CN114797692B - Preparation method of chitosan-based composite aerogel material capable of removing formaldehyde at room temperature - Google Patents
Preparation method of chitosan-based composite aerogel material capable of removing formaldehyde at room temperature Download PDFInfo
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 58
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 53
- 239000004964 aerogel Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 54
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000004108 freeze drying Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 25
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- 238000001723 curing Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- 241001233305 Xanthisma Species 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000004887 air purification Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229920002101 Chitin Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZFXYFBGIUFBOJW-UHFFFAOYSA-N theophylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1NC=N2 ZFXYFBGIUFBOJW-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 229940058573 b-d glucose Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000000850 deacetylating effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 229960000278 theophylline Drugs 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
Classifications
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
-
- 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
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
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- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B5/00—Drying solid materials or objects by processes not involving the application of heat
- F26B5/04—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
- F26B5/06—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum the process involving freezing
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- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0875—Gas
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Abstract
The invention discloses a preparation method of a chitosan-based composite aerogel material for removing formaldehyde at room temperature, and belongs to the field of air purification. The composite aerogel material is prepared by uniformly dispersing a modified Pt/TiO 2 catalyst in a dilute acetic acid aqueous solution to prepare a suspension, mixing the suspension with chitosan, freeze-drying and solidifying the mixture, and freeze-drying the mixture again. The composite aerogel material prepared by the invention has the characteristics of controllable shape, good strength, low density, large specific surface area, strong water resistance, easy recovery and the like, and the preparation process is simple, and can be directly used for preparing the filter element of the air purifier to realize the removal of formaldehyde by room-temperature catalytic oxidation.
Description
Technical Field
The invention belongs to the technical field of air purification, and particularly relates to a chitosan-based composite aerogel material for removing low-concentration formaldehyde by room-temperature high-efficiency catalytic oxidation, and a preparation method and application thereof.
Background
Formaldehyde is classified as a class of carcinogens in the carcinogenic list published by the world health organization international cancer research institute. Formaldehyde is used as a gas which is colorless at room temperature and has a specific pungent odor. Among the numerous means of removing low concentration formaldehyde in the room, such as adsorption, plant filtration, and room temperature catalytic oxidation, room temperature catalytic oxidation offers many advantages because the catalyst can be reused and formaldehyde can be completely oxidized to non-toxic CO 2 and H 2 O without additional energy input. However, the room temperature catalytic oxidation technology of TiO 2 loaded with noble metal is one of the most effective methods for removing formaldehyde by room temperature catalytic oxidation currently acknowledged, but the commonly used noble metal catalytic materials have some inconveniences in practical application for removing formaldehyde, such as easy loss of noble metal components, difficult protection, recovery and reuse, and limited industrialization progress of the air purifier due to expensive filter element molding and complicated filter material preparation process.
The Chitosan-based aerogel is prepared by taking Chitosan (Chitosan) as a precursor and performing supercritical drying or freeze drying. Chitosan (Chitosan) is also called as deacetylated Chitin, is a product obtained by deacetylating Chitin (Chitin) which is abundant in nature, and is the only natural alkaline polysaccharide discovered so far in nature. The molecular formula of chitosan is (C 6HO4 N) N, the chemical name is polyglucosamine (1-4) -2-amino-B-D glucose, the C2 position of the chitosan is amino, and the amino base is easy to form quaternary amine positive ions, so that the chitosan has weak alkaline anion exchange effect. Chitosan belongs to renewable resources, and has the advantages of abundant sources, wide biological activity, excellent biocompatibility, reproducibility and degradability. However, the chitosan-based aerogel is used alone, and has the defects of small specific surface area of chitosan raw materials and limited adsorption capacity to formaldehyde pollutants.
According to the invention, anatase TiO 2 with a microstructure of xanthium plants is adopted as a carrier for the first time, and a certain amount of nano noble metal Pt is loaded on the carrier by adopting an in-situ photochemical deposition method, so that the carrier can be subjected to catalytic oxidation at room temperature to remove low-concentration formaldehyde; and then the composite material is compounded with a natural chitosan-based aerogel material to prepare the high-efficiency composite formaldehyde-removing air purifier filter element material which has high specific surface area, high porosity, strong water resistance, easy molding and easy recovery, and the composite material has excellent performance in the practical application of catalyzing and removing low-concentration formaldehyde at room temperature, realizes the high-efficiency and high-value utilization of natural polysaccharide resources while solving the pollution of the low-concentration formaldehyde, and has important significance for sustainable development.
