CN116174048A - Functionalized silica grafted metal organic framework composite material and preparation method thereof - Google Patents
Functionalized silica grafted metal organic framework composite material and preparation method thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 25
- 239000012924 metal-organic framework composite Substances 0.000 title claims description 26
- 239000000463 material Substances 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 239000013148 Cu-BTC MOF Substances 0.000 claims abstract description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 238000006722 reduction reaction Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 14
- 235000019260 propionic acid Nutrition 0.000 claims description 14
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 239000012621 metal-organic framework Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000013335 mesoporous material Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 208000012839 conversion disease Diseases 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 239000012917 MOF crystal Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a functionalized silica grafted metal organic frame composite material and a preparation method thereof, and belongs to the technical field of composite materials, wherein the molecular formula of the composite material is HKUST-1@SBA-15C, the composite material takes carboxyl functionalized ordered mesoporous silica SBA-15C as a carrier, a metal-organic frame compound HKUST-1 active component is grafted on the carrier, the carrier SBA-15C of the composite material is prepared by co-condensing a carboxyl functionalization reagent and an inorganic silicon source, and the load capacity of the active component HKUST-1 is 10%. The HKUST-1@SBA-15C composite material has the advantages of simple preparation process, high reaction conversion rate, higher catalytic activity for reduction reaction of the composite material on nitrophenol, high product purity and clean and pollution-free reaction process.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a functionalized silica grafted metal-organic framework composite material and a preparation method thereof.
Background
The metal organic framework composite (MOF) material has the advantages of organic-inorganic hybridization structure, molecular level structure, designable/adjustable porosity, easy chemical modification and the like, the silicon dioxide has good chemical stability and mechanical property, after the metal organic framework composite (MOF) material is compounded with the silicon dioxide, the silicon dioxide provides structural support for the MOF material, the stability of the material is improved through hydrophobic effect and covalent bond, and the MOF material provides catalytic active sites for the silicon dioxide. The MOF/silicon dioxide composite material has excellent performance in various applications, and as a stationary phase of a chromatographic column, the MOF/silicon dioxide composite material with a highly uniform core-shell structure can improve the nonuniform accumulation of MOF particles and improve the separation efficiency; the structure guiding effect of the silicon dioxide has obvious influence on the growth of MOF crystals, thereby influencing the morphology and structural performance of the composite material. The interaction of the silanol groups on the silica surface with the metal center causes a change in the structure of the composite material, resulting in an increase in the surface area and micropore volume of the composite material.
MOF can be grown in the pores of the porous silicon material by an impregnation method, so that the morphology of the MOF/silicon dioxide composite material is well controlled. Anindita Chakraborty et al first prepared mesoporous silica (SBA-15) and then prepared the composite in situ by directly dispersing a metal organic framework (Mg-MOF-74) precursor in SBA-15. The results demonstrate that MOF grows in SBA-15 pores, and that the composite material contains more mesopores and has better catalysis in the reduction reaction than micropores of the original MOF nanocrystals. Therefore, we propose to design and prepare a functionalized silica grafted metal organic framework composite material and a preparation method thereof by adopting a one-step hydrothermal co-condensation technology, and synthesize the HKUST-1@SBA-15C composite material.
Disclosure of Invention
The technical problem to be solved by the invention is to prepare the functionalized silica grafted metal organic frame composite material by a one-step co-condensation hydrothermal treatment technology method. It is another object of the present invention to provide a method for preparing the composite material.
The invention relates to a functionalized silica grafted metal organic framework composite material which is characterized in that the structure of the composite material is HKUST-1@SBA-15C, the composite material takes carboxyl functionalized ordered mesoporous silica SBA-15C as a carrier, a metal-organic framework compound HKUST-1 active component is grafted on the carrier, the carrier SBA-15C of the composite material is prepared by co-condensing a carboxyl functionalization reagent and an inorganic silicon source, and the load capacity of the active component HKUST-1 is 10%. Preferably, the HKUST-1@SBA-15C composite material is a mesoporous material, and the average pore diameter of the HKUST-1@SBA-15C composite material is 7 nm.
Preferably, the carboxyl functionalization reagent is triphosphoryl propionic acid, the inorganic silicon source is tetraethoxysilane, and the triphosphoryl propionic acid and the tetraethoxysilane are prepared according to a molar ratio of 1:8.
