CN112076794B - Cu-MOF material based on triangular organic ligand, and preparation method and application thereof - Google Patents
Cu-MOF material based on triangular organic ligand, and preparation method and application thereof Download PDFInfo
- Publication number
- CN112076794B CN112076794B CN202010921110.7A CN202010921110A CN112076794B CN 112076794 B CN112076794 B CN 112076794B CN 202010921110 A CN202010921110 A CN 202010921110A CN 112076794 B CN112076794 B CN 112076794B
- Authority
- CN
- China
- Prior art keywords
- mof material
- organic ligand
- dmf
- mof
- triangular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000013084 copper-based metal-organic framework Substances 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 81
- 239000013110 organic ligand Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960003506 piperazine hexahydrate Drugs 0.000 claims abstract description 14
- AVRVZRUEXIEGMP-UHFFFAOYSA-N piperazine;hexahydrate Chemical compound O.O.O.O.O.O.C1CNCCN1 AVRVZRUEXIEGMP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- DELUNUNQVWNZKQ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ylidenemethanone Chemical compound O=C=C1CC=CC=C1 DELUNUNQVWNZKQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 12
- XRSQZFJLEPBPOZ-UHFFFAOYSA-N 4-amino-2-methylbenzoic acid Chemical compound CC1=CC(N)=CC=C1C(O)=O XRSQZFJLEPBPOZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 10
- 238000003828 vacuum filtration Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000004729 solvothermal method Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract description 34
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 34
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 21
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 19
- 239000011941 photocatalyst Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 239000003446 ligand Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000004074 biphenyls Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012887 quadratic function Methods 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- B01J35/39—
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/33—
-
- B01J35/40—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a Cu-MOF material based on a triangular organic ligand, which has a chemical formula of { [ Cu { [ 3 (L) 2 (H 2 O) 3 ]·14DMF·16H 2 O} n Wherein H is 3 L is 4,4',4' - [ benzenetriacyltris (carbonyl benzene)]-3,3',3 "-trimethyl-tribenzoic acid, DMF for N, N-dimethylformamide; the invention also discloses a preparation method of the Cu-MOF material, which comprises the following steps: under the closed condition, cu (NO) 3 ) 2 ·3H 2 O, organic ligand H 3 And mixing the L, the template agent piperazine hexahydrate, the N, N-dimethylformamide and the absolute ethyl alcohol, stirring, dropwise adding a concentrated nitric acid solution to adjust the pH, and reacting under the solvothermal condition to obtain the compound. The Cu-MOF material has good thermal stability, and shows good photocatalytic degradation efficiency, water stability and recyclable performance when the methylene blue in water is subjected to photocatalytic degradation.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a Cu-MOF material based on a triangular organic ligand, a preparation method of the Cu-MOF material, and application of the Cu-MOF material.
Background
With the rapid development of industrialization and the explosion of human mouths, human beings discharge a large amount of organic pollutants into water for a long time, which causes severe water pollution and water shortage. These organic contaminants are often toxic and difficult to biodegrade. Organic waste water is in a wide variety, mainly comprising organic dyes, phenols, biphenyls, pesticides, carbohydrates and other categories, and each type of organic pollutant can be subdivided into a plurality of categories. Taking organic dyes as an example, the demand for the application of industrial synthetic dyes in various industrial fields including industrial production processes of paper making, plastics, textiles, leather and food production has been rapidly increasing during the last decades, and the organic wastewater containing dyes discharged from these industrial fields has come to bring about an increasing pollution to water bodies, which has attracted widespread attention all over the world.
Many physical/chemical techniques have been used to remove dyes including coagulation/flocculation, adsorption, chemical oxidation, and photocatalysis. However, there are operational drawbacks, for example, the coagulation/flocculation technique converts the organic dye contaminants dissolved in the water into a large amount of sludge deposits that are difficult to handle; the chemical oxidation technology has extremely high consumption and short service life of the oxidant; the difficulty of adsorbent regeneration treatment of the physical adsorption method can cause secondary pollution to water. Photocatalytic degradation, which is characterized by simple operation, low cost and high efficiency, has proved to be a promising treatment method. However, the development of photodegradation catalysts with efficient visible light utilization efficiency still faces significant challenges. Metal-organic frameworks (MOFs) materials contain conduction and valence bands, corresponding to the outer orbitals of the metal central void and the outer orbitals of the organic part, respectively. The semiconductor material tends to have a broad uv-visible absorption with edges well within the range of the characteristic band gap values of the semiconductor material. The MOFs material with high hydrolysis resistance stability and high visible light absorption and response capability is constructed by reasonably selecting a metal center (semiconductor quantum dot) and an organic linking unit (light absorption antenna), and the MOFs material is taken as a photodegradation catalyst to carry out visible light catalytic degradation on dyes in water, which is a research hotspot at present.
