CN111518282B - Hydroxypyrazole cadmium carboxylate coordination polymer for visible light catalytic degradation of organic dye and preparation and application thereof - Google Patents
Hydroxypyrazole cadmium carboxylate coordination polymer for visible light catalytic degradation of organic dye and preparation and application thereof Download PDFInfo
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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 44
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 44
- -1 Hydroxypyrazole cadmium carboxylate Chemical class 0.000 title claims abstract description 23
- 230000015556 catabolic process Effects 0.000 title claims abstract description 16
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000975 dye Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 18
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 17
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- FERCTUUKKXAWIL-UHFFFAOYSA-N 5-oxo-1,2-dihydropyrazole-3-carboxylic acid Chemical compound OC(=O)C=1C=C(O)NN=1 FERCTUUKKXAWIL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
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- 150000002500 ions Chemical class 0.000 claims abstract description 4
- 239000013110 organic ligand Substances 0.000 claims abstract description 3
- 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 3
- 239000000243 solution Substances 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 12
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 10
- 230000000593 degrading effect Effects 0.000 claims description 10
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 10
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- 238000001308 synthesis method Methods 0.000 abstract description 2
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 15
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 230000032900 absorption of visible light Effects 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention discloses a hydroxypyrazole cadmium carboxylate coordination polymer for visible light catalytic degradation of organic dye and preparation and application thereof, wherein the chemical expression of the cadmium coordination polymer is [ Cd (hpCH) (H)2O)(DMF)]nIn the formula of hpCH3Is 5-hydroxypyrazole-3-carboxylic acid, each asymmetric unit of which contains 1 metal Cd2+Ionic, 1 deprotonated organic ligand (hpCH)2‑) 1 coordinated water molecule and 1 coordinated DMF molecule, Cd2+Ions are connected through a 5-hydroxypyrazole-3-carboxylic acid ligand to form a two-dimensional layered structure. The synthesis method of the cadmium coordination polymer is simple and has high yield; the material has stable dye photocatalytic degradation performance at normal temperature, can efficiently carry out photocatalytic degradation on Methylene Blue (MB) azo dye, and has high repeated utilization rate; meanwhile, the polymer has stable structure, is insoluble in water and common organic solvents, and can avoid the problem of secondary pollution.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a hydroxypyrazole cadmium carboxylate coordination polymer for degrading organic dye under catalysis of visible light, and preparation and application thereof.
Background
The discharge of large amounts of factory waste water causes serious environmental problems, and the waste water produced in many industrial processes often contains toxic organic compounds, and is therefore not suitable for direct biological treatment. Taking organic dyes as an example, there are over 10 million commercial dyes on the market, with annual yields of over 70 million tons. These organic dyes are chemically stable, are not easily degraded in water, and are potentially harmful to the ecological environment. Therefore, in order to better protect the global environment where we rely on to live, it is necessary to research and develop materials capable of efficiently degrading organic dyes in wastewater to put into the wastewater degradation field.
Photocatalysis is a degradation method based on in-situ generation of transition substances with strong reactivity, and has the advantages of good environmental operation conditions, low cost, high efficiency and the like compared with other traditional physical and chemical methods.
To date, a range of semiconductor photocatalysts such as metal oxides, chalcogenides and other metal salts and composites thereof have been found to be useful for dye degradation. Wherein, TiO2The composite material has the advantages of biological inertia, chemical inertia, no toxicity, low cost, strong ultraviolet oxidation resistance and the like, so that the composite material is widely concerned in recent years. However, TiO2Energy band gap (E)g3.2eV) and the response to ultraviolet light does not exceed 4%, limiting the absorption of visible light and thus affecting its practical application. Another type of semiconductor metal sulfide, e.g. CdS, In2S3、Sb2S3And CoS, etc., are also considered promising catalysts due to their high ability to respond to visible light, coupled with appropriate valence and conduction band positions. However, since sulfide ions are relatively easily dissolved in light, secondary pollution of heavy metal ions is caused. Therefore, the development of new efficient photocatalysts remains a great challenge.
