CN113842922B - Composite aerogel and preparation method and application thereof - Google Patents
Composite aerogel and preparation method and application thereof Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000499 gel Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000006228 supernatant Substances 0.000 claims abstract description 14
- 239000011240 wet gel Substances 0.000 claims abstract description 14
- 238000005303 weighing Methods 0.000 claims abstract description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 69
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 230000000844 anti-bacterial effect Effects 0.000 claims description 5
- 239000000411 inducer Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims 1
- 239000008204 material by function Substances 0.000 claims 1
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 19
- 210000000170 cell membrane Anatomy 0.000 description 11
- 244000005700 microbiome Species 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- 230000001954 sterilising effect Effects 0.000 description 8
- 238000004659 sterilization and disinfection Methods 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- -1 oxygen ions Chemical class 0.000 description 4
- 241000233866 Fungi Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 210000002421 cell wall Anatomy 0.000 description 3
- 238000005034 decoration Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 244000063299 Bacillus subtilis Species 0.000 description 2
- 235000014469 Bacillus subtilis Nutrition 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- SPOQSWFEPFFHCR-UHFFFAOYSA-N [Ce].[Mn].[Co] Chemical compound [Ce].[Mn].[Co] SPOQSWFEPFFHCR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/23—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
Composite aerogel, preparation method and application thereof, and weighing citric acid and MnCl with corresponding mass 2 ·4H 2 O、Ce(NO 3 ) 2 ·6H 2 O、CO(NO 3 ) 2 ·6H 2 Stirring O and absolute ethyl alcohol until the mixture is clear for later use, and marking the mixture as a solution A; adding propylene oxide into the solution A in a water bath at 30 ℃, uniformly stirring, and standing to obtain wet gel; completely immersing the wet gel in absolute ethyl alcohol, aging for 24-72 hours at 50 ℃, and then pouring the supernatant and replacing with isopropanol; drying the gel with supernatant removed, and roasting at 500deg.C for 3 hr to obtain Ce 1‑x Co x O n ‑MnO 2 Composite aerogel; and weighing dichloro octyl isothiazolinone (DCOIT), dissolving in absolute ethyl alcohol, marking as a solution B, soaking the baked composite aerogel in the solution B for 24 hours, and finally drying to obtain the composite aerogel.
Description
Technical Field
The invention relates to the field of air purification, in particular to a composite aerogel with formaldehyde catalytic decomposition at normal temperature and sterilization functions, and a preparation method and application thereof.
Background
In recent years, with the improvement of living standard and the enhancement of health consciousness, people are paying more attention to indoor air quality of buildings. The formaldehyde in the indoor air is widely sourced and limited by the indoor decoration technology, the material production process and the cost, and at present, the home decoration material without formaldehyde cannot be prepared, so that formaldehyde is mostly existed in the home decoration material and part of daily necessities, besides formaldehyde hazard, microorganisms such as bacteria and fungi propagate in the indoor to pollute the air, and indoor sterilization becomes a concern of people. At present, a plurality of formaldehyde purification treatment methods are important and commonly applied, namely, an air purifier is used for purifying formaldehyde, a formaldehyde filter screen used by the air purifier is formed by loading catalytic materials on the surfaces of porous carrier particle materials, then the particle materials are filled into honeycomb-shaped framework materials, in order to ensure that wind resistance is small and the porous carrier materials cannot fall off, the used porous carrier materials are required to be larger particles, so that the purification effect is influenced, and meanwhile, the materials only purify formaldehyde and cannot be sterilized, and a layer of sterilization material is compounded when sterilization is needed, so that the resistance of the filter screen is increased, and the cost is increased. The traditional porous adsorption materials such as zeolite, silica gel, alumina, activated carbon and the like are used as carriers, precious metal materials and rare earth metal materials with formaldehyde catalytic oxidation function and substances containing silver, zinc or copper with sterilization function are loaded on the carrier materials according to a certain proportion, the carriers such as zeolite, silica gel, alumina, activated carbon and the like are only saturated in adsorption in a short time, and the cost of the precious metal materials is high, so that the design and development of the novel composite function catalytic material are key to solve the defects, and have great practical significance for realizing formaldehyde degradation and bacteriostasis.
