CN109675607A - Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material - Google Patents

Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material Download PDF

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CN109675607A
CN109675607A CN201910042461.8A CN201910042461A CN109675607A CN 109675607 A CN109675607 A CN 109675607A CN 201910042461 A CN201910042461 A CN 201910042461A CN 109675607 A CN109675607 A CN 109675607A
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zif
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陈志文
赵骏如
王云
胡张军
黄守双
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University of Shanghai for Science and Technology
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
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Abstract

本发明公开了一种本发明公开了一种Fe3O4@ZnO@N‑C复合光催化材料的制备方法,以可控亚微米尺寸的Fe3O4磁性纳米粒子为载体,通过负载ZnO制备出Fe3O4@ZnO复合催化剂;利用Zn2+与二‑甲基咪唑之间的络合作用在Fe3O4@ZnO外层沉积金属有机框架材料ZIF‑8,制备出具有多重核壳结构的Fe3O4@ZnO@ZIF‑8复合材料;采用热处理工艺将ZIF‑8转变成ZnO和氮掺杂的碳。本发明制得的复合材料具有良好的光催化降解性能与稳定的循环使用性能,提高了回收率,降低了光生电子‑空穴对的复合。本发明制得复合材料可用于降解污水中的有机污染物,并提高光催化降解效率与循环使用率。The invention discloses a preparation method of Fe 3 O 4 @ZnO@N-C composite photocatalytic material. The Fe 3 O 4 magnetic nanoparticles with controllable submicron size are used as carriers, and ZnO Fe 3 O 4 @ZnO composite catalyst was prepared; metal-organic framework material ZIF-8 was deposited on the outer layer of Fe 3 O 4 @ZnO by using the complexation between Zn 2+ and di-methylimidazole, and the composite catalyst with multiple cores was prepared. Fe 3 O 4 @ZnO@ZIF‑8 composite with shell structure; ZIF‑8 was transformed into ZnO and nitrogen-doped carbon by a heat treatment process. The composite material prepared by the invention has good photocatalytic degradation performance and stable recycling performance, improves the recovery rate, and reduces the recombination of photogenerated electron-hole pairs. The composite material prepared by the invention can be used for degrading organic pollutants in sewage, and can improve photocatalytic degradation efficiency and recycling rate.

Description

Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material
Technical field
The present invention relates to a kind of preparation methods of composite photo-catalyst, more particularly to a kind of ZnO composite photo-catalyst Preparation method is applied to catalysis material fabricating technology field.
Background technique
Due to manufacturing fast development, a large amount of organic dyestuff in industrial fabrics and cosmetics be discharged into river and In ocean, this seriously destroys environment and the ecological balance, therefore the removal of pollutant becomes particularly important.Nature is miscellaneous within 1972 It reports in will in TiO2The important scientific research of photocatalytic water on electrode, this is also the mark that catalysis material research starts.? Environmental Chemistry field, common inorganic semiconductor catalysis material mainly include ZnO, TiO2, CdS, ZnS and MoS2Deng.ZnO because Its prepare simple, nontoxic, chemical property is stable, inexpensive and high catalytic activity and be considered as a kind of very promising nanometer material Material.But pure ZnO material band-gap energy is wider, reaches 3.2eV, can only excite and generate under ultraviolet light of the wavelength lower than 387nm Electron-hole pair, and the recycling and reusing that is difficult to of the high speed compound of photo-generate electron-hole pair and material limits answering for it With.Therefore, people are modified it by the methods of composite semiconductor, precious metal doping, different-shape regulation.In addition to this, Also composite photo-catalyst can be prepared by being fixed on ZnO on the carrier material with bigger serface, with larger catalyst Contact area between reactant prevents the aggregation of nano particle.But the preparation and repetition of current ZnO composite photo-catalyst Technical problem undesirable using there is also costs, that technique is more complex, degradation capability is to be improved is urgently to be resolved.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material, Fe3O4It is a kind of magnetic material, as in composite material The rate of recovery can be improved in core, to improve the recycling of material, the carbon material of N doping is a kind of porous material, this Porous material can effectively adsorb contaminant molecule, and can provide many electron traps, these electron traps can make The be excited light Shen electronics of generation of ZnO is easy to be transferred to porous carbon surface, reduces compound, the photoproduction of photo-generate electron-hole pair Electronics and O2In conjunction with the O for forming high activity2 -Free radical improves Photocatalytic Degradation Property.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material, it is characterised in that: with average grain diameter be 100~ The magnetic Fe of the submicron-scale of 150nm3O4Nanoparticle prepares Fe as carrier, by loading ZnO3O4@ZnO is compound to be urged Then agent utilizes Zn2+With the complexing between two-methylimidazoles, in Fe3O4@ZnO outer layer, which deposits one layer of metal, machine frame Frame material ZIF-8, prepares Fe3O4@ZnO@ZIF-8 composite material, finally by heat treatment process by ZIF-8 be transformed into ZnO and The carbon of N doping, to obtain Fe3O4@ZnO@N-C composite photocatalyst material.
