CN112174827A - Polyoxometalate compound containing tetranuclear cadmium cluster and preparation method and application thereof - Google Patents
Polyoxometalate compound containing tetranuclear cadmium cluster and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polyoxometallate compounds, and particularly relates to a tetranuclear cadmium cluster-containing polyoxometallate compound and a preparation method and application thereof. The chemical formula of the cadmium cluster substituted polyoxometallate compound provided by the invention is (H)2dap)6[Cd4Cl2(AsW9O34)2]The compound is sandwich transition metal substituted polyoxometallate constructed by tetranuclear cadmium cluster and three-vacancy Keggin structure arsenic molybdate; the present invention provides a tetranuclear cadmium cluster polyoxometallate compound in alcoholsThe solvent has the property of fluorescence enhanced response and the function of polycyclic aromatic hydrocarbon identification, can be used for preliminary screening detection of polycyclic aromatic hydrocarbon in chemical solutions, and has a relatively large application prospect.
Description
Technical Field
The invention relates to the technical field of fluorescent recognition of polyoxometallate compounds and polycyclic aromatic hydrocarbon compounds, in particular to a tetranuclear cadmium cluster-containing polyoxometallate compound and a preparation method and application thereof.
Background
Polyoxometalates (POMs) are coordination compounds with special structures, and have wide application in the fields of industrial catalysis, optical materials, medical science, storage materials, mechanical engineering and the like. Recently, many studies find that the coordination compound with the fluorescent function constructed by metal ions such as zinc and cadmium has a very wide application prospect in the identification aspects of dangerous goods, explosives, industrial raw materials and the like.
Polycyclic Aromatic Hydrocarbons (PAHs) are Hydrocarbons produced in the processing of coal chemical industry and petrochemical industry and in the incomplete combustion of organic matters such as wood, tobacco and organic high molecular compounds, are important environmental and food pollutants, and a considerable part of the Polycyclic Aromatic Hydrocarbons have extremely strong carcinogenicity. PAHs are widely distributed in the environment, and the compounds have elimination modes of biodegradation, hydrolysis, light action cracking and the like in nature, so that the content of the PAHs in the environment is always in dynamic balance, and the PAHs are kept at a lower concentration level. However, the elimination method is time-consuming, and PAHs can be rapidly produced in large quantity in the production, processing and use processes of modern chemical organic matters. These PAHs are present in environments where we are constantly moving, such as indoors and in-car decoration; substances which we often contact, such as printing and dyeing of clothes; and drinking water, such as soil, river, lake and underground water pollution caused by improper sewage treatment, become important factors of carcinogenesis, teratogenesis and mutagenesis in the environment. The existing detection method of PAHs mainly comprises means such as mass spectrum, gas chromatography or liquid chromatography, but the equipment and instruments used by the detection method are expensive. Compared with the prior art, the fluorescence detection equipment has low cost and simple and convenient operation. However, no relevant report about fluorescence detection of PAHs exists in the prior art at present.
Disclosure of Invention
The invention aims to provide a polyoxometallate compound containing a tetranuclear cadmium cluster, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polyoxometallate compound containing tetranuclear cadmium cluster, which has a chemical formula of (H)2dap)6[Cd4Cl2(AsW9O34)2]Wherein, [ Cd ]4Cl2(AsW9O34)2]12–Is a functional entity, [ H ]2dap]2+Is amine counter cation.
Preferably, the compound is a sandwich structure compound constructed based on a three-vacancy Keggin structure, and a three-dimensional supermolecular structure compound derived by hydrogen bond connection.
The invention also provides a preparation method of the polyoxometallate compound containing the tetranuclear cadmium cluster, which comprises the following steps:
mixing tungstate, cadmium salt, an arsenic-containing precursor and amine to obtain a suspension, wherein the arsenic-containing precursor is arsenite or arsenate;
adjusting the pH value of the suspension to 4.50-6.50 by using a pH regulator, and then carrying out a solvothermal reaction to obtain the tetranuclear cadmium cluster-containing polyoxometallate compound; the cadmium salt or the pH regulator contains chlorine element.
Preferably, the tungstate is sodium tungstate or potassium tungstate; the cadmium salt comprises cadmium nitrate, cadmium sulfate, a mixture of cadmium hydroxide and hydrochloric acid, a mixture of cadmium hydroxide and nitric acid, and cadmium acetate or cadmium chloride; the amine comprises ethylenediamine, 1, 2-propylenediamine, or 1, 3-propylenediamine.