Disclosure of Invention
The technical problems to be solved are as follows: aiming at the problems of saturated adsorption, low utilization rate, high price and the like of catalysts in the market, the invention provides a compositeAerogel, and preparation method and application thereof, the material is different from the traditional adsorption material, and the catalytic reaction between the material and formaldehyde is carried out, rather than simple physical adsorption. The gel has large specific surface area and high porosity, improves catalytic oxidation performance, obtains extremely high dispersity of manganese and cobalt on a cerium oxide carrier, and greatly increases the activity of oxygen species on the surface of the catalyst due to the interaction of rare earth metal-antibacterial metal-carrier, which is two important reasons for the activity of the composite aerogel in the room-temperature catalytic oxidation of formaldehyde. Metal ion Co 2+ When (Zn, ni, cu) contacts with the cell membrane of the microorganism, coulomb attraction is generated between the metal ions and the cell membrane due to negative charge of the cell membrane, so that the metal ions penetrate the cell membrane, enter the microorganism, react with sulfhydryl groups on proteins in the microorganism, destroy enzymes in the microorganism, interfere with the formation of microorganism DNA, and thus the aim of killing the microorganism is fulfilled. The manganese cobalt cerium catalytic center generates hydroxyl free radicals and active oxygen ions, and sterilization and bacteriostasis are performed through the strong oxidation-reduction capability of the hydroxyl free radicals and the active oxygen ions. Finally, the problem that metal ions only can act on cell membranes is solved by modifying the cell membrane with organic chlorine, and fungi can have one more cell wall than bacteria on the cell structure. The cobalt ions can enter the mould body to play a bactericidal effect only through a cell wall and cell membrane two-layer structure, so that the combination of inorganic antibacterial metal and organic chlorine can act on air purification more widely.
The technical scheme is as follows: the preparation method of the composite aerogel comprises the following preparation steps: (1) According to the molar ratio of n (citric acid) to n (Mn) to n (Ce) to n (Co) to n (EtOH) =1 to 1 (0.5-0.8) to 0.2-0.5 to 45-55, weighing the citric acid and MnCl with corresponding mass 2 ·4H 2 O、Ce(NO 3 ) 2 ·6H 2 O、CO(NO 3 ) 2 ·6H 2 Stirring O and absolute ethyl alcohol until the mixture is clear for later use, and marking the mixture as a solution A; (2) Adding 1,2 epoxypropane with the molar ratio of 1 (12-15) to citric acid into the solution A in a water bath at 30 ℃, uniformly stirring, and standing to obtain wet gel; (3) Immersing wet gel in absolute ethyl alcohol completely, aging at 50deg.C for 24-72 hr, pouring supernatant, and replacing with isopropanol for at least 3 timesThe method comprises the steps of carrying out a first treatment on the surface of the (4) Drying the gel with supernatant removed, and roasting at 500deg.C for 3 hr to obtain Ce 1-x Co x O n -MnO 2 Composite aerogel; (5) Weighing dichloro octyl isothiazolinone (DCOIT), dissolving in absolute ethyl alcohol, marking as a solution B, and soaking the baked composite aerogel in the solution B for 24 hours, wherein Ce is 1-x Co x On-MnO 2 The mass ratio of the composite aerogel to the dichlorooctyl isothiazolinone (DCOIT) to the absolute ethyl alcohol is 1 (0.45-1.8) (5-6), and finally the composite aerogel is obtained through drying.
Preferably, the molar ratio n (citric acid) n (Mn) n (Ce) n (Co) n (EtOH) =1:1:0.8:0.2:51 in step (1).
Preferably, in the step (2), the molar ratio of the citric acid to the 1,2 epoxypropane is 1:14, and the standing gel time is 5-30 min.
Preferably, the aging time in step (3) is 48 hours; the three times of replacement of the isopropanol is not less than 12 hours.
Preferably, the drying temperature in the step (4) is 80 ℃ and the drying time is 12 hours.
Preferably, the Ce of step (5) 1-x Co x On-MnO 2 The mass ratio of the composite aerogel to the dichlorooctyl isothiazolinone (DCOIT) to the absolute ethyl alcohol is 1:0.6:5.79.
Preferably, in the step (5), the drying temperature is 60 ℃ and the drying time is 20 hours.
The composite aerogel prepared by the preparation method.
The application of the composite aerogel in preparing materials with formaldehyde catalytic decomposition and sterilization functions at normal temperature.
The beneficial effects are that: 1. the composite aerogel is different from the traditional adsorption material, the manganese and cobalt have extremely high dispersity on the cerium oxide carrier, and meanwhile, the activity of oxygen species on the surface of the catalyst is greatly increased by the interaction of the rare earth metal, the antibacterial metal and the carrier, so that formaldehyde is better catalyzed and oxidized. 2. Metal ion Co 2+ When contacting with the cell membrane of microorganism, the cell membrane is negatively charged to cause coulomb attraction with metal ion, thereby leading to penetration of metal ionPenetrating the cell membrane, disrupting enzymes in the microorganism, interfering with the formation of microbial DNA. 3. Aerogel active oxygen is a metal ion catalytic microorganism active center, generates hydroxyl free radicals and active oxygen ions, and performs sterilization and bacteriostasis and better catalytic oxidation of formaldehyde through the strong oxidation-reduction capability of the hydroxyl free radicals and the active oxygen ions. 4. According to the invention, through modifying the surface chlorine of the material, the problem that Co metal ions can only act on cell membranes is solved, and fungi can be one layer of cell wall more than bacteria on cell structures.
