CN115155306B - Efficient remover for indoor formaldehyde and organic volatile matters, preparation method and application - Google Patents
Efficient remover for indoor formaldehyde and organic volatile matters, preparation method and application Download PDFInfo
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- CN115155306B CN115155306B CN202210794164.0A CN202210794164A CN115155306B CN 115155306 B CN115155306 B CN 115155306B CN 202210794164 A CN202210794164 A CN 202210794164A CN 115155306 B CN115155306 B CN 115155306B
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920001661 Chitosan Polymers 0.000 claims abstract description 100
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- QFTLTYBDMFRHQI-UHFFFAOYSA-M [Br-].[Ag].[Ag+] Chemical compound [Br-].[Ag].[Ag+] QFTLTYBDMFRHQI-UHFFFAOYSA-M 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000000017 hydrogel Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000080 wetting agent Substances 0.000 claims abstract description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 178
- 239000000243 solution Substances 0.000 claims description 96
- 235000019441 ethanol Nutrition 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 60
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims description 38
- 238000000502 dialysis Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000011148 porous material Substances 0.000 claims description 28
- 229910052710 silicon Inorganic materials 0.000 claims description 28
- 239000010703 silicon Substances 0.000 claims description 28
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- 239000004005 microsphere Substances 0.000 claims description 26
- WLNARFZDISHUGS-MIXBDBMTSA-N cholesteryl hemisuccinate Chemical compound C1C=C2C[C@@H](OC(=O)CCC(O)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 WLNARFZDISHUGS-MIXBDBMTSA-N 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- 235000012000 cholesterol Nutrition 0.000 claims description 19
- 230000007797 corrosion Effects 0.000 claims description 17
- 238000005260 corrosion Methods 0.000 claims description 17
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000004108 freeze drying Methods 0.000 claims description 16
- 229940014800 succinic anhydride Drugs 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 9
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000385 dialysis solution Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- 238000004887 air purification Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 5
- 229940082004 sodium laurate Drugs 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001817 Agar Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000008272 agar Substances 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 2
- 239000013530 defoamer Substances 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000012459 cleaning agent Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000957 no side effect Toxicity 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 19
- -1 formaldehyde, benzene series Chemical class 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 229920000578 graft copolymer Polymers 0.000 description 7
- 150000002751 molybdenum Chemical class 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000005495 cold plasma Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- 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
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- 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
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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
The invention relates to the technical field of environmental protection, in particular to a high-efficiency remover for indoor formaldehyde and organic volatile matters, a preparation method and application thereof, wherein the remover comprises a modified chitosan catalyst, silver bromide-silver/nano-silicon, hydrogel, a wetting agent, a defoaming agent and the balance of water; the modified chitosan catalyst is prepared by attaching molybdate to modified chitosan; the silver bromide-silver/nano silicon is formed by attaching silver-silver bromide to a nano silicon chip. Under visible light, the invention can play an excellent role in decomposing formaldehyde and removing odor molecules, not only can reduce the formaldehyde release of a base material, but also can purify and decompose formaldehyde and odor molecules in the air, and can maintain effective and sustainable purification of indoor air for a long time; in addition, the self-cleaning agent has a stronger self-cleaning effect on the surface of the base material, so that the surface of the base material is not easy to be polluted, and the service life of the base material is prolonged; the raw materials are nontoxic and have no side effects, and are safe and environment-friendly.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to an efficient remover for indoor formaldehyde and organic volatile matters, and a preparation method and application thereof.
Background
Formaldehyde is one of the main indoor pollutants, and is mainly derived from paint solvents, adhesives of plywood and some fabric surfaces. The main treatment methods of the indoor decoration pollution at present are a physical adsorption method, a chemical reaction method, a catalytic oxidation method, a biological method, a composite method and a cold plasma method. Among them, the adsorption method is the most commonly used method due to low price and easily available raw materials, but the adsorption method such as carbon adsorption is ideal for recycling volatile organic gases with low concentration, carbon dioxide, sulfur dioxide and the like, and has almost no purification effect on chemical emissions generated by decoration. From the comprehensive comparison, the catalytic oxidation method is a new method for purifying air with wider prospect. The photocatalyst is a general term of a photo-semiconductor material with a photocatalysis function represented by nano-scale titanium dioxide, and can effectively degrade toxic and harmful gases in air under the action of ultraviolet light and visible light when being coated on the surface of a substrate, but the existing photocatalyst still has the problems of single degradation pollutant species, poor catalytic degradation performance under visible light, limited chemical pollution only in a short period, incapability of effectively removing formaldehyde hidden in furniture and the like.
Disclosure of Invention
In order to solve the problems in the background technology, the invention provides the efficient remover which has good stability and can continuously purify pollutants such as formaldehyde, organic volatile matters and the like for a long time, and the preparation method and the application thereof.
