiosis and mildew resistance can be prepared.
(2) Secondly, adding a photoinitiator into the solution A to ensure that the mass percentage concentration of the photoinitiator is 0.1-0.5% so as to obtain a solution B.
According to a specific embodiment of the present invention, the photoinitiator is Esacure TZT. The inventor finds that the grafting efficiency and the grafting rate of the pyridinium monomer can be obviously improved by adopting the photoinitiator Esacure TZT. In addition, the inventors have found that the grafting of the above 4-vinylpyridine-octylammonium bromide onto the surface of granular activated carbon using a photoinitiator, Esacure TZT, works best. Therefore, in order to effectively graft a pyridinium monomer with antibacterial activity on granular activated carbon, the inventor optimizes the combination of the photoinitiator Esacure TZT and 4-vinylpyridine-octylammonium bromide, and further ensures that the pyridinium monomer can be effectively grafted on the surface of the activated carbon.
In addition, in the solution B containing the pyridinium monomer and the photoinitiator, the concentration of the pyridinium monomer and the photoinitiator is 0.5-1.0 mol/L in molar concentration and 0.1-0.5% in mass percentage. Therefore, the grafting efficiency and the grafting rate of the pyridinium monomer can be obviously improved by adopting the concentration ratio. The mass percentage concentration of the photoinitiator is obtained by matching according to the molar concentration of the pyridinium monomer, and the photoinitiator has the most appropriate initiation effect in the solution B, so that the grafting efficiency can be effectively improved. The inventors have also found that if the above-mentioned initiator concentration is too high, two problems arise: 1. the grafting reaction speed is too high, the grafting reaction is incomplete, the degradation and chain opening of a high molecular chain can be caused, the grafting efficiency is reduced, and the antibacterial effect is influenced; 2. the cost of the initiator is increased, so that the cost of the grafted activated carbon is increased, and the application of the product is not facilitated. Therefore, when the molar concentration of the pyridinium salt monomer is 0.5mol/L to 1.0mol/L, it is most preferable to control the mass percentage concentration of the photoinitiator to 0.1% to 0.5%.
(3) And then adding granular activated carbon into the solution B containing the pyridinium monomer and the photoinitiator, and uniformly stirring to ensure that the mass ratio of the granular activated carbon to the solution B is 1: 6-1: 20 so as to obtain a mixture C.
According to the specific embodiment of the invention, the mass ratio of the granular activated carbon to the solution B is controlled to be 1: 6-1: 20, so that the moderate ratio of the pyridinium monomer to the granular activated carbon can be ensured, and the prepared activated carbon monomer can maintain the adsorption performance to the maximum extent and simultaneously increase the effective antibacterial and antiseptic performance. According to a specific example of the present invention, the mass ratio of the granular activated carbon to the solution B may be 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1: 20. Therefore, the pyridinium monomer with enough quantity can be grafted on the surface of the activated carbon, so that the prepared activated carbon monomer has good antibacterial effect and a 0-grade mildew-proof grade. In addition, the inventor also finds that the adding amount of the activated carbon in the mixture C is not easy to be too large or too small, because the adding amount is too small, the yield of the grafted activated carbon is reduced, the production efficiency and the cost are influenced, a multi-graft network is easy to form on single-particle activated carbon, and the phenomenon of the barrier of a penetrating step caused by similar long molecular chains occurs, so that the antibacterial performance is reduced; and too much addition can cause poor dispersibility of the activated carbon particles in the solution and easy agglomeration, and the grafting reaction can not be carried out on the surfaces of most activated carbon particles, so that the antibacterial performance is reduced, and the product performance and the production efficiency of the grafted activated carbon are influenced.