Drawings
FIG. 1 is a schematic illustration of the composite aerogel activity test of example 1, example 2, example 3, example 4, exploring the effect of the catalytic oxidation of formaldehyde by chlorine modified aerogel;
FIG. 2 is a graph showing the inhibitory effects of the modified composite aerogel of example 1, example 2, example 3, and example 4 on Escherichia coli, staphylococcus and Bacillus subtilis.
Detailed Description
The present invention will be further described in detail with reference to the following examples, but the present invention is not limited thereto.
Example 1
(1) Weighing MnCl 2 •4H 2 O，Ce(NO 3 ) 2 •6H 2 O，CO(NO 3 ) 2 •6H 2 O, citric acid is dissolved in 30mL absolute ethanol, wherein the molar ratio of n (citric acid) to n (Mn) to n (Ce) to n (Co) to n (EtOH) =1 to 0.8 to 0.2 to 51 is stirred uniformly for standby, and is recorded as solution A;
(2) Adding 10mL of propylene oxide inducer into the solution A at the temperature of 30 ℃ in a water bath kettle, and standing to obtain wet gel;
(3) Adding 20mL of absolute ethanol to the wet gel, allowing the gel to be completely immersed in the solvent, aging at 50 ℃ for 48h, pouring the supernatant, and then replacing it with isopropanol at least three times;
(4) Placing the gel with the supernatant removed in a blast drying oven, drying, and roasting at 500 ℃ for 3 hours to obtain Ce1-xCo x O n -MnO 2 Composite aerogel;
(5) 0.9g of dichloro octyl isothiazolinone (DCOIT) and 2.0g of composite aerogel are weighed and dissolved in 20mL absolute ethyl alcohol, the mixture is stirred to be fully immersed, and then the mixture is dried at 60 ℃ to obtain the chlorine modified composite aerogel.
Example 2
(1) Weighing MnCl 2 •4H 2 O，Ce(NO 3 ) 2 •6H 2 O，CO(NO 3 ) 2 •6H 2 O, citric acid is dissolved in 30mL absolute ethanol, wherein the molar ratio of n (citric acid) to n (Mn) to n (Ce) to n (Co) to n (EtOH) =1 to 0.8 to 0.2 to 51 is stirred uniformly for standby, and is recorded as solution A;
(2) Adding 10mL of propylene oxide inducer into the solution A at the temperature of 30 ℃ in a water bath kettle, and standing to obtain wet gel;
(3) Adding 20mL of absolute ethanol to the wet gel, allowing the gel to be completely immersed in the solvent, aging at 50 ℃ for 48h, pouring the supernatant, and then replacing it with isopropanol at least three times;
(4) Placing the gel with the supernatant removed in a blast drying oven, drying, and roasting at 500 ℃ for 3 hours to obtain Ce1-xCo x O n -MnO 2 Composite aerogel;
(5) 1.2g of dichloro octyl isothiazolinone (DCOIT) and 2.0g of composite aerogel are weighed and dissolved in 20mL absolute ethyl alcohol, the mixture is stirred to be fully immersed, and then the mixture is dried at 60 ℃ to obtain the chlorine modified composite aerogel.
Example 3
(1) Weighing MnCl 2 •4H 2 O，Ce(NO 3 ) 2 •6H 2 O，CO(NO 3 ) 2 •6H 2 O, citric acid is dissolved in 30mL absolute ethanol, wherein the molar ratio of n (citric acid) to n (Mn) to n (Ce) to n (Co) to n (EtOH) =1 to 0.8 to 0.2 to 51 is stirred uniformly for standby, and is recorded as solution A;
(2) Adding 10mL of propylene oxide inducer into the solution A at the temperature of 30 ℃ in a water bath kettle, and standing to obtain wet gel;
(3) Adding 20mL of absolute ethanol to the wet gel, allowing the gel to be completely immersed in the solvent, aging at 50 ℃ for 48h, pouring the supernatant, and then replacing it with isopropanol at least three times;
(4) Placing the gel with the supernatant removed in a blast drying oven, drying, and roasting at 500 ℃ for 3 hours to obtain Ce1-xCo x O n -MnO 2 Composite aerogel;
(5) 2.4g of dichloro octyl isothiazolinone (DCOIT) and 2.0g of composite aerogel are weighed and dissolved in 20mL absolute ethyl alcohol, the mixture is stirred to be fully immersed, and then the mixture is dried at 60 ℃ to obtain the chlorine modified composite aerogel.
