CN111793218B - Preparation method and application of Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material - Google Patents
Preparation method and application of Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 55
- 239000003446 ligand Substances 0.000 title claims abstract description 50
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000002262 Schiff base Substances 0.000 title claims abstract description 47
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 47
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 51
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 238000007146 photocatalysis Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 239000011941 photocatalyst Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000002791 soaking Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- -1 polytetrafluoroethylene Polymers 0.000 claims description 24
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 24
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 13
- 239000007790 solid phase Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
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- 230000001678 irradiating effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000013032 photocatalytic reaction Methods 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 2
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- 238000002156 mixing Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 55
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 31
- 239000011701 zinc Substances 0.000 description 27
- 239000010949 copper Substances 0.000 description 26
- 238000004817 gas chromatography Methods 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000002329 infrared spectrum Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MPEUYAFVSNLHNG-UHFFFAOYSA-N 4-[2-[10-[2-(4-carboxyphenyl)ethynyl]anthracen-9-yl]ethynyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C#CC(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C#CC1=CC=C(C(O)=O)C=C1 MPEUYAFVSNLHNG-UHFFFAOYSA-N 0.000 description 1
- KVQMUHHSWICEIH-UHFFFAOYSA-N 6-(5-carboxypyridin-2-yl)pyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=N1 KVQMUHHSWICEIH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019695 Nb2O6 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- C08G83/008—Supramolecular polymers
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- 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]
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- 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
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
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- B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
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Abstract
The invention relates to a preparation method and application of a Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material, and aims to solve the problem of the existing MOFs photocatalysis CO2The reduction efficiency of (2) is low. The preparation method comprises the following steps: adding Schiff base dicarboxylic acid ligand and organic medium into the inner container of the reaction kettle, dissolving Zn salt or Cu salt in organic solvent, and adding HNO3And (3) mixing the solutions, reacting at 90-120 ℃, washing, soaking and drying to obtain the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material. The application is that Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework materials are used as a photocatalyst for photocatalysis of CO2And (4) reducing. The invention prepares the metal organic framework catalyst with good performance by designing the ligand and the central metal, shows good reduction efficiency and realizes better carbon dioxide photocatalytic reduction performance.
Description
Technical Field
The invention relates to a synthesis method of a Zn and Cu metal-organic framework material containing Schiff base dicarboxylic acid ligand, and application of the metal-organic framework material in photocatalysis of CO2Application in reduction.
Background
The rapid development of national economy has continued to increase the demand for fossil energy, and in particular, the consumption of fossil fuels has increased. The currently used fossil fuel coal, oil and natural gas are non-renewable energy sources. As its consumption increases, supply is necessarily strained. In addition, fossil fuels produce large amounts of carbon dioxide during combustion, resulting in an increasing carbon dioxide content in the atmosphere. Carbon dioxide can cause greenhouse effect and has certain influence on climate change. It is statistical that the concentration of carbon dioxide in the atmosphere is rising continuously, reaching 390ppm in 2011, and thereafter, the concentration of carbon dioxide in the atmosphere is continuously increasing. The emission of carbon dioxide is expected to increase further in the next decades. Therefore, the comprehensive utilization of carbon dioxide is of great significance from the viewpoints of resource saving, environmental protection and sustainable development.
The method for preparing chemical products by taking carbon dioxide as a raw material is an effective application for balancing carbon circulation and reducing carbon dioxide emissionOne of the diameters. In addition, the carbon dioxide is converted into fuel, so that a renewable energy source is hopefully provided. Has great practical significance for saving energy. Inspired by photosynthesis in nature, researchers have made active efforts in the field of photocatalytic carbon dioxide reduction using direct sunlight to produce simple C1/C2 fuels (e.g., CO, CH) by introducing solar energy into the carbon dioxide reduction process using a suitable photocatalyst4、CH3OH、C2H5OH, HCHO and HCOO-Etc.). Solar energy is a renewable energy source, the photocatalysis method can effectively utilize the solar energy, has the advantages of environmental protection and economy, and becomes a method for treating CO in recent years2An effective method of (1).
Early used photocatalyst was TiO2Photocatalytic reduction of carbon dioxide has been possible, and subsequently a number of inorganic semiconductor photocatalysts have been developed, including WO3，Sr2Nb2O6、Bi2WO6And the like. However, most inorganic semiconductors have a large band gap width, show photocatalytic activity only in the ultraviolet light range, and in addition, their inherent non-porous structure causes photocatalytic reaction to proceed only at the outer surface, thereby affecting catalytic performance.