In addition, the mass ratio of the granular activated carbon to the solution B is determined mainly according to the kind of the activated carbon and the dispersibility of the activated carbon granules in the solution, and other factors such as the irradiation intensity of the ultraviolet lamp and the grafting reaction temperature must be considered and combined. For different types of activated carbon, because of different particle sizes and ash contents, such as the wheat straw carbon has smaller particle size and higher ash content, and has poor dispersibility in solution, a larger mass ratio (more than 1: 12) is preferably adopted; for bamboo charcoal and coconut shell charcoal with large particle size and low ash content, the bamboo charcoal and coconut shell charcoal have good dispersibility in solution, and the mass ratio is preferably smaller (less than 1: 10). The influence of the irradiation intensity of the ultraviolet lamp and the grafting reaction temperature on the mass ratio is mainly reflected in the grafting reaction efficiency and the antibacterial performance, the high mass ratio is more suitable for the high irradiation intensity and the reaction temperature, and the low mass ratio is more suitable for the low irradiation intensity and the reaction temperature.
In addition, according to the specific embodiment of the present invention, the adopted granular activated carbon can be a natural plant carbon material. According to a specific example of the present invention, the natural plant charcoal material is preferably at least one of bamboo charcoal, coconut charcoal, rice hull charcoal and wheat straw charcoal. The activated carbon material prepared by the granular activated carbon has more stable volume form, and can easily keep the original adsorption performance, so that the influence of the grafted pyridinium monomer on the adsorption performance is reduced. In addition, the inventor finds that the activated carbon material prepared by adopting the preferred natural plant carbon-making materials is more suitable for an air filter in an automobile and an air filter in a fuel cell system, and further can effectively improve the quality of air in the automobile and prolong the service life of a fuel cell.
(4) And then, filling nitrogen into the mixture C, bubbling for 10min, sealing, and starting an ultraviolet lamp in a constant-temperature water bath to perform irradiation grafting reaction.
According to the specific embodiment of the invention, under the irradiation of an ultraviolet lamp, the photoinitiator in the mixture C enables carbon free radicals to be formed on the surface of the activated carbon, and the pyridinium monomer and the carbon free radicals are subjected to a grafting reaction under the irradiation to be grafted on the activated carbon.
According to the specific embodiment of the present invention, the inventors have found that when the pyridinium monomer is preferably 4-vinylpyridine-octylammonium bromide, the structural formula is
The grafting reaction with activated carbon is shown in figure 1. When 4-vinylpyridine-octylammonium bromide is adopted, the inventor finds that the length of a high molecular chain on the pyridinium is moderate, so that the density of an antibacterial group can be improved, the antibacterial performance of a grafted activated carbon product is improved, the gas penetration step caused by the high molecular weight long molecular chain can be prevented from being blocked, the high molecular chain is prevented from being broken under the action of high temperature, illumination and oxygen, harmful gases such as acetaldehyde and formaldehyde are formed, and the air quality in the whole vehicle is influenced, therefore, the adopted 4-vinylpyridine-bromo-n-octane with the moderate molecular weight is more suitable for being used in vehicle air conditioner filters and fuel cell filters compared with dodecane, hexadecane, octadecane and the like.
According to the specific embodiment of the invention, the inventor further researches the ultraviolet irradiation intensity of the pyridinium monomer grafted on the surface of the activated carbon, and finds that the irradiation intensity is 2-4W/m2When the method is used, the grafting efficiency and the grafting rate of the pyridinium monomer are optimal. When the irradiation intensity is too high, the high molecular chains such as bromo-n-octane, dodecane, hexadecane and octadecane are degraded and chain scission occurs, so that harmful gases such as acetaldehyde and formaldehyde are formed, and meanwhile, the density of the antibacterial group is reduced, so that the antibacterial performance of the grafted activated carbon product is reduced. In addition, if iodide is used as the pyridinium monomer, when the irradiation intensity is too high, the iodide is decomposed to form iodine simple substance, which affects the grafting reactionThis occurs.
