CN106967219A - Cadmium metal organic framework materials based on 3,3 ', 5,5 ' biphenyltetracarboxyacid acids and its preparation method and application - Google Patents
Cadmium metal organic framework materials based on 3,3 ', 5,5 ' biphenyltetracarboxyacid acids and its preparation method and application Download PDFInfo
- Publication number
- CN106967219A CN106967219A CN201710179182.7A CN201710179182A CN106967219A CN 106967219 A CN106967219 A CN 106967219A CN 201710179182 A CN201710179182 A CN 201710179182A CN 106967219 A CN106967219 A CN 106967219A
- Authority
- CN
- China
- Prior art keywords
- organic framework
- framework materials
- metal organic
- cadmium metal
- biphenyltetracarboxyacid acid
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000002253 acid Substances 0.000 title claims abstract description 42
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 34
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000007513 acids Chemical class 0.000 title abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 24
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229940107698 malachite green Drugs 0.000 claims abstract description 11
- 229940012189 methyl orange Drugs 0.000 claims abstract description 11
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 11
- 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 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 7
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims abstract description 4
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000000975 dye Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 6
- 229940113088 dimethylacetamide Drugs 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000004043 dyeing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002990 phenothiazines Chemical class 0.000 claims description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 abstract description 13
- 238000006731 degradation reaction Methods 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 3
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 8
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000013384 organic framework Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002050 diffraction method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000012922 MOF pore Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 101150039161 hasB gene Proteins 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/27—Cadmium
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of cadmium metal organic framework materials based on 3,3 ', 5,5 ' biphenyltetracarboxyacid acids and its preparation method and application.The construction unit of the material is [Cd4(BPTC)2(DMA)3(EtOH)(H2O) (NMF)] (DMA), wherein BPTC is represented and is lost 3 of H atom on four carboxyls, 3 ', 5,5 ' biphenyltetracarboxyacid acid anion, DMA represent N, N dimethyl acetamides, EtOH represent ethanol, NMF and represent N NMFs, belong to rhombic system Pbcn space groups, and cell parameter a isB isC isα is 90 °, β is 90 °, γ is 90 °, and V isThe material is using four nitric hydrate cadmiums as source metal, with 3,3 ', 5,5 ' biphenyltetracarboxyacid acids are part, it is prepared from using solvent-thermal method, it is used for degradating organic dye methylene blue, Synoptic model, crystal violet, butyl rhodamine b, malachite green, sunset yellow, methyl orange and Ponceaux etc. as photochemical catalyst and shows significant degradation effect.
Description
Technical field
The invention belongs to synthesize metal-organic framework materials technical field, and in particular to one kind is based on 3,3 ', 5,5 '-biphenyl
The cadmium metal organic framework materials of tetrabasic carboxylic acid, and the material preparation method and in ultraviolet light photocatalysis degradation organic dyestuff
Application.
Background technology
Current environmental pollution has become the significant challenge that human health, the ecological balance and socio-economic development are faced.
Especially China's trade effluent, industrial dye, rural sewage, toxic liquid are discharged into the natural waters such as nature lake, river, give
Environment brings pressure and destruction.The primary pollution source of current industrial wastewater discharge comes from dyeing industry industry, and therein organic
Dyestuff has the complicated feature such as composition complexity, high chroma, poisonous, strong acid and strong base, so as to cause severe water pollution, improvement
The features such as hardly possible, difficult degradation.And photocatalytic degradation of dye is then a kind of application and studies commonplace processing method, it is usually used in each
The processing of kind of waste water from dyestuff, this method has the advantages that efficient, quick, and this method is by occurring photochemical reaction, by water
Some materials remove, reach purification waste water purpose.
