CN113171799B - AZA/TiO 2 Nanocomposite material, preparation method and application thereof - Google Patents

AZA/TiO 2 Nanocomposite material, preparation method and application thereof Download PDF

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CN113171799B
CN113171799B CN202110416646.8A CN202110416646A CN113171799B CN 113171799 B CN113171799 B CN 113171799B CN 202110416646 A CN202110416646 A CN 202110416646A CN 113171799 B CN113171799 B CN 113171799B
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tio
cof
composite material
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CN113171799A (en
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蔡一啸
葛世洁
高国洪
吉鹏
王华平
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Jiangsu Guowang High Technique Fiber Co ltd
Donghua University
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Jiangsu Guowang High Technique Fiber Co ltd
Donghua University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38Catalysts 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
    • 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
    • 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
    • B01J35/40Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • CCHEMISTRY; METALLURGY
    • 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
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    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30Nature of the water, waste water, sewage or sludge to be treated from the textile industry
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

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Abstract

The invention relates to an AZA/TiO 2 The preparation method and application of the nanocomposite are as follows: AZA-COF and nano titanium dioxide are mixed by a mechanical ball milling method to obtain AZA/TiO 2 A nanocomposite; finally prepared AZA/TiO 2 The nano composite material is granular, and the grain diameter is 10-30 nm; the application is as follows: AZA/TiO 2 The nanocomposite is added into a RhB solution with the concentration of 5-20 mg/L, and the degradation of RhB reaches 99.5% in 60 minutes. AZA/TiO of the invention 2 Compared with the traditional solvothermal method, the preparation method of the nanocomposite has the advantages of simple process, less required solvent, environmental protection, simple post-treatment method, high yield and easy large-scale industrial production; AZA/TiO of the invention 2 The nanocomposite has higher degradation efficiency on RhB and wide application prospect.

Description

AZA/TiO 2 Nanocomposite material, preparation method and application thereof
Technical Field
The invention belongs to the technical field of narrow-band photocatalytic materials, and relates to an AZA/TiO 2 Nanocomposite materials, methods of making and uses thereof.
Background
Printing and dyeing wastewater is one of a plurality of industrial wastewater which is difficult to treat, and accounts for 35% of the total discharge amount of the whole industrial wastewater. Many enterprises face the problem that the treatment of printing and dyeing wastewater does not reach the standard, and the problem of treatment of printing and dyeing wastewater becomes the key of sustainable development of printing and dyeing enterprises. Common methods for sewage treatment include adsorption, membrane separation, extraction, wet oxidation, electrochemical and microbial degradation, and various technologies have respective advantages and limitations. For dye wastewater difficult to degrade, a treatment method with strong universality and low cost and economy is urgently needed.
The photocatalysis technology has great application potential in solving the water pollution problem. TiO (titanium dioxide) 2 As a widely used semiconductor photocatalytic material, it is generally used for wastewater purification because of its stable chemical properties, non-toxicity and low cost. But TiO 2 The band gap of the catalyst is wider, and the catalyst can only be effectively absorbed and utilized in the ultraviolet region, and electron holes are easy to be combined, thereby severely limiting pure TiO 2 Is practical for photocatalysis. The Covalent Organic Framework (COF) becomes an excellent carrier of the traditional inorganic semiconductor due to the adjustable aperture, stable chemical property and adjustable structure, and can effectively improve TiO 2 As a defect of the photocatalytic semiconductor. For nano TiO 2 Modification of (C) can reduce TiO 2 The forbidden bandwidth of the catalyst increases the photocatalytic activity and widens the spectral response range. The conventional doping method mainly comprises a sol-gel method, a hydrothermal method, a high-temperature atomization method, a sputtering method, a coprecipitation method and the like. However, the existing preparation method has the problems of large solvent consumption, complex process, high energy consumption, long required time and the like, and is not beneficial to industrial production and utilization.
