Preparation method and application of mesoporous material Ce / Ti-UiO-66-NH2

Abstract

The invention provides a preparation method and application of a mesoporous material Ce / Ti-UiO-66-NH2, and the preparation method comprises the following steps: 1) mixing a certain amount of template agent, ceric ammonium nitrate, terephthalic acid, TMB, acetic acid and sodium perchlorate, dissolving in deionized water, and reacting to obtain Ce-UiO-66; (2) adding a certain amount of tetrabutyl titanate into a N, N-dimethylformamide solution containing Ce-UiO-66, and carrying out hydrothermal reaction, so as to obtain a Ce / Ti-UiO-66 solid; and (3) carrying out ultrasonic treatment on a certain amount of 2-aminoterephthalic acid and the Ce / Ti-UiO-66 solid in a methanol solution to obtain a Ce / Ti-UiO-66-NH2 solid. According to the method, simple and convenient synthesis of mesoporous Ce-UiO-66 can be achieved, the problem that in the prior art, a mesoporous Ce-UiO-66 synthesis method is difficult is solved, the metal titanium ion-doped and amino-loaded Ce / Ti-UiO-66-NH2 mesoporous material is prepared, and meanwhile, a new material is provided for the fields of photocatalysis and the like.

Description

Technical Field

[0001] This invention relates to the field of novel mesoporous metal-organic framework synthesis technology, and particularly to a method for preparing and applying the mesoporous material Ce / Ti-UiO-66-NH2. Background Technology

[0002] Mesoporous materials, with pore sizes ranging from 2 to 50 nm, have attracted widespread attention since their discovery in the 1990s. They possess high specific surface areas and tunable pore sizes and volumes. Therefore, mesoporous materials hold great potential in adsorption, separation, sensing, catalysis, and biomedicine. The large and ordered mesoporous structure facilitates internal transport of substances and effectively encapsulates guest molecules, withstanding certain mechanical stresses. High specific surface areas and large pore volumes enhance adsorption, reactant contact, and the loading capacity of target molecules and ions. Thin pore walls provide effective channels for charge or small molecule transport. Multiple functional frameworks endow materials with inherent catalytic, optical, electrical, or other active properties.

[0003] UiO-66 exhibits excellent hydrothermal and chemical stability. Its crystal structure remains stable at 500℃, and its framework can withstand mechanical pressure of 1.0 MPa. Furthermore, UiO-66 maintains structural stability in solutions such as water, N,N-dimethylformamide, benzene, or acetone, and also possesses certain acid and alkali resistance. However, UiO-66 exhibits certain ligand defects in its structure. The degree of ligand defects in the UiO-66 structure directly affects its specific surface area.

[0004] Therefore, how to improve the coordination defects in the UiO-66 structure and synthesize a new mesoporous material is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] This invention provides a method for preparing and applying the mesoporous material Ce / Ti-UiO-66-NH2. This invention not only enables the simple synthesis of mesoporous Ce-UiO-66, solving the problem of difficult synthesis methods of mesoporous Ce-UiO-66 in the prior art, but also prepares mesoporous Ce / Ti-UiO-66-NH2 doped with titanium ions and loaded with amino groups, providing new materials for photocatalysis and other fields.

[0006] One objective of this invention is to provide a method for preparing the mesoporous material Ce / Ti-UiO-66-NH2, comprising the following steps:

[0007] 1) A certain amount of template agent, cerium ammonium nitrate, terephthalic acid, TMB, acetic acid, and sodium perchlorate were mixed and dissolved in deionized water. After stirring in a water bath, centrifuging, washing, and drying, Ce-UiO-66 was obtained.

[0008] 2) A certain amount of tetrabutyl titanate was added to an N,N-dimethylformamide solution containing Ce-UiO-66. After hydrothermal reaction, the mixture was centrifuged, washed, activated, and dried to obtain Ce / Ti-UiO-66 solid.

[0009] 3) A certain amount of 2-aminoterephthalic acid and Ce / Ti-UiO-66 solid were ultrasonically treated in methanol solution, followed by centrifugation, washing, and drying to obtain Ce / Ti-UiO-66-NH2 solid.

[0010] Preferably, the template agent surfactant Brij20 described in step 1) is used.