According to the specific embodiment of the invention, under the irradiation intensity, the reaction temperature of the irradiation grafting reaction is further controlled to be 30-60 ℃, and the reaction time is controlled to be 30-60 min. The grafting reaction can be further ensured to be smooth, the optimal grafting effect is achieved, namely the finally obtained activated carbon material basically keeps the original adsorption performance and effectively increases the antibacterial and anticorrosive performance, and the antibacterial effect is good through tests, and the anticorrosive grade reaches 0 level.
(5) And finally, washing the product after the irradiation grafting reaction by using acetone, extracting for 24 hours, and drying at the temperature of below 60 ℃ so as to obtain the activated carbon material.
According to the specific embodiment of the present invention, the method for preparing the obtained activated carbon material provided by the present invention is preferably as follows:
(1) adding 4-vinylpyridine-octylammonium bromide into deionized water, and uniformly stirring to ensure that the molar concentration of the 4-vinylpyridine-octylammonium bromide is 0.5-1.0 mol/L so as to obtain a solution A;
(2) adding Esacure TZT into the solution A to ensure that the mass percent concentration of the Esacure TZT is 0.1-0.5 percent so as to obtain a solution B;
(3) adding granular activated carbon into the solution B, and uniformly stirring to ensure that the mass ratio of the granular activated carbon to the solution B is 1: 6-1: 20 so as to obtain a mixture C;
(4) filling nitrogen into the mixture C, bubbling for 10min, sealing, and starting an ultraviolet lamp in a constant-temperature water bath to perform irradiation grafting reaction, wherein the irradiation intensity is 2-4W/m2The reaction temperature is 30-60 ℃, and the reaction time is 30-60 min; and
(5) and washing the product after the irradiation grafting reaction with acetone, extracting for 24 hours, and drying at the temperature of below 60 ℃ to obtain the activated carbon material.
Therefore, by adopting the method, a proper amount of 4-vinylpyridine-octylammonium bromide can be effectively grafted on the surface of the granular activated carbon, so that the finally obtained activated carbon material basically keeps the original adsorption performance and effectively increases the antibacterial and anticorrosive performances, and the antibacterial effect is good through tests, and the anticorrosive grade reaches 0 level.
According to another aspect of the present invention, the present invention also provides an activated carbon material prepared by the method of the previous embodiment, and according to an embodiment of the present invention, the activated carbon material comprises: the particle activated carbon comprises a particle activated carbon matrix and a pyridinium monomer layer, wherein the pyridinium monomer layer is formed on the surface of the particle activated carbon matrix through ultraviolet irradiation grafting. The activated carbon material basically keeps the original adsorption performance, simultaneously effectively increases the antibacterial and antiseptic performance, and has good antibacterial effect through tests, and the antiseptic grade reaches 0 grade.
According to a further aspect of the invention, the invention further provides the use of the activated carbon material according to the previous embodiment in a filter, which is an air conditioning filter for a vehicle or a filter for a fuel cell. The activated carbon material has strong adsorption performance and good antibacterial and anticorrosive performance, so that the activated carbon material can be used for an air conditioner filter or a fuel cell filter for a vehicle, and can obviously improve the quality of air in the vehicle and prolong the service life of the fuel cell.
Example 1
The invention provides a grafted pyridinium activated carbon material for an air conditioner filter for a vehicle and a preparation method thereof, which are characterized in that the surface of the activated carbon for the air conditioner filter is modified by oxidation-reduction grafting, and a grafted pyridinium monomer forms a grafted layer, and the method comprises the following steps:
(1) adding a pyridinium monomer material of 4-vinylpyridine-octylammonium bromide into deionized water, and uniformly stirring to ensure that the molar concentration of the pyridinium monomer is 0.5mol/L, thereby defining the solution A;
(2) adding an Esacure TZT photoinitiator into the solution A to ensure that the mass percent concentration of the photoinitiator is 0.1 percent, and defining the photoinitiator as a solution B;
(3) adding 10g of activated carbon (rice husk carbon) prepared by using rice husks as raw materials into the solution B, and uniformly stirring to ensure that the mass ratio of the activated carbon to the solution B is 1:6, thereby defining the solution B as a mixture C;
(4) charging nitrogen into the mixture C, bubbling for 10min, exhausting air, sealing, and starting ultraviolet lamp in constant temperature water bath for irradiationBranch reaction, irradiation intensity of 2W/m2The reaction temperature is 30 ℃, and the reaction time is 60 min;
(5) the grafted active carbon is washed by acetone, then extracted for 24 hours and dried below 60 ℃.
