CN118649553A - Adsorption and photocatalysis synergistic air purification material and preparation method and application thereof - Google Patents
Adsorption and photocatalysis synergistic air purification material and preparation method and application thereof Download PDFInfo
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- CN118649553A CN118649553A CN202410878441.5A CN202410878441A CN118649553A CN 118649553 A CN118649553 A CN 118649553A CN 202410878441 A CN202410878441 A CN 202410878441A CN 118649553 A CN118649553 A CN 118649553A
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- manganese oxide
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- 239000000463 material Substances 0.000 title claims abstract description 102
- 238000004887 air purification Methods 0.000 title claims abstract description 85
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 62
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 36
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 21
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 266
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 175
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 87
- 239000010439 graphite Substances 0.000 claims abstract description 87
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims abstract description 55
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical group [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims description 51
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 35
- -1 manganese oxide compound Chemical class 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 21
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- 238000000746 purification Methods 0.000 claims description 12
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003344 environmental pollutant Substances 0.000 claims description 10
- 231100000719 pollutant Toxicity 0.000 claims description 10
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- 229920000877 Melamine resin Polymers 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229940099596 manganese sulfate Drugs 0.000 claims description 8
- 239000011702 manganese sulphate Substances 0.000 claims description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 6
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 claims description 6
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 4
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 32
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- 238000012360 testing method Methods 0.000 description 24
- 229910016978 MnOx Inorganic materials 0.000 description 23
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- 238000006243 chemical reaction Methods 0.000 description 14
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- 238000011065 in-situ storage Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
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- 239000001301 oxygen Substances 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 238000010926 purge Methods 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229940087305 limonene Drugs 0.000 description 2
- 235000001510 limonene Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
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- 230000009257 reactivity Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
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- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
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Classifications
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- 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
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Abstract
The invention provides an adsorption and photocatalysis synergistic air purification material and a preparation method and application thereof, and belongs to the technical field of air purification. The adsorption and photocatalysis synergistic air purification material comprises: manganese oxide, graphite phase carbon nitride, activated carbon and periodic acid layer; wherein, the manganese oxide forms heterojunction with graphite phase carbon nitride, and is attached to the inner and outer surfaces of the activated carbon, and the periodic acid layer wraps the manganese oxide and the graphite phase carbon nitride forming heterojunction and the activated carbon.
Description
Technical Field
The invention belongs to the technical field of air purification, and particularly relates to an adsorption and photocatalysis synergistic air purification material, and a preparation method and application thereof.
Background
The dining place is a common indoor odor place. During cooking, a large amount of Volatile Organic Compounds (VOCs) and oil droplets are generated and discharged into the environment. VOCs in cooking fumes have been detected as containing various hydrocarbons, such as alkanes, alkenes, aldehydes, ketones, and aromatics. Wherein, acetaldehyde, limonene and the like are used as precursors of ozone, ozone can be generated through photochemical reaction, and olefins such as limonene and the like can generate secondary organic aerosol under the actions of ozone with a certain concentration and photolysis, thereby endangering natural environment and human health. In terms of odor perception, aldehyde ketone compounds are key species generating off-flavors in eating places, are the main volatiles of various food materials and oil smoke, and have higher concentration in the eating places. While the olfactory threshold of aldehyde ketones is relatively low (i.e., its characteristic pungent odor is perceived by humans at low concentrations), ranging from about 2.59 to 9.01 μg/m 3. In order to improve the air quality of the dining place, reduce the harm of gaseous organic matters to human bodies and remove gaseous aldehyde ketone pollutants, it is particularly important.
Purification techniques suitable for use in dining venues include: adsorption, catalytic oxidation, photocatalysis, ozone oxidation. In recent years, many adsorbent materials have been developed to remove indoor gaseous aldehyde-ketone pollutants. However, most of the adsorption materials have limited adsorption capacity, and desorption occurs after adsorption saturation, and secondary pollution is generated in the desorption process. Photocatalytic technology is considered to be the first technology for purifying gas with lower concentration because it is suitable for purifying gas with lower concentration and smaller flow rate and can operate under mild conditions. However, this technology also has its own application limitations, such as: the purification efficiency is low; ultraviolet light degradation produces ozone as a byproduct; and cannot selectively purify a single contaminant.
Disclosure of Invention
Aiming at the technical problems, the invention provides an adsorption and photocatalysis synergistic air purification material, and a preparation method and application thereof, so as to at least partially solve the technical problems.
As a first aspect of the present invention, there is provided an adsorption and photocatalytic synergistic air purification material comprising: manganese oxide, graphite phase carbon nitride, activated carbon and periodic acid layer; wherein, the manganese oxide forms heterojunction with graphite phase carbon nitride, and is attached to the inner and outer surfaces of the activated carbon, and the periodic acid layer wraps the manganese oxide and the graphite phase carbon nitride forming heterojunction and the activated carbon.
As a second aspect of the present invention, there is provided a method for preparing an adsorption and photocatalytic synergistic air purification material, comprising: mixing and calcining a manganese oxide, graphite-phase carbon nitride and active carbon to obtain an air purification precursor material; immersing an air purification precursor material in a periodic acid solution, and drying to obtain an air purification material; wherein, the manganese oxide and the graphite phase carbon nitride form heterojunction in the calcining process, and are attached to the inner and outer surfaces of the activated carbon, and the periodic acid layer wraps the manganese oxide and the graphite phase carbon nitride forming heterojunction and the activated carbon in the impregnating process.