[0011] Preferably, the ratio of the template agent, cerium ammonium nitrate, terephthalic acid, TMB, acetic acid, sodium perchlorate and deionized water in step 1) is: (20-100) mg: (400-700) mg: (50-150) mg: (40-80) μL: (50-100) μL: (200-500) mg: (2-10) mL.

[0012] Preferably, the water bath temperature in step 1) is 30-50℃, the stirring rate is 100-500 r / min, and the reaction time is 30-70 min;

[0013] And / or, the centrifugation rate is 7000-12000 r / min;

[0014] And / or, the washing is performed by washing with N,N-dimethylformamide 1-3 times and washing with anhydrous ethanol 1-3 times;

[0015] And / or, the drying is performed using vacuum drying at a temperature of 50-70°C.

[0016] Preferably, the ratio of tetrabutyl titanate titanate: Ce-UiO-66: N,N-dimethylformamide in step 2) is (50-100) μL: (80-200) mg: (5-30) mL.

[0017] Preferably, the hydrothermal reaction temperature in step 2) is 100-200℃, and the reaction time is 12-48 h;

[0018] And / or, the centrifugation rate is 7000-12000 r / min;

[0019] And / or, the washing is N,N-dimethylformamide washing 1-3 times;

[0020] And / or, the activation is performed by activating with methanol solution at room temperature for 2-5 days;

[0021] And / or, the drying is vacuum drying at a temperature of 50-70°C.

[0022] Preferably, the ratio of 2-aminoterephthalic acid:Ce / Ti-UiO-66:methanol in step 3) is (100-300)mg:(20-50)mg:(10-50)mL.

[0023] Preferably, the ultrasound time in step 3) is 2-10 min;

[0024] And / or, the centrifugation rate is 7000-12000 r / min;

[0025] And / or, the washing is N,N-dimethylformamide washing 1-3 times;

[0026] And / or, the drying is vacuum drying at a temperature of 50-70°C.

[0027] The second objective of this invention is to provide the application of Ce / Ti-UiO-66-NH2 obtained by the above-mentioned method for preparing mesoporous material Ce / Ti-UiO-66-NH2 in photocatalysis.

[0028] In summary, the present invention can achieve at least the following technical effects:

[0029] 1) By adding a template agent, the present invention can effectively adjust the mesoporous structure and change the pore size, and can easily control the shell thickness. This simple assembly method opens up new avenues for exploring the design of UiO-66 with complex multimodal mesoporous structures and provides more innovative ideas for various applications.

[0030] 2) This invention utilizes the surfactant Brij20 as a template agent to easily synthesize mesoporous Ce-UiO-66, which has a stable mesoporous structure. The doping of titanium metal ions increases the active sites, and the loaded amino polymer provides a three-dimensional network structure, while also providing amino active sites, thus offering more options for photocatalytic applications.

[0031] 3) The Ce / Ti-UiO-66-NH2 prepared by this invention has a high specific surface area, mesoporous structure, and multiple active sites, and the process is simple, providing a new approach for the synthesis of mesoporous materials. Attached Figure Description

[0032] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely embodiments of the present invention, and those skilled in the art can obtain other drawings based on the provided drawings without creative effort.

[0033] Figure 1This is a flowchart of the preparation process for Example 1;

[0034] Figure 2 This is a scanning electron microscope image showing the sequential changes in products during the preparation of Ce / Ti-UiO-66-NH2 in Example 1;

[0035] Where a represents Ce-UiO-66; b represents Ce / Ti-UiO-66; c represents Ce / Ti-UiO-66-NH2;

[0036] Figure 3 High-resolution transmission electron microscopy image of Ce / Ti-UiO-66-NH2 prepared in Example 1;

[0037] Figure 4 X-ray diffraction pattern of Ce / Ti-UiO-66-NH2 prepared in Example 1;

[0038] Figure 5 The image shows the Ce / Ti-UiO-66-NH2BET curve prepared in Example 1.

[0039] Figure 6 The infrared image of Ce-UiO-66 prepared in step 1) of Example 1;

[0040] Figure 7 Thermogravimetric analysis of Ce / Ti-UiO-66-NH2 prepared in Example 1;

[0041] Figure 8 The image shows a scanning electron microscope (SEM) image of Ce-UiO-66 prepared in step 1) of Examples 2-4.