Preferably, the molar ratio of the tungstate to the cadmium salt to the arsenic-containing precursor to the amine is 0.01-0.06: 0.03-0.10.
Preferably, the solvent of the solvothermal reaction is water or a mixed solution of water and an organic solvent.
Preferably, the temperature of the solvothermal reaction is 100-170 ℃ and the time is 2-5 days.
Preferably, the organic solvent comprises methanol or ethanol.
Preferably, the solvothermal reaction further comprises: naturally cooling the obtained material.
The invention also provides the application of the polyoxometallate compound containing the tetranuclear cadmium cluster prepared by the technical scheme or the polyoxometallate compound containing the tetranuclear cadmium cluster prepared by the preparation method in the technical scheme in fluorescence identification detection.
The invention provides a polyoxometallate compound (CdAW for short) containing tetranuclear cadmium cluster, which has a chemical formula of (H)2dap)6[Cd4Cl2(AsW9O34)2]Wherein, [ Cd ]4Cl2(AsW9O34)2]12–Is a functional entity, [ H ]2dap]2+Is amine counter cation. The compound is sandwich type transition metal substituted polyoxometallate constructed by a tetranuclear cadmium cluster and a three-vacancy Keggin structural oxygen cluster; in CdAW provided by the invention, Cd2+As having d10The metal ions of the electronic layer structure have better fluorescence property; the oxygen cluster with the triple-vacancy Keggin structure has better electron donating capability, and is combined with Cd2+After coordination, Cd is greatly improved and enhanced2+The fluorescence signal of (1). However, two Cd in the structure2+Cd if it has an electron-withdrawing group such as chlorine atom (Cl)2+The fluorescence signal generated by the Keggin structure oxygen cluster will be weakened. The CdAW provided by the invention belongs to the example; in the alcohol solvent, due to the solvation effect, the Cl electron-withdrawing ability of the CdAw on the benzene ring is reduced, so that the quenching effect of Cl on CdAw fluorescence is relieved, and the fluorescence signal of CdAw is enhanced in effect, so that the CdAw provided by the invention has the function of identifying some polycyclic aromatic hydrocarbons by fluorescence in the alcohol solvent, and can be used for polycyclic aromatic hydrocarbons in various chemicalsThe primary screening detection of the aromatic hydrocarbon has a relatively large application prospect.
Drawings
FIG. 1 is a schematic perspective view of CdAW, where A is a schematic main structure of CdAW (hydrogen atoms and water molecules are omitted); b is a structural schematic diagram of a four-core cadmium cluster ball; c is a polyhedral structure schematic diagram of a tetranuclear cadmium cluster; d is a schematic diagram of a three-vacancy Keggin structure oxygen cluster polyhedron structure; e is the coordination environment of cadmium ions connected with chlorine atoms in the tetranuclear cadmium cluster; f is the coordination environment of cadmium ions which are not connected with chlorine atoms in the tetranuclear cadmium cluster;
FIG. 2 is a schematic representation of CdAw three-dimensional supramolecular structures linked by hydrogen bonds;
FIG. 3 is an IR spectrum of a CdAW crystal prepared in example 1;
FIG. 4 is a graph of the fluorescence emission spectra of CdAw in various common solvents under 202nm excitation light;
FIG. 5 is a spectrum of the fluorescence emission of CdAw from a solid with 202nm excitation light;
FIG. 6 is a schematic diagram of the molecular structure of a common carcinogen in a dye;
FIG. 7 is a spectrum of fluorescence emission of CdAW in the presence of 202nm excitation light after interaction with naphthalene and its derivatives of FIG. 6;
FIG. 8 is a spectrum of fluorescence emission of CdAW in FIG. 6 with 202nm excitation light after interaction with aniline and its derivatives;
FIG. 9 is a spectrum of fluorescence emission at 202nm excitation light after interaction of CdAW with pyridine and its derivatives of FIG. 6;
FIG. 10 shows the fluorescence emission spectrum of CdAW after interaction with the secondary amine of FIG. 6 under 202nm excitation.
Detailed Description
The invention provides a polyoxometallate compound (CdAW for short) containing tetranuclear cadmium cluster, which has a chemical formula of (H)2dap)6[Cd4Cl2(AsW9O34)2]Wherein, [ Cd ]4Cl2(AsW9O34)2]12–Is a functional entity, [ H ]2dap]2+Amine counter cations (dap is the general name for amine substances).