As currently preferred technical solution, Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material, step is such as Under:
A. Fe is synthesized3O4Magnetic nano-particle material:
Take the FeCl of 1.0~3.0g3·6H2O, the sodium citrate of 0.5~1.0g and the anhydrous sodium acetate of 3.0~5.0g add Enter in 100mL alcohols solvent, stirs at least 30min, make it completely dissolved mixing, be then transferred to obtained mixed solution instead It answers in kettle, carries out hydro-thermal reaction in 150~200 DEG C of 5~10h of heating, obtain hydrothermal product mixed liquor, then carry out magnetic point From, obtain black product, then respectively cleaned product at least three times with ethyl alcohol and distilled water, then by obtained solid carry out vacuum Drying is to get Fe3O4Magnetic nano-particle material;
B. Fe is synthesized3O4@ZnO material:
Take the Zn (Ac) of 1.0~3.0g2·H2The NaOH of O and 0.5~1.0g is respectively dissolved in 40mL distilled water, respectively To Zn (Ac)2·H2O solution and NaOH solution;Then under constant stirring, NaOH solution is added to Zn (Ac)2·H2O solution In, after mixing evenly, obtain raw material mixed liquor;Take 0.1~0.5g Fe made from the step a3O4Magnetic nano-particle material It is added into raw material mixed liquor, after ultrasound at least 10min, Fe will be added3O4Raw material mixed liquor be transferred in reaction kettle, 150~200 DEG C of 10~20h of heating, obtain hydrothermal product mixed liquor;Then Magnetic Isolation obtains product, with ethyl alcohol and distilled water Product is respectively cleaned at least three times, then obtained solid is dried in vacuo to get Fe3O4@ZnO material;
c.Fe3O4The preparation of@ZnO@ZIF-8 intermediate product:
Take 0.1~0.5g Fe made from the step b3O4The 2-methylimidazole of@ZnO material and 0.1~0.5g be added to 32mL contains in the reaction kettle of the mixed solvent of DMF and water, and after ultrasound at least 10min, reaction kettle is transferred in baking oven, 50~80 DEG C of 10~30h of heating, obtain hydrothermal product mixed liquor;Then Magnetic Isolation obtains product, with ethyl alcohol that product is each clear It is washed till and lacks three times, then obtained solid is dried in vacuo to get Fe3O4@ZnO@ZIF-8 intermediate product, by Fe3O4@ ZnO is coated in the metal organic frame of ZIF-8, forms envelope structure;
D. Fe is synthesized3O4@ZnO@N-C composite photocatalyst material:
It, will the Fe made from the step c under nitrogen or atmosphere of inert gases3O4@ZnO@ZIF-8 intermediate product is 500 ~900 DEG C carry out 1~4h of annealing, then under air atmosphere and 200~400 DEG C of progress 1~5h of calcination processing to get To Fe3O4@ZnO@N-C composite photocatalyst material.
Synthesis Fe is carried out in the step a as currently preferred technical solution3O4Magnetic nano-particle material supplier When skill, the FeCl of 1.5~3.0g is taken3·6H2O, the anhydrous sodium acetate of the sodium citrate of 0.6~0.85g and 3.6~5.0g are added In 100mL alcohols solvent, at least 30min is stirred, mixing is made it completely dissolved, obtained mixed solution is then transferred to reaction In kettle, hydro-thermal reaction is carried out in 150~190 DEG C of 6~10h of heating, obtains hydrothermal product mixed liquor.
Synthesis Fe is carried out in the step b as currently preferred technical solution3O4When@ZnO material technique, take The Zn (Ac) of 1.5~2.5g2·H2The NaOH of O and 0.5~1.0g is respectively dissolved in 40mL distilled water, respectively obtains Zn (Ac)2· H2O solution and NaOH solution;Then under constant stirring, NaOH solution is added to Zn (Ac)2·H2In O solution, stir evenly Afterwards, raw material mixed liquor is obtained;Take 0.2~0.5g Fe made from the step a3O4Magnetic nano-particle material is added to raw material In mixed liquor, after ultrasound at least 10min, Fe will be added3O4Raw material mixed liquor be transferred in reaction kettle, at 150~200 DEG C It heats 10~16h and carries out hydro-thermal reaction, obtain hydrothermal product mixed liquor.
As currently preferred technical solution, in the step c, Fe is carried out3O4The system of@ZnO@ZIF-8 intermediate product When standby technique, 0.1~0.3g Fe made from the step b is taken3O4The 2-methylimidazole of@ZnO material and 0.25~0.4g are added In the reaction kettle for containing the mixed solvent of DMF and water to 32mL, after ultrasound at least 10min, reaction kettle is transferred in baking oven, Hydro-thermal reaction is carried out in 50~80 DEG C of 12~20h of heating, obtains hydrothermal product mixed liquor.
As currently preferred technical solution, in the step c, Fe is carried out3O4The system of@ZnO@ZIF-8 intermediate product When standby technique, the dosage volume ratio of the DMF and water is (1~4): 1.
Obtained solid is dried under vacuum in the step a~c as currently preferred technical solution Few 8h, obtains dry hydrothermal product.
It, will the Fe made from the step c in the step d as currently preferred technical solution3O4@ZnO@ ZIF-8 intermediate product carries out 1~4h of annealing at 500~800 DEG C, then carries out under air atmosphere and at 200~400 DEG C 2~4h of calcination processing to get arrive Fe3O4@ZnO@N-C composite photocatalyst material.
As currently preferred technical solution, in the step d, the liter of the annealing and the use of calcination processing technique Warm rate is 1~4 DEG C/min.
Fe of the present invention3O4The preparation method of@ZnO@N-C composite photocatalyst material, with the Fe of controllable sub-micron size3O4Magnetic Property nanoparticle be carrier, Fe is prepared by loading ZnO3O4@ZnO composite catalyst;Utilize Zn2+With two-methylimidazoles it Between complexing in Fe3O4@ZnO outer layer deposits one layer of metal-organic framework material ZIF-8, prepares with multiple nucleocapsid knot The Fe of structure3O4@ZnO@ZIF-8 composite material;Select heat treatment process appropriate that ZIF-8 is transformed into the carbon of ZnO and N doping. Composite material produced by the present invention has good Photocatalytic Degradation Property and stable recycling performance, Fe3O4It is a kind of magnetic The rate of recovery can be improved as the kernel of composite material in property material, so that the recycling of material is improved, N doping Carbon material be a kind of porous material, there is biggish specific surface area, this porous material can effectively adsorb pollutant point Son, and can provide many electron traps, these electron traps can make the be excited light induced electron of generation of ZnO be easy to turn Porous carbon surface is moved on to, compound, light induced electron and the O of photo-generate electron-hole pair are reduced2In conjunction with the O for forming high activity2 -Freely Base improves Photocatalytic Degradation Property.The organic pollutant that composite material can be used for degrading in sewage is made in the present invention, and can mention High photocatalytic degradation efficiency and recycling rate.The present invention is prepared for nanoporous carbon, due to adsorptivity, chemical stabilization Property, corrosion resistance, electric conductivity, can with catalyst formed heterojunction structure.In addition, material also can be improved in the carbon material of N doping of the present invention The catalytic performance of material.Therefore, there is the ZnO@N-C composite material of core-shell structure can effectively improve its photocatalysis performance for preparation. , can be compound with magnetic material in order to improve the recyclability and recycling after photocatalyst for degrading organic matter, convenient for magnetism Separation.Magnetic Fe3O4Nano material can be extensively due to its unique property, including strong superparamagnetism, hypotoxicity and easy preparation Application field applied to magnetic composite.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the preparation process that the method for the present invention prepares material is relatively easy, cost is relatively low;
2. the method for the present invention uses Fe3O4It is that a kind of magnetic material can be improved back as the kernel of composite material Yield, reduces the loss of material, to improve the recycling of material;
3. the method for the present invention is a kind of porous material using the carbon material of N doping, this porous material specific surface area compared with Greatly, the contact area that can increase material and pollutant, effectively adsorbs contaminant molecule;
4. the method for the present invention can provide many electron traps using the carbon material of N doping, these electron traps can make The be excited light induced electron of generation of ZnO is easy to be transferred to porous carbon surface, reduces compound, the photoproduction of photo-generate electron-hole pair Electronics and O2In conjunction with the O for forming high activity2 -Free radical improves Photocatalytic Degradation Property.
