CN113499801A - ZIF-8/TiO2Composite material, preparation method thereof and wastewater treatment method - Google Patents
ZIF-8/TiO2Composite material, preparation method thereof and wastewater treatment method Download PDFInfo
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- CN113499801A CN113499801A CN202110949083.9A CN202110949083A CN113499801A CN 113499801 A CN113499801 A CN 113499801A CN 202110949083 A CN202110949083 A CN 202110949083A CN 113499801 A CN113499801 A CN 113499801A
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- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 82
- 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 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title description 11
- 239000002131 composite material Substances 0.000 claims abstract description 51
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 14
- 231100000719 pollutant Toxicity 0.000 claims abstract description 14
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 24
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 23
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 14
- 229940012189 methyl orange Drugs 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 229910052724 xenon Inorganic materials 0.000 claims description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 22
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000011259 mixed solution Substances 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 3
- 239000002360 explosive Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 9
- 239000012621 metal-organic framework Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002429 nitrogen sorption measurement Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004246 zinc acetate 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]
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
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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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- 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
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C02F2305/10—Photocatalysts
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to the technical field of composite materials, in particular to ZIF-8/TiO2A composite material, a preparation method thereof and a wastewater treatment method. The preparation method comprises the following steps: (1) preparing ZIF-8 powder by taking zinc acetate dihydrate as a zinc source; (2) mixing ZIF-8 powder with anhydrous ethanol to obtain ZIF-8 precursor solution, adding nanometer TiO2Obtaining ZIF-8, TiO2Mixing the solution; (3) hydrothermal treatment of ZIF-8, TiO2Cooling the mixed solution, centrifuging to obtain precipitate, and freeze drying to obtain ZIF-8/TiO2A composite material. The wastewater treatment method adopts ZIF-8/TiO2The composite material treats wastewater containing organic pollutants and/or heavy metal pollutants. The invention prepares the composite material with high photocatalytic activity on the basis of avoiding using explosive medicaments and ensuring safe production, and can realize effective degradation of organic pollutants and heavy metal pollutants.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to ZIF-8/TiO2A composite material, a preparation method thereof and a wastewater treatment method.
Background
The Metal-organic framework (MOF) is a novel porous material and has the advantages of large specific surface area, high porosity, controllable pore structure and the like. However, the application space of the MOF is limited due to poor thermal, hydrothermal stability and solvent resistance of the MOF. Zeolite imidazole-like ester framework materials (ZIFs for short) are MOF materials which take imidazole and derivatives thereof as ligands and have zeolite framework structures, combine the advantages of zeolite and MOF, and can be used for adsorption, separation, catalysis and the like, wherein ZIF-8 is the most representative ZIFs. At present, the application research of ZIF-8 relates to a plurality of fields such as gas adsorption, hydrogen storage, catalysis and the like, and is the most widely researched class of ZIFs.
TiO since the use of semiconductor materials in photocatalytic technology2The photocatalyst has the unique advantages of high catalytic activity, good chemical stability and biological inertia, no toxicity to human bodies, low price and the like, is the most active photocatalytic material researched in recent years, and is widely applied to organic pollutant degradation, water decomposition and CO2Reduction and the like. Adding TiO into the mixture2The composite material is compounded with ZIF-8 to form a heterojunction, and the advantages of the two materials can be combined to prepare the composite photocatalyst with better performance. The Chinese patent application with the publication number of CN105170097A discloses a TiO2/ZThe IF-8 core-shell structure nano composite material is prepared by adopting zinc nitrate as a zinc source2Amorphous nano-spheres are used as a load main body, and TiO is added2Adding precursor solution of ZIF-8 into the amorphous nano-spheres to make the ZIF-8 in TiO2Surface generation to reduce TiO2The forbidden band width of the photocatalyst can inhibit the rapid recombination of photo-generated electron-hole pairs and improve the activity of the photocatalyst and the conversion efficiency of the photocatalytic reaction. The zinc nitrate used in the technical scheme is an easily-exploded medicine, and the ZIF-8 prepared from the zinc nitrate also has the problem of poor crystal form; TiO finally prepared by the technical scheme2The specific surface area of the/ZIF-8 core-shell structure nano composite material is only 300.4m2And/g, the utilization rate of the excessively loaded ZIF-8 is not high. Meanwhile, the selection of proper pollutants and a proper pollutant treatment mode are also the key points of material application, and have important significance for the full play of material performance.