Disclosure of Invention
Aiming at the problem and defect that the existing catalytic material for removing formaldehyde at room temperature is difficult to remove low-concentration formaldehyde in the application process, the invention provides the composite aerogel material which has the advantages of simple process, low production cost and excellent performance of removing low-concentration methanol, and the preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The preparation method of the composite aerogel material with the performance of removing low-concentration formaldehyde at room temperature comprises the following steps:
a) Carrying out solvothermal reaction for 12 hours at 180 ℃ in an aqueous solution of ethylenediamine with the volume fraction of 30% by using a certain amount of ammonium fluotitanate, washing with ethanol and deionized water, centrifuging, and drying at 60 ℃ to obtain a TiO 2 modified carrier;
b) Soaking the TiO 2 modified carrier obtained in the step a) in a certain amount of hexahydrated chloroplatinic acid aqueous solution for 30min by adopting an initial soaking method, irradiating for 1h under a 254nm ultraviolet lamp, stirring for 1-2h, washing with water, filtering, and drying at 60 ℃ to obtain a Pt/TiO 2 catalyst;
c) Uniformly dispersing the Pt/TiO 2 catalyst obtained in the step b) in a 1wt% acetic acid aqueous solution to obtain a Pt/TiO 2 suspension;
d) Adding chitosan into the Pt/TiO 2 suspension, stirring to dissolve completely, and continuing stirring for 0.5h;
e) Defoaming the mixed solution obtained in the step d), pouring the defoamed mixed solution into a mold, and freeze-drying the mixed solution to obtain a block material;
f) Immersing the block material obtained in the step e) into an alkaline curing agent solution, curing the block material and neutralizing the residual acetic acid in the block material, then flushing the block material with deionized water to neutrality, and freeze-drying the block material again to obtain the chitosan-based Pt/TiO 2 composite aerogel material.
The microstructure of the TiO 2 modified carrier obtained in the step a) is in a xanthium plant shape.
The Pt loading in the Pt/TiO 2 catalyst obtained in the step b) is 0.1-5wt%.
And c), the concentration of the Pt/TiO 2 suspension in the step c) is 1-3 g/L.
The concentration of the Pt/TiO 2 catalyst in the mixed solution obtained in the step d) is 1-3 g/L, and the concentration of chitosan is 10-250 g/L;
The concentration of the curing agent solution in the step f) is 1-5wt%, and the curing agent is any one or more of KOH, naOH and alkali metal carbonate.
The curing time in the step f) is 1 min-48 h.
And e) cooling to-50 to-10 ℃ at a speed of 0.1-10 ℃/min, freezing for 6-24 h, and drying for 6-36 h at-15-25 ℃ under a vacuum degree of 200-1000 Pa.
The deacetylation degree of the chitosan is more than or equal to 95%.
Application: the chitosan-based composite aerogel material is applied to the preparation of the filter element of the formaldehyde-removing air purifier.
The composite aerogel material has excellent activity of catalyzing and oxidizing formaldehyde at room temperature, has the characteristics of controllable shape, good strength, low density, high porosity, large specific surface area, strong water resistance, easy recovery and the like, and can be directly used as a filter element in a formaldehyde-removing air purifier.
Compared with the prior art, the method provided by the invention has the advantages that the composite aerogel material with higher strength is obtained through a step-by-step curing method, and meanwhile, the high dispersion and effective load of the noble metal active components are realized. The prepared composite aerogel material has the advantages of high porosity, large specific surface area, strong water resistance, easy molding, easy recovery and the like, can effectively catalyze and remove formaldehyde at room temperature, has simple process, low cost and easily controlled conditions, and is suitable for large-scale production.