Detailed description of the invention
Fig. 1 is intermediate product prepared by one method of the embodiment of the present invention and the Fe finally prepared3O4@ZnO@N-C complex light is urged Change the XRD spectrum comparison diagram of material.
Fig. 2 is the Fe of one method of embodiment of the present invention preparation3O4The XPS map of@ZnO@N-C composite photocatalyst material.
Fig. 3 is the Fe of one method of embodiment of the present invention preparation3O4The TEM picture of@ZnO@N-C composite photocatalyst material.
Fig. 4 is the Fe of one method of embodiment of the present invention preparation3O4The photocatalysis performance of@ZnO@N-C composite photocatalyst material Figure.
Fig. 5 is the Fe of one method of embodiment of the present invention preparation3O4Performance is recycled in@ZnO N-C composite photocatalyst material Figure.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as Under:
Embodiment one:
In the present embodiment, referring to FIG. 1 to FIG. 5, a kind of Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material, packet Include following steps:
A. Fe is synthesized3O4Magnetic nano-particle material:
Take the FeCl of 1.5g3·6H2O, 100mL alcohols solvent is added in the anhydrous sodium acetate of the sodium citrate of 0.8g and 4.0g In, 30min is stirred, mixing is made it completely dissolved, then obtained mixed solution is transferred in reaction kettle, is heated at 160 DEG C 7h carries out hydro-thermal reaction, obtains hydrothermal product mixed liquor, then carries out Magnetic Isolation, obtains black product, then with ethyl alcohol and steaming Distilled water respectively cleans product three times, and obtained solid is then carried out vacuum drying 8h to get Fe3O4Magnetic nano-particle material;
B. Fe is synthesized3O4@ZnO material:
Take the Zn (Ac) of 1.8g2·H2The NaOH of O and 0.6g is respectively dissolved in 40mL distilled water, respectively obtains Zn (Ac)2· H2O solution and NaOH solution;Then under constant stirring, NaOH solution is added to Zn (Ac)2·H2In O solution, stir evenly Afterwards, raw material mixed liquor is obtained;Take 0.4g Fe made from the step a3O4Magnetic nano-particle material is added to raw material mixed liquor In, after ultrasonic 10min, Fe will be added3O4Raw material mixed liquor be transferred in reaction kettle, in 180 DEG C of heating 12h, obtain hydro-thermal Product mixture;Then Magnetic Isolation obtains product, respectively cleans three times product with ethyl alcohol and distilled water, then consolidates what is obtained Body carries out vacuum drying 8h to get Fe3O4@ZnO material;
c.Fe3O4The preparation of@ZnO@ZIF-8 intermediate product:
Take 0.2g Fe made from the step b3O4The 2-methylimidazole of@ZnO material and 0.4g, which are added to 32mL, to be contained In the reaction kettle of the mixed solvent of DMF and water, wherein the dosage volume ratio (v/v) of DMF and water is 3:1, after ultrasonic 10min, Reaction kettle is transferred in baking oven, in 50 DEG C of heating 15h, obtains hydrothermal product mixed liquor;Then Magnetic Isolation obtains product, uses Ethyl alcohol respectively cleans product three times, and obtained solid is then carried out vacuum drying 8h to get Fe3O4It is produced among@ZnO@ZIF-8 Object, by Fe3O4@ZnO is coated in the metal organic frame of ZIF-8, forms envelope structure;
D. Fe is synthesized3O4@ZnO@N-C composite photocatalyst material:
Under nitrogen atmosphere, control heating rate is 1 DEG C/min, will the Fe made from the step c3O4@ZnO@ZIF-8 Intermediate product carries out annealing 1h at 500 DEG C;Then control heating rate is 2 DEG C/min, under air atmosphere and at 200 DEG C Calcination processing 3h is carried out to get Fe is arrived3O4@ZnO@N-C composite photocatalyst material.
The present embodiment Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material is 100~150nm's with average grain diameter The magnetic Fe of submicron-scale3O4Nanoparticle prepares Fe as carrier, by loading ZnO3O4@ZnO composite catalyst, so Zn is utilized afterwards2+With the complexing between two-methylimidazoles, in Fe3O4@ZnO outer layer deposits one layer of metal-organic framework material ZIF-8 prepares Fe3O4@ZnO@ZIF-8 composite material, is transformed into ZnO and N doping for ZIF-8 finally by heat treatment process Carbon, to obtain Fe3O4@ZnO@N-C composite photocatalyst material.
