CN115090326A - High-activity cubic Ti-MOF photocatalyst, preparation method and application - Google Patents
High-activity cubic Ti-MOF photocatalyst, preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000000694 effects Effects 0.000 title claims abstract description 12
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- 230000000593 degrading effect Effects 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 8
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- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- B01J31/2208—Oxygen, e.g. acetylacetonates
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- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a high-activity cubic Ti-MOF photocatalyst, a preparation method and application thereof, wherein the method comprises the following steps: mixing titanium salt, an organic ligand, an organic solvent and anhydrous methanol to obtain a mixed solution, wherein the molar ratio of the titanium salt to the organic ligand and the volume ratio of the organic solvent to the anhydrous methanol are respectively 1:1-6 and 10-1: 1; the organic machine is matchedThe body is terephthalic acid or 2-amino terephthalic acid; carrying out ultrasonic dispersion on the mixed solution to obtain a reaction solution; carrying out hydro-thermal synthesis reaction on the reaction liquid to obtain a Ti-MOF precursor; and drying the Ti-MOF precursor to obtain the cubic Ti-MOF photocatalyst. The invention obtains the cubic Ti-MOF catalyst with high specific surface area by a hydrothermal synthesis method, the cubic Ti-MOF catalyst has better tetracycline hydrochloride degradation performance, and the obtained higher reaction rate constant k is 0.00106-0.00660min ‑1 And has better stability.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to a high-activity cubic Ti-MOF photocatalyst, and a preparation method and application thereof.
Background
Tetracycline (TC) is an organic compound with broad-spectrum antibacterial action, which belongs to the most basic compound among the antibiotics of the tetracycline family, and is currently classified as an emerging pollutant of interest (CECs) by the United States Environmental Protection Agency (USEPA) and the European Union (EU). Tetracycline and its derivatives are generally resistant to biodegradation processes, and studies have reported concentrations of tetracycline in untreated wastewater in the nanogram/liter to microgram/liter range.
At present, the treatment of the residual wastewater containing tetracycline mainly comprises the following methods: physical treatment, biological treatment, chemical treatment, and the like. The physical treatment method mainly comprises methods such as adsorption, air flotation, coagulation-precipitation, reverse osmosis and the like, and the physical treatment method (such as activated carbon adsorption and the like) generally transfers organic matters from a liquid phase to a solid phase and does not completely eliminate the organic matters; the biological treatment method, namely the traditional activated sludge method, is a common method for treating sewage at present, and because the single aerobic biological treatment technology or anaerobic treatment technology has limitations, the method is used at the present place with high-concentration wastewaterIn the middle of treatment, researchers generally adopt an anaerobic treatment process as a pretreatment process of aerobic biological treatment, so that the chemical oxygen demand concentration of the wastewater is reduced, and the biodegradability of the wastewater is improved; chemical treatment is a technique for stabilizing and detoxifying pollutants in wastewater by adding certain chemicals or using certain techniques. The chemical treatment method includes a general chemical method and an advanced oxidation method. The common chemical treatment method is mainly a coagulation method, and the coagulation method is to add a coagulant into wastewater to enable micro suspended solids and colloidal impurities in the wastewater to form flocculent precipitates, so that the purpose of removing pollutants is achieved. The advanced oxidation method is a method of degrading contaminants by using hydroxyl radicals (. OH) having strong oxidizing properties generated during the reaction. Currently, the commonly used advanced oxidation methods are: fenton method, O 3 Oxidation method, photocatalytic oxidation method. Fenton oxidation process and O 3 The oxidation method generates hydroxyl free radicals under the catalytic condition, and removes tetracycline by utilizing the strong oxidizing property of the hydroxyl free radicals, wherein the former has the problem of sludge generation, and the latter has the problem of utilization rate reduction. The photocatalytic oxidation technology is a novel advanced oxidation technology, which attracts people's attention to advanced treatment of wastewater, and the photocatalytic oxidation technology has the greatest advantage of being capable of utilizing solar energy to thoroughly mineralize pollutants without generating secondary pollution, so that the purposes of saving and environmental protection are achieved, and the photocatalytic oxidation technology is a wastewater treatment method with great potential.
