CN114456398A - Copper transition metal coordination polymer and preparation method and application thereof - Google Patents
Copper transition metal coordination polymer and preparation method and application thereof Download PDFInfo
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 61
- -1 Copper transition metal Chemical class 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 6
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- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 16
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- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
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- 238000003756 stirring Methods 0.000 claims description 11
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- 150000002500 ions Chemical class 0.000 claims description 8
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- 239000002184 metal Substances 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 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 description 29
- 229960000907 methylthioninium chloride Drugs 0.000 description 29
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 21
- 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 description 17
- 229940012189 methyl orange Drugs 0.000 description 17
- 229940043267 rhodamine b Drugs 0.000 description 16
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 15
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- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
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- IGRCWJPBLWGNPX-UHFFFAOYSA-N 3-(2-chlorophenyl)-n-(4-chlorophenyl)-n,5-dimethyl-1,2-oxazole-4-carboxamide Chemical compound C=1C=C(Cl)C=CC=1N(C)C(=O)C1=C(C)ON=C1C1=CC=CC=C1Cl IGRCWJPBLWGNPX-UHFFFAOYSA-N 0.000 description 1
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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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
-
- B01J35/39—
-
- 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
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- 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
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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
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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
- 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
- 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
Abstract
The invention discloses a copper transition metal coordination polymer and a preparation method and application thereof, wherein the coordination polymer is prepared from a p-hydroxyphenylacetic acid ligand (H)2L), 4' -bipyridine ligand and Cu (NO)3)2·3H2O is prepared from (C) Cu (L)2(4,4’‑bipy)(H2O)]n·nH2O and L are p-hydroxyphenylacetic acid, and the asymmetric unit of the compound consists of 1 metal Cu2+2 coordinating p-hydroxyphenylacetic acid anion ligand, 14, 4' -bipyridine, 1 coordinating water molecule and 1 free water molecule, wherein adjacent Cu2+The 1D chain structure is formed by the connection of 4, 4' -bipyridine ligands, and then the 1D chain structure is formed byThe hydrogen bond connection of the p-hydroxyphenylacetic acid ligand in the other direction constructs a two-dimensional network structure; the two-dimensional network structure is expanded into a three-dimensional network structure through weak interaction force. The coordination polymer has a great prospect in application of photocatalytic degradation of organic pollutants in water.
Description
Technical Field
The invention belongs to the technical field of metal-organic framework material photocatalysts, and particularly relates to a copper transition metal coordination polymer and a preparation method and application thereof.
Background
With the rapid development of modern industry, dye wastewater discharged in large quantity in the industries of textile, paper making, printing and the like has become one of the main sources of water pollution. Due to the structural stability of dyes and the increasing discharge amount, the treatment of dye wastewater is always a great challenge to human beings. At present, the technologies of adsorption, separation, chemical oxidation, flocculation, photocatalytic degradation and the like are used for effectively removing the dye in the wastewater. Of the many technologies, photocatalytic technology has received much worldwide attention in removing pollutants from wastewater because it provides sustainable, abundant solar energy utilization and mild conditions to drive reactions to occur. And the semiconductor photocatalyst can be directly driven by light, so that the semiconductor photocatalyst is considered to be an ideal technology for treating environmental pollution.
Metal organic framework Materials (MOFs) have various potential applications such as gas storage, separation, heterogeneous catalysis and the like due to their large surface area, diverse topological structures and abundant active nodes. In addition, some MOFs exhibit semiconductor properties under light irradiation, and compared with conventional inorganic semiconductors, MOFs have unique advantages of open metal sites, unsaturated metal centers, even catalytically active organic linkers, etc., which means that they can be used as photocatalysts for photocatalytic degradation of dye wastewater.
Disclosure of Invention
The invention aims to provide a copper transition metal coordination polymer, a preparation method and an application thereof.
