CN114479100A - Boron-containing zirconium-based metal organic framework material UiO-67-B and preparation method and application thereof - Google Patents
Boron-containing zirconium-based metal organic framework material UiO-67-B and preparation method and application thereof Download PDFInfo
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 55
- 239000013096 zirconium-based metal-organic framework Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000013110 organic ligand Substances 0.000 claims abstract description 12
- 150000003754 zirconium Chemical class 0.000 claims abstract description 12
- 230000001699 photocatalysis Effects 0.000 claims abstract description 11
- 238000004729 solvothermal method Methods 0.000 claims abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 9
- HGHPQUIZVKPZEU-UHFFFAOYSA-N boranylidynezirconium Chemical compound [B].[Zr] HGHPQUIZVKPZEU-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 19
- 238000006352 cycloaddition reaction Methods 0.000 claims description 18
- 239000011941 photocatalyst Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 11
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
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- 150000002118 epoxides Chemical class 0.000 claims 1
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- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
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- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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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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Abstract
The invention discloses a boron-zirconium-based metal organic framework material UiO-67-B containing boron, a preparation method and application thereof, wherein the preparation method comprises the following steps: zirconium salt and 4- (carboxyl) biphenyl-4-boric acid organic ligand are mixed to carry out solvothermal reaction to obtain the boron-containing zirconium-based metal organic framework material UiO-67-B. The invention is based on UiO-67, and introduces boron into a metal organic framework by changing the type of an organic ligand. Through experiments, the 4- (carboxyl) biphenyl-4-boracic acid is adoptedThe 4, 4' -biphenyl dicarboxylic acid has no influence on the topological structure, and boron and CO are introduced2The lone pair of electrons of the intermediate oxygen and the electron-deficient boron interact to generate chemical adsorption, thereby obviously improving the CO2Adsorption and activation capacity. Meanwhile, the introduction of boron enhances the Lewis acidity of the catalyst, and promotes the carrier separation and charge transmission, thereby obviously improving the photocatalytic effect.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a boron-zirconium-based metal organic framework material UiO-67-B and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
CO2Has resulted in severe greenhouse effect and global warming, and therefore CO2Capture and conversion of (2) to eliminate CO2The rise in level is of great importance. In various CO2In the conversion reaction, CO2Cycloaddition with epoxy compounds is a preferred mode. The atom utilization rate in the reaction is 100%, and the product cyclic carbonate is widely applied in the fields of medicine and fine chemical industry.
According to the study of the inventors, CO is known2Two major technical difficulties exist in the cycloaddition reaction, one is the capture and ring-opening of epoxide, and the other is CO2Capture and activation. This process is not difficult, however, since a large number of studies have now found that lewis acids act as capture sites for epoxides and promote the ring opening of the epoxide with the aid of a cocatalyst such as tetrabutylammonium bromide. In contrast, due to CO2The bond energy of the medium carbon oxygen bond (C ═ O) is large (+805kJ mol-1) Result in CO2Activation of (a) is not easy.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a boron-containing zirconium-based metal organic framework material UiO-67-B and a preparation method and application thereof.
In order to realize the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a preparation method of a boron-containing zirconium-based metal organic framework material UiO-67-B, which comprises the following steps: zirconium salt and 4- (carboxyl) biphenyl-4-boric acid organic ligand are mixed to carry out solvothermal reaction to obtain the boron-containing zirconium-based metal organic framework material UiO-67-B.
In a second aspect, the invention provides a boron-containing zirconium-based metal organic framework material UiO-67-B prepared by the preparation method.
In a third aspect, the invention provides the use of the boron-containing zirconium-based metal organic framework material as CO2Use as adsorbent or as photocatalyst, especially as CO2Application in cycloaddition reaction photocatalyst.
In a fourth aspect, the invention provides a photocatalyst, which comprises a carrier and an active substance loaded on the carrier, wherein the active substance is the boron-containing zirconium-based metal organic framework material UiO-67-B.
In a fifth aspect, the present invention provides a CO2A cycloaddition reaction process comprising the steps of: under light conditions, with CO2And an epoxide as starting material, photocatalytic CO2Preparing cyclic carbonate through cycloaddition reaction, wherein the photocatalyst of the photocatalytic reaction is the boron-containing zirconium-based metal organic framework material or the photocatalyst.
The above one or more embodiments of the invention achieve the following advantageous effects:
the invention is based on UiO-67, and introduces boron into a metal organic framework by changing the type of an organic ligand. Experiments show that 4- (carboxyl) biphenyl-4-boric acid is adopted to replace 4, 4' -biphenyldicarboxylic acid, the topological structure of the compound is not influenced, and boron and CO are introduced2The lone pair of electrons of the intermediate oxygen and the electron-deficient boron interact to generate chemical adsorption, thereby obviously improving the CO2Adsorption and activationAnd (4) capacity of transformation. Meanwhile, the introduction of boron enhances the Lewis acidity of the catalyst, and promotes the carrier separation and charge transmission, thereby obviously improving the photocatalytic effect.