The MOFs are porous materials with periodic structures formed by linking central metal ions or central metal clusters and organic ligands with each other through self-assembly. Besides high specific surface area and high porosity, MOFs can also obtain structurally and functionally diverse metal-organic framework compounds by changing the species of central ions or clusters. When the size is reduced to a nanometer level, the nanoscale metal organic framework compounds (Nano-MOFs) show a series of special properties such as different shapes, sizes, high drug loading rates, excellent biocompatibility and degradability in the field of nanobiology. The titanium-based metal-organic frameworks (Ti-MOFs) are formed by Ti-oxo clusters, have good visible light response and catalytic activity, and MIL-125(Ti) takes metal Ti as a core and is connected with benzeneThe stable frame structure formed by the dicarboxylic acid is Ti-MOF [ Y.Z.He, S.Luo, X.L.Hu, Y.L.Cheng, Y.M.Huang, S.M.Chen, M.Fu, Y.M.Jia, X.Y.Liu, NH-containing metal ions which are most widely applied at present 2 -MIL-125(Ti)encapsulated with in situ-formed carbon nanodots with up-conversion effect for improving photocatalytic NO removal and H 2 evolution.Chem.Eng.J.,2021,420,127643.]. Because the titanium element is low in toxicity, has redox activity and photosensitivity, and can be used for synthesizing MOF with photocatalytic performance.
Meanwhile, Ti-MOF has rich pore structure, larger porosity and higher specific surface area as other MOFs materials, and the Ti-MOF nano material can obtain TiO with high specific surface area with maintained shape and size through different post-treatments 2 The Ti-MOF has wide application prospect in the fields of photocatalysis, pollutant degradation, biological medicine carrying, photodynamic therapy and the like. At present, Ti-MOF catalysts are mostly prepared by a solvothermal method, but decahedron, flat decahedron, cuboid and other morphologies are mostly obtained by the preparation methods, and research documents show that the catalysts with the above mentioned morphologies have low catalytic efficiency, so that the catalysts with the cubic morphologies are synthesized by a hydrothermal method.
Disclosure of Invention
In view of the above problems, the present invention aims to improve the synthesis method to prepare a cubic catalyst, thereby further improving the photocatalytic degradation activity. The invention changes the solvent proportion and the precursor feed ratio in the synthesis process, and prepares the cubic Ti-MOF catalyst for efficiently removing tetracycline hydrochloride by a hydrothermal synthesis method.
The technical scheme adopted by the invention is as follows:
a method for preparing a high activity cubic Ti-MOF photocatalyst, comprising the steps of:
(1) mixing titanium salt, an organic ligand, an organic solvent and anhydrous methanol to obtain a mixed solution, wherein the molar ratio of the titanium salt to the organic ligand and the volume ratio of the organic solvent to the anhydrous methanol are respectively 1:1-6 and 10-1: 1; the organic ligand is terephthalic acid or 2-amino terephthalic acid;
carrying out ultrasonic dispersion on the mixed solution in the step (1) to obtain a reaction solution;
(3) carrying out hydro-thermal synthesis reaction on the reaction liquid in the step (2) to obtain a Ti-MOF precursor;
(4) and (4) drying the Ti-MOF precursor in the step (3) to obtain the cubic Ti-MOF photocatalyst.
Further, the titanium salt includes n-tetrabutyl titanate, titanium tetrachloride, or isopropyl titanate.
Further, the temperature of the hydrothermal synthesis reaction in the step (3) is 140-160 ℃, and the time of the hydrothermal synthesis reaction is 12-72 h.
Further, the drying temperature in the step (4) is 50-100 ℃, and the drying time is 8-24 h.
Further, before drying the Ti-MOF precursor in the step (4), cleaning the Ti-MOF precursor with an organic solvent and anhydrous methanol for multiple times.
Further, the organic solvent is N, N-dimethylformamide.
