CN109499620B - TiO2Preparation method of/ZIF-8 composite photocatalyst - Google Patents
TiO2Preparation method of/ZIF-8 composite photocatalyst Download PDFInfo
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- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 74
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title description 8
- 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 72
- 239000003960 organic solvent Substances 0.000 claims abstract description 45
- 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 31
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000003751 zinc Chemical class 0.000 claims abstract description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000010438 heat treatment 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
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000010355 oscillation Effects 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring 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
- 238000004729 solvothermal method Methods 0.000 claims description 8
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-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
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 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
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000011148 porous material 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
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 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 description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000009835 boiling Methods 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
- 238000001816 cooling Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 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 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
- 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
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000013163 zeolitic imidazolate framework-82 Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 101710184444 Complexin Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 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
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing 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
- 239000011550 stock solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- 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
Abstract
Loaded TiO (titanium dioxide)2The preparation method of the composite photocatalyst comprises the following steps: putting a mixed solution of soluble zinc salt, 2-methylimidazole and a first organic solvent into a high-pressure reaction kettle, heating for reaction, deprotonating 2-methylimidazole, self-assembling zinc ions into ZIF-8, filtering, washing, drying and grinding to obtain ZIF-8 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 ZIF-8 powder into the second solution, fully mixing by ultrasonic oscillation, filtering, washing and drying to obtain TiO2/ZIF-8 composite photocatalyst.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to TiO2A preparation method of a ZIF-8 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 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.
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 process2Absorb itThe ultraviolet light plays 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.
The zeolite imidazolate framework material ZIF is a tetrahedral framework material formed by connecting organic imidazolate to transition metal in a crosslinking manner, wherein extremely strong interaction exists between metal ions and imidazole or imidazole derivatives. ZIFs are excellent new materials with very stable thermal stability and chemical properties, some ZIFs can stably exist in boiling water or boiling organic solvents without destroying the original structure, and some ZIFs can still keep the original structure even at 400 ℃, have very stable thermal stability, are very excellent catalysts and have very wide application in many aspects. ZIF-8 is a typical representative thereof, and the combination of titanium dioxide and ZIF-8 can accommodate a large amount of TiO by utilizing not only the huge specific surface area and pore volume of ZIF-82It is also possible to increase the thermal stability of the material, but how to incorporate TiO2Loading onto ZIF-8 is a difficult problem.
Disclosure of Invention
In view of the above, it is necessary to provide a TiO compound against the problem of difficulty in supporting ZIF-82A preparation method of a ZIF-8 composite photocatalyst.
The invention provides a TiO compound2The preparation method of the/ZIF-8 composite photocatalyst comprises the following steps:
carrying out solvothermal reaction on a mixed solution of soluble zinc salt, 2-methylimidazole and a first organic solvent to deprotonate 2-methylimidazole and self-assemble zinc ions into ZIF-8, filtering, washing, drying and grinding to obtain ZIF-8 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 ZIF-8 powder into the second solution, fully mixing by ultrasonic oscillation, filtering, washing and drying to obtain TiO2/ZIF-8 composite photocatalyst.
In one embodiment, the mass ratio of the ZIF-8 to the second solution is 1:10 to 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 2-methylimidazole is 1: 1.5-1: 2.5, the mass ratio of the soluble zinc salt to the first organic solvent is 1: 80-1: 100, and the soluble zinc salt includes at least one of zinc acetate dihydrate, zinc nitrate hexahydrate and zinc chloride.
In one embodiment, the temperature of the solvothermal reaction is 130-160 ℃ and the time is 12-28 hours.
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.
According to the preparation method of the TiO2/ZIF-8 composite photocatalyst, ZIF-8 is prepared by a self-assembly method, a solution of nano-scale titanium dioxide sol is prepared by utilizing a hydrolysis reaction of a titanium source, the concentration of the sol is increased by concentration, so that the nano-scale titanium dioxide sol can be uniformly and stably loaded in a ZIF-8 pore channel, the catalytic degradation efficiency of the TiO2/ZIF-8 composite photocatalyst is improved, the catalyst material has high thermal stability, and the application range is wider.