The Metal Organic Frameworks (MOFs) are porous crystalline materials with a network structure, which are formed by self-assembling metal ions or oxygen clusters thereof and organic ligands through chemical coordination bonds. The MOFs has the advantages of large specific surface area, adjustable aperture and shape, large pores, long channels and the like, shows excellent performance in the aspects of gas storage and separation, catalysis, chemical sensing and the like, and is widely concerned. At present, MOFs are in CO2By adjusting the pore structure and surface charge of the MOFs, excellent performance can be obtained. In the photocatalysis of CO2In reduction, MOFs are usually used as photocatalysts, wherein organic ligands absorb visible light, metal is used as an active site, and solar photocatalysis is utilized to reduce CO2. Wang et al (Journal of the American Chemical Society,2011,133:13445-13454) synthesized a visible-light-responsive photosensitizer function using a 2,2 '-bipyridine-5, 5' -dicarboxylic acid ligand coordinated to rhenium and then complexed with zirconium ionsThe MOF photocatalyst is used for catalyzing and reducing CO under visible light2CO is generated. Li et al (Chemical Science,2014,5:3808-2Reducing power. Xu et al (Journal of the American Chemical Society,2015,137:13440-2Photoreduction efficiency. Chen et al (Journal of Materials Chemistry A,2016,4:2657-2662) synthesized a metal-organic framework material by reacting an electron-rich conjugated linker 4,4' - (anthracene-9, 10-diylbis (acetylene-2, 1-diyl)) dibenzoic acid with zirconium tetrachloride, which can catalytically reduce CO under visible light2Generating HCOO-。
Researchers have made a great deal of research on the catalytic conversion of carbon dioxide. Due to CO2Is thermodynamically very stable, and its selective activation and transformation are difficult. Therefore, how to prepare a high-efficiency catalyst and improve the conversion efficiency of carbon dioxide become a main problem in the field. From the current research, although MOFs are in photocatalysis of CO2Although some progress is made in reduction, from the practical application point of view, the development of a metal organic framework material with more excellent performance is necessary to realize better high-efficiency photocatalysis of CO2And (4) reducing.
Disclosure of Invention
The invention aims to solve the problem of the existing MOFs photocatalytic CO2The reduction efficiency is low, and provides a preparation method and application of Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework materials.
The preparation method of the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material is realized according to the following steps:
to a reaction vesselAdding Schiff base dicarboxylic acid ligand and organic medium into polytetrafluoroethylene inner container, and adding Zn (NO)3)2·6H2O or Cu (NO)3)2·3H2Dissolving O in organic solvent to obtain metal salt solution, adding the metal salt solution into the inner container of polytetrafluoroethylene, adding HNO3Stirring the solution for 0.5-2 hours, then placing a polytetrafluoroethylene inner container into a reaction kettle, reacting for 18-36 hours at 90-120 ℃, terminating the reaction, (slowly) cooling to room temperature, filtering the reaction solution, washing the collected solid phase substance for multiple times by using an organic solvent, soaking in the organic solvent, washing and drying to obtain the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material;
the Schiff base dicarboxylic acid ligand is
Or
The application of the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material is to use the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material as a photocatalyst for photocatalysis of CO2And (4) reducing.
The invention utilizes Schiff base dicarboxylic acid ligand to synthesize zinc and copper metal organic framework materials, and the metal organic framework materials can reduce carbon dioxide by photocatalysis. The zinc and the copper have the advantages of low cost, good stability of the formed metal organic framework and the like. In addition, zinc and copper are used as the centers of the metal clusters, so that the semiconductor has better semiconductor performance. The Schiff base dicarboxylic acid ligand of the invention contains a larger conjugated structure, which is beneficial to enhancing and expanding spectrum absorption, and-OH groups introduced into the organic ligand can enhance the interaction with carbon dioxide molecules and is beneficial to improving the catalytic performance of a metal organic framework. The invention prepares the metal organic framework catalyst with good performance by designing the ligand and the central metal, shows good reduction efficiency, realizes better carbon dioxide photocatalytic reduction performance, and has the formaldehyde yield of 65 mu mol g-1h-1The above.