[0042] Wherein, a represents Ce-UiO-66 prepared in Example 3; b represents Ce-UiO-66 prepared in Example 2; and c represents Ce-UiO-66 prepared in Example 4.

[0043] Figure 9 BET diagrams of Ce / Ti-UiO-66-NH2 prepared in Examples 2-4;

[0044] Where a represents the N2 adsorption isotherm; b represents the BJH pore size distribution;

[0045] Figure 10 Scanning electron microscope images of the Ce / Ti-UiO-66-NH2 samples prepared in Examples 5-7;

[0046] Wherein, a represents Ce / Ti-UiO-66-NH2 prepared in Example 5; b represents Ce / Ti-UiO-66-NH2 prepared in Example 6; and c represents Ce / Ti-UiO-66-NH2 prepared in Example 7.

[0047] Figure 11 BET diagrams of Ce / Ti-UiO-66-NH2 prepared in Examples 5-7;

[0048] Where a represents the N2 adsorption isotherm; b represents the BJH pore size distribution;

[0049] Figure 12 NMR spectra of Ce / Ti-UiO-66-NH2 prepared in Examples 5-7;

[0050] a represents Ce / Ti-UiO-66-NH2 prepared in Example 5; b represents Ce / Ti-UiO-66-NH2 prepared in Example 6; c represents Ce / Ti-UiO-66-NH2 prepared in Example 7;

[0051] Figure 13 EIS spectra of Ce / Ti-UiO66-NH2, CdS QDs, and Ce / Ti-UiO66-NH2@CdS QDs;

[0052] Figure 14 The It curves for Ce / Ti-UiO66-NH2, CdS QDs, and Ce / Ti-UiO66-NH2@CdS QDs;

[0053] Figure 15 Mott-Schottky curves for Ce / Ti-UiO66-NH2, CdS QDs, and Ce / Ti-UiO66-NH2@CdS QDs. Detailed Implementation

[0054] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0055] Table 1 lists the manufacturers, specifications, and specific chemical formulas of the raw materials used in the specific embodiments.

[0056] Table 1

[0057] name Chemical formula Specification Manufacturer Brij20 Brij20 AR (≥99%) Shanghai Aladdin Reagent Co., Ltd. 1,3,5-Trimethylbenzene / TMB <![CDATA[C9H 12 ]]> AR (≥99%) Shanghai Maclean Reagent Co., Ltd. Acetic acid <![CDATA[CH3COOH]]> AR (≥99%) Shanghai Damao Chemical Reagent Factory N,N-Dimethylformamide <![CDATA[C3H7NO]]> AR (≥99.5%) Shanghai Damao Chemical Reagent Factory Cerium ammonium nitrate <![CDATA[(NH4)2Ce(NO3)6]]> AR (≥99%) Shanghai Maclean Reagent Co., Ltd. Anhydrous ethanol <![CDATA[C2H6O]]> AR (≥99%) Shanghai Damao Chemical Reagent Factory Tetrabutyl titanate <![CDATA[C 16 H 36 O4Ti]]> AR (≥98%) Beijing Changhua Fine Chemical Plant 2-Aminoterephthalic acid <![CDATA[C8H7NO4]]> AR (≥98%) Shanghai Maclean Reagent Co., Ltd. Sodium perchlorate <![CDATA[NaClO4]]> AR (≥99%) Beijing Nanshang Le Chemical Plant terephthalic acid <![CDATA[C8H6O4]]> AR (≥99%) Shanghai Aladdin Reagent Co., Ltd. methanol <![CDATA[CH3OH]]> AR (≥99.5%) Shanghai Damao Chemical Reagent Factory Dimethyl sulfoxide <![CDATA[C2H6OS]]> AR (≥99%) Shanghai Damao Chemical Reagent Factory Cadmium acetate <![CDATA[(CH3COO)2Cd]]> AR (≥99%) Shanghai Damao Chemical Reagent Factory

[0058] Example 1

[0059] This embodiment provides a method for preparing the mesoporous material Ce / Ti-UiO-66-NH2, specifically including:

[0060] 1) Mix 50 mg Brij20 with 60 μL TMB, 6 mL deionized water, and 70 μL acetic acid, and sonicate for about 10 min to form a white emulsion; add 300 mg sodium perchlorate, 548 mg cerium ammonium nitrate, and 100 mg terephthalic acid to the emulsion, stir at 400 r / min for 50 min in a 40℃ water bath, centrifuge at 10000 r / min, wash twice with N,N-dimethylformamide and anhydrous ethanol, and dry under vacuum at 60 ℃ to obtain Ce-UiO-66 solid;

[0061] 2) 160 mg Ce-UiO-66 and 90 μL tetrabutyl titanate were placed in 10 mL N,N-dimethylformamide solution and hydrothermally reacted at 100 °C for 24 h. The resulting mixture was collected by centrifugation at 10000 r / min, washed twice with N,N-dimethylformamide, activated with methanol at room temperature for 3 days with methanol replaced daily, and vacuum dried at 60 °C to obtain Ce / Ti-UiO-66 solid.

[0062] 3) Add 181.1 mg of 2-aminoterephthalic acid and 35 mg of Ce / Ti-UiO-66 to 35 mL of methanol solution, sonicate for 5 min, collect the mixture by centrifugation at 10000 r / min, wash twice with N,N-dimethylformamide, and dry under vacuum at 60 ℃ to obtain Ce / Ti-UiO-66-NH2 solid.

[0063] In Example 1, Ce-UiO-66, Ce / Ti-UiO-66, and Ce / Ti-UiO-66-NH2 were prepared respectively.

[0064] Field emission scanning electron microscopy (FESEM) images Figure 2 The particles appear as spherical solid particles with a diameter of 500-700 nanometers. Transmission electron microscopy (TEM) further confirmed the extensive distribution of mesopores in the crystal matrix, and the elemental distribution map showed that Ce, Ti, C, N, and O were uniformly distributed in the structure, confirming the homogeneity of composition. Figure 3 X-ray diffraction (XRD) verified the integrity of the crystal structure. Figure 4 ).

[0065] Ce-UiO-66 has a BET specific surface area of ​​1105.92 m² / g and a total pore volume of 1.48 cm³ / g, with a pore size of 10.8 nm.

[0066] Ce / Ti-UiO-66 has a BET specific surface area of ​​752.78 m² / g and a total pore volume of 1.01 cm³ / g, with a pore size of 10.06 nm.

[0067] The BET specific surface area and total pore volume of Ce / Ti-UiO-66-NH2 reached 418.59 m² / g and 0.68 cm³ / g, respectively, with a pore size of 9.8 nm. Figure 5 ).

[0068] Fourier transform infrared spectroscopy (FT-IR) Figure 6 This confirms complete template removal, as evidenced by the Brij20 characteristic peak (1477 cm⁻¹) in Ce-UiO-66. -1 CH bending vibration at 2900 cm -1 The disappearance of the C–H stretching vibration at the location.

[0069] Thermogravimetric analysis showed that the load Ti 4+ After amination, the collapse temperature only changes slightly. Figure 7 ).

[0070] Example 2

[0071] The only difference between this embodiment and Embodiment 1 is that the amount of TMB added in step 1) is 30 μL.

[0072] Example 3

[0073] This embodiment is the same as Embodiment 1.

[0074] Example 4

[0075] The only difference between this embodiment and Embodiment 1 is that the amount of TMB added in step 1) is 90 μL.

[0076] Example 5

[0077] The only difference between this embodiment and Example 1 is that the amount of 2-aminoterephthalic acid added in step 3) is 90.55 mg.

[0078] Example 6

[0079] This embodiment is the same as Embodiment 1.

[0080] Example 7

[0081] The only difference between this embodiment and Example 1 is that the amount of 2-aminoterephthalic acid added in step 3) is 362.2 mg.

[0082] The instruments and models used for the following experimental data testing are shown in Table 2.

