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CN-122011408-A - Mesoporous material Ce/Ti-UiO-66-NH2Preparation method and application of (C)

CN122011408ACN 122011408 ACN122011408 ACN 122011408ACN-122011408-A

Abstract

The invention provides a preparation method and application of a mesoporous material Ce/Ti-UiO-66-NH 2 , comprising the following steps of 1) mixing a certain amount of template agent, ceric ammonium nitrate, terephthalic acid, TMB, acetic acid and sodium perchlorate, dissolving in deionized water, reacting to obtain Ce-UiO-66, 2) adding a certain amount of tetrabutyl titanate into an N, N-dimethylformamide solution containing Ce-UiO-66, performing hydrothermal reaction to obtain Ce/Ti-UiO-66 solid, and 3) performing ultrasonic treatment on a certain amount of 2-amino terephthalic acid and the Ce/Ti-UiO-66 solid in a methanol solution to obtain Ce/Ti-UiO-66-NH 2 solid. The invention not only can realize simple synthesis of mesoporous Ce-UiO-66, solves the problem that the mesoporous Ce-UiO-66 synthesis method in the prior art is difficult, prepares the mesoporous material doped with metal titanium ions and loaded with amino Ce/Ti-UiO-66-NH 2 , and provides new materials for the fields of photocatalysis and the like.

Inventors

  • LI KE
  • ZHANG XUE

Assignees

  • 吉林化工大学

Dates

Publication Date
20260512
Application Date
20260202

Claims (9)

  1. 1. The preparation method of the mesoporous material Ce/Ti-UiO-66-NH 2 is characterized by comprising 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, stirring in a water bath, centrifugally washing and drying to obtain Ce-UIO-66; 2) Adding a certain amount of tetrabutyl titanate into an N, N-dimethylformamide solution containing Ce-UiO-66, performing a hydrothermal reaction, performing centrifugal washing, activating and drying to obtain Ce/Ti-UiO-66 solid; 3) And (3) carrying out ultrasonic treatment on a certain amount of 2-amino terephthalic acid and Ce/Ti-UiO-66 solid in a methanol solution, then centrifugally washing, and drying to obtain the Ce/Ti-UiO-66-NH 2 solid.
  2. 2. The method for preparing the mesoporous material Ce/Ti-UiO-66-NH 2 according to claim 1, wherein, The template agent surface active agent Brij20 in the step 1).
  3. 3. The method for preparing the mesoporous material Ce/Ti-UiO-66-NH 2 according to claim 1 or 2, wherein, The ratio relation of the template agent, ceric ammonium nitrate, terephthalic acid, TMB, acetic acid, sodium perchlorate and deionized water in the step 1) is (20-100) mg (400-700) mg (50-150) mg (40-80) mu L (50-100) mu L (200-500) mg (2-10) mL.
  4. 4. The method for preparing the mesoporous material Ce/Ti-UiO-66-NH 2 according to claim 3, wherein, The water bath temperature in the step 1) is 30-50 ℃, the stirring speed is 100-500r/min, and the reaction time is 30-70 min; and/or, the centrifugation rate is 7000-12000 r/min; And/or washing for 1-3 times by using N, N-dimethylformamide and 1-3 times by using absolute ethyl alcohol; And/or, the drying is vacuum drying, and the temperature is 50-70 ℃.
  5. 5. The method for preparing the mesoporous material Ce/Ti-UiO-66-NH 2 according to claim 1, wherein, The proportioning relation of the tetrabutyl titanate titanic acid to the Ce-UiO-66 to the N, N-dimethylformamide in the step 2) is (50-100) mu L (80-200) mg (5-30) mL.
  6. 6. The method for preparing the mesoporous material Ce/Ti-UiO-66-NH 2 according to claim 1 or 5, wherein, 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 that the N, N-dimethylformamide is washed 1 to 3 times; and/or, the activation is carried out with methanol solution for 2-5 days at room temperature; and/or, the drying is vacuum drying, and the temperature is 50-70 ℃.
  7. 7. The method for preparing the mesoporous material Ce/Ti-UiO-66-NH 2 according to claim 1, wherein, The proportioning relation of the 2-amino terephthalic acid, ce/Ti-UIO-66 and methanol in the step 3) is (100-300) mg (20-50) mg (10-50) mL.
  8. 8. The method for preparing the mesoporous material Ce/Ti-UiO-66-NH 2 according to claim 1, wherein, Step 3) the ultrasonic time is 2-10 min; and/or, the centrifugation rate is 7000-12000 r/min; And/or, the washing is that the N, N-dimethylformamide is washed 1 to 3 times; And/or, the drying is vacuum drying, and the temperature is 50-70 ℃.
  9. 9. Mesoporous material Ce/Ti-UiO-66-NH according to any one of claims 1 to 8 2 Ce/Ti-UiO-66-NH obtained by the preparation method of (2) 2 Application in photocatalysis.