Drawings
FIG. 1 shows TiO prepared according to an embodiment of the present invention2An XRD spectrogram of the/ZIF-8 composite photocatalyst;
FIG. 2 shows TiO prepared in accordance with an embodiment of the present invention2SEM image of/ZIF-8 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 TiO2The preparation method of the/ZIF-8 composite photocatalyst comprises the following steps:
s10, carrying out solvothermal reaction on a mixed solution of soluble zinc salt, 2-methylimidazole and a first organic solvent to deprotonate 2-methylimidazole and self-assemble zinc ions into ZIF-8, filtering, washing, drying and grinding to obtain ZIF-8 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 ZIF-8 powder into the second solution, fully mixing by ultrasonic oscillation, filtering, washing and drying to obtain TiO2/ZIF-8 composite photocatalyst.
The TiO provided by the invention2The preparation method of the/ZIF-8 composite photocatalyst comprises the steps of preparing ZIF-8 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 in a ZIF-8 pore channel, and increasing TiO content2The catalytic degradation efficiency of the ZIF-8 composite photocatalyst is improved.
In step S10, the method for preparing the mixed solution of the soluble zinc salt, the 2-methylimidazole and the first organic solvent may include dissolving the soluble zinc salt in the first organic solvent and then adding the 2-methylimidazole, or dissolving the 2-methylimidazole in the first organic solvent and then adding the soluble zinc salt, or may include dissolving the soluble zinc salt and the 2-methylimidazole in the first organic solvent respectively and then mixing the soluble zinc salt solution and the 2-methylimidazole solution, or may include mixing the soluble zinc salt and the 2-methylimidazole and then adding the mixture to the first organic solvent for dissolution. 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 2-methylimidazole are sufficiently 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: 80-1: 100, more preferably 1: 30-1: 40, and the molar ratio of the soluble zinc salt to 2-methylimidazole is preferably 1: 1.5-1: 2.5, more preferably 1: 1.8-1: 2.2.
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 zinc source and coordinates with the 2-methylimidazole to obtain ZIF-8.
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 2-methylimidazole and does not affect the coordination of the 2-methylimidazole with zinc ions. The solvent thermal reaction is to transfer the mixed solution into a sealed high-pressure reaction kettle for heating, and the pressure higher than 1 atmosphere is generated in the reaction kettle under the heating and sealing conditions, so that the reaction is carried out in a high-pressure environment. Experiments show that different organic solvents have certain differences in the morphology of ZIF-8 due to the differences in the solubilities of soluble zinc salt and 2-methylimidazole and the differences in the physicochemical properties of solvents such as saturated vapor pressure, boiling point and the like when the different first organic solvents are used in the solvothermal reaction for synthesizing ZIF-8. Preferably, the first organic solvent is N, N-dimethylformamide, and the obtained ZIF-8 has larger specific surface area and pore volume, is more favorable for being combined with titanium dioxide sol, so that the titanium dioxide sol can easily enter holes of the ZIF-8 to form stable combination with the ZIF-8, and further improves TiO2The catalytic degradation efficiency of the ZIF-8 composite photocatalyst is improved.
The condition of the solvothermal reaction also has certain influence on the shape of the ZIF-8, and preferably, the temperature of the solvothermal reaction is 130-160 ℃, and the reaction time is 12-28 hours.
And after the solvent thermal reaction is finished, naturally cooling to room temperature, taking the product out of the reaction kettle, performing centrifugal separation, washing the solid obtained by centrifugation by using an organic solvent to remove unreacted reagents, then putting the washed solid into an oven for drying, preferably overnight drying at 80 ℃, and finally grinding the dried solid into powder to obtain the ZIF-8 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 acidic pH regulator, the titanium source, the second organic solvent and deionized waterThe volume ratio is preferably 1:8 to 15:80 to 150:150 to 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 ZIF-8. 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 ZIF-8 load2Preferably, 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 ZIF-8 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 was loaded on the ZIF-8, and then loaded with TiO2The ZIF-8 is filtered, washed and dried, and the drying temperature is preferably 80-120 ℃. Specifically, the TiO-supported material obtained by filtration may be2And (3) filtering the ZIF-8 solid under vacuum, washing the solid for 3 to 4 times by using deionized water or an organic solvent, and then putting the solid obtained by filtering into an oven for drying.
The TiO is2The XRD pattern of the/ZIF-8 composite photocatalyst is shown in figure 1, and the pattern shows the peak characteristics of ZIF-8 and TiO2The peak characteristics of the TiO proved2/ZIF-8 complexIn the photocatalyst, anatase type TiO can be obtained by a solution method without high-temperature calcination2Crystalline, and TiO2The crystal is loaded on ZIF-8.