The coordination polymer as a novel multifunctional material has the advantages of adjustability and designability, and the structure of the coordination polymer can be controlled by selecting different organic connecting agents, metal centers/metal clusters and reaction conditions. Therefore, the method has attracted wide attention in the fields of adsorption, catalysis, photoelectric devices, gas storage and separation and the like. Due to the abundant metal nodes and organic bridging agents and the controllability of synthesis, the coordination polymer with adjustable light absorption property is easy to construct, thereby providing an ideal photocatalytic material for the degradation of organic pollutants. Based on the cadmium coordination polymer, the cadmium coordination polymer based on the novel structure of the 5-hydroxypyrazole-3-carboxylic acid is designed, so that the organic dye can be efficiently degraded in a photocatalytic manner.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a cadmium coordination polymer based on a novel structure of 5-hydroxypyrazole-3-carboxylic acid, which has a simple synthesis process and can efficiently degrade organic dyes in a photocatalytic manner.
In order to achieve the technical purpose, the invention is realized by the following technical scheme: the invention provides a hydroxypyrazole cadmium carboxylate coordination polymer for visible light catalytic degradation of organic dye, wherein the chemical expression of the cadmium coordination polymer is [ Cd (hpCH) (H)2O)(DMF)]nIn the formula of hpCH3Is 5-hydroxypyrazole-3-carboxylic acid, each asymmetric unit of which contains 1 metal Cd2+Ionic, 1 deprotonated organic ligand (hpCH)2-) 1 coordinated water molecule and 1 coordinated DMF molecule, Cd2+Ions are connected through a 5-hydroxypyrazole-3-carboxylic acid ligand to form a two-dimensional layered structure, and the molecular structure of the two-dimensional layered structure is as follows:
further, the coordination polymer belongs to monoclinic system, P21/c space group, and the unit cell parameters are as follows:
α＝90°，β＝92.916(2)°，γ＝90°，
the preparation method of the hydroxypyrazole cadmium carboxylate coordination polymer for degrading organic dye by visible light catalysis comprises the following steps: dissolving 5-hydroxypyrazole-3-carboxylic acid in a mixed solution of distilled water and DMF, dissolving cadmium nitrate in distilled water, uniformly mixing the two solutions, carrying out heating reaction in a closed oven, and naturally cooling to room temperature after the reaction is finished to obtain the hydroxypyrazole cadmium carboxylate coordination polymer for degrading the organic dye by visible light catalysis.
Furthermore, the molar ratio of the 5-hydroxypyrazole-3-carboxylic acid to the cadmium nitrate is 1: 1.5-1: 2, and the volume ratio of the distilled water to the DMF is 2: 1-3: 1.
Further, the temperature of the oven is 80-100 ℃, and the heating reaction time is 1-2 days.
The cadmium coordination polymer can be used for efficiently degrading Methylene Blue (MB) azo dye through photocatalysis, has high cycle stability, and can be recycled.
The invention has the beneficial effects that:
the synthesis method of the hydroxypyrazole cadmium carboxylate coordination polymer for degrading the organic dye by visible light catalysis is simple, convenient and fast to operate and high in preparation efficiency;
the obtained cadmium coordination polymer has stable structure, is insoluble in water and common organic solvents, and can avoid the problem of secondary pollution;
the cadmium coordination polymer disclosed by the invention has excellent performance, organic dyes, especially Methylene Blue (MB) azo dyes, can be efficiently degraded in a photocatalytic manner at normal temperature, and the photocatalytic degradation rate can even reach 96.7% under the irradiation of visible light.
Drawings
FIG. 1 is a crystal structure diagram of a cadmium hydroxypyrazole carboxylate coordination polymer for visible light photocatalytic degradation of organic dyes;
FIG. 2 is a graph of the ultraviolet absorption spectrum of a cadmium hydroxypyrazole carboxylate coordination polymer for photocatalytic degradation of methylene blue by visible light;
FIG. 3 is a graph of the rate of change of methylene blue concentration upon photocatalytic degradation of methylene blue by a cadmium hydroxypyrazole carboxylate coordination polymer of a visible photocatalytic degradation organic dye;
FIG. 4 is a graph of the rate of change of cyclic concentration of cadmium hydroxypyrazole carboxylate coordination polymer photocatalytically degrading methylene blue 5 times with visible photocatalytic degradation of organic dyes;
FIG. 5 is a PXRD pattern of photocatalytic degradation of methylene blue by a cadmium hydroxypyrazole carboxylate coordination polymer of visible photocatalytic degradation of organic dyes.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1: preparation of hydroxypyrazole cadmium carboxylate coordination polymer for visible light catalytic degradation of organic dye
Weighing 5-hydroxypyrazole-3-carboxylic acid (0.05mmol, 0.0064g) and dissolving in a mixed solution of 1.6mL of DMF and 2mL of distilled water to prepare a ligand solution, weighing cadmium nitrate (0.1mmol, 0.0308g) and dissolving in 1mL of distilled water, adding the cadmium nitrate solution into the ligand solution, uniformly mixing to obtain a transparent colorless solution, reacting in an oven at 90 ℃ for 2 days, cooling to room temperature to obtain a light yellow blocky crystal, and obtaining the yield: 54.7 percent. And (3) performing infrared characterization on the product, wherein the specific result is as follows: IR (KBr, cm)-1)：3252(m)，2360(w)，1665(s)，1580(s)，1446(s)，1359(m)，1263(w)，1149(m)，1014(m)，846(w)，752(m)，648(m)，570(w)。
Example 2: preparation of hydroxypyrazole cadmium carboxylate coordination polymer for visible light catalytic degradation of organic dye
Weighing 5-hydroxypyrazole-3-carboxylic acid (0.05mmol, 0.0064g) and dissolving in a mixed solution of 1mL of DMF and 2mL of distilled water to prepare a ligand solution, weighing cadmium nitrate (0.1mmol, 0.0308g) and dissolving in 1mL of distilled water, adding the cadmium nitrate solution into the ligand solution, uniformly mixing to obtain a transparent colorless solution, reacting in an oven at 90 ℃ for 1 day, cooling to room temperature to obtain a light yellow blocky crystal, wherein the yield is as follows: 51.4 percent. To pairThe product is subjected to infrared characterization, and the specific result is as follows: IR (KBr, cm)-1)：3252(m)，2358(w)，1659(s)，1581(s)，1444(s)，1363(m)，1263(w)，1147(m)，1013(m)，848(w)，750(m)，649(m)，571(w)。
The infrared test results show that the product of this example is the same as the product of example 1.
Example 3: preparation of hydroxypyrazole cadmium carboxylate coordination polymer for visible light catalytic degradation of organic dye
Weighing 5-hydroxypyrazole-3-carboxylic acid (0.05mmol, 0.0064g) and dissolving in a mixed solution of 1.5mL of DMF and 2mL of distilled water to prepare a ligand solution, weighing cadmium nitrate (0.08mmol, 0.0246g) and dissolving in 1mL of distilled water, adding the cadmium nitrate solution into the ligand solution and uniformly mixing to obtain a colorless transparent solution, reacting in an oven at 100 ℃ for 1 day, cooling to room temperature to obtain a light yellow blocky crystal, wherein the yield is as follows: 53.2 percent. And (3) performing infrared characterization on the product, wherein the specific result is as follows: IR (KBr, cm)-1)：3250(m)，2361(w)，1667(s)，1580(s)，1442(s)，1360(m)，1259(w)，1148(m)，1015(m)，846(w)，753(m)，645(m)，573(w)。
The infrared test results show that the product of this example is the same as the product of example 1.
The relevant crystallographic data for the Cd complex are as follows:
the complex is as follows: [ Cd (hpch)) (H2O)(DMF)]
The molecular formula is as follows: c7H11O5N3Cd
Molecular weight: 329.59
Crystal system: monoclinic
Space group: p21/c
Unit cell parameters:
90°、92.916(2)°、90°
volume:
and (3) performance testing: application of hydroxypyrazole cadmium carboxylate coordination polymer in photocatalytic degradation of methylene blue
A xenon lamp is used as a visible light source, and the cadmium coordination polymer obtained in example 1 is subjected to a photocatalytic degradation reaction of methylene blue, wherein the molecular formula of the methylene blue is shown as follows:
50mL of a methylene blue aqueous solution having a concentration of 5mg/L was put into a quartz reaction vessel, 30mg of the cadmium coordination polymer obtained in example 1 was added thereto, and the mixture was stirred in the dark for 30 minutes. After reaching the adsorption-desorption equilibrium, sampling is carried out once. Taking a xenon lamp as a visible light source to perform photocatalytic degradation reaction, sampling once every 10min for 10 times in total, centrifuging the taken suspension at a rotating speed of 10000r/min for 4min, and taking supernatant to measure the ultraviolet visible absorption spectrum (figure 2). The result shows that after 90min of photocatalytic degradation, the degradation rate of the cadmium coordination polymer on methylene blue reaches 96.7% (fig. 3). PXRD test results show that after 5 cycles, the structure of the cadmium coordination polymer photocatalyst is not obviously changed (figure 5), and the catalytic effect is not basically changed (figure 4), which shows that the cadmium coordination polymer photocatalyst not only has the characteristic of efficiently degrading methylene blue through photocatalysis, but also has high stability and can be recycled.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (5)
1. The cadmium hydroxypyrazole carboxylate coordination polymer for degrading organic dye under catalysis of visible light is characterized in that the chemical expression of the cadmium coordination polymer is [ Cd (hpCH) (H)2O)(DMF)]nIn the formula of hpCH3Is 5-hydroxypyrazole-3-carboxylic acid, each asymmetric unit of which contains 1 metal Cd2+Ionic, 1 deprotonated organic ligand(hpcH2-) 1 coordinated water molecule and 1 coordinated DMF molecule, Cd2+Ions are connected through a 5-hydroxypyrazole-3-carboxylic acid ligand to form a two-dimensional layered structure, and the molecular structure of the two-dimensional layered structure is as follows:
the cadmium coordination polymer can be used for efficiently degrading methylene blue azo dyes in a photocatalytic manner, and can keep stable structure and catalytic effect after being recycled for several times.
2. The cadmium hydroxypyrazole carboxylate coordination polymer for the catalytic degradation of organic dyes according to claim 1, wherein the coordination polymer belongs to the monoclinic system, P21/c space group, and has the unit cell parameters:
α＝90°，β＝92.916(2)°，γ＝90°，
3. the preparation method of the cadmium hydroxypyrazole carboxylate coordination polymer for visible light catalytic degradation of organic dyes according to any one of claims 1 to 2, which comprises the following specific preparation steps: dissolving 5-hydroxypyrazole-3-carboxylic acid in a mixed solution of distilled water and DMF, dissolving cadmium nitrate in distilled water, uniformly mixing the two solutions, carrying out heating reaction in a closed oven, and naturally cooling to room temperature after the reaction is finished to obtain the cadmium coordination polymer.
4. The method for preparing the cadmium hydroxypyrazole carboxylate coordination polymer for visible light catalytic degradation of organic dyes according to claim 3, wherein the molar ratio of 5-hydroxypyrazole-3-carboxylic acid to cadmium nitrate is 1: 1.5-1: 2, and the volume ratio of distilled water to DMF is 2: 1-3: 1.
5. The preparation method of the cadmium hydroxypyrazole carboxylate coordination polymer for visible light catalytic degradation of organic dyes according to claim 3, wherein the oven temperature is 80-100 ℃, and the heating reaction time is 1-2 days.
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