The invention also provides the Ti-MOF photocatalyst prepared by the preparation method, and the Ti-MOF photocatalyst is of a cubic structure.
Further, the specific surface area of the Ti-MOF photocatalyst is 1000-1400m 2 /g。
Further, the efficiency of the Ti-MOF photocatalyst in degrading tetracycline hydrochloride is 20% -75%.
The invention also provides application of the Ti-MOF photocatalyst in photocatalytic degradation of tetracycline hydrochloride.
Compared with the prior art, the Ti-MOF catalyst with cubic morphology, high activity and high stability is prepared by controlling the volume ratio of an organic solvent DMF (N, N-2-methylformamide) to absolute methanol, the molar ratio of an organic ligand to a titanium source and the temperature and time of hydrothermal reaction. The invention has the following beneficial effects:
1. a preparation method of the Ti-MOF catalyst with the cubic morphology is developed;
2. obtaining the cubic Ti-MOF catalyst with high specific surface area by a hydrothermal synthesis method, wherein the cubic Ti-MOF catalyst has better tetracycline hydrochloride degradation performance, and obtaining the productThe higher reaction rate constant k is 0.00106-0.00660min -1 And has better stability;
3. the catalyst has the advantages of simple preparation process, simple and convenient operation, common reagents used in synthesis, low price and good application prospect.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an XRD pattern of a Ti-MOF photocatalyst prepared in example 1;
FIG. 2 is an SEM image of the Ti-MOF photocatalyst prepared in example 1;
FIG. 3 is an SEM image of the Ti-MOF photocatalyst prepared in example 1 after the tetracycline is degraded by photocatalysis;
FIG. 4 is an SEM image of the Ti-MOF photocatalyst prepared in example 1 after being subjected to high temperature treatment of Ar gas at 400 ℃;
FIG. 5 is a graph of Ti-MOF photocatalyst prepared in example 1 over O 2 SEM atlas after 400 ℃ high temperature treatment of Ar gas;
FIG. 6 is an SEM image of a Ti-MOF photocatalyst prepared in comparative example 1;
FIG. 7 is an SEM image of a Ti-MOF photocatalyst prepared according to comparative example 2;
FIG. 8a, FIG. 8b and FIG. 8c are the reaction curves of the Ti-MOF photocatalysts prepared in example 1, comparative example 1 and comparative example 2 for the catalytic degradation of tetracycline hydrochloride.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Terephthalic acid, 2-aminoterephthalic acid, tetrabutyl titanate, N-dimethylformamide and anhydrous methanol reagents used in the examples of the present invention were all commercially available.
The invention provides a preparation method of a high-activity cubic Ti-MOF photocatalyst, which comprises the following steps:
(1) mixing titanium salt, an organic ligand, an organic solvent and anhydrous methanol to obtain a mixed solution;
(2) carrying out ultrasonic dispersion on the mixed solution in the step (1) to obtain a reaction solution;
(3) carrying out hydro-thermal synthesis reaction on the reaction liquid in the step (2) to obtain a Ti-MOF precursor;
(4) and (4) drying the Ti-MOF precursor in the step (3) to obtain the cubic Ti-MOF photocatalyst.
In the embodiment of the invention, the molar ratio of the titanium salt to the organic ligand and the volume ratio of the organic solvent to the anhydrous methanol are preferably 1:1-6 and 10-1:1 respectively; more preferably 1:4 and 9: 1.
In the embodiment of the invention, the titanium salt is tetrabutyl titanate, titanium tetrachloride or isopropyl titanate. In the embodiment of the invention, the organic ligand is terephthalic acid or 2-amino terephthalic acid. The kind of the organic solvent is not limited in the present invention, and any organic solvent known to those skilled in the art for dissolving the organic ligand may be used, specifically, N-Dimethylformamide (DMF) and/or anhydrous methanol. DMF has strong deprotonation capacity, high boiling point and can provide a solvent thermal environment required by crystal growth, and anhydrous methanol has strong hydrogen bond providing capacity, so the activity and the morphology of Ti-MOF can be influenced by the anhydrous methanol.