The activated carbon materials prepared by the steps (1) to (5) are tested, and the results are as follows: the specific surface grade of the rice hull activated carbon material before surface grafting treatment is 1375m2G, average pore diameter of 2.28nm and pore volume of 0.568cm3(ii) in terms of/g. After the surface grafting treatment, the specific surface level of the activated carbon material is 1331m2G, average pore diameter of 2.06nm and pore volume of 0.545cm3(ii) in terms of/g. From the change in the specific surface area, it was judged that the adsorption performance of the activated carbon was hardly lowered. In addition, the rice hull activated carbon material for in-vehicle air purification has good antibacterial and mildewproof effects, and is prepared according to GB/T20944.1-2007 evaluation part 1 of antibacterial performance of textiles: the evaluation results of the agar plate diffusion method are good, which shows that the antibacterial effect is achieved; the test is carried out according to the GB/T24346-one 2009 evaluation of the mildew-proof performance of the textile, the mildew-proof grade is 0 grade, and the good mildew-proof effect is shown.
Example 2
The invention provides a grafted pyridinium activated carbon material for an air conditioner filter for a vehicle and a preparation method thereof, which are characterized in that the surface of the activated carbon for the air conditioner filter is grafted and modified by ultraviolet irradiation, and a grafted pyridinium monomer forms a grafted layer, and the method comprises the following steps:
(1) adding a pyridinium monomer material of 4-vinylpyridine-octylammonium bromide into deionized water, and uniformly stirring to ensure that the molar concentration of the pyridinium monomer is 1.0mol/L, thereby defining the solution A;
(2) adding an Esacure TZT photoinitiator into the solution A to ensure that the mass percent concentration of the photoinitiator is 0.5 percent, and defining the photoinitiator as a solution B;
(3) adding 10g of activated carbon (rice husk carbon) prepared by using rice husks as raw materials into the solution B, and uniformly stirring to ensure that the mass ratio of the activated carbon to the solution B is 1:20, thereby defining the solution B as a mixture C;
(4) charging nitrogen into the mixture C, bubbling for 10min, exhausting air, sealing, and starting an ultraviolet lamp in a constant-temperature water bath to perform irradiation grafting reaction with irradiation intensity of 4W/m2The reaction temperature is 60 ℃, and the reaction time is 30 min;
(5) the grafted active carbon is washed by acetone, then extracted for 24 hours and dried below 60 ℃.
The activated carbon materials prepared by the steps (1) to (5) are tested, and the results are as follows: the specific surface of the coconut shell activated carbon material before surface grafting treatment is 1375m2G, average pore diameter of 2.28nm and pore volume of 0.568cm3(ii) in terms of/g. After the surface grafting treatment, the specific surface level of the activated carbon material is 1286m2(ii)/g, average pore diameter of 1.89nm and pore volume of 0.533cm3(ii) in terms of/g. From the change in the specific surface area, it was judged that the adsorption performance of the activated carbon was hardly lowered. In addition, the coconut shell activated carbon material for in-vehicle air purification has good antibacterial and mildewproof effects, and is prepared according to GB/T20944.1-2007 evaluation part 1 of antibacterial properties of textiles: the evaluation results of the agar plate diffusion method are good, which shows that the antibacterial effect is achieved; the test is carried out according to the GB/T24346-one 2009 evaluation of the mildew-proof performance of the textile, the mildew-proof grade is 0 grade, and the good mildew-proof effect is shown.