Drawings
FIG. 1 shows the metal-organic framework C obtained in example3(ii) an infrared spectrum;
FIG. 2 shows the metal-organic framework C obtained in the example4(ii) an infrared spectrum;
FIG. 3 is a graph showing the performance of photocatalytic carbon dioxide reduction by using different solvent sacrificial agents in six and seven of the application examples, wherein 1 represents CH3CN + TEOA, 2 for DMF + TEOA, 3 for CH3CN + TEA, 4 represents DMF + TEA;
FIG. 4 is a graph showing the measurement of the amount of formaldehyde generated in the eighth, ninth and tenth application examples with the change of temperature;
FIG. 5 is a graph showing the reduction performance of photocatalytic carbon dioxide measured by the amount of catalyst used in the twelfth application example.
Detailed Description
The first embodiment is as follows: the preparation method of the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material is implemented according to the following steps:
the preparation method of the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material is realized according to the following steps:
adding Schiff base dicarboxylic acid ligand and organic medium into a polytetrafluoroethylene inner container of a reaction kettle, and then adding Zn (NO)3)2·6H2O or Cu (NO)3)2·3H2Dissolving O in organic solvent to obtain metal salt solution, adding the metal salt solution into the inner container of polytetrafluoroethylene, adding HNO3Stirring the solution for 0.5-2 hours, then placing a polytetrafluoroethylene inner container into a reaction kettle, reacting for 18-36 hours at 90-120 ℃, terminating the reaction, (slowly) cooling to room temperature, filtering the reaction solution, washing the collected solid phase substance for multiple times by using an organic solvent, soaking in the organic solvent, washing and drying to obtain the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material;
the Schiff base dicarboxylic acid ligand is
Or
The second embodiment is as follows: the present embodiment differs from the first embodiment in that the Schiff base dicarboxylic acid ligand and Zn (NO)3)2·6H2O or Cu (NO)3)2·3H2The molar ratio of O is 1: 1.5-1: 3.
The third concrete implementation mode: this embodiment differs from the first or second embodiment in that the organic medium is N, N-Dimethylformamide (DMF), N-Diethylformamide (DEF), or methanol (CH)3OH) is used.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is that the organic solvent is one or more of DMF, DEF, methanol, Tetrahydrofuran (THF), and acetone.
The fifth concrete implementation mode: the present embodiment is different from one of the first to fourth embodiments in that the HNO3The concentration of the solution is 1-5 mol/L.
HNO of the present embodiment3The addition amount of the solution is 50-200 mu L.
The sixth specific implementation mode: the present embodiment is different from the first to the fifth embodiments in that the soaking treatment time in the organic solvent is 24 to 48 hours.
The seventh embodiment: the application of the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material of the embodiment is to use the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material as a photocatalyst for photocatalysis of CO2And (4) reducing.
The specific implementation mode is eight: the seventh embodiment is different from the seventh embodiment in that the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material is used as a photocatalyst for catalyzing CO2The reduction process is as follows:
adding Schiff base dicarboxylic acid ligand Zn, Cu metal organic framework material, sacrificial agent, solvent and deionized water into a reaction bottle, carrying out nitrogen bubbling and carbon dioxide bubbling in sequence, and carrying out photocatalytic reaction under the illumination of a xenon lamp.
The dosage of the Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework material is 10-50mg, the solvent is 5-50mL, the sacrificial agent is 1-5mL, and the deionized water is 1-5 mL.
The specific implementation method nine: the difference between this embodiment and the eighth embodiment is that the sacrificial agent is triethanolamine, triethylamine, or a mixture of the two.
The detailed implementation mode is ten: the eighth embodiment is different from the eighth embodiment in that the light irradiation is performed by a xenon lamp, and the photocatalytic reaction time is 3 to 10 hours at a temperature of 25 to 50 ℃.
Example 1: the preparation method of the Schiff base dicarboxylic acid ligand Zn metal organic framework material is implemented according to the following steps:
adding Schiff base dicarboxylic acid ligand L into a polytetrafluoroethylene inner container of a reaction kettle1(0.16g, 0.40mmol) and 50mL of DMF, followed by addition of Zn (NO)3)2·6H2Dissolving O (0.24g, 0.8mmol) in DMF solution (6mL) to obtain metal salt solution, adding the metal salt solution into the inner container of polytetrafluoroethylene, adding 3mol/L HNO3Stirring for 0.5 hr, adding polytetrafluoroethylene liner into reaction kettle, drying at 100 deg.C for 36 hr, stopping reaction, slowly cooling to room temperature, filtering the reaction solution, collecting solid phase, and adding DMF/CH3OH is washed for 3 times, then soaked in acetone for 36 hours, washed for 3 times by acetone and dried to obtain the zinc metal organic framework material C1(brown solid).