Although the mechanical ball milling method is a technology which has long history and mature development, the mechanical ball milling method has remarkable advantages in large-scale preparation of high-performance composite materials. The method is simple in operation and low in cost, and is widely applied to the preparation of advanced nanoparticle materials. Ball milling is generally carried out in pairs by known commercial materialsAnd mixing phases or phases, such as the patent CN 109524652A, compounding GO and COF by using a ball milling method, and generating the RGO/COF composite material in situ in one step for the lithium battery anode material. In the field of photocatalytic degradation, modified TiO 2 The preparation of the photocatalytic composite material generally adopts a hydrothermal method. Modification of TiO with GO has been reported in the literature 2 The composite material is prepared by a hydrothermal method, and the post-treatment requires high-temperature roasting, so that the preparation method has certain limit on large-scale preparation (Chemical Engineering Journal 350 (2018) 1043-1055). Meanwhile, the existing report (Journal of Hazardous Materials 369 (2019) 494-502) clearly suggests that in the process of preparing a COF material for degrading organic pollutants by using a ball milling method, a suitable solvent or a catalyst-assisted synthesis route needs to be selected, and the condition settings aim to obtain a COF photocatalyst with stable properties. The invention firstly proposes to mix nano TiO 2 Two effects on nanocomposite photocatalyst modulation: on the one hand, as the main catalytic unit in the traditional composite catalyst, and on the other hand, as a co-stabilizer (Stabilizing additive) of the COF material from the precursor to the final formation and exhibiting high performance.
Disclosure of Invention
The present invention has for its object to solve the above problems in the prior art and to provide an AZA/TiO 2 Nanocomposite materials, methods of making and uses thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
AZA/TiO 2 The preparation method of the nanocomposite comprises the steps of mixing AZA-COF and nano titanium dioxide by a ball milling method to obtain AZA/TiO 2 A nanocomposite.
The prior art generally uses GO and TiO 2 In-situ compounding, and after compounding and high-temperature roasting, bisphenol A (BPA) with the concentration of 2g/L and the concentration of 2.5mg/L is degraded by the catalyst concentration, and the optimal degradation rate constant is 0.049min -1 . Compared with GO, the layered two-dimensional nitrogen heteroatom in the AZA-COF adopted by the invention has a conjugated structure, and the high nitrogen concentration (the AZA-COF has high nitrogen concentration as seen from the chemical structure) can increase the delocalized electrons on Px and Py orbitals of the nitrogen atoms, thereby leading to energyShrinkage of the tape, helping to generate photogenerated carriers, improving TiO 2 Thereby enhancing the catalytic performance. AZA/TiO according to the invention 2 The optimal degradation rate constant of the composite material is 0.8984min when rhodamine B (RhB) with the concentration of 10mg/L is degraded by the catalyst concentration of 1g/L -1 Far superior to the prior art.
The prior art adopts a hydrothermal method, a solvothermal method and the like to combine covalent organic frameworks with TiO 2 Compounding, the methods have the problems of large solvent consumption, complex process, high energy consumption, long required time and the like, are not beneficial to industrial production and utilization, and the photocatalytic degradation rate constant of the catalyst obtained by the methods is mostly 10 -2 The invention adopts ball milling method to mix AZA-COF and TiO 2 Compounding, no heating, solvent saving, simple post-treatment method, high yield, and suitability for large-scale industrial production, and the prepared AZA/TiO 2 The nanocomposite has excellent photocatalytic performance and a degradation rate constant of 10 -1 On the order of magnitude.
As a preferable technical scheme:
AZA/TiO as described above 2 The preparation method of the nanocomposite material specifically comprises the following steps:
(1) Dissolving cyclohexane octahydrate and tetra-aniline hydrochloride (TAB & HCl) in a solvent I, heating to reflux, reacting for 2-5 days, performing vacuum filtration and washing to obtain black solid, performing thermal extraction on the black solid by using methanol at a temperature of 80-110 ℃ for ensuring that the methanol is in a reflux state, and then placing the black solid into a vacuum oven for drying at 60 ℃ for overnight to obtain black powder AZA-COF;
(2) Loading the mixture of AZA-COF and nano titanium dioxide into a ball milling tank, adding a solvent II for ball milling, drying by a rotary evaporator after ball milling is finished, and then placing the mixture into a vacuum oven for drying overnight to obtain grey AZA/TiO 2 A nano titanium dioxide composite material.