Example 3
The invention provides a grafted pyridinium activated carbon material for an air conditioner filter for a vehicle and a preparation method thereof, which are characterized in that the surface of the activated carbon for the air conditioner filter is grafted and modified by ultraviolet irradiation, and a grafted pyridinium monomer forms a grafted layer, and the method comprises the following steps:
(1) adding a pyridinium monomer material of 4-vinylpyridine-octylammonium bromide into deionized water, and uniformly stirring to ensure that the molar concentration of the pyridinium monomer is 1.0mol/L, thereby defining the solution A;
(2) adding an Esacure TZT photoinitiator into the solution A to ensure that the mass percent concentration of the photoinitiator is 0.4 percent, and defining the photoinitiator as a solution B;
(3) adding 10g of activated carbon (coconut shell carbon) prepared by taking coconut shells as raw materials into the solution B, and uniformly stirring to ensure that the mass ratio of the activated carbon to the solution B is 1:10, thereby defining the mixture C;
(4) charging nitrogen into the mixture C, bubbling for 10min, exhausting air, sealing, and starting an ultraviolet lamp in a constant-temperature water bath to perform irradiation grafting reaction with irradiation intensity of 4W/m2The reaction temperature is 60 ℃, and the reaction time is 40 min;
(5) the grafted active carbon is washed by acetone, then extracted for 24 hours and dried below 60 ℃.
The activated carbon materials prepared by the steps (1) to (5) are tested, and the results are as follows: the specific surface level of the coconut shell activated carbon material before surface grafting treatment is 1280m2Per g, average pore diameter of 1.95nm and pore volume of 0.555cm3(ii) in terms of/g. After the surface grafting treatment, the specific surface level of the activated carbon material is 1253m2G, average pore diameter of 1.72nm and pore volume of 0.537cm3(ii) in terms of/g. From the change in the specific surface area, it was judged that the adsorption performance of the activated carbon was hardly lowered. In addition, the coconut shell activated carbon material for in-vehicle air purification has good antibacterial and mildewproof effects, and is prepared according to GB/T20944.1-2007 evaluation part 1 of antibacterial properties of textiles: the evaluation results of the agar plate diffusion method are good, which shows that the antibacterial effect is achieved; the test is carried out according to the GB/T24346-one 2009 evaluation of the mildew-proof performance of the textile, the mildew-proof grade is 0 grade, and the good mildew-proof effect is shown. The EDS element distribution diagram of the activated carbon material prepared in the example is shown in FIG. 2.
Comparative example 1
A comparative experiment was carried out using the other type of pyridinium monomer, 4-vinylpyridine-octadecylammonium iodide, relative to example 1, and comprising the following steps:
(1) adding a pyridinium salt monomer material of 4-vinylpyridine-octadecyl ammonium iodide into deionized water, and uniformly stirring to ensure that the molar concentration of the pyridinium salt monomer is 0.5mol/L, which is defined as a solution L;
(2) adding an Esacure TZT photoinitiator into the solution L to ensure that the mass percent concentration of the photoinitiator is 0.1 percent, and defining the photoinitiator as a solution M;
(3) adding 10g of activated carbon (rice husk carbon) prepared by using rice husks as raw materials into the solution M, and uniformly stirring to ensure that the mass ratio of the activated carbon to the solution M is 1:6, and defining the solution as a mixture N;
(4) charging nitrogen into the mixture N, bubbling for 10min, exhausting air, sealing, and starting an ultraviolet lamp in a constant-temperature water bath to perform irradiation grafting reaction with irradiation intensity of 2W/m2The reaction temperature is 30 ℃, and the reaction time is 60 min;
(5) the grafted active carbon is washed by acetone, then extracted for 24 hours and dried below 60 ℃.