Therefore, it is necessary to provide a novel ZIF-8/TiO2A composite material, a preparation method thereof and a wastewater treatment method.
Disclosure of Invention
Aiming at the existing ZIF-8/TiO2The invention provides a ZIF-8/TiO composite material, which has the problems of low catalytic efficiency and poor pollutant treatment effect2ZIF-8 with high specific surface area is prepared by taking zinc acetate as a zinc source and is used as a load main body to load nano TiO, and the preparation method thereof and a wastewater treatment method2Preparation of ZIF-8/TiO which can be used as micro-nano reaction container2A composite material. The invention prepares the composite material with high photocatalytic activity on the basis of avoiding using explosive medicaments and ensuring safe production, and can realize effective degradation of organic pollutants and heavy metal pollutants.
In a first aspect, the present invention provides a ZIF-8/TiO2The preparation method of the composite material comprises the following steps:
(1) preparing ZIF-8 powder by taking zinc acetate dihydrate as a zinc source;
(2) uniformly mixing ZIF-8 powder with absolute ethyl alcohol to obtain a ZIF-8 precursor solution, and adding nano TiO into the ZIF-8 precursor solution2Mixing uniformly to obtainTo ZIF-8, TiO2Mixing the solution;
(3) hydrothermal treatment of ZIF-8, TiO2Mixing the solution, cooling, centrifuging to obtain precipitate, and freeze drying to obtain ZIF-8 loaded TiO2Of composite materials, i.e. ZIF-8/TiO2A composite material.
Further, the step (1) is specifically that zinc acetate dihydrate and 2-methylimidazole are uniformly mixed in absolute ethyl alcohol and then subjected to hydrothermal treatment, and after the reaction is finished, the mixture is cooled, centrifuged, precipitated and freeze-dried to obtain ZIF-8 powder.
Further, in the step (1), the molar ratio of zinc acetate dihydrate to 2-methylimidazole is 1: 10-1: 20, preferably 1: 20; the hydrothermal temperature is 120-150 ℃, and preferably 150 ℃; the hydrothermal time is 3-10 h, preferably 6 h.
Further, in the step (2), ZIF-8 powder and TiO2The weight ratio of (1): 1-1: 4, preferably 1: 2.
further, in the step (3), the hydrothermal reaction temperature is 120-150 ℃, and preferably 150 ℃; the hydrothermal reaction time is 6-18 h, and preferably 12 h.
In a second aspect, the invention provides a ZIF-8/TiO prepared by the above preparation method2A composite material.
In a third aspect, the present invention provides a wastewater treatment process using the ZIF-8/TiO of the present invention2The composite material treats wastewater containing organic pollutants and/or heavy metal pollutants.
Further, the wastewater is mixed wastewater of hexavalent chromium and methyl orange.
Further, the wastewater treatment method comprises the step of firstly ZIF-8/TiO2The composite material is uniformly mixed with the wastewater, stirred for 30-120 min in the dark, and then irradiated by a xenon lamp light source for 5-180 min.
