CN109482241B - TiO2/MOF-5 photocatalyst and preparation method thereof - Google Patents
TiO2/MOF-5 photocatalyst and preparation method thereof Download PDFInfo
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- 239000013132 MOF-5 Substances 0.000 title claims abstract description 65
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 79
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229960000583 acetic acid Drugs 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000011701 zinc Substances 0.000 description 11
- 238000000227 grinding Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
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- 229940093915 gynecological organic acid Drugs 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- PZASAAIJIFDWSB-CKPDSHCKSA-N 8-[(1S)-1-[8-(trifluoromethyl)-7-[4-(trifluoromethyl)cyclohexyl]oxynaphthalen-2-yl]ethyl]-8-azabicyclo[3.2.1]octane-3-carboxylic acid Chemical compound FC(F)(F)C=1C2=CC([C@@H](N3C4CCC3CC(C4)C(O)=O)C)=CC=C2C=CC=1OC1CCC(C(F)(F)F)CC1 PZASAAIJIFDWSB-CKPDSHCKSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
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- 239000012621 metal-organic framework Substances 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- ZSBDPRIWBYHIAF-UHFFFAOYSA-N n-acetylacetamide Chemical compound CC(=O)NC(C)=O ZSBDPRIWBYHIAF-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention relates to a TiO compound2/MOF-5 photocatalyst, preparation method thereof and TiO2The preparation method of the/MOF-5 photocatalyst comprises the following steps: providing a MOF-5 material; preparing a mixed solution of ethanol and water, and adjusting the pH value to 2-4 to obtain a first solution; mixing tetrabutyl titanate, glacial acetic acid and ethanol to form a second solution; adding an MOF-5 material into the second solution to obtain a third solution; adding the first solution into the third solution and stirring uniformly; filtering, aging the obtained filtrate, drying and calcining to obtain TiO2a/MOF-5 photocatalyst. TiO prepared by the method2the/MOF-5 photocatalyst has higher photocatalytic efficiency.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to TiO2A/MOF-5 photocatalyst and a preparation method thereof.
Background
The photocatalysis technology, namely the semiconductor photocatalyst technology, can be used for degrading organic wastewater, reducing heavy metal ions, purifying air, sterilizing, preventing fog and the like. Nano titanium dioxide (TiO)2) As a photocatalyst, the photocatalyst is an n-type semiconductor material with excellent performance, can fully utilize solar energy, is efficient, energy-saving and environment-friendly, shows better light stability and higher reaction activity when in reaction, is nontoxic, has low cost and no secondary pollution, and is a nano functional material with the widest application prospect at present.
MOF-5 is one of the most typical representatives of the family of metal-organic framework complexes and has milestone significance in the history of metal-organic complex development. MOF-5 is composed of 4 Zn2+And 1O2-Formed [ Zn ]4O]6+Inorganic and organic radicals [ O ]2C-C-C6H4-CO2]2-Three-dimensional rigid skeleton structure formed by octahedron connection, and the chemical basic unit of the three-dimensional rigid skeleton structure is Zn4O(BDC)3The structure is as follows:
each Zn4The O clusters are respectively connected with 6 organic ligand units, and each organic ligand is connected with 2 Zn4The O units are connected and have a three-dimensional orthogonal pore channel structure. The data published by researchers about the study of the Langmuir specific surface area of MOF-5 materials are not the same, and the Yaghi subject group Hailian Li et al report specific surface areas as high as 2900m2The specific surface area reported by Rowsell and the like is larger and can reach 3362m2(ii) in terms of/g. In summary, MOF-5 is a very potential framework compound with higher specific surface area and higher porosity than the commonly used solid supports, activated carbon, zeolites, molecular sieves, silica, etc. Because MOF-5 has very large specific surface area and rich pore channel structure, TiO can be synthesized2Combined with MOF-5 to form a composite material, i.e. TiO2a/MOF-5 photocatalyst.
TiO commonly used at present2The synthesis method of the/MOF-5 comprises the steps of directly adding tetrabutyl titanate into the MOF-5, stirring, sealing, aging, drying and grinding. Even if the MOF-5 has a large specific surface area, the loading amount of titanium oxide on the MOF-5 is still low, so that the catalytic efficiency of the prepared catalyst is low, and the application of the catalyst is limited.
