CN113499801B - ZIF-8/TiO 2 Composite material, preparation method thereof and wastewater treatment method - Google Patents

ZIF-8/TiO 2 Composite material, preparation method thereof and wastewater treatment method Download PDF

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CN113499801B
CN113499801B CN202110949083.9A CN202110949083A CN113499801B CN 113499801 B CN113499801 B CN 113499801B CN 202110949083 A CN202110949083 A CN 202110949083A CN 113499801 B CN113499801 B CN 113499801B
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zif
tio
composite material
wastewater
powder
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CN113499801A (en
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马洪芳
高翔
宋宇
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Qilu University of Technology
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    • 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
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    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
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Abstract

The invention relates to the technical field of composite materials, in particular to a ZIF-8/TiO 2 Composite material, preparation method and wastewater treatment method thereof. The preparation method 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 ZIF-8 precursor solution, and adding nano TiO 2 Obtaining ZIF-8 and TiO 2 A mixed solution; (3) Hydrothermal treatment of ZIF-8 and TiO 2 Cooling and centrifuging the mixed solution to obtain precipitate, and freeze-drying to obtain ZIF-8/TiO 2 A composite material. The wastewater treatment method adopts ZIF-8/TiO 2 The composite material is used for treating wastewater containing organic pollutants and/or heavy metal pollutants. According to the invention, on the basis of avoiding the use of explosive drugs and ensuring safe production, the composite material with high photocatalytic activity is prepared, and the effective degradation of organic pollutants and heavy metal pollutants can be realized.