The functionalized silica grafted metal organic framework composite material comprises the following steps:
(1) Weighing 2.0 g of P123, dissolving in 60 mL concentration 2 mol/L dilute hydrochloric acid, adding 7.5 mL water, and magnetically stirring at 40 ℃ until P123 is completely dissolved to obtain a clear solution containing a structure directing agent;
(2) Adding 4 g tetraethoxysilane and 0.37 g triphosphoryl propionic acid to the clear solution prepared in the step (1), wherein the molar ratio of the tetraethoxysilane to the triphosphoryl propionic acid is 8:1, after the dripping is finished, continuously heating and stirring for 24 hours at 35 ℃ to gradually convert the mixture into sol;
(3) The sol used in the step (2) is put into a vacuum drying box to be dried for 10 hours at 80 ℃, and the dried white precipitate is ground for 10-30 minutes to obtain dry white solid powder;
(4) Adding the white powder obtained in the step (3) into 400 mL ethanol solution, dropwise adding 1.5 mL concentrated hydrochloric acid into the solution, extracting for 24 hours at the temperature of 80 ℃ under condensation reflux, filtering, placing the obtained white precipitate in a vacuum drying oven, drying for 10 hours at the temperature of 80 ℃, and grinding the dried white precipitate for 10-30 minutes to obtain dry white solid powder;
(5) Weighing 0.085 g copper nitrate powder, dissolving in 5 mL water, dispersing 0.2 g SBA-15C obtained in the step (4) in copper nitrate water solution, carrying out ultrasonic treatment for 30 minutes, then placing the copper nitrate water solution in a box, drying at 90 ℃ for 5 hours, and grinding the dried blue precipitate for 10-30 minutes to obtain dry blue solid powder;
(6) Weighing 0.053 g of 1,3, 5-benzene tricarboxylic acid, dissolving in 10 mL ethanol solution, adding the solution into the blue solid powder obtained in the step (5), dissolving in 10 mL water, carrying out ultrasonic treatment for 30 minutes, stirring at room temperature for 30 minutes, placing the blue solution in 120 ℃ for hydrothermal reaction for 12 hours, cooling to room temperature, respectively washing with distilled water and ethanol for three times, carrying out suction filtration, placing the obtained blue precipitate in a vacuum drying oven, drying at 80 ℃ for 10 hours, and grinding the dried blue precipitate for 10-30 minutes to obtain HKUST-1@SBA-15C composite material which is blue powder;
compared with the prior art, the invention has the following innovation: the invention uses the mesoporous silicon-based material as a carrier, so that the stability of the structure of the MOF@mesoporous silicon-based composite material is improved; the surface of the mesoporous silicon-based material is modified by using the carboxylation functional reagent, and the carboxyl forms a coordination bond with metal ions in the MOF material, so that the effect of the MOF and the silicon-based carrier is enhanced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only individual embodiments of the present invention, and that other drawings can be obtained according to these drawings for a person skilled in the art according to the idea of the present invention.
FIG. 1 is a transmission electron microscope image of HKUST-1@SBA-15C composite material prepared in example 1 of the invention.
Detailed Description
The invention will be further described with reference to specific examples and figures.
Example 1
(1) Weighing 2.0 g of P123, dissolving in 60 mL concentration 2 mol/L dilute hydrochloric acid, adding 7.5 mL water, and magnetically stirring at 40 ℃ until P123 is completely dissolved to obtain a clear solution containing a structure directing agent;
(2) Adding 4 g tetraethoxysilane and 0.37 g triphosphoryl propionic acid to the clear solution prepared in the step (1), wherein the molar ratio of the tetraethoxysilane to the triphosphoryl propionic acid is 8:1, after the dripping is finished, continuously heating and stirring for 24 hours at 35 ℃ to gradually convert the mixture into sol;
(3) The sol used in the step (2) is put into a vacuum drying box to be dried for 10 hours at 80 ℃, and the dried white precipitate is ground for 10-30 minutes to obtain dry white solid powder;
(4) Adding the white powder obtained in the step (3) into 400 mL ethanol solution, dropwise adding 1.5 mL concentrated hydrochloric acid into the solution, extracting for 24 hours at the temperature of 80 ℃ under condensation reflux, filtering, placing the obtained white precipitate in a vacuum drying oven, drying for 10 hours at the temperature of 80 ℃, and grinding the dried white precipitate for 10-30 minutes to obtain dry white solid powder;
(5) Weighing 0.085 g copper nitrate powder, dissolving in 5 mL water, dispersing 0.2 g SBA-15C obtained in the step (4) in copper nitrate water solution, carrying out ultrasonic treatment for 30 minutes, then placing the copper nitrate water solution in a box, drying at 90 ℃ for 5 hours, and grinding the dried blue precipitate for 10-30 minutes to obtain dry blue solid powder;
(6) 0.053 g of 1,3, 5-benzene tricarboxylic acid is weighed and dissolved in 10 mL ethanol solution, the solution is added into the blue solid powder obtained in the step (5) to be dissolved in 10 mL water, the solution is ultrasonically treated for 30 minutes, stirred at room temperature for 30 minutes, the blue solution is placed in 120 ℃ for hydrothermal reaction for 12 hours and then cooled to room temperature, distilled water and ethanol are respectively washed for three times, suction filtration is carried out, the obtained blue precipitate is then placed in a vacuum drying box for drying at 80 ℃ for 10 hours, and the dried blue precipitate is ground for 10-30 minutes, so as to obtain the HKUST-1@SBA-15C composite material which is in a blue powder shape.