Disclosure of Invention
Based on this, there is a need to provide a TiO with higher catalytic efficiency2A/MOF-5 photocatalyst and a preparation method thereof.
TiO 22A preparation method of the/MOF-5 photocatalyst comprises the following steps:
providing a MOF-5 material;
preparing a mixed solution of ethanol and water, and adjusting the pH value to 2-4 to obtain a first solution;
mixing tetrabutyl titanate, glacial acetic acid and ethanol to form a second solution;
mixing the MOF-5 material with the second solution to obtain a third solution;
adding the first solution into the third solution and stirring uniformly;
filtering, aging the obtained filtrate, drying and calcining to obtain the TiO2a/MOF-5 photocatalyst.
The above TiO compound2The preparation method of the/MOF-5 photocatalyst comprises the steps of mixing tetrabutyl titanate and glacial acetic acid to form a second solution, mixing the second solution with an MOF-5 material to form a third solution, and then dripping an alcohol-water mixed solution with the pH of 2-4 into the third solution, so that the local concentration of hydrolysis can be effectively improved, the tetrabutyl titanate can be rapidly hydrolyzed at the moment of dripping the alcohol-water mixed solution and is loaded on the MOF-5 material, the loading capacity of titanium oxide on the MOF-5 can be effectively improved, and meanwhile, the obtained TiO is2the/MOF-5 photocatalyst has excellent properties and can effectively improve the TiO of unit mass2The catalytic efficiency of the MOF-5 photocatalyst.
In one embodiment, the pH is adjusted to 2-4 with 4-6 mol/L nitric acid.
In one embodiment, in the first solution, the volume ratio of the ethanol to the water is (1.5-3): 1.
in one embodiment, in the second solution, the volume ratio of the glacial acetic acid to the ethanol is 1: (1.5-8).
In one embodiment, in the second solution, the volume ratio of the glacial acetic acid to the ethanol is 1: (1.5-4).
In one embodiment, in the second solution, the ratio of the total volume of both glacial acetic acid and ethanol to the volume of tetrabutyl titanate is (2.5-4): 1.
in one embodiment, in the step of adding the first solution into the third solution and stirring uniformly, the first solution is added into the third solution dropwise at a speed of 1-3 drops per second.
In one embodiment, the calcining temperature is 200-700 ℃, and the calcining time is 1-4 h.
In one embodiment, the temperature of the calcination is 450 ℃ to 700 ℃.
In one embodiment, the calcining gas atmosphere is a mixed gas composed of oxygen and an inert gas, and the volume ratio of the oxygen to the inert gas is 1: (2-5).
In one embodiment, the method further comprises the step of preparing the MOF-5 material:
mixing zinc nitrate, terephthalic acid and N, N-dimethylformamide, adding triethylamine, reacting to obtain a solid, collecting the solid, washing and drying to obtain the MOF-5.
In one embodiment, the molar ratio of terephthalic acid to zinc nitrate is in the range of 1: (0.8-1.5).
TiO prepared by the method2a/MOF-5 photocatalyst.
TiO prepared by the method2the/MOF-5 photocatalyst has higher load capacity, and can effectively improve the catalytic efficiency of the catalyst.
Drawings
FIG. 1 is the TiO of example 12XRD pattern of/MOF-5 photocatalyst;
FIG. 2 shows TiO of example 12Electron micrograph of/MOF-5 photocatalyst.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The present invention will be described below with reference to specific examples.
Example 1
The first step is as follows: the synthesis reagent of MOF-5 is Zn (NO)3)2·6H2O, 1, 4-benzenedicarboxylic acid (H)2BDC), N-Dimethylformamide (DMF) and Triethylamine (TEAC).
First, 1.21g of Zn (NO) is added3)2·6H2O and 40ml of N, N-Dimethylformamide (DMF) were placed in a beaker, and 0.34g of terephthalic acid (H) was added at room temperature2BDC) was added to a beaker, stirred continuously, after the solid was completely dissolved, 1.3mL of triethylamine TEAC was added to the mixed solution, stirred continuously, and allowed to react for about 3 hours to obtain a white solid, which was filtered under suction, and washed with DMF 3-4 times during suction filtration to remove unreacted inorganic salts and organic acids from the product. And finally, putting the sample into an oven for drying. And grinding and sample loading after drying.
The second step is that: mixing 4.5ml of distilled water and 8.9ml of absolute ethyl alcohol, and adjusting the pH to 3 by using a prepared 5mol/L nitric acid solution to prepare a first solution; adding 4.5ml of glacial acetic acid into 26.7ml of absolute ethyl alcohol, and slowly adding 8.9ml of tetrabutyl titanate into the solution under vigorous stirring to form a light yellow transparent solution to form a second solution; 0.6546g of MOFs-5 material is weighed, the MOF-5 material is slowly poured into the second solution, and the second solution is uniformly stirred and mixed to obtain a third solution; the first solution was slowly added to the third solution at a rate of 1 drop per second with vigorous stirring, and the stirring was stopped after the addition of the drops was completed. And carrying out reduced pressure filtration on sol-gel generated by the reaction, aging at normal temperature, and then putting the product into an oven to dry at 100 ℃. Grinding the dried product (in the form of particles), then calcining the product in a high-temperature furnace at 500 ℃ for 2h, and introducing mixed gas of oxygen and nitrogen in a ratio of 1:3 in the calcining process to obtain the TiO of example 12The XRD pattern of the/MOF-5 photocatalyst is shown in figure 1, and the electron microscope image is shown in figure 2.
Example 2
The first step is as follows: the synthesis reagent of MOF-5 is Zn (NO)3)2·6H2O, 1, 4-benzenedicarboxylic acid (H)2BDC), N-Dimethylformamide (DMF) and Triethylamine (TEAC).
First, 1.21g of Zn (NO) is added3)2·6H2O and 40ml of N, N-Dimethylformamide (DMF) were placed in a beaker, and 0.34g of terephthalic acid (H) was added at room temperature2BDC) was added to a beaker, stirred continuously, after the solid was completely dissolved, 1.3mL of triethylamine TEAC was added to the mixed solution, stirred continuously, and allowed to react for about 3 hours to obtain a white solid, which was filtered under suction, and washed with DMF 3-4 times during suction filtration to remove unreacted inorganic salts and organic acids from the product. And finally, putting the sample into an oven for drying. And grinding and sample loading after drying.
The second step is that: mixing 8.9ml of distilled water and 8.9ml of absolute ethyl alcohol, and adjusting the pH to 3 by using a prepared 5mol/L nitric acid solution to prepare a first solution; adding 4.5ml of glacial acetic acid into 26.7ml of absolute ethyl alcohol, and slowly adding 8.9ml of tetrabutyl titanate into the solution under vigorous stirring to form a light yellow transparent solution to form a second solution; 0.6546g of MOFs-5 material is weighed, the MOF-5 material is slowly poured into the second solution, and the second solution is uniformly stirred and mixed to obtain a third solution; the first solution was slowly added to the third solution at a rate of 1 drop per second with vigorous stirring, and the stirring was stopped after the addition of the drops was completed. And carrying out reduced pressure filtration on sol-gel generated by the reaction, aging at normal temperature, and then putting the product into an oven to dry at 100 ℃. Grinding the dried product (in the form of particles), then calcining the product in a high-temperature furnace at 500 ℃ for 2h, and introducing mixed gas of oxygen and nitrogen in a ratio of 1:3 in the calcining process to obtain the TiO of example 12a/MOF-5 photocatalyst.
Example 3
The first step is as follows: the synthesis reagent of MOF-5 is Zn (NO)3)2·6H2O, 1, 4-benzenedicarboxylic acid (H)2BDC), N-Dimethylformamide (DMF) and Triethylamine (TEAC).
First, 1.21g of Zn (NO) is added3)2·6H2O and 40ml of N, N-dimethylformylAmine (DMF) was placed in a beaker and 0.34g of terephthalic acid (H) was added at room temperature2BDC) was added to a beaker, stirred continuously, after the solid was completely dissolved, 1.3mL of triethylamine TEAC was added to the mixed solution, stirred continuously, and allowed to react for about 3 hours to obtain a white solid, which was filtered under suction, and washed with DMF 3-4 times during suction filtration to remove unreacted inorganic salts and organic acids from the product. And finally, putting the sample into an oven for drying, and grinding and loading the sample after drying.
The second step is that: mixing 4.5ml of distilled water and 8.9ml of absolute ethyl alcohol, and adjusting the pH to 3 by using a prepared 5mol/L nitric acid solution to prepare a first solution; adding 4.5ml of glacial acetic acid into 26.7ml of absolute ethyl alcohol, and slowly adding 8.9ml of tetrabutyl titanate into the solution under vigorous stirring to form a light yellow transparent solution to form a second solution; 0.6546g of MOFs-5 material is weighed, the MOF-5 material is slowly poured into the second solution, and the second solution is uniformly stirred and mixed to obtain a third solution; the first solution was slowly added to the third solution at a rate of 1 drop per second with vigorous stirring, and the stirring was stopped after the addition of the drops was completed. And carrying out reduced pressure filtration on sol-gel generated by the reaction, aging at normal temperature, and then putting the product into an oven to dry at 100 ℃. Grinding the dried product (in the form of particles), then calcining the product in a high-temperature furnace at 300 ℃ for 2h, and introducing mixed gas of oxygen and nitrogen in a ratio of 1:3 in the calcining process to obtain the TiO of example 22a/MOF-5 photocatalyst.
Comparative example 1
The first step is as follows: the synthesis reagent of MOF-5 is Zn (NO)3)2·6H2O, 1, 4-benzenedicarboxylic acid (H)2BDC), N-Dimethylformamide (DMF) and Triethylamine (TEAC).
First, 1.21g of Zn (NO) is added3)2·6H2O and 40ml of N, N-Dimethylformamide (DMF) were placed in a beaker, and 0.34g of terephthalic acid (H) was added at room temperature2BDC) into a beaker, continuously stirring, after the solid is completely dissolved, adding 1.3mL of triethylamine TEAC into the mixed solution, continuously stirring, stirring to react for about 3h to obtain a white solid, carrying out suction filtration, and carrying out suction filtration for a suction filtration periodWashing with DMF for 3-4 times to remove unreacted inorganic salt and organic acid. And finally, putting the sample into an oven for drying, and grinding and loading the sample after drying.
The second step is that: adding 4.5ml of glacial acetic acid into a mixed solution formed by mixing 35.6ml of absolute ethyl alcohol and 4.5ml of distilled water, slowly adding 8.9ml of tetrabutyl titanate into the mixed solution under vigorous stirring to form a light yellow transparent solution, and adjusting the pH value of the solution to 3 by using 5mol/L nitric acid solution to form a first solution; 0.6546g of MOFs-5 material was weighed and the MOF-5 material was slowly poured into the above first solution and mixed well with stirring. And carrying out reduced pressure filtration on sol-gel generated by the reaction, aging at normal temperature, and then putting the product into an oven to dry at 100 ℃. Grinding the dried product (in the form of particles), then calcining the product in a high-temperature furnace at 300 ℃ for 2h, and introducing mixed gas of oxygen and nitrogen in a ratio of 1:3 in the calcining process to obtain the TiO of the comparative example 12a/MOF-5 photocatalyst.
Formaldehyde photocatalytic degradation test
TiO of example 1-example 3 and comparative example 12Carrying out a formaldehyde photocatalytic degradation test on the MOF-5 photocatalyst;
the test principle is as follows: TiO is carried out in a self-made photocatalysis experiment box2The experiment for degrading formaldehyde by photocatalysis realizes the degradation of formaldehyde in aqueous solution by irradiating a catalyst by an ultraviolet light source, and the reaction activity of the photocatalyst is evaluated by measuring the degradation rate of formaldehyde after the irradiation of light for a certain time.
The test method comprises the following steps: accurately transferring 2mL of formaldehyde stock solution and 100mL of water in a reaction tank, and shaking up. Accurately transferring 2.5mL of solution into a test tube to be detected in absorbance. Weighing 0.25g of catalyst in a reaction tank, shaking up, putting into a reactor, opening an ultraviolet lamp for illumination degradation for 5h, wherein a sample is taken once per hour, the reaction tank is firstly shaken lightly before the sample is taken, so that the solutions are mixed uniformly, then standing for a moment, and then a pipette is used for transferring about 5mL of the solution to the absorbance to be measured in a test tube. Meanwhile, a blank comparative experiment without adding a catalyst is carried out.
Adding deionized water into a test tube containing the sampling solution to 25mL, simultaneously carrying out a blank test, replacing a sample with 25mL of water, adding 2.5mL of acetylacetone solution, shaking up, heating in a water bath at 909100 ℃ for 10min, taking out and cooling. The absorbance was measured at a wavelength of 414nm with water as a reference. The formaldehyde concentration can be calculated by substituting the light absorption value into a formula obtained by a standard curve, and the degradation rate D% is calculated by using a formula 1.3:
in the formula A0，AtThe absorbance of the solution before the reaction and at the reaction time t are respectively; finally, a degradation rate and time curve is prepared, the degradation performance of the catalyst is compared, the degradation performance is compared with that of a blank test, and the test results are shown in the following table 1.
TABLE 1
It can be seen from examples 1-3 that the Ni-doped TiO prepared by the above method2the/MOF-5 photocatalyst has stronger photocatalysis effect.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. TiO 22A preparation method of the/MOF-5 photocatalyst is characterized by comprising the following steps:
providing a MOF-5 material;
preparing a mixed solution of absolute ethyl alcohol and water, and adjusting the pH value to 2-4 to obtain a first solution;
mixing tetrabutyl titanate, glacial acetic acid and absolute ethyl alcohol to form a second solution;
mixing the MOF-5 material with the second solution to obtain a third solution;
adding the first solution into the third solution and stirring uniformly;
filtering, aging the obtained filtrate, drying and calcining to obtain the TiO2a/MOF-5 photocatalyst;
the calcining temperature is 450-700 ℃;
in the first solution, the volume ratio of the absolute ethyl alcohol to the water is (1.5-3) to 1;
in the second solution, the volume ratio of the glacial acetic acid to the absolute ethyl alcohol is 1 (1.5-8);
in the second solution, the ratio of the total volume of both the glacial acetic acid and the absolute ethyl alcohol to the volume of the tetrabutyl titanate is (2.5-4): 1.
2. The TiO of claim 12The preparation method of the/MOF-5 photocatalyst is characterized in that the calcination time is 1-4 h.
3. The TiO of claim 22The preparation method of the/MOF-5 photocatalyst is characterized in that the calcining gas atmosphere is a mixed gas consisting of oxygen and inert gas, and the volume ratio of the oxygen to the inert gas is 1 (2-5).
4. The TiO of claim 12Preparation method of/MOF-5 photocatalystThe method is characterized in that the volume ratio of the glacial acetic acid to the absolute ethyl alcohol in the second solution is 1 (1.5-4).
5. The TiO of claim 12The preparation method of the/MOF-5 photocatalyst is characterized in that the pH is adjusted to 2-4 by adopting 4-6 mol/L nitric acid.
6. The TiO of claim 12The preparation method of the/MOF-5 photocatalyst is characterized in that in the step of adding the first solution into the third solution and uniformly stirring, the first solution is dropwise added into the third solution at the speed of 1-3 drops per second.
7. TiO according to any one of claims 1 to 62The preparation method of the MOF-5 photocatalyst is characterized by further comprising the following steps of:
mixing zinc nitrate, terephthalic acid and N, N-dimethylformamide, adding triethylamine, reacting to obtain a solid, collecting the solid, washing and drying to obtain the MOF-5 material.
8. The TiO of claim 72The preparation method of the/MOF-5 photocatalyst is characterized in that the molar ratio of the terephthalic acid to the zinc nitrate is 1 (0.8-1.5).
9. TiO produced by the process according to any one of claims 1 to 82a/MOF-5 photocatalyst.
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