Description

ZIF-8/TiO 2 Composite material, preparation method thereof and wastewater treatment method
Technical Field
The invention relates to the technical field of composite materials, in particular to a ZIF-8/TiO 2 Composite material, preparation method and wastewater treatment method thereof.
Background
The Metal-organic framework material (MOF for short) is a novel porous material and has the advantages of large specific surface area, high porosity, controllable pore channel structure and the like. However, MOFs have limited application space due to their poor self-heating, hydrothermal stability and solvent resistance. The zeolite-like imidazole ester framework material (Zeolitic Imidazolate Frameworks, abbreviated as ZIFs) is a MOF material which takes imidazole and derivatives thereof as ligands and has a zeolite framework structure, combines the advantages of zeolite and MOF, can be used for adsorption, separation, catalysis and other aspects, and is the most representative one of the 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 ZIFs material with the most extensive research.
Since semiconductor materials are used in photocatalytic technology, tiO 2 The photocatalyst has the unique advantages of high catalytic activity, good chemical stability and biological inertia, no toxicity to human body, low cost and the like, becomes the most actively researched photocatalytic material in recent years, and is widely applied to organic pollutant degradation, water decomposition and CO 2 Photocatalytic fields such as reduction. TiO is mixed with 2 And the composite photocatalyst is compounded with ZIF-8 to form a heterojunction, so that the advantages of the two materials can be combined to prepare the composite photocatalyst with better performance. The Chinese patent application with publication number CN105170097A discloses a TiO 2 Nano composite material with/ZIF-8 core-shell structure and preparation method thereof, zinc nitrate is adopted as zinc source to prepare TiO 2 Amorphous nano-spheres are used as a load main body, and TiO is used as a material 2 Adding the precursor solution of ZIF-8 into the amorphous nano-spheres to enable the ZIF-8 to be in TiO 2 Surface generation, thereby reducing TiO 2 The forbidden bandwidth 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 proposal is an explosive drug, and the ZIF-8 prepared by the zinc nitrate has the problem of poor crystal form; the TiO finally prepared by the technical proposal 2 The specific surface area of the nano composite material with the/ZIF-8 core-shell structure is only 300.4m 2 And/g, the ZIF-8 utilization rate of overload is not high. At the same time, the selection of the proper contaminants and the proper contaminant treatment is also the key of the material applicationThe material has important significance for fully playing the material performance.
Therefore, there is a need to provide a new ZIF-8/TiO 2 Composite material, preparation method and wastewater treatment method thereof.
Disclosure of Invention
Aiming at the existing ZIF-8/TiO 2 The invention provides a ZIF-8/TiO, which has the problems of low catalytic efficiency and poor pollutant treatment effect of a composite material 2 Composite material, preparation method thereof and wastewater treatment method, zinc acetate is used as zinc source to prepare ZIF-8 with high specific surface area, and nano TiO is loaded by taking the composite material as a loading main body 2 Preparation of ZIF-8/TiO which can be used as a micro-nano reaction vessel 2 A composite material. According to the invention, on the basis of avoiding the use of explosive drugs and ensuring safe production, the composite material with high photocatalytic activity is prepared, and the effective degradation of organic pollutants and heavy metal pollutants can be realized.
In a first aspect, the present invention provides a ZIF-8/TiO 2 The 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 ZIF-8 precursor solution, and adding nano TiO into the ZIF-8 precursor solution 2 Uniformly mixing to obtain ZIF-8 and TiO 2 A mixed solution;
(3) Hydrothermal treatment of ZIF-8 and TiO 2 Cooling and centrifuging the mixed solution after the reaction is finished to obtain precipitate, and freeze-drying to obtain the ZIF-8 loaded TiO 2 Of (2), i.e. ZIF-8/TiO 2 A composite material.
And (2) uniformly mixing zinc acetate dihydrate and 2-methylimidazole in absolute ethyl alcohol, performing hydrothermal treatment, cooling, centrifuging after the reaction is finished, taking precipitate, and freeze-drying to obtain ZIF-8 powder.
Further, in the step (1), the molar ratio of zinc acetate dihydrate to 2-methylimidazole is 1:10 to 1:20, preferably 1:20, a step of; the hydrothermal temperature is 120-150 ℃, preferably 150 ℃; the hydrothermal time is 3-10 hours, preferably 6 hours.
Further, in the step (2), ZIF-8 powder and TiO 2 The weight ratio of (2) is 1:1 to 1:4, preferably 1:2.
further, in the step (3), the hydrothermal reaction temperature is 120-150 ℃, preferably 150 ℃; the hydrothermal reaction time is 6 to 18 hours, preferably 12 hours.
In a second aspect, the present invention provides a ZIF-8/TiO composition prepared by the above-described process 2 A composite material.
In a third aspect, the present invention provides a wastewater treatment process employing the ZIF-8/TiO of the present invention 2 The composite material is used for treating 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 specifically comprises the steps of firstly treating ZIF-8/TiO 2 The composite material and the wastewater are evenly mixed, stirred for 30-120 min in the dark, and then the wastewater is irradiated by a xenon lamp light source for 5-180 min.
The invention has the advantages that,
the ZIF-8/TiO provided by the invention 2 Preparation method of composite material by dosage ratio of zinc acetate dihydrate and 2-methylimidazole and ZIF-8 and TiO 2 The dosage ratio of the catalyst is reasonably selected to prepare ZIF-8/TiO with excellent photocatalytic capability 2 The method of the composite material is simple and easy to control. ZIF-8 and TiO are enhanced by a hydrothermal method 2 The bonding strength of the composite material is improved, and the stability of the composite material is improved by TiO 2 The surface load of the (2) makes up the defect that ZIF-8 is not easy to dissolve 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 simply and physically mixing two substances together.
ZIF-8/TiO synthesized by the invention 2 The composite material takes ZIF-8 as a main body and TiO 2 The self-contained defect of ZIF-8 is made up for as the heterostructure of the object, the conduction capacity of electrons between interfaces is improved, and the photo-generated electron-hole pair is accelerated between ZIF-8 and TiO 2 Transfer on interface, enhancing ZIF-8/TiO 2 Catalytic capability of the composite material; in particular, the inventionZIF-8/TiO 2 The composite material has 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 utilizing ZIF-8/TiO 2 Method for treating wastewater by using composite material, wherein ZIF-8/TiO is utilized 2 The composite material can be used as a micro-nano reaction container, and the adsorption and photocatalysis treatment methods are combined, so that the pollutants are firstly adsorbed on the composite material, and then the pollutants adsorbed on the composite material are treated preferentially, thereby improving the degradation efficiency of organic pollutants and heavy metal pollutants.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is an SEM photograph of ZIF-8 powder prepared according to example 1;