On one hand, the invention provides an efficient remover for indoor formaldehyde and organic volatile matters, which is characterized in that: comprises the following components in parts by weight: 12-18 parts of modified chitosan catalyst, 8-15 parts of silver bromide-silver/nano silicon, 20-25 parts of hydrogel, 1-3 parts of wetting agent, 0.5-2 parts of defoamer and the balance of water;
the modified chitosan catalyst is prepared by attaching molybdate to modified chitosan;
the silver bromide-silver/nano silicon is formed by attaching silver-silver bromide to a nano silicon chip. The modified chitosan catalyst and silver bromide-silver/nano silicon in the scheme have adsorption and visible light catalytic degradation performances, so that the modified chitosan catalyst not only can absorb and decompose indoor formaldehyde, but also can purify and decompose other gas pollutants in indoor air, and has high visible light degradation performance.
Preferably, the modified chitosan catalyst is prepared by the following method: adding 0.5-1.2 wt% molybdenum salt aqueous solution and 70-80% ethanol into the modified chitosan, heating to 75-85 ℃, reacting for 2-3h, filtering and drying to obtain the product. In the scheme, the preferable concentration of the ammonium molybdate solution is 0.8-1.1%wt, the preferable amine content of the modified chitosan is more than 11%wt, and the immobilization rate of molybdate on the prepared modified chitosan catalyst is as high as more than 90%.
Preferably, the modified chitosan is prepared by the following method: after dissolving cholesterol in pyridine, succinic anhydride was added, the molar ratio of cholesterol to succinic anhydride was 1: (2-3); reacting for 20-28h at 80-90 ℃, washing, filtering and drying reactants, and adding acetone for dissolving and crystallizing to obtain cholesterol hemisuccinate; after the chitosan microspheres are put into water for swelling, absolute ethyl alcohol, a coupling agent and an ethanol solution of cholesterol hemisuccinate are sequentially added, wherein the molar ratio of the chitosan microspheres to the cholesterol hemisuccinate is 1: (0.2-0.35), reacting for 2-4d, placing the reaction solution in a dialysis bag, dialyzing with dialysis medium, filtering the dialysis solution, and freeze drying. According to the scheme, the chitosan is subjected to physical and chemical double modification to obtain the spherical cholesterol hydrophobically modified chitosan with excellent performance, and the spherical cholesterol hydrophobically modified chitosan has the advantages of no toxicity, biodegradability, developed micropore structure, large specific surface area, no loss of acidic environment, large adsorption capacity and high adsorption speed.
Preferably, the dialysis process is: sequentially using ethanol solutions with different concentrations as dialysis media and distilled water to dialyze for 2-3d respectively, and changing the dialysis media every 4-5 h. In this case, the concentration of the ethanol solution is not more than 90% by weight, and the concentration of the ethanol solution is sequentially changed from high to low to perform dialysis, whereby the fat-soluble substances which have not been reacted can be removed.
Preferably, the dialysis medium is an 85% ethanol solution, a 75% ethanol solution, a 65% ethanol solution, a 55% ethanol solution. In the scheme, the 85% ethanol solution can not only enable fat-soluble substances (such as cholesterol hemisuccinate and N-hydroxysuccinimide) which are not reacted completely to avoid influencing the performance of the cholesterol hydrophobically modified chitosan, but also enable other ethanol solutions with other concentrations to carry out gradient dialysis to remove other reaction substances.
Preferably, the mass ratio of the coupling agent is 1: (1.5-2) 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide.
Preferably, the chitosan microsphere is prepared by the following method: dissolving chitosan powder in acetic acid solution with the mass fraction of 1-5%, then injecting the chitosan solution into NaOH alcohol solution with the mass fraction of 5-10% to obtain hollow spheres, and washing and freeze-drying the hollow spheres to obtain the chitosan gel. According to the scheme, chitosan can be physically modified into a microsphere structure with good mechanical strength, and rapid and uniform adsorption is realized.
Preferably, the silver bromide-silver/nano-silicon catalyst is prepared by the following method: dispersing nano silicon in deionized water to form 1-3% nano silicon suspension, stirring, adding silver bromide solution, adjusting pH value to 7-9, stirring for 4-7h in dark environment, centrifuging, and drying to obtain silver bromide/nano silicon; dispersing silver bromide/nano silicon in deionized water to form 1-3% suspension, stirring for 1-1.5h under illumination, centrifuging, and drying. In this scheme, the molar mass ratio of silver bromide to nano-silicon is preferably (1-3) mol:1g, the produced electron and hole numbers of the silver bromide-silver/nano silicon catalyst are high, and meanwhile, the nano silicon increases the dispersibility of the silver bromide, avoids particle agglomeration and improves the photocatalytic activity.
Preferably, the nano-silicon is prepared by the following method: the monocrystalline silicon wafer is used as a base material, a hydrothermal corrosion method is adopted to form a silicon nano-pore array, the pore diameter on a silicon column is gradually reduced from 40+/-5 nm on the top of the column to 15+/-5 nm on the bottom of the column, the size range of the silicon column is 1.9-4.5nm, and the thickness of a pore array area is 2-20 mu m. The band gap energy of monocrystalline silicon is widened due to the existence of the silicon nano column, and the specific surface area of the nano silicon prepared by the scheme is greatly increased due to the regular array structure and the special nano porous structure.