Example 2: the preparation method of the Schiff base dicarboxylic acid ligand Zn metal organic framework material is implemented according to the following steps:
adding Schiff base dicarboxylic acid ligand L into a polytetrafluoroethylene inner container of a reaction kettle2(0.18g, 0.35mmol) and 60mL of DMF, followed by addition of Zn (NO)3)2·6H2Dissolving O (0.21g, 0.7mmol) in DMF solution (5mL) to obtain metal salt solution, adding the metal salt solution into the inner container of polytetrafluoroethylene, adding 3mol/L HNO3(150 mu L), stirring for 1 hour, putting the polytetrafluoroethylene liner into a reaction kettle, putting the reaction kettle into a drying box, reacting for 24 hours at 100 ℃, stopping the reaction, (slowing down)Slowly) cooling to room temperature, filtering the reaction solution, collecting the solid phase substance with DMF/CH3OH is washed for 3 times, then soaked in acetone for 24 hours, washed for 3 times by acetone and dried to obtain the zinc metal organic framework material C2(brown solid).
Example 3: the preparation method of the Schiff base dicarboxylic acid ligand Cu metal organic framework material is implemented according to the following steps:
adding Schiff base dicarboxylic acid ligand L into a polytetrafluoroethylene inner container of a reaction kettle1(0.16g, 0.40mmol) and 50mL of DMF, then adding Cu (NO)3)2·3H2Dissolving O (0.19g, 0.8mmol) in DMF solution (5mL) to obtain metal salt solution, adding the metal salt solution into the inner container of polytetrafluoroethylene, adding 3mol/L HNO3(200 mu L), stirring for 0.5 h, placing the polytetrafluoroethylene liner into a reaction kettle, placing the reaction kettle into a drying box, reacting at 100 ℃ for 24 h, stopping the reaction, slowly cooling to room temperature, filtering the reaction solution, collecting the solid phase substance, and using THF/CH3OH is washed for 3 times, then soaked in acetone for 24 hours, washed for 3 times by acetone and dried to obtain the copper metal organic framework material C3(greenish black solid).
Example 4: the preparation method of the Schiff base dicarboxylic acid ligand Cu metal organic framework material is implemented according to the following steps:
adding Schiff base dicarboxylic acid ligand L into a polytetrafluoroethylene inner container of a reaction kettle2(0.18g, 0.35mmol) and 60mL of DMF, then adding Cu (NO)3)2·3H2Dissolving O (0.17g, 0.7mmol) in DMF solution (5mL) to obtain metal salt solution, adding the metal salt solution into the inner container of polytetrafluoroethylene, adding 3mol/L HNO3Stirring for 0.5 hr (150 μ L), adding polytetrafluoroethylene liner into reaction kettle, drying at 110 deg.C for 24 hr, stopping reaction, slowly cooling to room temperature, filtering the reaction solution, collecting solid phase, and adding DMF/CH3OH is washed for 3 times, then soaked in acetone for 24 hours, washed for 3 times by acetone and dried to obtain the copper metal organic framework material C4(greenish black solid).
Example 5: the preparation method of the Schiff base dicarboxylic acid ligand Cu metal organic framework material is implemented according to the following steps:
adding Schiff base dicarboxylic acid ligand L into a polytetrafluoroethylene inner container of a reaction kettle1(0.16g, 0.40mmol) and 50mL of DMF, then adding Cu (NO)3)2·3H2Dissolving O (0.19g, 0.8mmol) in MeOH solution (5mL) to obtain metal salt solution, adding the metal salt solution into the inner container of polytetrafluoroethylene, adding 5mol/L HNO3(150 mu L), stirring for 1 hour, then placing the polytetrafluoroethylene inner container into a reaction kettle, placing the reaction kettle into a drying box, reacting for 36 hours at the temperature of 100 ℃, stopping the reaction, (slowly) cooling to room temperature, filtering the reaction solution, washing the collected solid phase substance with DMF/THF for 3 times, soaking the solid phase substance in acetone for 24 hours, washing the solid phase substance with acetone for 3 times, and drying to obtain the copper metal organic framework material C3(greenish black solid).
The first application embodiment: mixing the metal organic framework material C1(0.015g), triethanolamine (5mL), deionized water (5mL) and DMF (25mL) were added to the reaction flask, nitrogen was bubbled for 20 minutes, carbon dioxide was bubbled for 30 minutes, and the reaction was terminated by irradiating 300W Xe light with a constant temperature system maintained at 25 ℃ for 7 hours.