FIG. 2 is a graph showing the nitrogen adsorption and desorption curves of the ZIF-8 powder prepared in example 1;
FIG. 3 is a ZIF-8/TiO prepared in example 2 2 SEM photographs of the composite material;
FIG. 4 is a graph showing the change in hexavalent chromium content in example 6;
FIG. 5 is a graph showing the content change of hexavalent chromium and methyl orange in example 7;
FIG. 6 is a graph showing the change in hexavalent chromium content in example 8;
in FIGS. 4 to 6, C 0 C as initial concentration of contaminant t C as the instantaneous concentration of the contaminant t /C 0 Indicating the proportion of pollutants in the wastewater.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
The apparatus and main reagents used in the embodiments of the present invention are shown in tables 1 and 2 below.
Table 1 instrument table
Instrument for measuring and controlling the intensity of light Model number Manufacturing factories
Scanning electron microscope Regulus8220 Hitachi Co Ltd
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 into a 100mL beaker, dissolved with 30mL of absolute ethanol, sonicated to complete dissolution, 4.1g of 2-methylimidazole is weighed into a 100mL beaker, dissolved with 30mL of absolute ethanol, sonicated to complete dissolution. Mixing the two solutions together, performing ultrasonic treatment for 3 hr, adding the mixed solution into polytetrafluoroethylene-lined high-pressure reaction kettle (100 mL), sealing, continuously heating the high-pressure reaction kettle at 150deg.C for 6 hr, cooling to room temperature, centrifuging, collecting precipitate, washing with anhydrous ethanol and deionized water, and lyophilizing for 12 hr to obtain ZIF-8 powder, wherein the scanning electron microscope of ZIF-8 powder is shown in figure 1, and BET specific surface area of ZIF-8 powder can reach 1899m according to nitrogen adsorption and desorption test in figure 2 3 /g。
Example 2
0.5g of the ZIF-8 powder of example 1 was weighed, added to 60mL of absolute ethanol, and stirred for 30min to obtain a ZIF-8 precursor solution, and 0.5g of TiO was weighed 2 (10-20 nm) is added into the ZIF-8 precursor solution and is continuously stirred for 1h to obtain ZIF-8 and TiO 2 Mixing the above solutions, and adding ZIF-8 and TiO 2 The mixed solution was sonicated for 3h to form a homogeneous solution. Transferring the uniform solution into a polytetrafluoroethylene-lined high-pressure reaction kettle (100 mL), sealing, continuously heating the high-pressure reaction kettle at 150 ℃ for 12h, cooling to room temperature, centrifuging, taking precipitate, washing with anhydrous ethanol and deionized water, and freeze-drying for 12h to obtain ZIF-8/TiO 2 A scanning electron microscope image of the composite material, designated as Z150T150, is shown in FIG. 3.
Example 3
Example 3 TiO 2 The addition amount of (2) is replaced by 1.0g from 0.5g, and the rest is preparedThe procedure is as in example 2, and the ZIF-8/TiO is prepared 2 The composite material was designated as Z100T200.
Example 4
Example 4 TiO 2 The added amount of (2) was changed from 0.5g to 1.5g, and the other preparation steps were the same as in example 2, to obtain ZIF-8/TiO 2 The composite was designated as Z75T225.
Example 5
Example 5 TiO 2 The added amount of (2) was changed from 0.5g to 2.0g, and the other preparation steps were the same as in example 2, to obtain ZIF-8/TiO 2 The composite material was designated as Z60T240.
Example 6
Weighing TiO 2 (10-20 nm) and 0.01g of ZIF-8 powder of example 1 are added into 60mL of 20mg/L hexavalent chromium solution in sequence, and stirred for 60min in darkness after being mixed uniformly by ultrasound to reach adsorption balance; then irradiating under 300W xenon lamp light source, testing hexavalent chromium content in different time solutions, and obtaining ZIF-8+TiO as shown in FIG. 4 2 The curve shows.
Weighing 0.02g of the Z150T150 composite material of the embodiment 2, adding the composite material into 60mL of 20mg/L hexavalent chromium solution, uniformly mixing by ultrasonic, and stirring for 60min in the dark to reach adsorption balance; hexavalent chromium content in the different time solutions was then tested by irradiation under a 300W xenon lamp light source, the results of which are shown in the Z150T150 curve in fig. 4.
As can be seen from FIG. 4, ZIF-8/TiO after hydrothermal treatment 2 The wastewater treatment effect of the composite material is obviously higher than that of the simple physical mixing, which shows that the hydrothermal method can effectively improve the adsorption and catalytic capability of the composite material.
Example 7
Weighing 3 parts of Z150T150 composite material, adding 0.02g of each part into 60mL of 20mg/L methyl orange solution, 20mg/L hexavalent chromium/methyl orange mixed solution and 30mg/L hexavalent chromium/methyl orange mixed solution respectively, and stirring for 60min in darkness after ultrasonic mixing uniformly to achieve adsorption balance; then, the hexavalent chromium and methyl orange contents in the solutions of different times were tested by irradiation under a 300W xenon lamp light source.
As a result, FIG. 5 shows that MO 20mg/L curve shows the effect of removing methyl orange solution at a concentration of 20mg/L, mix-Cr (VI) 20mg/L curve and Mix-MO 20mg/L curve show the effect of removing hexavalent chromium and methyl orange respectively from hexavalent chromium and methyl orange mixed solution at a concentration of 20mg/L, mix-Cr (VI) 30mg/L curve and Mix-MO 30mg/L curve show the effect of removing hexavalent chromium and methyl orange respectively from hexavalent chromium and methyl orange mixed solution at a concentration of 30 mg/L.
As can be seen from FIG. 5, the treatment effect of the Z150T150 composite material on the mixed wastewater containing hexavalent chromium and methyl orange is better than the treatment effect of the composite material on the single wastewater containing only hexavalent chromium, particularly the treatment effect of the composite material on the mixed solution containing hexavalent chromium and methyl orange with the concentration of 30mg/L is optimal, the degradation rate of the methyl orange reaches 95% after 5min of irradiation of a xenon lamp, 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 cooperatively degrading heavy metal pollutants and organic pollutants by photocatalysis, and the two pollutants are respectively combined with photo-generated electrons and holes generated by the composite material, so that the catalytic efficiency is further improved, and the treatment effect is obviously enhanced.
Example 8
Weighing TiO 2 (10-20 nm), the ZIF-8 powder of the example 1 and the composite materials of the examples 2-5 are respectively added into 60mL of 20mg/L hexavalent chromium solution, and after being mixed uniformly by ultrasonic, the mixture is stirred for 60min in the dark to reach adsorption balance; the hexavalent chromium content in the solution was then tested under a 300W xenon lamp light source and the results are shown in fig. 6, as can be seen, Z100T200 exhibited the best removal effect.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.