Preferably, the hydrothermal corrosion liquid is a mixed aqueous solution of hydrofluoric acid and ferric nitrate, wherein the concentration of the hydrofluoric acid is 12-15mol/L, and the concentration of the ferric nitrate is 0.04-0.07mol/L.
Preferably, the hydrogel is one or more than two of sodium laurate hydrogel, sodium alginate hydrogel, polyvinyl alcohol hydrogel, polyacrylamide hydrogel, agar hydrogel and polyethylene glycol hydrogel. The gel has the characteristic of thermal reversible phase transition to form a three-dimensional fiber grid structure, so that aggregation and precipitation of nano particles are effectively avoided, the surface hydrophilicity of a base material can be increased, and the self-cleaning capability is improved.
On the other hand, the invention provides a preparation method of an efficient remover for indoor formaldehyde and organic volatile matters, which is characterized by comprising the following steps: heating and dissolving the hydrogel until the hydrogel is transparent, adding a wetting agent and a defoaming agent, and dispersing at medium speed for 20-40min; then adding modified chitosan catalyst, silver bromide-silver/nano silicon, and dispersing at high speed for 30-40min; water was added to adjust the viscosity.
In another aspect, the invention provides an application of the high-efficiency remover in indoor air purification. In practical application, the air purification comprises toxic gas purification, such as formaldehyde, benzene series, ammonia, total volatile organic compounds, sulfur dioxide, carbon monoxide and other toxic gases; also comprises peculiar smell adsorption, such as indoor smoke smell, toilet smell, garbage smell, animal smell, etc.
Preferably, the high efficiency remover is coated on the surface of the substrate in a brushing, roller coating, dip coating or spraying mode.
The beneficial effects are that: compared with the prior art, the invention can play an excellent role in decomposing formaldehyde and removing odor molecules under visible light, can not only reduce the formaldehyde release of a base material, but also purify and decompose formaldehyde and odor molecules in the air, and can maintain the effectiveness for a long time, thereby continuously purifying the indoor air; in addition, the self-cleaning agent has a stronger self-cleaning effect on the surface of the base material, so that the surface of the base material is not easy to be polluted, and the service life of the base material is prolonged; the raw materials are nontoxic and have no side effects, and are safe and environment-friendly.
Drawings
FIGS. 1a and 1b show field emission scanning electron microscope (FE-SEM) micrographs of nano-silicon and silver-silver bromide/nano-silicon;
fig. 2 shows a Transmission Electron Microscope (TEM) photograph of the modified chitosan.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to specific embodiments. It should be further noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the specific embodiments, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1 high Performance remover
Comprises the following components in parts by weight: 12 parts of modified chitosan catalyst, 8 parts of silver bromide-silver/nano silicon, 20 parts of sodium laurate hydrogel, 1 part of polyether-dimethylsiloxane graft copolymer, 0.5 part of modified polydimethylsiloxane and the balance of water;
wherein the modified chitosan catalyst is prepared by the following method: after dissolving cholesterol in pyridine, succinic anhydride was added, the molar ratio of cholesterol to succinic anhydride was 1:2; reacting for 20 hours at 80 ℃, washing, filtering and drying reactants, and adding acetone for dissolving and crystallizing to obtain cholesterol hemisuccinate; dissolving chitosan powder in acetic acid solution with the mass fraction of 1%wt, then injecting the chitosan solution into NaOH alcohol solution with the mass fraction of 5%wt to obtain hollow spheres, and washing and freeze-drying to obtain chitosan microspheres; placing chitosan microspheres in water for swelling, and sequentially adding absolute ethyl alcohol and a mass ratio of 1:1.5 ethanol solution of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, cholesterol hemisuccinate, molar ratio of chitosan microspheres to cholesterol hemisuccinate 1:0.2, after reacting for 2-4d, placing the reaction solution in a dialysis bag, sequentially dialyzing for 2-3d by using 85% ethanol solution, 75% ethanol solution, 65% ethanol solution and 55% ethanol solution as dialysis media and distilled water respectively, changing the dialysis media every 4-5h, filtering the dialysis solution, and freeze-drying to obtain modified chitosan; adding 0.5 wt% molybdenum salt aqueous solution and 70% ethanol into the modified chitosan, heating to 75-85 ℃, reacting for 2-3h, filtering and drying to obtain the product;
silver bromide-silver/nano-silicon is prepared by the following method: the monocrystalline silicon wafer is used as a base material, a columnar silicon nano-pore array is formed by adopting a hydrothermal corrosion method, and the hydrothermal corrosion method comprises the following conditions: the concentration of hydrofluoric acid is 12mol/L, the concentration of ferric nitrate is 0.04mol/L, and the etching is carried out for 5min at 70 ℃; the pore diameter of the silicon column on the substrate gradually decreases from 40+/-5 nm at the top of the column to 15+/-5 nm at the bottom of the column, the size range of the silicon column is 1.9-2.5nm, the distance between two adjacent pore walls is 3-8 mu m, and the thickness of the pore array area is 15-20 mu m; dispersing nano silicon in deionized water to form a 1% nano silicon suspension, stirring, adding silver bromide solution, adjusting the pH value to 7, stirring for 4-7h in dark environment, centrifuging, and drying to obtain silver bromide/nano silicon; dispersing silver bromide/nano silicon in deionized water to form a 1% suspension, stirring for 1-1.5h under illumination, centrifuging, and drying.