The beneficial effect of the invention is that,
the ZIF-8/TiO provided by the invention2The preparation method of the composite material comprises the steps of comparing the dosage of zinc acetate dihydrate with 2-methylimidazole and mixing ZIF-8 with TiO2The dosage ratio of the compound is reasonably selected to prepare the photocatalystZIF-8/TiO with superior capability2The method for preparing the composite material is simple and easy to control. Enhancement of ZIF-8 and/or of TiO by hydrothermal method2The bonding strength of the composite material is improved, and the stability of the composite material is improved through TiO2The surface loading of (2) makes up for the disadvantage that ZIF-8 is not easily soluble in water. Experimental results show that the treatment effect of the composite material synthesized by the hydrothermal method is obviously higher than the effect of mixing two substances purely physically together.
ZIF-8/TiO synthesized by the invention2The composite material is mainly ZIF-8 and TiO2Is a heterostructure of an object, makes up the defects of ZIF-8, improves the conduction capability of electrons between interfaces, and accelerates the generation of photo-generated electron-hole pairs in ZIF-8 and TiO2The transfer on the interface enhances the ZIF-8/TiO2The catalytic ability of the composite; in particular, the ZIF-8/TiO of the present invention2The composite material has an outstanding degradation effect on multi-element pollutants, and can effectively catalyze and degrade hexavalent chromium and methyl orange under ultraviolet light.
The invention also provides a method for preparing the same by using ZIF-8/TiO2Method for treating wastewater by using composite material, and ZIF-8/TiO2The composite material can be used as a micro-nano reaction vessel, the adsorption and photocatalysis treatment methods are combined, pollutants are firstly adsorbed onto the composite material, and then the pollutants adsorbed onto the composite material are preferentially treated, so that the degradation efficiency of organic pollutants and heavy metal pollutants is improved.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is an SEM photograph of ZIF-8 powder prepared in example 1;
FIG. 2 is a nitrogen sorption and desorption curve of ZIF-8 powder prepared in example 1;
FIG. 3 is the ZIF-8/TiO prepared in example 22SEM photograph of the composite;
FIG. 4 is a graph showing the variation of the hexavalent chromium content in example 6;
FIG. 5 is a graph showing the variation of the contents of hexavalent chromium and methyl orange in example 7;
FIG. 6 is a graph showing the variation of the hexavalent chromium content in example 8;
in FIGS. 4 to 6, C0Is the initial concentration of the contaminant, CtIs the instantaneous concentration of the contaminant, Ct/C0Indicating the proportion of contaminants in the wastewater.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The apparatus and main reagents used in the embodiment of the present invention are shown in tables 1 and 2 below.
TABLE 1 Instrument table
| Instrument for measuring the position of a moving object | Model number | Manufacturer of the product |
| Scanning electron microscope | Regulus8220 | Hitachi Co of Japan |
| Numerical control ultrasonic cleaner | KQ-300DE | KUNSHAN ULTRASONIC INSTRUMENTS Co.,Ltd. |
| Photochemical reaction box | CEL-LB70 | BEIJING CHINA EDUCATION AU-LIGHT Co.,Ltd. |
| Xenon lamp | CEL-HXF300 | BEIJING CHINA EDUCATION AU-LIGHT Co.,Ltd. |
TABLE 2 Main reagent Table
Example 1
0.44g of zinc acetate dihydrate is weighed and added into a 100mL beaker, dissolved with 30mL of absolute ethanol and ultrasonically treated until the zinc acetate dihydrate is completely dissolved, 4.1g of 2-methylimidazole is weighed and added into a 100mL beaker, dissolved with 30mL of absolute ethanol and ultrasonically treated until the zinc acetate dihydrate is completely dissolved. Mixing the two solutions together, performing ultrasonic treatment for 3h, adding the mixed solution into a polytetrafluoroethylene-lined high-pressure reaction kettle (100mL), sealing, continuously heating the high-pressure reaction kettle at 150 ℃ for 6h, cooling to room temperature, centrifuging, taking the precipitate, cleaning with absolute ethanol and deionized water, and freeze-drying for 12h to obtain ZIF-8 powder, wherein a scanning electron microscope image of the ZIF-8 powder is shown in figure 1, and a nitrogen adsorption and desorption test is shown in figure 2 to obtain the ZIF-8 powder with a BET specific surface area of 1899m3/g。
Example 2
0.5g of the ZIF of example 1 was weighedAdding the-8 powder into 60mL of absolute ethanol, stirring for 30min to obtain a ZIF-8 precursor solution, and weighing 0.5g of TiO2(10-20 nm) is added into the precursor solution of ZIF-8 and continuously stirred for 1h to obtain ZIF-8 and TiO2Mixing the solution, and adding ZIF-8 and TiO2The mixture was sonicated for 3h to form a homogeneous solution. Transferring the homogeneous solution into a polytetrafluoroethylene-lined high-pressure reaction kettle (100mL), sealing, continuously heating the high-pressure reaction kettle at 150 ℃ for 12h, cooling to room temperature, centrifuging, washing the precipitate with absolute ethanol and deionized water, and freeze-drying for 12h to obtain ZIF-8/TiO2The composite material is named as Z150T150, and the scanning electron micrograph of the Z150T150 is shown in FIG. 3.