Taking 4- (carboxyl) biphenyl-4-boric acid as a boron-containing organic ligand and zirconium salt as a metal source, and carrying out solvothermal reaction in an organic solvent to obtain a precipitate of the boron-zirconium-containing metal organic framework material UiO-67-B. The metal organic framework has larger specific surface area, thereby being beneficial to CO2And boron in the metal organic framework as CO2The synergistic effect of the two greatly improves CO2Adsorption and activation capacity of.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron microscope image of a boron-containing zirconium-based metal organic framework material UiO-67-B prepared in example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of the boron-containing zirconium-based metal organic framework material UiO-67-B prepared in example 1 of the present invention.
FIG. 3 is an X-ray photoelectron spectrum of the boron-containing zirconium-based metal organic framework material UiO-67-B prepared in example 1 of the present invention.
FIG. 4 is a Fourier transform infrared spectrum of a boron-containing zirconium-based metal organic framework material UiO-67-B prepared in example 1 of the present invention.
FIG. 5 is a graph showing the CO content of the boron-containing zirconium-based metal organic framework material UiO-67-B prepared in example 1 of the present invention and the zirconium-based metal organic framework material UiO-67 prepared in comparative example 12Adsorption and desorption comparison graph.
FIG. 6 shows the photocatalytic CO under simulated sunlight irradiation of the boron-containing zirconium-based metal organic framework material UiO-67-B prepared in example 1 of the present invention and the zirconium-based metal organic framework material UiO-67 prepared in comparative example 12Comparative performance plots of cycloaddition reaction rates.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The industrial use of high temperature and high pressure processes for CO2Cycloaddition reaction, however, has disadvantages such as high energy consumption and high risk. And photocatalytic CO using solar energy as driving force2Cycloaddition reaction has the advantages of cleanness, simplicity, environmental friendliness and the like, and is considered to be the most ideal CO2Cycloaddition reaction pathway. Therefore, development of inexpensive, efficient, stable photocatalysts for the realization of photocatalytic CO2The industrial application of the cycloaddition reaction is of great importance.
In a first aspect, the invention provides a preparation method of a boron-containing zirconium-based metal organic framework material UiO-67-B, which comprises the following steps: zirconium salt and 4- (carboxyl) biphenyl-4-boric acid organic ligand are mixed, and the solvent thermal reaction is carried out under the closed condition to obtain the boron-containing zirconium-based metal organic framework material UiO-67-B.
The boron-containing zirconium-based metal organic framework material UiO-67-B has the same topological structure as UiO-67.
In some embodiments, the zirconium salt is zirconium tetrachloride.
The zirconium salt refers to a compound having a cation of zirconium ion.
In some embodiments, the solvent of the solvothermal reaction is N, N-dimethylformamide.
The main reasons for using N, N-dimethylformamide as a solvent are: the organic ligand is difficult to deprotonate, and N, N-dimethylformamide upon heating can decompose a small amount of dimethylamine, which can facilitate the deprotonation of the ligand, thereby coordinating the ligand with the cation.
In some embodiments, the temperature of the solvothermal reaction is 145-155 deg.C (e.g., 149-151 deg.C, 150-155 deg.C, 152-155 deg.C, etc.). The material prepared at the temperature has better photocatalytic performance.
Preferably, the reaction time is 55-65 h.
In some embodiments, the solvothermal reaction system has a ratio of the feed volume to the reactor volume of 0.5 to 0.7: 1.
In some embodiments, after the zirconium salt and the organic ligand are added into the organic solvent, the mixing time is 15-25 min, so that the materials can be uniformly mixed, and the reaction is facilitated.
Preferably, the molar ratio of the organic ligand to the zirconium salt is 0.9-1.1: 1.
In some embodiments, the solvothermal reaction is completed, and the method further comprises the steps of separating a reaction product precipitate, washing and drying.
Preferably, the washing is performed sequentially with N, N-dimethylformamide and acetone. Using N, N-dimethylformamide: dissolving to remove unreacted ligand; acetone: the main purpose is to remove N, N-dimethylformamide, and N, N-dimethylformamide in MOF pores is easily removed due to smaller acetone molecules, and acetone is extremely easy to volatilize, so that residues are reduced.
Preferably, the drying temperature is 55-65 ℃, and the drying time is 10-24 h.
In a second aspect, the invention provides a boron-containing zirconium-based metal organic framework material UiO-67-B prepared by the preparation method.
