CN113731501A - Preparation method and application of bromine-doped MOF derivative photocatalyst - Google Patents
Preparation method and application of bromine-doped MOF derivative photocatalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 150000003842 bromide salts Chemical class 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- 239000013207 UiO-66 Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000012855 volatile organic compound Substances 0.000 claims description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 238000006731 degradation reaction Methods 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 230000015556 catabolic process Effects 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000013110 organic ligand Substances 0.000 claims description 10
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229940093915 gynecological organic acid Drugs 0.000 claims description 2
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 40
- 239000003054 catalyst Substances 0.000 abstract description 13
- 239000003463 adsorbent Substances 0.000 abstract description 9
- 230000008929 regeneration Effects 0.000 abstract description 9
- 238000011069 regeneration method Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 102100033069 Histone acetyltransferase KAT8 Human genes 0.000 abstract 7
- 101000944170 Homo sapiens Histone acetyltransferase KAT8 Proteins 0.000 abstract 5
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 64
- 239000000523 sample Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- 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
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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Abstract
The invention discloses a preparation method and application of a bromine-doped MOF derivative photocatalyst. The method comprises the following steps: firstly synthesizing MOF by a hydrothermal method, then adding the MOF into a methanol solution containing bromide salt, stirring, drying and calcining to synthesize 300Brx@ MOF composite photocatalytic material. The catalyst prepared by the invention not only maintains the high adsorption capacity of MOFs, but also overcomes the defect of poor photocatalytic activity of MOFs. On the one hand 300BrxThe @ MOF material is used for catalyzing and enriching pollutants, so that the activity of the catalyst is improved, and on the other hand, the in-situ regeneration of the adsorption material can be realized through the catalytic action of the @ MOF material, so that the problem of adsorbent regeneration is solved. 300Br prepared by the inventionxThe @ MOF composite photocatalytic material has simple preparation methodAnd the cost is low, and the method is favorable for industrial popularization and application.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a preparation method and application of a bromine-doped MOF derivative photocatalyst.
Background
Volatile Organic Compounds (VOCs) as ozone and PM2.5The important precursor seriously harms the natural ecological environment and the human health, so the treatment of the precursor is not slow. The current techniques for controlling VOCs mainly include: adsorption, biological, low-temperature plasma, catalytic combustion, photocatalytic oxidation, and the like. The adsorption method is to perform physical and chemical actions on VOCs in the waste gas through an adsorption material so as to achieve the purpose of enriching the VOCs, and the adsorption method is widely applied to industrial application due to the characteristics of simple operation and low cost. However, the traditional adsorbing materials such as activated carbon, ZSM-5, SAPO-34 and the like simply enrich the VOCs in the exhaust gas, and cannot achieve the purpose of destruction, and after the materials are saturated in adsorption, if the adsorbent is not replaced in time, the enriched VOCs may be desorbed, which brings secondary pollution to the environment.
Metal Organic Frameworks (MOFs) are widely used in the fields of gas adsorption, separation, heterogeneous catalysis and the like due to their advantages of adjustable pore structure, large specific surface area, functionable framework structure and the like. In addition, compared with the traditional adsorption material, the similar semiconductor characteristics of the MOFs can enable the MOFs to be applied to the field of environmental photocatalysis, and free radicals with strong oxidation capacity are generated under illumination, so that VOCs are oxidized and degraded into harmless CO2And H2O。
However, as the MOFs are used as photocatalysts, the oxidation capability mainly depends on the utilization efficiency of photo-generated electrons. However, because most MOFs have low photo-generated charge transfer rates due to their inherent poor conductivity, there is a strong need to increase the photo-generated charge transfer rates of MOFs in order to increase the photocatalytic capabilities of MOFs. In view of the above, the invention firstly obtains UiO-66 by self-assembling the organic ligand and the metal source in situ in a specific solvent, washing and vacuum drying, and then the UiO-66 and brominatingThe salt solution is evenly stirred in methanol, washed, dried and ground, and then the evenly ground material is roasted in a tube furnace under the atmosphere of inert gas to prepare 300Brx@ UiO-66 material. On the one hand, the high-concentration polluted environment can be provided for catalysis through the porous adsorption effect of the adsorbent, the activity of the catalyst is improved, on the other hand, the in-situ desorption regeneration of the adsorbent can be realized through the catalysis, the adsorption capacity of the adsorbent is increased, and the difficult problem of adsorbent regeneration is solved, so that the purification efficiency of the VOCs is effectively improved. The invention provides a new idea for material preparation and VOCs treatment.