In the present invention, the CdAW is a sandwich-type structural compound constructed based on a triple-vacancy Keggin structure and a tetranuclear cadmium cluster (fig. 1), and is a three-dimensional supramolecular structural compound derived by hydrogen bond connection (fig. 2). As shown in FIG. 1, in this monomer unit, A is [ Cd ] in CdAw4Cl2(AsW9O34)2]12-The coordination structure (hydrogen atoms are omitted) of (A), two groups of three-vacancy Keggin structure oxygen clusters { AsW in CdAw)9O34By sharing oxygen atoms with the tetranuclear cadmium cluster { Cd } (FIG. 1D)4Cl2Are connected to form a sandwich structure (FIG. 1B, C). The Cd (II) ion is of a six-coordination octahedral configuration and is divided into two types according to different coordination environments: 1. as shown in fig. 1E, the six coordination sites are occupied by four bridging oxygens and two chlorine atoms in two sets of three-vacancy Keggin structural oxygen clusters to form a distorted octahedral structure; 2. the six coordination sites are occupied by six bridge oxygens in two groups of three-vacancy Keggin structure oxygen clusters to form an approximate octahedral structure. As shown in fig. 2, adjacent CdAW form a three-dimensional supramolecular structure through hydrogen bonding.
In the present invention, the dap preferably comprises ethylenediamine, 1, 2-propylenediamine or 1, 3-propylenediamine.
The invention provides a preparation method of a polyoxometallate compound containing a tetranuclear cadmium cluster, which comprises the following steps:
mixing tungstate, cadmium salt, an arsenic-containing precursor and amine to obtain a suspension, wherein the arsenic-containing precursor is arsenite or arsenate;
adjusting the pH value of the suspension to 4.50-6.50 by using a pH regulator, and then carrying out a solvothermal reaction to obtain the tetranuclear cadmium cluster-containing polyoxometallate compound; the cadmium salt or the pH regulator contains chlorine element.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
In the present invention, the tungstate is preferably sodium tungstate (Na)2WO4) Or potassium tungstate (K)2WO4) (ii) a The cadmium salt preferably comprises cadmium nitrate and sulfurCadmium acid, mixture of cadmium hydroxide and hydrochloric acid, mixture of cadmium hydroxide and nitric acid, cadmium acetate or cadmium chloride, more preferably cadmium chloride (CdCl)2) (ii) a More preferably, the arsenite is sodium arsenite (NaAsO)2) (ii) a The amine preferably comprises ethylene diamine, 1, 2-propane diamine or 1, 3-propane diamine; in the invention, the molar ratio of the tungstate to the cadmium salt to the arsenic-containing precursor to the amine is preferably 0.01-0.06: 0.03-0.10; the invention further accurately selects and controls the raw materials and the proportion thereof, thereby ensuring that the final product of the polyoxometallate compound containing the tetranuclear cadmium cluster maintains higher yield.
In the invention, the solvent for the solvothermal reaction preferably comprises water or a mixed solution of water and an organic solvent, and the pH value is more preferably 5.30-5.80, and most preferably 5.66; the organic solvent preferably comprises methanol or ethanol, the dosage of the methanol or the ethanol in the solvent is not particularly limited, the pH value is preferably adjusted to 4.50-6.50 by using hydrochloric acid or sodium hydroxide, and the dosage of the hydrochloric acid or the sodium hydroxide is not particularly limited.
In the invention, the mixing of the tungstate, the cadmium salt, the arsenic-containing precursor and the amine is preferably carried out under the condition of stirring, and the stirring speed is preferably 200-600 r/min, and more preferably 300-500 r/min.
In the invention, the temperature of the solvothermal reaction is preferably 100-170 ℃, more preferably 110-140 ℃, and most preferably 130 ℃; the time is preferably 2 to 5 days, and more preferably 3 days. The present invention preferably performs the solvothermal reaction in a reaction kettle. In the process of the solvothermal reaction, arsenite ion AsO is generated at high temperature and high pressure2 –Oxidized to arsenate ion AsO4 4–And as a template with tungstate radical ions WO4 2–Self-assembled into three-vacancy Keggin configuration oxoacid salt cluster AsW9O34 9–. Keggin configuration oxosalt cluster AsW at three-vacancy position9O34 9–The cadmium ions form a tetranuclear cadmium cluster and a CdAW compound under the induction of the (A), and then are connected into a three-dimensional supermolecular structure through hydrogen bonds. The invention is provided withThe pH value, the temperature and the reaction time of the reaction are further controlled, so that the yield of the polyoxometallate compound containing the tetranuclear cadmium cluster can be maintained at a higher level.