The TiO is2The SEM image of a scanning electron microscope of the/ZIF-8 composite photocatalyst is shown in figure 2, and TiO can be seen more directly from the SEM image2Loaded in the pore channel of ZIF-8.
Example 1
S10, 0.89g of Zn (NO) is added3)2·6H2O and 0.49g of 2-methylimidazole were dissolved in 80ml of N, N-Dimethylformamide (DMF), and the mixed solution was transferred to an autoclave with a tetrafluoroethylene liner at 5 ℃ C. min-1The temperature rising rate is raised to 140 ℃, the reaction is carried out for 24 hours, the solid is obtained by centrifugal separation, and the solid is washed 3 times by 50ml of DMF and methanol respectively and then is put into an oven to be dried at 80 ℃ overnight. And grinding the powder into powder after drying to obtain ZIF-8 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 ZIF-8 powder into the second solution, carrying out ultrasonic oscillation for 40min, filtering, washing and drying at 100 ℃ to obtain TiO2/ZIF-8 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 substantially the same as that of example 1, except that step S30 is not performed, 5g of ZIF-8 powder is directly added to the first solution, ultrasonic oscillation is performed for 40min, and drying is performed at 100 ℃ after filtering and washing to obtain TiO2/ZIF-8 composite photocatalyst.
Examples of the experiments
TiO prepared by examples 1-3 and comparative example2the/ZIF-8 composite photocatalyst is used for an experiment for degrading formaldehyde through photocatalysis, 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. Absorbance A was measured at a wavelength of 414nm with reference to watert。
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 | 90％ | 84％ | 69％ | 58％ |
As can be seen from Table 1, the TiO prepared in examples 1-32The formaldehyde degradation rate of the/ZIF-8 composite photocatalyst is higher than that of a comparative 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 ZIF-8 composite photocatalyst is improved.
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 (9)
1. TiO22The preparation method of the/ZIF-8 composite photocatalyst is characterized by comprising the following steps:
carrying out solvothermal reaction on a mixed solution of soluble zinc salt, 2-methylimidazole and a first organic solvent to deprotonate 2-methylimidazole and self-assemble zinc ions into ZIF-8, filtering, washing, drying and grinding to obtain ZIF-8 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 ZIF-8 powder into the second solution, fully mixing by ultrasonic oscillation, filtering, washing and drying to obtain TiO2/ZIF-8 composite photocatalyst.
2. The TiO of claim 12The preparation method of the/ZIF-8 composite photocatalyst is characterized in that the mass ratio of the added ZIF-8 to the second solution is 1: 10-1: 100.
3. The TiO of claim 12/ZIF-8The preparation method of the composite photocatalyst is characterized in that the hydrolysis reaction comprises the following steps: 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.
4. The TiO of claim 32The preparation method of the/ZIF-8 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 ℃.
5. The TiO of claim 42The preparation method of the/ZIF-8 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.
6. The TiO of claim 12The preparation method of the/ZIF-8 composite photocatalyst is characterized in that the molar ratio of the soluble zinc salt to the 2-methylimidazole is 1: 1.5-1: 2.5, the mass ratio of the soluble zinc salt to the first organic solvent is 1: 80-1: 100, and 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/ZIF-8 composite photocatalyst is characterized in that the temperature of the solvothermal reaction is 130-160 ℃, and the time is 12-28 hours.
8. The TiO of claim 12The preparation method of the/ZIF-8 composite photocatalyst is characterized in that the titanium source comprises tetrabutyl titanate, tetraethyl titanate and tetraisopropyl titanateTitanium tert-butoxide, diethyl titanate and titanium tetrachloride.
9. The TiO of claim 12The preparation method of the/ZIF-8 composite photocatalyst is characterized in that 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.
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| CN112958054B (en) * | 2021-02-02 | 2022-08-30 | 天津城建大学 | TiO 2 2 @ ZIF-67 composite nano material and preparation method and application thereof |
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| CN113262824B (en) * | 2021-04-27 | 2021-11-30 | 广州紫科环保科技股份有限公司 | Preparation of composite photocatalyst and application of composite photocatalyst in VOCs purification |
| CN113499801B (en) * | 2021-08-18 | 2023-11-03 | 齐鲁工业大学 | ZIF-8/TiO 2 Composite material, preparation method thereof and wastewater treatment method |
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