According to the preparation method of the AZA/TiO2 nanocomposite, in the step (1), the solvent I is N-methylpyrrolidone (NMP) or N, N-Dimethylformamide (DMF), when the N-methylpyrrolidone is used as the solvent, sulfuric acid is required to catalyze the reaction, the molar ratio of the octahydrated cyclohexanedione to the tetra-hydrotic acid is 3:2, and the total mass concentration of the octahydrated cyclohexanedione and the tetra-hydrotic acid in the solution is 0.05-0.075 g/mL.
The preparation method of the AZA/TiO2 nanocomposite comprises the steps that (1) heating is carried out until the temperature required by reflux is 120 ℃;
the washing is carried out by water and acetone, and the washing times are 3-5 times.
According to the preparation method of the AZA/TiO2 nanocomposite, in the step (2), the solvent II is methanol, isopropanol or ethanol, the total mass concentration of the AZA-COF and the nano titanium dioxide is 0.05-0.075 g/mL, and the mass ratio of the AZA-COF to the nano titanium dioxide is 3-10:90-97.
The preparation method of the AZA/TiO2 nanocomposite comprises the following steps that ball milling is carried out in a planetary ball mill in the step (2), the temperature is room temperature, the rotating speed is 500-800 rpm, and the ball milling time is 2-10 h.
According to the preparation method of the AZA/TiO2 nanocomposite, the drying temperature of the rotary evaporator in the step (2) is 40 ℃.
The preparation method of the AZA/TiO2 nanocomposite comprises the step (2), wherein the particle size of the nano titanium dioxide is 5-25 nm.
The invention also provides AZA/TiO prepared by the method as described in any one of the above 2 The nano composite material is gray granular, and the grain diameter is 10-30 nm.
The invention also provides AZA/TiO as described above 2 Application of nanocomposite material, AZA/TiO 2 The nanocomposite is added into a RhB (rhodamine B) solution with the concentration of 5-20 mg/L, and the degradation of the RhB reaches 99.5% in 60 minutes; test results show that the AZA/TiO prepared by the invention 2 In the degradation of 10mg/L RhB, the degradation rate constant of the nanocomposite photocatalyst is pure TiO 2 Is 18.7 times as large as the above.
The principle of the invention is as follows:
the layered two-dimensional nitrogen heteroatom in AZA-COF has conjugationThe structure, high nitrogen concentration (as can be seen from chemical structure, AZA-COF has high concentration of nitrogen) can increase the delocalized electrons on Px and Py orbitals of nitrogen atoms, thereby leading to the contraction of energy bands, facilitating the generation of photo-generated carriers and improving TiO 2 Thereby enhancing the catalytic performance.
The invention uses AZA-COF and TiO 2 Ball milling method for preparing photocatalysis nano composite material, ball milling for TiO 2 The composite material has smaller particle size, is more beneficial to carrier transmission, improves photocatalytic degradation performance, and compared with the common hydrothermal method and solvothermal method for preparing the nano composite photocatalyst, the invention provides the effective utilization of nano TiO for the first time 2 As a main catalyst and an important auxiliary stabilizer (Stabilizing additive) from a precursor to final formation and actual photocatalytic performance of the COF material, the COF material can maintain the crystalline ordered structure, the internal aperture and the thermal stability of the COF material in the process of efficient adsorption-oxidation desorption of organic pollutants in photocatalysis, and the stability of the whole photocatalytic composite material system is realized, compared with TiO in the prior art 2 The scheme as catalyst only has a large difference. The whole preparation method does not need heating, saves the solvent, has simple post-treatment method and high yield, is beneficial to large-scale industrial production and is beneficial to promoting the industrialization process of the photocatalysis nano catalyst.
AZA/TiO prepared by the invention 2 The nanocomposite has good stability and repeated utilization rate, and can realize continuous photocatalytic degradation of RhB in the actual water treatment process.
The beneficial effects are that:
(1) AZA/TiO of the invention 2 Compared with the traditional solvothermal method, the preparation method of the nanocomposite has the advantages of simple process, less required solvent, environmental protection, simple post-treatment method and high yield, and is beneficial to large-scale industrial production;
(2) AZA/TiO of the invention 2 The nanocomposite has higher degradation efficiency on RhB and wide application prospect.