The preparation method comprises the following steps: heating the sodium laurate hydrogel with the formula amount at 50-60 ℃, stirring and dissolving, when the mixed solution is transparent, adding the polyether, the dimethyl siloxane graft copolymer and the modified polydimethylsiloxane in sequence at the stirring speed of 3500 revolutions per minute, and stirring for 20-40min; stirring at 5500 rpm, adding modified chitosan catalyst and silver bromide-silver/nano silicon in turn, and dispersing for 30-40min; the aqueous solution is slowly injected along the wall to adjust the viscosity, continuously stirred at 2000 rpm, gradually cooled, stirred for 60 minutes and cooled to room temperature, and the finished product is prepared.
Example 2
Comprises the following components in parts by weight: 18 parts of modified chitosan catalyst, 15 parts of silver bromide-silver/nano silicon, 25 parts of sodium alginate hydrogel, 3 parts of polyether and dimethylsiloxane graft copolymer, 2 parts of modified polydimethylsiloxane and the balance of water;
wherein the modified chitosan catalyst is prepared by the following method: after dissolving cholesterol in pyridine, succinic anhydride was added, the molar ratio of cholesterol to succinic anhydride was 1:3, a step of; reacting for 28h at 90 ℃, washing, filtering and drying reactants, and adding acetone for dissolving and crystallizing to obtain cholesterol hemisuccinate; dissolving chitosan powder in acetic acid solution with the mass fraction of 5%wt, then injecting the chitosan solution into NaOH alcohol solution with the mass fraction of 10%wt to obtain hollow spheres, and washing and freeze-drying to obtain chitosan microspheres; placing chitosan microspheres in water for swelling, and sequentially adding absolute ethyl alcohol and a mass ratio of 1:2, and an ethanol solution of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, cholesterol hemisuccinate, wherein the molar ratio of the chitosan microsphere to the cholesterol hemisuccinate is 1:0.35, after reacting for 2-4d, placing the reaction solution in a dialysis bag, sequentially dialyzing for 2-3d by using 85% ethanol solution, 75% ethanol solution, 65% ethanol solution and 55% ethanol solution as dialysis media and distilled water respectively, changing the dialysis media every 4-5h, filtering the dialysis solution, and freeze-drying to obtain modified chitosan; adding 1.2 wt% molybdenum salt water solution and 80% ethanol into the modified chitosan, heating to 75-85 ℃, reacting for 2-3h, filtering and drying to obtain the product;
silver bromide-silver/nano-silicon is prepared by the following method: the monocrystalline silicon wafer is used as a base material, a columnar silicon nano-pore array is formed by adopting a hydrothermal corrosion method, and the hydrothermal corrosion method comprises the following conditions: the concentration of hydrofluoric acid is 12mol/L, the concentration of ferric nitrate is 0.04mol/L, and the etching is carried out for 5min at 70 ℃; the pore diameter of the silicon column on the substrate gradually decreases from 40+/-5 nm at the top of the column to 15+/-5 nm at the bottom of the column, the size range of the silicon column is 1.9-2.5nm, the distance between two adjacent pore walls is 3-8 mu m, and the thickness of the pore array area is 15-20 mu m; dispersing nano silicon in deionized water to form a 1% nano silicon suspension, stirring, adding silver bromide solution, adjusting the pH value to 7, stirring for 4-7h in dark environment, centrifuging, and drying to obtain silver bromide/nano silicon; dispersing silver bromide/nano silicon in deionized water to form a 1% suspension, stirring for 1-1.5h under illumination, centrifuging, and drying.
The preparation method is the same as in example 1.