To achieve the above object, the present invention provides a copper transition metal complex polymer, the copper transition metal complex polymerThe chemical formula of the compound is [ Cu (L) ]2(4,4’-bipy)(H2O)]n·nH2O, wherein H2L is p-hydroxyphenylacetic acid, the asymmetric unit of the coordination polymer is composed of 1 Cu2+Ion, 2 p-hydroxyphenylacetic acid anion ligands, 14, 4' -bipyridine ligand, 1 coordinated water molecule and 1 free water molecule, wherein n represents the degree of polymerization and is a natural number.
Furthermore, the copper transition metal coordination polymer belongs to a monoclinic system P-1 space group, and the unit cell parameters are as follows:
α＝108.630(1)°，β＝96.494(1)°，γ＝90.970(1)°。
further, the structural formula of the copper transition metal coordination polymer is shown as a formula I,
wherein, Cu1 ion and three oxygen atoms in two different oxygen-containing L ligands, two nitrogen atoms in two different nitrogen-containing 4, 4' -bipyridine ligands and one oxygen atom in one coordinated water molecule form a six-coordinated deformed octahedral configuration, and the three oxygen atoms in two different nitrogen-containing L ligands are O1, O4 and O5 respectively; the two different nitrogen-containing ligands are N1 and N2, respectively; one oxygen atom in one coordinated water molecule is O7.
Further, O1, O4, O5 and O7 in the distorted octahedral configuration occupy four equatorial vertices of the octahedral configuration, N1 and N2 occupy two vertex positions of the distorted octahedral configuration, and the bond length of Cu — N in the distorted octahedral configuration is 2.028(2) and
bond length of Cu-O of
The bond angles of O-Cu-N and O-Cu-O are 81.34(9) to 95.08(10) ° and 50.32(7) to 177.42(8) ° respectively, and the bond angle of N-Cu-N is 172.50(10) °.
Furthermore, in the copper transition metal coordination polymer, 4, 4' -bipyridyl ligand is monodentate bridged with Cu2+Coordination, L and water molecules with metallic Cu2+Ion coordinated, adjacent Cu2+A1D chain structure is formed by the connection of 4,4 '-bipyridine ligands, a two-dimensional network structure is constructed by the connection of the 4, 4' -bipyridine ligands in the other direction, and the two-dimensional network structure is expanded into a three-dimensional network structure by weak interaction force.
Further, the weak interaction force is at least one of O-H.cndot. O, C-H.cndot.O and a hydrogen bond.
Further, the copper transition metal coordination polymer can be kept stable within 200 ℃.
The preparation method of the copper transition metal coordination polymer comprises the following steps:
p-hydroxyphenylacetic acid, 4' -bipyridine and Cu (NO)3)2·3H2And dissolving O in the mixed solution of water and methanol, hermetically stirring at room temperature for 25-35 min, adding triethylamine, continuously stirring for 25-35 min, filtering and standing to obtain the product.
Further, the volume ratio of water to methanol in the mixed solution of water and methanol is 1:1, the p-hydroxyphenylacetic acid ligand, 4' -bipyridine and Cu (NO)3)2·3H2The molar ratio of O is 2:1: 2.
Further, the application of the copper transition metal coordination polymer in photocatalytic degradation of organic pollutants in water.
In summary, the invention has the following advantages:
1. the copper transition metal coordination polymer prepared by the invention can maintain stability within 200 ℃.
2. The copper transition metal coordination polymer prepared by the invention can be used as a photocatalyst and applied to degrading organic pollutants in water, wherein the photocatalytic degradation rate of Methylene Blue (MB) is 74.83%, the photocatalytic degradation rate of rhodamine B (RhB) is 48.94%, and the photocatalytic degradation rate of Methyl Orange (MO) is 25.99%.