Experimental test and analysis:
Fe is made to the present embodiment3O4@ZnO@N-C composite photocatalyst material carries out photocatalysis performance test: by answering for 25mg Condensation material is dispersed in the aqueous solution of methylene blue that 50mL concentration is 10mg/L and forms suspension, ultrasonic disperse 5min.In dark Under the conditions of, it is sufficiently mixed 60min, makes to reach between catalyst and dyestuff absorption-desorption balance, during this, every 10min is taken 2mL solution measures its absorbance.Methylene blue solution is placed under the xenon lamp of 300W and irradiates 90min, in entire During Illumination Air-blowing stirring is maintained, takes 2mL solution to measure its absorbance every 30min, the degradation rate η (%) of dyestuff can pass through following equation meter It obtains:
η (%)=(C0-C)/C0× 100%=(A0-A)/A0× 100%
C0It is respectively initial concentration and residual concentration, A with C0The absorbance at 664nm wavelength is respectively corresponded with A.Product As shown in Figure 1, wherein Fig. 1 (a) indicates that the present embodiment synthesizes Fe to XRD3O4The XRD spectrum of magnetic nano-particle material, Fig. 1 (b) table Show the XRD spectrum of the present embodiment ZnO, Fig. 1 (c) indicates that the present embodiment synthesizes Fe3O4The XRD spectrum of@ZnO material, Fig. 1 (d) are indicated Fe manufactured in the present embodiment3O4The XRD spectrum of@ZnO@ZIF-8 intermediate product, Fig. 1 (e) indicate the Fe of preparation3O4@ZnO@N-C is multiple The XRD spectrum of light combination catalysis material.Contain Fe in composite material manufactured in the present embodiment as shown in Figure 13O4And ZnO, nothing in the product Obvious impurity peaks.Fig. 2 is the XPS figure of composite material manufactured in the present embodiment, as shown in Figure 2 composite material manufactured in the present embodiment Contain Zn, Fe, O, C and N element.Fig. 3 is the TEM figure of composite material manufactured in the present embodiment, as can be seen from Figure 3 N doping Carbon-coating be wrapped in Fe3O4@ZnO outer layer.Fig. 4 is composite material manufactured in the present embodiment under the irradiation of 300W xenon lamp to methylene Blue Photocatalytic Degradation Property figure, as shown in Figure 4, Fe3O4@ZnO@N-C composite material is in 90min to methylene blue degradation rate It can achieve 93%, compared to simple Fe3O4@ZnO, degradation rate improve 30%.Fig. 5 is composite wood manufactured in the present embodiment The recycling performance figure of material, as shown in Figure 5, degradation of the composite material after 6 circulation degradation tests, to methylene blue Rate is 87%, and photocatalysis performance is not decreased obviously, this shows Fe3O4@ZnO@N-C composite material photocatalytic degradation methylene Repeatability, the stability of base indigo plant are preferable.
The present embodiment Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material, with the Fe of controllable sub-micron size3O4 Magnetic nano-particle is carrier, prepares Fe by loading ZnO3O4@ZnO composite catalyst;Utilize Zn2+With two-methylimidazoles Between complexing in Fe3O4@ZnO outer layer deposits one layer of metal-organic framework material ZIF-8, prepares with multiple nucleocapsid The Fe of structure3O4@ZnO@ZIF-8 composite material;ZIF-8 is transformed into the carbon of ZnO and N doping using heat treatment process.This reality Composite material made from a method is applied with good Photocatalytic Degradation Property and stable recycling performance, Fe3O4It is a kind of The rate of recovery can be improved as the kernel of composite material in magnetic material, to improve the recycling of material, nitrogen is mixed Miscellaneous carbon material is a kind of porous material, has biggish specific surface area, and this porous material can effectively adsorb pollutant Molecule, and can provide many electron traps, these electron traps can be such that the be excited light induced electron of generation of ZnO is easy to It is transferred to porous carbon surface, reduces compound, light induced electron and the O of photo-generate electron-hole pair2In conjunction with the O for forming high activity2 -From Photocatalytic Degradation Property is improved by base.The organic pollutant that composite material can be used for degrading in sewage is made in the present embodiment, and Photocatalytic degradation efficiency and recycling rate can be improved.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a kind of Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material, includes the following steps:
A. Fe is synthesized3O4Magnetic nano-particle material:
Take the FeCl of 2.0g3·6H2O, 100mL alcohols solvent is added in the anhydrous sodium acetate of the sodium citrate of 0.6g and 3.6g In, 30min is stirred, mixing is made it completely dissolved, then obtained mixed solution is transferred in reaction kettle, is heated at 150 DEG C 8h carries out hydro-thermal reaction, obtains hydrothermal product mixed liquor, then carries out Magnetic Isolation, obtains black product, then with ethyl alcohol and steaming Distilled water respectively cleans product three times, and obtained solid is then carried out vacuum drying 8h to get Fe3O4Magnetic nano-particle material;
B. Fe is synthesized3O4@ZnO material:
Take the Zn (Ac) of 2.0g2·H2The NaOH of O and 0.7g is respectively dissolved in 40mL distilled water, respectively obtains Zn (Ac)2· H2O solution and NaOH solution;Then under constant stirring, NaOH solution is added to Zn (Ac)2·H2In O solution, stir evenly Afterwards, raw material mixed liquor is obtained;Take 0.3g Fe made from the step a3O4Magnetic nano-particle material is added to raw material mixed liquor In, after ultrasonic 10min, Fe will be added3O4Raw material mixed liquor be transferred in reaction kettle, in 200 DEG C of heating 10h, obtain hydro-thermal Product mixture;Then Magnetic Isolation obtains product, respectively cleans three times product with ethyl alcohol and distilled water, then consolidates what is obtained Body carries out vacuum drying 8h to get Fe3O4@ZnO material;
c.Fe3O4The preparation of@ZnO@ZIF-8 intermediate product:
Take 0.3g Fe made from the step b3O4The 2-methylimidazole of@ZnO material and 0.3g, which are added to 32mL, to be contained In the reaction kettle of the mixed solvent of DMF and water, wherein the dosage volume ratio (v/v) of DMF and water is 1:1, after ultrasonic 10min, Reaction kettle is transferred in baking oven, in 80 DEG C of heating 18h, obtains hydrothermal product mixed liquor;Then Magnetic Isolation obtains product, uses Ethyl alcohol respectively cleans product three times, and obtained solid is then carried out vacuum drying 8h to get Fe3O4It is produced among@ZnO@ZIF-8 Object, by Fe3O4@ZnO is coated in the metal organic frame of ZIF-8, forms envelope structure;
D. Fe is synthesized3O4@ZnO@N-C composite photocatalyst material:
Under nitrogen atmosphere, control heating rate is 2 DEG C/min, will the Fe made from the step c3O4@ZnO@ZIF-8 Intermediate product carries out annealing 1h at 600 DEG C;Then control heating rate is 3 DEG C/min, under air atmosphere and at 250 DEG C Calcination processing 2h is carried out to get Fe is arrived3O4@ZnO@N-C composite photocatalyst material.