Disclosure of Invention
The invention provides a preparation method and application of a bromine-doped MOF derivative photocatalyst. The photocatalyst prepared by the method not only maintains the high adsorption capacity of the MOF, but also overcomes the defect of poor photocatalytic activity of the MOF, and the in-situ regeneration of the adsorption material can be realized by the catalytic action of the photocatalyst, so that the problem of difficult regeneration of the adsorbent is solved.
The purpose of the invention is realized by the following technical scheme:
a preparation method and application of a bromine-doped MOF derivative photocatalyst are characterized in that organic ligands, metal sources and organic acids are hydrothermally synthesized into UiO-66 in a reaction kettle, and then the UiO-66 is added into a methanol solution containing bromide salt to be stirred, dried and calcined to synthesize 300Brx@ UiO-66 composite photocatalytic material.
300BrxThe preparation method of the @ UiO-66 photocatalyst comprises the following steps:
(1) preparation of UiO-66: adding 0.1-0.4g of metal source and 0.1-0.4g of organic ligand into 50-70mL of N, N-dimethylformamide to obtain a mixed solution A, stirring at room temperature for 0.5-1h to completely dissolve the metal source and the organic ligand, adding organic acid into the mixed solution A, mixing and stirring for 0.5-1h to obtain a mixed solution B, transferring the mixed solution B into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 12-48h, naturally cooling, centrifuging, washing, activating, vacuum drying and grinding the precipitate to finally obtain UiO-66; the metal source comprises zirconium tetrachloride, zirconium nitrate, or zirconium sulfate; the organic ligand comprises terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid or 2-bromoterephthalic acid;
(2)300Brxpreparation of @ UiO-66: drying UiO-66 in vacuum, taking a certain amount of the solution to be uniformly dispersed in methanol solution, adding x mL of bromide solution, stirring and ultrasonically treating for 4h at room temperature, drying in a vacuum drying oven, grinding, putting into a crucible, placing in a tubular furnace, calcining for 3-6h at 300 ℃ in nitrogen atmosphere, and naturally cooling to room temperature to obtain a sample of 300Brx@UiO-66；
In the method, in the step (1), the stirring temperature at room temperature is 25-35 ℃, and the stirring speed is 150-300 r/min. The organic acid is glacial acetic acid, propionic acid or butyric acid. The mass percentage concentration of the organic acid solution is 30-60%; the dosage of the acid solution is 2-8 mL.
In the method, in the step (1), the hydrothermal temperature is 100-160 ℃, the hydrothermal reaction pressure is 0.15-0.4 MPa, the solvents used for washing and activating are N, N-dimethylformamide and methanol, the washing centrifugal speed is 5000-7000 r/min, and the vacuum drying temperature is 100-140 ℃.
In the method, in the step (2), the stirring temperature at room temperature is 25-35 ℃, the stirring speed is 150-300 r/min, the vacuum drying temperature is 100-140 ℃, and the volume of the methanol solution is 10-40 mL.
In the method, in the step (2), the concentration of the bromide solution is 0.1-0.5mol/L, and the addition amount of the bromide solution is 0.1-1 mL; the ultrasonic time is 4-6 h.
In the method, in the step (2), the calcination temperature of the tubular furnace is 300-.
A bromine-doped MOF derivative photocatalyst is applied to the field of degradation of volatile organic compounds in the atmosphere.