Drawings
FIG. 1 is an asymmetric environment diagram of a copper transition metal coordination polymer;
FIG. 2 is a 1D chain structure in a copper transition metal coordination polymer;
FIG. 3 is a 2D network structure in a copper transition metal coordination polymer;
FIG. 4 is a thermogravimetric analysis of a copper transition metal coordination polymer;
FIG. 5 is an X-powder diffraction pattern of experimental testing and computer simulation of a copper transition metal coordination polymer;
FIG. 6 is an infrared spectrum of a copper transition metal coordination polymer;
FIG. 7 is a spectrum of a copper transition metal coordination polymer vs. Methylene Blue (MB) photocatalytic UV light;
FIG. 8 shows the ultraviolet spectrum of copper transition metal coordination polymer for rhodamine B (RhB) photocatalysis;
FIG. 9 is a photo-catalytic ultraviolet spectrum of a copper transition metal coordination polymer on Methyl Orange (MO);
FIG. 10 is a bar graph of the detection results of copper transition metal coordination polymers for different organic dyes (MB, RhB, and MO);
FIG. 11 is a graph comparing the catalytic degradation of copper transition metal coordination polymers for different organic dyes (MB, RhB, and MO);
FIG. 12 shows that the catalytic mechanism of copper transition metal coordination polymer on MB is tested (H)2Histograms of the detection results of O, TBA, BQ and AO);
FIG. 13 shows copper transition metal coordination polymer vs. different capture agents (H)2Catalytic degradation of O, TBA, BQ, and AO) are compared.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
A copper transition metal coordination polymer with a chemical formula of [ Cu (L) ]2(4,4’-bipy)(H2O)]n·nH2O, the copper transition metal coordination polymer is prepared by the following steps:
0.3mol of p-hydroxyphenylacetic acid anion ligand H2L, 0.15mol of 4, 4' -bipyridine and 0.3mol of Cu (NO)3)2·3H2And mixing O uniformly, then mixing the mixture with 10mL of water-methanol mixed solvent uniformly, wherein the volume ratio of water to methanol in the water-methanol mixed solvent is 1:1, sealing and stirring the mixture at normal temperature for 30min, adding 1 drop of triethylamine, stirring the mixture for 30min, filtering the mixture, sealing the obtained filtrate with a preservative film, uniformly pricking small holes, and standing the mixture for one week to finally obtain a needle-tip-shaped blue crystal.
Example 2
A copper transition metal coordination polymer with a chemical formula of [ Cu (L) ]2(4,4’-bipy)(H2O)]n·nH2O, the copper transition metal coordination polymer is prepared by the following steps:
0.6mol of p-hydroxyphenylacetic acid ligand L, 0.3mol of 4, 4' -bipyridine and 0.6mol of Cu (NO)3)2·3H2And uniformly mixing the mixture with 15mL of water-methanol mixed solvent, wherein the volume ratio of water to methanol in the water-methanol mixed solvent is 1:1, sealing and stirring the mixture at normal temperature for 25min, adding 1 drop of triethylamine, stirring the mixture for 35min, filtering the mixture, sealing the obtained filtrate with a preservative film, uniformly pricking small holes, and standing the mixture for one week to finally obtain a needle-tip-shaped blue crystal.
Example 3
A copper transition metal coordination polymer with a chemical formula of [ Cu (L) ]2(4,4’-bipy)(H2O)]n·nH2O, the copper transition metal coordination polymer is prepared by the following steps:
3mol of p-hydroxyphenylacetic acid anion ligand H2L, 1.5mol of 4, 4' -bipyridine and 3mol of Cu (NO)3)2·3H2O is mixed evenly and then mixed with 50mL of water-methanolUniformly mixing the mixed solvent, wherein the volume ratio of water to methanol in the water-methanol mixed solvent is 1:1, sealing and stirring for 30min at normal temperature, adding 1 drop of triethylamine, stirring for 35min, filtering, sealing the obtained filtrate with a preservative film, uniformly pricking small holes, and standing for one week to finally obtain a needle-tip-shaped blue crystal.
Test example 1
The copper transition metal coordination polymer prepared in example 1 was characterized to obtain the crystallographic parameters shown in table 1, and the partial bond length and bond angle data and the hydrogen bond length and bond angle data shown in tables 2 and 3. Elemental analysis theoretical value C of the complex: 55.96, H: 4.70, N: 5.02 (from CCDC: 2128563), Experimental value C: 55.75, H: 4.73, N: 5.05.
TABLE 1 crystallographic parameters of the complexes
*R＝∑(Fo–Fc)/∑(Fo)，**wR2＝{∑[w(Fo 2–Fc 2)2]/∑(Fo 2)2}1/2.
TABLE 2 partial bond length of the complexes
Angle of harmony key (°)
Symmetry Codes：#1＝x，1+y，z。
TABLE 3 partial hydrogen bond length of the complexes
Angle of harmony key (°)
Test example 2
The asymmetric environment diagram of the copper metal organic coordination polymer prepared in example 1 (the following experiments are all based on the copper metal organic coordination polymer prepared in example 1) is shown in fig. 1, the 1D chain structure thereof is shown in fig. 2, and the 2D network structure thereof is shown in fig. 3. As can be seen from fig. 1 to 3, Cu1 ion forms a six-coordinate distorted octahedral configuration with three oxygen atoms (O1, O4, and O5) of two different oxycarboxylic acid L ligands, two different nitrogen-containing 4, 4' -bipyridine (N1 and N2), and one oxygen atom (O7) of one coordinated water molecule. N1 and N2 in the octahedral configuration occupy the axial positions of the octahedron, and O1, O4, O5 and O7 occupy the equatorial positions of the octahedron. P-hydroxyphenylacetic acid ligand (L) is monodentate bridged and bidentate chelated with Cu2+Coordination (. mu.)1-η1And mu1-η1:η1) 4, 4' -Bipyridinyl monodentate bridging (mu)2-η1:η1) And Cu2+Coordination, coordination of water molecules with metallic Cu2+Coordination of ions (. mu.)1-η1). The bond length of Cu-N is 2.028(2) and
a Cu-O bond length of
The bond angles of O-Cu-N and O-Cu-O are in the ranges of 81.34(9) -95.08(10) ° and 50.32(7) -177.42(8) ° respectively, and the bond angle of N-Cu-N is 172.50(10) °. Adjacent Cu2+A 1D chain structure is formed by bridging and connecting 4, 4' -bipyridine, and a two-dimensional network structure is constructed by hydrogen bond connection of hydroxyl in a p-hydroxyphenylacetic acid ligand in the other direction; the two-dimensional network structure is expanded into a three-dimensional network structure through other weak interaction forces (O-H.O and C-H.O).
Test example 3
Thermogravimetric analysis of copper transition metal coordination polymers
FIG. 4 is a thermogravimetric analysis chart of the Cu-transition metal coordination polymer, and it can be seen from FIG. 4 that the thermogravimetric curve of the polymer is: n is a radical of2Thermogravimetric analysis was performed on copper transition metal coordination polymer samples under the conditions. The copper transition metal coordination polymer has a small weight loss in the range of 25-200 ℃, which is the weight loss of the coordinated water molecules. When the temperature rises to over 270 ℃, the organic ligand in the copper transition metal coordination polymer begins to be decomposed, the whole skeleton of the organic ligand molecule in the molecule begins to collapse, and finally the organic ligand molecule is decomposed into metal oxide.
Test example 4
Experimental testing and computer-simulated X-powder diffraction evaluation of copper transition metal coordination polymers
FIG. 5 is an X-powder diffraction pattern of experimental testing and computer simulation of the copper transition metal coordination polymer of the present invention, as can be seen: by comparing the theoretical simulated powder XRD patterns and experimental data test patterns of the samples, the results showed that the peak shapes and positions of the theoretical data patterns and the experimental actual patterns were consistent in the range of 5-50 degrees (2 θ). Meanwhile, the result is consistent with the element analysis result of the sample, which shows that the sample for synthesizing the complex is pure phase.
Test example 5
Infrared spectroscopic testing of copper transition metal coordination polymers
FIG. 6 is an infrared spectrum of the copper transition metal coordination polymer of the present invention, from which it can be seen that: at 3424cm-1The absorption peak is the absorption peak of O-H in the crystal water in the coordination polymer, 3212cm-1Absorption peak at 1600cm of O-H in para-hydroxyphenylacetic acid-1The peak at 1390cm is the C ═ O double bond stretching vibration in p-hydroxyphenylacetic acid-1The peak at (A) is the bending vibration of C-O-C. The C-H out-of-plane bending vibration is respectively positioned at 814 and 699cm-1The wave number is close.