Example 3
Comprises the following components in parts by weight: 15 parts of modified chitosan catalyst, 10 parts of silver bromide-silver/nano silicon, 22 parts of polyvinyl alcohol hydrogel, 1.5 parts of polyether-dimethylsiloxane graft copolymer, 1 part of modified polydimethylsiloxane and the balance of water;
wherein the modified chitosan catalyst is prepared by the following method: after dissolving cholesterol in pyridine, succinic anhydride was added, the molar ratio of cholesterol to succinic anhydride was 1:2.6; reacting for 20-28h at 80-90 ℃, washing, filtering and drying reactants, and adding acetone for dissolving and crystallizing to obtain cholesterol hemisuccinate; dissolving chitosan powder in acetic acid solution with the mass fraction of 3.5 percent, then injecting the chitosan solution into NaOH alcohol solution with the mass fraction of 8 percent to obtain hollow spheres, and washing and freeze-drying to obtain chitosan microspheres; placing chitosan microspheres in water for swelling, and sequentially adding absolute ethyl alcohol and a mass ratio of 1:1.8 ethanol solution of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, cholesterol hemisuccinate, molar ratio of chitosan microspheres to cholesterol hemisuccinate 1:0.28, after reacting for 2-4d, placing the reaction solution in a dialysis bag, sequentially dialyzing for 2-3d by using 85% ethanol solution, 75% ethanol solution, 65% ethanol solution and 55% ethanol solution as dialysis media and distilled water respectively, changing the dialysis media every 4-5h, filtering the dialysis solution, and freeze-drying to obtain modified chitosan; adding 1.0 wt% molybdenum salt water solution and 75% ethanol into the modified chitosan, heating to 75-85 ℃, reacting for 2-3h, filtering and drying to obtain the product;
silver bromide-silver/nano-silicon is prepared by the following method: the monocrystalline silicon wafer is used as a base material, a columnar silicon nano-pore array is formed by adopting a hydrothermal corrosion method, and the hydrothermal corrosion method comprises the following conditions: the concentration of hydrofluoric acid is 12mol/L, the concentration of ferric nitrate is 0.04mol/L, and the etching is carried out for 5min at 70 ℃; the pore diameter of the silicon column on the substrate gradually decreases from 40+/-5 nm at the top of the column to 15+/-5 nm at the bottom of the column, the size range of the silicon column is 1.9-2.5nm, the distance between two adjacent pore walls is 3-8 mu m, and the thickness of the pore array area is 15-20 mu m; dispersing nano silicon in deionized water to form a 1% nano silicon suspension, stirring, adding silver bromide solution, adjusting the pH value to 7, stirring for 4-7h in dark environment, centrifuging, and drying to obtain silver bromide/nano silicon; dispersing silver bromide/nano silicon in deionized water to form a 1% suspension, stirring for 1-1.5h under illumination, centrifuging, and drying.
The preparation method is the same as in example 1.
Example 4
Comprises the following components in parts by weight: 18 parts of modified chitosan catalyst, 8 parts of silver bromide-silver/nano silicon, 22 parts of polyacrylamide hydrogel, 2 parts of polyether and dimethylsiloxane graft copolymer, 1.5 parts of modified polydimethylsiloxane and the balance of water;
wherein the modified chitosan catalyst is prepared by the following method: after dissolving cholesterol in pyridine, succinic anhydride was added, the molar ratio of cholesterol to succinic anhydride was 1:2.5; reacting at 80 ℃ for 24 hours, washing, filtering and drying reactants, and adding acetone for dissolving and crystallizing to obtain cholesterol hemisuccinate; dissolving chitosan powder in acetic acid solution with the mass fraction of 4.5 percent, then injecting the chitosan solution into NaOH alcohol solution with the mass fraction of 6 percent to obtain hollow spheres, and washing and freeze-drying to obtain chitosan microspheres; placing chitosan microspheres in water for swelling, and sequentially adding absolute ethyl alcohol and a mass ratio of 1:1.8 ethanol solution of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, cholesterol hemisuccinate, molar ratio of chitosan microspheres to cholesterol hemisuccinate 1:0.3, after reacting for 2-4d, placing the reaction solution in a dialysis bag, sequentially dialyzing for 2-3d by using 85% ethanol solution, 75% ethanol solution, 65% ethanol solution and 55% ethanol solution as dialysis media and distilled water respectively, changing the dialysis media every 4-5h, filtering the dialysis solution, and freeze-drying to obtain modified chitosan; adding 0.8 wt% molybdenum salt water solution and 80% ethanol into the modified chitosan, heating to 75-85 ℃, reacting for 2-3h, filtering and drying to obtain the product;
silver bromide-silver/nano-silicon is prepared by the following method: the monocrystalline silicon wafer is used as a base material, a columnar silicon nano-pore array is formed by adopting a hydrothermal corrosion method, and the hydrothermal corrosion method comprises the following conditions: the concentration of hydrofluoric acid is 15mol/L, the concentration of ferric nitrate is 0.07mol/L, and the etching is carried out for 60min at 170 ℃; the pore diameter of the silicon column on the substrate gradually decreases from 40+/-5 nm at the top of the column to 15+/-5 nm at the bottom of the column, the size range of the silicon column is 4.0-4.5nm, the distance between two adjacent pore walls is 20-25 mu m, and the thickness of the pore array area is 2-10 mu m; dispersing nano silicon in deionized water to form a 3% nano silicon suspension, stirring, adding silver bromide solution, adjusting the pH value to 9, stirring for 4-7h in dark environment, centrifuging, and drying to obtain silver bromide/nano silicon; dispersing silver bromide/nano silicon in deionized water to form a 3% suspension, stirring for 1-1.5h under illumination, centrifuging, and drying.