As a third aspect of the present invention, there is provided an application of an adsorption and photocatalytic synergistic air purification material in air purification.
Based on the technical scheme, the adsorption and photocatalysis synergistic air purification material provided by the invention has at least one of the following beneficial effects:
(1) In the embodiment of the invention, the air purifying material consists of manganese oxide, graphite phase carbon nitride, active carbon and a periodic acid layer. The manganese oxide and the graphite phase carbon nitride form a heterojunction, part of the manganese oxide and the graphite phase carbon nitride are loaded on the outer surface of the activated carbon, and part of the manganese oxide and the graphite phase carbon nitride enter the pores of the activated carbon and are anchored on the inner surface of the activated carbon; the periodic acid layer encapsulates the manganese oxide, graphite phase carbon nitride and activated carbon. And selectively adsorbing and fixing hydrophilic volatile organic compounds in the air by utilizing a periodic acid layer, generating superoxide radicals by using a heterojunction formed by a manganese oxide compound and graphite-phase carbon nitride under illumination, and oxidatively decomposing the adsorbed and fixed hydrophilic volatile organic compounds into carbon dioxide and water. The active carbon provides more adsorption sites for the manganese oxide and the graphite phase carbon nitride so as to enhance the contact between the manganese oxide and the graphite phase carbon nitride and the hydrophilic volatile organic compound and enhance the oxidative decomposition of the hydrophilic volatile organic compound. The invention combines adsorption and photocatalysis, solves the problem that adsorption saturation exists in the activated carbon of the adsorption material, and solves the problem that the adsorption sites of the manganese oxide compound and the graphite phase carbon nitride of the photocatalyst are less, prolongs the service life of the activated carbon of the adsorption material, and improves the catalytic efficiency of the manganese oxide compound and the graphite phase carbon nitride of the photocatalyst, thereby improving the purification efficiency of the air purification material.
(2) In the embodiment of the invention, the manganese oxide, the graphite phase carbon nitride and the activated carbon are mixed and calcined, the manganese oxide and the graphite phase carbon nitride form a heterojunction in the calcining process, part of the manganese oxide and the graphite phase carbon nitride are loaded on the outer surface of the activated carbon, and part of the manganese oxide and the graphite phase carbon nitride enter the pores of the activated carbon and are anchored on the inner surface of the activated carbon, so that the air purification precursor material is obtained. And (3) immersing the air purification precursor material in a periodic acid solution, forming a periodic acid layer on the surfaces of a manganese oxide compound, graphite-phase carbon nitride and active carbon which form heterojunction in the immersing process, and drying to obtain the air purification material. The method for preparing the air purifying material is simple and convenient, is easy to operate, and has a large-scale production prospect.
(3) In the embodiment of the invention, the periodic acid layer is used for adsorbing water vapor in the air to form an in-situ water layer (self-wetting layer) on the surface of the air purification material, so that a unique air/water/air purification material three-phase system is formed. The in-situ water layer adsorbs hydrophilic volatile organic compounds, and the activated carbon adsorbs hydrophilic volatile organic compounds in the in-situ water layer, so that more reaction sites are provided for oxidizing and decomposing the hydrophilic volatile organic compounds by manganese oxide and graphite phase carbon nitride. Under illumination, the heterojunction formed by the manganese oxide and the graphite phase carbon nitride generates superoxide radical, and the hydrophilic volatile organic compound adsorbed by the activated carbon is oxidized and decomposed into carbon dioxide and water. By utilizing the synergistic effect of adsorption and photocatalysis, the purification efficiency of the air purification material can be effectively improved, and the purposes of more economical, efficient and selective air purification are realized.
Drawings
FIG. 1 is a scanning electron microscope image of the activated carbon of example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of graphite phase carbon nitride of comparative example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the air purification material of example 1 of the present invention;
FIG. 4 is a graph showing the nitrogen adsorption and desorption of the activated carbon of example 1 and the air purge precursor materials of examples 1, 3, 5 and comparative example 1 and the graphite phase carbon nitride of comparative example 1 according to the present invention;
FIG. 5 is a schematic diagram of a continuous flow piping system for testing acetaldehyde cleaning capacity in accordance with an embodiment of the invention;
FIG. 6 is a schematic diagram of a glass fiber filter groove required for loading a test material in a catalytic reaction chamber in the continuous flow piping system of FIG. 5;
FIG. 7 is a graph showing the results of the acetaldehyde removal test in comparative examples 1 to 4 and example 10;
FIG. 8 is a graph showing the results of the test of the adsorption performance of acetaldehyde in the continuous flow dark environment of examples 1 to 5 and comparative example 1 according to the present invention;
FIG. 9 is a graph showing the results of the acetaldehyde removal test in examples 1 to 10 and comparative example 4 of the present invention.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
In the process of realizing the inventive concept, the prior art has the problems of short service life and no selectivity of the adsorption material caused by adsorption saturation when the adsorption material is used for air purification. When the photocatalytic material is independently used for purifying air, the problems of fewer adsorption sites and lower purification efficiency exist. Therefore, the invention provides an adsorption and photocatalysis synergistic air purification material, and a preparation method and application thereof. The adsorption and photocatalysis synergistic air purification material comprises manganese oxide, graphite phase carbon nitride, activated carbon and periodic acid.
The activated carbon has the problem of adsorption saturation when used as an adsorption material for air purification, so that the service life is lower; when the activated carbon is saturated, desorption occurs, so that secondary pollution is caused; and the activated carbon has no selectivity and cannot effectively remove single pollutant. Graphite phase carbon nitride is an excellent photocatalytic material, but has low quantum efficiency, low visible light photoelectric conversion rate, limited active sites and difficult recovery.