The present embodiment Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material is 100~150nm's with average grain diameter The magnetic Fe of submicron-scale3O4Nanoparticle prepares Fe as carrier, by loading ZnO3O4@ZnO composite catalyst, so Zn is utilized afterwards2+With the complexing between two-methylimidazoles, in Fe3O4@ZnO outer layer deposits one layer of metal-organic framework material ZIF-8 prepares Fe3O4@ZnO@ZIF-8 composite material, is transformed into ZnO and N doping for ZIF-8 finally by heat treatment process Carbon, to obtain Fe3O4@ZnO@N-C composite photocatalyst material.
Experimental test and analysis:
Fe is made to the present embodiment3O4@ZnO@N-C composite photocatalyst material carries out photocatalysis performance test: by answering for 25mg Condensation material is dispersed in the aqueous solution of methylene blue that 50mL concentration is 10mg/L and forms suspension, ultrasonic disperse 5min.In dark Under the conditions of, it is sufficiently mixed 60min, makes to reach between catalyst and dyestuff absorption-desorption balance, during this, every 10min is taken 2mL solution measures its absorbance.Methylene blue solution is placed under the xenon lamp of 300W and irradiates 90min, in entire During Illumination Air-blowing stirring is maintained, takes 2mL solution to measure its absorbance every 30min.Fe manufactured in the present embodiment3O4@ZnO@N-C composite wood Material can achieve 88% to methylene blue degradation rate in 90min, compared to simple Fe3O4@ZnO, degradation rate improve 25%.To Fe manufactured in the present embodiment3O4@ZnO N-C composite material carries out that performance test is recycled, and composite material passes through 6 times After circulation degradation test, the degradation rate to methylene blue is 82%, and photocatalysis performance is not decreased obviously, this shows Fe3O4Repeatability, the stability of@ZnO@N-C composite material photocatalytic degradation methylene blue are preferable.The present embodiment Fe3O4@ZnO@ The preparation method of N-C composite photocatalyst material, with the Fe of controllable sub-micron size3O4Magnetic nano-particle is carrier, passes through load ZnO prepares Fe3O4@ZnO composite catalyst;Utilize Zn2+Complexing between two-methylimidazoles is in Fe3O4@ZnO outer layer One layer of metal-organic framework material ZIF-8 is deposited, the Fe with multiple core-shell structure is prepared3O4@ZnO@ZIF-8 composite material; ZIF-8 is transformed into the carbon of ZnO and N doping using heat treatment process.Composite material made from the present embodiment method has good Photocatalytic Degradation Property and stable recycling performance, Fe3O4It is a kind of magnetic material, as in composite material The rate of recovery can be improved in core, to improve the recycling of material, the carbon material of N doping is a kind of porous material, has Biggish specific surface area, this porous material can effectively adsorb contaminant molecule, and can provide many electron traps, These electron traps can make the be excited light induced electron of generation of ZnO be easy to be transferred to porous carbon surface, reduce light induced electron- Compound, light induced electron and the O in hole pair2In conjunction with the O for forming high activity2 -Free radical improves Photocatalytic Degradation Property.This reality It applies example and the organic pollutant that composite material can be used for degrading in sewage is made, and photocatalytic degradation efficiency can be improved and be recycled Rate.
Embodiment three:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material, includes the following steps:
A. Fe is synthesized3O4Magnetic nano-particle material:
Take the FeCl of 2.5g3·6H2O, 100mL alcohols solvent is added in the anhydrous sodium acetate of the sodium citrate of 0.68g and 4.4g In, 30min is stirred, mixing is made it completely dissolved, then obtained mixed solution is transferred in reaction kettle, is heated at 190 DEG C 6h carries out hydro-thermal reaction, obtains hydrothermal product mixed liquor, then carries out Magnetic Isolation, obtains black product, then with ethyl alcohol and steaming Distilled water respectively cleans product three times, and obtained solid is then carried out vacuum drying 8h to get Fe3O4Magnetic nano-particle material;
B. Fe is synthesized3O4@ZnO material:
Take the Zn (Ac) of 1.5g2·H2The NaOH of O and 0.5g is respectively dissolved in 40mL distilled water, respectively obtains Zn (Ac)2· H2O solution and NaOH solution;Then under constant stirring, NaOH solution is added to Zn (Ac)2·H2In O solution, stir evenly Afterwards, raw material mixed liquor is obtained;Take 0.2g Fe made from the step a3O4Magnetic nano-particle material is added to raw material mixed liquor In, after ultrasonic 10min, Fe will be added3O4Raw material mixed liquor be transferred in reaction kettle, in 150 DEG C of heating 15h, obtain hydro-thermal Product mixture;Then Magnetic Isolation obtains product, respectively cleans three times product with ethyl alcohol and distilled water, then consolidates what is obtained Body carries out vacuum drying 8h to get Fe3O4@ZnO material;
c.Fe3O4The preparation of@ZnO@ZIF-8 intermediate product:
Take 0.1g Fe made from the step b3O4The 2-methylimidazole of@ZnO material and 0.25g, which are added to 32mL, to be contained In the reaction kettle of the mixed solvent of DMF and water, wherein the dosage volume ratio (v/v) of DMF and water is 2:1, after ultrasonic 10min, Reaction kettle is transferred in baking oven, in 70 DEG C of heating 12h, obtains hydrothermal product mixed liquor;Then Magnetic Isolation obtains product, uses Ethyl alcohol respectively cleans product three times, and obtained solid is then carried out vacuum drying 8h to get Fe3O4It is produced among@ZnO@ZIF-8 Object, by Fe3O4@ZnO is coated in the metal organic frame of ZIF-8, forms envelope structure;
D. Fe is synthesized3O4@ZnO@N-C composite photocatalyst material:
Under nitrogen atmosphere, control heating rate is 2 DEG C/min, will the Fe made from the step c3O4@ZnO@ZIF-8 Intermediate product carries out annealing 3h at 800 DEG C;Then control heating rate is 1 DEG C/min, under air atmosphere and at 300 DEG C Calcination processing 3h is carried out to get Fe is arrived3O4@ZnO@N-C composite photocatalyst material.