After the solvothermal reaction is finished, the obtained product material is preferably naturally cooled to room temperature. In the cooling process, the product material is crystallized to obtain a crystal, namely the polyoxometallate compound containing the tetranuclear cadmium cluster, which is marked as CdAW. The invention can ensure the quality of the crystal by further controlling the cooling process.
The invention provides application of the polyoxometallate compound containing the tetranuclear cadmium cluster in the technical scheme or the polyoxometallate compound containing the tetranuclear cadmium cluster prepared by the preparation method in the technical scheme in fluorescence identification detection. The invention preferably detects the polycyclic aromatic hydrocarbon in an alcohol solvent by fluorescence recognition, and the method for the application is not particularly limited, and the method well known by the technical personnel in the field can be selected. In the present invention, the monomer unit of CdAw is an anion [ Cd ]4Cl2(AsW9O34)2]12–Wherein the tetranuclear cadmium cluster is a core structure part for identifying the polycyclic aromatic hydrocarbon.
The zinc metal organic framework compound provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
4.00g of Na2WO4、2.00g NaAsO2And 2.52g CdCl2Dissolving in water (150mL), and stirring and mixing at 300r/min to obtain suspension; 8mL of 1, 2-propanediamine is dripped into the mixed solution, the mixture is stirred and mixed evenly, and hydrochloric acid (6mol/L) is used for adjusting the pH value of the suspension to 5.66.
Pouring 15mL of the suspension into a reaction kettle, and reacting for 3d at 150 ℃; after the reaction is finished, naturally cooling the obtained material to room temperature to obtain colorless transparent crystals (the polyoxometallate compound containing tetranuclear cadmium cluster) with a chemical formula of (H)2dap)6[Cd4Cl2(AsW9O34)2]Denoted as CdAW; the yield was 40%.
Example 2
4.00g of Na2WO4、3.20g Na3AsO4And 2.52g CdCl2Dissolving in water (150mL), and stirring and mixing at 600r/min to obtain suspension; 8mL of 1, 3-propanediamine is dripped into the mixed solution, the mixture is stirred and mixed evenly, and nitric acid (6mol/L) is used for adjusting the pH value of the suspension to 5.80.
Pouring 15mL of the suspension into a reaction kettle, and reacting for 5d at 130 ℃; after the reaction is finished, naturally cooling the obtained material to room temperature to obtain colorless transparent crystals (the polyoxometallate compound containing tetranuclear cadmium cluster) with a chemical formula of (H)2dap)6[Cd4Cl2(AsW9O34)2]The yield was 35%.
Example 3
3.80g (NH)4)2WO4、2.00g NaAsO2And 3.00g Cd (NO)3)2Dissolving in water (150mL), and stirring and mixing at 500r/min to obtain suspension; 8mL of ethylenediamine is added into the mixed solution dropwise, the mixture is stirred and mixed evenly, and hydrochloric acid (6mol/L) is used for adjusting the pH value of the suspension to 5.30.
Pouring 15mL of the suspension into a reaction kettle, and reacting for 4d at 140 ℃; after the reaction is finished, naturally cooling the obtained material to room temperature to obtain colorless transparent crystals (the polyoxometallate compound containing tetranuclear cadmium cluster) with a chemical formula of (H)2dap)6[Cd4Cl2(AsW9O34)2]The yield was 29%.
Data characterization and performance testing
1) Using the CdAW crystal prepared in example 1 as an example, a sample of a bulk single crystal of 0.38X 0.23X 0.18mm in size was placed on a Bruker Apex-II CCD diffractometer using Mo Ka radiation through a graphite monochromatorAs a radiation source, diffraction data was collected in an omega-2 theta scan. Wherein all intensity data is corrected by Lp factor and empirically absorbedAnd (4) correcting, wherein all non-hydrogen atom coordinates are obtained by a direct method, and hydrogen atoms on organic molecules are obtained by a geometric hydrogenation method. All non-hydrogen atom coordinates are refined by a full matrix least square method, anisotropic thermal parameter correction is adopted, all calculation is completed by using a SHELXL-97 program, and specific data are shown in tables 1 and 2.