Example 5
Comprises the following components in parts by weight: 16 parts of modified chitosan catalyst, 15 parts of silver bromide-silver/nano silicon, 15 parts of sodium laurate hydrogel, 10 parts of agar hydrogel, 3 parts of polyether-dimethylsiloxane graft copolymer, 2 parts of modified polydimethylsiloxane and the balance of water;
wherein the modified chitosan catalyst is prepared by the following method: after dissolving cholesterol in pyridine, succinic anhydride was added, the molar ratio of cholesterol to succinic anhydride was 1:2.5; reacting at 80 ℃ for 24 hours, washing, filtering and drying reactants, and adding acetone for dissolving and crystallizing to obtain cholesterol hemisuccinate; dissolving chitosan powder in acetic acid solution with the mass fraction of 4.5 percent, then injecting the chitosan solution into NaOH alcohol solution with the mass fraction of 6 percent to obtain hollow spheres, and washing and freeze-drying to obtain chitosan microspheres; placing chitosan microspheres in water for swelling, and sequentially adding absolute ethyl alcohol and a mass ratio of 1:1.8 ethanol solution of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, cholesterol hemisuccinate, molar ratio of chitosan microspheres to cholesterol hemisuccinate 1:0.3, after reacting for 2-4d, placing the reaction solution in a dialysis bag, sequentially dialyzing for 2-3d by using 85% ethanol solution, 75% ethanol solution, 65% ethanol solution and 55% ethanol solution as dialysis media and distilled water respectively, changing the dialysis media every 4-5h, filtering the dialysis solution, and freeze-drying to obtain modified chitosan; adding 0.8 wt% molybdenum salt water solution and 80% ethanol into the modified chitosan, heating to 75-85 ℃, reacting for 2-3h, filtering and drying to obtain the product;
silver bromide-silver/nano-silicon is prepared by the following method: the monocrystalline silicon wafer is used as a base material, a columnar silicon nano-pore array is formed by adopting a hydrothermal corrosion method, and the hydrothermal corrosion method comprises the following conditions: the concentration of hydrofluoric acid is 13mol/L, the concentration of ferric nitrate is 0.05mol/L, and the etching is carried out for 60min at 100 ℃; the pore diameter of the silicon column on the substrate gradually decreases from 40+/-5 nm at the top of the column to 15+/-5 nm at the bottom of the column, the size range of the silicon column is 3-3.5nm, the distance between two adjacent pore walls is 10-15 mu m, and the thickness of the pore array area is 18-23 mu m; dispersing nano silicon in deionized water to form 1.5% nano silicon suspension, stirring, adding silver bromide solution, adjusting the pH value to 8, stirring for 4-7h in dark environment, centrifuging, and drying to obtain silver bromide/nano silicon; dispersing silver bromide/nano silicon in deionized water to form a 1.5% suspension, stirring for 1-1.5h under illumination, centrifuging, and drying.
Example 6
Comprises the following components in parts by weight: 12 parts of modified chitosan catalyst, 15 parts of silver bromide-silver/nano silicon, 22 parts of polyethylene glycol hydrogel, 2 parts of polyether and dimethylsiloxane graft copolymer, 2 parts of modified polydimethylsiloxane and the balance of water;
wherein the modified chitosan catalyst is prepared by the following method: after dissolving cholesterol in pyridine, succinic anhydride was added, the molar ratio of cholesterol to succinic anhydride was 1:2.5; reacting at 80 ℃ for 24 hours, washing, filtering and drying reactants, and adding acetone for dissolving and crystallizing to obtain cholesterol hemisuccinate; dissolving chitosan powder in acetic acid solution with the mass fraction of 4.5 percent, then injecting the chitosan solution into NaOH alcohol solution with the mass fraction of 6 percent to obtain hollow spheres, and washing and freeze-drying to obtain chitosan microspheres; placing chitosan microspheres in water for swelling, and sequentially adding absolute ethyl alcohol and a mass ratio of 1:1.8 ethanol solution of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide, cholesterol hemisuccinate, molar ratio of chitosan microspheres to cholesterol hemisuccinate 1:0.3, after reacting for 2-4d, placing the reaction solution in a dialysis bag, sequentially dialyzing for 2-3d by using 85% ethanol solution, 75% ethanol solution, 65% ethanol solution and 55% ethanol solution as dialysis media and distilled water respectively, changing the dialysis media every 4-5h, filtering the dialysis solution, and freeze-drying to obtain modified chitosan; adding 0.8 wt% molybdenum salt water solution and 80% ethanol into the modified chitosan, heating to 75-85 ℃, reacting for 2-3h, filtering and drying to obtain the product;
silver bromide-silver/nano-silicon is prepared by the following method: the monocrystalline silicon wafer is used as a base material, a columnar silicon nano-pore array is formed by adopting a hydrothermal corrosion method, and the hydrothermal corrosion method comprises the following conditions: the concentration of hydrofluoric acid is 15mol/L, the concentration of ferric nitrate is 0.07mol/L, and the etching is carried out for 40min at 150 ℃; the pore diameter of the silicon column on the substrate gradually decreases from 40+/-5 nm at the top of the column to 15+/-5 nm at the bottom of the column, the size range of the silicon column is 3.8-4.2nm, the distance between two adjacent pore walls is 16-23 mu m, and the thickness of the pore array area is 8-15 mu m; dispersing nano silicon in deionized water to form 2.5% nano silicon suspension, stirring, adding silver bromide solution, adjusting pH value to 8, stirring for 4-7h in dark environment, centrifuging, and drying to obtain silver bromide/nano silicon; dispersing silver bromide/nano silicon in deionized water to form 2.5% suspension, stirring for 1-1.5h under illumination, centrifuging, and drying.