Drawings
FIG. 1 is AZA/TiO 2 Schematic process diagram of the preparation of nanocomposite;
FIG. 2 shows AZA-COF and AZA/TiO prepared in example 1 2 XRD diffractogram of (2);
FIG. 3 shows AZA-COF and AZA/TiO prepared in example 1 2 Is a piece of infrared spectrogram data;
FIG. 4 shows AZA-COF and AZA/TiO prepared in example 1 2 An ultraviolet-visible light absorption range curve of (2);
FIG. 5 shows AZA-COF and AZA/TiO prepared in example 1 2 Is a degradation curve for RhB;
FIG. 6 shows degradation curves of AZA-COF prepared in example 1 and comparative examples 1 and 2;
in FIGS. 5 and 6, C t /C 0 Representing the experimental/initial concentration, can be used to characterize degradation efficiency.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The method for measuring the concentration change of the RhB by using an ultraviolet spectrophotometer comprises the following steps: 100mg of the sample is weighed and placed in a 250mL double-layer beaker filled with 100mL of 10mg/L RhB solution, and a 300W xenon lamp with a 420nm optical filter is used as a light source to carry out photocatalytic degradation reaction. The dark reaction time was 1h, samples were taken every 10 minutes after illumination, and filtered with a 0.45 μm filter head and filled into a centrifuge tube, and the concentration change of RhB was measured with an ultraviolet spectrophotometer.
FIG. 1 is AZA/TiO 2 Schematic process diagram of the preparation of nanocomposite; specifically, heating and refluxing cyclohexane hexaketone octahydrate and tetra-aniline hydrochloride in DMF for 2-5 days to obtain AZA-COF, and then AZA-COF and TiO 2 Compounding in proper proportion to obtain AZA/TiO 2 A composite material.
Example 1
AZA/TiO 2 The preparation method of the nanocomposite comprises the following specific steps:
(1) Dissolving octa-hydrated cyclohexenone and tetra-hydrotetronic acid in a molar ratio of 3:2 into N-methyl pyrrolidone to obtain a mixed solution, wherein the total mass concentration of the octa-hydrated cyclohexenone and the tetra-hydrotetronic acid in the mixed solution is 0.075g/mL; heating to 120 ℃, refluxing, reacting for 5 days, performing vacuum filtration, alternately washing with water and acetone for 3 times, performing thermal extraction with methanol at 80 ℃, and finally drying in a vacuum oven at 60 ℃ to obtain AZA-COF;
(2) Loading a mixture of AZA-COF with the mass ratio of 5:95 and nano titanium dioxide with the particle size of 10nm into a ball milling tank, adding ethanol, performing ball milling in a planetary ball mill at the rotating speed of 800rpm for 10 hours, drying at 40 ℃ by a rotary evaporator after ball milling is completed to remove the solvent, and then putting into a vacuum oven for drying to obtain AZA/TiO 2 A nano titanium dioxide composite material; wherein the total mass concentration of AZA-COF and nano titanium dioxide in ethanol is 0.06g/mL.
The prepared AZA/TiO 2 The nano composite material is granular, and the grain diameter is 10-19 nm; AZA/TiO 2 The nanocomposite was added to a 10mg/L RhB solution to achieve 99.5% RhB degradation in 60 minutes, as shown in FIG. 5, AZA/TiO 2 In the degradation process of the nanocomposite material on RhB, the degradation rate is TiO 2 Can realize the photocatalysis complete degradation of the RhB by 18.7 times.