TABLE 1 Crystal and Structure refinement data Table for CdAw prepared in example 1
From tables 1 and 2, it can be seen that the main bond lengths in the CdAW crystals are within a reasonable range.
2) The CdAW crystal prepared in example 1 was subjected to X-ray single crystal diffraction analysis using an X-ray single crystal diffraction analyzer, and the specific results are shown in FIG. 1.
The results of X-ray single crystal diffraction analysis are shown in FIG. 1, and in this monomer unit, A is [ Cd ] in CdAw4Cl2(AsW9O34)2]12-The coordination structure (hydrogen atoms are omitted) of (A), two groups of three-vacancy Keggin structure oxygen clusters { AsW in CdAw)9O34By sharing oxygen atoms with the tetranuclear cadmium cluster { Cd } (FIG. 1D)4Cl2Are connected to form a sandwich structure (FIG. 1B, C). The Cd (II) ion is of a six-coordination octahedral configuration and is divided into two types according to different coordination environments: 1. as shown in fig. 1E, the six coordination sites are occupied by four bridging oxygens and two chlorine atoms in two sets of three-vacancy Keggin structural oxygen clusters to form a distorted octahedral structure; 2. the six coordination sites are occupied by six bridge oxygens in two groups of three-vacancy Keggin structure oxygen clusters to form an approximate octahedral structure. As shown in fig. 2, adjacent CdAW form a three-dimensional supramolecular structure through hydrogen bonding.
3) Infrared analysis of CdAW crystals prepared in example 1 was performed using a fourier infrared spectrometer and the results are shown in fig. 3.
As can be seen from FIG. 3, 940cm–1(w),783(m)-733cm–1(m) and 625cm–1(m) is assigned as μ (W-O)Terminal oxygen),μ(W–ODouble bridge oxygen) And mu (W-O)Triple bridge oxygen) The vibration peak of (1); 874cm–1(s) a vibrational peak attributed to μ (As-O); 3410cm–1(m) and 1614cm–1(s) is the-OH hydroxyl oscillation peak, 1485-1352cm–1(m) is the-C-N bond vibration peak, 1069cm–1(w) and 1003cm–1(m) are the oscillation peaks of C-C and C-H, respectively. The infrared characterization result is consistent with the X-single crystal diffraction result.
4) The CdAW crystals prepared in example 1 were subjected to fluorescence identification performance test, and the specific results are shown in fig. 4 and fig. 5.
In order to test the fluorescence signals of CdAw in different solvents, CdAw is ground and dissolved in different solvents, ultrasonic waves are used for forming a suspension, and then the fluorescence emission peak of CdAw is tested under the excitation of 204nm light. As shown in FIG. 4, CdAw has characteristic emission peaks in the range of 350 to 400nm in water and in solvents having hydroxyl groups (-OH) such as common alcohols, which also matches the solid fluorescence of CdAw (as shown in FIG. 5). As shown in FIG. 4, CdAw is present in water (H)2O) has the highest fluorescence intensity, and has a strong emission peak at 375 nm. And CdAW bitCharacteristic emission peaks in the range of 350 to 400nm all have strong fluorescence signals in methanol (MeOH), 1,2-ethanediol (1,2-ethanediol), isopropanol (isopropanol), n-butanol (buton-1-ol), ethanol (EtOH) solvents. In addition, CdAw also has a strong fluorescence emission peak in acetonitrile (acetonitrile) solvent. As shown in FIG. 4, the characteristic emission peak of CdAw in the range of 350 to 400nm has a more significant emission signal in non-alcoholic solvents commonly used in industry, such as N-methylpyrrolidone (NMP), Dimethylacetamide (DMA), acetone (acetone), Tetrahydrofuran (THF), Dimethylformamide (DMF), but the intensity is lower than that of CdAw in alcoholic solvents. In some non-polar solvents, such as chloroform and dichloromethane, the fluorescence signal of CdAw is low and even tends to be quenched. It is known that the physical interaction between CdAW and the solvent plays an important role, for example, the polarity, hydrogen bond, and coordination bond of the solvent all change the fluorescence of CdAW. The existence of certain harmful substances in the solvent can be detected through the characteristic fluorescence emission peak of the CdAW, and the content of the harmful substances can be analyzed through the fluorescence intensity of the CdAW.