Example 3
Example 3 preparation of TiO2The amount of ZIF-8/TiO was changed from 0.5g to 1.0g, and the remaining preparation steps were the same as in example 22The composite material was designated as Z100T 200.
Example 4
Example 4 preparation of TiO2The amount of ZIF-8/TiO was changed from 0.5g to 1.5g, and the remaining preparation steps were the same as in example 22The composite material was named Z75T 225.
Example 5
Example 5 preparation of TiO2The amount of ZIF-8/TiO was changed from 0.5g to 2.0g, and the remaining preparation steps were the same as in example 22The composite material was named Z60T 240.
Example 6
Weighing TiO2(10-20 nm) and 0.01g of ZIF-8 powder in example 1 are sequentially added into 60mL of 20mg/L hexavalent chromium solution, uniformly mixed by ultrasonic waves and stirred in the dark for 60min to achieve adsorption balance; then irradiating under 300W xenon lamp light source, testing hexavalent chromium content in the solution at different time, the result is ZIF-8+ TiO shown in figure 42Shown in the graph.
0.02g of the Z150T150 composite material obtained in the embodiment 2 is weighed and added into 60mL of 20mg/L hexavalent chromium solution, and after uniform ultrasonic mixing, the mixture is stirred for 60min in the dark to achieve adsorption balance; the solution was then irradiated under a 300W xenon lamp to measure the hexavalent chromium content at various times, and the results are shown in the Z150T150 curve in FIG. 4.
As can be seen from FIG. 4, ZIF-8/TiO was treated with hydrothermal treatment2The wastewater treatment effect of the composite material is obviously higher than that of pure physical mixing, and the hydrothermal method can effectively improve the adsorption and catalytic capabilities of the composite material.
Example 7
Weighing 3 parts of Z150T150 composite material, wherein each part is 0.02g, adding the 3 parts of Z150T150 composite material into 60mL of 20mg/L methyl orange solution, mixed solution of hexavalent chromium and methyl orange with the concentration of 20mg/L respectively and mixed solution of hexavalent chromium and methyl orange with the concentration of 30mg/L respectively, uniformly mixing by ultrasonic waves, and stirring in the dark for 60min to achieve adsorption balance; and then irradiating under a 300W xenon lamp light source, and testing the contents of hexavalent chromium and methyl orange in the solution at different times.
As shown in FIG. 5, the MO 20mg/L curve shows the removing effect of the methyl orange solution with a concentration of 20mg/L, the Mix-Cr (VI)20mg/L curve and the Mix-MO 20mg/L curve show the removing effect of the hexavalent chromium and the methyl orange in the mixed solution of the hexavalent chromium and the methyl orange with a concentration of 20mg/L, respectively, and the Mix-Cr (VI)30mg/L curve and the Mix-MO 30mg/L curve show the removing effect of the hexavalent chromium and the methyl orange in the mixed solution of the hexavalent chromium and the methyl orange with a concentration of 30mg/L, respectively.