Example 4
(1) Weighing MnCl 2 •4H 2 O，Ce(NO 3 ) 2 •6H 2 O，CO(NO 3 ) 2 •6H 2 O, citric acid is dissolved in 30mL absolute ethanol, wherein the molar ratio of n (citric acid) to n (Mn) to n (Ce) to n (Co) to n (EtOH) =1 to 0.8 to 0.2 to 51 is stirred uniformly for standby, and is recorded as solution A;
(2) Adding 10mL of propylene oxide inducer into the solution A at the temperature of 30 ℃ in a water bath kettle, and standing to obtain wet gel;
(3) Adding 20mL of absolute ethanol to the wet gel, allowing the gel to be completely immersed in the solvent, aging at 50 ℃ for 48h, pouring the supernatant, and then replacing it with isopropanol at least three times;
(4) Placing the gel with the supernatant removed in a blast drying oven, drying, and roasting at 500 ℃ for 3 hours to obtain Ce1-xCo x O n -MnO 2 Composite aerogel;
(5) 3.6g of dichloro octyl isothiazolinone (DCOIT) and 2.0g of composite aerogel are weighed and dissolved in 20mL absolute ethyl alcohol, the mixture is stirred to be fully immersed, and then the mixture is dried at 60 ℃ to obtain the chlorine modified composite aerogel.
Performance test the composite aerogel prepared in all the above examples was used as a test object
All Ce modified with dichlorooctyl isothiazolinone 1-x Co x On-MnO 2 The composite aerogel is applied to room temperature formaldehyde catalysis and bacteriostasis experiments, wherein the formaldehyde test condition concentration is that1.2±0.1mg/m 3 The concentration of the diluted bacteria (such as Escherichia coli, staphylococcus aureus and Bacillus subtilis) is about 10 5 -10 6 cfu/mL, 0.2g of the sample of the example is weighed, and the formaldehyde catalysis performance and the antibacterial effect of the sample are tested, and the data are shown in figures 1 and 2. It can be derived from the modification of Ce by dichlorooctyl isothiazolinone 1-x Co x On-MnO 2 The composite aerogel has remarkable influence on formaldehyde catalysis and bacteriostasis performance, is doped in a proper amount, improves the formaldehyde catalysis performance and has a better bacteriostasis effect, but after being excessively introduced, the bacteriostasis and the formaldehyde catalysis effect all show obvious descending trend. The above examples are only for the analytical understanding of the preparation method and the application scope of the present invention, but the present invention is not limited to the above examples. It should be understood that the invention may be directly changed, substituted, modified, etc. by those skilled in the art, and thus, it is within the scope of the present invention.
Claims (3)
1. The preparation method of the composite aerogel is characterized by comprising the following preparation steps: (1) Weighing MnCl 2 •4H 2 O，Ce(NO 3 ) 2 •6H 2 O，Co(NO 3 ) 2 •6H 2 O, citric acid is dissolved in 30mL absolute ethanol, wherein the molar ratio of n (citric acid) to n (Mn) to n (Ce) to n (Co) to n (EtOH) =1 to 0.8 to 0.2 to 51 is stirred uniformly for standby, and is recorded as solution A; (2) Adding 10mL of propylene oxide inducer into the solution A at the temperature of 30 ℃ in a water bath kettle, and standing to obtain wet gel; (3) Adding 20mL of absolute ethanol to the wet gel, allowing the gel to be completely immersed in the solvent, aging at 50 ℃ for 48h, pouring the supernatant, and then replacing it with isopropanol at least three times; (4) Placing the gel with the supernatant removed in a forced air drying oven, drying, and roasting at 500deg.C for 3 hr to obtain Ce 1-x Co x O n -MnO 2 Composite aerogel; (5) 1.2g of dichloro octyl isothiazolinone (DCOIT) and 2.0g of composite aerogel are weighed and dissolved in 20mL absolute ethyl alcohol, the mixture is stirred to be fully immersed, and then the mixture is dried at 60 ℃ to obtain the chlorine modified composite aerogel.
2. The composite aerogel produced by the method of claim 1.
3. The use of the composite aerogel of claim 2 in preparing formaldehyde and bactericidal functional materials by normal temperature catalytic decomposition.
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