CN114849751A - Modified catalyst for removing formaldehyde through photocatalysis, and preparation method and application thereof - Google Patents
Modified catalyst for removing formaldehyde through photocatalysis, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114849751A CN114849751A CN202210429312.9A CN202210429312A CN114849751A CN 114849751 A CN114849751 A CN 114849751A CN 202210429312 A CN202210429312 A CN 202210429312A CN 114849751 A CN114849751 A CN 114849751A
- Authority
- CN
- China
- Prior art keywords
- mixture
- modified catalyst
- photocatalysis
- formaldehyde
- removing formaldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 273
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019441 ethanol Nutrition 0.000 claims abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 239000002131 composite material Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000012855 volatile organic compound Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229940011182 cobalt acetate Drugs 0.000 description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229920005372 Plexiglas® Polymers 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 208000002454 Nasopharyngeal Carcinoma Diseases 0.000 description 1
- 206010061306 Nasopharyngeal cancer Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000032839 leukemia Diseases 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 201000011216 nasopharynx carcinoma Diseases 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01D53/34—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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B01J35/39—
-
- B01J35/61—
-
- 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
- B01D2257/704—Solvents not covered by groups B01D2257/702 - B01D2257/7027
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/06—Polluted air
-
- 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 discloses a modified catalyst for removing formaldehyde by photocatalysis, and a preparation method and application thereof. The preparation method of the modified catalyst for removing formaldehyde by photocatalysis comprises the following steps: grinding urea, placing the ground urea into a muffle furnace for calcining, and naturally cooling to room temperature to obtain g-C 3 N 4 (ii) a G to C 3 N 4 Dispersing in a mixture of a DMF solvent and absolute ethyl alcohol, then carrying out ultrasonic treatment, adding cobalt acetate tetrahydrate, polyvinylpyrrolidone and pyrazine, and stirring to obtain a mixture A; dispersing TCPP in a mixture of DMF solvent and absolute ethyl alcohol to obtain a mixture B; mixing the raw materialsAdding the B into the mixture A, stirring, transferring into a high-pressure autoclave sealed by polytetrafluoroethylene for reaction, washing the obtained product with ethanol for a plurality of times, and drying the precipitate to obtain the photocatalytic formaldehyde removal modified catalyst. The modified catalyst for removing formaldehyde by photocatalysis is prepared by a preparation method of the modified catalyst for removing formaldehyde by photocatalysis. The invention also provides an application of the modified catalyst for removing formaldehyde by photocatalysis.
Description
Technical Field
The invention relates to the technical field of formaldehyde purification materials, in particular to a modified catalyst for removing formaldehyde through photocatalysis, and a preparation method and application thereof.
Background
With the gradual improvement of living standard of people, the indoor air quality is also gradually paid much attention, and among them, the harm of formaldehyde to human health as the most widely known Volatile Organic Compounds (VOCs) is more and more paid much attention. According to related research reports, the incidence of diseases such as nasopharyngeal carcinoma and leukemia is increased due to harmful gases such as formaldehyde. Indoor formaldehyde is mainly from indoor decoration materials such as furniture, paint and the like. The potential risk caused by long-term exposure of human body to the air with high concentration of formaldehyde is not negligible. Therefore, in the modern society, the formaldehyde in the indoor air is purified, the indoor air quality is improved, and the formaldehyde purification device has extremely important significance for human life.
At present, in the treatment technology for removing formaldehyde, the adsorption and formaldehyde removal technology has the defects of low adsorption capacity, slow adsorption rate and unsatisfactory regeneration performance; the defects of the thermocatalytic method and the plasma treatment technology are that additional energy input is needed, expensive equipment is required, auxiliary accessories are required, the operation cost is high, and the like; biological processes are limited by inefficient processing, unstable operation and lengthy process times. Based on the comparison and balance of various methods and technologies, the photocatalysis aldehyde removal technology utilizes a semiconductor material, generates a catalytic effect through the irradiation of sunlight, can degrade harmful substances such as formaldehyde and the like in indoor air into formic acid or carbon dioxide and water, and can play a role in sterilizing and removing peculiar smell while removing aldehyde. However, the current materials for removing aldehyde by photocatalysis still face some common difficulties and need to be broken through, such as most of the existing conventional commercial materials for removing aldehyde by photocatalysis have unsatisfactory performance, and particularly, the materials for removing formaldehyde by visible light catalysis are environment-friendly functional materials. Therefore, it is important to develop an economical and environment-friendly material capable of efficiently and rapidly purifying formaldehyde in air at room temperature in response to visible light.
Disclosure of Invention
Based on the above, the invention aims to provide a modified catalyst for removing formaldehyde by photocatalysis, and a preparation method and application thereof, so as to solve the technical problem that the existing catalyst in the prior art can remove formaldehyde only under the ultraviolet absorption condition.
In a first aspect, a preparation method of a modified catalyst for removing formaldehyde by photocatalysis comprises the following steps:
grinding urea, placing the ground urea into a muffle furnace for calcining, and naturally cooling to room temperature to obtain g-C 3 N 4 ；
G to C 3 N 4 Dispersing in a mixture of a DMF solvent and absolute ethyl alcohol, then carrying out ultrasonic treatment, adding cobalt acetate tetrahydrate, polyvinylpyrrolidone and pyrazine, and stirring to obtain a mixture A; dispersing TCPP in a mixture of DMF solvent and absolute ethyl alcohol to obtain a mixture B; adding the mixture B into the mixture A, stirring, transferring into a high-pressure autoclave sealed by polytetrafluoroethylene for reaction, washing the obtained product with ethanol for a plurality of times, and drying the precipitate to obtain the photocatalytic formaldehyde removal modified catalyst.
According to the technical scheme, in one implementation mode, 20g of urea is ground, placed into a muffle furnace to be heated to 550 ℃ and calcined for 4h, wherein the heating rate is 5 ℃/min, and naturally cooled to room temperature to obtain light yellow g-C 3 N 4 。
In one embodiment, 20.1mg of g-C is added 3 N 4 Dispersing in a mixture of 30ml DMF solvent and 10ml absolute ethanol, then performing ultrasonic treatment for 30min, and adding 1mmol cobalt acetate tetrahydrate, 100mg polyvinylpyrrolidone and2.4mg of pyrazine, and stirring for 0.5h to obtain a mixture A; dispersing 13.2mg TCPP in a mixture of 30ml DMF solvent and 10ml absolute ethanol to give mixture B; adding the mixture B into the mixture A, stirring for 0.5h, transferring into an autoclave sealed by polytetrafluoroethylene, reacting for 12h at 100 ℃, washing the obtained product with ethanol for several times, and drying the precipitate in a vacuum drying oven at 60 ℃ to obtain the modified g-C 3 N 4 A catalyst.
In a second aspect, the invention provides a photocatalytic formaldehyde-removing modified catalyst, which is prepared by any one of the preparation methods of the photocatalytic formaldehyde-removing modified catalyst.
In a third aspect, the application of the modified catalyst for removing formaldehyde by photocatalysis is the application of the modified catalyst for removing formaldehyde by photocatalysis in the field of removing formaldehyde by photocatalysis.
In one embodiment, the application method includes: spraying the modified catalyst for removing formaldehyde by photocatalysis on the surface of an object, and irradiating by using visible light.
Compared with the prior art, the preparation method of the photocatalytic formaldehyde-removing modified catalyst has the advantages of simple preparation process, high stability and easy industrialization, the prepared photocatalytic formaldehyde-removing modified catalyst has the characteristics of high purification rate, high specific surface area, high porosity, good thermal stability and the like, the heterojunction coupling construction composite material can promote charge separation, can realize high-efficiency catalytic oxidation on VOCs (formaldehyde) at room temperature, provides a solution for the environmental problem of the VOCs, has obvious economic benefit, and is suitable for being used indoors, in vehicles, in offices and the like.
For a better understanding and practice, the invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 is a SEM picture of a photocatalytic formaldehyde removal modified catalyst of the present invention.
FIG. 2 shows g-C in comparative example 1, comparative example 2 and Experimental example 3 N 4 Material, Co-TCPPMOF material, and photocatalysis of modified catalyst for removing formaldehyde by photocatalysisAnd (3) a formaldehyde removal performance diagram.
FIG. 3 is a graph of the stability of photocatalytic formaldehyde removal in five experiments with the photocatalytic formaldehyde removal modified catalyst.
Detailed Description
The terms of orientation of up, down, left, right, front, back, top, bottom, and the like, referred to or may be referred to in this specification, are defined relative to their configuration, and are relative concepts. Therefore, it may be changed according to different positions and different use states. Therefore, these and other directional terms should not be construed as limiting terms.
The implementations described in the exemplary embodiments below are not intended to represent all implementations consistent with the present disclosure. Rather, they are merely examples of implementations consistent with certain aspects of the present disclosure.
The terminology used in the present disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used in this disclosure, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
There are a number of photocatalyst materials on the market today, among which g-C as a graphite analogue 3 N 4 Layered structures are of great interest because of their relatively narrow band gap, reasonable production cost and excellent durability. However, g-C is a defect of low visible light absorption, high electron-hole recombination rate, small specific surface area, and the like 3 N 4 The photocatalytic contaminant removal activity of (a) is limited. For which e.g. g-C based building with other semiconductors has been developed 3 N 4 To address these limitations, heterostructures, co-catalyst modifications, and the like. The Co-TCPPMOF material has the characteristics of excellent light absorption capacity, high specific surface area, large porosity, good thermal stability and the like, is considered as a feasible photocatalyst, and the open and through pore channel of the Co-TCPPMOF material is favorable for adsorption and concentrationContaminant molecules in the environment reach the surface and the interior of the material. However, photocatalytic activity is also limited due to the high electron-hole recombination rate. To improve photocatalytic efficiency, heterojunction coupled composites can be constructed to facilitate charge separation.
In a first aspect, the invention provides a preparation method of a photocatalytic formaldehyde removal modified catalyst, wherein the prepared photocatalytic formaldehyde removal modified catalyst has a heterojunction coupling composite material, and the preparation method specifically comprises the following steps:
step 101, preparing g-C by adopting a calcination method 3 N 4 。
Specifically, grinding urea, calcining in a muffle furnace, and naturally cooling to room temperature to obtain g-C 3 N 4 。
In one embodiment, 20g of urea is ground, placed into a muffle furnace to be heated to 550 ℃ and calcined for 4h, wherein the heating rate is 5 ℃/min, and naturally cooled to room temperature to obtain light yellow g-C 3 N 4 。
Step 102, preparing a photocatalytic formaldehyde removal modified catalyst (Co-TCPPMOF @ g-C) by adopting a solvothermal method 3 N 4 Composite materials).
Specifically, g-C 3 N 4 Dispersing in a mixture of a DMF solvent and absolute ethyl alcohol, then carrying out ultrasonic treatment, adding cobalt acetate tetrahydrate, polyvinylpyrrolidone and pyrazine, and stirring to obtain a mixture A; dispersing TCPP in a mixture of DMF solvent and absolute ethyl alcohol to obtain a mixture B; adding the mixture B into the mixture A, stirring, transferring into a high-pressure autoclave sealed by polytetrafluoroethylene for reaction, washing the obtained product with ethanol for a plurality of times, and drying the precipitate to obtain the photocatalytic formaldehyde removal modified catalyst.
In one embodiment, 20.1mg of g-C is added 3 N 4 Dispersing in a mixture of 30ml of DMF solvent and 10ml of absolute ethyl alcohol, then carrying out ultrasonic treatment for 30min, adding 1mmol of cobalt acetate tetrahydrate, 100mg of polyvinylpyrrolidone and 2.4mg of pyrazine, and stirring for 0.5h to obtain a mixture A; dispersing 13.2mg TCPP in a mixture of 30ml DMF solvent and 10ml absolute ethanol to give mixture B;adding the mixture B into the mixture A, stirring for 0.5h, transferring into an autoclave sealed by polytetrafluoroethylene, reacting for 12h at 100 ℃, washing the obtained product with ethanol for several times, and drying the precipitate in a vacuum drying oven at 60 ℃ to obtain the modified g-C 3 N 4 A catalyst.
The preparation method of the photocatalytic formaldehyde removal modified catalyst obtains the stable photocatalytic formaldehyde removal modified catalyst (Co-TCPPMOF @ g-C) through a simple and convenient process synthesis method 3 N 4 Composite material) for the research of photocatalytic purification of formaldehyde.
In a second aspect, the invention provides a photocatalytic formaldehyde-removing modified catalyst, which is prepared by the preparation method of the photocatalytic formaldehyde-removing modified catalyst.
Referring to fig. 1, it can be seen from fig. 1 that the morphology of the photocatalytic formaldehyde removal modified catalyst is a typical two-dimensional layered material, and the photocatalytic formaldehyde removal modified catalyst has a suitable visible light absorption range and a synergistic catalytic ability, promotes the photocatalytic formaldehyde to be converted into relatively nontoxic formic acid or carbon dioxide and water, and simultaneously avoids secondary pollution caused by desorption after adsorption saturation, thereby facilitating the regeneration of the catalyst.
The modified catalyst for removing formaldehyde by photocatalysis provided by the invention has the characteristics of high stability, simple preparation process, good environmental compatibility, wide application range and the like, can be used for catalytically degrading formaldehyde under the irradiation of a fluorescent lamp at room temperature, and has a formaldehyde removal rate of 97%.
In a third aspect, the application of the modified catalyst for removing formaldehyde by photocatalysis is the application of the modified catalyst for removing formaldehyde by photocatalysis in the field of removing formaldehyde by photocatalysis. The specific application method comprises the following steps: spraying the modified catalyst for removing formaldehyde by photocatalysis on the surface of an object, and irradiating by using visible light.
Comparative example 1
g-C with photocatalytic formaldehyde removal 3 N 4 And (3) preparation and performance test of the material.
(1) Preparation of g-C by calcination 3 N 4 A material.
Collecting 20g urineGrinding the element, putting the element into a muffle furnace, heating to 550 ℃, and calcining for 4h at the heating rate of 5 ℃/min. Naturally cooling to room temperature to obtain a light yellow product g-C 3 N 4 。
(2)g-C 3 N 4 The performance of the material for removing formaldehyde by photocatalysis is researched.
The photocatalytic formaldehyde removal test is carried out at 25 ℃ in a sealed plexiglas chamber, 10mg of g-C 3 N 4 Uniformly spraying the material on a glass culture dish with a diameter of 5cm, injecting formaldehyde solution with a concentration of 1ppm on a glass plate through a liquid-transferring gun, starting a fan, stirring for 1min to uniformly mix air in a cabin and released pollutants, then closing the fan, determining the concentration value of the pollutants as an initial concentration, and recording the concentration value as C 1 . And (3) starting a simulated solar lamp to irradiate the glass culture dish, starting a U.S. Interscan portable 4160-2 formaldehyde detector, and recording data every 20 min.
Comparative example 2
Preparation and performance test of Co-TCPPMOF material with photocatalysis formaldehyde removal performance.
(1) And preparing the Co-TCPPMOF material by adopting an organic solvent method.
17.7mg of cobalt acetate Co (OAc) 2 And 13.2mg of TCPP, 30mL of DMF solvent and 10mL of absolute ethanol are added into a 100mL round-bottom flask, the mixture is heated to 100 ℃ for reaction for 12 hours, the mixture is cooled to room temperature, the centrifugal cleaning operation is carried out, the mixture is washed by ethanol for a plurality of times, and the precipitate is put into a vacuum drying oven to be dried at 60 ℃ to prepare the Co-TCPPMOF material.
It is to be noted that the use of cobalt acetate is not limited, and 1mmol of cobalt nitrate (Co (NO) may be used 3 ) 2 ) 1mmol of cobalt acetate ((CH) 3 CO 2 ) 2 Co), 1mmol of cobalt sulfate (CoSO) 4 ) And the like.
(2) The performance research of the Co-TCPPMOF material for removing formaldehyde by photocatalysis.
The photocatalytic formaldehyde removal test was carried out at 25 ℃ in a sealed plexiglass cabinet, 10mg of Co-TCPPMOF material was uniformly sprayed onto a glass petri dish 5cm in diameter, and 1ppm formaldehyde solution was passed throughInjecting the liquid-transfering gun on the glass plate, starting fan, stirring for 1min to make the air in the cabin and pollutant released from falsehood be uniformly mixed, closing fan, measuring the concentration value of pollutant as initial concentration and recording it as C 1 . And (3) starting a simulated solar lamp, irradiating the glass culture dish, starting the American Interscan portable 4160-2 formaldehyde detector, and recording data every 20 min.
Examples of the experiments
Modified catalyst (Co-TCPPMOF @ g-C) for removing formaldehyde by photocatalysis 3 N 4 Composite material) preparation and performance testing.
(1) Method for preparing modified catalyst (Co-TCPPMOF @ g-C) for removing formaldehyde by photocatalysis through solvothermal method 3 N 4 Composite materials).
20.1mg of g-C 3 N 4 (same as the preparation method in comparative example 1) was dispersed in a mixture of 30ml of DMF and 10ml of anhydrous ethanol, followed by sonication for 30 min. Then 17.7mg of cobalt acetate Co (OAc) were added 2 100mg polyvinylpyrrolidone (PVP) and 2.4mg pyrazine, stirred for 0.5h to give mixture A. Meanwhile, 13.2mg of TCPP was dispersed in a mixture of 30ml of DMF and 10ml of anhydrous ethanol to give a mixture B. The mixture B was added to the mixture A and stirred for 0.5h, then transferred to a polytetrafluoroethylene-sealed autoclave and reacted at 100 ℃ for 12 h. And finally, washing the obtained substance with ethanol for a plurality of times, and putting the precipitate into a vacuum drying oven to be dried at 60 ℃ to obtain the product.
(2) Modified catalyst (Co-TCPPMOF @ g-C) for removing formaldehyde by photocatalysis 3 N 4 Composite material) and performance research of removing formaldehyde by photocatalysis.
The test of removing formaldehyde by photocatalysis is carried out in a sealed organic glass box at 25 ℃, 10mg of modified catalyst for removing formaldehyde by photocatalysis is uniformly sprayed on a glass culture dish with the diameter of 5cm, formaldehyde solution with the concentration of 1ppm is injected on a glass plate by a liquid-transferring gun, a fan is started and stirred for 1min, after the air in the cabin is uniformly mixed with the pollutant released by falsehood, the fan is closed, the concentration value of the pollutant is determined as initial concentration and is marked as C 1 . Starting the simulated solar lamp to irradiate on the glass culture dish, and starting American IntersThe can portable 4160-2 formaldehyde detector records data every 20 min.
The experimental results of comparative example 1, comparative example 2 and experimental example are shown in the attached figure 2. The results show that g-C 3 N 4 The material photocatalysis formaldehyde removal rate is 70%, the Co-TCPPMOF material photocatalysis formaldehyde removal rate is 40%, and the photocatalysis formaldehyde removal modified catalyst photocatalysis formaldehyde removal rate is 97%. Therefore, the modified catalyst for removing formaldehyde by photocatalysis can overcome the pure g-C 3 N 4 And the defect of insufficient photocatalytic activity of the Co-TCPPMOF material, and can effectively remove formaldehyde. The modified catalyst for removing formaldehyde by photocatalysis can efficiently and quickly purify formaldehyde in air by visible light response at room temperature, and provides a new composite material for formaldehyde purification.
The photocatalytic formaldehyde removal modified catalyst is subjected to five times of photocatalytic formaldehyde removal experiments, and the experimental results are shown in the attached figure 3. The five-time formaldehyde removal rate of the photocatalytic formaldehyde removal modified catalyst is about 97 percent, which shows that the catalyst has the advantage of good formaldehyde removal stability.
Compared with the prior art, the preparation method of the photocatalytic formaldehyde-removing modified catalyst has the advantages of simple preparation process, high stability and easy industrialization, the prepared photocatalytic formaldehyde-removing modified catalyst has the characteristics of high purification rate, high specific surface area, high porosity, good thermal stability and the like, the heterojunction coupling construction composite material can promote charge separation, can realize higher-efficiency catalytic oxidation of VOCs (formaldehyde) at room temperature, provides a solution for the environmental problem of VOCs, has obvious economic benefit, and is suitable for indoor use, in-car use, office places and the like.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (6)
1. A preparation method of a modified catalyst for removing formaldehyde by photocatalysis is characterized by comprising the following steps:
grinding urea, placing the ground urea into a muffle furnace for calcining, and naturally cooling to room temperature to obtain g-C 3 N 4 ；
G to C 3 N 4 Dispersing in a mixture of a DMF solvent and absolute ethyl alcohol, then carrying out ultrasonic treatment, adding cobalt acetate tetrahydrate, polyvinylpyrrolidone and pyrazine, and stirring to obtain a mixture A; dispersing TCPP in a mixture of DMF solvent and absolute ethyl alcohol to obtain a mixture B; adding the mixture B into the mixture A, stirring, transferring into a high-pressure autoclave sealed by polytetrafluoroethylene for reaction, washing the obtained product with ethanol for a plurality of times, and drying the precipitate to obtain the photocatalytic formaldehyde removal modified catalyst.
2. The preparation method of the modified catalyst for removing formaldehyde through photocatalysis according to claim 1, characterized in that 20g of urea is ground, put into a muffle furnace to be heated to 550 ℃ and calcined for 4h, wherein the heating rate is 5 ℃/min, and the mixture is naturally cooled to room temperature to obtain light yellow g-C 3 N 4 。
3. The method for preparing the modified catalyst for removing formaldehyde by photocatalysis according to claim 2, characterized in that 20.1mg of g-C is added 3 N 4 Dispersing in a mixture of 30ml of DMF solvent and 10ml of absolute ethyl alcohol, then carrying out ultrasonic treatment for 30min, adding 1mmol of cobalt acetate tetrahydrate, 100mg of polyvinylpyrrolidone and 2.4mg of pyrazine, and stirring for 0.5h to obtain a mixture A; dispersing 13.2mg TCPP in a mixture of 30ml DMF solvent and 10ml absolute ethanol to give mixture B; adding the mixture B into the mixture A, stirring for 0.5h, transferring into an autoclave sealed by polytetrafluoroethylene, reacting for 12h at 100 ℃, washing the obtained product with ethanol for several times, and drying the precipitate in a vacuum drying oven at 60 ℃ to obtain the modified g-C 3 N 4 A catalyst.
4. A photocatalytic formaldehyde-removing modified catalyst, which is characterized by being prepared by the preparation method of the photocatalytic formaldehyde-removing modified catalyst as claimed in any one of claims 1 to 3.
5. The application of the modified catalyst for removing formaldehyde by photocatalysis is characterized in that the application is the application of the modified catalyst for removing formaldehyde by photocatalysis in the field of removing formaldehyde by photocatalysis.
6. The application of the modified catalyst for removing formaldehyde by photocatalysis according to claim 5, is characterized in that the application method comprises the following steps: spraying the modified catalyst for removing formaldehyde by photocatalysis on the surface of an object, and irradiating by using visible light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210429312.9A CN114849751A (en) | 2022-04-22 | 2022-04-22 | Modified catalyst for removing formaldehyde through photocatalysis, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210429312.9A CN114849751A (en) | 2022-04-22 | 2022-04-22 | Modified catalyst for removing formaldehyde through photocatalysis, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114849751A true CN114849751A (en) | 2022-08-05 |
Family
ID=82633483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210429312.9A Pending CN114849751A (en) | 2022-04-22 | 2022-04-22 | Modified catalyst for removing formaldehyde through photocatalysis, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114849751A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113441001A (en) * | 2021-06-10 | 2021-09-28 | 香港理工大学深圳研究院 | Application of composite photocatalytic material in photocatalytic degradation of formaldehyde |
| CN113957458A (en) * | 2021-10-21 | 2022-01-21 | 天津理工大学 | g-C3N4Preparation and electrocatalytic properties of/two-dimensional porphyrin MOF material |
-
2022
- 2022-04-22 CN CN202210429312.9A patent/CN114849751A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113441001A (en) * | 2021-06-10 | 2021-09-28 | 香港理工大学深圳研究院 | Application of composite photocatalytic material in photocatalytic degradation of formaldehyde |
| CN113957458A (en) * | 2021-10-21 | 2022-01-21 | 天津理工大学 | g-C3N4Preparation and electrocatalytic properties of/two-dimensional porphyrin MOF material |
Non-Patent Citations (3)
| Title |
|---|
| JIAMIN LI，ET AL: "Construction of 2D Co-TCPP MOF decorated on B-TiO2 X nanosheets: Oxygen vacancy and 2D-2D heterojunctions for enhancing visible light-driven photocatalytic degradation of bisphenol A", JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING, pages 1 - 12 * |
| WENXIAN LI，ET AL: "Cobalt porphyrin (CoTCPP) advanced visible light response of g-C3N4 nanosheets", SUSTAINABLE MATERIALS AND TECHNOLOGIES, pages 1 - 10 * |
| 孙艳兵;吕日文;韩雪雯;钟玮鸿;黄剑;刘畅;戴荧;曹小红;: "铀(Ⅵ)在卟啉基MOF上的吸附行为", 材料导报, no. 10 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3750626A1 (en) | Transition metal and nitrogen co-doped carbon composite material for use in formaldehyde purification and preparation method therefor | |
| CN107876035A (en) | A kind of carbon quantum dot/titanic oxide composite photochemical catalyst material and its preparation method and application | |
| CN106381682B (en) | A kind of nano-titanium dioxide/active carbon fiber felt three-dimensional porous material of high absorption-photocatalysis performance and preparation method thereof | |
| CN113262808B (en) | Water-soluble graphite-phase carbon nitride nanosheet catalyst for efficiently removing formaldehyde at room temperature and preparation method thereof | |
| CN113926443B (en) | Multi-component composite material for removing aldehyde through visible light catalysis, preparation method and air purifier | |
| CN1513040A (en) | Photocatalytic coating material having photocatalytic activity and adsorption property and method for preparating same | |
| WO2020192722A1 (en) | Application of fullerene and derivative composite material thereof in degrading formaldehyde, indoor vocs or antibacterial | |
| CN106362736B (en) | Low-load amount palladium platinum catalyst with core-casing structure and the preparation method and application thereof | |
| CN108927157B (en) | Cu2O/{001}TiO2Preparation method of composite catalyst and application of composite catalyst to dynamic purification of ammonia gas | |
| CN105148836A (en) | Catalytic decomposition type air purification material and preparation method thereof | |
| CN108940264A (en) | A kind of Mn/Ce base catalyst and preparation method thereof with room temperature decomposing formaldehyde performance | |
| CN110813306A (en) | Zinc ferrite/bismuth tungstate composite catalyst, preparation method thereof and application thereof in waste gas treatment | |
| CN109078477A (en) | A kind of hydroxy-amino-acid is except purifying formaldehyde material and preparation method thereof | |
| CN106179372B (en) | A kind of C@Fe based on biomass porous carbon3O4The Preparation method and use of@Bi composite photo-catalyst | |
| CN114849729A (en) | Ultraviolet light catalytic oxidation degradation pet peculiar smell composite material for air purification and preparation method thereof | |
| CN114409917A (en) | Moisture-resistant iron-based metal organic framework material with catalytic ozonolysis capability and preparation method and application thereof | |
| CN114849751A (en) | Modified catalyst for removing formaldehyde through photocatalysis, and preparation method and application thereof | |
| CN114570340B (en) | Application of graphene oxide/metal organic framework composite material in light-controlled desorption of volatile organic compounds | |
| CN109926033A (en) | Modified small-porosity adsorbent of molecular sieve and its preparation method and application | |
| CN113058630B (en) | Preparation method and application of photocatalyst suitable for efficiently removing formaldehyde at room temperature | |
| CN115870011A (en) | Nano-catalyst for efficiently degrading ammonia pollutants and application method thereof | |
| CN114887667A (en) | Preparation method of novel photocatalytic air purification material | |
| CN111790421B (en) | Graphite-phase carbon nitride modified fabric visible-light-driven photocatalyst and one-step preparation method and application thereof | |
| CN114887655A (en) | Nano NiO-VO X /TiO 2 -molecular sieve composite catalyst and preparation method and application thereof | |
| CN108786919A (en) | The preparation method of carried metallocene catalyst and its preparation method and application and methyl acrylate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |