CN116889866A - Diatomite-based composite material and preparation method and application thereof - Google Patents
Diatomite-based composite material and preparation method and application thereof Download PDFInfo
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- CN116889866A CN116889866A CN202311043452.3A CN202311043452A CN116889866A CN 116889866 A CN116889866 A CN 116889866A CN 202311043452 A CN202311043452 A CN 202311043452A CN 116889866 A CN116889866 A CN 116889866A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000002131 composite material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 36
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 150000003751 zinc Chemical class 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 239000005909 Kieselgur Substances 0.000 claims description 41
- 230000015556 catabolic process Effects 0.000 claims description 22
- 238000006731 degradation reaction Methods 0.000 claims description 22
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 9
- 239000012621 metal-organic framework Substances 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 3
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 24
- 238000006555 catalytic reaction Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000031700 light absorption Effects 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 176
- 230000000052 comparative effect Effects 0.000 description 50
- 239000000463 material Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 30
- 230000003197 catalytic effect Effects 0.000 description 22
- 239000007789 gas Substances 0.000 description 22
- 239000010453 quartz Substances 0.000 description 22
- 230000000694 effects Effects 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
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- 230000009471 action Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003642 reactive oxygen metabolite Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003256 environmental substance Substances 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- SXGZJKUKBWWHRA-UHFFFAOYSA-N 2-(N-morpholiniumyl)ethanesulfonate Chemical compound [O-]S(=O)(=O)CC[NH+]1CCOCC1 SXGZJKUKBWWHRA-UHFFFAOYSA-N 0.000 description 1
- 239000007987 MES buffer Substances 0.000 description 1
- 101000860173 Myxococcus xanthus C-factor Proteins 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- -1 carbon modified diatomite Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 230000006798 recombination Effects 0.000 description 1
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- 238000000985 reflectance spectrum Methods 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a diatomite-based composite material, a preparation method and application thereof, wherein the method comprises the following steps: dissolving zinc salt in a first solvent, and then adding diatomite to obtain a first solution; adding a second solvent to the ligand as a second solution; adding the second solution into the first solution, and stirring to obtain a ZIF-8/diatomite composite material; heating up and then cooling down to calcine the mixture in two stages, and naturally cooling the mixture to room temperature to obtain the ZIF-8 derived carbon/diatomite composite substrate; dissolving a manganese-containing salt in a third solvent as a third solution; adding a fourth solvent into the composite substrate, and soaking to obtain a fourth solution; and adding the solid matters obtained after the filtration of the fourth solution into the third solution, stirring, and calcining to obtain the manganese dioxide@ZIF-8 derived carbon/diatomite composite material. Compared with the prior art, the invention has excellent volatile organic compound adsorption performance, light absorption performance, photo-thermal conversion performance and photo-thermal catalysis performance, and can be recycled for multiple times.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a diatomite-based composite material, and a preparation method and application thereof.
Background
In recent years, due to the widespread use of paints and the like, formaldehyde gas released by the paints and the like for a long time has seriously affected indoor air quality and is greatly threatening the life health of people, and thus has received a great deal of attention (IU C, MIAO X, LI J.Outdor formaldehyde matters and substantially impacts indoor formaldehyde concentrations [ J ] Building and Environment,2019, 158:145-150.). Strategies such as physical adsorption, membrane separation, primary biological filtration (BELLAT J, BEZVERKHYY I, WEBER G, et al Capture of formaldehyde by adsorption on nanoporous materials [ J ]. Journal of Hazardous Materials,2015, 300:711-717.) have been developed in recent years for removing indoor formaldehyde, wherein physical adsorption is favored for its advantages of simplicity in use, high formaldehyde removal efficiency, and high speed, such as molecular sieves (SHEN X, DUX, YANG D, et al Influence of physical structures and chemical modification on VOCs adsorption characteristics of molecular sieves [ J ]. Journal of Environmental Chemical Engineering,2021,9 (6): 106729.), activated carbon (SHEN X, DUX, YANG D, et al Influence of physical structures and chemical modification on VOCs adsorption characteristics of molecular sieves [ J ]. Journal of Environmental Chemical Engineering,2021,9 (6): 106729.), and diatomaceous earth (CHEN Z, ZHANG H, LUO W, et al Diatomite in situ loaded by MOF (ZIF-8) and its application in removing methylene orange from aqueous solutions [ J ]. 275-265), and 2019,15): 275-265 have been more widely paid attention to porous materials.
Diatomaceous earth (DA) has received a great deal of attention in recent years due to its low cost, environmental friendliness and excellent adsorption capacity for Volatile Organic Compounds (VOCs), and has been successfully marketed as an adsorbent coating. However, the mechanism of removing formaldehyde by DA is mainlyIn order to realize the adsorption based on intermolecular forces, the adsorbed formaldehyde is desorbed once the high-temperature weather is met, so that secondary pollution is caused. Because DA surface is rich in hydroxyl (-OH) and has regular morphology, the catalyst is extremely suitable for being used as a matrix material of a catalyst (LIC, WANG M, CHEN Z, et al enhanced thermal conductivity and photo-to-thermal performance of diatomite-based composite phase change materials for thermal energy storage [ J)]Journal of Energy Storage,2021, 34:102171) the use of catalyst modification is therefore a promising solution. Manganese dioxide (MnO) 2 ) Is an excellent thermal catalyst, can rapidly degrade formaldehyde into water and carbon dioxide at a certain temperature, and is expected to solve the problem of secondary pollution caused by high temperature of DA. However, the temperature provided by the high temperature weather is still different from the temperature required by catalysis, and is insufficient to fully activate MnO 2 Catalysis, and therefore, the catalytic efficiency is limited. MnO has been reported 2 Electrons of the solar energy collector can be subjected to non-radiative recombination under the irradiation of infrared light, heat is released, and the solar energy collector has strong photo-thermal conversion capability, so that MnO is carried out under the irradiation of the sun 2 Can provide heat for self-catalysis, and photo-thermo-catalytically degrade formaldehyde (HUANG J, ZHONGS, DAI Y, et al Effect of MnO) 2 Phase Structure on the Oxidative Reactivity toward Bisphenol A Degradation[J].Environmental Science&Technology,2018,52 (19): 11309-11318.). Thus, mnO is utilized 2 The composite DA catalyst (MD) can photo-thermally degrade formaldehyde to avoid secondary pollution caused by diatomite, and has a good application prospect. However, the low heat conduction and weak light absorption capabilities of diatomaceous earth limit the photo-thermal conversion capabilities of the composite material, thereby limiting its photo-thermal catalytic effect.
In recent years, metal-organic framework (MOF) materials are widely used in the fields of gas adsorption, catalysis and the like due to the extremely large specific surface area and excellent micro-mesoporous structure, and ZIF-8 (a Zn has been reported 2+ MOF as center) can obtain the carbon material with micro-mesoporous structure by high temperature carbonization under inert gas atmosphere, thus being applied to improving the light absorption capacity, the photo-thermal conversion capacity and the heat conduction capacity (Cao Fengli, teng Shuai, high rise, etc. of the material with different carbonization temperaturesInfluence of degree on ZIF-8 carbide catalytic Activity [ J]Shandong chemical industry, 2018,47 (7): 4-6.). In addition, researches indicate that ZIF-8 can uniformly grow on the surface of diatomite by taking-OH on the surface of diatomite as an anchor point, and the adsorption performance of the material is improved, so that the carbonized ZIF-8 modified MD is expected to strengthen the light absorption capacity, the photo-thermal conversion capacity and the heat conduction capacity, and further improve the adsorption capacity and promote the catalysis.
Patent CN111715287A discloses a ZIF-67/GO photocatalysis-photo-thermal composite film, and a preparation method and application thereof, and the preparation method comprises the following steps: adding graphene oxide into ultrapure water, and performing ultrasonic treatment to obtain a uniform solution of the graphene oxide, namely a GO aqueous solution; filtering the GO aqueous solution on a PTFE membrane, and drying at normal temperature to obtain a GO membrane; co (NO) 3 ) 2 ·6H 2 Pouring the O solution into a culture dish with GO membrane, keeping at 35-45 ℃ for 8-24 hours, pouring the solution, and cleaning the membrane with methanol; pouring the 2-methylimidazole solution into a solution containing Co (NO) 3 ) 2 ·6H 2 The GO membrane soaked by the O solution is placed in a culture dish, kept at 35-45 ℃ for 8-24 hours, then the solution is poured out, and the membrane is washed by methanol; finally, drying in a vacuum drying oven at 60 ℃ to obtain the ZIF-67/GO photocatalysis-photo-thermal composite film. However, the preparation process of the composite film material requires longer time, and the prepared ZIF-67/GO photocatalysis-photo-thermal composite film is of a lamellar structure, so that the composite film material is difficult to prepare in a large area and cannot meet the requirement of large-area application; meanwhile, the prepared composite film can catalyze and reduce metal ions only under the photocatalysis-photo-thermal synergistic catalysis condition, and whether the metal ions can be catalyzed and reduced under the thermal catalysis is unknown; in the application field, in addition to catalytic reduction of metal ions, whether VOCs in the air can be catalytically degraded is also a critical problem.
Disclosure of Invention
The invention aims to overcome at least one defect in the prior art and provide a diatomite-based composite material, a preparation method and application thereof.
The aim of the invention can be achieved by the following technical scheme:
one of the technical schemes of the invention is to provide a preparation method of a diatomite-based composite material, which comprises the following steps:
(1) The zinc salt was dissolved in the first solvent, then diatomaceous earth (DA) was added, and stirred vigorously overnight to give zinc ions (Zn 2+ ) Hydroxyl (-OH) groups bonded to the surface of diatomaceous earth as a first solution; adding a second solvent into the ligand, and fully stirring until the second solvent is dissolved to obtain a second solution; then slowly adding the second solution into the first solution, stirring, carrying out coordination assembly on the ligand around zinc ions, thereby growing ZIF-8 on the surface of diatomite, centrifuging, washing and drying the product overnight to obtain a ZIF-8/diatomite (ZIF-8/DA, ZD) composite material; heating two sections of the ZIF-8/diatomite composite material, cooling and calcining, and naturally cooling to room temperature to obtain a ZIF-8 derived carbon/diatomite (ZIF-8-C/DA, ZCD) composite substrate;
(2) Dissolving manganese-containing salt in a third solvent, and stirring until the manganese-containing salt is completely dissolved to obtain a third solution; adding a fourth solvent into the ZIF-8 derived carbon/diatomite composite substrate, sealing and soaking to enable the fourth solvent to be connected to hydroxyl on the surface of the diatomite to be used as a fourth solution; the solid material after filtration of the fourth solution was then added to the third solution under agitation, after sealing, the product was stirred, centrifuged, washed, dried overnight and calcined to remove residual fourth solvent to yield manganese dioxide @ ZIF-8 derived carbon/diatomaceous earth (MnO) 2 @ ZIF-8-C/DA, MZCD) composite.
Further, the zinc salt in step (1) comprises zinc nitrate (Zn (NO 3 ) 2 ) Or zinc carbonate (Zn (CO) 3 ) 2 ) The first solvent comprises methanol or ethanol;
the ligand comprises 2-methylimidazole or 4-methylimidazole, and the second solvent comprises methanol or ethylene glycol.
Further, in the step (1), the concentration of zinc ions is 40-50mmol/L, and the mass ratio of zinc ions to diatomite is (0.005-0.009): 1;
the ligand concentration is 170-180mmol/L, and the molar ratio of zinc ions to ligand is 1 (4-4.2).
Further, in the steps (1) and (2), the stirring and soaking time is 10-13h.
As a preferable technical scheme, the washing solvent in the step (1) is methanol or ethanol.
As a preferred technical scheme, the drying temperature in the steps (1) and (2) is 50-70 ℃.
As a preferable technical scheme, the calcination environment in the step (1) is argon or helium.
Further, in the step (1), calcining for a period of time with the temperature rising rate of 3-6 ℃/min, the temperature of 250-350 ℃ and the heat preservation time of 2-4h;
the second stage heating rate is 4-6deg.C/min, the temperature is 750-850 deg.C, and the heat preservation time is 2-4h;
the cooling rate is 1-3 ℃/min, the temperature is 150-250 ℃, and the heat preservation time is 8-12min.
Further, the manganese-containing salt in step (2) comprises potassium permanganate (KMnO) 4 ) Or potassium manganate (K) 2 MnO 4 ) The third solvent comprises water or methanol;
the fourth solvent includes n-butanol, ethanol or methanol.
Further, the concentration of manganese ions in the step (2) is 50-450mmol/L;
the concentration of the ZIF-8 derived carbon/diatomite composite substrate is 20-30g/L, and the mol/mass ratio of manganese ions to the ZIF-8 derived carbon/diatomite composite substrate is (2-18 mmol) 1g.
As a preferable technical scheme, the washing solvent in the step (2) is ethanol or methanol.
Further, in the step (2), the calcining temperature rising rate is 3-6 ℃/min, the temperature is 150-250 ℃ and the time is 1-3h.
One of the technical proposal of the invention is to provide a diatomite-based composite material prepared by the method, which is Metal Organic Framework (MOF) derived carbon modified diatomite-loaded manganese dioxide (MnO) 2 ) Is a composite material of (a).
One of the technical schemes of the invention is to provide an application of the diatomite-based composite material, wherein the composite material is applied to adsorption catalytic degradation of volatile organic compounds.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, diatomite is taken as a substrate, ZIF-8 is uniformly loaded on the substrate in an in-situ growth manner to obtain a ZIF-8/diatomite composite material, the ZIF-8 derived C/diatomite composite substrate is obtained through carbonization, and finally manganese dioxide is loaded on the composite substrate by using a redox method and an in-situ growth method to obtain a manganese dioxide@ZIF-8 derived C/diatomite composite material, wherein the composite material has a larger specific surface area, more excellent capability of adsorbing volatile organic matters and photo-thermal catalytic degradation capability of volatile organic matters compared with the traditional diatomite material;
(2) The invention has the advantages that the synthesis time is short, the specific surface area of the composite material is large, and the existence of the pore structure further increases the catalytic degradation efficiency;
(3) The invention has good adsorption and degradation efficiency and photo-thermal conversion characteristics, and can obviously improve the light absorption efficiency and the photo-thermal catalytic degradation capability of volatile organic compounds of the material;
(4) The invention can rapidly generate heat and completely degrade volatile organic compounds into nontoxic and harmless water and carbon dioxide, can be recycled for multiple times, can simply and thoroughly eradicate indoor volatile organic compounds, can be used as a wall coating, and has wider application area and range.
Drawings
FIG. 1 is a field emission scanning electron microscope (FE-SEM) image of diatomaceous earth-based materials of example 3 and comparative examples 1 to 4 at various magnifications;
FIG. 2 is a Scanning Electron Microscope (SEM), EDS and Mapping image of the diatomaceous earth-based material of example 3 and comparative examples 1 to 4 at 10k magnification;
FIG. 3 is an X-ray diffraction (XRD) spectrum of the material of example 3 and comparative examples 1 to 3, 5 and 6 of the present invention;
FIG. 4 is a Fourier Transform Infrared (FTIR) spectrum of the material of example 3 and comparative examples 1 to 3, 5 and 6 of the present invention;
FIG. 5 is an overall view and a partial enlarged view of BET nitrogen adsorption-desorption curves of the materials of example 3 and comparative examples 3, 4 and 6 according to the present invention;
FIG. 6 is an X-ray photoelectron spectroscopy (XPS) chart of the diatomite-based composite material of example 3 and comparative example 4 of the present invention;
FIG. 7 is a graph showing the results of a pseudo-first and pseudo-second order adsorption kinetics fit for the diatomite-based material of example 3 and comparative examples 1 and 3 of the present invention;
FIG. 8 is a graph showing the thermocatalytic effect of the diatomite-based material of example 3 and comparative examples 1 and 4 of the present invention;
FIG. 9 is a graph showing diffuse reflectance spectra of ultraviolet-visible-near infrared (UV-vis-NIR) transmittance, reflectance and absorbance values of diatomite-based materials in example 3 and comparative examples 1,3 and 4 according to the present invention, and a graph showing the effect of photothermal conversion;
FIG. 10 is a graph of the photocatalytic effect of the diatomite-based material of the present invention in examples and comparative examples 1,3 and 4, including a graph of the photocatalytic formaldehyde degradation rate of examples at different concentrations, a graph of the photocatalytic formaldehyde degradation rate of different samples, a graph of the photocatalytic formaldehyde mineralization effect of different samples, and a graph of the cyclic catalytic formaldehyde degradation rate of example 3;
FIG. 11 is a graph showing the catalytic formaldehyde degradation rate of the diatomite-based composite material under different conditions in example 3 of the present invention;
FIG. 12 is a graph showing the photo-thermal conversion effect and Tauc plot of the diatomite-based composite material of example 3 of the present invention;
FIG. 13 is a schematic diagram of a catalytic formaldehyde degradation mechanism of a diatomite-based composite material under ultraviolet-visible light in an embodiment of the present invention;
FIG. 14 is a schematic diagram of the overall catalytic mechanism of a diatomite-based composite material in an embodiment of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
The equipment used in the following examples is representative of conventional equipment in the art unless otherwise specified; unless otherwise indicated, all reagents used are commercially available or prepared by methods conventional in the art, and all of the following examples, not specifically described, are accomplished by means of conventional experimentation in the art.
Examples 1 to 4:
a diatomite-based composite material and a preparation method thereof specifically comprises the following steps:
(1) Preparation of ZIF-8 derived carbon/diatomaceous earth (ZIF-8-C/DA, ZCD) composite substrate:
0.64g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) in a beaker, 50mL of methanol was added, followed by 2g of diatomaceous earth (DA) and vigorously stirred overnight to give zinc ions (Zn) 2+ ) Hydroxyl (-OH) bonded to the DA surface as solution A; 0.72g of 2-methylimidazole was placed in a beaker, 50mL of methanol was added thereto, and the mixture was sufficiently stirred until dissolved, to obtain a solution B; solution B was then slowly added to solution A and stirred for 12h, 2-methylimidazole was taken over Zn 2+ Assembling around the catalyst, so as to grow ZIF-8 on the surface of DA, centrifuging the product, washing the product with methanol for three times, and drying the product in a baking oven at 60 ℃ overnight to obtain a ZIF-8/diatomite (ZIF-8/DA, ZD) composite material; ZD was placed in a tube furnace and calcined under argon atmosphere according to the following procedure: heating to 300 ℃ at a speed of 5 ℃/min, preserving heat for 3 hours, then continuously heating to 800 ℃ at a speed of 5 ℃/min, preserving heat for 3 hours, then cooling to 200 ℃ at a speed of 2 ℃/min, preserving heat for 10 minutes, and naturally cooling to room temperature to obtain a black powdery product, namely ZCD;
(2) Manganese dioxide @ ZIF-8 derived C/diatomaceous earth (MnO) 2 Preparation of @ ZIF-8-C/DA, MZCD) composite material:
potassium permanganate (KMnO) 0.316g, 0.623g, 0.948g and 1.264g, respectively 4 ) Placing in a beaker, adding 20mL deionized water, stirring to KMnO 4 Completely dissolved, configured into 100mmol/L, 200mmol/L, 300mmol/L and 400mmol/L solution; placing 0.5g of ZCD in a beaker, adding 20mL of n-butanol, sealing, and soaking for 12h to enable the n-butanol to be connected to-OH on the surface of DA; subsequently filtering off excess n-butanol and separating the remaining solid materialAdding KMnO to the stirring 4 In the solution, stirring for 12h after sealing, centrifuging and washing with ethanol for three times, drying overnight in a 60 ℃ oven, placing the product in a muffle furnace, calcining at a temperature rising rate of 5 ℃/min and at 200 ℃ for 2h to remove residual n-butanol, and collecting the product, namely xMZCD, wherein x=100, 200, 300 or 400.
Comparative example 1:
diatomaceous earth, directly purchased from Alatting, was immersed in methanol at the time of the experiment to increase the dispersibility of DA.
Comparative example 2:
the preparation method of the ZIF-8/diatomite composite material is the same as that of ZD in examples.
Comparative example 3:
the preparation method of the ZIF-8 derived carbon/diatomite composite substrate is the same as that of ZCD in the examples.
Comparative example 4:
manganese dioxide @ diatomite (MnO) 2 @DA, MD) composite material and a preparation method thereof, wherein the specific steps are as follows:
0.948g KMnO 4 Placing in a beaker, adding 20mL deionized water, stirring to KMnO 4 Completely dissolving; placing 0.5g DA in beaker, adding 20mL n-butanol, sealing, soaking for 12 hr, filtering to remove excessive n-butanol, adding the rest solid material into KMnO under stirring 4 The solution is stirred for 12 hours after sealing, centrifuged and washed 3 times by ethanol, then the solution is dried overnight in a baking oven at 60 ℃, the product is placed in a muffle furnace and calcined for 2 hours at 200 ℃ at a heating rate of 5 ℃/min to remove residual n-butanol, and the product is collected to be MD.
Comparative example 5:
a ZIF-8 and a preparation method thereof specifically comprises the following steps:
0.3g of zinc acetate was placed in a beaker and dissolved in 10mL of deionized water as solution a; 1.12g of 2-methylimidazole was placed in a beaker and dissolved in 10mL of deionized water as solution B; solution B was then slowly added to solution A and stirred at room temperature (-33 ℃) for 24 hours, after which the product was centrifuged and washed three times with deionized water and dried in an oven at 40℃for 5 hours to give ZIF-8.
Comparative example 6:
manganese dioxide (MnO) 2 ) The preparation method comprises the following specific steps:
79mg KMnO 4 Placing in beaker, dissolving in 10mL deionized water, adding 5mL 2- (N-morpholino) ethanesulfonic acid buffer solution (MES buffer solution, pH is 6.5,0.1M), stirring for 30min until oxidation-reduction reaction is completed, centrifuging the product, washing with deionized water for three times, and drying in oven at 40deg.C for 5h to obtain brown black product (MnO) 2 。
As shown in FIG. 1, A represents comparative example 1DA, B represents comparative example 2ZD, C represents comparative example 3ZCD, D represents example 3 MZD, and E represents comparative example 4MD, it can be seen that the DA of example 3 successfully supports a Metal Organic Framework (MOF) and the pore structure of the DA remains intact, undamaged or masked.
As shown in FIG. 2, the small particle on comparative example 2ZD is ZIF-8; mn signals are present in both comparative example 4MD and example 3MZCD, indicating MnO 2 Is introduced successfully; example 3 the presence of a C signal in the MZCD further indicates the successful loading and carbonization of ZIF-8.
The experiment adopts X-ray diffraction analysis, an X-ray diffractometer is used for detection, cu-K alpha is used as a radiation source, the voltage is 40kV, the current is 200mA, the scanning range is 5-80 degrees, and the scanning speed is 10 degrees/min.
As shown in FIG. 3, the characteristic peaks of comparative example 2ZD were similar to those of comparative example 5ZIF-8, demonstrating the successful loading of ZIF-8; characteristic peak of example 3MZCD with comparative example 6MnO 2 Is similar to the characteristic peak of the (C) to prove MnO 2 Is introduced successfully; the characteristic peaks of MZD of example 3 are similar to those of comparative example 1DA, comparative example 2ZD and comparative example 3ZCD, demonstrating successful synthesis of MZD.
As shown in FIG. 4, the absorption peak of comparative example 2ZD was similar to that of comparative example 5ZIF-8, demonstrating the successful loading of ZIF-8; example 3 absorption peak of MZCD with comparative example 6MnO 2 Is similar to the absorption peak of (a) to prove MnO 2 Is introduced successfully; example 3 absorption peak of MZCD and comparative examples 1DA, 2ZD and 1DAThe absorption peaks of 3ZCD are similar, demonstrating successful synthesis of MZD.
As shown in FIG. 5, mnO can be seen by the change of the curve 2 The original pore channel of the MZDD of the embodiment 3 (comparative example 3 ZCD) is not covered, and the overall specific surface area of the MZDD of the embodiment 3 is further improved.
As shown in fig. 6, a to C represent comparative example 4MD, d to F represent example 3MZCD, and by comparing the peaks of Mn, O, C and Si, it can be seen that example 3MZCD can capture more free oxygen than comparative example 4MD, which has a key promoting effect on oxygen supplementation in the catalytic cycle.
To study ZIF-8-C and MnO 2 The influence of the addition of the material on the formaldehyde adsorption capacity of the material is tested, and the specific steps are as follows:
introducing mixed gas of formaldehyde and air with the volume ratio of 4:1 into a 500mL quartz bottle, and stabilizing the concentration of the formaldehyde gas to 180mg/m 3 And then, sealing the quartz bottle, connecting a quartz tube (0.1 g of sample is placed in the quartz tube), quickly transferring a guide pipe of the quartz tube into a gas monitor, and recording the change of the formaldehyde concentration in the system within 3 hours.
As shown in FIG. 7, after ZIF-8-C is introduced, the adsorption property of the material to formaldehyde is improved from 0.11mg/g of comparative example 1DA to 0.35mg/g of comparative example 3ZCD, mnO 2 After introduction, the adsorption performance was further improved to 0.42mg/g of MZCD of example 3, indicating ZIF-8-C and MnO 2 The introduction of (3) greatly improves the adsorption performance of the material to formaldehyde due to ZIF-8-C and MnO 2 The introduction of the (C) improves the pore structure and the specific surface area of the material, thereby improving the adsorption capacity.
In order to verify that the material can completely remove formaldehyde under the action of heat, the thermocatalytic effect of the material at 100 ℃ is tested, and the specific steps are as follows:
introducing mixed gas of formaldehyde and air with the volume ratio of 4:1 into a 500mL quartz bottle, and stabilizing the concentration of the formaldehyde gas to 180mg/m 3 After that, the quartz bottle was closed and placed in a muffle furnace and a system of equipment for gas monitoring (the tube furnace was preheated to 100 ℃ C., insideA sample of 0.1g was placed in a quartz tube), and the change in the formaldehyde concentration in the system was recorded over 2 hours.
As shown in FIG. 8, the formaldehyde in the system was reduced to some extent at 100deg.C, and comparative example 1DA, comparative example 4MD and example 3MZCD reduced formaldehyde by 17.91%, 59.17% and 79.76%, respectively, indicating MnO under the action of heat 2 The formaldehyde removal performance of the material is greatly improved by doping; both comparative example 4MD and example 3MZCD produced a certain amount of carbon dioxide (CO 2 ) This suggests that MD and MZD promote formaldehyde degradation, MZD more completely degrades formaldehyde, produces water (H 2 O) and CO 2 While DA is free of CO 2 The generation shows that formaldehyde caused by DA is reduced to chemisorption, which indicates that DA is subjected to chemisorption, and is consistent with the research result of adsorption kinetics; in addition, CO 2 The content of (2) is far higher than the theoretical yield because the formaldehyde gas in the experiment is derived from the volatilization of the formaldehyde solution, and part of methanol contained in the formaldehyde solution is volatilized together with the formaldehyde gas in the process and degraded together with the formaldehyde gas, thereby causing CO 2 The yield of (2) is far higher than the theoretical yield.
The photothermal conversion efficiency test was irradiated with light of full spectrum, and the change in material temperature from the time of turning on was recorded using an AS877 two-channel thermocouple thermometer, once every 15s, for 10min.
As shown in FIG. 9, comparative example 1DA has a certain absorption capacity only for ultraviolet light below 320nm, shows a strong reflection and transmission capacity for light in other wave bands, and after ZIF-8-C is doped (comparative example 3 ZCD), the absorption capacity of the material is greatly improved, and shows good absorption for the whole wave band, when MnO is doped 2 After that (example 3 MZCD), the light absorption capacity of the material in the ultraviolet visible region was further enhanced, and the absorption capacity in the near infrared region was slightly decreased but still far stronger than that of comparative example 1DA, which suggests that the introduction of ZIF-8-C successfully improved the light absorption capacity of the material, while MnO 2 The light absorption performance is not reduced by the introduction of the catalyst, so that the expected effect is met; meanwhile, the full spectrum absorption capacity of example 3MZCD is much stronger than that of comparative example 4MD without ZIF-8-C added, because the presence of carbon makes the materialThe light absorption capacity is greatly improved, so that the MZD shows strong light absorption;
comparative example 1DA the temperature of which was raised to about 64.5℃under full spectrum xenon irradiation, and the photothermal temperature rise of which was raised to 79.5℃after ZIF-8-C was introduced (comparative example 3 ZCD), because the introduction of carbon increased the absorption of DA in the infrared region, reduced reflection and transmission, increased the thermal effect of infrared light, resulting in a temperature rise, while MnO was continued to be introduced 2 (example 3 MZCD) the photothermal heating of the material was further raised to 132.6℃because of MnO 2 Has extremely strong photo-thermal conversion efficiency, and compared with comparative example 4MD, the photo-thermal temperature rise of the MZCD of example 3 is increased by 27.7 ℃, which improves the photo-absorption performance of the material due to the introduction of ZIF-8-C, improves the MnO 2 More light energy is obtained, and finally better photo-thermal effect is obtained for the MZD.
To select the most suitable MnO 2 Load capacity we tested different KMnO 4 The catalytic effect of the prepared MZD is under the concentration, and the 300 MZD composite material is continuously recycled for five times to catalyze and degrade formaldehyde, and the specific steps are as follows:
introducing mixed gas of formaldehyde and air with the volume ratio of 4:1 into a 500mL quartz bottle, and stabilizing the concentration of the formaldehyde gas to 180mg/m 3 And then, sealing the quartz bottle, connecting a quartz tube (0.1 g of sample is placed in the quartz tube), quickly transferring a guide tube of the quartz tube into a gas monitor, recording the change of the formaldehyde concentration in a system within 2-3 hours, and continuously circulating for 5 times.
As shown in FIG. 10, the formaldehyde degradation rate of the material in the example is over 80%, when KMnO with the concentration of 300mmol/L is used 4 When the catalyst is used (300 MZCD in example 3), the catalytic degradation effect is best and reaches 99.71%; comparative example 3ZCD and comparative example 1DA both have a certain formaldehyde removal effect, but their CO 2 The yield was almost 0, which means that both are mainly adsorbed, and ZCD showed higher chemisorption ratio than DA according to adsorption kinetics analysis, so that ZCD adsorbed gas was more difficult to desorb, showing relatively higher formaldehyde removal rate, and comparative example 4MD and example 3 MZD showed 92.48% and 99.71%, respectivelyAt the same time they have a large amount of CO in the system 2 Generated, which indicates that the two can promote the degradation of formaldehyde and MZCD shows stronger catalytic activity, because compared with MD, the ZIF-8-C is introduced to lead the MZCD to obtain stronger photo-thermal conversion capability, the temperature of the MZCD is higher, and MnO on the composite material 2 The catalytic ability of (2) is shown to be temperature dependent, so that MZCD has stronger catalytic activity, and at the same time, the introduction of ZIF-8-C improves the pore structure of the material, so that the material has better adsorption performance and gradually changes from physical adsorption to chemical adsorption, and besides, according to the result of FIG. 6, the material has more Mn due to the addition of ZIF-8-C 3+ The oxygen vacancies are increased, so that more oxygen can be captured, and further the catalytic reaction is promoted;
the formaldehyde degradation rate in each of the five cycles reaches more than 99%, which shows that the 300MZCD of the embodiment 3 has good reusability and can be repeatedly used without being deactivated basically.
In order to determine the catalytic mechanism of MZCD, we tested the degradation effect of the material on formaldehyde under two different conditions of 130 ℃ (determined by photo-thermal conversion effect) and simulated sunlight irradiation, and the specific steps are as follows:
introducing mixed gas of formaldehyde and air with the volume ratio of 4:1 into a 500mL quartz bottle, and stabilizing the concentration of the formaldehyde gas to 180mg/m 3 After that, the quartz bottle was closed, placed in a system of a muffle furnace and a gas monitor (the tube furnace was preheated to 130 ℃ C., and 0.1g of example 3MZCD was placed in the inner quartz tube), and the change in the formaldehyde concentration in the system was recorded over 2 hours.
Introducing mixed gas of formaldehyde and air with the volume ratio of 4:1 into a 500mL quartz bottle, and stabilizing the concentration of the formaldehyde gas to 180mg/m 3 After that, the quartz bottle was closed and connected to a quartz tube (0.1 g of example 3MZCD was placed in the inside quartz tube), the tube of the quartz tube was rapidly transferred to a gas monitor, the quartz tube was irradiated with a xenon lamp, and the change in the formaldehyde concentration in the system within 2 hours was recorded.
As shown in fig. 11, the degradation rate of formaldehyde reaches 94.55% in 2h at 130 ℃, and the degradation efficiency reaches 99.71% under the irradiation of simulated sunlight, and the catalysis rate is faster, which indicates that the material not only degrades formaldehyde through thermal catalysis, but also exerts a certain effect; considering that the photo-thermal effect of the material is mainly generated by infrared light, we test the ultraviolet and visible light catalytic effect of the material, and as a result, the degradation rate of the material to formaldehyde reaches 86.44%, which indicates that the MZD also has a certain ultraviolet and visible light catalytic effect.
As shown in FIG. 12, example 3MZCD was able to reach 60.7℃in 600 seconds under UV-visible light irradiation, at which temperature delta-MnO was found 2 Formaldehyde gas can be degraded to a certain extent, but the efficiency is lower; in addition, we studied the band gap of MZCD by Tauc plot method, which is 1.94eV.
As shown in fig. 13, when the MZCD absorbs uv-visible light, electrons are transited from the valence band to the conduction band, holes are generated in the valence band, OH-occupying holes on the surface of the catalyst are converted into OH, and OH has extremely strong oxidative degradation capability, so that formaldehyde is degraded, and therefore, the catalytic rate and efficiency of the MZCD under full spectrum irradiation are higher than those of pure thermal catalysis due to the contribution of not only thermal catalysis but also photocatalysis in the catalytic process of the MZCD.
As shown in FIG. 14, formaldehyde is first bonded to the hydroxyl groups on the DA surface of MZD through hydrogen bonds, adsorbed on the MZD surface, and MnO in MZD under sunlight 2 The temperature rises and simultaneously starts to photo-catalyze and thermo-catalyze formaldehyde degradation; mnO (MnO) 2 After absorbing sunlight, electrons of the sunlight undergo transition to form a photo-generated hole at a valence band position, OH-is converted into OH, and the OH further degrades formaldehyde into H 2 O and CO 2 The method comprises the steps of carrying out a first treatment on the surface of the At the same time, mnO 2 After absorbing sunlight, the sunlight is converted into heat, and under the action of the heat, the surface of the heat adsorbs oxygen to be coated by MnO 2 Converts into Reactive Oxygen Species (ROS) and simultaneously forms a positively charged oxygen vacancy, the ROS further oxidatively degrading formaldehyde into H 2 O and CO 2 At the same time Mn 4+ Is reduced to Mn 3+ Subsequently, positively charged oxygen vacancies capture oxygen in the air, again Mn 3+ Oxidation to Mn 4+ One cycle is completed.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the diatomite-based composite material is characterized by comprising the following steps of:
(1) Dissolving zinc salt in a first solvent, and then adding diatomite to obtain a first solution; adding a second solvent to the ligand as a second solution; adding the second solution into the first solution, stirring, and centrifuging the product to obtain a ZIF-8/diatomite composite material; heating the ZIF-8/diatomite composite material for two sections, cooling and calcining, and naturally cooling to room temperature to obtain the ZIF-8 derived carbon/diatomite composite substrate;
(2) Dissolving a manganese-containing salt in a third solvent as a third solution; adding a fourth solvent into the ZIF-8 derived carbon/diatomite composite substrate, and soaking to obtain a fourth solution; and adding the solid matters obtained after the filtration of the fourth solution into the third solution, stirring, centrifuging and calcining the product to obtain the manganese dioxide@ZIF-8 derived carbon/diatomite composite material.
2. The method of preparing a diatomaceous earth-based composite according to claim 1, wherein in step (1), the zinc salt comprises zinc nitrate or zinc carbonate, and the first solvent comprises methanol or ethanol;
the ligand comprises 2-methylimidazole or 4-methylimidazole, and the second solvent comprises methanol or ethylene glycol.
3. The method for producing a diatomaceous earth-based composite according to claim 1, wherein the concentration of zinc ions in the step (1) is 40 to 50mmol/L, and the mass ratio of zinc ions to diatomaceous earth is (0.005 to 0.009): 1;
the ligand concentration is 170-180mmol/L, and the molar ratio of zinc ions to ligand is 1 (4-4.2).
4. The method for preparing a diatomite-based composite material as set forth in claim 1, wherein the stirring and soaking times in steps (1) and (2) are each 10-13 hours.
5. The method for preparing a diatomite-based composite material according to claim 1, wherein the calcination in the step (1) has a heating rate of 3-6 ℃/min, a temperature of 250-350 ℃ and a heat preservation time of 2-4 hours;
the second stage heating rate is 4-6deg.C/min, the temperature is 750-850 deg.C, and the heat preservation time is 2-4h;
the cooling rate is 1-3 ℃/min, the temperature is 150-250 ℃, and the heat preservation time is 8-12min.
6. The method of preparing a diatomite-based composite material of claim 1, wherein in step (2), the manganese-containing salt comprises potassium permanganate or potassium manganate, and the third solvent comprises water or methanol;
the fourth solvent includes n-butanol, ethanol or methanol.
7. The method for preparing a diatomite-based composite material of claim 1, wherein in step (2), the manganese ion concentration is 50-450mmol/L;
the concentration of the ZIF-8 derived carbon/diatomite composite substrate is 20-30g/L, and the mol/mass ratio of manganese ions to the ZIF-8 derived carbon/diatomite composite substrate is (2-18 mmol) 1g.
8. The method for preparing a diatomite-based composite material according to claim 1, wherein the calcination temperature rise rate in step (2) is 3-6 ℃/min, the temperature is 150-250 ℃, and the time is 1-3 hours.
9. A diatomite-based composite material prepared by the method of any one of claims 1 to 8, wherein the composite material is a metal organic framework-derived carbon-modified diatomite-supported manganese dioxide composite material.
10. Use of the diatomite-based composite material of claim 9, wherein said composite material is applied to adsorption-catalyzed degradation of volatile organic compounds.
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