CN116515126A - Two-dimensional copper coordination polymer and preparation method and application thereof - Google Patents
Two-dimensional copper coordination polymer and preparation method and application thereof Download PDFInfo
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- CN116515126A CN116515126A CN202310540228.9A CN202310540228A CN116515126A CN 116515126 A CN116515126 A CN 116515126A CN 202310540228 A CN202310540228 A CN 202310540228A CN 116515126 A CN116515126 A CN 116515126A
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 39
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 39
- 239000010949 copper Substances 0.000 title claims abstract description 37
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 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 31
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 oxy terephthalic acid Chemical compound 0.000 claims abstract description 15
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000000593 degrading effect Effects 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 239000000975 dye Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000011160 research 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DUXQSXACBMFRPZ-UHFFFAOYSA-N 2-(4-carboxyphenoxy)terephthalic acid Chemical class C1=CC(C(=O)O)=CC=C1OC1=CC(C(O)=O)=CC=C1C(O)=O DUXQSXACBMFRPZ-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- 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
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms 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
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- 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
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- 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
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- 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
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/40—Organic compounds containing sulfur
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- 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
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- 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
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Abstract
The invention discloses a two-dimensional copper coordination polymer, a preparation method and application thereof, and a request protection of the two-dimensional copper coordination polymer, wherein the chemical formula of the two-dimensional copper coordination polymer is [ Cu (Hcpota) (4, 4' -bpy) (H) 2 O)] n Hcpota in the formula refers to Hcpota 2‑ Is o- (p-carboxybenzene) oxy terephthalic acid H 3 Deprotonated form of cpota, 4'-bpy is 4,4' -bipyridine, n represents a polymerization; the structural formula of the polymer is as follows. The copper coordination polymer not only can exist in water stably, but also can be used as a photocatalyst for degrading methylene blue in water. In addition, the copper coordination polymer is obtained under the hydrothermal synthesis condition, and the preparation process is simple, and the yield and purity are high.
Description
Technical Field
The invention belongs to the field of chemistry, and relates to a coordination polymer, in particular to a two-dimensional copper coordination polymer, a preparation method and catalytic application of the two-dimensional copper coordination polymer.
Background
Water pollution worldwide is increasingly serious due to the continuous rapid development of industry. One of the most abundant, most commonly observed contaminants, water, is a dye molecule. Most dyes are toxic, for example methylene blue was listed as a class 3 carcinogen by the world health organization cancer research institute in 2017, damaging human health, and in addition, the dye can consume large amounts of oxygen in water, resulting in lack of oxygen in the water body, affecting the growth of aquatic organisms and microorganisms. Therefore, it is very important to find a method for effectively treating an organic dye from the viewpoints of environmental protection and human safety. At present, the waste treatment process, aqueous organic dyes, mainly rely on microbiological degradation, adsorption, photocatalysis and advanced oxidation processes. Among them, catalytic degradation is an effective method for treating sewage. However, these methods have the following disadvantages: expensive, limited application range, etc., more efficient and economical water purification catalytic systems remain an important direction of research. Recently, the use of metal organic coordination polymers as efficient heterogeneous photocatalysts has been rapidly developed because they can provide a simple, rapid, highly selective and cost-effective photocatalytic process. However, some materials in these coordination polymer catalysts cannot exist stably in aqueous solutions, and their applications are greatly limited. Therefore, the design and synthesis of the coordination polymer with the function of selectively and efficiently catalyzing and degrading the dye in the sewage in the aqueous solution are the problems which are urgently needed to be solved at present, and are also one important direction of the research.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a two-dimensional copper coordination polymer, a preparation method thereof and application of the coordination polymer as an efficient heterogeneous photocatalyst in catalytic degradation of methylene blue in aqueous solution.
The above object of the present invention is achieved by the following technical scheme:
a two-dimensional copper coordination polymer has a chemical formula of [ Cu (Hcpota) (4, 4' -bpy) (H) 2 O)] n Hcpota in the formula refers to Hcpota 2- Is o- (p-carboxybenzene) oxy terephthalic acid H 3 The deprotonated form of cpota, 4'-bpy being 4,4' -bipyridine, n representing the polymerization; the structural formula of the polymer is as follows:
the crystal of the copper coordination polymer belongs to monoclinic system, and the space group isThe unit cell parameters are: α=90°, β=95.41 (3) °, γ=90°. The copper atom is a penta-coordinated tetragonal cone which coordinates to two O atoms of two different carboxyl groups, one coordinated water and two N atoms from 4,4' -bipyridine, respectively; the Cu-O bond length is in the range +.>The length of the Cu-N bond is in the range ofHcpota 2– The two carboxyl groups of the ligand are respectively connected with two Cu ions in a single-link mode, and simultaneously, each Cu ion is connected with two Hcpotas 2– Ligand and two 4,4' -bipyridines form a length +.>Square junction of (2)The structure is continuously expanded into a two-dimensional copper metal organic coordination polymer by taking the structure as a unit. X-ray powder diffraction confirmed that the crystal samples were uniform and stable.
The preparation method of the two-dimensional copper coordination polymer comprises the following steps:
(1) Cu (NO) was added in a molar ratio of 2:2:1 3 ) 2 ·3H 2 O, 4' -bipyridine and O- (p-carboxybenzene) oxy terephthalic acid are added into a polytetrafluoroethylene tube;
(2) Adding a proper amount of water and a proper amount of N, N-dimethylformamide solvent into the polytetrafluoroethylene tube, wherein the total filling degree is 47%, and the volume ratio is 6:1;
(3) Adjusting the pH to 5 by using 2mol/L HCl;
(4) And (3) placing the polytetrafluoroethylene tube in a stainless steel reaction kettle, reacting for 48 hours at 393K, naturally cooling to normal temperature, separating out blue blocky crystals, collecting the crystals, washing with water, and drying in vacuum to obtain the polytetrafluoroethylene tube.
The two-dimensional copper coordination polymer is applied to degradation of methylene blue in water as a high-efficiency heterogeneous photocatalyst.
The beneficial effects are that:
the two-dimensional copper coordination polymer provided by the invention is prepared from partially deprotonated 2- (4-carboxyphenoxy) terephthalic acid (H 3 cpota) ligand-structured, partially deprotonated hcpona 2– The ligand and 4,4' -bipyridine are connected with tetragonal cone copper ions to form a two-dimensional structure. The copper coordination polymer not only can exist in water stably, but also can be used as a photocatalyst for degrading methylene blue in water. The copper coordination polymer is obtained under the hydrothermal synthesis condition, and has simple preparation process and high yield and purity.
Drawings
FIG. 1 is a crystal structure diagram of a copper coordination polymer of the present invention;
FIG. 2 is an X-ray powder diffraction pattern of a copper coordination polymer of the present invention at 298K;
FIG. 3 shows the concentration of methylene blue as a function of time ([ MB ] under various conditions]＝10mg L -1 ,[H 2 O 2 ]＝50mM,complex 1＝5mg,T＝25℃,pH＝9)；
FIG. 4 is a graph of complex 1 (5 mg) at pH= 9,H 2 O 2 Uv absorbance profile of catalytically degraded methylene blue at=50 mM;
FIG. 5 is MB (10 mg L) -1 ) Quasi-first order kinetics curve-ln (C/C) of photocatalytic degradation 0 ) Graph of time.
Detailed Description
The following describes the essential aspects of the present invention in detail with reference to examples, but is not intended to limit the scope of the present invention.
Example 1: preparation and assay of copper coordination polymers
Weigh 0.2mmol H 3 cpota,0.2mmol of 4,4' -bpy and 0.1mmol of Cu (NO 3 ) 2 ·3H 2 O is added to the mixture containing 6mLH 2 To a 15mL polytetrafluoroethylene tube of O, 1mL of DMF was added, HCl at a concentration of 2mol/L was slowly added dropwise to the mixture under stirring to adjust the pH to 5, and stirring was continued for 30 minutes. The polytetrafluoroethylene tube is placed in a stainless steel reaction kettle, heated for 48 hours at 393K, naturally cooled to room temperature, and then blue massive crystals can be separated out, washed by water and dried in vacuum, and the yield is 83%. Elemental analysis: c (C) 25 H 18 CuN 2 O 8 Calculated as C55.56,H 3.33,N 5.19%; the experimental value is C55.84,H 3.21,N 5.78%.
Crystal structure determination: the crystal X-ray diffraction data are collected at a Beijing synchrotron radiation 3W1A line station, a detector for collecting the data is MARDCCD-165, the wavelength is 0.7200, the working voltage is 2.5GeV, and the diffraction data are collected under the protection of 100 (2) K liquid nitrogen. The data were processed after reduction by HKL2000 procedure. The crystal structure was solved by the SHELXL-2014 direct method and modified by the full matrix minimization scheme using SHELXL-2014. The detailed crystal measurement data are shown in Table 1, and the crystal structure is shown in two-dimensional structure shown in FIG. 1.
TABLE 1 crystallographic data for copper coordination polymer materials
Powder diffraction method analyte phases: the X-ray powder diffraction experimental pattern is consistent with the simulated pattern, which shows that the copper coordination polymer crystal sample of the invention has uniform phase, and is shown in figure 2.
Example 2: the copper coordination polymer of the invention has high-efficiency catalytic degradation on methylene blue in water
First, a Methylene Blue (MB) solution was prepared at a concentration of 10 mg/L. 5mg of the coordination polymer, copper ions and H 3 The cpota ligand was added to 10mL of Methylene Blue (MB) solution and a blank sample was prepared, pH was adjusted to 9 with KOH, and then wrapped with tinfoil, and stirred in the dark to reach adsorption-desorption equilibrium (MB concentration no longer changed). Removing tinfoil paper, illuminating, and adding a certain amount of H 2 O 2 Uv testing was performed at the same time intervals. As shown in fig. 3, H without additional catalyst 2 O 2 The degradation rate of the/MB system within 32 minutes was 25%, indicating H 2 O 2 Only MB is degraded slowly. Under the same time and condition, H 3 cpota/H 2 O 2 MB system and Cu 2+ /H 2 O 2 the/MB system also only degrades MB slowly, 1/H 2 O 2 The degradation rate of the/MB system can reach 97%, and the degradation efficiency of the copper complex to methylene blue is obviously higher than that of a single ligand and a single metal respectively. The results show that: at H 2 O 2 When present, the complex 1 can act as an effective photocatalyst to degrade the dye methylene blue.
Example 3: sensitivity of the copper coordination polymer of the invention to degradation of methylene blue in water
10mL of Methylene Blue (MB) solution having a concentration of 10mg/L was added to 5mg of the coordination polymer, the pH was adjusted to 9 with KOH, and then the coordination polymer was covered with tinfoil, and stirred in the dark to reach adsorption/desorption equilibrium (MB concentration was not changed). Removing tinfoil paper, illuminating, and adding a certain amount of H 2 O 2 In the phase ofUv testing was performed at the same time intervals. As shown in fig. 4, the ultraviolet absorption of the solution decreased significantly with time. Furthermore, as shown in fig. 5, degradation of most organic contaminants follows a quasi-first order reaction kinetic model, which can be treated with a quasi-first order reaction equation: ln (C/C) 0 )＝-ln(A/A 0 ) =kt, C and C 0 Respectively representing the concentration of the dye at time "t" and the initial concentration of the dye, A and A 0 The absorbance of the dye at time "t" and the initial absorbance of the dye, respectively; k is a rate constant, higher rate constant K indicates higher catalytic activity. The rate constant of the coordination polymer on methylene blue degradation is K=0.074 min -1 The coordination polymer has higher response sensitivity to degradation of methylene blue in aqueous solution. The experiment shows that the coordination polymer can be used as a photocatalyst to catalyze and degrade methylene blue in aqueous solution.
The above-described embodiments serve to describe the substance of the present invention in detail, but those skilled in the art should understand that the scope of the present invention should not be limited to this specific embodiment.
Claims (3)
1. A two-dimensional copper coordination polymer has a chemical formula of [ Cu (Hcpota) (4, 4' -bpy) (H) 2 O)] n Hcpota in the formula refers to Hcpota 2- Is o- (p-carboxybenzene) oxy terephthalic acid H 3 The deprotonated form of cpota, 4'-bpy being 4,4' -bipyridine, n representing the polymerization; the structural formula of the polymer is as follows:
2. the method for preparing the two-dimensional copper coordination polymer according to claim 1, comprising the following steps:
(1) Cu (NO) was added in a molar ratio of 2:2:1 3 ) 2 ·3H 2 O, 4' -bipyridine and O- (p-carboxybenzene) oxy terephthalic acid are added into a polytetrafluoroethylene tubeIn (a) and (b);
(2) Adding a proper amount of water and a proper amount of N, N-dimethylformamide solvent into the polytetrafluoroethylene tube, wherein the total filling degree is 47%, and the volume ratio is 6:1;
(3) Adjusting the pH to 5 by using 2mol/L HCl;
(4) And (3) placing the polytetrafluoroethylene tube in a stainless steel reaction kettle, reacting for 48 hours at 393K, naturally cooling to normal temperature, separating out blue blocky crystals, collecting the crystals, washing with water, and drying in vacuum to obtain the polytetrafluoroethylene tube.
3. The use of the two-dimensional copper coordination polymer according to claim 1 as a high-efficiency heterogeneous photocatalyst for degrading methylene blue in water.
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