Claims (2)

1. A wastewater treatment method is characterized in that ZIF-8/TiO is adopted 2 The composite material is used for treating mixed wastewater of hexavalent chromium and methyl orange;
ZIF-8/TiO 2 the preparation method of the composite material comprises the following steps:
(1) Uniformly mixing zinc acetate dihydrate and 2-methylimidazole in absolute ethyl alcohol, performing hydrothermal treatment, cooling, centrifuging to obtain precipitate after the reaction is finished, and freeze-drying to obtain ZIF-8 powder;
(2) Uniformly mixing ZIF-8 powder with absolute ethyl alcohol to obtain ZIF-8 precursor solution, and adding nano TiO into the ZIF-8 precursor solution 2 Uniformly mixing to obtain ZIF-8 and TiO 2 A mixed solution;
(3) Hydrothermal treatment of ZIF-8 and TiO 2 Cooling and centrifuging the mixed solution after the reaction is finished to obtain precipitate, and freeze-drying to obtain the ZIF-8 loaded TiO 2 Of (2), i.e. ZIF-8/TiO 2 A composite material;
in the step (1), the molar ratio of zinc acetate dihydrate to 2-methylimidazole is 1: 10-1: 20, a step of; the hydrothermal temperature is 120-150 ℃; the hydrothermal time is 3-10 h;
in the step (2), ZIF-8 powder and TiO 2 The weight ratio of (2) is 1: 1-1: 4, a step of;
in the step (3), the hydrothermal reaction temperature is 120-150 ℃; the hydrothermal reaction time is 6-18 h.
2. The method for treating wastewater according to claim 1, wherein the method for treating wastewater comprises the steps of first treating ZIF-8/TiO 2 And uniformly mixing the composite material and the wastewater, stirring for 30-120 min in the dark, and then irradiating the wastewater for 5-180 min by using a xenon lamp light source.
CN202110949083.9A 2021-08-18 2021-08-18 ZIF-8/TiO 2 Composite material, preparation method thereof and wastewater treatment method Active CN113499801B (en)

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