[0083] Table 2

[0084] Instrument Name model Manufacturer X-ray diffractometer (XRD) D8 FOCUS Brook Thermogravimetric analyzer (TGA) TG7 Swiss METTLER TGA / DSC3+ Fourier transform infrared spectroscopy (FI-IR) Nicolet IS5 Thermo Fisher Field emission scanning electron microscopy (FESEM) JEOL JSM-7610F Plus Japan Electronics Transmission electron microscopy (TEM) JEM-2100F(200Kv) Nippon Electronics Co., Ltd. MRI Ascend 600M Brook Xenon lamps MICROSOLAR 300 Pofilai Technology Co., Ltd. All-round automated gas analysis system Labsolar-6A Pofilai Technology Co., Ltd. Condensate circulating water DC-0506 Pofilai Technology Co., Ltd. Electrochemical workstation CH1706E Chenhua Instruments Co., Ltd. Gas chromatography GC-2014 Shimadzu Corporation hydrogen generator SPH-300 HP Analytics Research Institute

[0085] Test data 1

[0086] In Example 1, Ce-UiO-66, Ce / Ti-UiO-66, and Ce / Ti-UiO-66-NH2 were prepared in steps 1), 2), and 3), respectively.

[0087] like Figure 2 As shown: Field emission scanning electron microscopy (FESEM) image, showing spherical solid particles with a diameter of 500-700 nanometers.

[0088] like Figure 3 As shown: Transmission electron microscopy (TEM) further confirmed the extensive distribution of mesopores in the crystal matrix, and the elemental distribution map showed that Ce, Ti, C, N and O were uniformly distributed in the structure, confirming the homogeneity of composition.

[0089] like Figure 4 As shown: X-ray diffraction (XRD) verified the integrity of the crystal structure.

[0090] like Figure 5 As shown: Ce-UiO-66 has a BET specific surface area of ​​1105.92 m² / g and a total pore volume of 1.48 cm³ / g, with a pore size of 10.8 nm. Ce / Ti-UiO-66 has a BET specific surface area of ​​752.78 m² / g and a total pore volume of 1.01 cm³ / g, with a pore size of 10.06 nm. Ce / Ti-UiO-66-NH2 has a BET specific surface area of ​​418.59 m² / g and a total pore volume of 0.68 cm³ / g, with a pore size of 9.8 nm.

[0091] like Figure 6 As shown: Fourier transform infrared spectroscopy (FT-IR) confirms complete template removal, as evidenced by the Brij20 characteristic peak (1477 cm⁻¹) in Ce-UiO-66. -1 CH bending vibration at 2900 cm -1 The disappearance of the C–H stretching vibration at the location.

[0092] like Figure 7 As shown: Thermogravimetric analysis shows that the load Ti 4+ After amination, the collapse temperature changes only slightly.

[0093] Test Data 2

[0094] Scanning electron microscope images of Ce-UiO-66 prepared in step 1) of Examples 2-4 are shown below. Figure 8 As shown:

[0095] Examples 2-4, compared with Example 1, did not change any other synthesis conditions, only the amount of TMB added was changed. The amount added was changed from 60 μL to 30 μL and 90 μL respectively in the experiments. Figure 8 It can be observed that its pore size increases with the amount of TMB added.

[0096] Figure 9 The pore size diagram confirms this, showing that the pore size gradually increases with increasing TMB. The specific surface area also gradually increases. When the addition amount is 30 μL, the BET specific surface area and total pore volume reach 987.5 m² / g and 1.24 cm³ / g, respectively, with a pore size of 7.9 nm; when the addition amount is 60 μL, the BET specific surface area and total pore volume reach 1105.92 m² / g and 1.48 cm³ / g, respectively, with a pore size of 10.8 nm; and when the addition amount is 90 μL, the BET specific surface area and total pore volume reach 1215.92 m² / g and 1.78 cm³ / g, respectively, with a pore size of 11 nm.

[0097] Test data 3

[0098] Examples 5-7 were conducted without altering any of the other synthesis conditions compared to Example 1, except for the amount of 2-aminoterephthalic acid added, which was changed from 181.1 mg to 90.5 mg and 362.2 mg respectively.