The mixing method of the present invention is not limited, and a mixing method known to those skilled in the art, for example, magnetic stirring, may be employed.
After the mixed solution is obtained, the mixed solution is subjected to ultrasonic dispersion to obtain a reaction solution. In the present invention, the frequency of the ultrasonic dispersion is preferably 40 to 60kHz, more preferably 40 kHz; the time for the ultrasonic dispersion is preferably 5 to 30min, more preferably 10 min.
After the reaction liquid is obtained, the reaction liquid is subjected to hydro-thermal synthesis reaction in a reaction kettle to obtain a Ti-MOF precursor. The crystal formation in the synthesis process of the MOFs material comprises two stages, namely nucleation and crystal growth, when the crystallization reaction is carried out for a period of time, the concentration of reactants is reduced to be lower than the concentration required for forming the crystal nuclei, at the moment, the nucleation process is finished, and when the crystallization time is continuously prolonged, the crystal growth stage is promoted to be carried out, so that the size of the crystal is increased. When the crystallization time is too short, the reaction is not completely carried out, and the crystallinity of the sample is poor; when the crystallization time is too long, the concentration of the synthetic liquid is reduced, and the requirement of crystal growth cannot be met. In addition, the excessive hydrothermal synthesis temperature can cause the decomposition of N, N-2 methyl formamide to cause the change of pH of the synthetic liquid, thereby influencing the crystallization condition of the material; secondly, excessive temperature may cause the crystallization process to generate partial byproducts, which may affect the porosity properties of the material, and finally lead to the reduction of the adsorption capacity of the material and the reduction of the catalytic activity. Therefore, in the present invention, the temperature of the hydrothermal reaction is preferably 140-; the hydrothermal reaction time is preferably 12 to 72h, more preferably 24 to 60h, and most preferably 48 h.
After the hydrothermal synthesis reaction is finished, cleaning the Ti-MOF precursor by using N, N-dimethylformamide and anhydrous methanol for multiple times, and then placing the precursor in an oven for vacuum drying. The number of washing is preferably 3 to 8. In the present invention, the drying is preferably vacuum drying. In the present invention, the temperature of the drying is preferably 50 to 100 ℃, more preferably 60 to 80 ℃, and most preferably 60 ℃; the degree of vacuum of the drying is preferably 0 to 2X 10 3 Pa, more preferably0-2×10 2 Pa, most preferably 0 Pa; the drying time is preferably 8-24h, more preferably 10-20h, most preferably 12 h.
In the embodiment of the invention, N-dimethylformamide and anhydrous methanol are selected as the organic solvent during the preparation of the mixed solution, and the cubic morphology of the final Ti-MOF photocatalyst can be effectively improved by controlling the proportion of the N, N-dimethylformamide and the anhydrous methanol, so that the efficiency of degrading tetracycline hydrochloride by photocatalysis is improved.
The invention also provides the Ti-MOF photocatalyst prepared by the preparation method of the technical scheme, the Ti-MOF photocatalyst is of a cubic structure, and the specific surface area of the Ti-MOF photocatalyst is 1000-1400m 2 (ii)/g; the efficiency of the Ti-MOF photocatalyst in degrading tetracycline hydrochloride is 20-75%.
The invention also provides application of the Ti-MOF photocatalyst in the technical scheme in photocatalytic degradation of tetracycline hydrochloride.
In order to further illustrate the present invention, the following examples are given to describe the Ti-MOF photocatalyst provided by the present invention in detail, and the preparation method and application thereof, but they should not be construed as limiting the scope of the present invention.