Disclosure of Invention
The invention aims to provide a Cu-MOF material based on a triangular organic ligand.
It is another object of the present invention to provide a method for preparing the above Cu-MOF material based on triangular organic ligands.
A third object of the present invention is to provide the above Cu-MOF material based on triangular organic ligands for photocatalytic degradation of the cationic dye methylene blue in a body of water.
The technical scheme adopted by the invention is that the Cu-MOF material based on the triangular organic ligand has a chemical formula of { [ Cu ] 3 (L) 2 (H 2 O) 3 ]·14DMF·16H 2 O} n Wherein H is 3 L is a triangular organic ligand 4,4' - [ benzene triacyl tri (carbonyl benzene)]-3,3',3 "-trimethyl-tribenzoic acid, DMF for N, N-dimethylformamide;
the crystal structure of the Cu-MOF material belongs to a cubic system, pn-3n space group, and the unit cell parameters are as follows:
α＝90°，β＝90°，γ＝90°。
the invention adopts another technical scheme that the preparation method of the Cu-MOF material based on the triangular organic ligand specifically comprises the following steps:
under closed conditions, copper nitrate trihydrate Cu (NO) 3 ) 2 ·3H 2 O, organic ligand H 3 L, piperazine hexahydrate as template agent, N-dimethylformamide and absolute ethyl alcohol are mixed uniformlyAnd (3) uniformly stirring, dropwise adding a concentrated nitric acid solution to adjust the pH of the reaction system to 4.0-6.0, and reacting under a solvothermal condition to obtain the Cu-MOF material.
The present invention is also characterized in that,
every 0.04mmol of copper nitrate trihydrate and 0.02mmol of organic ligand H 3 L, 0.004mmol of piperazine hexahydrate corresponding to 5mL of N, N-dimethylformamide and 3mL of absolute ethanol; the temperature of the solvothermal reaction is 75 ℃, and the reaction time is 48h.
Triangular organic ligands H 3 The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step a within 15min, dripping triethylamine into the mixed solution obtained in the step a within 10min, reacting in an ice water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, drying the obtained white solid to obtain the organic ligand H 3 L; the drying temperature is 70 ℃, and the drying time is 8h.
The third technical scheme adopted by the invention is that the Cu-MOF material is used for photocatalytic degradation of cationic dye methylene blue in a water body.
The invention has the beneficial effects that the invention adopts transition metal copper ions and a triangular organic ligand H 3 L, constructing a Cu-MOF material through coordination self-assembly, wherein the absorption wavelength range of the material to visible light is 500-800nm, and the material shows excellent visible light response capability; the Cu-MOF material has good thermal stability, and can keep the framework below 188 DEG CThe composite material has good photocatalytic degradation efficiency, water stability and recyclable performance when the methylene blue in water is subjected to photocatalytic degradation. In addition, the preparation method is simple, the reaction condition for applying the photocatalyst degradation is mild, the recovery is easy, and no secondary pollution is caused.
Drawings
FIG. 1 is a drawing showing [ Cu ] of a prepared Cu-MOF material 2 (O 2 C-) 4 ]Secondary structural units (central metal copper and oxygen and nitrogen atoms are labeled in the figure, and carbon atoms are not labeled);
FIG. 2 is a diagram of the coordination environment of the Cu-MOF material prepared (the central metal copper (II) and the oxygen and nitrogen atoms are labeled in the figure, and the carbon atom is not labeled);
FIG. 3 is a three-dimensional block diagram of one of the mononets of the prepared Cu-MOF material;
FIG. 4 is a final three-dimensional structure diagram formed by mutually interpenetrating and nesting two identical three-dimensional mononetwork structures of the prepared Cu-MOF material;
FIG. 5 is a graph of the thermal weight loss of the prepared Cu-MOF-based photocatalyst;
FIG. 6 is an infrared spectrum of the prepared Cu-MOF-based photocatalyst;
FIG. 7 is a simulated X-ray powder diffraction pattern (theoretical value) of a single crystal of the prepared Cu-MOF-based photocatalyst and an actually tested X-ray powder diffraction pattern (actual value) of a large number of crystal samples;
FIG. 8 is a scanning electron microscope image of the prepared Cu-MOF-based photocatalyst;
FIG. 9 is a UV-VIS diffuse reflectance spectrum of the prepared Cu-MOF based photocatalyst;
FIG. 10 is a chart of UV-VIS absorption spectra of methylene blue liquid at various concentrations in water.