Test example 6
Photocatalytic properties of copper transition metal coordination polymers
The photocatalytic degradation organic dye experiment is as follows: 50mg of the sample was finely ground and added to 100mL of an aqueous solution of methylene blue, rhodamine B or methyl orange with stirring to attain an adsorption-desorption equilibrium. The mixed solution was then placed under an ultraviolet Hg lamp and stirred for 30min, taking 5mL of solution every 10 min.
The photocatalytic activity of copper transition metal coordination polymer samples was investigated by selecting aqueous solutions of the organic dyes methylene blue, rhodamine B or methyl orange.
Wherein, fig. 7 is a photocatalytic ultraviolet spectrum of the copper transition coordination polymer of the invention to Methylene Blue (MB), fig. 8 is a photocatalytic ultraviolet spectrum of the copper transition metal coordination polymer of the invention to rhodamine b (rhb), and fig. 9 is a photocatalytic ultraviolet spectrum of the copper transition metal coordination polymer of the invention to Methyl Orange (MO), and a catalytic degradation experiment proves that when methylene blue is irradiated under an ultraviolet lamp, an ultraviolet absorption peak of the methylene blue is slowly weakened along with the increase of time, which indicates that the photocatalytic degradation capability of the methylene blue is weaker without the presence of a catalyst. However, in the presence of the complex catalyst, the UV absorption peak intensities of MB, RhB and MO are significantly reduced with increasing reaction time.
FIG. 10 is a bar graph showing the results of detection of different organic dyes (MB, RhB and MO) by the copper transition metal coordination polymer of the present invention, and FIG. 11 is a graph showing the comparison of the catalytic degradation of different organic dyes (MB, RhB and MO) by the copper transition metal coordination polymer of the present invention. According to the concentration C/C of the solution0The calculation shows that (C is the absorption peak intensity at a certain time, C0Absorption peak intensity of initial concentration), the adsorption decolorization rate (degradation rate) of MB under the condition of no catalyst is 11.49%, and the photocatalytic degradation rate of the metal organic complex material is 74.83%; the adsorption decoloration rate of RhB is 28.92% under the condition of no catalyst, and the photocatalytic degradation rate of the metal organic complex material is 48.94%; the adsorption decolorization rate of MO under the condition of no catalyst is 2.93%, and the photocatalytic degradation rate of the metal organic complex material is 25.99%; compared with the organic dye degradation of a photocatalyst without a catalyst and a metal organic complex material, the photocatalyst with the metal organic complex material has better photocatalytic performance.
The catalytic mechanism of the copper transition metal coordination polymer in MB is tested, and an OH trapping agent tert-butyl alcohol (TBA) and an OH trapping agent are respectively added into a photocatalytic reaction system,Capture agents for vacancies Ammonium Oxalate (AO) and. O2-The trapping agent Benzoquinone (BQ).
FIG. 12 shows that the copper transition metal coordination polymer of the present invention tests the catalytic mechanism for MB (H)2O, TBA, BQ and AO) in a sample, and FIG. 13 is a histogram of the results of detecting different capture agents (H) by the copper transition metal coordination polymer of the present invention2Catalytic degradation of O, TBA, BQ, and AO) are compared. According to the concentration C/C of the solution0The calculation shows that (C is the absorption peak intensity at a certain time, C0Absorption peak intensity of initial concentration), the adsorption decolorization rate (degradation rate) of MB was 74.83% under the condition of adding water, the adsorption decolorization rate (degradation rate) of MB was 60.28% under the condition of adding TBA, the adsorption decolorization rate (degradation rate) of MB was 73.1% under the condition of adding BQ, and the adsorption decolorization rate (degradation rate) of MB was 72.27% under the condition of adding AO. By comparing the data in the presence of different capture agents, the photodegradation of MB is dominated by OH radicals.