The product of this example was analyzed by Gas Chromatography (GC) to give 6.86. mu. mol of formaldehyde (formaldehyde yield: 65umol g)-1h-1)。
Application example two: mixing the metal organic framework material C1(0.015g), triethylamine (2mL), deionized water (2mL) and DMF (6mL) were added to the reaction flask, nitrogen was bubbled for 20 minutes, carbon dioxide was bubbled for 30 minutes, and the reaction was terminated by 300W Xe lamp light reaction at a constant temperature of 25 ℃ for 7 hours.
The product was analyzed by Gas Chromatography (GC). Formaldehyde was obtained in an amount of 5.58. mu. mol.
Application example three: mixing the metal organic framework material C2(0.015g), triethylamine (2mL), deionized water (2mL) and acetonitrile (8mL) were added to the reaction flask, nitrogen was bubbled for 20 minutes, carbon dioxide was bubbled for 30 minutes, and the reaction was terminated by applying 300W Xe lamp light to the flask while maintaining the temperature at 25 ℃ in a constant temperature system for 6 hours.
This example is carried out in the gas phaseThe product was analyzed by chromatography (GC) to give 5.73. mu. mol of formaldehyde (formaldehyde yield: 63umol g)-1h-1)。
Application example four: mixing the metal organic framework material C2(0.010g), triethanolamine (3mL), deionized water (3mL) and DMF (9mL) were added to a reaction flask, nitrogen was bubbled for 20 minutes, carbon dioxide was bubbled for 30 minutes, and a constant temperature system was maintained at 25 ℃ and Xe lamp at 300W was irradiated for 6 hours to terminate the reaction.
The product was analyzed by Gas Chromatography (GC). Formaldehyde was obtained in 6.77. mu. mol.
Application example five: mixing the metal organic framework material C2(0.015g), triethylamine (2mL), deionized water (2mL) and DMF (10mL) were added to the reaction flask, nitrogen was bubbled for 20 minutes, carbon dioxide was bubbled for 30 minutes, and the reaction was terminated by 300W Xe lamp light reaction at a constant temperature of 35 ℃ for 7 hours.
The product of this example was analyzed by Gas Chromatography (GC) to give 9.33. mu. mol of formaldehyde (formaldehyde yield: 88umol g)-1h-1)。
Application example six: respectively adding a metal organic framework material C into two reaction bottles2(0.010g), triethanolamine (2mL) and deionized water (3mL), acetonitrile (6mL) and DMF (6mL) were added to each of the two reaction vials, and the mixture was bubbled with nitrogen for 20 minutes and carbon dioxide for 30 minutes, while maintaining the temperature at 25 ℃ in a constant temperature system and irradiating with 300W Xe light for 7 hours to terminate the reaction.
This example analyzed the product in both reaction vials by Gas Chromatography (GC) to give 7.75. mu. mol and 9.31. mu. mol formaldehyde (as shown in FIG. 3).
Application example seven: respectively adding a metal organic framework material C into two reaction bottles2(0.010g), triethylamine (2mL) and deionized water (3mL) were added to the reaction flask, and acetonitrile (6mL) and DMF (6mL) were bubbled with nitrogen and carbon dioxide for 20 minutes and 30 minutes, respectively, and the reaction was terminated by irradiating 300W Xe light with a constant temperature system maintained at 25 ℃ for 7 hours.
This example analyzed the product in both reaction vials by Gas Chromatography (GC) to yield 3.83. mu. mol and 3.92. mu. mol formaldehyde (as shown in FIG. 3).
Application example eight: mixing the metal organic framework material C2(0.015g), triethanolamine (2mL), deionized water (2mL) and DMF (6mL) were added to the reaction flask, nitrogen was bubbled for 20 minutes, carbon dioxide was bubbled for 30 minutes, and the reaction was terminated by irradiating 300W Xe light with a constant temperature system maintained at 25 ℃ for 6 hours.
The product was analyzed by Gas Chromatography (GC). Formaldehyde was obtained in an amount of 6.73. mu. mol (as shown in FIG. 4).
Application example nine: mixing the metal organic framework material C2(0.015g), triethanolamine (2mL), deionized water (2mL) and DMF (6mL) were added to the reaction flask, nitrogen was bubbled for 20 minutes, carbon dioxide was bubbled for 30 minutes, and the reaction was terminated by irradiating 300W Xe light with a constant temperature system maintained at 35 ℃ for 6 hours.