As shown in fig. 2, tiO 2 AZA-COF prepared in example 1, AZA/TiO prepared in example 1 2 In the XRD pattern of AZA/TiO 2 Diffraction characteristic peaks of the composite material at 25.3 °, 37.8 °, 48.0 °, 53.9 °, 55.1 ° and 62.8 ° are TiO 2 Due to the characteristic diffraction peak with TiO 2 Compared with the AZA-COF material, the content of the AZA-COF material is relatively small, and the AZA/TiO material is used for preparing the AZA-COF material 2 No characteristic peaks of the corresponding azo-COF materials were observed in the composites. It can thus be demonstrated that TiO 2 Compounding with AZA-COF does not alter TiO 2 A crystalline form of itself;
as shown in FIG. 3, an example1 AZA-COF prepared, AZA/TiO prepared in example 1 2 Is a spectrum of infrared light of (a) is obtained. As can be seen from the figure, AZA/TiO 2 The infrared spectrum of the composite material fuses AZA-COF and TiO 2 Characteristic peak of AZA-COF at 1724cm -1 And 1484cm -1 The peak at this point became very weak in the composite, indicating AZA-COF and TiO 2 The composition is full and uniform;
as shown in FIG. 4, AZA-COF absorbs in the full band of the ultraviolet-visible-near infrared region, AZA/TiO 2 The composite material has strong absorption peak in ultraviolet light region (320-400 nm), absorption in visible light region (400-760 nm), AZA/TiO 2 The light absorption performance of the composite material is better than that of TiO 2
Comparative example 1
GO/TiO 2 The preparation method of the nanocomposite photocatalyst is basically the same as that of example 1, except that step (1) is omitted and the AZA-COF in step (2) is replaced with GO.
The prepared GO/TiO 2 The nanocomposite was added to a 10mg/L RhB solution, as shown in FIG. 6, with only 20.4% degradation of RhB in 60 minutes.
Compared with example 1, the composite photocatalyst prepared in comparative example 1 has lower degradation to RhB in 60 minutes than that in example 1, because high nitrogen concentration (AZA-COF has high nitrogen concentration as seen from chemical structure) can increase delocalized electrons on Px and Py orbitals of nitrogen atoms, thereby causing shrinkage of energy bands, helping to generate photo-generated carriers and improving TiO 2 Thereby enhancing the catalytic performance.
Comparative example 2
AZA/TiO 2 The preparation method of the nanocomposite is basically the same as in example 1, except that the method for realizing the compounding of the azo-COF and the titanium dioxide in the step (2) is not a ball milling method, but a solvothermal method, specifically: the mass ratio is 5:95 AZA-COF with TiO having a particle size of 10nm 2 Adding into 100mL reactor, adding 20mL ethanol as solvent, stirring and mixing for 1 hr, placing into 200 deg.C oven for 10 hr, vacuum filtering and drying to obtain composite material, and placing into 60 deg.C oven for dryingDrying overnight.
The prepared AZA/TiO 2 The nanocomposite was added to a 10mg/L RhB solution, as shown in FIG. 6, with only 31.1% degradation of RhB in 60 minutes.
Compared with example 1, the nanocomposite prepared in comparative example 2 has lower degradation to RhB in 60 minutes than that of example 1 because of the strong mechanical force of ball milling method, and can promote AZA-COF and TiO 2 To more uniformly mix the materials and thereby inhibit TiO 2 Promotes the transport of photogenerated carriers, thereby enhancing photocatalytic performance.
Example 2
AZA/TiO 2 The preparation method of the nanocomposite comprises the following specific steps:
(1) Dissolving octa-hydrated cyclohexenone and tetra-hydrotetronic acid in a molar ratio of 3:2 into N-methyl pyrrolidone to obtain a mixed solution, wherein the total mass concentration of octa-hydrated cyclohexenone and tetra-hydrotetronic acid in the mixed solution is 0.05g/mL; heating to 120 ℃, refluxing, reacting for 2 days, performing vacuum filtration, alternately washing with water and acetone for 3 times, performing thermal extraction with methanol at 80 ℃, and finally drying in a vacuum oven at 60 ℃ to obtain AZA-COF;
(2) Loading a mixture of AZA-COF with the mass ratio of 5:95 and nano titanium dioxide with the particle size of 10nm into a ball milling tank, adding ethanol, performing ball milling in a planetary ball mill at the rotating speed of 800rpm for 10 hours, drying at 40 ℃ by a rotary evaporator after ball milling is completed to remove the solvent, and then putting into a vacuum oven for drying to obtain AZA/TiO 2 A nano titanium dioxide composite material; wherein the total mass concentration of AZA-COF and nano titanium dioxide in ethanol is 0.06g/mL.