Comparative example 1
On the basis of example 1, titanium dioxide was replaced equally with the modified chitosan catalyst.
Comparative example 2
Based on example 2, chitosan was replaced with chitosan microspheres in equal amounts.
Comparative example 3
On the basis of example 3, chitosan was replaced with an equal amount of modified chitosan.
Comparative example 4
Based on example 4, the silver bromide-silver/molecular sieve was replaced with an equal amount of silver bromide-silver/nano-silicon.
Comparative example 5
Based on example 5, the natural silicon was replaced with the silver bromide-silver/nano-silicon in equal amounts.
Comparative example 6
On the basis of example 6, the natural silicon is replaced by the nano silicon in equal amount.
The following tests were carried out on the high-efficiency remover prepared by the invention:
(1) Structure and composition testing (example 1):
FIG. 1a is a FESEM of nano-silicon, which is observed to consist of a large number of regularly arranged, micron-sized silicon pillars; fig. 1b is a FESEM photograph of silver-silver bromide/nano silicon, and it is observed that the top of the column of the sample forms a film composed of particles with smaller particle size, while the inter-column region is a large number of nano-grains with relatively uniform size and loose distribution, and the particle size and dispersibility of the silver bromide are very good, and the mass percentages of the elements obtained from EDS spectrum are: 64.13% of O, 34.64% of Si, 0.48% of Br, 0.75% of Ag, and the content of Ag is slightly larger than Br, which indicates that a small amount of Ag+ in AgBr is reduced to Ag under visible light, so that the content of Ag on the surface of the Ag is larger than Br.
Fig. 2 is a TEM image of modified chitosan, and left and right images are 20000 x and 40000 x magnification, respectively, and it is observed that the nanoparticles have a uniform spherical structure, good sphericity and uniform particle size distribution, indicating that smooth non-sticky materials are present.
(2) Air purification performance test:
the method comprises the steps of simulating an environment with pollution concentration of formaldehyde of 200 mug/L in a sealed light-resistant climatic box, spraying a sample on non-woven fabrics of 0.1m multiplied by 0.1m in the sealed light-resistant climatic box, wherein the spraying amount in each box is the same, the climatic box is placed in an indoor visible light environment, the sample to be tested fully receives visible light, a climatic box cover is closed and sealed, a bottom air pressure balance port is connected to a water tank so as to keep the air pressure in the climatic box and the pollution gas concentration during sampling, a convection fan is started, the gas concentration in each place in the climatic box is kept equal, an air inlet is closed after the pollution gas is introduced to the initial concentration, and a photodegradation process is started; sampling air in a climatic box by a micro sampling pump, and determining the gas content change in the degradation process by adopting a gas chromatography;
the contaminant gas removal rate is calculated according to equation (1): n= (C 0 —C t )V/(S×t) (1)
Where n is the sample contaminant gas removal rate, μg/(m2·s); c (C) 0 To initiate concentration of contaminating gases at the beginning of degradation, μg/m 3 ；C t For the equilibrium concentration of the contaminating gases at time t, μg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the V is the gas volume of the experiment box, m 3 The method comprises the steps of carrying out a first treatment on the surface of the S is the surface area of the paint, m 2 The method comprises the steps of carrying out a first treatment on the surface of the t is the time elapsed from the start of the test to the end of degradation, s;
the removal rate of the polluted gas is calculated according to the formula (2): q= (C 0 —C t )/C 0 ×100％ (2)
Wherein q is the removal rate of the polluted gas,%; c (C) 0 To initiate concentration of contaminating gases at the beginning of degradation, μg/m 3 ；C t For the equilibrium concentration of the contaminating gases at time t, μg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the t is the time elapsed from the start of the test to the end of degradation, s; the formaldehyde is replaced by ammonia, NOx, methyl mercaptan and methylBenzene was repeatedly tested in the same manner and the 6h test results are shown in table 1 below:
TABLE 1
(3) Air purification durability test
The environment with the pollution concentration of 200 mug/L of the simulated formaldehyde is simulated in a sealed light-resistant climatic box, a sample is sprayed on a non-woven fabric with the concentration of 0.1m multiplied by 0.1m in the sealed light-resistant climatic box, the spraying amount in each box is the same, the climatic box is placed in an indoor visible light environment, the sample to be tested fully receives visible light, a climatic box cover is closed and sealed, a bottom air pressure balance port is connected to a water tank so as to keep the air pressure in the climatic box and the pollution gas concentration during sampling, a convection fan is started, the concentration of each gas in the climatic box is kept equal, an air inlet is closed after the pollution gas is introduced to the initial concentration, the detection is carried out, the initial concentration of the formaldehyde in the box is recorded, the formaldehyde concentration in the box is recorded again after 6h, 24h, 3d, 7d, 15d and 30d, the formaldehyde clearance is calculated, and the test results are shown in the following table 2:
TABLE 2
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered by the scope of the claims of the present invention.