The present embodiment Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material is 100~150nm's with average grain diameter The magnetic Fe of submicron-scale3O4Nanoparticle prepares Fe as carrier, by loading ZnO3O4@ZnO composite catalyst, so Zn is utilized afterwards2+With the complexing between two-methylimidazoles, in Fe3O4@ZnO outer layer deposits one layer of metal-organic framework material ZIF-8 prepares Fe3O4@ZnO@ZIF-8 composite material, is transformed into ZnO and N doping for ZIF-8 finally by heat treatment process Carbon, to obtain Fe3O4@ZnO@N-C composite photocatalyst material.
Experimental test and analysis:
Fe is made to the present embodiment3O4@ZnO@N-C composite photocatalyst material carries out photocatalysis performance test: by answering for 25mg Condensation material is dispersed in the aqueous solution of methylene blue that 50mL concentration is 10mg/L and forms suspension, ultrasonic disperse 5min.In dark Under the conditions of, it is sufficiently mixed 60min, makes to reach between catalyst and dyestuff absorption-desorption balance, during this, every 10min is taken 2mL solution measures its absorbance.Methylene blue solution is placed under the xenon lamp of 300W and irradiates 90min, in entire During Illumination Air-blowing stirring is maintained, takes 2mL solution to measure its absorbance every 30min.Fe manufactured in the present embodiment3O4@ZnO@N-C composite wood Material can achieve 90% to methylene blue degradation rate in 90min, compared to simple Fe3O4@ZnO, degradation rate improve 28%.To Fe manufactured in the present embodiment3O4@ZnO N-C composite material carries out that performance test is recycled, and composite material passes through 6 times After circulation degradation test, the degradation rate to methylene blue is 84%, and photocatalysis performance is not decreased obviously, this shows Fe3O4Repeatability, the stability of@ZnO@N-C composite material photocatalytic degradation methylene blue are preferable.The present embodiment Fe3O4@ZnO@ The preparation method of N-C composite photocatalyst material, with the Fe of controllable sub-micron size3O4Magnetic nano-particle is carrier, passes through load ZnO prepares Fe3O4@ZnO composite catalyst;Utilize Zn2+Complexing between two-methylimidazoles is in Fe3O4@ZnO outer layer One layer of metal-organic framework material ZIF-8 is deposited, the Fe with multiple core-shell structure is prepared3O4@ZnO@ZIF-8 composite material; ZIF-8 is transformed into the carbon of ZnO and N doping using heat treatment process.Composite material made from the present embodiment method has good Photocatalytic Degradation Property and stable recycling performance, Fe3O4It is a kind of magnetic material, as in composite material The rate of recovery can be improved in core, to improve the recycling of material, the carbon material of N doping is a kind of porous material, has Biggish specific surface area, this porous material can effectively adsorb contaminant molecule, and can provide many electron traps, These electron traps can make the be excited light induced electron of generation of ZnO be easy to be transferred to porous carbon surface, reduce light induced electron- Compound, light induced electron and the O in hole pair2In conjunction with the O for forming high activity2 -Free radical improves Photocatalytic Degradation Property.This reality It applies example and the organic pollutant that composite material can be used for degrading in sewage is made, and photocatalytic degradation efficiency can be improved and be recycled Rate.
Example IV:
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material, includes the following steps:
A. Fe is synthesized3O4Magnetic nano-particle material:
Take the FeCl of 3.0g3·6H2O, 100mL alcohols solvent is added in the anhydrous sodium acetate of the sodium citrate of 0.85g and 5.0g In, 30min is stirred, mixing is made it completely dissolved, then obtained mixed solution is transferred in reaction kettle, is heated at 180 DEG C 10h carries out hydro-thermal reaction, obtains hydrothermal product mixed liquor, then carries out Magnetic Isolation, obtains black product, then with ethyl alcohol and steaming Distilled water respectively cleans product three times, and obtained solid is then carried out vacuum drying 8h to get Fe3O4Magnetic nano-particle material;
B. Fe is synthesized3O4@ZnO material:
Take the Zn (Ac) of 2.5g2·H2The NaOH of O and 1.0g is respectively dissolved in 40mL distilled water, respectively obtains Zn (Ac)2· H2O solution and NaOH solution;Then under constant stirring, NaOH solution is added to Zn (Ac)2·H2In O solution, stir evenly Afterwards, raw material mixed liquor is obtained;Take 0.5g Fe made from the step a3O4Magnetic nano-particle material is added to raw material mixed liquor In, after ultrasonic 10min, Fe will be added3O4Raw material mixed liquor be transferred in reaction kettle, in 180 DEG C of heating 16h, obtain hydro-thermal Product mixture;Then Magnetic Isolation obtains product, respectively cleans three times product with ethyl alcohol and distilled water, then consolidates what is obtained Body carries out vacuum drying 8h to get Fe3O4@ZnO material;
c.Fe3O4The preparation of@ZnO@ZIF-8 intermediate product:
Take 0.3g Fe made from the step b3O4The 2-methylimidazole of@ZnO material and 0.4g, which are added to 32mL, to be contained In the reaction kettle of the mixed solvent of DMF and water, wherein the dosage volume ratio (v/v) of DMF and water is 4:1, after ultrasonic 10min, Reaction kettle is transferred in baking oven, in 60 DEG C of heating 20h, obtains hydrothermal product mixed liquor;Then Magnetic Isolation obtains product, uses Ethyl alcohol respectively cleans product three times, and obtained solid is then carried out vacuum drying 8h to get Fe3O4It is produced among@ZnO@ZIF-8 Object, by Fe3O4@ZnO is coated in the metal organic frame of ZIF-8, forms envelope structure;
D. Fe is synthesized3O4@ZnO@N-C composite photocatalyst material:
Under nitrogen atmosphere, control heating rate is 2 DEG C/min, will the Fe made from the step c3O4@ZnO@ZIF-8 Intermediate product carries out annealing 4h at 700 DEG C;Then control heating rate is 3 DEG C/min, under air atmosphere and at 400 DEG C Calcination processing 4h is carried out to get Fe is arrived3O4@ZnO@N-C composite photocatalyst material.