FIG. 11 is a standard curve of absorbance Y versus concentration X for the UV-VIS absorption spectra of different concentrations of methylene blue liquid in water.
FIG. 12 is a diagram of the UV-VIS absorption spectrum of an aqueous solution of methylene blue with an initial concentration of 18.02mg/L in water when a Cu-MOF photocatalytic material is used for photocatalytic degradation.
FIG. 13 is a graph showing the concentration ratio C/C of the UV-VIS spectrum of the methylene blue liquid of FIG. 12 0 Curve over time t, wherein C 0 Initial concentration, C real-time concentration.
FIG. 14 is a graph showing the UV-VIS spectra versus the concentration ratio C/C of the methylene blue liquid of FIG. 12 0 Is plotted against time t.
FIG. 15 is a graph of the photocatalytic degradation efficiency of the prepared Cu-MOF photocatalytic material in 5 consecutive cycles of photocatalytic degradation of an aqueous solution of 18.02mg/L methylene blue.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a Cu-MOF material based on a triangular organic ligand, which has a chemical formula of { [ Cu { [ 3 (L) 2 (H 2 O) 3 ]·14DMF·16H 2 O} n In which H 3 L is a triangular organic ligand 4,4' - [ benzene triacyl tri (carbonyl benzene)]-3,3',3 "-trimethyl-tribenzoic acid, DMF for N, N-dimethylformamide, N for a natural number from 1 to positive infinity; triangular organic ligand H 3 The molecular structural formula of L is as follows:
from the construction of a space framework structure, the crystal structure of the solid crystalline material Cu-MOF belongs to a cubic system, pn-3n space group, and unit cell parameters are as follows:
α＝90°，β＝90°，γ＝90°。
the Cu-MOF material is used for carrying out photocatalytic degradation on cationic dye methylene blue in a water body; the method specifically comprises the following steps: pouring a dye solution containing methylene blue into a quartz tube reactor, adding a Cu-MOF material, continuously stirring for 1h-3h in a dark box by isolating light to ensure that adsorption-desorption balance is achieved between the methylene blue and the Cu-MOF, and then continuously stirring for 0.5-1h under the irradiation of a 300W xenon lamp until photocatalytic degradation is completed.
More preferably, the concentration of methylene blue in the dye aqueous solution is controlled to be 0.5-24mg/L, and 5-20mg of Cu-MOF material is added into 60mL of the dye aqueous solution with the concentration; after the photocatalytic degradation is finished, the Cu-MOF material is separated out through centrifugation and recycled according to the method.
The Cu-MOF material provided by the invention has three important conditions for efficiently catalyzing and degrading methylene blue in water by visible light under visible light irradiation simulated by a xenon lamp: firstly, an ultraviolet-visible diffuse reflection (UV-Vis DRS) spectrogram of the photocatalyst shows that the absorption wavelength range of the photocatalyst to visible light is 550-800nm; secondly, the Cu-MOF framework of the photocatalyst has a three-dimensional structure which is embedded in a double penetration way, and the deprotonated aromatic H in the framework 3 The L ligands are highly orderly arranged, so that the light absorption and pi electron supply effects are enhanced, the generation and transfer of photoproduction electrons are promoted, the separation efficiency of photoproduction electrons and holes is improved, and the photocatalysis efficiency is improved.
Infrared spectroscopy tests related to the present invention: the Cu-MOF material was uniformly mixed with potassium bromide powder in a mass ratio of 1.
The invention relates to a test of a thermal weight loss curve: weighing 8-20 mg of naturally dried Cu-MOF material, putting the Cu-MOF material into an alumina crucible, and testing on a thermal weight loss analyzer.
The photocatalytic degradation test related by the invention comprises the following steps: after the Cu-MOF material reaches the adsorption-desorption balance in a dye solution of methylene blue, taking out supernatant liquid at intervals under the irradiation of a 300W xenon lamp, placing the supernatant liquid in a cuvette, and testing the cuvette on an ultraviolet-visible spectrophotometer.
In the Cu-MOF material, 1 Cu 2+ Metal centre with 4H from deprotonation 3 L carboxyl groups of the organic ligand, 2 from H 2 Coordination of O atoms of O molecules to form paddle-like [ Cu ] 2 (O 2 C-) 4 (H 2 O) 2 ]Secondary structural unit, deprotonated H 3 The L ligands are further connected to construct a three-dimensional space network structure, and the two completely same three-dimensional network structures are further mutually interpenetrated and nested to form a final three-dimensional framework structure of the Cu-MOF.