Example 1:
firstly measuring 7mL of anhydrous methanol, then measuring 63mL of anhydrous N, N-Dimethylformamide (DMF), and magnetically stirring for 30min to form a mixed organic solvent; 4.4706g of 2-amino terephthalic acid is weighed and added into 70mL of mixed organic solvent, magnetic stirring is carried out for 3min, ultrasonic treatment is carried out for 10min, 2.1mL of tetrabutyl titanate is taken by a liquid-transferring gun, dropwise addition is carried out slowly to enable the tetrabutyl titanate to react fully, then magnetic stirring is carried out for 5min, ultrasonic treatment is carried out for 10min, and the process is repeated twice. Then magnetically stirring for 3h, putting into a 100mL reaction kettle, reacting for 48h at 150 ℃, cooling to room temperature and taking out. Taking 50mL of DMF each time, washing for 3 times, each time for 30min, taking 50mL of anhydrous methanol each time, washing for 3 times, each time for 30min, and drying for 12h in a drying oven at 60 ℃ to obtain the bright yellow solid Ti-MOF catalyst.
As shown in FIG. 1, the X-ray diffraction pattern (XRD) of the Ti-MOF photocatalyst shows that 6.8 degrees corresponds to the (101) diffraction peak, 9.5 degrees corresponds to the (002) diffraction peak, 11.5 degrees corresponds to the (211) diffraction peak, 16.5 degrees corresponds to the (222) diffraction peak, 17.9 degrees corresponds to the (312) diffraction peak and 19.6 degrees corresponds to the (004) diffraction peak in the figure 1, and the peaks are consistent with the reported peaks in the literature, thereby demonstrating that the Ti-MOF material can be synthesized by the hydrothermal synthesis method of the invention. As shown in fig. 2, which is an SEM image of the Ti-MOF photocatalyst, it can be seen from fig. 2 that the Ti-MOF photocatalyst prepared by hydrothermal synthesis has uniformly distributed particles and an overall morphology structure in the form of a cube.
As shown in fig. 3, which is an SEM image of the Ti-MOF photocatalyst prepared in example 1 after degrading tetracycline hydrochloride through photocatalysis, it can be seen from fig. 3 that the Ti-MOF photocatalyst can still maintain a better cubic morphology structure after degrading tetracycline hydrochloride through catalysis, which indicates that the Ti-MOF photocatalyst can maintain better morphology stability before and after catalytic reaction.
FIG. 4 shows an SEM image of the cubic Ti-MOF photocatalyst prepared in example 1 after being treated with Ar gas at a high temperature of 400 ℃; FIG. 5 shows the cubic Ti-MOF photocatalyst prepared in example 1 via O 2 SEM atlas after 400 ℃ high temperature treatment of Ar gas. As can be seen from FIGS. 4 and 5, the Ti-MOF photocatalyst after high-temperature treatment still has a highly ordered cubic morphology, which indicates that the Ti-MOF catalyst with the cubic morphology has better morphology maintenance.
Taking 10mg of the catalyst, taking 2mg of tetracycline, fixing the volume to 100mL, placing the tetracycline into a photocatalytic reactor, carrying out dark reaction for 1h to achieve adsorption balance, and then carrying out photocatalytic degradation reaction by using a 300W Xe lamp. FIG. 8a is the reaction curve of the Ti-MOF photocatalyst prepared in example 1 for catalytic degradation of tetracycline hydrochloride, and it can be seen that the degradation rate of tetracycline hydrochloride is 50.84% after 210min of full-wave reaction, and the reaction rate constant k is 0.00436min -1 。
Example 2:
firstly measuring 9mL of anhydrous methanol, then measuring 63mL of anhydrous N, N-Dimethylformamide (DMF), and magnetically stirring for 30min to form a mixed organic solvent; 4.4706g of 2-amino terephthalic acid is weighed and added into 70mL of mixed organic solvent, magnetic stirring is carried out for 3min, ultrasonic treatment is carried out for 10min, 2.1mL of titanium tetrachloride is taken by a liquid-transferring gun, dropwise addition is carried out to enable the titanium tetrachloride to react fully, then magnetic stirring is carried out for 5min, ultrasonic treatment is carried out for 10min, and the process is repeated twice. Then magnetically stirring for 3h, putting into a 100mL reaction kettle, reacting for 48h at 150 ℃, cooling to room temperature and taking out. Taking 50mL of DMF each time, washing for 3 times, each time for 30min, taking 50mL of anhydrous methanol each time, washing for 3 times, each time for 30min, and drying in an oven at 60 ℃ for 12h to obtain the bright yellow solid Ti-MOF catalyst.