[0099] pass Figure 10 It can be observed that its pore size decreases as the amount of 2-aminoterephthalic acid added increases; Figure 11 The pore size diagram confirms this: the pore size gradually decreases with increasing 2-aminoterephthalic acid (2-HT) concentration. At an addition of 90.5 mg, the BET specific surface area and total pore volume reach 695.3 m² / g and 0.98 cm³ / g, respectively, with a pore size of 10 nm. At an addition of 181.1 mg, the BET specific surface area and total pore volume reach 619.3 m² / g and 0.68 cm³ / g, respectively, with a pore size of 9.8 nm. At an addition of 362.2 mg, the BET specific surface area and total pore volume reach 564.4 m² / g and 1.1 cm³ / g, respectively, with a pore size of 8.9 nm.

[0100] Depend on Figure 12 As shown: NMR can be used to calculate the amination ratio. When the added amount is 90.5 mg, BDC:BDC-NH2=1:4.19; when the added amount is 181.1 mg, BDC:BDC-NH2=1:4.93; when the added amount is 362.2 mg, BDC:BDC-NH2=1:7.1.

[0101] Test data 4

[0102] CdS QDs Synthesis Method

[0103] 50 mg of cadmium acetate and 150 mL of dimethyl sulfoxide were sonicated for 1 hour and stirred at 400 r / min for 1 hour at room temperature. The mixture was then reacted in a hydrothermal reactor at 180 °C for 12 h. The sample was washed three times with deionized water and anhydrous ethanol and dried under vacuum at 60 °C to obtain a solid sample (Reference: Chemical Engineering Journal 525 (2025) 17041).

[0104] Ce / Ti-UiO66-NH2@CdS QDs loading method

[0105] 45 mg of Ce / Ti-UiO66-NH2 prepared in Example 1 and 5 mg of CdS QDs were weighed and dissolved in 20 mL of deionized water. The mixture was stirred at 400 r / min for 2 h at room temperature, washed twice with anhydrous ethanol, and dried under vacuum at 60 °C to obtain a solid sample.

[0106] Under xenon lamp simulated sunlight conditions, 20 mg of sample and 20 mL of sacrificial acid (20% by mass concentration) were added as a sacrificial agent. The sample was then subjected to photocatalytic hydrogen production testing using a Pofil photocatalytic hydrogen production instrument for a total testing time of 3.5 h. The sample included the product prepared in Example 1 and the aforementioned CdS QDs and Ce / Ti-UiO66-NH2@CdS QDs.

[0107] The results are shown in Table 3: Pure Ce-UiO66 showed no hydrogen production activity, while Ti-supported Ce-UiO66 showed no hydrogen production activity. 4+ The hydrogen production of Ce-Ti-UiO66 is approximately 17 μmol g. -1 h -1 The hydrogen production of the amination sample Ce / Ti-UiO66-NH2 was approximately 31 μmol g. -1 h -1 Photocatalytic hydrogen production data for the samples: The catalytic hydrogen production activity of the pure CdS QDs sample is 1328 μmol g. -1 h -1 The hydrogen production after loading CdS QDs onto Ce / Ti-UiO66-NH2 was 2425 μmol g. -1 h -1 .

[0108] To confirm the advantages of Ce / Ti-UiO66-NH2@CdS QDs in the photoinduced charge transfer process, the EIS spectra of Ce / Ti-UiO66-NH2, CdS QDs, and Ce / Ti-UiO66-NH2@CdS QDs were measured.

[0109] like Figure 13 As shown, Ce / Ti-UiO66-NH2 and CdS QDs have the smallest radius.

[0110] Figure 14 The It curves of Ce / Ti-UiO66-NH2, CdS QDs, and Ce / Ti-UiO66-NH2@CdS QDs are shown. The results indicate that the Ce / Ti-UiO66-NH2@CdS QDs composite photocatalyst has the highest photocurrent density, thus demonstrating that Ce / Ti-UiO66-NH2 plays a positive role in the transfer of photogenerated electrons and holes in CdS QDs.

[0111] Figure 15 The results show that the E values ​​of Ce / Ti-UiO66-NH2 and CdS QDs are... CB At -0.33 eV and -0.36 eV respectively, electrons are more readily transferred from CdS QDs to Ce / Ti-UiO66-NH2.