A preparation method of a Cu-MOF material based on a triangular organic ligand specifically comprises the following steps:
under closed conditions, copper nitrate trihydrate Cu (NO) 3 ) 2 ·3H 2 O, organic ligand H 3 L, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol are uniformly mixed, continuously stirred, and dropwise added with concentrated nitric acid solution to adjust the pH of a reaction system to 4.0-6.0, and the mixture is reacted under the solvothermal condition to obtain the Cu-MOF material;
copper nitrate trihydrate, organic ligand H 3 The molar ratio of L to piperazine hexahydrate is 2-4:1:0.2-0.5; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5:1-3; the mass fraction of the concentrated nitric acid solution is 65 percent; the temperature of the solvothermal reaction is 65-85 ℃, and the required reaction time is 24-72 hours;
more preferably, copper nitrate trihydrate and organic ligand H 3 The mol ratio of L to the template piperazine hexahydrate is 2:1:0.2, and the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5:3, specifically 0.02mmol (12.22 mg) of organic ligand H per 0.04mmol (7.18 mg) of copper nitrate trihydrate 3 L, 0.004mmol (0.78 mg) of piperazine hexahydrate, corresponding to 5mL of N, N-dimethylformamide and 3mL of absolute ethanol; the temperature of the solvothermal reaction is 75 ℃, and the reaction time is 48h;
triangular organic ligands H 3 The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step a within 15min, dripping triethylamine into the mixed solution obtained in the step a within 10min, reacting in an ice water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, drying the obtained white solid to obtain the organic ligand H 3 L；
The drying temperature is 70 ℃, and the drying time is 8 hours;
example 1
Organic ligand H 3 L(0.02mmol，12.22mg)、Cu(NO 3 ) 2 ·3H 2 O (0.04mmol, 7.18mg) and piperazine hexahydrate (0.004mmol, 0.78mg) were uniformly mixed in 8.0mL of a mixed solution of N, N-dimethylformamide and absolute ethanol (volume ratio: 5), and then a concentrated nitric acid solution having a mass fraction of 65% was added dropwise thereto to adjust the pH of the reaction system to 5.0, followed by sealing in a 25mL glass vial. And carrying out solvothermal reaction at 75 ℃ for 48 hours, and naturally cooling to room temperature to obtain a dark green Cu-MOF material.
The crystal structure test method and structure of the Cu-MOF material obtained in the above embodiment are the same, and the specific points are as follows:
determination of crystal structure: single crystals of clear, crack-free Cu-MOF material were selected, single crystal structure testing and diffraction data collection were performed at room temperature (about 296K) using a Bruker Aper II CCD type single crystal X-ray diffractometer from Bruker, germany, monochromator monochromated Mo-Ka
And (3) analyzing the crystal structure of the crystal cell parameters obtained by least square correction by adopting a SHELXS-97 software package, and completing the absorption correction of the collected data by adopting an SADABS program. The crystallographic data are shown in table 1, and the crystal structures are shown in fig. 1 to 4.
TABLE 1 crystallographic data Table
The structure of FIG. 1 shows that Cu 2+ With H from 4 deprotonations 3 Carboxy oxygen atom and 2 free H of L ligand 2 The oxygen atom of the O molecule coordinates to construct [ Cu ] with a typical paddle-shaped structure 2 (O 2 C-) 4 (H 2 O) 2 ]A secondary building block.
The structure of FIG. 2 shows that in the asymmetric structural unit of Cu-MOF, there is one deprotonated coordinated H 3 L ligand, 1 [ Cu ] 2 (O 2 C-) 4 (H 2 O) 2 ]A secondary building block.
The structure of FIG. 3 shows that the [ Cu ] of the paddle structure 2 (O 2 C-) 4 (H 2 O) 2 ]Secondary building block, deprotonated H of triangular form 3 The L ligands are further connected to form a three-dimensional space single-net framework structure.
The structure of fig. 4 shows that 2 identical spatial single-net framework junctions are further mutually interpenetrated and nested to form a final three-dimensional double-interpenetration framework structure of the Cu-MOF.
FIG. 5 is a graph of the thermal weight loss of the prepared Cu-MOF material, which shows that the Cu-MOF material undergoes 2 main weight loss stages within the temperature range of 30-800 ℃ when the temperature is raised at 10 ℃/min under flowing nitrogen; a weight loss rate of about 44.76% between 30-187 ℃, resulting from the leaving of small guest molecules and coordinated DMF molecules within the Cu-MOF material cavity; between 188 ℃ and 572 ℃, the weight loss rate of 34.92 percent is from the collapse of the framework of the Cu-MOF material and the decomposition of part of organic ligands; the remaining 20.32% of the mass was undecomposed ligand, ash and CuO, indicating that the Cu-MOF material had good thermal stability.
FIG. 6 is an infrared spectrum of the prepared Cu-MOF material, 3270cm -1 NearbyIs caused by stretching vibration of amide groups on organic ligands of the Cu-MOF material; at 1387cm -1 The nearby stretching vibration peak is attributed to the asymmetric stretching vibration of carbonyl groups on the aromatic ring of the Cu-MOF material framework.
FIG. 7 is a simulated X-ray powder diffraction pattern (theoretical values) for single crystals of the prepared Cu-MOF material and an actual X-ray powder diffraction pattern (actual values) for a large number of crystal samples. The results in fig. 7 show that the actual values (i.e. 2 theta angle values) of the diffraction peaks of the X-ray powder diffraction spectrum of a plurality of samples of the Cu-MOF material are basically consistent with the theoretical values obtained by the diffraction test of a Cu-MOF single crystal, which shows that the spatial structures of a plurality of synthesized Cu-MOF and Cu-MOF materials are consistent with the spatial structure of a single crystal used in the single crystal test, and the difference of the intensities of the individual diffraction peaks is related to the preferred orientation of the samples.
FIG. 8 is a scanning electron micrograph of the Cu-MOF material prepared, showing that the appearance of the Cu-MOF crystals shows a polygonal octahedral shape with single crystal size of about 300X 300 μm 3 。
FIG. 9 is a UV-visible diffuse reflectance spectrum of the prepared Cu-MOF material; the uv-vis diffuse reflectance curve of fig. 9 shows that with a white barium sulfate white plate as the blank, the absorption wavelength range of the Cu-MOF material for visible light is 550-800nm in the range of 200-800 nm.
When the Cu-MOF material prepared in the example 1 is used for degrading methylene blue under the catalysis of visible light, the concentration range of the dye aqueous solution is 0.1 mg/L-24 mg/L.
Preparing 11 methylene blue aqueous solutions with the concentrations of 0.05, 0.1, 1, 2, 4, 8, 10, 12, 16, 20 and 24mg/L by using distilled water as an experimental group, and testing the absorbance values of the methylene blue aqueous solutions with different concentrations at the maximum absorption wavelength of 664nm by using an ultraviolet-visible spectrophotometer by using the distilled water as a blank control, wherein as shown in figure 10, the absorbance values of the prepared dye methylene blue at the 664nm are increased along with the gradual increase of the concentration of the prepared dye methylene blue; and drawing a standard curve by taking the concentration of the methylene blue aqueous solution as an X axis and the corresponding absorbance value as a Y axis, as shown in FIG. 11, wherein a standard one is presented between the absorbance value Y of the dye and the concentration X thereofCurve of a relation of a quadratic function, R 2 Was 0.999.
The Cu-MOF material prepared in example 1 is used for visible light catalysis degradation of methylene blue with the concentration of 18.02 mg/L;
weighing 10mg of the Cu-MOF material agent prepared in example 1, placing the Cu-MOF material agent in a 100mL quartz tube reactor, pouring 60mL of methylene blue aqueous solution with certain concentration into the reactor, transferring the mixture into a dark box at room temperature, and placing the mixture for about 1h under magnetic stirring until adsorption-desorption equilibrium between dye molecules and a photocatalyst is achieved. Taking out 4mL of methylene blue supernatant to test the absorbance value, determining the concentration of the supernatant to be 18.02mg/L through a standard curve, then starting a 300W xenon lamp for irradiation under magnetic stirring, setting 18.02mg/L of methylene blue aqueous solution without adding other photocatalysts as a blank reference sample, taking out 4mL of supernatant at regular intervals (quickly pouring back into a quartz tube after the test is finished), and testing an ultraviolet-visible absorption spectrogram by using an ultraviolet-visible spectrophotometer, wherein as shown in figure 12, the absorbance value of the methylene blue at 664nm is quickly reduced along with the extension of the illumination time, and the characteristic absorption peak almost completely disappears after 60 min. The change of the concentration of methylene blue with time was read from the standard curve of FIG. 11, and the concentration C at that time was compared with the initial concentration C 0 Ratio of C/C 0 The photocatalytic degradation efficiency of the Cu-MOF material to methylene blue is obtained by taking time as an X axis and a Y axis, as shown in FIG. 13, within 60min, the visible photocatalytic degradation efficiency of the Cu-MOF material to methylene blue is 99.36%; in the blank control without the photocatalyst, the concentration of the dye changes only slightly and negligibly, which indicates that the Cu-MOF material has significant visible light photocatalytic degradation efficiency on methylene blue. Further, as shown in FIG. 14, ln (C/C) is used 0 ) Plotted as Y-axis and time as X-axis, the resulting photocatalytic degradation rate constant (i.e., the slope of the line in FIG. 10) was 3.577h -1 (R 2 ＝0.992)。
Continuously circulating visible light catalytic degradation is carried out on methylene blue by circularly utilizing a Cu-MOF material; the Cu-MOF material was separated from the bottom of the quartz tube by centrifugation and the photocatalytic degradation experimental operation was repeated again. As shown in fig. 15, in the following 4 consecutive photocatalytic degradation cycle experiments, the photocatalytic degradation efficiency of the cyclically used Cu-MOF material on methylene blue is 99.51%, 99.23%, 98.13% and 98.34%, respectively, and the experimental results show that the Cu-MOF material is stable in the process of catalytically degrading methylene blue by visible light and has a good catalytic degradation effect.
Example 2
A preparation method of a Cu-MOF material based on a triangular organic ligand specifically comprises the following steps:
under closed conditions, copper nitrate trihydrate Cu (NO) 3 ) 2 ·3H 2 O, organic ligand H 3 L, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol are uniformly mixed, continuously stirred, concentrated nitric acid solution is dripped to adjust the pH value of a reaction system to 4.0, and the reaction is carried out under the solvothermal condition to obtain the Cu-MOF material;
copper nitrate trihydrate, organic ligand H 3 The molar ratio of L to piperazine hexahydrate is 2:1:0.2; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5:1; the mass fraction of the concentrated nitric acid solution is 65 percent; the temperature of the solvothermal reaction is 65 ℃, and the required reaction time is 24 hours;
triangular organic ligands H 3 The preparation method of the L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
step b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dropwise adding the solution into the mixed solution obtained in the step 1.1 within 15min, dropwise adding triethylamine within 10min, reacting in an ice water bath for 3h, and reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction solution under the condition of continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, and obtaining white solidDrying to obtain the organic ligand H 3 L；
The drying temperature is 70 ℃, and the drying time is 8 hours;
example 3
A preparation method of a Cu-MOF material based on a triangular organic ligand specifically comprises the following steps:
under closed conditions, copper nitrate trihydrate Cu (NO) 3 ) 2 ·3H 2 O, organic ligand H 3 L, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol are uniformly mixed, continuously stirred, concentrated nitric acid solution is dripped to adjust the pH value of a reaction system to 6.0, and the reaction is carried out under the solvothermal condition to obtain the Cu-MOF material;
copper nitrate trihydrate, organic ligand H 3 The molar ratio of L to piperazine hexahydrate is 4:1:0.5; the volume ratio of the N, N-dimethylformamide to the absolute ethyl alcohol is 5:3; the mass fraction of the concentrated nitric acid solution is 65 percent; the temperature of the solvothermal reaction is 85 ℃, and the required reaction time is 72 hours;
triangular organic ligands H 3 The preparation method of the L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF, and continuously magnetically stirring under the condition of ice-water bath until the mixture is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
step b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step 1.1 within 15min, dripping triethylamine into the mixed solution within 10min, reacting in an ice-water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction solution under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, drying the obtained white solid to obtain the organic ligand H 3 L；
The drying temperature is 70 ℃, and the drying time is 8h.
Claims (2)
1. Cu-MOF material based on triangular organic ligands, characterized in that the chemical formula is { [ Cu ] 3 (L) 2 (H 2 O) 3 ]·14DMF·16H 2 O} n Wherein H is 3 L is a triangular organic ligand 4, 4'' - [ benzene triacyl tris (carbonyl benzene)]-3,3',3 "-trimethyl-tribenzoic acid, DMF being N, N-dimethylformamide;
the crystal structure of the Cu-MOF material belongs to a cubic system, pn-3n space group, and the unit cell parameters are as follows: a = 33.249 (11) a, b = 33.249 (11) a, c = 33.249 (11) a; α = 90 °, β = 90 °, γ = 90 °.
2. The preparation method of the Cu-MOF material based on the triangular organic ligand is further characterized by comprising the following steps:
under closed conditions, copper nitrate trihydrate Cu (NO) 3 ) 2 ·3H 2 O, organic ligand H 3 L, template agent piperazine hexahydrate, N-dimethylformamide and absolute ethyl alcohol are uniformly mixed, continuously stirred, and dropwise added with concentrated nitric acid solution to adjust the pH of a reaction system to 4.0-6.0, and the mixture is reacted under the solvothermal condition to obtain the Cu-MOF material;
every 0.04mmol of copper nitrate trihydrate and 0.02mmol of organic ligand H 3 L, 0.004mmol of piperazine hexahydrate corresponding to 5mL of N, N-dimethylformamide and 3mL of absolute ethanol; the temperature of the solvothermal reaction is 75 ℃, and the reaction time is 48h;
the triangular organic ligand H 3 The preparation method of L specifically comprises the following steps:
step a, dissolving 4-amino-2-methylbenzoic acid in DMF (dimethyl formamide), and continuously magnetically stirring under the condition of ice-water bath until the 4-amino-2-methylbenzoic acid is completely dissolved to obtain a mixed solution;
65mL of DMF is corresponding to each 1mol of 4-amino-2-methylbenzoic acid;
b, dissolving trimesoyl chloride in DMF, stirring until the trimesoyl chloride is dissolved, slowly dripping the trimesoyl chloride into the mixed solution obtained in the step a within 15min, dripping triethylamine into the mixed solution obtained in the step a within 10min, reacting in an ice water bath for 3h, and then reacting at room temperature for 24h to obtain a reaction solution;
every 1mol of trimesoyl chloride corresponds to 100mL of DMF and 0.36mol of triethylamine
Step c, adding distilled water into the reaction liquid under continuous magnetic stirring, removing DMF and distilled water by vacuum filtration through a Buchner funnel after 30min, namely washing and vacuum filtration through distilled water and methanol in sequence, drying the obtained white solid to obtain the organic ligand H 3 L; the drying temperature is 70 ℃, and the drying time is 8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010921110.7A CN112076794B (en) | 2020-09-04 | 2020-09-04 | Cu-MOF material based on triangular organic ligand, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010921110.7A CN112076794B (en) | 2020-09-04 | 2020-09-04 | Cu-MOF material based on triangular organic ligand, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112076794A CN112076794A (en) | 2020-12-15 |
| CN112076794B true CN112076794B (en) | 2022-12-09 |
Family
ID=73731994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010921110.7A Active CN112076794B (en) | 2020-09-04 | 2020-09-04 | Cu-MOF material based on triangular organic ligand, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112076794B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113318791B (en) * | 2021-06-30 | 2022-06-14 | 武汉大学 | Preparation method and application of amino-modified Fe/Cu-MOF photocatalyst |
| CN113893852B (en) * | 2021-09-09 | 2023-07-25 | 广东医科大学 | Preparation method and application of copper metal organic framework derived porous carbon composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106955742A (en) * | 2017-03-29 | 2017-07-18 | 华南理工大学 | A kind of Ce MOF catalysis materials and preparation method and application |
| CN108080028A (en) * | 2017-12-22 | 2018-05-29 | 安徽工业大学 | The preparation method of 8-hydroxyquinoline iron class organic dyestuff Photodegradation catalyst |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2578593A1 (en) * | 2011-10-04 | 2013-04-10 | Fundació Privada Institut Català de Nanotecnologia | Method for the preparation of metal organic frameworks |
| CN105524007B (en) * | 2015-11-30 | 2018-04-03 | 山东师范大学 | A kind of preparation method and application of nanometer of Cu organic coordination compound crystal |
| CN111205470B (en) * | 2020-02-11 | 2021-08-10 | 河北大学 | Azole functionalized divalent copper frame coordination material, preparation method and application thereof, and p-nitrophenol detection method |
-
2020
- 2020-09-04 CN CN202010921110.7A patent/CN112076794B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106955742A (en) * | 2017-03-29 | 2017-07-18 | 华南理工大学 | A kind of Ce MOF catalysis materials and preparation method and application |
| CN108080028A (en) * | 2017-12-22 | 2018-05-29 | 安徽工业大学 | The preparation method of 8-hydroxyquinoline iron class organic dyestuff Photodegradation catalyst |
Non-Patent Citations (3)
| Title |
|---|
| A two-fold interpenetrated (3,6)-connected metal–organic framework;Xiaokai Song et al.;《New Journal of Chemistry》;20100726;第34卷;第2398页实验部分 * |
| Conformational control of ligands to create a finite metal–organic cluster and an extended metal–organic framework;Lalit Rajput et al.;《CrystEngComm》;20121004;第15卷;摘要、第260页试验部分 * |
| 水稳定型In/Zr-有机骨架材料的设计、合成与光催化降解有机染料;李庆;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20190415(第4期);第49页第2-3段、第2.1.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112076794A (en) | 2020-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fu et al. | Fabrication of visible-light-active MR/NH2-MIL-125 (Ti) homojunction with boosted photocatalytic performance | |
| CN106076421B (en) | A kind of MIL-53 (Fe)/g-C3N4The preparation method of nanometer sheet composite photocatalyst material | |
| CN111303445B (en) | Cobalt-based metal organic framework material and application | |
| Nguyen et al. | Microwave-assisted solvothermal synthesis and photocatalytic activity of bismuth (III) based metal–organic framework | |
| CN112076794B (en) | Cu-MOF material based on triangular organic ligand, and preparation method and application thereof | |
| CN112076796B (en) | Preparation method and application of magnetic Cu-MOF-based photocatalyst | |
| CN104525266A (en) | Preparation method of metal-organic framework material photocatalyst and application | |
| Zhang et al. | Effects of different defective linkers on the photocatalytic properties of Cu-BTC for overall water decomposition | |
| Yang et al. | An acid–base resistant paddle-wheel Cu (II) coordination polymer for visible-light-driven photodegradation of organic dyes | |
| Chen et al. | Recent progress in mixed rare earth metal-organic frameworks: From synthesis to application | |
| CN111004397B (en) | Metal organic framework molecular material of electron-rich system and application thereof in photocatalytic reduction of heavy metal ions | |
| Li et al. | Fe-MIL tuned and bound with Bi 4 O 5 Br 2 for boosting photocatalytic reduction of CO 2 to CH 4 under simulated sunlight | |
| Guo et al. | Precise regulation of defect concentration in MOF and its influence on photocatalytic overall water splitting | |
| Song et al. | Active site regulated Z-scheme MIL-101 (Fe)/Bi 2 WO 6/Fe (iii) with the synergy of hydrogen peroxide and visible-light-driven photo-Fenton degradation of organic contaminants | |
| Sun et al. | Two new hexa-Ni-substituted polyoxometalates in the form of an isolated cluster and 1-D chain: Syntheses, structures, and properties | |
| Xin et al. | A series of porous 3D inorganic–organic hybrid framework crystalline materials based on 5-aminoisophthalic acid for photocatalytic degradation of crystal violet | |
| CN111848654A (en) | Zinc complex with property of catalyzing photo-degradation of methyl orange dye and preparation method thereof | |
| CN112076793B (en) | In-MOF material based on tricarboxylic acid ligand, preparation method and application | |
| CN111909383B (en) | Preparation method and application of copper-based MOF (metal organic framework) for adsorbing Congo red | |
| CN112691704A (en) | Flower-ball-shaped Cu-MOF-74/GO visible light catalyst and preparation method thereof | |
| CN111171054B (en) | Copper complex with properties of catalyzing photodegradation and adsorbing dye and preparation method thereof | |
| Endashaw et al. | Review on the removal of dyes by photodegradation using metal-organic frameworks under light irradiation | |
| Tran et al. | Synthesis of Mn-Doped Fe-MOFs with Different Ratios and Its Application for Photocatalytic Degradation of Rhodamine B Dye | |
| CN111171055A (en) | Copper complex with dye catalytic photodegradation property and preparation method thereof | |
| CN112076795B (en) | Preparation method and application of magnetic In-MOF-based photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Qing Inventor after: Cai Xinbin Inventor after: Fan Zenglu Inventor after: Zhang Luohong Inventor after: Wu Zhansheng Inventor after: Wang Liming Inventor after: Zhu Wei Inventor before: Li Qing Inventor before: Fan Zenglu Inventor before: Zhang Luohong Inventor before: Wu Zhansheng Inventor before: Wang Liming Inventor before: Zhu Wei |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230629 Address after: No. 201 Xigan Road, Meicun, New District, Wuxi City, Jiangsu Province, 214112 Patentee after: Wuxi Qinbang new packaging material Co.,Ltd. Address before: 710048 Shaanxi province Xi'an Beilin District Jinhua Road No. 19 Patentee before: XI'AN POLYTECHNIC University |
|
| TR01 | Transfer of patent right |