As can be seen from FIG. 5, the Z150T150 composite material has better treatment effect on the mixed wastewater of hexavalent chromium and methyl orange than the treatment effect on the single wastewater only containing hexavalent chromium, particularly has the best treatment effect on the mixed solution of hexavalent chromium and methyl orange with the concentration of 30mg/L respectively, the degradation rate of the methyl orange reaches 95% after xenon lamp irradiation for 5min, and the degradation rate of the hexavalent chromium is nearly 100% after 45 min. Therefore, the composite material prepared by the invention can be used for degrading heavy metal pollutants and organic pollutants in a coordinated manner by photocatalysis, and the two pollutants are respectively combined with photoproduction electrons and holes generated by the composite material, so that the catalysis efficiency is further improved, and the treatment effect is obviously enhanced.
Example 8
Weighing TiO2(10-20 nm), 0.02g each of the ZIF-8 powder of example 1 and the composite material of examples 2-5 were added to 60mL of a 20mg/L hexavalent chromium solution, respectively, to obtain a mixtureAfter sound mixing is carried out uniformly, stirring for 60min in the dark to achieve adsorption balance; then, the solution was irradiated under a 300W xenon lamp light source, and the hexavalent chromium content in the solution was measured at different times, and as a result, as shown in FIG. 6, it can be seen that Z100T200 exhibited the best removal effect.
Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention.
Claims (9)
1. ZIF-8/TiO2The preparation method of the composite material is characterized by comprising the following steps:
(1) preparing ZIF-8 powder by taking zinc acetate dihydrate as a zinc source;
(2) uniformly mixing ZIF-8 powder with absolute ethyl alcohol to obtain a ZIF-8 precursor solution, and adding nano TiO into the ZIF-8 precursor solution2Mixing uniformly to obtain ZIF-8 and TiO2Mixing the solution;
(3) hydrothermal treatment of ZIF-8, TiO2Mixing the solution, cooling, centrifuging to obtain precipitate, and freeze drying to obtain ZIF-8 loaded TiO2Of composite materials, i.e. ZIF-8/TiO2A composite material.
2. The preparation method according to claim 1, wherein the step (1) is specifically carried out by uniformly mixing zinc acetate dihydrate and 2-methylimidazole in anhydrous ethanol, carrying out hydrothermal treatment, cooling, centrifuging after the reaction is finished, taking the precipitate, and freeze-drying to obtain the ZIF-8 powder.
3. The method according to claim 2, wherein in the step (1), the molar ratio of zinc acetate dihydrate to 2-methylimidazole is 1: 10-1: 20; the hydrothermal temperature is 120-150 ℃; the hydrothermal time is 3-10 h.
4. The method of claim 1, wherein in the step (2), the ZIF-8 powder is mixed with TiO2The weight ratio of (1): 1-1: 4.
5. the preparation method according to claim 1, wherein in the step (3), the hydrothermal reaction temperature is 120 to 150 ℃; the hydrothermal reaction time is 6-18 h.
6. ZIF-8/TiO prepared by the preparation method of any one of claims 1 to 52A composite material.
7. A wastewater treatment method characterized by using the ZIF-8/TiO according to claim 62The composite material treats wastewater containing organic pollutants and/or heavy metal pollutants.
8. The wastewater treatment method according to claim 7, wherein the wastewater is a mixed wastewater of hexavalent chromium and methyl orange.
9. The wastewater treatment method according to claim 7, wherein the wastewater treatment method comprises first treating ZIF-8/TiO2The composite material is uniformly mixed with the wastewater, stirred for 30-120 min in the dark, and then irradiated by a xenon lamp light source for 5-180 min.
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| CN115739099A (en) * | 2022-12-07 | 2023-03-07 | 广东工业大学 | Zinc-ion-rich ZnNi LDHs nanosheet material as well as preparation method and application thereof |
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