The material prepared by the invention is essentially different from the existing material, and the invention successfully dopes bromide ions into MOFs by uniformly mixing MOF and bromide salt, drying, roasting in a tube furnace under an inert atmosphere, and finally preparing 300Br with high adsorption capacity and high catalytic activityx@ UiO-66 photocatalyst. 300Br in comparison with pure UiO-66x@ UiO-66 in SecurityWhile maintaining high adsorption capacity, the doping of the bromide ions obviously promotes the effective separation of photoproduction electrons and holes, thereby improving the photocatalysis efficiency.
Compared with the prior art, the invention has the following advantages:
inventive 300BrxCompared with the conventional adsorbing materials (such as activated carbon, ZSM-5, SAPO-34 and the like), the @ UiO-66 has 300BrxThe @ UiO-66 has larger specific surface area and higher adsorption capacity and photocatalytic performance on VOCs. On the one hand 300BrxThe @ UiO-66 material is used for catalyzing and enriching pollutants, improves the activity of the catalyst, and on the other hand is 300BrxAfter the @ UiO-66 material is adsorbed and saturated, the enriched VOCs are not easy to desorb, and the catalytic action of the material can degrade the VOCs, so that the in-situ regeneration of the adsorbing material is realized, and the difficult problem of adsorbent regeneration is solved. Provides basis and guidance for developing VOCs control, adsorption and catalysis integrated technology, and is favorable for solving the problem of prominent volatile organic compound pollution. 300Br prepared by the inventionxThe @ UiO-66 photocatalytic material has the advantages of simple preparation method, lower cost and strong repeatability, and is favorable for industrial popularization and application.
Drawings
FIG. 1 shows UiO-66, 300Br0.2The XRD pattern of @ UiO-66;
FIG. 2 shows UiO-66, 300Br0.2SEM picture of @ UiO-66;
FIG. 3 shows UiO-66, 300Br0.2UV-vis diagram of @ UiO-66;
FIG. 4 is a graph showing the dynamic adsorption of gaseous acetaldehyde by different adsorption materials over time;
FIG. 5 shows 300Br0.2Photocatalytic performance of @ UiO-66 catalyst on acetaldehyde and CO2Generating a quantity graph;
FIG. 6 shows 300Br0.2The @ UiO-66 catalyst is used for dynamic adsorption-catalytic two-stage degradation of acetaldehyde.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
Preparation of UiO-66: adding 0.3g of zirconium tetrachloride and 0.2g of terephthalic acid into 50mL of N, N-dimethylformamide to obtain a mixed solution A, stirring at room temperature for 0.5-1h to completely dissolve the zirconium tetrachloride and the terephthalic acid, adding 6mL of glacial acetic acid into the mixed solution A, mixing and stirring for 0.5-1h to obtain a mixed solution B, transferring the mixed solution B into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 24h, naturally cooling, centrifuging and washing a precipitate with N, N-dimethylformamide and methanol, activating, drying in vacuum, and grinding to finally obtain UiO-66.
Example 2
Preparation of UiO-66: adding 0.3g of zirconium tetrachloride and 0.2g of terephthalic acid into 50mL of N, N-dimethylformamide to obtain a mixed solution A, stirring at room temperature for 0.5-1h to completely dissolve the zirconium tetrachloride and the terephthalic acid, adding 6mL of glacial acetic acid into the mixed solution A, mixing and stirring for 0.5-1h to obtain a mixed solution B, transferring the mixed solution B into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 24h, naturally cooling, centrifuging and washing a precipitate with N, N-dimethylformamide and methanol, activating, drying in vacuum, and grinding to finally obtain UiO-66;
preparation of 300 UiO-66: drying the UiO-66 in vacuum, grinding, putting into a crucible, putting into a tube furnace, calcining for 3-6h at the temperature of 300 ℃ in the nitrogen atmosphere at the heating rate of 1 ℃/min, and naturally cooling to the room temperature to obtain a sample which is 300 UiO-66;
example 3
Preparation of UiO-66: adding 0.3g of zirconium tetrachloride and 0.2g of terephthalic acid into 50mL of N, N-dimethylformamide to obtain a mixed solution A, stirring at room temperature for 0.5-1h to completely dissolve the zirconium tetrachloride and the terephthalic acid, adding 6mL of glacial acetic acid into the mixed solution A, mixing and stirring for 0.5-1h to obtain a mixed solution B, transferring the mixed solution B into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 24h, naturally cooling, centrifuging and washing a precipitate with N, N-dimethylformamide and methanol, activating, drying in vacuum, and grinding to finally obtain UiO-66;
300Br0.2preparation of @ UiO-66: after the UiO-66 is dried in vacuum, 0.4g is taken to be evenly dispersed in 15mL of methanol solution, 0.2mL of potassium bromide solution is added, the mixture is stirred for 4 hours at room temperature,drying in a vacuum drying oven, grinding, placing into a crucible, placing into a tube furnace, calcining at 300 deg.C in nitrogen atmosphere at a heating rate of 1 deg.C/min for 3-6h, and naturally cooling to room temperature to obtain 300Br0.2@UiO-66；
Example 4
Preparation of UiO-66: adding 0.3g of zirconium tetrachloride and 0.2g of terephthalic acid into 50mL of N, N-dimethylformamide to obtain a mixed solution A, stirring at room temperature for 0.5-1h to completely dissolve the zirconium tetrachloride and the terephthalic acid, adding 6mL of glacial acetic acid into the mixed solution A, mixing and stirring for 0.5-1h to obtain a mixed solution B, transferring the mixed solution B into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction for 24h, naturally cooling, centrifuging and washing a precipitate with N, N-dimethylformamide and methanol, activating, drying in vacuum, and grinding to finally obtain UiO-66;
300Br0.8preparation of @ UiO-66: after the UiO-66 is dried in vacuum, 0.4g of the solution is uniformly dispersed in 15mL of methanol solution, 0.8mL of potassium bromide solution is added, the solution is stirred for 4 hours at room temperature, the solution is dried in a vacuum drying oven, the dried solution is put into a crucible after being ground, the crucible is put into a tubular furnace, the calcined solution is calcined for 3 to 6 hours at the temperature of 300 ℃ under the nitrogen atmosphere at the heating rate of 1 ℃/min, the calcined solution is naturally cooled to the room temperature, and the obtained sample is 300Br0.8@UiO-66；
Example 5
And (3) material characterization and analysis: FIG. 1 shows UiO-66, 300Br0.2The XRD pattern of @ UiO-66 shows that the positions of the diffraction peaks of the different materials are substantially identical, and no significant shift occurs. This indicates that the crystal structure of the calcined sample is not changed and the framework structure is maintained. FIG. 2 shows UiO-66, 300Br0.2The SEM image of @ UiO-66 shows that different materials are octahedral configurations with regular morphological structures, and the skeletal structure of the materials can be maintained after calcination. The sample of UiO-66 prepared in the above example was white, the color was yellow after calcination with nitrogen at 300 ℃ (300UiO-66), and after calcination with nitrogen at 300 ℃ (300 Br) after doping with bromine0.2@ UiO-66) is white, indicating that bromine doping changes the valence state of the metal in the derivative, resulting in a change in the color of the sample. FIG. 3 shows UiO-66, 300Br0.2UV-vis diagram of @ UiO-66, from whichIt is known that the edge of the absorption band of the UiO-66 sample is around 320nm, the absorption band of the UiO-66 sample is red-shifted after being calcined in nitrogen at 300 ℃ (300UiO-66), and the absorption band is red-shifted to the right after bromine ion doping, which indicates the successful bromine ion doping.
Example 6
Dynamic adsorption of gas phase acetaldehyde: acetaldehyde is used as a probe molecule, and the adsorption capacity of the catalyst on the acetaldehyde is researched. The acetaldehyde adsorption reaction was carried out in a quartz glass tube having an inner diameter of 6mm and a length of 300mm under the test conditions: the dosage of the catalyst is 100 mg; the initial concentration of acetaldehyde is about 85 ppm; the flow rate of the reaction gas was 50 mL/min. As shown in a of fig. 4, activated carbon, ZSM-5 and SAPO-34 are only used for simply enriching VOCs in exhaust gas, and cannot achieve the purpose of destroying the VOCs, and after the adsorption of the material is saturated, the enriched acetaldehyde is desorbed to bring secondary pollution to the environment, while 300Br is used for enriching VOCs in exhaust gas0.2After the @ UiO-66 is saturated in adsorption, the enriched acetaldehyde cannot be desorbed. In addition 300Br0.2The breakthrough times (840min) for acetaldehyde adsorption of @ UiO-66 were 42, 5.25 and 14 times higher for AC (20min), ZSM-5(160min) and SAPO-34(60min), respectively, indicating 300Br0.2The adsorption capacity of @ UiO-66 for acetaldehyde is much greater than that of commercially available porous materials. The effect of bromine doping at different concentrations on the adsorption capacity of acetaldehyde is shown in graph b of FIG. 4, 300Br0.2The adsorption capacity of @ UiO-66 to acetaldehyde is obviously greater than 300Br0.8@ UiO-66 and 300UiO-66, because the bromine doping changes the chemical environment of the metal site of the UiO-66 derivative, changes the valence state and the channel structure of the metal in the derivative, and thus changes the adsorption performance of the UiO-66.
Example 7
Photocatalytic activity analysis: acetaldehyde is adopted as a probe molecule to explore the photocatalytic activity of the catalyst. The photocatalytic acetaldehyde degradation reaction is carried out in a self-made reactor, ultraviolet light is adopted for irradiation, and the light intensity is 100 mW/cm; the volume of the reactor is 120 mL; the dosage of the catalyst is 100 mg; the initial concentration of acetaldehyde is about 85 ppm; the flow rate of the reaction gas is 50 mL/min; after the dark adsorption reaction reaches the adsorption/desorption balance for a period of time, turning on the lamp; detecting acetaldehyde concentration value by gas chromatography with FID detector, and detecting CO and C by nickel converterO2The amount of production. According to the dynamic adsorption-catalysis synchronous degradation of gas phase acetaldehyde shown in FIG. 5, the experimental result shows that 300Br0.2@ UiO-66 has excellent ability of degrading acetaldehyde and CO by photocatalysis2The formation amount and the anti-carbon deactivation performance.
Example 8
Dynamic adsorption-catalytic two-stage degradation of gas phase acetaldehyde: in order to consider the situation that adsorption catalysis cannot be carried out simultaneously in practical application, dynamic adsorption-catalysis two-stage degradation of gas-phase acetaldehyde is tested, namely, dark adsorption is carried out on VOCs, illumination degradation is carried out after adsorption saturation, and the two steps are carried out separately. Acetaldehyde is used as a probe molecule in an experiment, and dynamic adsorption-catalytic two-stage degradation of the catalyst on gas-phase acetaldehyde is explored. The acetaldehyde adsorption reaction was carried out in a quartz glass tube having an inner diameter of 6mm and a length of 300mm under the test conditions: the dosage of the catalyst is 100 mg; the initial concentration of acetaldehyde is about 85 ppm; the flow rate of the reaction gas was 50 mL/min. The photocatalytic acetaldehyde degradation reaction is carried out in a self-made reactor, ultraviolet light is adopted for irradiation, and the light intensity is 100 mW/cm; the volume of the reactor is 120 mL; the dosage of the catalyst is 100 mg; the initial concentration of acetaldehyde is about 85 ppm; the flow rate of the reaction gas is 50 mL/min; directly placing a sample with acetaldehyde saturated in adsorption into a photocatalytic reactor for illumination; acetaldehyde concentration values were determined by gas chromatography with FID detector. As shown in FIG. 6, 300Br0.2The @ UiO-66 firstly carries out dark adsorption on acetaldehyde, and then carries out light degradation after adsorption saturation. The experimental result shows that 300Br0.2The @ UiO-66 has better acetaldehyde adsorption and catalytic degradation capacity on acetaldehyde, and the regenerated 300Br0.2The @ UiO-66 still keeps better acetaldehyde adsorption and catalytic degradation capability for 4 times of cyclic adsorption-catalytic degradation of acetaldehyde, and realizes in-situ adsorption and destruction of VOCs, thereby solving the problem of adsorbent regeneration.
The above examples are merely illustrative of the technical solutions of the present invention and not restrictive, and it will be understood by those of ordinary skill in the art that various changes in the details or forms thereof may be made without departing from the spirit and scope of the present invention as defined by the claims.
Claims (10)
1. A preparation method of a bromine-doped MOF derivative photocatalyst is characterized in that organic ligands, metal sources and organic acids are hydrothermally synthesized into UiO-66 in a reaction kettle, then the UiO-66 is added into a methanol solution containing bromide salt, stirred, dried, calcined at a high temperature under a nitrogen atmosphere, and naturally cooled to room temperature to obtain a sample of 300Brx@ UiO-66 composite photocatalytic material.
2. A method of preparing a bromine-doped MOF derivative photocatalyst according to claim 1, comprising the steps of:
(1) preparation of UiO-66: adding a metal source and an organic ligand into N, N-dimethylformamide to obtain a mixed solution A, stirring at room temperature until the metal source and the organic ligand are completely dissolved, then adding an acid into the mixed solution A, mixing and stirring to obtain a mixed solution B, transferring the mixed solution B into a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction, naturally cooling, centrifugally washing, activating and vacuum drying a precipitate, and grinding to finally obtain an MOF (metal organic framework), namely UiO-66; the metal source comprises zirconium tetrachloride, zirconium nitrate, or zirconium sulfate; the organic ligand comprises terephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid or 2-bromoterephthalic acid;
(2)300Brxpreparation of @ UiO-66: vacuum drying UiO-66, dispersing UiO-66 in methanol solution, adding bromide solution, stirring at room temperature, ultrasonic treating, drying in vacuum drying oven, grinding, placing in crucible, calcining at 300 deg.C in nitrogen atmosphere, and naturally cooling to room temperature to obtain 300Brx@UiO-66。
3. The preparation method of the bromine-doped MOF derivative photocatalyst is characterized in that in the step (1), the addition amount of the metal source is 0.1-0.4 g; the addition amount of the organic ligand is 0.1-0.4 g; the addition amount of the N, N-dimethylformamide is 50-70 mL.
4. The preparation method of the bromine-doped MOF derivative photocatalyst according to claim 2, wherein in the step (1), the stirring temperature at room temperature is 25-35 ℃, and the stirring speed is 150-300 r/min; the time is as follows: 0.5-1 h; the organic acid is glacial acetic acid, propionic acid or butyric acid; the mass percentage concentration of the organic acid solution is 30-60%; the dosage of the acid solution is 2-8 mL.
5. The preparation method of the bromine-doped MOF derivative photocatalyst according to claim 2, wherein in the step (1), the hydrothermal temperature is 100-160 ℃, the hydrothermal reaction pressure is 0.15-0.4 MPa, and the hydrothermal reaction time is 12-48 h; solvents used for washing and activating are N, N-dimethylformamide and methanol, the washing centrifugal speed is 5000-7000 r/min, and the vacuum drying temperature is 100-140 ℃.
6. The preparation method of the bromine-doped MOF derivative photocatalyst according to claim 2, wherein in the step (2), the stirring temperature at room temperature is 25-35 ℃, the stirring speed is 150-300 r/min, the vacuum drying temperature is 100-140 ℃, and the volume of the methanol solution is 10-40 mL.
7. The preparation method of the bromine-doped MOF derivative photocatalyst according to claim 2, wherein in the step (2), the concentration of the bromide solution is 0.1-0.5mol/L, and the addition amount of the bromide solution is 0.1-1 mL; the ultrasonic time is 4-6 h.
8. The method for preparing the bromine-doped MOF derivative photocatalyst according to claim 2, wherein in the step (2), the calcination temperature of the tubular furnace is 300-500 ℃, the time is 3-6h, and the temperature rise rate is 1-3 ℃/min.
9. A bromine-doped MOF derivative photocatalyst prepared by the preparation method of any one of claims 1 to 8.
10. The bromine-doped MOF derivative photocatalyst of claim 9 is applied to the field of degradation of volatile organic compounds in the atmosphere.
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