[0112] Table 3

[0113] Material <![CDATA[Hydrogen production amount (μmol g -1 h -1 )]]> Ce-UiO66 0 Ce / Ti-UiO66 17 <![CDATA[Ce / Ti-UiO66-NH2]]> 31 CdS QDs 1328 <![CDATA[Ce / Ti-UiO66-NH2@CdS QDs]]> 2425

[0114] The embodiments of this invention have been described in detail. Specific examples have been used to illustrate the principles and implementation methods of this invention. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of this invention. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this invention. Therefore, the content of this specification should not be construed as a limitation of this invention.

[0115] In this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, without necessarily requiring or implying any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

Claims

1. A method for preparing a mesoporous material Ce / Ti-UiO-66-NH2, characterized in that, Includes the following steps: 1) A certain amount of template agent, cerium ammonium nitrate, terephthalic acid, TMB, acetic acid, and sodium perchlorate were mixed and dissolved in deionized water. After stirring in a water bath, centrifuging, washing, and drying, Ce-UiO-66 was obtained. 2) A certain amount of tetrabutyl titanate was added to an N,N-dimethylformamide solution containing Ce-UiO-66. After hydrothermal reaction, the mixture was centrifuged, washed, activated, and dried to obtain Ce / Ti-UiO-66 solid. 3) A certain amount of 2-aminoterephthalic acid and Ce / Ti-UiO-66 solid were ultrasonically treated in methanol solution, followed by centrifugation, washing, and drying to obtain Ce / Ti-UiO-66-NH2 solid.

2. The method for preparing the mesoporous material Ce / Ti-UiO-66-NH2 according to claim 1, characterized in that, Step 1) describes the template agent surfactant Brij20.

3. The method for preparing the mesoporous material Ce / Ti-UiO-66-NH2 according to claim 1 or 2, characterized in that, The ratio of the template agent, cerium ammonium nitrate, terephthalic acid, TMB, acetic acid, sodium perchlorate and deionized water in step 1) is: (20-100) mg: (400-700) mg: (50-150) mg: (40-80) μL: (50-100) μL: (200-500) mg: (2-10) mL.

4. The method for preparing the mesoporous material Ce / Ti-UiO-66-NH2 according to claim 3, characterized in that, The water bath temperature in step 1) is 30-50℃, the stirring rate is 100-500 r / min, and the reaction time is 30-70 min; And / or, the centrifugation rate is 7000-12000 r / min; And / or, the washing is performed by washing with N,N-dimethylformamide 1-3 times and washing with anhydrous ethanol 1-3 times; And / or, the drying is performed using vacuum drying at a temperature of 50-70°C.

5. The method for preparing the mesoporous material Ce / Ti-UiO-66-NH2 according to claim 1, characterized in that, Step 2) The ratio of tetrabutyl titanate titanate: Ce-UiO-66: N,N-dimethylformamide is (50-100) μL: (80-200) mg: (5-30) mL.

6. A method for preparing a mesoporous material Ce / Ti-UiO-66-NH2 according to claim 1 or 5, characterized in that, Step 2) The hydrothermal reaction temperature is 100-200℃, and the reaction time is 12-48 h; And / or, the centrifugation rate is 7000-12000 r / min; And / or, the washing is N,N-dimethylformamide washing 1-3 times; And / or, the activation is performed by activating with methanol solution at room temperature for 2-5 days; And / or, the drying is vacuum drying at a temperature of 50-70°C.

7. The method for preparing the mesoporous material Ce / Ti-UiO-66-NH2 according to claim 1, characterized in that, Step 3) The ratio of 2-aminoterephthalic acid: Ce / Ti-UiO-66: methanol is (100-300) mg: (20-50) mg: (10-50) mL.

8. The method for preparing the mesoporous material Ce / Ti-UiO-66-NH2 according to claim 1, characterized in that, Step 3) The ultrasound time is 2-10 min; And / or, the centrifugation rate is 7000-12000 r / min; And / or, the washing is N,N-dimethylformamide washing 1-3 times; And / or, the drying is vacuum drying at a temperature of 50-70°C.

9. The mesoporous material Ce / Ti-UiO-66-NH2 according to any one of claims 1-8 The Ce / Ti-UiO-66-NH2 prepared by the method Applications in photocatalysis.

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