The experimental differences in the air purification research are large, and the advantages and disadvantages of the base materials cannot be systematically compared, so that the more mature formaldehyde purification research is mainly referred to when the base materials are screened. The reactivity of the different metal oxides with aldehydes is different, wherein the removal rate of silver oxide, palladium oxide, cobalt oxide, manganese dioxide, titanium dioxide, cerium oxide and manganic oxide on formaldehyde is higher than 50%, and lanthanum oxide, zinc oxide and vanadium pentoxide have little effect on formaldehyde removal. Among these materials, manganese dioxide has high formaldehyde purifying reactivity, and manganese dioxide has different crystal structures such as α, β, γ, λ, δ and ε -MnO 2, and these structurally-regulated manganese dioxide can significantly affect the activity of oxidative decomposition of formaldehyde. However, when a manganese oxide is used alone as a photocatalyst, there are problems of low catalytic efficiency and limited light absorption range. The external electronic structure of manganese is 3d 54s2, the manganese oxide compound obtained by mixing and calcining manganese dioxide and manganous manganic oxide has multiple valence states ranging from-3 to +7, and electrons can be regulated to generate a mobile electronic environment required by oxidation-reduction reaction. Thus, when manganese oxide is doped with other photocatalysts, a synergistic effect is generated, and oxygen vacancies having strong redox characteristics can be significantly increased.
However, when manganese oxide and graphite phase carbon nitride are mixed and calcined to form a heterojunction and used as a photocatalyst for air purification, the problem of insufficient adsorption sites exists, and secondary pollution is caused by volatilization of intermediate products in the purification process. Further, when the air purification material composed of the activated carbon, the manganese oxide and the graphite phase carbon nitride is used for air purification, inorganic salts and macromolecular volatile organic compounds in the air occupy adsorption sites of the activated carbon, so that super oxygen free radicals generated by the manganese oxide and the graphite phase carbon nitride are consumed, and the air purification efficiency is reduced.
Therefore, the invention provides an adsorption and photocatalysis synergistic air purification material which comprises manganese oxide, graphite phase carbon nitride, active carbon and periodic acid. Wrapping a layer of periodic acid outside the activated carbon, the manganese oxide and the graphite phase carbon nitride, and utilizing the periodic acid to selectively adsorb and fix hydrophilic volatile organic compounds (such as aldehyde ketone) in the air, so that the hydrophilic volatile organic compounds which are adsorbed and fixed are conveyed to the activated carbon. On the one hand, the active carbon is used as a carrier to load manganese oxide and graphite phase carbon nitride which form heterojunction; on the other hand, reaction sites are provided for the manganese oxide and graphite phase carbon nitride forming the heterojunction to enhance oxidative decomposition of the hydrophilic volatile organic compounds. Wherein, manganese oxide forming heterojunction and graphite phase carbon nitride oxidative decomposition hydrophilic volatile organic compound generate active oxygen substances through photocatalysis reaction. The mechanism of the photocatalytic reaction is as follows: when light having an energy greater than or equal to the catalyst energy gap is irradiated to the catalyst surface, electrons in the valence band of the catalyst will be excited to transition to its conduction band, leaving relatively stable holes in the valence band, thereby forming electron-hole pairs. Holes in the valence band of the catalyst can react with water or hydroxyl groups adsorbed on the surface to generate hydroxyl radicals (.oh). Electrons in the conduction band may combine with oxygen to produce superoxide radicals (.o 2 -). Semiconductors whose Conduction Band (CB) edge is more negative than the O 2/•O2 - potential can transfer photogenerated electrons to pi orbitals of oxygen molecules, thereby readily generating superoxide radicals. Superoxide radicals are more prone to react with compounds containing carbon-oxygen double bonds (e.g., aldehyde ketones), while hydroxyl radicals are more prone to react with compounds containing unsaturated bonds (e.g., benzoenes). Graphite-phase carbon nitrides, because of their relatively negative conduction bands, readily generate superoxide radicals under illumination, while graphite-phase carbon nitrides more readily generate superoxide radicals under illumination in the mobile electronic environment provided by manganese oxide compounds. Therefore, on the basis of selective adsorption of hydrophilic volatile organic compounds by periodic acid, the air purification material provided by the invention can selectively oxidize and decompose hydrophilic volatile organic compounds containing carbon-oxygen double bonds under the condition that manganese oxide and graphite phase carbon nitride are easier to generate superoxide radicals. According to the invention, the adsorption effect of the periodic acid and the activated carbon is cooperated with the oxidative decomposition of the photocatalyst, so that the air purification efficiency can be effectively improved while the service life of the air purification material is prolonged and the problem of insufficient adsorption saturation and reactive sites is solved.
As a first aspect of the present invention, there is provided an adsorption and photocatalytic synergistic air purification material comprising: manganese oxide, graphite phase carbon nitride, activated carbon and periodic acid layer; wherein, the manganese oxide forms heterojunction with graphite phase carbon nitride, and is attached to the inner and outer surfaces of the activated carbon, and the periodic acid layer wraps the manganese oxide and the graphite phase carbon nitride forming heterojunction and the activated carbon.
In the embodiment of the invention, the air purifying material consists of manganese oxide, graphite phase carbon nitride, active carbon and a periodic acid layer. The manganese oxide and the graphite phase carbon nitride form a heterojunction, part of the manganese oxide and the graphite phase carbon nitride are loaded on the outer surface of the activated carbon, and part of the manganese oxide and the graphite phase carbon nitride enter the pores of the activated carbon and are anchored on the inner surface of the activated carbon; the periodic acid layer encapsulates the manganese oxide, graphite phase carbon nitride and activated carbon. And selectively adsorbing and fixing hydrophilic volatile organic compounds in the air by utilizing a periodic acid layer, generating superoxide radicals by using a heterojunction formed by a manganese oxide compound and graphite-phase carbon nitride under illumination, and oxidatively decomposing the adsorbed and fixed hydrophilic volatile organic compounds into carbon dioxide and water. The active carbon provides more adsorption sites for the manganese oxide and the graphite phase carbon nitride so as to enhance the contact between the manganese oxide and the graphite phase carbon nitride and the hydrophilic volatile organic compound and enhance the oxidative decomposition of the hydrophilic volatile organic compound. The invention combines adsorption and photocatalysis, solves the problem that adsorption saturation exists in the activated carbon of the adsorption material, and solves the problem that the adsorption sites of the manganese oxide compound and the graphite phase carbon nitride of the photocatalyst are less, prolongs the service life of the activated carbon of the adsorption material, and improves the catalytic efficiency of the manganese oxide compound and the graphite phase carbon nitride of the photocatalyst, thereby improving the purification efficiency of the air purification material.
As a second aspect of the present invention, there is provided a method for preparing an adsorption and photocatalytic synergistic air purification material, comprising: mixing and calcining a manganese oxide, graphite-phase carbon nitride and active carbon to obtain an air purification precursor material; immersing an air purification precursor material in a periodic acid solution, and drying to obtain an air purification material; wherein, the manganese oxide and the graphite phase carbon nitride form heterojunction in the calcining process, and are attached to the inner and outer surfaces of the activated carbon, and the periodic acid layer wraps the manganese oxide and the graphite phase carbon nitride forming heterojunction and the activated carbon in the impregnating process.
In the embodiment of the invention, the manganese oxide, the graphite phase carbon nitride and the activated carbon are mixed and calcined, the manganese oxide and the graphite phase carbon nitride form a heterojunction in the calcining process, part of the manganese oxide and the graphite phase carbon nitride are loaded on the outer surface of the activated carbon, and part of the manganese oxide and the graphite phase carbon nitride enter the pores of the activated carbon and are anchored on the inner surface of the activated carbon, so that the air purification precursor material is obtained. And (3) immersing the air purification precursor material in a periodic acid solution, forming a periodic acid layer on the surfaces of a manganese oxide compound, graphite-phase carbon nitride and active carbon which form heterojunction in the immersing process, and drying to obtain the air purification material. The method for preparing the air purifying material is simple and convenient, is easy to operate, and has a large-scale production prospect.
According to an embodiment of the present invention, the periodic acid loading in the air cleaning material is 30-50%. Hydroxyl on the surface of periodic acid makes the periodic acid have higher hygroscopicity, hydrogen bonds are formed between water molecules and the hydroxyl, an in-situ water layer is formed on the surface of the air purification material, and then a unique air/water/air purification material three-phase system is formed. The in-situ water layer can be used for adsorbing hydrophilic volatile organic compounds more easily and reducing the adsorption of non-hydrophilic volatile organic compounds, so that the air purifying material can be used for selectively purifying pollutants in the air.
According to an embodiment of the present invention, the manganese oxide has a size of 10-300nm, the graphite phase carbon nitride has a size of 10-300nm, and the activated carbon has a size of 150-425 μm. The sizes of the manganese oxide, the graphite phase carbon nitride and the activated carbon can influence the specific surface area of the air purification material, so that the reaction site and the adsorption site during the purification reaction are influenced, and finally the purification efficiency of the air purification material is influenced.
According to an embodiment of the present invention, a manganese oxide, a graphite phase carbon nitride, and activated carbon are mixed and calcined to obtain an air-purifying precursor material, comprising: manganese oxide, graphite phase carbon nitride and active carbon are mixed and calcined at 320-370 ℃ for 2.5-4 hours. Specifically, the preparation method comprises the following steps: mixing manganese oxide, graphite phase carbon nitride and active carbon, adding into deionized water, and magnetically stirring at 30 ℃ for 30-60min to form a uniform mixed solution; then the mixed solution is kept for 8 to 16 hours at the temperature of 120 to 200 ℃; after the reaction is finished, respectively centrifugally washing with water and absolute ethyl alcohol for 3-5 times, and drying at 60-100 ℃ for 12-14h after washing; drying, heating to 320-370deg.C at a heating rate of 9-11 deg.C/min, and calcining at 320-370deg.C for 6-9 hr. In the mixing process, part of manganese oxide and graphite phase carbon nitride are loaded on the outer surface of the activated carbon, and part of manganese oxide and graphite phase carbon nitride enter the pores of the activated carbon and are anchored on the inner surface of the activated carbon; during calcination, the manganese oxide and the graphite phase carbon nitride form a heterojunction. Too high a calcination temperature or too low a calcination time may damage the heterojunction formed between the manganese oxide and the graphite phase carbon nitride.
According to an embodiment of the invention, the graphite phase carbon nitride is obtained by calcination of urea or melamine, wherein the calcination temperature at which the graphite phase carbon nitride is formed is 500-550 ℃ and the calcination time is 1.5-2.5h. Specifically, the preparation method comprises the following steps: placing urea or melamine in a ceramic crucible (the amount of urea or melamine is not more than half of the volume of the crucible), covering a crucible cover, wrapping the periphery of the crucible by aluminum foil paper, packaging, and placing in a muffle furnace for calcination; heating from room temperature to 500-550 ℃ at a heating rate of 3-8 ℃/min, calcining at 500-550 ℃ for 1.5-2.5h, naturally cooling to room temperature, and grinding to obtain powdered graphite-phase carbon nitride. The proper calcination temperature helps to promote the formation of graphite phase carbon nitride and the improvement of photocatalytic performance. Too high a temperature may lead to a decrease in active sites and a decrease in photocatalytic performance, while too low a temperature may lead to incomplete reactions. A suitable calcination time is to ensure that the starting materials are fully reacted and converted to graphitic carbon nitride. Too short a time may result in incomplete reaction, while too long a time may result in degradation of photocatalytic performance.
According to an embodiment of the present invention, the manganese oxide compound is obtained by mixing manganese dioxide and trimanganese tetroxide and calcining at a calcining temperature of 120-200 ℃ for 8-16 hours. Specifically, the preparation method comprises the following steps: mixing manganese dioxide and manganous-manganic oxide according to the mass ratio of 0-1, adding into deionized water, and magnetically stirring for 60-90min at 30 ℃; calcining at 120-200deg.C for 8-16h. Calcination is performed at a suitable temperature range to facilitate the formation of the manganese oxide compound and the improvement of the photocatalytic performance. Too low a temperature may result in incomplete reaction, while too high a temperature may result in destruction of the crystal structure and degradation of photocatalytic performance. A suitable calcination time is to ensure that the starting materials are fully reacted and converted to the manganese oxide compound. Too short a time may result in incomplete reaction, while too long a time may increase energy consumption and cost.
According to an embodiment of the present invention, manganese dioxide is obtained by mixing and calcining manganese sulfate and potassium permanganate, or by mixing and calcining manganese sulfate and ammonium persulfate. The gamma-MnO 2 is obtained by mixing and calcining manganese sulfate and potassium permanganate, and the specific preparation process comprises the following steps: manganese sulfate and potassium permanganate are mixed according to the mass ratio of 5:1 and added into deionized water, and the mixture is magnetically stirred for 30-60min at 30 ℃ to form a uniform mixed solution; then the mixed solution is kept for 8 to 16 hours at the temperature of 120 to 200 ℃; after the reaction is finished, respectively centrifugally washing with water and absolute ethyl alcohol for 3-5 times, and drying at 60-100 ℃ for 6-12h after washing; drying and calcining at 280-330 ℃ for 6-9h to obtain gamma-MnO 2. The beta-MnO 2 is obtained by mixing and calcining manganese sulfate and ammonium persulfate, and the specific preparation process comprises the following steps: adding manganese sulfate and ammonium persulfate into deionized water according to a mass ratio of 1.5:1, and magnetically stirring for 30-60min to form a uniform mixed solution; then the mixed solution is kept for 8 to 16 hours at the temperature of 120 to 200 ℃; after the reaction is finished, respectively centrifugally washing with water and absolute ethyl alcohol for 3-5 times; washing, and drying at 60-100deg.C for 6-12 hr; drying and calcining at 130-160 ℃ for 8-12h to obtain the beta-MnO 2. In addition to the above-mentioned methods for preparing manganese dioxide, other methods for preparing manganese dioxide may be used, or purchased manganese dioxide may be used.
According to an embodiment of the present invention, manganese oxide, graphite-phase carbon nitride and activated carbon are mixed and calcined to obtain an air-purifying precursor material, further comprising: manganese dioxide, manganous-manganic oxide, graphite phase carbon nitride and active carbon are mixed and calcined for 8-16 hours at 120-200 ℃, and a manganese oxide compound is formed in the calcining process, so that a heterojunction between the manganese oxide compound and the graphite phase carbon nitride is formed; or mixing manganese oxide, urea or melamine and active carbon, and calcining at 500-550 ℃ for 1.5-2.5h, wherein graphite-phase carbon nitride is formed in the calcining process, so that a heterojunction between the manganese oxide and the graphite-phase carbon nitride is formed; or mixing manganese dioxide, manganous oxide, urea or melamine and active carbon, calcining at 120-200 ℃ for 8-16h, then calcining at 500-550 ℃ for 1.5-2.5h, forming manganese oxide compound in the calcining process, and forming graphite phase carbon nitride, thus forming heterojunction between the manganese oxide compound and the graphite phase carbon nitride.
In embodiments of the present invention, in addition to activated carbon, common volatile organic compound adsorption materials, including novel porous carbon materials, zeolite molecular sieves, clay-based adsorbents, metal organic frameworks, mesoporous silicon, and the like, may also be used.
As a third aspect of the present invention, there is provided an application of an adsorption and photocatalytic synergistic air purification material in air purification.
In the embodiment of the invention, the periodic acid layer is used for adsorbing water vapor in the air to form an in-situ water layer (self-wetting layer) on the surface of the air purification material, so that a unique air/water/air purification material three-phase system is formed. The in-situ water layer adsorbs hydrophilic volatile organic compounds, and the activated carbon adsorbs hydrophilic volatile organic compounds in the in-situ water layer, so that more reaction sites are provided for oxidizing and decomposing the hydrophilic volatile organic compounds by manganese oxide and graphite phase carbon nitride. Under illumination, the heterojunction formed by the manganese oxide and the graphite phase carbon nitride generates superoxide radical, and the hydrophilic volatile organic compound adsorbed by the activated carbon is oxidized and decomposed into carbon dioxide and water. By utilizing the synergistic effect of adsorption and photocatalysis, the purification efficiency of the air purification material can be effectively improved, and the purposes of more economical, efficient and selective air purification are realized.
According to an embodiment of the invention, the air purification material is used for purifying gaseous aldehyde ketone pollutants in indoor odor places. Preferably, the concentration of gaseous aldehyde ketone pollutants is 5-50ppm. The gaseous aldehyde ketone pollutant includes formaldehyde, acetaldehyde, propionaldehyde, valeraldehyde, octyl aldehyde, acrolein and acetone. Formaldehyde, acetaldehyde, propionaldehyde, valeraldehyde, caprylic aldehyde, acrolein and acetone all have certain hydrophilia and can be adsorbed by an in-situ water layer formed by periodic acid.
The invention is further illustrated by the following examples and related test experiments. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the invention. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, the details of the various embodiments below may be arbitrarily combined into other viable embodiments without conflict. All of the instruments, consumables, reagents, etc. in the examples below are commercially available unless otherwise specified.
Example 1
An air purification material was prepared in this example 1, and the specific operation steps were as follows.
Preparation of graphite phase carbon nitride: and placing 1g of urea into a ceramic crucible (the urea does not exceed half of the volume of the crucible), covering a crucible cover, wrapping the periphery of the crucible by aluminum foil paper, packaging, and placing the crucible in a muffle furnace for calcination. Heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min, calcining at constant temperature for 2.5 hours, naturally cooling to room temperature, and grinding to obtain graphite-phase carbon nitride, namely g-C 3N4.
Preparation of air purification precursor material: mixing g-C 3N4、MnO2、Mn3O4 and Active Carbon (AC) in deionized water, and magnetically stirring at 30deg.C for 2h; placing in a baking oven at 200 ℃ for 8 hours, naturally cooling to room temperature, wherein in the calcining process, mnO 2、Mn3O4 forms a manganese oxide compound (MnO x), and the manganese oxide compound and graphite phase carbon nitride form a heterojunction and are attached to the inner and outer surfaces of the activated carbon, so that the air purification precursor material, namely the AC@g-C 3N4/MnOx, is obtained. Wherein the weight ratio of g-C 3N4、MnO2、Mn3O4 is 1:1:1, the sieving size of the activated carbon is 40-50 meshes, and the addition amount of the activated carbon is 5wt% of the air purification precursor material.
Preparation of air purification material: 1g of AC@g-C 3N4/MnOx is added into 10mL of 8wt% Periodic Acid (PA) solution, 5mL of deionized water is added, magnetic stirring is carried out for 1h at 30 ℃, and a periodic acid layer is obtained after drying, so that heterojunction-formed manganese oxide, graphite-phase carbon nitride and active carbon-coated air purification material, namely AC@g-C 3N4/MnOx (PA) are obtained.
Example 2
The method for preparing the air cleaning material of this example 2 is the same as that of example 1, except that: the addition amount of the activated carbon is 10wt% of the air purification precursor material.
Example 3
The method for preparing the air cleaning material of this example 3 is the same as that of example 1, except that: the addition amount of the activated carbon is 12.5wt% of the air purification precursor material.
Example 4
The method for preparing the air cleaning material of this example 4 is the same as that of example 1, except that: the addition amount of the activated carbon is 15wt% of the air purification precursor material.
Example 5
The air cleaning material of this example 5 was prepared in the same manner as in example 1, except that: the addition amount of the activated carbon is 20wt% of the air purification precursor material.
Example 6
The air cleaning material of this example 6 was prepared in the same manner as in example 1, except that: the addition amount of the activated carbon is 25wt% of the air purification precursor material.
Example 7
The preparation method of the air cleaning material of this example 7 is the same as that of example 1, except that: the addition amount of the activated carbon was 62.5wt% of the air purification precursor material.
Example 8
The air cleaning material of this example 8 was prepared in the same manner as in example 1, except that: g-C 3N4、MnO2、Mn3O4 and active carbon in the weight ratio of 1:5:1:1.
Example 9
The air cleaning material of this example 9 was prepared in the same manner as in example 1, except that: g-C 3N4、MnO2、Mn3O4 and active carbon in the weight ratio of 1:1:5:1.
Example 10
The air cleaning material of this example 10 was prepared in the same manner as in example 1, except that: g-C 3N4、MnO2、Mn3O4 and the weight ratio of the active carbon is 5:1:1:1.
Comparative example 1
The graphite phase carbon nitride was prepared in this comparative example 1, and the specific operation procedure was as follows.
And placing 1g of urea into a ceramic crucible (the urea does not exceed half of the volume of the crucible), covering a crucible cover, wrapping the periphery of the crucible by aluminum foil paper, packaging, and placing the crucible in a muffle furnace for calcination. Heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min, calcining at constant temperature for 2.5 hours, naturally cooling to room temperature, and grinding to obtain graphite-phase carbon nitride, namely g-C 3N4.
Comparative example 2
This comparative example 2 uses g-C 3N4 of comparative example 1 to prepare a periodic acid-coated graphite-phase carbon nitride, and the specific procedure is as follows.
1G g-C 3N4 is added into 10mL of 8wt% PA solution, 5mL of deionized water is added, the mixture is magnetically stirred for 1h at 30 ℃, and graphite phase carbon nitride coated with periodic acid, namely g-C 3N4 (PA) is obtained after drying.
Comparative example 3
This comparative example 3 is identical to the preparation of ac@g-C 3N4/MnOx in example 1, except that: the product obtained without adding active carbon is g-C 3N4/MnOx.
Comparative example 4
Comparative example 4 periodic acid coated g-C 3N4/MnOx was prepared using g-C 3N4/MnOx of comparative example 3, and the procedure is as follows.
1G g-C 3N4/MnOx was added to 10mL of 8wt% PA solution, followed by another 5mL of deionized water, magnetically stirred at 30℃for 1h, and dried to give g-C 3N4/MnOx, g-C 3N4/MnOx (PA), of periodic acid.
Testing and characterization:
the samples obtained in the above examples and comparative examples were subjected to relevant tests and characterization.
Fig. 1 is a scanning electron microscope image of the activated carbon of example 1 of the present invention, fig. 2 is a scanning electron microscope image of the graphite phase carbon nitride of comparative example 1 of the present invention, and fig. 3 is a scanning electron microscope image of the air purification material of example 1 of the present invention.
As can be seen from FIGS. 1-3, the rolled g-C 3N4 nanosheets and g-C 3N4/MnOx consisting of particulate MnO x are wrapped around the inner and outer surfaces of the AC, and MnO x is concentrated on the outer surfaces, the distribution of which inhibits the accumulation of g-C 3N4. When doped with MnO x, the AC structure becomes smaller and the particles approach a sphere. In addition, some g-C 3N4/MnOx molecules deposited in the internal pores of the AC, indicating that g-C 3N4/MnOx not only covered the surface of the AC, but also entered the pores and anchored to the internal surface of the AC.
Fig. 4 is a graph showing nitrogen adsorption and desorption of the activated carbon of example 1 and the air cleaning precursor materials of examples 1, 3, 5 and comparative example 1 and the graphite phase carbon nitride of comparative example 1 according to the present invention.
As can be seen from fig. 4, as the AC ratio in ac@g-C 3N4/MnOx (PA) increases from 5% to 20%, the hysteresis loop moves toward the region where the relative pressure is low, and the hysteresis loop width becomes wider, indicating that a large number of mesoporous structures (2-50 nm) are formed in the air cleaning material. Specifically, the hysteresis loop (or isothermal adsorption curve) is a curve used to describe the adsorption behavior of a material to a gas as a function of relative pressure. When the hysteresis loop is moved towards the region of lower relative pressure, this means that at lower relative pressure the test sample has begun to exhibit significant gas adsorption. This is related to the presence of a large number of mesoporous structures in the test sample, since mesoporous structures have a large specific surface area and good gas diffusion properties, allowing the gas to be efficiently adsorbed at a low relative pressure. The width of the hysteresis loop reflects the range of variation of the gas adsorption capacity of the test sample in the adsorption and desorption processes. A wider hysteresis loop means that the test sample has a larger variation in the amount of gas adsorbed during adsorption and desorption, which is related to the presence of more pore structure or a wider pore size distribution in the test sample. When the hysteresis loop width was widened, it was shown that a large number of mesoporous structures were formed in the test sample. The mesoporous structure not only has larger specific surface area, but also is beneficial to the diffusion and transmission of gas molecules, thereby improving the photocatalysis performance of the test sample. The mesoporous structure plays an important role in the photocatalyst. First, they can provide more reactive sites, facilitating the progress of the photocatalytic reaction. And secondly, the mesoporous structure is beneficial to the diffusion and transmission of reactants and products, reduces mass transfer resistance and improves photocatalysis efficiency. In addition, the mesoporous structure can also enhance the absorption and utilization of the photocatalyst to light, and further improve the photocatalytic performance. The significantly increased BET specific surface area and pore volume (476.9 m 2/g,0.306cm3/g) of AC@g-C 3N4/MnOx in example 3 compared to the BET specific surface area and pore volume (14.4 m 2/g,0.053cm3/g) of g-C 3N4 in comparative example 1, indicates that AC@g-C 3N4/MnOx in example 3 has a stronger adsorption capacity than g-C 3N4 in comparative example 1.
Further, in order to test the purifying ability of the samples obtained in the above examples and comparative examples to acetaldehyde in the air, the following test was conducted.
FIG. 5 is a schematic diagram of a continuous flow piping system for testing acetaldehyde cleaning capacity in accordance with an embodiment of the invention. Wherein, the initial concentration of acetaldehyde is 3.5mg/m 3, the flow is 0.5L/min, and the illumination time is 1h during the test.
FIG. 6 is a schematic diagram of a glass fiber filter groove required for loading a test material in a catalytic reaction chamber in the continuous flow piping system of FIG. 5. Specifically, the loading method for loading the test sample on the glass fiber filter membrane groove comprises the following steps: dissolving a test sample in deionized water, pouring the deionized water into a glass fiber filter membrane groove, placing the glass fiber filter membrane groove into a continuous flow pipeline system, and blowing the glass fiber filter membrane groove by clean air until no obvious water drops are attached; wherein the bottom area of the glass fiber filter membrane groove is 0.02-0.2m 2, the clean air purging flow is 0.1-5L/min, and the purging mode is an external mechanical device (a manual fan and a blower) or a continuous flow pipeline system. The test sample can be directly coated in the groove of the glass fiber filter membrane, and the wet loading method can uniformly load the test sample on the glass fiber filter membrane, so that the problem of nonuniform powder coated manually is effectively solved.
Fig. 7 is a graph showing the results of the acetaldehyde removal performance test of comparative examples 1 to 4 and 10 according to the present invention, fig. 8 is a graph showing the results of the acetaldehyde adsorption performance test of examples 1 to 5 and 1 according to the present invention under a continuous flow dark environment, and fig. 9 is a graph showing the results of the acetaldehyde removal performance test of examples 1 to 10 and 4 according to the present invention.