Comparative example 1
(1) Weighing 2.0 g of P123, dissolving in 60 mL concentration 2 mol/L dilute hydrochloric acid, adding 7.5 mL water, and magnetically stirring at 40 ℃ until P123 is completely dissolved to obtain a clear solution containing a structure directing agent;
(2) Adding 4 g tetraethoxysilane and 0.43 g triphosphoryl propionic acid to the clear solution prepared in the step (1), wherein the molar ratio of the tetraethoxysilane to the triphosphoryl propionic acid is 7:1, after the dripping is finished, continuously heating and stirring for 24 hours at 35 ℃ to gradually convert the mixture into sol;
(3) The sol used in the step (2) is put into a vacuum drying box to be dried for 10 hours at 80 ℃, and the dried white precipitate is ground for 10-30 minutes to obtain dry white solid powder;
(4) Adding the white powder obtained in the step (3) into 400 mL ethanol solution, dropwise adding 1.5 mL concentrated hydrochloric acid into the solution, extracting for 24 hours at the temperature of 80 ℃ under condensation reflux, filtering, placing the obtained white precipitate in a vacuum drying oven, drying for 10 hours at the temperature of 80 ℃, and grinding the dried white precipitate for 10-30 minutes to obtain dry white solid powder;
(5) Weighing 0.085 g copper nitrate powder, dissolving in 5 mL water, dispersing 0.2 g SBA-15C obtained in the step (4) in copper nitrate water solution, carrying out ultrasonic treatment for 30 minutes, then placing the copper nitrate water solution in a box, drying at 90 ℃ for 5 hours, and grinding the dried blue precipitate for 10-30 minutes to obtain dry blue solid powder;
(6) 0.053 g of 1,3, 5-benzene tricarboxylic acid is weighed and dissolved in 10 mL ethanol solution, the solution is added into the blue solid powder obtained in the step (5) to be dissolved in 10 mL water, the solution is ultrasonically treated for 30 minutes, stirred at room temperature for 30 minutes, the blue solution is placed in 120 ℃ for hydrothermal reaction for 12 hours and then cooled to room temperature, distilled water and ethanol are respectively washed for three times, suction filtration is carried out, the obtained blue precipitate is then placed in a vacuum drying box for drying at 80 ℃ for 10 hours, and the dried blue precipitate is ground for 10-30 minutes, so as to obtain the HKUST-1@SBA-15C composite material which is in a blue powder shape.
Comparative example 2
(1) Weighing 2.0 g of P123, dissolving in 60 mL concentration 2 mol/L dilute hydrochloric acid, adding 7.5 mL water, and magnetically stirring at 40 ℃ until P123 is completely dissolved to obtain a clear solution containing a structure directing agent;
(2) Adding 4 g tetraethoxysilane and 0.32 g triphosphoryl propionic acid to the clear solution prepared in the step (1), wherein the molar ratio of the tetraethoxysilane to the triphosphoryl propionic acid is 9:1, after the dripping is finished, continuously heating and stirring for 24 hours at 35 ℃ to gradually convert the mixture into sol;
(3) The sol used in the step (2) is put into a vacuum drying box to be dried for 10 hours at 80 ℃, and the dried white precipitate is ground for 10-30 minutes to obtain dry white solid powder;
(4) Adding the white powder obtained in the step (3) into 400 mL ethanol solution, dropwise adding 1.5 mL concentrated hydrochloric acid into the solution, extracting for 24 hours at the temperature of 80 ℃ under condensation reflux, filtering, placing the obtained white precipitate in a vacuum drying oven, drying for 10 hours at the temperature of 80 ℃, and grinding the dried white precipitate for 10-30 minutes to obtain dry white solid powder;
(5) Weighing 0.085 g copper nitrate powder, dissolving in 5 mL water, dispersing 0.2 g SBA-15C obtained in the step (4) in copper nitrate water solution, carrying out ultrasonic treatment for 30 minutes, then placing the copper nitrate water solution in a box, drying at 90 ℃ for 5 hours, and grinding the dried blue precipitate for 10-30 minutes to obtain dry blue solid powder;
(6) 0.053 g of 1,3, 5-benzene tricarboxylic acid is weighed and dissolved in 10 mL ethanol solution, the solution is added into the blue solid powder obtained in the step (5) to be dissolved in 10 mL water, the solution is ultrasonically treated for 30 minutes, stirred at room temperature for 30 minutes, the blue solution is placed in 120 ℃ for hydrothermal reaction for 12 hours and then cooled to room temperature, distilled water and ethanol are respectively washed for three times, suction filtration is carried out, the obtained blue precipitate is then placed in a vacuum drying box for drying at 80 ℃ for 10 hours, and the dried blue precipitate is ground for 10-30 minutes to obtain HKUST-1@SBA-15C composite material which is in a blue powder shape.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to assist in understanding the methods of the present invention and the core ideas thereof; also, it is within the scope of the present invention to be modified by those of ordinary skill in the art in light of the present teachings. In view of the foregoing, this description should not be construed as limiting the invention.