The activated carbon materials prepared by the steps (1) to (5) are tested, and the results are as follows: the rice hull activated carbon material of the comparative example had a specific surface level of 1375m before the surface graft treatment2G, average pore diameter of 2.28nm and pore volume of 0.568cm3(ii) in terms of/g. After the surface grafting treatment, the specific surface level of the activated carbon material is 1073m2G, average pore diameter of 1.78nm and pore volume of 0.462cm3(ii) in terms of/g. The change of the specific surface area can be used for judging that the adsorption performance of the activated carbon is reduced to a certain degree. In addition, the grafted activated carbon material obtained by the process has good antibacterial and mildewproof effects, and is prepared according to GB/T20944.1-2007 evaluation part 1 of antibacterial properties of textiles: when the evaluation results of escherichia coli and staphylococcus aureus are better when the standard of agar plate diffusion method is tested, the antibacterial effect is shown, but the antibacterial effect is reduced compared with that of the example 1; the test is carried out according to the GB/T24346-one 2009 evaluation of the mildew-proof performance of the textile, the mildew-proof grade is grade 1, which shows that the mildew-proof effect is better, but the effect is reduced compared with the embodiment 1.
Comparative example 2
Comparative tests were carried out with respect to example 1, using other irradiation intensity conditions, comprising the following steps:
(1) adding a pyridinium monomer material of 4-vinylpyridine-octylammonium bromide into deionized water, and uniformly stirring to ensure that the molar concentration of the pyridinium monomer is 0.5mol/L, thereby defining the solution A;
(2) adding an Esacure TZT photoinitiator into the solution A to ensure that the mass percent concentration of the photoinitiator is 0.1 percent, and defining the photoinitiator as a solution B;
(3) adding 10g of activated carbon (rice husk carbon) prepared by using rice husks as raw materials into the solution B, and uniformly stirring to ensure that the mass ratio of the activated carbon to the solution B is 1:6, thereby defining the solution B as a mixture C;
(4) charging nitrogen into the mixture C, bubbling for 10min, exhausting air, sealing, and starting an ultraviolet lamp in a constant-temperature water bath to perform irradiation grafting reaction with irradiation intensity of 10W/m2The reaction temperature is 30 ℃, and the reaction time is 60 min;
(5) the grafted active carbon is washed by acetone, then extracted for 24 hours and dried below 60 ℃.
The activated carbon materials prepared by the steps (1) to (5) are tested, and the results are as follows: the rice hull activated carbon material of the comparative example had a specific surface level of 1375m before the surface graft treatment2G, average pore diameter of 2.28nm and pore volume of 0.568cm3(ii) in terms of/g. After the surface grafting treatment, the specific surface level of the activated carbon material is 1242m2G, average pore diameter of 1.90nm and pore volume of 0.502cm3(ii) in terms of/g. It is judged from the change of the specific surface area that the adsorption performance of the activated carbon is slightly lowered. In addition, the grafted activated carbon material obtained by the process has good antibacterial and mildewproof effects, and is prepared according to GB/T20944.1-2007 evaluation part 1 of antibacterial properties of textiles: when the evaluation results of escherichia coli and staphylococcus aureus are better when the standard of agar plate diffusion method is tested, the antibacterial effect is shown, but the antibacterial effect is reduced compared with that of the example 1; the test is carried out according to the GB/T24346-2009 'evaluation on the mildew-proof performance of textiles', the mildew-proof grade is grade 1, which shows that the mildew-proof effect is better, but the effect is reduced compared with that of the example 1.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A method of making an activated carbon material, comprising:
(1) adding a pyridinium monomer into deionized water, and uniformly stirring to ensure that the molar concentration of the pyridinium monomer is 0.5-1.0 mol/L so as to obtain a solution A;
(2) adding a photoinitiator into the solution A to ensure that the mass percentage concentration of the photoinitiator is 0.1-0.5% so as to obtain a solution B;
(3) adding granular activated carbon into the solution B, and uniformly stirring to ensure that the mass ratio of the granular activated carbon to the solution B is 1: 6-1: 20 so as to obtain a mixture C;
(4) filling nitrogen into the mixture C, bubbling for 10min, sealing, and starting an ultraviolet lamp in a constant-temperature water bath to perform irradiation grafting reaction; and
(5) and washing the product after the irradiation grafting reaction with acetone, extracting for 24 hours, and drying at the temperature of below 60 ℃ to obtain the activated carbon material.