Claims (11)
1. The efficient remover for indoor formaldehyde and organic volatile matters is characterized by comprising the following components in parts by weight:
12-18 parts of modified chitosan catalyst, 8-15 parts of silver bromide-silver/nano silicon, 20-25 parts of hydrogel, 1-3 parts of wetting agent, 0.5-2 parts of defoamer and the balance of water;
the modified chitosan catalyst is prepared by attaching molybdate to modified chitosan; the modified chitosan is prepared by the following method: after dissolving cholesterol in pyridine, succinic anhydride was added, the molar ratio of cholesterol to succinic anhydride was 1: (2-3); reacting for 20-28h at 80-90 ℃, washing, filtering and drying reactants, and adding acetone for dissolving and crystallizing to obtain cholesterol hemisuccinate; after the chitosan microspheres are put into water for swelling, absolute ethyl alcohol, a coupling agent and an ethanol solution of cholesterol hemisuccinate are sequentially added, wherein the molar ratio of the chitosan microspheres to the cholesterol hemisuccinate is 1: (0.2-0.35), after 2-4d of reaction, placing the reaction solution into a dialysis bag, dialyzing with a dialysis medium, filtering the dialysis solution, and freeze-drying to obtain the product;
silver bromide-silver/nano-silicon is prepared by the following method: dispersing nano silicon in deionized water to form 1-3% nano silicon suspension, stirring, adding silver bromide solution, adjusting pH value to 7-9, stirring for 4-7h in dark environment, centrifuging, and drying to obtain silver bromide/nano silicon; dispersing silver bromide/nano silicon in deionized water to form a 1-3% suspension, stirring for 1-1.5h under illumination, centrifuging, and drying to obtain the final product; the nano silicon uses monocrystalline silicon wafer as base material, adopts hydrothermal corrosion method to form silicon nano hole array, the pore diameter on the silicon column is gradually reduced from 40+ -5 nm on the top of the column to 15+ -5 nm on the bottom of the column, the size range of the silicon column is 1.9-4.5nm, and the thickness of the hole array region is 2-20 μm.
2. The efficient remover for indoor formaldehyde and organic volatile matters as set forth in claim 1, wherein: the modified chitosan catalyst is prepared by the following method: adding 0.5-1.2 wt% molybdic acid salt water solution and 70-80% ethanol into the modified chitosan, heating to 75-85 ℃, reacting for 2-3h, filtering and drying to obtain the final product.
3. The efficient remover for indoor formaldehyde and organic volatile matters as set forth in claim 1, wherein: the dialysis process is as follows: sequentially using ethanol solutions with different concentrations as dialysis media and distilled water to dialyze for 2-3d respectively, and changing the dialysis media every 4-5 h.
4. The efficient remover for indoor formaldehyde and organic volatile matters as set forth in claim 1, wherein: the dialysis medium is 85% ethanol solution, 75% ethanol solution, 65% ethanol solution, 55% ethanol solution.
5. The efficient remover for indoor formaldehyde and organic volatile matters as set forth in claim 1, wherein: the mass ratio of the coupling agent is 1: (1.5-2) 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and N-hydroxysuccinimide.
6. The efficient remover for indoor formaldehyde and organic volatile matters as set forth in claim 1, wherein: the chitosan microsphere is prepared by the following method: dissolving chitosan powder in acetic acid solution with the mass fraction of 1-5%, then injecting the chitosan solution into NaOH alcohol solution with the mass fraction of 5-10% to obtain hollow spheres, and washing and freeze-drying the hollow spheres to obtain the chitosan gel.
7. The efficient remover for indoor formaldehyde and organic volatile matters as set forth in claim 1, wherein: the hydrothermal corrosion method adopts a mixed aqueous solution of hydrofluoric acid and ferric nitrate as the hydrothermal corrosion liquid, wherein the concentration of the hydrofluoric acid is 12-15mol/L, and the concentration of the ferric nitrate is 0.04-0.07mol/L.
8. The efficient remover for indoor formaldehyde and organic volatile matters as set forth in claim 1, wherein: the hydrogel is one or more than two of sodium laurate hydrogel, sodium alginate hydrogel, polyvinyl alcohol hydrogel, polyacrylamide hydrogel, agar hydrogel and polyethylene glycol hydrogel.
9. A method for preparing the efficient remover for indoor formaldehyde and organic volatile matters as claimed in any one of claims 1 to 8, which is characterized by comprising the following steps: heating and dissolving the hydrogel until the hydrogel is transparent, adding a wetting agent and a defoaming agent, and dispersing at medium speed for 20-40min; then adding modified chitosan catalyst, silver bromide-silver/nano silicon, and dispersing at high speed for 30-40min; water was added to adjust the viscosity.
10. Use of a high efficiency remover according to any of claims 1-8 in indoor air purification.
11. The use according to claim 10, characterized in that: the remover is coated on the surface of the substrate in a brushing, roller coating, dip coating or spraying mode.
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