Taking 10mg of the catalyst, taking 2mg of tetracycline hydrochloride, metering to 100mL, placing the tetracycline hydrochloride into a photocatalytic reactor, carrying out dark reaction for 1h to achieve adsorption balance, and carrying out photocatalytic degradation reaction by using a 300W Xe lamp. The degradation rate of tetracycline hydrochloride after the reaction for 210min under the full wave condition is 38.89 percent, and the reaction rate constant k is 0.00241min -1 The specific surface area of the catalyst is 1104m 2 /g。
Example 3:
firstly measuring 7mL of anhydrous methanol, then measuring 63mL of anhydrous N, N-Dimethylformamide (DMF), and magnetically stirring for 30min to form a mixed organic solvent; 4.4706g of terephthalic acid is weighed and added into 70mL of mixed organic solvent, magnetic stirring is carried out for 3min, ultrasonic treatment is carried out for 10min, a liquid-moving gun is used for taking 2.1mL of isopropyl titanate, dropwise addition is carried out slowly to enable the isopropyl titanate to react fully, then magnetic stirring is carried out for 5min, ultrasonic treatment is carried out for 10min, and the process is repeated twice. Then magnetically stirring for 3h, putting into a 100mL reaction kettle, reacting for 48h at 150 ℃, cooling to room temperature and taking out. Taking 50mL of DMF each time, washing for 3 times, each time for 30min, taking 50mL of anhydrous methanol each time, washing for 3 times, each time for 30min, and drying for 12h in a drying oven at 60 ℃ to obtain the bright yellow solid Ti-MOF catalyst.
Taking 10mg of the catalyst, taking 2mg of tetracycline hydrochloride, metering to 100mL, placing the tetracycline hydrochloride into a photocatalytic reactor, carrying out dark reaction for 1h to achieve adsorption balance, then carrying out photocatalytic degradation reaction by using a 300W Xe lamp, wherein the degradation rate of the tetracycline hydrochloride is 37.58% after the reaction is carried out for 210min under full wave conditions, and the reaction rate constant k is 0.00235min -1 The specific surface area of the catalyst was 1059m 2 /g。
Comparative example 1:
weighing 70mL of anhydrous N, N-Dimethylformamide (DMF), weighing 4.4706g of 2-aminoterephthalic acid, adding the weighed 2-aminoterephthalic acid into 70mL of organic solvent, magnetically stirring for 3min, ultrasonically treating for 10min, taking 2.1mL of tetrabutyl titanate by using a liquid transfer gun, slowly adding the tetrabutyl titanate in a dropwise manner to fully react, magnetically stirring for 5min, ultrasonically treating for 10min, and repeating the process twice. Then magnetically stirring for 3h, putting into a 100mL reaction kettle, reacting for 48h at 150 ℃, cooling to room temperature and taking out. Taking 50mL of DMF each time, washing for 3 times, 30min each time, taking 50mL of anhydrous methanol each time, washing for 3 times, 30min each time, drying for 12h in a 60 ℃ oven to obtain the catalyst prepared in the comparative example 1, and as can be seen from FIG. 6, the catalyst has no regular morphology.