The product was analyzed by Gas Chromatography (GC) in this example to give 7.12. mu. mol formaldehyde (as shown in FIG. 4).
Application example ten: mixing the metal organic framework material C2(0.015g), triethanolamine (2mL), deionized water (2mL) and DMF (6mL) were added to the reaction flask, nitrogen was bubbled for 20 minutes, carbon dioxide was bubbled for 30 minutes, and the reaction was terminated by irradiating 300W Xe light with a constant temperature system maintained at 50 ℃ for 6 hours.
The product was analyzed by Gas Chromatography (GC) in this example to give 9.36. mu. mol formaldehyde (as shown in FIG. 4).
Application example eleven: a metal organic framework C3(0.015g), triethanolamine (3mL), deionized water (3mL) and DMF (12mL) were added to the reaction flask, nitrogen was bubbled for 20 minutes, carbon dioxide was bubbled for 30 minutes, and the reaction was terminated by irradiating 300W Xe light with a constant temperature system maintained at 25 ℃ for 7 hours.
The product was analyzed by Gas Chromatography (GC) in this example to give 6.06. mu. mol of formaldehyde.
Application example twelve: respectively adding 0.010g, 0.015g, 0.020g and 0.025g of metal organic framework material C into four reaction bottles2Respectively adding intoTriethanolamine (2mL), deionized water (4mL) and DMF (8mL), nitrogen bubbling for 20 minutes, carbon dioxide bubbling for 30 minutes, and Xe lamp light reaction at 300W with a constant temperature system maintained at 25 ℃ for 6 hours to terminate the reaction.
This example was analyzed by Gas Chromatography (GC) for the product in 4 reaction vials. The obtained formaldehyde was 7.83, 9.32, 8.57, 7.86. mu. mol (as shown in FIG. 5).
Application example thirteen: mixing the metal organic framework material C1(0.020g), triethylamine (2mL), deionized water (2mL) and acetonitrile (8mL) were added to the reaction flask, nitrogen was bubbled for 20 minutes, carbon dioxide was bubbled for 30 minutes, and the reaction was terminated by applying 300W Xe lamp light at a constant temperature of 35 ℃ for 6 hours.
The product was analyzed by Gas Chromatography (GC) in this example to give 6.69. mu. mol formaldehyde and 1.36. mu. mol formic acid.
Claims (4)
1. The application of Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework materials is realized according to the following steps:
adding Schiff base dicarboxylic acid ligand and organic medium into a polytetrafluoroethylene inner container of a reaction kettle, and then adding Zn (NO)3)2·6H2O or Cu (NO)3)2·3H2Dissolving O in organic solvent to obtain metal salt solution, adding the metal salt solution into the inner container of polytetrafluoroethylene, adding HNO3Stirring the solution for 0.5-2 hours, then placing a polytetrafluoroethylene inner container into a reaction kettle, reacting for 18-36 hours at 90-120 ℃, stopping the reaction, cooling to room temperature, filtering the reaction solution, washing the collected solid phase substance for multiple times by using an organic solvent, soaking in the organic solvent, washing and drying to obtain Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework materials;
the Schiff base dicarboxylic acid ligand is
Or
The method is characterized in that Schiff base dicarboxylic acid ligand Zn and Cu metal organic framework materials are used as photocatalysts for photocatalysis of CO2And (4) reducing.
2. The use of the Schiff base dicarboxylic acid ligand Zn, Cu metal organic framework material according to claim 1, wherein the Schiff base dicarboxylic acid ligand Zn, Cu metal organic framework material is used as a photocatalyst for photocatalysis of CO2The reduction process is as follows:
adding Schiff base dicarboxylic acid ligand Zn, Cu metal organic framework material, sacrificial agent, solvent and deionized water into a reaction bottle, carrying out nitrogen bubbling and carbon dioxide bubbling in sequence, and carrying out photocatalytic reaction under the illumination of a xenon lamp.
3. The use of Schiff base dicarboxylic acid ligand Zn, Cu metal organic framework material according to claim 2, wherein the sacrificial agent is triethanolamine, triethylamine or a mixture of the two.
4. The application of the Schiff base dicarboxylic acid ligand Zn and Cu metal-organic framework material according to claim 2, wherein the application is characterized in that the application is realized by irradiating with a xenon lamp, and the photocatalytic reaction time is 3-10 hours at 25-50 ℃.
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