Claims (5)
1. A functionalized silica grafted metal organic framework composite material is characterized in that the structure of the composite material is HKUST-1@SBA-15C, the composite material takes carboxyl functionalized ordered mesoporous silica SBA-15C as a carrier, a metal-organic framework compound HKUST-1 active component is grafted on the carrier, the carrier SBA-15C of the composite material is prepared by co-condensing a carboxyl functionalization reagent and an inorganic silicon source, and the load capacity of the active component HKUST-1 is 10%.
2. The functionalized silica grafted metal organic framework composite of claim 1 wherein the HKUST-1@sba-15C composite is a mesoporous material having an average pore size of 7 nm.
3. The functionalized silica grafted metal organic framework composite of claim 1 wherein the carboxyl functionalizing agent is triphosphoryl propionic acid and the inorganic silicon source is ethyl orthosilicate, the triphosphoryl propionic acid and ethyl orthosilicate being prepared at a molar ratio of 1:8.
4. A method of preparing a functionalized silica grafted metal organic framework composite according to any of claims 1 to 3, comprising the steps of:
(1) Weighing 2.0 g of P123, dissolving in 60 mL concentration 2 mol/L dilute hydrochloric acid, adding 7.5 mL water, and magnetically stirring at 40 ℃ until P123 is completely dissolved to obtain a clear solution containing a structure directing agent;
(2) Adding 4 g tetraethoxysilane and 0.37 g triphosphoryl propionic acid to the clear solution prepared in the step (1), wherein the molar ratio of the tetraethoxysilane to the triphosphoryl propionic acid is 8:1, after the dripping is finished, continuously heating and stirring for 24 hours at 35 ℃ to gradually convert the mixture into sol;
(3) The sol used in the step (2) is put into a vacuum drying box to be dried for 10 hours at 80 ℃, and the dried white precipitate is ground for 10-30 minutes to obtain dry white solid powder;
(4) Adding the white powder obtained in the step (3) into 400 mL ethanol solution, dropwise adding 1.5 mL concentrated hydrochloric acid into the solution, extracting 24 h under the condition of condensing reflux at 80 ℃, filtering, drying the obtained white precipitate for 10 hours at 80 ℃ in a vacuum drying oven, and grinding the dried white precipitate for 10-30 minutes to obtain dry white solid powder;
(5) Weighing 0.085 g copper nitrate powder, dissolving in 5 mL water, dispersing 0.2 g SBA-15C obtained in the step (4) in copper nitrate water solution, carrying out ultrasonic treatment for 30 min, then placing the solution in a box, drying at 90 ℃ for 5 hours, and grinding the dried blue precipitate for 10-30 min to obtain dry blue solid powder;
(6) Weighing 0.053 g of 1,3, 5-benzene tricarboxylic acid, dissolving in 10 mL ethanol solution, adding the solution into the blue solid powder obtained in the step (5), dissolving in 10 mL water, carrying out ultrasonic treatment for 30 min, stirring at room temperature for 30 min, placing the blue solution in 120 ℃ for hydrothermal reaction for 12 h, cooling to room temperature, respectively washing with distilled water and ethanol for three times, carrying out suction filtration, placing the obtained blue precipitate in a vacuum drying oven, drying at 80 ℃ for 10 h, and grinding the dried blue precipitate for 10-30 min to obtain the HKUST-1@SBA-15C composite material in a blue powder shape.
5. Use of a composite material according to any one of claims 1-3, characterized in that the composite material is used as a catalyst in a reduction reaction.
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CN110369003A (en) * | 2019-07-25 | 2019-10-25 | 长春工业大学 | A kind of phosphotungstic acid titanium silicon composite and preparation method thereof with meso-hole structure |
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YIBO ZHANG ETAL.: "Synthesis of HKUST-1 embedded in SBA-15 functionalized with carboxyl groups as a catalyst for 4-nitrophenol to 4-aminophenol", 《APPLIED SURFACE SCIENCE》, vol. 573, 11 October 2021 (2021-10-11), pages 1 - 6 * |
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