The present embodiment Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material is 100~150nm's with average grain diameter The magnetic Fe of submicron-scale3O4Nanoparticle prepares Fe as carrier, by loading ZnO3O4@ZnO composite catalyst, so Zn is utilized afterwards2+With the complexing between two-methylimidazoles, in Fe3O4@ZnO outer layer deposits one layer of metal-organic framework material ZIF-8 prepares Fe3O4@ZnO@ZIF-8 composite material, is transformed into ZnO and N doping for ZIF-8 finally by heat treatment process Carbon, to obtain Fe3O4@ZnO@N-C composite photocatalyst material.
Experimental test and analysis:
Fe is made to the present embodiment3O4@ZnO@N-C composite photocatalyst material carries out photocatalysis performance test: by answering for 25mg Condensation material is dispersed in the aqueous solution of methylene blue that 50mL concentration is 10mg/L and forms suspension, ultrasonic disperse 5min.In dark Under the conditions of, it is sufficiently mixed 60min, makes to reach between catalyst and dyestuff absorption-desorption balance, during this, every 10min is taken 2mL solution measures its absorbance.Methylene blue solution is placed under the xenon lamp of 300W and irradiates 90min, in entire During Illumination Air-blowing stirring is maintained, takes 2mL solution to measure its absorbance every 30min.Fe manufactured in the present embodiment3O4@ZnO@N-C composite wood Material can achieve 87% to methylene blue degradation rate in 90min, compared to simple Fe3O4@ZnO, degradation rate improve 20%.To Fe manufactured in the present embodiment3O4@ZnO N-C composite material carries out that performance test is recycled, and composite material passes through 6 times After circulation degradation test, the degradation rate to methylene blue is 80%, and photocatalysis performance is not decreased obviously, this shows Fe3O4Repeatability, the stability of@ZnO@N-C composite material photocatalytic degradation methylene blue are preferable.The present embodiment Fe3O4@ZnO@ The preparation method of N-C composite photocatalyst material, with the Fe of controllable sub-micron size3O4Magnetic nano-particle is carrier, passes through load ZnO prepares Fe3O4@ZnO composite catalyst;Utilize Zn2+Complexing between two-methylimidazoles is in Fe3O4@ZnO outer layer One layer of metal-organic framework material ZIF-8 is deposited, the Fe with multiple core-shell structure is prepared3O4@ZnO@ZIF-8 composite material; ZIF-8 is transformed into the carbon of ZnO and N doping using heat treatment process.Composite material made from the present embodiment method has good Photocatalytic Degradation Property and stable recycling performance, Fe3O4It is a kind of magnetic material, as in composite material The rate of recovery can be improved in core, to improve the recycling of material, the carbon material of N doping is a kind of porous material, has Biggish specific surface area, this porous material can effectively adsorb contaminant molecule, and can provide many electron traps, These electron traps can make the be excited light induced electron of generation of ZnO be easy to be transferred to porous carbon surface, reduce light induced electron- Compound, light induced electron and the O in hole pair2In conjunction with the O for forming high activity2 -Free radical improves Photocatalytic Degradation Property.This reality It applies example and the organic pollutant that composite material can be used for degrading in sewage is made, and photocatalytic degradation efficiency can be improved and be recycled Rate.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention, Without departing from Fe of the present invention3O4The technical principle and inventive concept of the preparation method of@ZnO@N-C composite photocatalyst material, all belong to In protection scope of the present invention.

Claims (9)

1. a kind of Fe3O4The preparation method of@ZnO@N-C composite photocatalyst material, it is characterised in that: with average grain diameter be 100~ The magnetic Fe of the submicron-scale of 150nm3O4Nanoparticle prepares Fe as carrier, by loading ZnO3O4@ZnO is compound to be urged Then agent utilizes Zn2+With the complexing between two-methylimidazoles, in Fe3O4@ZnO outer layer, which deposits one layer of metal, machine frame Frame material ZIF-8, prepares Fe3O4@ZnO@ZIF-8 composite material, finally by heat treatment process by ZIF-8 be transformed into ZnO and The carbon of N doping, to obtain Fe3O4@ZnO@N-C composite photocatalyst material.
2. Fe according to claim 13O4The preparation method of@ZnO@N-C composite photocatalyst material, which is characterized in that including such as Lower step:
A. Fe is synthesized3O4Magnetic nano-particle material:
Take the FeCl of 1.0~3.0g3·6H2O, the anhydrous sodium acetate of the sodium citrate of 0.5~1.0g and 3.0~5.0g are added In 100mL alcohols solvent, at least 30min is stirred, mixing is made it completely dissolved, obtained mixed solution is then transferred to reaction In kettle, hydro-thermal reaction is carried out in 150~200 DEG C of 5~10h of heating, hydrothermal product mixed liquor is obtained, then carries out Magnetic Isolation, Black product is obtained, then is respectively cleaned product at least three times with ethyl alcohol and distilled water, then does obtained solid progress vacuum It is dry to get Fe3O4Magnetic nano-particle material;
B. Fe is synthesized3O4@ZnO material:
Take the Zn (Ac) of 1.0~3.0g2·H2The NaOH of O and 0.5~1.0g is respectively dissolved in 40mL distilled water, respectively obtains Zn (Ac)2·H2O solution and NaOH solution;Then under constant stirring, NaOH solution is added to Zn (Ac)2·H2In O solution, After mixing evenly, raw material mixed liquor is obtained;Take 0.1~0.5g Fe made from the step a3O4Magnetic nano-particle material adds Enter into raw material mixed liquor, after ultrasound at least 10min, Fe will be added3O4Raw material mixed liquor be transferred in reaction kettle, 150 ~200 DEG C of 10~20h of heating, obtain hydrothermal product mixed liquor;Then Magnetic Isolation obtains product, will be produced with ethyl alcohol and distilled water Object respectively cleans at least three times, and then obtained solid is dried in vacuo to get Fe3O4@ZnO material;
c.Fe3O4The preparation of@ZnO@ZIF-8 intermediate product:
Take 0.1~0.5g Fe made from the step b3O4The 2-methylimidazole of@ZnO material and 0.1~0.5g are added to 32mL In the reaction kettle of mixed solvent containing DMF and water, after ultrasound at least 10min, reaction kettle is transferred in baking oven, 50~ 80 DEG C of 10~30h of heating, obtain hydrothermal product mixed liquor;Then Magnetic Isolation obtains product, product respectively cleaned with ethyl alcohol to Less three times, then obtained solid is dried in vacuo to get Fe3O4@ZnO@ZIF-8 intermediate product, by Fe3O4@ZnO packet It is overlying in the metal organic frame of ZIF-8, forms envelope structure;
D. Fe is synthesized3O4@ZnO@N-C composite photocatalyst material:
It, will the Fe made from the step c under nitrogen or atmosphere of inert gases3O4@ZnO@ZIF-8 intermediate product 500~ 900 DEG C carry out 1~4h of annealing, then to get arriving under air atmosphere and in 200~400 DEG C of progress 1~5h of calcination processing Fe3O4@ZnO@N-C composite photocatalyst material.
3. Fe according to claim 23O4The preparation method of@ZnO@N-C composite photocatalyst material, it is characterised in that: described In step a, synthesis Fe is carried out3O4When magnetic nano-particle material technology, the FeCl of 1.5~3.0g is taken3·6H20.6 O ,~ The sodium citrate of 0.85g and the anhydrous sodium acetate of 3.6~5.0g are added in 100mL alcohols solvent, stir at least 30min, make it It is completely dissolved mixing, then obtained mixed solution is transferred in reaction kettle, carries out water in 150~190 DEG C of 6~10h of heating Thermal response obtains hydrothermal product mixed liquor.
4. Fe according to claim 23O4The preparation method of@ZnO@N-C composite photocatalyst material, it is characterised in that: described In step b, synthesis Fe is carried out3O4When@ZnO material technique, the Zn (Ac) of 1.5~2.5g is taken2·H2The NaOH of O and 0.5~1.0g It is respectively dissolved in 40mL distilled water, respectively obtains Zn (Ac)2·H2O solution and NaOH solution;Then under constant stirring, will NaOH solution is added to Zn (Ac)2·H2In O solution, after mixing evenly, raw material mixed liquor is obtained;Take 0.2~0.5g in the step Fe made from rapid a3O4Magnetic nano-particle material is added into raw material mixed liquor, and after ultrasound at least 10min, Fe will be added3O4 Raw material mixed liquor be transferred in reaction kettle, carry out hydro-thermal reactions in 150~200 DEG C of 10~16h of heating, it is mixed to obtain hydrothermal product Close liquid.
5. Fe according to claim 23O4The preparation method of@ZnO@N-C composite photocatalyst material, it is characterised in that: described In step c, Fe is carried out3O4When the preparation process of@ZnO@ZIF-8 intermediate product, take 0.1~0.3g made from the step b Fe3O4The reaction kettle for the mixed solvent for containing DMF and water to 32mL is added in the 2-methylimidazole of@ZnO material and 0.25~0.4g In, after ultrasound at least 10min, reaction kettle is transferred in baking oven, carries out hydro-thermal reaction in 50~80 DEG C of 12~20h of heating, Obtain hydrothermal product mixed liquor.
6. Fe according to claim 23O4The preparation method of@ZnO@N-C composite photocatalyst material, it is characterised in that: described In step c, Fe is carried out3O4When the preparation process of@ZnO@ZIF-8 intermediate product, the dosage volume ratio of the DMF and water is (1 ~4): 1.
7. Fe according to claim 23O4The preparation method of@ZnO@N-C composite photocatalyst material, it is characterised in that: described In step a~c, obtained solid is dried in vacuo at least 8h, obtains dry hydrothermal product.
8. Fe according to claim 23O4The preparation method of@ZnO@N-C composite photocatalyst material, it is characterised in that: described It, will the Fe made from the step c in step d3O4@ZnO@ZIF-8 intermediate product carried out at 500~800 DEG C annealing 1~ 4h, then under air atmosphere and 200~400 DEG C of progress 2~4h of calcination processing to get arrive Fe3O4@ZnO@N-C complex light is urged Change material.
9. Fe according to claim 23O4The preparation method of@ZnO@N-C composite photocatalyst material, it is characterised in that: described In step d, the heating rate that the annealing is used with calcination processing technique is 1~4 DEG C/min.
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CN110479318A (en) * 2019-07-19 2019-11-22 深圳信息职业技术学院 Magnetic photocatalytic complexing agent and the preparation method and application thereof for water process
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CN114939404A (en) * 2022-07-01 2022-08-26 丽水市农林科学研究院 Be used for degrading aflatoxin B 1 And a method for preparing the same
CN114895536A (en) * 2022-07-14 2022-08-12 之江实验室 Preparation method of patterned Zn-MOF film based on laser direct writing
CN116408093A (en) * 2023-04-04 2023-07-11 上海市农业科学院 A nanocomposite material for degrading T-2 toxin and its preparation method

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Application publication date: 20190426