The fluorescence recognition of CdAW in methanol for some carcinogens common in the dye industry (see figure 6 for structure) is exemplified. FIG. 7 shows the fluorescence emission spectrum of the naphthalene and its derivatives in FIG. 6 under 202nm excitation light after the action of CdAW, which can improve the original fluorescence level and generate new characteristic emission peak according to the difference of substituents on the naphthalene ring. FIG. 8 shows the fluorescence emission spectrum under 202nm excitation light after the reaction of CdAW with aniline and its derivatives in FIG. 6, and after the reaction of aniline and its derivatives with CdAW, except that 3, 3-diaminobiphenyl phenomenon is unchanged, the fluorescence signals are all greatly improved, and a new emission peak appears near 475 nm. In addition, 3, 5-dimethylaniline newly appeared several fingerprint peaks, which will help to distinguish and identify the kind of compound in the solution. FIG. 9 shows the fluorescence emission spectrum of the compound of FIG. 6 after the action of CdAW on pyridine and its derivatives under 202nm excitation light, and the fluorescence signal peaks of the pyridine and its derivatives after the action of most of the compounds on CdAW not only show obvious enhancement but also show a large number of recognizable fingerprint peaks, except that 2, 2-dicarboxy bipyridine has no obvious change. FIG. 10 shows the fluorescence emission spectrum under 202nm excitation light after the action of CdAW and the secondary amine in FIG. 6, which shows that the fluorescence signal enhancement and new emission peak also appear after the action of the representative secondary amine and CdAW.
From the above examples, the present invention provides a tetranuclear cadmium cluster-containing polyoxometallate compound, a preparation method and applications thereof, wherein the tetranuclear cadmium cluster-containing polyoxometallate compound has a chemical formula of (H)2dap)6[Cd4Cl2(AsW9O34)2]The compound has the function of identifying some polycyclic aromatic hydrocarbons by fluorescence, can be used for preliminary screening detection of polycyclic aromatic hydrocarbons in various chemical solutions, and has a relatively large application prospect.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A polyoxometallate compound containing tetranuclear cadmium cluster has a chemical formula of (H)2dap)6[Cd4Cl2(AsW9O34)2]Wherein, [ Cd ]4Cl2(AsW9O34)2]12–Is a functional entity, [ H ]2dap]2+Is amine counter cation.
2. The tetranuclear cadmium cluster-containing polyoxometalate compound according to claim 1, wherein the compound is a sandwich-type structural compound constructed based on a triple-vacancy Keggin structure, and a three-dimensional supramolecular structural compound derived from hydrogen bonds.
3. The method for preparing a tetranuclear cadmium cluster-containing polyoxometalate compound according to claim 1 or 2, characterized by comprising the steps of:
mixing tungstate, cadmium salt, an arsenic-containing precursor and amine to obtain a suspension, wherein the arsenic-containing precursor is arsenite or arsenate;
adjusting the pH value of the suspension to 4.50-6.50 by using a pH regulator, and then carrying out a solvothermal reaction to obtain the tetranuclear cadmium cluster-containing polyoxometallate compound; the cadmium salt or the pH regulator contains chlorine element.
4. The method of claim 3, wherein the tungstate is sodium tungstate or potassium tungstate; the cadmium salt comprises cadmium nitrate, cadmium sulfate, a mixture of cadmium hydroxide and hydrochloric acid, a mixture of cadmium hydroxide and nitric acid, and cadmium acetate or cadmium chloride; the amine comprises ethylenediamine, 1, 2-propylenediamine, or 1, 3-propylenediamine.
5. The preparation method according to claim 3 or 4, wherein the molar ratio of the tungstate, the cadmium salt, the arsenic-containing precursor, and the amine is 0.01 to 0.06:0.03 to 0.10.
6. The production method according to claim 3, wherein the solvent for the solvothermal reaction is water or a mixed solution of water and an organic solvent.
7. The method according to claim 3 or 6, wherein the temperature of the solvothermal reaction is 100 to 170 ℃ for 2 to 5 days.
8. The method of claim 6, wherein the organic solvent comprises methanol or ethanol.
9. The method according to claim 3, further comprising, after completion of the solvothermal reaction: naturally cooling the obtained material.
10. Use of the tetranuclear cadmium cluster-containing polyoxometalate compound of claim 1 or 2 or the tetranuclear cadmium cluster-containing polyoxometalate compound prepared by the preparation method of any one of claims 3 to 9 in fluorescence recognition detection.
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