In a third aspect, the invention provides the use of said boron-containing zirconium-based metal organic framework material as CO2Use as adsorbent or as photocatalyst, especially as CO2Application in cycloaddition reaction photocatalyst.
In a fourth aspect, the invention provides a photocatalyst, which comprises a carrier and an active substance loaded on the carrier, wherein the active substance is the boron-containing zirconium-based metal organic framework material UiO-67-B.
In a fifth aspect, the present invention provides a CO2A cycloaddition reaction process comprising the steps of: under light conditions, with CO2And an epoxide as starting material, photocatalytic CO2Preparing cyclic carbonate through cycloaddition reaction, wherein the photocatalyst of the photocatalytic reaction is the boron-containing zirconium-based metal organic framework material or the photocatalyst.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
The test materials used in the following examples are all conventional in the art and are commercially available.
Example 1
The preparation method of the boron-containing zirconium-based metal organic framework material UiO-67-B comprises the following steps:
1) weighing 20 ml of N, N-dimethylformamide solvent, weighing 120 mg of zirconium tetrachloride powder, and fully mixing the N, N-dimethylformamide solvent and the zirconium tetrachloride powder and stirring at room temperature for 20 minutes to prepare a first mixed solution;
2) weighing 124 mg of 4- (carboxyl) biphenyl-4-boric acid powder, adding the powder into the first mixed solution obtained in the step 1), and stirring the mixture at room temperature for 20 minutes to prepare a second mixed solution;
3) placing the second mixed solution obtained in the step 2) in a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 60 hours at 150 ℃ to prepare a third mixed solution;
4) filtering the third mixed solution in the step 3), washing the obtained precipitate with N, N-dimethylformamide and acetone, and then carrying out vacuum drying at 60 ℃ for 12 hours to obtain the boron-containing zirconium-based metal organic framework material, which is recorded as UiO-67-B.
Comparative example 1
The preparation method of the zirconium-based metal organic framework material is the same as the preparation method of the embodiment 1, and the difference is that: in the step (2), 124 mg of 4, 4' -biphenyldicarboxylic acid powder is weighed and added into the first mixed solution in the step (1), and the mixture is stirred for 20 minutes at room temperature to prepare a second mixed solution, and the obtained zirconium-based metal organic framework material is marked as UiO-67.
Performance testing
(1) When the boron-containing zirconium-based metal organic framework material UiO-67-B prepared in example 1 is observed under a scanning electron microscope, the result is shown in FIG. 1, and it can be seen from the figure that: the prepared boron-containing zirconium-based metal organic framework material UiO-67-B is in a uniform nanoparticle structure.
(2) The boron-containing zirconium-based metal organic framework material UiO-67-B prepared in example 1 was analyzed for phase and chemical structure, and FIGS. 2, 3 and 4 are respectively an X-ray diffraction spectrum, an X-ray photoelectron spectrum and a Fourier transform infrared spectrum of the prepared boron-containing zirconium-based metal organic framework material UiO-67-B. According to data analysis in the figure, the boron-containing zirconium-based metal organic framework material UiO-67-B still maintains the topological structure of UiO-67, and the introduction of boron has no influence on the crystallinity and the topological structure of the material.
(3) CO was performed on the boron-containing zirconium-based metal organic framework material UiO-67-B prepared in example 1 and the zirconium-based metal organic framework material UiO-67 prepared in comparative example 12Adsorption and desorption test (CO)2Adsorption and desorption testing: with CO2As adsorbates, the CO of samples at room temperature was tested using a gas adsorber2Adsorption and desorption capacities) as shown in fig. 5, from which it can be seen that: introduction of boron to CO2Chemical adsorption is generated, which is favorable for CO2And (4) carrying out reduction.
(4) The boron-containing zirconium-based metal organic framework material UiO-67-B prepared in example 1 and the zirconium-based metal organic framework material UiO-67 prepared in comparative example 1 were subjected to photocatalysis CO under simulated sunlight irradiation2Cycloaddition test (10 mg of catalyst and 0.5 mmol of cocatalyst dispersed in 5 ml of propylene oxide (wherein the cocatalyst is tetrabutylammonium bromide) gives a suspension which is then aerated with CO2，CO2And (5) after the adsorption saturation is achieved, placing the turbid liquid under simulated sunlight for illumination. After 6 hours of the reaction, 100. mu.l of the reaction mixture was taken out, and 1 ml of deionized water and 1 ml of ethyl acetate were added to the reaction mixture, followed by centrifugation. After centrifugation, 2 microliter of the mixture of the ethyl acetate in the upper layer and the propylene carbonate product is injected into GC-MS chromatography, and the propylene carbonate product is detectedYield of ester. The test results are shown in fig. 6, from which it can be seen that: compared with the boron-free zirconium-based metal organic framework material UiO-67, the boron-containing zirconium-based metal organic framework material UiO-67-B can be used for photocatalysis of CO2The cycloaddition reaction shows excellent performance, and the yield of the propylene carbonate is 3.3 times that of the propylene carbonate.