2. The method according to claim 1, wherein the pyridinium salt monomer is at least one selected from the group consisting of 4-vinylpyridine-alkylammonium bromide, 4-vinylpyridine-alkoxyammonium bromide, 4-vinylpyridine-alkylammonium bromide containing an aromatic ring and 4-vinylpyridine-alkoxyammonium bromide containing an aromatic ring.
3. The method of claim 2, wherein the 4-vinylpyridine-alkylammonium bromide is 4-vinylpyridine-octylammonium bromide.
4. The method of claim 3, wherein the photoinitiator is Esacure TZT.
5. The method of claim 1 or 4, wherein the granular activated carbon is a natural plant-made charcoal material.
6. The method as claimed in claim 5, wherein the natural plant charcoal material is at least one selected from bamboo charcoal, coconut shell charcoal, rice hull charcoal and wheat straw charcoal.
7. The method according to claim 1, wherein the irradiation intensity of the irradiation grafting reaction is 2-4W/m2。
8. The method according to claim 7, wherein the reaction temperature of the irradiation grafting reaction is 30-60 ℃ and the reaction time is 30-60 min.
9. An activated carbon material produced by the method of any one of claims 1-8, comprising: the particle activated carbon comprises a particle activated carbon matrix and a pyridinium monomer layer, wherein the pyridinium monomer layer is formed on the surface of the particle activated carbon matrix through ultraviolet irradiation grafting.
10. Use of the activated carbon material of claim 9 in a filter, which is an air conditioning filter for a vehicle or a filter for a fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010399335.0A CN111591990A (en) | 2020-05-12 | 2020-05-12 | Activated carbon material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010399335.0A CN111591990A (en) | 2020-05-12 | 2020-05-12 | Activated carbon material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111591990A true CN111591990A (en) | 2020-08-28 |
Family
ID=72183592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010399335.0A Pending CN111591990A (en) | 2020-05-12 | 2020-05-12 | Activated carbon material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111591990A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5942041A (en) * | 1982-09-02 | 1984-03-08 | Nitto Electric Ind Co Ltd | Production of metallic ion adsorbent |
| CN1223273A (en) * | 1998-11-02 | 1999-07-21 | 华南理工大学 | Radiation graft process for preparing antiseptic material of pyridine salt type polymer |
| CN1986614A (en) * | 2006-12-15 | 2007-06-27 | 清华大学 | Process of optically grafting long fatty carbon chain pyridine salt to the surface of polymer |
| CN102432779A (en) * | 2011-09-07 | 2012-05-02 | 苏州大学 | Modifying method for activated carbon |
| CN102585556A (en) * | 2011-12-31 | 2012-07-18 | 上海东升新材料有限公司 | Method for preparing salt-resistant dispersing agent by photo-initiated polymerization |
| CN109260823A (en) * | 2018-11-07 | 2019-01-25 | 北京福田戴姆勒汽车有限公司 | A kind of filter core of automotive air-conditioner activated carbon filtering cloth material and its preparation process |
-
2020
- 2020-05-12 CN CN202010399335.0A patent/CN111591990A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5942041A (en) * | 1982-09-02 | 1984-03-08 | Nitto Electric Ind Co Ltd | Production of metallic ion adsorbent |
| CN1223273A (en) * | 1998-11-02 | 1999-07-21 | 华南理工大学 | Radiation graft process for preparing antiseptic material of pyridine salt type polymer |
| CN1986614A (en) * | 2006-12-15 | 2007-06-27 | 清华大学 | Process of optically grafting long fatty carbon chain pyridine salt to the surface of polymer |
| CN102432779A (en) * | 2011-09-07 | 2012-05-02 | 苏州大学 | Modifying method for activated carbon |
| CN102585556A (en) * | 2011-12-31 | 2012-07-18 | 上海东升新材料有限公司 | Method for preparing salt-resistant dispersing agent by photo-initiated polymerization |