The TiO 2 nano-particle with the xanthium morphology is prepared for the first time, and the morphology not only can endow TiO 2 with higher specific surface area (which is beneficial to improving catalytic reaction activity and Pt noble metal loading capacity), but also can improve anchoring firmness of the TiO 2 nano-particle on a carrier. Therefore, the invention adopts the xanthine anatase TiO 2 as a carrier, and loads a certain amount of nano noble metal Pt on the carrier by an in-situ photochemical deposition method, so that the carrier can remove low-concentration formaldehyde by catalytic oxidation at room temperature; in order to further improve the utilization and the recoverability of the nano Pt-TiO 2 catalyst, the nano Pt-TiO 2 catalyst is compounded with a natural chitosan-based aerogel material to prepare the air purifier filter element material which has high specific surface area, high porosity, strong water resistance, easy molding and easy recovery and is efficient for compounding and removing formaldehyde. The composite aerogel filter core material has excellent performance in the practical application of catalyzing and removing low-concentration formaldehyde at room temperature, realizes the high-efficiency and high-value utilization of natural polysaccharide resources while solving the pollution of the low-concentration formaldehyde, and has great significance for sustainable development.
The nano Pt-TiO 2 catalyst has good performance, but is difficult to use and recycle due to small size particles. In addition, because the powdery Pt-TiO 2 catalyst has poor adsorption performance on formaldehyde gas, the pure powdery Pt-TiO 2 catalyst has no good formaldehyde removal performance, and the chitosan aerogel has no formaldehyde removal effect, but has a certain adsorption effect on formaldehyde. After the aerogel is compounded with the Pt-TiO 2, the aerogel firstly adsorbs formaldehyde and then combines the formaldehyde removal effect of the Pt-TiO 2 catalyst, and the formaldehyde removal performance can be obviously improved by mutual matching of the aerogel and the Pt-TiO 2, and the recycling and recovery of the catalyst are facilitated.
Drawings
FIG. 1 is an SEM image of the TiO 2 support prepared in step a of comparative example 2.
FIG. 2 is a sample plot of the composite aerogel material prepared in example 4.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Comparative example 1
A) Adding 5g of chitosan into 100mL of 1 wt% acetic acid aqueous solution under stirring, stirring to dissolve completely, wherein the concentration of chitosan in the solution is 50g/L, and then continuing stirring for 0.5h;
b) Performing ultrasonic defoaming and vacuum air extraction on the chitosan solution obtained in the step b), wherein the ultrasonic time is 1h, and the air extraction time is 1h so as to discharge dissolved gas in the mixed solution;
c) Pouring the discharged chitosan solution into a culture dish with the diameter of 50mm for freeze drying treatment to obtain a block material; the freeze drying is to cool to-25 ℃ at a speed of 1 ℃/min, freeze for 2 hours, and then dry for 24 hours under the conditions of-5 ℃ and a vacuum degree of 400 Pa;
d) And (3) putting the obtained block material into a Na 2CO3 solution with the concentration of 2wt% to be solidified for 30min, and performing primary freeze drying according to the conditions to obtain the blank chitosan aerogel material.
Comparative example 2
A) Ammonium fluotitanate is subjected to hydrothermal reaction for 12 hours at 180 ℃ in an aqueous solution of ethylenediamine with the volume fraction of 30%, and then is washed by ethanol/deionized water, centrifuged and dried at 60 ℃ to obtain a white modified xanthium plant-like anatase TiO 2 carrier (specific surface: 102.3m 2/g);
b) Dissolving 0.053g of chloroplatinic acid hexahydrate into 20mL of water, adding 2g of the modified TiO 2 carrier, stirring for 30min, irradiating with a 254nm ultraviolet lamp for 1h under the condition of continuous stirring to obtain Pt/TiO 2 catalyst suspension, washing with water, centrifuging, and drying at 60 ℃ to obtain the Pt/TiO 2 catalyst of the uncomplexed aerogel.
Comparative example 3
A) 0.053g chloroplatinic acid hexahydrate was dissolved in 20mL water, and 2g commercial de-solid brand P25 (TiO 2, specific surface: 50m 2/g, irregular particles) as a carrier, stirring for 30min, irradiating with 254nm ultraviolet lamp for 1h under the condition of continuous stirring to obtain Pt/P25 catalyst suspension, washing with water, centrifuging, and drying at 60 ℃ to obtain the Pt/P25 catalyst without the composite aerogel.