The prepared AZA/TiO 2 The nano composite material is granular, and the grain diameter is 10-19 nm; AZA/TiO 2 The nanocomposite was added to a 10mg/L RhB solution, reaching 99.5% for RhB degradation in 60 minutes.
Example 3
AZA/TiO 2 Preparation of nanocomposite materialsThe preparation method comprises the following specific steps:
(1) Dissolving octa-hydrated cyclohexenone and tetra-hydrotetronic acid in a molar ratio of 3:2 into N-methyl pyrrolidone to obtain a mixed solution, wherein the total mass concentration of octa-hydrated cyclohexenone and tetra-hydrotetronic acid in the mixed solution is 0.05g/mL; heating to 120 ℃, refluxing, reacting for 2 days, performing vacuum filtration, alternately washing with water and acetone for 3 times, performing thermal extraction with methanol at 80 ℃, and finally drying in a vacuum oven at 60 ℃ to obtain AZA-COF;
(2) Loading a mixture of AZA-COF with the mass ratio of 3:97 and nano titanium dioxide with the particle size of 10nm into a ball milling tank, adding ethanol, performing ball milling in a planetary ball mill at the rotating speed of 800rpm for 10 hours, drying at 40 ℃ by a rotary evaporator after ball milling is completed to remove the solvent, and then putting into a vacuum oven for drying to obtain AZA/TiO 2 A nano titanium dioxide composite material; wherein the total mass concentration of AZA-COF and nano titanium dioxide in ethanol is 0.06g/mL.
The prepared AZA/TiO 2 The nano composite material is granular, and the grain diameter is 10-30 nm; AZA/TiO 2 The nanocomposite was added to a 10mg/L RhB solution, reaching 99.5% for RhB degradation in 60 minutes.
Example 4
AZA/TiO 2 The preparation method of the nanocomposite comprises the following specific steps:
(1) Dissolving octa-hydrated cyclohexenone and tetra-hydrotetronic acid in a molar ratio of 3:2 into N-methyl pyrrolidone to obtain a mixed solution, wherein the total mass concentration of octa-hydrated cyclohexenone and tetra-hydrotetronic acid in the mixed solution is 0.05g/mL; heating to 120 ℃, refluxing, reacting for 2 days, performing vacuum filtration, alternately washing with water and acetone for 3 times, performing thermal extraction with methanol at 90 ℃, and finally drying in a vacuum oven at 60 ℃ to obtain AZA-COF;
(2) The mixture of AZA-COF with the mass ratio of 7:93 and nano titanium dioxide with the particle size of 10nm is put into a ball milling tank, ethanol is added into the ball milling tank to carry out ball milling in a planetary ball mill with the rotating speed of 800rpm,ball milling for 10h, drying at 40deg.C by rotary evaporator to remove solvent, and drying in vacuum oven to obtain AZA/TiO 2 A nano titanium dioxide composite material; wherein the total mass concentration of AZA-COF and nano titanium dioxide in ethanol is 0.06g/mL.
The prepared AZA/TiO 2 The nano composite material is granular, and the grain diameter is 10-15 nm; AZA/TiO 2 The nanocomposite was added to a 10mg/L RhB solution, reaching 99.5% for RhB degradation in 60 minutes.
Example 5
AZA/TiO 2 The preparation method of the nanocomposite comprises the following specific steps:
(1) Dissolving octa-hydrated cyclohexenone and tetra-hydrotetronic acid in a molar ratio of 3:2 into N-methyl pyrrolidone to obtain a mixed solution, wherein the total mass concentration of octa-hydrated cyclohexenone and tetra-hydrotetronic acid in the mixed solution is 0.05g/mL; heating to 120 ℃, refluxing, reacting for 2 days, performing vacuum filtration, alternately washing with water and acetone for 3 times, performing thermal extraction with methanol at 80 ℃, and finally drying in a vacuum oven at 60 ℃ to obtain AZA-COF;
(2) Loading a mixture of AZA-COF with the mass ratio of 10:90 and nano titanium dioxide with the particle size of 10nm into a ball milling tank, adding ethanol, performing ball milling in a planetary ball mill at the rotating speed of 800rpm for 10 hours, drying at 40 ℃ by a rotary evaporator after ball milling is completed to remove the solvent, and then placing into a vacuum oven for drying to obtain AZA/TiO 2 A nano titanium dioxide composite material; wherein the total mass concentration of AZA-COF and nano titanium dioxide in ethanol is 0.06g/mL.
The prepared AZA/TiO 2 The nano composite material is granular, and the grain diameter is 10-13 nm; AZA/TiO 2 The nanocomposite was added to a 10mg/L RhB solution, reaching 99.5% for RhB degradation in 60 minutes.
Example 6
AZA/TiO 2 The preparation method of the nanocomposite comprises the following specific steps:
(1) Dissolving octa-hydrated cyclohexenone and tetra-hydrotetronic acid in a molar ratio of 3:2 in N, N-dimethylformamide to obtain a mixed solution, wherein the total mass concentration of octa-hydrated cyclohexenone and tetra-hydrotetronic acid in the mixed solution is 0.05g/mL; heating to 120 ℃, refluxing, reacting for 2 days, performing vacuum filtration, alternately washing with water and acetone for 4 times, performing thermal extraction with methanol at 100 ℃, and finally drying in a vacuum oven at 60 ℃ to obtain AZA-COF;
(2) Loading a mixture of AZA-COF with the mass ratio of 5:95 and nano titanium dioxide with the particle size of 5nm into a ball milling tank, adding isopropanol, performing ball milling in a planetary ball mill at the rotating speed of 500rpm for 2 hours, drying at 40 ℃ by a rotary evaporator after ball milling is completed to remove the solvent, and then putting into a vacuum oven for drying to obtain AZA/TiO 2 A nano titanium dioxide composite material; wherein the total mass concentration of AZA-COF and nano titanium dioxide in isopropanol is 0.1g/mL.
The prepared AZA/TiO 2 The nano composite material is granular, and the grain diameter is 10-19 nm; AZA/TiO 2 The nanocomposite was added to a RhB solution at a concentration of 5mg/L, reaching 99.5% for RhB degradation in 60 minutes.
Example 7
AZA/TiO 2 The preparation method of the nanocomposite comprises the following specific steps:
(1) Dissolving octa-hydrated cyclohexenone and tetra-hydrotetronic acid in a molar ratio of 3:2 in N, N-dimethylformamide to obtain a mixed solution, wherein the total mass concentration of octa-hydrated cyclohexenone and tetra-hydrotetronic acid in the mixed solution is 0.05g/mL; heating to 120 ℃, refluxing, reacting for 2 days, performing vacuum filtration, alternately washing with water and acetone for 5 times, performing thermal extraction with methanol at 110 ℃, and finally drying in a vacuum oven at 60 ℃ to obtain AZA-COF;
(2) Filling a mixture of AZA-COF with the mass ratio of 5:95 and nano titanium dioxide with the particle size of 25nm into a ball milling tank, adding methanol into the ball milling tank, performing ball milling in a planetary ball mill at the rotating speed of 650rpm for 7h, and passing through a rotary evaporator after the ball milling is completedDrying at 40deg.C to remove solvent, and vacuum oven drying to obtain AZA/TiO 2 A nano titanium dioxide composite material; wherein the total mass concentration of AZA-COF and nano titanium dioxide in methanol is 0.06g/mL.
The prepared AZA/TiO 2 The nano composite material is granular, and the grain diameter is 10-19 nm; AZA/TiO 2 The nanocomposite was added to a 20mg/L RhB solution, reaching 99.5% for RhB degradation in 60 minutes.
Example 8
AZA/TiO 2 The preparation method of the nanocomposite comprises the following specific steps:
(1) Dissolving octa-hydrated cyclohexenone and tetra-hydrotetronic acid in a molar ratio of 3:2 in N, N-dimethylformamide to obtain a mixed solution, wherein the total mass concentration of the octa-hydrated cyclohexenone and the tetra-hydrotetronic acid in the mixed solution is 0.075g/mL; heating to 120 ℃, refluxing, reacting for 2 days, performing vacuum filtration, alternately washing with water and acetone for 3 times, performing thermal extraction with methanol at 110 ℃, and finally drying in a vacuum oven at 60 ℃ to obtain AZA-COF;
(2) Loading a mixture of AZA-COF with the mass ratio of 5:95 and nano titanium dioxide with the particle size of 10nm into a ball milling tank, adding methanol into the ball milling tank, performing ball milling in a planetary ball mill at the rotating speed of 500rpm for 3 hours, drying at 40 ℃ by a rotary evaporator after ball milling is completed to remove the solvent, and then placing the mixture into a vacuum oven for drying to obtain AZA/TiO 2 A nano titanium dioxide composite material; wherein the total mass concentration of AZA-COF and nano titanium dioxide in methanol is 0.05g/mL.
The prepared AZA/TiO 2 The nano composite material is granular, and the grain diameter is 10-19 nm; AZA/TiO 2 The nanocomposite was added to a 25mg/L RhB solution, reaching 99.5% for RhB degradation in 60 minutes.

Claims (7)

1. AZA/TiO 2 The preparation method of the photocatalysis nano composite material is characterized by comprising the following steps: AZA-COF and nano titanium dioxide are mixed by a ball milling method to obtain AZA/TiO 2 A photocatalytic nanocomposite;
the preparation method comprises the following specific steps:
(1) Dissolving octahydrated cyclohexanedione and 1,2,4, 5-tetraaminobenzene hydrochloride in a solvent I, heating to reflux, reacting for 2-5 days, decompressing, filtering, washing, thermally extracting with methanol at 80-110 ℃, and then drying in a vacuum oven at 60 ℃ to obtain AZA-COF;
(2) Loading the mixture of AZA-COF and nano titanium dioxide into a ball milling tank, adding a solvent II for ball milling, drying by a rotary evaporator after ball milling is finished, and then drying in a vacuum oven to obtain AZA/TiO 2 Photocatalytic nano titanium dioxide composite material;
in the step (1), the solvent I is N-methylpyrrolidone or N, N-dimethylformamide, the molar ratio of the octahydrated cyclohexanedione to the 1,2,4, 5-tetraaminobenzene hydrochloride is 3:2, and the total mass concentration of the octahydrated cyclohexanedione and the 1,2,4, 5-tetraaminobenzene hydrochloride in the solution is 0.05-0.075 g/mL;
in the step (2), the solvent II is methanol, isopropanol or ethanol, the total mass concentration of the AZA-COF and the nano titanium dioxide is 0.05-0.075 g/mL, and the mass ratio of the AZA-COF to the nano titanium dioxide is 3-10:90-97.
2. An AZA/TiO according to claim 1 2 The preparation method of the photocatalysis nano composite material is characterized in that the temperature required by heating to reflux in the step (1) is 120 ℃;
the washing is carried out by using water and acetone, and the washing times are 3-5 times.
3. An AZA/TiO according to claim 1 2 The preparation method of the photocatalysis nano composite material is characterized in that ball milling in the step (2) is carried out in a planetary ball mill, the rotating speed is 500-800 rpm, and the ball milling time is 2-10 h.
4. An AZA/TiO according to claim 1 2 A preparation method of a photocatalysis nano composite material is characterized in that,the drying temperature of the rotary evaporator in the step (2) is 40 ℃.
5. An AZA/TiO according to claim 1 2 The preparation method of the photocatalysis nano composite material is characterized in that the particle size of the nano titanium dioxide in the step (2) is 5-25 nm.
6. AZA/TiO as claimed in any one of claims 1 to 5 2 The photocatalysis nanometer composite material is characterized in that: the AZA/TiO 2 The photocatalysis nano composite material is granular, and the grain diameter is 10-30 nm.
7. AZA/TiO as claimed in claim 6 2 The application of the photocatalysis nano composite material is characterized in that: AZA/TiO 2 The photocatalytic nanocomposite is added into a RhB solution with the concentration of 5-20 mg/L, and the degradation rate of the RhB reaches 99.5% within 60 minutes.
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