In conclusion, the photocatalytic degradation rate of the copper metal organic complex material prepared by the invention on Methylene Blue (MB) is 74.83% (the decolorization rate of blank methylene blue is 11.49%); the photocatalytic degradation rate of rhodamine B (RhB) is 48.94% (the adsorption decoloration rate of blank RhB is 28.92%); the photocatalytic degradation rate of Methyl Orange (MO) was 25.99% (adsorption decolorization rate of blank MO 2.93%). Compared with the photocatalytic organic dye degradation of copper metal organic complexes, the catalyst of the copper metal organic complexes has the best photocatalytic performance on methylene blue, and can be used as a potential photocatalyst for catalytic degradation of organic pollutants in water.
While the present invention has been described in detail with reference to the illustrated embodiments, it should not be construed as limited to the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (9)
1. A copper transition metal coordination polymer characterized in that the chemical formula of the copper transition metal coordination polymer is [ Cu (L) ]2(4,4’-bipy)(H2O)]n·nH2O, wherein, the H2L is p-hydroxyphenylacetic acid, and the asymmetric unit of the coordination polymer is composed of 1 Cu2+Ions, 2 p-hydroxyphenylacetic acid anion ligands, 14, 4' -bipyridine ligand, 1 coordinated water molecule and 1 free water molecule, wherein n represents the degree of polymerization and is a natural number.
2. The copper-transition metal coordination polymer of claim 1, wherein said copper-transition metal coordination polymer belongs to the monoclinic P-1 space group and has unit cell parameters of:
α＝108.630(1)°，β＝96.494(1)°，γ＝90.970(1)°。
3. the copper-transition metal coordination polymer according to claim 1, wherein the structural formula of said copper-transition metal coordination polymer is represented by formula I,
wherein, Cu1 ion forms a six-coordinate deformed octahedral configuration with three oxygen atoms in two different oxygen-containing L ligands, two nitrogen atoms in two different nitrogen-containing 4, 4' -bipyridine ligands and one oxygen atom in one coordinated water molecule, and the three oxygen atoms in the two different nitrogen-containing L ligands are O1, O4 and O5 respectively; the two different nitrogen-containing ligands are N1 and N2, respectively; one oxygen atom in the one coordinated water molecule is O7.
4. The copper transition metal coordination polymer of claim 3, wherein said distorted octahedral configuration of O1, O4, O5, and O7 occupy four equatorial vertices of the octahedral configuration, and N1 and N2 occupy two vertex positions of said distorted octahedral configurationThe bond length of Cu-N in the distorted octahedral configuration is 2.028(2) and
bond length of Cu-O of
The bond angles of O-Cu-N and O-Cu-O are 81.34(9) to 95.08(10) ° and 50.32(7) to 177.42(8) ° respectively, and the bond angle of N-Cu-N is 172.50(10) °.
5. The copper-transition metal coordination polymer of claim 1, wherein in said copper-transition metal coordination polymer, 4, 4' -bipyridine ligand monodentate bridging is with Cu2+Coordination, L and water molecules with metallic Cu2+Coordination of ions, of said adjacent Cu2+A1D chain structure is formed by connecting 4,4 '-bipyridyl ligands, a two-dimensional network structure is constructed by connecting the 4, 4' -bipyridyl ligands in the other direction, and the two-dimensional network structure is expanded into a three-dimensional network structure by weak interaction force.
6. The copper-transition metal coordination polymer of claim 5, wherein said weak interaction is at least one of O-H-O, C-H-O and hydrogen bonding.
7. The method for producing a copper-transition metal coordination polymer according to any one of claims 1 to 6, comprising the steps of:
mixing p-hydroxyphenylacetic acid, 4' -bipyridine and Cu (NO)3)2·3H2And dissolving O in the mixed solution of water and methanol, hermetically stirring at room temperature for 25-35 min, adding triethylamine, continuously stirring for 25-35 min, filtering and standing to obtain the product.
8. The method for producing a copper-transition metal coordination polymer according to claim 7, wherein the volume ratio of water to methanol in the mixed solution of water and methanol is 1:1, and the p-hydroxyl groupPhenylacetic acid ligands, 4' -bipyridine and Cu (NO)3)2·3H2The molar ratio of O is 2:1: 2.
9. The use of the copper-transition metal coordination polymer according to claims 1-6 in photocatalytic degradation of organic pollutants in water.
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