| CN109260823A (en) * | 2018-11-07 | 2019-01-25 | 北京福田戴姆勒汽车有限公司 | A kind of filter core of automotive air-conditioner activated carbon filtering cloth material and its preparation process |
Non-Patent Citations (3)
| Title |
|---|
| SIQI HONG ET AL.: "Sulfate removal from acid mine drainage using polypyrrole-grafted granular activated carbon", 《CARBON》 * |
| 周其凤等: "《高分子化学》", 31 October 2001, 化学工业出版社 * |
| 李涛等: "氨基吡啶分子在活性炭表面的键合研究", 《林产化学与工业》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Recent advances in metal organic framework and cellulose nanomaterial composites | |
| Kamel et al. | Preparation and application of acrylonitrile‐grafted cyanoethyl cellulose for the removal of copper (II) ions | |
| Shaari et al. | Potential of sodium alginate/titanium oxide biomembrane nanocomposite in dmfc application | |
| CN111450806B (en) | Preparation method of porous adsorption antibacterial composite material based on waste corncobs | |
| CN106378108A (en) | Preparation method of nano-cellulose-base heavy metal adsorbing material | |
| CN111154027B (en) | Preparation method and application of temperature-sensitive composite hydrogel utilizing photocatalysis and temperature-sensitive synergistic effect | |
| CN111204817B (en) | Magnetic composite carbon prepared from harmful algal bloom and plastic and preparation method thereof | |
| Fan et al. | Efficient photocatalytic inactivation of Microcystis aeruginosa via self-floating Ag3VO4/BiVO4 hydrogel under visible light | |
| Liu et al. | Optimization preparation of composite membranes as proton exchange membrane for gaseous acetone fed microbial fuel cells | |
| CN111437778A (en) | Amino modified microcrystalline cellulose/graphene oxide aerogel and preparation method and application thereof | |
| Chen et al. | Enhanced and selective uranium extraction onto electrospun nanofibers by regulating the functional groups and photothermal conversion performance | |
| Wu et al. | Green synthesis and environmental applications of alginate/polyacrylamide/titanium dioxide composite hydrogel | |
| Li | Preparation and Adsorption Properties of Biochar/g‐C3N4 Composites for Methylene Blue in Aqueous Solution | |
| US11577219B2 (en) | Method for preparing natural organic macromolecular water treatment agent | |
| Wang et al. | Facile Chemical Vapor Modification Strategy to Construct Surface Cyano‐Rich Polymer Carbon Nitrides for Highly Efficient Photocatalytic H2 Evolution | |
| Song et al. | One-step construction of silver–polyaniline nanocomposite modified multifunctional sponges for wastewater remediation: adsorption, catalysis and antimicrobial applications | |
| CN111549529B (en) | Non-woven fabric material and preparation method and application thereof | |
| CN111519432B (en) | Non-woven fabric material and preparation method and application thereof | |
| CN113980295A (en) | Chitosan/sodium alginate hydrogel and preparation method and use method thereof | |
| CN111591989A (en) | Activated carbon material and preparation method and application thereof | |
| CN112452310B (en) | Nitrogen-doped carbon adsorbent, preparation method thereof and application of nitrogen-doped carbon adsorbent to adsorption of organic dye | |
| CN111591990A (en) | Activated carbon material and preparation method and application thereof | |
| CN111440278B (en) | Activated carbon material and preparation method and application thereof | |
| CN112758922B (en) | Preparation process and system of high-pyridine nitrogen-doped activated carbon | |
| CN114539562A (en) | Green synthesis method of antibacterial super-large porous hydrogel, product thereof and application of antibacterial super-large porous hydrogel in degradation of various pollutants in wastewater treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |