CN109482243B - TiO2Preparation method of/MOF-5 composite photocatalyst - Google Patents
TiO2Preparation method of/MOF-5 composite photocatalyst Download PDFInfo
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- 239000013132 MOF-5 Substances 0.000 title claims abstract description 74
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title description 10
- 239000000243 solution Substances 0.000 claims abstract description 82
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003960 organic solvent Substances 0.000 claims abstract description 42
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 39
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003751 zinc Chemical class 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000010355 oscillation Effects 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- -1 diethyl titanate Chemical compound 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
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- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination 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
- 239000008204 material by function Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J31/26—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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Loaded TiO (titanium dioxide)2The preparation method of the composite photocatalyst comprises the following steps: adding triethylamine into a mixed solution of soluble zinc salt, terephthalic acid and a first organic solvent to deprotonate the terephthalic acid and self-assemble zinc ions into MOF-5, filtering, washing, drying and grinding to obtain MOF-5 powder; hydrolyzing a hydrolyzable titanium source with water in a second organic solvent to obtain a first solution containing nano titanium dioxide; concentrating the first solution, and increasing the concentration of the nano titanium dioxide sol to obtain a second solution; adding the MOF-5 powder into the second solution, fully mixing by ultrasonic oscillation, filtering, washing and drying to obtain TiO2A MOF-5 composite photocatalyst.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to TiO2A preparation method of a MOF-5 composite photocatalyst.
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. Therefore, the semiconductor photocatalytic material has attracted extensive attention in the aspect of controlling environmental pollution. In order to improve the photocatalytic efficiency and the service life of semiconductor materials and ensure the stability and the safety of the materials, it is important to continuously develop novel photocatalytic materials.
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 in reaction, is nontoxic, has low cost and no secondary pollution, and has the best current application prospectIs a wide range of nanometer functional materials.
However, the nanometer titanium dioxide as the photocatalyst has some problems. On the one hand, TiO2The spectrum range is narrow, the ultraviolet light is needed to excite and generate electrons, the ultraviolet content under the sunlight is less than 5 percent, and the nano titanium dioxide is usually powdery, and only a small amount of TiO on the surface is generated in the reaction process2Absorbs ultraviolet light to play a role of photocatalysis, thereby causing low light quantum efficiency. On the other hand, a suspension reaction system is usually adopted when the pollutants in the solution are degraded by photocatalysis, and the ultrafine particle form of the nano titanium dioxide causes the nano titanium dioxide to be in a stable milky dispersion form in the reaction system, namely TiO2Difficult separation and recovery in the degradation process, and is not beneficial to the reuse of the catalyst.
MOF-5 is the most typical representative of a family of metal-organic framework complexes, MOF-5 being 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)3. 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. Yaghi topic group Hailian Li et al reported that MOF-5 prepared by them had a specific surface area as high as 2900m2The specific surface area of MOF-5 reported by Rowsell and the like can reach 3362m2(ii) in terms of/g. The MOF-5 has large specific surface area and pore volume and can accommodate a large amount of TiO2Can also adsorb and enrich organic matters to improve the mass transfer rate and greatly increase TiO2Efficiency of catalytic degradation, MOF-5 is a very potential framework compound. But how to incorporate TiO2Loading onto MOF-5 is a problem.
Disclosure of Invention
Based on this, it is necessary to provide a TiO against the problem of MOF-5 difficult to load2A preparation method of a MOF-5 composite photocatalyst.
The invention provides a TiO compound2The preparation method of the/MOF-5 composite photocatalyst comprises the following steps:
adding triethylamine into a mixed solution of soluble zinc salt, terephthalic acid and a first organic solvent to deprotonate the terephthalic acid and self-assemble zinc ions into MOF-5, filtering, washing, drying and grinding to obtain MOF-5 powder;
hydrolyzing a hydrolyzable titanium source with water in a second organic solvent to obtain a first solution containing nano titanium dioxide;
concentrating the first solution, and increasing the concentration of the nano titanium dioxide sol to obtain a second solution; and
adding the MOF-5 powder into the second solution, fully mixing by ultrasonic oscillation, filtering, washing and drying to obtain TiO2A MOF-5 composite photocatalyst.
In one embodiment, the mass ratio of the added MOF-5 to the second solution is 1: 10-1: 100.
In one embodiment, the concentrating step comprises evaporating the first solution by a volume of 1/5-1/2.
In one embodiment, the step of hydrolysis comprises: and dropwise adding deionized water into a mixed solution of a second organic solvent, an acidic pH regulator and a titanium source, and then heating and stirring at 40-65 ℃ to obtain a titanium dioxide sol solution, wherein the volume ratio of the acidic pH regulator to the titanium source to the organic solvent to the deionized water is 1: 8-15: 80-150: 150-250.
In one embodiment, the step of forming the first solution further comprises: and (3) dropwise adding a strong oxidizing acid solution into the titanium dioxide sol solution, and then heating and refluxing at 60-85 ℃.
In one embodiment, the strong oxidizing acid solution is nitric acid or sulfuric acid, and H in the strong oxidizing acid solution+The concentration of the strong oxidizing acid solution is 0.1-0.2 mol/L, and the volume ratio of the strong oxidizing acid solution to the titanium dioxide sol solution is 1: 1.2-2.
In one embodiment, the molar ratio of the soluble zinc salt to the terephthalic acid is 1: 0.8-1: 1.5, the mass ratio of the soluble zinc salt to the first organic solvent is 1: 30-1: 50, and the mass ratio of the triethylamine to the soluble zinc salt is 1: 0.5-1: 3.
In one embodiment, the soluble zinc salt comprises at least one of zinc acetate dihydrate, zinc nitrate hexahydrate, and zinc chloride.
In one embodiment, the titanium source comprises at least one of tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium tert-butoxide, diethyl titanate, and titanium tetrachloride.
In one embodiment, the first organic solvent comprises at least one of N, N-dimethylformamide, N-methylpyrrolidone, N-diethylformamide, dimethyl sulfoxide, deionized water, triethylamine, and hydrogen peroxide; the second organic solvent includes at least one of methanol, ethanol, and isopropanol.
The TiO provided by the invention2The preparation method of the MOF-5 composite photocatalyst comprises the steps of preparing MOF-5 by a self-assembly method, preparing a solution of nano-scale titanium dioxide sol by utilizing a hydrolysis reaction of a titanium source, increasing the concentration of the sol by concentration to enable the nano-scale titanium dioxide sol to be uniformly and stably loaded into MOF-5 pore channels, and increasing TiO content2The catalytic degradation efficiency of the MOF-5 composite photocatalyst is improved.
Drawings
FIG. 1 shows TiO prepared according to an embodiment of the present invention2XRD spectrogram of the/MOF-5 composite photocatalyst;
FIG. 2 shows TiO prepared in accordance with an embodiment of the present invention2SEM image of/MOF-5 composite photocatalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below by way of embodiments with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides TiO2Preparation of/MOF-5 composite photocatalystThe method comprises the following steps:
s10, adding triethylamine into a mixed solution of soluble zinc salt, terephthalic acid and a first organic solvent, deprotonating the terephthalic acid, self-assembling the terephthalic acid and zinc ions into MOF-5, filtering, washing, drying, and grinding to obtain MOF-5 powder;
s20, hydrolyzing the hydrolyzable titanium source with water in a second organic solvent to obtain a first solution containing nano titanium dioxide sol;
s30, concentrating the first solution, and increasing the concentration of the nano titanium dioxide sol to obtain a second solution; and
s40, adding the MOF-5 powder into the second solution, fully mixing by ultrasonic oscillation, filtering, washing and drying to obtain TiO2A MOF-5 composite photocatalyst.
The TiO provided by the invention2The preparation method of the MOF-5 composite photocatalyst comprises the steps of preparing MOF-5 by a self-assembly method, preparing a solution of nano-scale titanium dioxide sol by utilizing a hydrolysis reaction of a titanium source, increasing the concentration of the sol by concentration to enable the nano-scale titanium dioxide sol to be uniformly and stably loaded into MOF-5 pore channels, and increasing TiO content2The catalytic degradation efficiency of the MOF-5 composite photocatalyst is improved.
In step S10, the method for preparing the mixed solution of soluble zinc salt, terephthalic acid and first organic solvent may include dissolving the soluble zinc salt in the first organic solvent and then adding the terephthalic acid, or dissolving the terephthalic acid in the first organic solvent and then adding the soluble zinc salt, or dissolving the soluble zinc salt and the terephthalic acid in the first organic solvent, respectively, and then mixing the soluble zinc salt solution and the terephthalic acid solution, or mixing the soluble zinc salt and the terephthalic acid and then adding the mixture to the first organic solvent; preferably, the soluble zinc salt is dissolved in the first organic solvent and the terephthalic acid is added. The above mixing step may be carried out at normal temperature, for example at 10 ℃ to 30 ℃, preferably at 25 ℃. The mixing step may be mechanical stirring or ultrasonic oscillation, so that the zinc salt and the terephthalic acid are fully dissolved in the first organic solvent and are uniformly mixed with each other.
The mass ratio of the soluble zinc salt to the first organic solvent is preferably 1: 30-1: 50, more preferably 1: 30-1: 40, and the molar ratio of the terephthalic acid to the soluble zinc salt is preferably 1: 0.8-1: 2, more preferably 1: 1.5-1: 2.
Preferably, the soluble zinc salt comprises at least one of zinc acetate dihydrate, zinc nitrate hexahydrate and zinc chloride. The soluble zinc salt provides a source of zinc that coordinates to the terephthalic acid to give MOF-5.
Preferably, the first organic solvent includes at least one of N, N-dimethylformamide, N-methylpyrrolidone, N-diethylformamide, and dimethylsulfoxide. The first organic solvent can dissolve the soluble zinc salt and the terephthalic acid and does not affect the coordination of the terephthalic acid and zinc ions.
In step S10, the triethylamine may be added at normal temperature, for example at 10 ℃ to 30 ℃, preferably at 25 ℃. And continuously stirring while adding the triethylamine, wherein the stirring time is preferably 1-3 h, and the mass ratio of the added triethylamine to the soluble zinc salt is preferably 1: 0.5-1: 3, and more preferably 1: 1-1: 3. By adding the triethylamine, the terephthalic acid can be deprotonated and self-assembled with zinc ions to form MOF-5. And (3) generating a white solid in the stirring process, performing suction pressure filtration on the white solid after stirring for enough time, washing for 3-4 times by using the first organic solvent to remove unreacted inorganic salt and organic acid, then putting the solid obtained by filtration into an oven for drying, and finally grinding the dried solid into powder to obtain the MOF-5 powder.
In step S20, the step of hydrolysis reaction includes:
s22, adding deionized water dropwise into the mixed solution of the second organic solvent, the acidic pH regulator and the titanium source, and then heating and stirring at 40-65 ℃ to obtain the titanium dioxide sol solution.
The volume ratio of the acidic pH regulator, the titanium source, the second organic solvent and the deionized water is preferably 1: 8-15: 80-150: 150 ℃ 250. The titanium source comprises at least one of tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium tert-butoxide, diethyl titanate and titanium tetrachloride. The second organic solvent includes at least one of methanol, ethanol, and isopropanol. The pH value of the mixed solution of the second organic solvent, the acidic pH regulator and the titanium source is preferably 3-4. The acidic pH regulator is preferably a weak acid, such as at least one of glacial acetic acid and citric acid. By adding weak acid and adjusting the pH value to 3-4, TiO can be stably generated by hydrolysis2Nano-level sol to avoid over-fast hydrolysis.
The preparation method of the mixed solution of the second organic solvent, the acidic pH adjuster, and the titanium source may include: the method comprises the steps of firstly, magnetically stirring the second organic solvent and the acidic pH regulator for 5-30 min, fully mixing to obtain a mixed solution of the second organic solvent and the acidic pH regulator, then, adding the titanium source into the mixed solution of the second organic solvent and the acidic pH regulator, fully mixing, and magnetically stirring for 5-30 min to obtain a mixed solution of the second organic solvent, the acidic pH regulator and the titanium source.
In the step of dropwise adding deionized water into a mixed solution of a second organic solvent, an acidic pH regulator and a titanium source, the speed of the hydrolysis reaction can be controlled by the adding speed of the deionized water, and in order to enable the hydrolysis reaction to be stably carried out, the deionized water is preferably slowly added dropwise while continuously stirring, and in one embodiment, the adding time of the deionized water is 15-30 min. The steps of preparing the mixed solution of the second organic solvent, the acidic pH adjuster, and the titanium source, and dropping deionized water in the mixed solution are preferably performed at normal temperature. Dropwise adding deionized water to react to obtain white turbid solution, and generating TiO in the solution2And (3) sol.
After the deionized water is dripped, heating the mixed solution to 40-65 ℃, continuously heating and stirring at constant temperature to fully perform hydrolysis reaction, wherein the heating and stirring time is preferably 10-40 min.
In a preferred embodiment, the step of forming the titania sol solution further includes:
s24, dropwise adding a strong oxidizing acid solution into the white turbid titanium dioxide sol solution, and then heating and refluxing at 60-85 ℃ to convert the white turbid solution into a semitransparent stable sol solution. The step can lead amorphous TiO to be under the combined action of strong oxidation acid environment and temperature2Sol to nano grade anatase type TiO2The crystal is transformed, so that nano-scale anatase type crystal phase is generated in the titanium dioxide colloid. On the one hand, anatase type TiO2Has higher catalytic activity, and on the other hand, TiO is directly generated in the solution2The crystalline phase may eliminate the need for a high temperature sintering step of the crystals after loading with MOF-5. The strong oxidizing acid solution is nitric acid or sulfuric acid, and H in the strong oxidizing acid solution+The concentration of (b) is preferably 0.1-0.2 mol/L, and the volume ratio of the strong oxidizing acid solution to the titanium dioxide sol solution is preferably 1: 1.2-2.
TiO for increasing MOF-5 loading2Preferably, in step S30, the concentration step includes evaporating 1/5 to 1/2 volumes of the first solution. The evaporation step can be carried out in an oven at 70-100 ℃, so that the volatile second organic solvent in the first solution is evaporated, and the concentration of the nano titanium dioxide sol is increased.
In the step S40, the mass ratio of the added MOF-5 to the second solution is preferably 1:10 to 1:100, and more preferably 1:20 to 1: 50. The ultrasonic oscillation time is preferably 30-60min, so that TiO in the second solution can be dissolved2As much as possible is loaded on the MOF-5, which is then loaded with TiO2The MOF-5 is filtered, washed and dried, and the drying temperature is preferably 80-120 ℃. Specifically, the TiO-supported material obtained by filtration may be2The MOF-5 solid is filtered by suction pressure, washed by deionized water or an organic solvent for 3 to 4 times, and then the solid obtained by filtering is put into an oven for drying.
The TiO is2The XRD pattern of the/MOF-5 composite photocatalyst is shown in figure 1, and the pattern shows the peak characteristics of MOF-5 and TiO2The peak characteristics of the TiO proved2In the/MOF-5 composite photocatalyst, high-temperature calcination is not carried out,anatase type TiO can be obtained by solution method2Crystalline, and TiO2The crystals were supported on MOF-5.
The TiO is2The SEM image of a scanning electron microscope of the/MOF-5 composite photocatalyst is shown in figure 2, and TiO can be seen more directly from the SEM image2Loaded in the pore channels of the MOF-5.
Example 1
S10, first, 1.21g of Zn (NO)3)2·6H2O and 40ml of N, N-Dimethylformamide (DMF) were contained in a beaker, and then 0.34g of terephthalic acid (H) was added at room temperature2BDC) was added to a beaker, and stirred continuously, after the solid was completely dissolved, 1.3mL of triethylamine TEAC was added to the mixed solution, and stirred continuously, reacted for about 3 hours, filtered under suction, and washed with DMF 3-4 times during the filtration under suction to remove unreacted inorganic salts and organic acids, and a white solid was obtained. And finally, putting the white solid into an oven for drying. And grinding the mixture into powder after drying to obtain the MOF-5 powder.
S22, adding 20ml of absolute ethyl alcohol into a clean and dry flask, dripping 4 drops of 0.2ml of glacial acetic acid by using a rubber head dropper, and stirring for 5min by magnetic force; adding 2ml of tetrabutyl titanate into the mixed solution, and magnetically stirring for 5 min; slowly dripping 38ml of deionized water while stirring, wherein the dripping time is more than 15min, heating the solution to 45 ℃ after the dripping is finished, and continuously stirring for 30min to obtain a white turbid solution.
S24, dropwise adding 40ml of 0.15mol/L nitric acid into the white turbid solution, wherein the dropwise adding speed can be higher, the dropwise adding is finished within 5-10 min, a condenser tube is added to a flask after the dropwise adding is finished, and the water bath temperature is increased to 75 ℃ and is continuously stirred for 5h to obtain the semitransparent stable first solution containing the nano titanium dioxide sol.
S30, 50ml of the first solution is placed in an oven at 80 ℃, and the volume of the first solution 1/3 is evaporated to obtain a second solution.
S40, adding 5g of MOF-5 powder into the second solution, ultrasonically oscillating for 40min, filtering, washing and drying at 100 ℃ to obtain TiO2A MOF-5 composite photocatalyst.
Example 2
The preparation method was substantially the same as in example 1 except that, in step S30, the volume of the first solution 1/2 was evaporated.
Example 3
The preparation method was substantially the same as in example 1 except that, in step S30, the volume of the first solution 1/4 was evaporated.
Comparative example
The preparation method is basically the same as that of example 1, except that step S30 is not performed, 5g of MOF-5 powder is directly added into the first solution, ultrasonic oscillation is performed for 40min, and drying is performed at 100 ℃ after filtering and washing to obtain TiO2A MOF-5 composite photocatalyst.
Examples of the experiments
TiO prepared by examples 1-3 and comparative example2the/MOF-5 composite photocatalyst is used for a formaldehyde photocatalytic degradation experiment, and the experiment method comprises the following steps:
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 to obtain a solution a.
Accurately transferring 2.5mL of formaldehyde aqueous solution into a test tube, adding deionized water to 25mL, and simultaneously performing a blank test by replacing the test with 25mL of water. Then adding 2.5mL of acetylacetone solution, shaking up, heating in a water bath at 90-100 ℃ for 10min, taking out and cooling. Absorbance A was measured at a wavelength of 414nm with reference to water0。
Weighing 0.25g of catalyst into a reaction tank, shaking up to obtain a solution b, placing the solution b into a reactor, opening an ultraviolet lamp to perform illumination degradation for 5 hours, wherein a sample is taken once per hour, the reaction tank is firstly shaken lightly before the sample is taken to mix the solution b uniformly, then the solution b is kept stand for a moment, a pipette is used for transferring about 5mL of the solution b into a test tube, deionized water is added to 25mL, meanwhile, a blank test is performed, and 25mL of water is used for replacing the test. Then adding 2.5mL of acetylacetone solution, shaking up, heating in a water bath at 90-100 ℃ for 10min, taking out and cooling. At the wavelength of 414nm, the wavelength of the light,absorbance A was measured with water as a referencet。
The degradation rate D% was calculated using the following formula:
in the formula A0，AtThe absorbance of the solution before the reaction and at the reaction time t are respectively;
the results of the experiment are shown in table 1:
TABLE 1
| Examples | Example 1 | Example 2 | Example 3 | Comparative example |
| Degradation rate of formaldehyde | 86％ | 88％ | 67％ | 54％ |
As can be seen from Table 1, the TiO prepared in examples 1-32The formaldehyde degradation rate ratio of the MOF-5 composite photocatalyst is higher than the proportion, which shows that the concentrated solution improves the concentration of the nano titanium dioxide sol and is beneficial to improving the TiO2The catalytic efficiency of the MOF-5 composite photocatalyst.
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 present 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 (8)
1. TiO 22The preparation method of the/MOF-5 composite photocatalyst is characterized by comprising the following steps:
adding triethylamine into a mixed solution of soluble zinc salt, terephthalic acid and a first organic solvent to deprotonate the terephthalic acid and self-assemble zinc ions into MOF-5, filtering, washing, drying and grinding to obtain MOF-5 powder;
hydrolyzing a hydrolyzable titanium source with water in a second organic solvent to obtain a first solution containing nano titanium dioxide;
concentrating the first solution, evaporating the first solution by 1/3-1/2 to increase the concentration of the nano titanium dioxide sol to obtain a second solution; and
adding the MOF-5 powder into the second solution, fully mixing by ultrasonic oscillation, filtering, washing and drying to obtain TiO2The MOF-5 composite photocatalyst is characterized in that the mass ratio of the added MOF-5 to the second solution is 1: 10-1: 100.
2. The TiO of claim 12The preparation method of the/MOF-5 composite photocatalyst is characterized in that the hydrolysis reaction comprises the following steps: in a second organic solvent, an acidic pH regulator and titaniumAnd dropwise adding deionized water into the mixed solution of the sources, and then heating and stirring at 40-65 ℃ to obtain a titanium dioxide sol solution, wherein the volume ratio of the acidic pH regulator to the titanium source to the organic solvent to the deionized water is 1: 8-15: 80-150: 150-250.
3. The TiO of claim 22The preparation method of the/MOF-5 composite photocatalyst is characterized in that the step of forming the first solution further comprises the following steps: and (3) dropwise adding a strong oxidizing acid solution into the titanium dioxide sol solution, and then heating and refluxing at 60-85 ℃.
4. The TiO of claim 32The preparation method of the/MOF-5 composite photocatalyst is characterized in that the strong oxidizing acid solution is nitric acid or sulfuric acid, and H in the strong oxidizing acid solution+The concentration of the strong oxidizing acid solution is 0.1-0.2 mol/L, and the volume ratio of the strong oxidizing acid solution to the titanium dioxide sol solution is 1: 1.2-2.
5. The TiO of claim 12The preparation method of the/MOF-5 composite photocatalyst is characterized in that the molar ratio of the soluble zinc salt to the terephthalic acid is 1: 0.8-1: 1.5, the mass ratio of the soluble zinc salt to the first organic solvent is 1: 30-1: 50, and the mass ratio of the triethylamine to the soluble zinc salt is 1: 0.5-1: 3.
6. The TiO of claim 12The preparation method of the/MOF-5 composite photocatalyst is characterized in that the soluble zinc salt comprises at least one of zinc acetate dihydrate, zinc nitrate hexahydrate and zinc chloride.
7. The TiO of claim 12The preparation method of the/MOF-5 composite photocatalyst is characterized in that the titanium source comprises at least one of tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium tert-butoxide, diethyl titanate and titanium tetrachloride.
8. According to claim1 said TiO2The preparation method of the/MOF-5 composite photocatalyst is characterized in that the first organic solvent comprises at least one of N, N-dimethylformamide, N-methylpyrrolidone, N-diethylformamide, dimethyl sulfoxide and triethylamine; the second organic solvent includes at least one of methanol, ethanol, and isopropanol.
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| CN115416125A (en) * | 2022-09-22 | 2022-12-02 | 陕西科技大学 | Method for reinforcing rotten wood by synthesizing nano MOF-5 under assistance of ultrasonic waves |
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