Example 2
The preparation method of the boron-containing zirconium-based metal organic framework material UiO-67-B comprises the following steps:
1) weighing 20 ml of N, N-dimethylformamide solvent, weighing 120 mg of zirconium tetrachloride powder, and fully mixing the N, N-dimethylformamide solvent and the zirconium tetrachloride powder and stirring at room temperature for 20 minutes to prepare a first mixed solution;
2) weighing 124 mg of 4- (carboxyl) biphenyl-4-boric acid powder, adding the powder into the first mixed solution obtained in the step 1), and stirring the mixture at room temperature for 25 minutes to prepare a second mixed solution;
3) placing the second mixed solution obtained in the step 2) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 63 hours at 155 ℃ to prepare a third mixed solution;
4) filtering the third mixed solution in the step 3), washing the obtained precipitate with N, N-dimethylformamide and acetone, and then carrying out vacuum drying at 65 ℃ for 20 hours to obtain the boron-containing zirconium-based metal organic framework material, which is recorded as UiO-67-B.
Example 3
The preparation method of the boron-containing zirconium-based metal organic framework material UiO-67-B comprises the following steps:
1) weighing 20 ml of N, N-dimethylformamide solvent, weighing 120 mg of zirconium tetrachloride powder, and fully mixing the N, N-dimethylformamide solvent and the zirconium tetrachloride powder and stirring at room temperature for 20 minutes to prepare a first mixed solution;
2) weighing 124 mg of 4- (carboxyl) biphenyl-4-boric acid powder, adding the powder into the first mixed solution obtained in the step 1), and stirring the mixture at room temperature for 20 minutes to prepare a second mixed solution;
3) placing the second mixed solution obtained in the step 2) into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 55 hours at 145 ℃ to prepare a third mixed solution;
4) filtering the third mixed solution in the step 3), washing the obtained precipitate with N, N-dimethylformamide and acetone, and then carrying out vacuum drying at 55 ℃ for 18 hours to obtain the boron-containing zirconium-based metal organic framework material, which is recorded as UiO-67-B.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a boron-containing zirconium-based metal organic framework material UiO-67-B is characterized by comprising the following steps: the method comprises the following steps: zirconium salt and 4- (carboxyl) biphenyl-4-boric acid organic ligand are mixed, and the solvent thermal reaction is carried out under the closed condition to obtain the boron-containing zirconium-based metal organic framework material UiO-67-B.
2. The method according to claim 1, wherein the method comprises the steps of: the zirconium salt is zirconium tetrachloride.
3. The method according to claim 1, wherein the method comprises the steps of: the solvent for the solvothermal reaction is N, N-dimethylformamide.
4. The method according to claim 1, wherein the method comprises the steps of: the temperature of the solvothermal reaction is 145-155 ℃;
preferably, the reaction time is 55-65 h;
preferably, the ratio of the volume of the feedstock to the volume of the reactor of the solvothermal reaction system is from 0.5 to 0.7: 1.
5. The method according to claim 1, wherein the method comprises the steps of: after the zirconium salt and the organic ligand are added into the organic solvent, the mixing time is 15-25 min, so that the materials can be uniformly mixed, and the reaction is favorably carried out;
preferably, the molar ratio of the organic ligand to the zirconium salt is 0.9-1.1: 1.
6. The method according to claim 1, wherein the method comprises the steps of: after the solvothermal reaction is finished, the method also comprises the steps of precipitating, separating, washing and drying a reaction product;
preferably, washing is sequentially carried out by adopting N, N-dimethylformamide and acetone;
preferably, the drying temperature is 55-65 ℃, and the drying time is 10-24 h.
7. A boron-containing zirconium-based metal organic framework material UiO-67-B is characterized in that: prepared by the preparation method of any one of claims 1 to 6.
8. The boron-containing zirconium-based metal organic framework material of claim 7 as CO2Use as adsorbent or as photocatalyst, especially as CO2Application in cycloaddition reaction photocatalyst.
9. A photocatalyst, characterized in that: comprises a carrier and an active material loaded on the carrier, wherein the active material is the boron-zirconium-based metal organic framework material UiO-67-B in claim 7.
10. CO (carbon monoxide)2The cycloaddition reaction method is characterized in that: the method comprises the following steps: under light conditions, with CO2And an epoxide as starting material, photocatalytic CO2A cyclic carbonate is prepared by cycloaddition reaction, and the photocatalyst of the photocatalytic reaction is the boron-containing zirconium-based metal organic framework material or the photocatalyst in claim 7.
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