Description

Preparation method and application of mesoporous material Ce/Ti-UiO-66-NH 2 Technical Field The invention relates to the technical field of novel mesoporous metal organic framework synthesis, in particular to a preparation method and application of a mesoporous material Ce/Ti-UiO-66-NH 2. Background Mesoporous materials are porous materials with pore sizes in the range of 2-50 nm a, which have been found to be of great interest in the 90 s of the 20 th century. It has high specific surface area, adjustable pore diameter and pore volume. Therefore, mesoporous materials have great potential in the fields of adsorption, separation, sensing, catalysis, biological medicine and the like. The large and ordered mesoporous structure is beneficial to the internal transportation of substances, can effectively encapsulate guest molecules and bear certain mechanical stress. The high specific surface area and large pore volume can enhance adsorption, reactant contact, and loading capacity of target molecules and ions. The thin pore walls provide efficient channels for the transport of charges or small molecules. The various functional backbones impart catalytic, optical, electrical, or other active properties inherent to the material. The UiO-66 has superior hydrothermal stability and chemical stability, the crystal structure of the UiO-66 can be kept stable at 500 ℃, and the skeleton structure can bear mechanical pressure of 1.0 MPa. Secondly, the UiO-66 can keep stable structure in water, N-dimethylformamide, benzene or acetone and other solutions, and also has certain acid and alkali resistance. However, the structure of UiO-66 has a certain ligand defect phenomenon. The extent of ligand defect of the UiO-66 structure directly affects the size of its specific surface area. Therefore, how to improve the coordination defect in the UiO-66 structure and synthesize a new mesoporous material is a technical problem to be solved by the technicians in the field. Disclosure of Invention The invention provides a preparation method and application of a mesoporous material Ce/Ti-UiO-66-NH 2, which not only can realize simple synthesis of mesoporous Ce-UiO-66, but also can solve the problems that the mesoporous Ce-UiO-66 synthesis method is difficult in the prior art, and can prepare a mesoporous material doped with metal titanium ions and loaded with amino groups, and simultaneously provide a new material for the fields of photocatalysis and the like. The invention provides a preparation method of a mesoporous material Ce/Ti-UiO-66-NH 2, which 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, stirring in a water bath, centrifugally washing and drying to obtain Ce-UIO-66; 2) Adding a certain amount of tetrabutyl titanate into an N, N-dimethylformamide solution containing Ce-UiO-66, performing a hydrothermal reaction, performing centrifugal washing, activating and drying to obtain Ce/Ti-UiO-66 solid; 3) And (3) carrying out ultrasonic treatment on a certain amount of 2-amino terephthalic acid and Ce/Ti-UiO-66 solid in a methanol solution, then centrifugally washing, and drying to obtain the Ce/Ti-UiO-66-NH 2 solid. Preferably, the template surfactant Brij20 in step 1). Preferably, the ratio of the template agent, ceric ammonium nitrate, terephthalic acid, TMB, acetic acid, sodium perchlorate and deionized water in the step 1) is (20-100) mg (400-700) mg (50-150) mu L (40-80) mu L (50-100) mu L (200-500) mg (2-10) mL. Preferably, the water bath temperature in the step 1) is 30-50 ℃, the stirring speed is 100-500r/min, and the reaction time is 30-70 min; and/or, the centrifugation rate is 7000-12000 r/min; And/or washing for 1-3 times by using N, N-dimethylformamide and 1-3 times by using absolute ethyl alcohol; And/or, the drying is vacuum drying, and the temperature is 50-70 ℃. Preferably, the ratio of the tetrabutyl titanate titanic acid to the Ce-UiO-66 to the N, N-dimethylformamide in the step 2) is (50-100) mu L (80-200) mg (5-30) mL. Preferably, the hydrothermal reaction temperature in the step 2) 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 that the N, N-dimethylformamide is washed 1 to 3 times; and/or, the activation is carried out with methanol solution for 2-5 days at room temperature; and/or, the drying is vacuum drying, and the temperature is 50-70 ℃. Preferably, the ratio relation of the 2-amino terephthalic acid to the Ce/Ti-UiO-66 to the methanol in the step 3) is (100-300) mg (20-50) mg (10-50) mL. Preferably, step 3) the ultrasound time is 2-10 min; and/or, the centrifugation rate is 7000-12000 r/min; And/or, the washing is that the N, N-dimethylformamide is washed 1 to 3 times; And/or, the drying is vacuum drying, and the temperature is 50-70 ℃. The second purpose of the invention is to provide the a