Taking 10mg of the catalyst, taking 2mg of tetracycline hydrochloride, fixing the volume to 100mL, placing the catalyst in a photocatalytic reactor, carrying out dark reaction for 1h to achieve adsorption equilibrium, then carrying out photocatalytic degradation reaction by using a 300W Xe lamp, and taking a reaction curve of the Ti-MOF photocatalyst prepared in the comparative example 1 to carry out catalytic degradation on the tetracycline hydrochloride, wherein the degradation rate of the tetracycline hydrochloride is 5.93% after the tetracycline hydrochloride reacts for 210min under the full-wave condition, and the reaction rate constant k is 0.00029min -1 。
Comparative example 2:
firstly measuring 21mL of anhydrous methanol, then measuring 49mL of anhydrous N, N-Dimethylformamide (DMF), and magnetically stirring for 30min to form a mixed organic solvent; 4.4706g of 2-amino terephthalic acid is weighed and added into 70mL of mixed organic solvent, magnetic stirring is carried out for 3min, ultrasonic processing is carried out for 10min, 2.1mL of tetrabutyl titanate is taken by a liquid transfer gun, dropwise addition is carried out slowly to enable the tetrabutyl titanate to react fully, then magnetic stirring is carried out for 5min, ultrasonic processing is carried out for 10min, and the process is repeated twice. Then magnetically stirring for 3h, putting into a 100mL reaction kettle, reacting for 48h at 150 ℃, cooling to room temperature and taking out. Taking 50mL of DMF each time, washing for 3 times, each time for 30min, taking 50mL of anhydrous methanol each time, washing for 3 times, each time for 30min, and drying for 12h in a drying oven at 60 ℃ to obtain the bright yellow solid Ti-MOF catalyst. As shown in fig. 7, the catalyst is decahedral in morphology.
Taking 10mg of the catalyst, taking 2mg of tetracycline hydrochloride, fixing the volume to 100mL, placing the tetracycline hydrochloride into a photocatalytic reactor, performing a dark reaction for 1h to achieve adsorption balance, and performing a photocatalytic degradation reaction by using a 300W Xe lamp, wherein FIG. 8c shows the Ti-MOF prepared in the comparative example 2The reaction curve of the tetracycline hydrochloride catalyzed by the catalyst shows that the degradation rate of the tetracycline hydrochloride is 32.34 percent after the tetracycline hydrochloride reacts for 210min under the full-wave condition, and the reaction rate constant k is 0.00190min -1 (ii) a The specific surface area of the catalyst was 1013m 2 /g。
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a high-activity cubic Ti-MOF photocatalyst is characterized by comprising the following steps:
(1) mixing titanium salt, an organic ligand, an organic solvent and anhydrous methanol to obtain a mixed solution; the molar ratio of the titanium salt to the organic ligand and the volume ratio of the organic solvent to the anhydrous methanol are respectively 1:1-6 and 10-1: 1; the organic ligand is terephthalic acid or 2-amino terephthalic acid;
(2) carrying out ultrasonic dispersion on the mixed solution in the step (1) to obtain a reaction solution;
(3) carrying out hydro-thermal synthesis reaction on the reaction liquid in the step (2) to obtain a Ti-MOF precursor;
(4) and (4) drying the Ti-MOF precursor in the step (3) to obtain the cubic Ti-MOF photocatalyst.
2. The method of claim 1, wherein the titanium salt comprises n-tetrabutyl titanate, titanium tetrachloride, or isopropyl titanate.
3. The method as claimed in claim 1, wherein the temperature of the hydrothermal synthesis reaction in step (3) is 140-160 ℃, and the time of the hydrothermal synthesis reaction is 12-72 h.
4. The method according to claim 1, wherein the drying temperature in the step (4) is 50-100 ℃ and the drying time is 8-24 h.
5. The preparation method of claim 1, wherein the Ti-MOF precursor is washed with an organic solvent and anhydrous methanol several times before being dried in step (4).
6. The production method according to any one of claims 1 to 5, wherein the organic solvent is N, N-dimethylformamide.
7. A Ti-MOF photocatalyst prepared by a preparation process according to any one of claims 1 to 6, wherein the Ti-MOF photocatalyst has a cubic structure.
8. A Ti-MOF photocatalyst as claimed in claim 7, characterized in that the Ti-MOF photocatalyst has a specific surface area of 1000-1400m 2 /g。
9. The Ti-MOF photocatalyst according to claim 7, wherein the Ti-MOF photocatalyst has an efficiency of degrading tetracycline hydrochloride of 20% to 75%.
10. Use of a Ti-MOF photocatalyst according to any one of claims 7 to 9 for the photocatalytic degradation of tetracycline hydrochloride.
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