As can be seen from fig. 7, the ordering ：AC@g-C3N4/MnOx（PA）＞g-C3N4/MnOx（PA）＞g-C3N4/MnOx＞g-C3N4（PA）＞g-C3N4. of the acetaldehyde removal efficiencies of the different air cleaning materials can be seen from fig. 8, and as the active carbon content (5%, 10%, 12.5%, 15%, 20%) increases, the total adsorption amount of the air cleaning materials is improved by 3.5-4.2 times compared with g-C 3N4. As can be seen from FIG. 9, the acetaldehyde removal rate of AC@g-C 3N4/MnOx (PA) in example 10 can reach 91.9%, and the acetaldehyde removal rate of g-C 3N4 in comparative example 1 is only 49%. The acetaldehyde removal rate of the air purification material can be remarkably improved by only adding 5% of AC, which is 1.69 times of that of the air purification material without adding AC. With the increase of the content of the active carbon, the acetaldehyde removal rate is increased and then reduced, the optimal addition proportion of the active carbon is 5-15%, and the acetaldehyde removal rate of the air purification material reaches the highest value when the AC content is 12.5%. The removal rate of AC@g-C 3N4/MnOx of example 10 was significantly higher than that of the other examples, AC@g-C 3N4/MnOx, among the different principal components. In a continuous flow system, when g-C 3N4：MnO2：Mn3O4: at ac=5:1:1:1, the removal rate was highest, reaching 91.9%.
From the above, it can be seen that: the air purification material AC@g-C 3N4/MnOx (PA) can realize the application purpose of degrading gaseous aldehyde ketone pollutants more economically, efficiently and selectively under indoor peculiar smell environment, and solves the technical defects that the existing photocatalytic material has low photodegradation efficiency of a single catalyst and can not degrade single type of pollutants selectively.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the invention thereto, but to limit the invention thereto, and any modifications, equivalents, improvements and equivalents thereof may be made without departing from the spirit and principles of the invention.
Claims (10)
1. An adsorption and photocatalysis synergistic air purification material, characterized in that the air purification material comprises: manganese oxide, graphite phase carbon nitride, activated carbon and periodic acid layer;
Wherein the manganese oxide forms a heterojunction with the graphite-phase carbon nitride and is attached to the inner and outer surfaces of the activated carbon, and the periodic acid layer wraps the manganese oxide, the graphite-phase carbon nitride and the activated carbon which form the heterojunction.
2. The preparation method of the adsorption and photocatalysis synergistic air purification material is characterized by comprising the following steps of:
mixing and calcining a manganese oxide, graphite-phase carbon nitride and active carbon to obtain an air purification precursor material;
Immersing the air purification precursor material in a periodic acid solution, and drying to obtain the air purification material;
wherein the manganese oxide and the graphite phase carbon nitride form heterojunction in the calcining process, and are attached to the inner and outer surfaces of the activated carbon, and the periodic acid layer wraps the manganese oxide and the graphite phase carbon nitride and the activated carbon which form heterojunction in the impregnating process.
3. The method of claim 2, wherein the periodic acid loading in the air purification material is 30-50%.
4. The method according to claim 2, wherein the manganese oxide has a size of 10 to 300nm, the graphite phase carbon nitride has a size of 10 to 300nm, and the activated carbon has a size of 150 to 425 μm.
5. The method of claim 2, wherein the mixing and calcining of the manganese oxide, graphite phase carbon nitride and activated carbon to obtain the air purifying precursor material comprises:
Manganese oxide, graphite phase carbon nitride and active carbon are mixed and calcined at 320-370 ℃ for 2.5-4 hours.
6. The method of claim 5, wherein the graphite phase carbon nitride is calcined from urea or melamine at a calcination temperature of 500-550 ℃ for a calcination time of 1.5-2.5 hours;
the manganese oxide compound is obtained by mixing manganese dioxide and manganous-manganic oxide and calcining, wherein the calcining temperature for forming the manganese oxide compound is 120-200 ℃, and the calcining time is 8-16h;
the manganese dioxide is obtained by mixing and calcining manganese sulfate and potassium permanganate, or is obtained by mixing and calcining manganese sulfate and ammonium persulfate.
7. The method of claim 2, wherein the manganese oxide, graphite phase carbon nitride and activated carbon are mixed and calcined to obtain the air cleaning precursor material, further comprising:
Manganese dioxide, manganous-manganic oxide, graphite phase carbon nitride and active carbon are mixed and calcined for 8 to 16 hours at the temperature of 120 to 200 ℃; or alternatively
Mixing manganese oxide, urea or melamine and active carbon and calcining at 500-550 ℃ for 1.5-2.5h; or alternatively
Manganese dioxide, manganous oxide, urea or melamine and active carbon are mixed, calcined for 8 to 16 hours at the temperature of 120 to 200 ℃ and then calcined for 1.5 to 2.5 hours at the temperature of 500 to 550 ℃.
8. Use of the air purification material according to claim 1 for air purification.
9. The use according to claim 8, wherein the air purification material is used for purification of gaseous aldehyde ketone pollutants in indoor off-flavor sites.
10. The use according to claim 9, wherein the gaseous aldehyde ketone contaminants comprise any one or more of formaldehyde, acetaldehyde, propionaldehyde, valeraldehyde, caprylic aldehyde, acrolein, acetone.
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