Example 1
A) 0.5g of the Pt/TiO 2 catalyst of comparative example 2 was weighed and added into 100mL of 1wt% acetic acid aqueous solution, and the mixture was mechanically stirred for 10min to prepare a Pt/TiO 2 dispersion with a concentration of 5 g/L;
b) Adding 10g of chitosan into the Pt/TiO 2 dispersion liquid under stirring, stirring to completely dissolve the chitosan, wherein the concentration of the chitosan in the solution is 100g/L, and then continuing stirring for 0.5h;
c) Ultrasonic defoaming and vacuum air extraction are carried out on the mixed solution, wherein the ultrasonic time is 30min, and the air extraction time is 30min so as to discharge dissolved gas in the mixed solution;
d) Pouring the mixed solution after the exhaust into a culture dish with the diameter of 50mm for freeze drying to obtain a block material; the freeze drying is to cool to-30 ℃ at a speed of 1 ℃/min, freeze for 2 hours, and then dry for 12 hours under the conditions of-5 ℃ and a vacuum degree of 100 Pa;
e) And (3) putting the freeze-dried block material into a NaOH solution with the concentration of 1wt% for curing for 30min, and performing primary freeze drying according to the conditions to obtain the chitosan-based Pt/TiO 2 composite aerogel material, wherein the number is recorded as 1.
Example 2
A) 0.5g of the Pt/P25 catalyst of comparative example 3 was weighed and added to 100mL of a 1wt% aqueous acetic acid solution, and mechanically stirred for 10 minutes to prepare a Pt/P25 dispersion having a concentration of 5 g/L;
b) Adding 10g of chitosan into the Pt/P25 dispersion liquid under stirring, stirring to completely dissolve the chitosan, wherein the concentration of the chitosan in the solution is 100g/L, and then continuing stirring for 0.5h;
c) Ultrasonic defoaming and vacuum air extraction are carried out on the mixed solution, wherein the ultrasonic time is 30min, and the air extraction time is 30min so as to discharge dissolved gas in the mixed solution;
d) Pouring the mixed solution after the exhaust into a culture dish with the diameter of 50mm for freeze drying to obtain a block material; the freeze drying is to cool to-30 ℃ at a speed of 1 ℃/min, freeze for 2 hours, and then dry for 12 hours under the conditions of-5 ℃ and a vacuum degree of 100 Pa;
e) And (3) putting the freeze-dried block material into a NaOH solution with the concentration of 1wt% for curing for 30min, and performing primary freeze drying according to the conditions, wherein the number of the comparative sample chitosan-based Pt/P25 composite aerogel material is 2.
Example 3
B) 1.0 g of the Pt/TiO 2 catalyst of comparative example 2 is weighed and added into 100mL of 1wt% acetic acid aqueous solution, and the mixture is mechanically stirred for 10min to prepare Pt/TiO 2 dispersion with the concentration of 10 g/L;
c) Adding 23g of chitosan into the Pt/TiO 2 dispersion liquid under stirring, stirring to completely dissolve the chitosan, wherein the concentration of the chitosan in the solution is 230g/L, and then continuing stirring for 0.5h;
d) Ultrasonic defoaming and vacuum air extraction are carried out on the mixed solution, wherein the ultrasonic time is 30min, and the air extraction time is 30min so as to discharge dissolved gas in the mixed solution;
e) Pouring the mixed solution after the exhaust into a culture dish with the diameter of 50mm for freeze drying to obtain a block material; the freeze drying is to cool to-30 ℃ at a speed of 1 ℃/min, freeze for 2 hours, and then dry for 12 hours under the conditions of-5 ℃ and a vacuum degree of 100 Pa;
f) And (3) putting the freeze-dried block material into a NaOH solution with the concentration of 1wt% for curing for 30min, and performing primary freeze drying according to the conditions to obtain the chitosan-based Pt/TiO 2 composite aerogel material with the number of 3.
Example 4
A) 2g of the Pt/TiO 2 catalyst prepared in comparative example 2 was weighed and added into 100mL of 1wt% acetic acid aqueous solution, and mechanically stirred for 10min to prepare a Pt/TiO 2 dispersion with a concentration of 20 g/L;
b) Under stirring, adding 18g of chitosan into the Pt/TiO 2 dispersion liquid, stirring to completely dissolve the chitosan, wherein the concentration of the chitosan in the solution is 180g/L, and then continuously stirring for 0.5h;
c) Ultrasonic defoaming and vacuum air extraction are carried out on the mixed solution, wherein the ultrasonic time is 1h, and the air extraction time is 30min so as to discharge dissolved gas in the mixed solution;
d) Pouring the mixed solution after the exhaust into a culture dish with the diameter of 50mm for freeze drying to obtain a block material; the freeze drying is to cool to-30 ℃ at a speed of 1 ℃/min, freeze for 2 hours, and then dry for 12 hours under the conditions of-5 ℃ and a vacuum degree of 100 Pa;
e) And (3) putting the freeze-dried block material into a KOH solution with the concentration of 2.5 weight percent for curing for 30min, and performing freeze drying for the first time according to the conditions to obtain the chitosan-based Pt/TiO 2 composite aerogel material with the number of 4.
The materials obtained in comparative examples 1 to 3 and examples 1 to 4 were subjected to a low concentration formaldehyde removal test. The test is carried out in a continuous fixed bed at room temperature and normal pressure, the catalyst is placed in a quartz tube with 50mm, the raw material is mixed gas of formaldehyde with high purity He with the concentration of 60ppm, the point of the reaction for 1h is taken for gas chromatography detection, and the result is shown in Table 1.
Table 1 oxidation removal rate of formaldehyde at room temperature for each example material
As can be seen from Table 1, by comparing the results, the composite aerogel material prepared by the invention can efficiently oxidize and remove formaldehyde at room temperature, and the removal rate of formaldehyde at room temperature for 1 hour of the composite chitosan-based Pt/TiO 2 composite aerogel material prepared by the example 4 can reach 98.12%, so that the composite aerogel material can be directly used as a filter element material to be applied to an air purifier, and has great potential industrial application prospect.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A preparation method of a chitosan-based composite aerogel material for removing formaldehyde at room temperature is characterized by comprising the following steps: the method comprises the following steps:
a) Carrying out hydrothermal reaction for 12 hours at 180 ℃ in an ethylenediamine aqueous solution by using a certain amount of ammonium fluotitanate, washing with ethanol and deionized water, centrifuging, and drying at 60 ℃ to obtain a TiO 2 modified carrier;
b) Soaking the TiO 2 modified carrier obtained in the step a) in a certain amount of hexahydrated chloroplatinic acid aqueous solution for 30min by adopting an initial soaking method, irradiating for 1h under a 254nm ultraviolet lamp, stirring for 1-2h, washing with water, filtering, and drying at 60 ℃ to obtain a Pt/TiO 2 catalyst;
c) Uniformly dispersing the Pt/TiO 2 catalyst obtained in the step b) in a 1wt% acetic acid aqueous solution to obtain a Pt/TiO 2 suspension;
d) Adding chitosan into the Pt/TiO 2 suspension, stirring to dissolve completely, and continuing stirring for 0.5h;
e) Defoaming the mixed solution obtained in the step d), pouring the defoamed mixed solution into a mold, and freeze-drying the mixed solution to obtain a block material;
f) Immersing the block material obtained in the step e) into an alkaline curing agent solution, curing the block material and neutralizing the residual acetic acid in the block material, then flushing the block material with deionized water to neutrality, and freeze-drying the block material again to obtain the chitosan-based composite aerogel material;
The microstructure of the TiO 2 modified carrier obtained in the step a) is in a xanthium plant shape.
2. The method of manufacturing according to claim 1, characterized in that: the Pt loading in the Pt/TiO 2 catalyst obtained in the step b) is 0.1-5wt%.
3. The method of manufacturing according to claim 1, characterized in that: the concentration of the Pt/TiO 2 catalyst in the mixed solution obtained in the step d) is 1-3 g/L, and the concentration of chitosan is 10-250 g/L.
4. The method of manufacturing according to claim 1, characterized in that: the deacetylation degree of the chitosan is more than or equal to 95%.
5. The method of manufacturing according to claim 1, characterized in that: the concentration of the alkaline curing agent solution in the step f) is 1-5wt%; the alkaline curing agent is any one or more of KOH, naOH and alkali metal carbonate.
6. The method of manufacturing according to claim 1, characterized in that: the curing time in the step f) is 1 min-48 h.
7. The method of manufacturing according to claim 1, characterized in that: and e) cooling to-50 to-10 ℃ at a speed of 0.1-10 ℃/min, freezing for 6-24 h, and drying for 6-36 h at-15-25 ℃ under a vacuum degree of 200-2000 Pa.
8. A chitosan-based composite aerogel material produced by the method of any of claims 1-7.
9. Use of the chitosan-based composite aerogel material of claim 8 in the preparation of a formaldehyde-removing air purifier filter element.
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