With developing rapidly for catalysis material, the metal-organic framework materials (Metal- with semiconducting behavior
Organic Frameworks, abbreviation MOFs) paid close attention in photocatalysis field.Such material is by single metallic atom
The organic ligand composition tactical rule that (or metal cluster) is rolled into a ball with multidentate, the polyporous materials with Rigid Porous net.And
And such porous MOFs material has the features such as controllable duct, specific surface area are higher, pore structure is regular, then adsorbable particular dye
Molecule；Other MOFs materials itself have abundant unsaturated site, and this kind of metallic site is the avtive spot in catalytic reaction,
And the selection with height.Therefore, based on MOFs materials catalytic field important function and its wide development space, and
Such porous metal organic frameworks are applied to photocatalysis, and it has reaction efficiency high, and speed is fast, and to a variety of organic dirts
Contaminate thing degradation effect notable.Therefore, new environment-friendly, efficient metal-organic framework material is prepared, as photochemical catalyst,
With broad base researching value and application prospect.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of cadmium metal for being based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid
Organic framework materials, and provide a kind of preparation method and application for the material.
Solving the technical scheme that is used of above-mentioned technical problem is：Should the cadmium metal based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid
The construction unit of organic framework materials is：[Cd4(BPTC)2(DMA)3(EtOH)(H2O) (NMF)] (DMA), wherein BPTC generations
Table lose H atom on four carboxyls 3,3 ', 5,5 '-biphenyltetracarboxyacid acid anion, DMA represent DMAC N,N' dimethyl acetamide,
EtOH represents ethanol, NMF and represents N-METHYLFORMAMIDE；The material belongs to rhombic system Pbcn space groups, and cell parameter a isB isC isα is 90 °, β is 90 °, γ is 90 °, and V is
The preparation method of cadmium metal organic framework materials of the present invention based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid be：With N, N-
Dimethyl acetamide is 5~8 with ethanol, deionized water volume ratio:1~3:1 mixed liquor be solvent, by four nitric hydrate cadmiums with
3,3 ', 5,5 '-biphenyltetracarboxyacid acid is 1 in molar ratio:2~4,110~130 DEG C of constant temperature, which are stood, in confined conditions reacts 4~6
My god, room temperature is cooled to, is filtered, is washed, dries, is prepared into based on 3,3 ', 5, the cadmium metal organic frame material of 5 '-biphenyltetracarboxyacid acid
Material.
In above-mentioned preparation method, preferably using DMA and ethanol, deionized water volume ratio as 6:2:1 it is mixed
Conjunction liquid is solvent.
In above-mentioned preparation method, preferred four nitric hydrate cadmiums and 3,3 ', 5, the mol ratio of 5 '-biphenyltetracarboxyacid acid is 1:2.7.
In above-mentioned preparation method, further preferably 120 DEG C of constant temperature stand reaction 5 days in confined conditions.
Cadmium metal organic framework materials of the present invention based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid are in degradating organic dye
Using, wherein described organic dyestuff is any one in azo, phenothiazines, triphenylmethane, pyran dyestuff, tool
Body such as methylene blue, Synoptic model, crystal violet, butyl rhodamine b, malachite green, sunset yellow, methyl orange, Ponceaux etc..
The present invention is using four nitric hydrate cadmiums as source metal, and with 3,3 ', 5,5 '-biphenyltetracarboxyacid acid is part, in mixed solvent
DMAC N,N' dimethyl acetamide in ethanol, deionization using solvent-thermal process method with being prepared into based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid
Cadmium metal organic framework materials, the material is used for degradation of dye methylene blue (MB) and Synoptic model (AZ) as photochemical catalyst, ties
Crystalviolet (CV), butyl rhodamine b (BB), malachite green (MG), sunset yellow (SY), methyl orange (MO) and Ponceaux (PS) etc. are a variety of
Organic pollution shows significant degradation effect, and reaction efficiency is high, and speed is fast.
Brief description of the drawings
Fig. 1 is the coordination structure figure of cadmium metal organic framework materials of the present invention based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid.
Fig. 2 is the A form coordination mode figures of 3,3 ', 5,5 '-biphenyltetracarboxyacid acid of part.
Fig. 3 is the B form coordination mode figures of 3,3 ', 5,5 '-biphenyltetracarboxyacid acid of part.
Fig. 4 is the two dimension 4 of cadmium metal organic framework materials of the present invention based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid4Grid
Figure.
Fig. 5 is the tomograph of cadmium metal organic framework materials of the present invention based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid.
Fig. 6 is the topology diagram of cadmium metal organic framework materials of the present invention based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid.
Fig. 7 is that the solid of cadmium metal organic framework materials of the present invention based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid is ultraviolet unrestrained anti-
Penetrate figure.
Fig. 8 is cadmium metal organic framework materials of the present invention based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid to dyestuff methylene blue
(MB) and Synoptic model (AZ) degradation rate and time chart.
Fig. 9 is cadmium metal organic framework materials of the present invention based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid to Crystal Violet
(CV), butyl rhodamine b (BB), malachite green (MG), sunset yellow (SY), methyl orange (MO) and the degradation rate of Ponceaux (PS) with
Time chart.
Embodiment 1
By 0.057g Cd (NO3)2·4H2O, 0.025g 3,3 ', 5,5 '-biphenyltetracarboxyacid acid (H4BPTC), 6mL N, N- bis-
Methylacetamide, 2mL ethanol and 1mL deionized waters are added in 25mL flasks, after stirring, sealing, and 120 DEG C of constant temperature stand anti-
Answer 5 days, then naturally cool to room temperature, filter, spontaneously dried, be prepared into based on 3,3 ', 5 with distilling in water washing, air,
The cadmium metal organic framework materials of 5 '-biphenyltetracarboxyacid acid, its construction unit is [Cd4(BPTC)2(DMA)3(ETOH)(H2O)
(NMF)] (DMA), wherein BPTC is represented and is lost 3,3 ', 5 of H atom on four carboxyls, 5 '-biphenyltetracarboxyacid acid anion, DMA
Represent DMAC N,N' dimethyl acetamide, EtOH and represent ethanol, NMF and represent N-METHYLFORMAMIDE.The yield of the material is calculated according to cadmium
About 54%.
Coordination structure such as Fig. 1 institutes of the prepared cadmium metal organic framework materials based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid
Show, belong to rhombic system Pbcn space groups, cell parameter a isB isC isα is 90 °, β is 90 °, γ is 90 °, and unit cell volume V isThe material is independent in crystallography
There is the Cd of 4 crystallography independence in unit2+Ion, 2 BPTC parts, 4 DMA molecules, the H of 1 coordination2O molecules and 1 match somebody with somebody
The EtOH molecules of position.Structural analysis shows 4 Cd2+Ion takes octahedral geometric configuration, wherein Cd1 and Cd4 respectively at
6 carboxyl oxygen atoms coordination from 3 different BPTC parts, and with 6 oxygen atoms of Cd2 Atomic coordinates, wherein 3 are come
From carboxyl oxygen atom in 3 different BPTC parts, 3 oxygen atoms are then respectively from DMA molecules, coordination H in addition2O molecules and
Oxygen atom in the EtOH molecules of coordination.Bond distance's scope of wherein Cd-O keys isWherein Cd1 and
Cd2, Cd3 and Cd4 atom distinguish 2 carboxyls of bridging to form Cd2(CO2)2Two core clustering architecture units, wherein metal
Bond distance between Cd1Cd2 isBond distance between Cd3Cd4 isFrom Fig. 2 and 3, tie herein
Part BPTC has A (see Fig. 2), the torsion angle of B (see Fig. 3) two kinds of forms in structure unit, wherein in A forms two phenyl ring planes it
Between torsion angle be 28.41 °, wherein carboxyl oxygen takes μ2-η2:η2:η2:η2Coordination mode；In B forms two phenyl ring planes it
Between torsion angle be only 9.03 °, and carboxyl oxygen takes μ1-η1:η1,μ2-η2:η2Coordination mode.As shown in figure 4, each
Two core Cd2(CO2)2Cluster connects four part BPTC, in addition each four two core Cd of part BPTC connections2(CO2)2Cluster is flat in ac-
Face is extended to the 4 of two kinds of pore passage structures4Grid；Further have along b- direction of principal axis by part BPTC formationOne-dimensional channels A, while 4 one-dimensional channels A pass through share four two core Cd2(CO2)2Cluster and four match somebody with somebody
Body BPTC and being formed hasB ducts, and then be extended to the 3-dimensional metal with two kinds of duct types of A, B and have
Machine frame (see Fig. 5).In order to further simplify its structure chart, by two core Cd2(CO2)2Cluster is 4- connecting nodes, and BPTC connects for 4-
Connect node, be further expanded into the topological structure with 4,4- connections (see Fig. 6).
The elementary analysis of prepared product：Theoretical value H, 3.90；C,40.56；N,4.38；Experiment value H, 3.95；C,
40.87；N,4.56.
As seen from Figure 7, solid uv drses determine its band gap magnitude for 3.43eV, illustrate that it has preferable semiconductive
Can, and the performance with potential ultraviolet light photocatalysis.
Embodiment 2
Cadmium metal organic framework materials based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid prepared by embodiment 1 have engine dyeing in degraded
Application in material
The cadmium metal organic framework materials point based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid that inventor is prepared using embodiment 1
Other degradation of methylene blue (MB), Synoptic model (AZ), crystal violet (CV), butyl rhodamine b (BB), malachite green (MG), sunset yellow
(SY), methyl orange (MO), Ponceaux (PS), as a result as shown in FIG. 8 and 9.
From Fig. 8, Fig. 9, the present invention is based on 3,3 ', 5, and the cadmium metal organic framework materials of 5 '-biphenyltetracarboxyacid acid are to Asia
Methyl blue (MB) has ultrafast degradation rate, is degradable 89.3% in 15min；Synoptic model (AZ) is then degraded in 60min
51.1%；In 420min, to crystal violet (CV) degraded 97.1%, butyl rhodamine b (BB) degraded 90.7%, malachite green (MG)
Degraded 87.8%；It is that 52.5%, methyl orange (MO) degradation rate is 43.6%, beautiful spring to sunset yellow (SY) degradation rate in 600min
Red (PS) degradation rate is 40.0%.
Claims (7)
1. one kind is based on 3,3 ', 5, the cadmium metal organic framework materials of 5 '-biphenyltetracarboxyacid acid, it is characterised in that the structure of the material
Unit is：[Cd4(BPTC)2(DMA)3(EtOH)(H2O) (NMF)] (DMA), wherein BPTC, which is represented, loses H originals on four carboxyls
3,3 ', 5,5 '-biphenyltetracarboxyacid acid anion, the DMA of son, which represent DMAC N,N' dimethyl acetamide, EtOH and represent ethanol, NMF, represents N-
NMF；The material belongs to rhombic system Pbcn space groups, and cell parameter a isB isC isα is 90 °, β is 90 °, γ is 90 °, and V is
2. a kind of preparation side of the cadmium metal organic framework materials based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid described in claim 1
Method, it is characterised in that：Using DMAC N,N' dimethyl acetamide and ethanol, deionized water volume ratio as 5~8:1~3:1 mixed liquor is
Solvent, by four nitric hydrate cadmiums and 3,3 ', 5,5 '-biphenyltetracarboxyacid acid is 1 in molar ratio:2~4, in confined conditions 110~
130 DEG C of constant temperature stand reaction 4~6 days, are cooled to room temperature, filter, and wash, and dry, are prepared into based on 3,3 ', 5,5 '-biphenyl four
The cadmium metal organic framework materials of carboxylic acid.
3. the preparation side of the cadmium metal organic framework materials according to claim 2 for being based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid
Method, it is characterised in that：Using DMAC N,N' dimethyl acetamide and ethanol, deionized water volume ratio as 6:2:1 mixed liquor is solvent.
4. the preparation side of the cadmium metal organic framework materials according to claim 2 for being based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid
Method, it is characterised in that：Four described nitric hydrate cadmiums and 3,3 ', the mol ratio of 5,5 '-biphenyltetracarboxyacid acid is 1:2.7.
5. the preparation side of the cadmium metal organic framework materials according to claim 2 for being based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid
Method, it is characterised in that：120 DEG C of constant temperature stand reaction 5 days in confined conditions.
6. the cadmium metal organic framework materials based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid described in claim 1 have engine dyeing in degraded
Application in material, wherein described organic dyestuff is any in azo, phenothiazines, triphenylmethane, pyran dyestuff
It is a kind of.
7. the cadmium metal organic framework materials according to claim 6 for being based on 3,3 ', 5,5 '-biphenyltetracarboxyacid acid have in degraded
Application in engine dyeing material, it is characterised in that：Described organic dyestuff be methylene blue, Synoptic model, crystal violet, butyl rhodamine b,
Any one in malachite green, sunset yellow, methyl orange, Ponceaux.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710179182.7A CN106967219B (en) | 2017-03-23 | 2017-03-23 | Cadmium metal organic framework material based on 3,3 ', 5, 5' -biphenyltetracarboxylic acid and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710179182.7A CN106967219B (en) | 2017-03-23 | 2017-03-23 | Cadmium metal organic framework material based on 3,3 ', 5, 5' -biphenyltetracarboxylic acid and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106967219A true CN106967219A (en) | 2017-07-21 |
| CN106967219B CN106967219B (en) | 2020-05-22 |
Family
ID=59329546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710179182.7A Expired - Fee Related CN106967219B (en) | 2017-03-23 | 2017-03-23 | Cadmium metal organic framework material based on 3,3 ', 5, 5' -biphenyltetracarboxylic acid and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106967219B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250450A (en) * | 2018-01-19 | 2018-07-06 | 淮北师范大学 | A kind of cadmium coordination polymer and its preparation method and application |
| CN108558918A (en) * | 2018-05-21 | 2018-09-21 | 吉林师范大学 | A kind of 3-dimensional metal-organic framework material and its preparation method and application |
| CN109265485A (en) * | 2018-10-12 | 2019-01-25 | 山西师范大学 | Cobalt metal-organic framework material and preparation method and fluorescence sense rich in Louis's base identify Fe3+Application |
| CN110698687A (en) * | 2019-11-01 | 2020-01-17 | 北京工业大学 | Synthesis method of cadmium-metal-organic framework material |
| CN111349246A (en) * | 2020-02-17 | 2020-06-30 | 山东师范大学 | Metal organic framework for nitrogen adsorption and/or storage and application thereof |
| CN113185698A (en) * | 2021-05-20 | 2021-07-30 | 山西师范大学 | Preparation method and application of four-core cadmium cluster organic framework |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190471A (en) * | 2014-09-04 | 2014-12-10 | 天津工业大学 | Photocatalytic performance of bi-(3, 5-dicarboxylphenyl)-p-phthalamide zinc complex |
| CN105384947A (en) * | 2015-10-27 | 2016-03-09 | 辽宁大学 | 3D coordination polymer of Cd as well as preparation method and application thereof |
-
2017
- 2017-03-23 CN CN201710179182.7A patent/CN106967219B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190471A (en) * | 2014-09-04 | 2014-12-10 | 天津工业大学 | Photocatalytic performance of bi-(3, 5-dicarboxylphenyl)-p-phthalamide zinc complex |
| CN105384947A (en) * | 2015-10-27 | 2016-03-09 | 辽宁大学 | 3D coordination polymer of Cd as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| LING ZHU等: ""A new PtS-type heterometallic compound constructed from biphenyl-3,30,5,50-tetracarboxylate: Synthesis, structure and luminescent property"", 《JOURNAL OF MOLECULAR STRUCTURE》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250450A (en) * | 2018-01-19 | 2018-07-06 | 淮北师范大学 | A kind of cadmium coordination polymer and its preparation method and application |
| CN108250450B (en) * | 2018-01-19 | 2020-10-30 | 淮北师范大学 | Cadmium coordination polymer and preparation method and application thereof |
| CN108558918A (en) * | 2018-05-21 | 2018-09-21 | 吉林师范大学 | A kind of 3-dimensional metal-organic framework material and its preparation method and application |
| CN109265485A (en) * | 2018-10-12 | 2019-01-25 | 山西师范大学 | Cobalt metal-organic framework material and preparation method and fluorescence sense rich in Louis's base identify Fe3+Application |
| CN109265485B (en) * | 2018-10-12 | 2020-11-27 | 山西师范大学 | Cobalt metal organic framework material rich in Lewis base, preparation method and fluorescent sensing recognition Fe3+Application of |
| CN110698687A (en) * | 2019-11-01 | 2020-01-17 | 北京工业大学 | Synthesis method of cadmium-metal-organic framework material |
| CN111349246A (en) * | 2020-02-17 | 2020-06-30 | 山东师范大学 | Metal organic framework for nitrogen adsorption and/or storage and application thereof |
| CN111349246B (en) * | 2020-02-17 | 2021-11-09 | 山东师范大学 | Metal organic framework for nitrogen adsorption and/or storage and application thereof |
| CN113185698A (en) * | 2021-05-20 | 2021-07-30 | 山西师范大学 | Preparation method and application of four-core cadmium cluster organic framework |
| CN113185698B (en) * | 2021-05-20 | 2022-11-15 | 山西师范大学 | Preparation method and application of four-core cadmium cluster organic framework |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106967219B (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106967219A (en) | Cadmium metal organic framework materials based on 3,3 ', 5,5 ' biphenyltetracarboxyacid acids and its preparation method and application | |
| Zhou et al. | Facile fabrication and enhanced photocatalytic performance of visible light responsive UiO-66-NH2/Ag2CO3 composite | |
| CN109289927A (en) | The preparation method and applications of the iron-based MOF visible light composite catalyst of nano-titanium dioxide@ | |
| CN105330681B (en) | A kind of rare earth cluster metal organic anion skeleton of micropore and its preparation method and application | |
| CN103934011B (en) | A kind of biomimetic synthesis method of high-activity nano bismuth phosphate photocatalyst | |
| CN107433206B (en) | A kind of polynary zirconium base porous material, preparation method, photocatalysis take off the application in chromium | |
| CN102380424B (en) | Heteropoly acid zeolite coated rare earth-organic framework material and its preparation method | |
| CN105170190A (en) | Preparation method of phosphotungstic acid @MIL(Fe) photocatalyst | |
| CN114316291B (en) | Metal-organic framework based on trispyrazole ligand, preparation method and application of metal-organic framework in organic dye degradation | |
| CN107497402B (en) | Water-stable dye adsorbent and preparation method thereof | |
| CN108745393A (en) | A kind of bismuth-bismuthyl carbonate heterojunction structure catalysis material and preparation method thereof | |
| CN107673439A (en) | A kind of sewage disposal medicament | |
| CN104324690A (en) | Magnetic two-peak mesoporous carbon containing iron-nickel double metals, preparation method and application thereof | |
| CN108160042A (en) | Utilize the method for ZnO thin film metal-organic framework materials processing antibiotic waste water | |
| CN106582812A (en) | Composite photocatalyst with titanium dioxide axially functionalized by metallic zinc porphyrin and preparation method thereof | |
| CN106220661A (en) | The metallic organic framework of a kind of In, preparation method and the application at dye adsorption aspect thereof | |
| CN103785452A (en) | Preparation method for catalyst capable of removing odor in domestic sludge drying tail gas | |
| CN104971748B (en) | The preparation method of molecular engram optic catalytic composite material of the one kind based on 3D Graphenes/BiOI | |
| CN110449162A (en) | A kind of modified manganese slag-iron vitriol slag mixing slag catalyst and its preparation method and application | |
| CN105482025B (en) | Reverse microemulsion polymerization preparation absorption methylene blue molecularly imprinted polymer | |
| CN105268479B (en) | The preparation method of high efficiency photocatalyst based on iron and Phen | |
| CN109046456B (en) | Preparation method and application of load type manganese-metal organic framework composite material | |
| CN103224264A (en) | Application of covalent triazine framework (CTF) material in removal of organic dyes in water phase | |
| CN105417508A (en) | Preparation method of macroporous g-C3N4 | |
| CN103950978A (en) | Biomimetic synthesis method of bismuth vanadate visible-light photocatalyst having hierarchical structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200522 Termination date: 20210323 |