CN110346339B - Application of nitrate type layered europium hydroxide in detection of molybdate - Google Patents
Application of nitrate type layered europium hydroxide in detection of molybdate Download PDFInfo
- Publication number
- CN110346339B CN110346339B CN201910651677.4A CN201910651677A CN110346339B CN 110346339 B CN110346339 B CN 110346339B CN 201910651677 A CN201910651677 A CN 201910651677A CN 110346339 B CN110346339 B CN 110346339B
- Authority
- CN
- China
- Prior art keywords
- molybdate
- type layered
- leuh
- europium hydroxide
- detection
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 51
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000001514 detection method Methods 0.000 title claims abstract description 38
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- CQQZFSZWNXAJQN-UHFFFAOYSA-K europium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Eu+3] CQQZFSZWNXAJQN-UHFFFAOYSA-K 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 230000005284 excitation Effects 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 16
- 238000000695 excitation spectrum Methods 0.000 claims description 16
- 238000002329 infrared spectrum Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000004566 IR spectroscopy Methods 0.000 claims description 2
- 238000001506 fluorescence spectroscopy Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 19
- 239000007864 aqueous solution Substances 0.000 abstract description 13
- -1 rare earth hydroxide Chemical class 0.000 abstract description 11
- 230000008859 change Effects 0.000 abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910001940 europium oxide Inorganic materials 0.000 description 5
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910015667 MoO4 Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 229910017299 Mo—O Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
Landscapes
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Molecular Biology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention relates to the technical field of substance detection, in particular to application of nitrate type layered europium hydroxide in detection of molybdate. The invention providesIn application, the layered rare earth hydroxide is used as a detection agent for the first time, the existence of the molybdate radical can be detected through the change of fluorescence intensity due to the antenna effect between the molybdate radical and rare earth elements under the normal temperature condition, and the trace MoO can be judged through the change of fluorescence in a short time4 2ˉIs present. It was confirmed that a molybdate solution having a concentration of 100ppm was detected within 30 minutes using 0.1g of nitrate type layered europium hydroxide. Provides a mild, simple and effective method for detecting molybdate radicals in aqueous solution. The application provides a new idea for detecting molybdate radicals, and also plays a promoting role in the application of optical materials in the fields of industry, medicine and the like.
Description
Technical Field
The invention relates to the technical field of substance detection, in particular to application of nitrate type layered europium hydroxide in detection of molybdate.
Background
Lamellar rare earth hydroxides (LRHs) with the general formula of Ln2(OH)6–mAm·nH2O (m is more than or equal to 0.5 and less than or equal to 2.0, wherein Ln represents rare earth ions, and A represents interlayer anions) is taken as a novel inorganic layered compound, and due to the unique optical property of the rare earth ions on the laminate and the controllable advantages of the interlayer object anions, more opportunities are provided for designing and synthesizing novel functional materials, so that the novel inorganic layered compound is widely applied to the fields of magnetics, catalysis, optics, adsorption and the like.
The existing methods for detecting molybdate mainly comprise a color development method, a spectrophotometry method and an ion chromatography method, but the development of the methods is limited by complicated operation, interference of ions and strict and limited conditions.
Disclosure of Invention
Based on the drawbacks of the prior art, the present invention firstly provides nitrate type layered europium hydroxide (NO)3 ˉ-LeuH) in the detection of molybdate.
Preferably nitrate type layered europium hydroxide NO3 ˉ-LEuH in the application of detecting molybdate, and nitrate type layered europium hydroxide NO3 ˉAdsorption of LEuH on solutions containing molybdate radicalsA product, the adsorbed product being detected by fluorescence and/or infrared spectroscopy.
The application of the invention, the nitrate type layered europium hydroxide NO3 ˉ-LEuH is prepared as follows:
eu (NO)3)3And NaNO3Hexamethylenetetramine (HMT) according to (0.5-1): (5-20): (1-5), dissolving in exhaust water after mixing according to the molar ratio, carrying out hydrothermal reaction at 80-95 ℃ for 10-15h, and carrying out vacuum drying to obtain the catalyst; preferably, the molar ratio is 1: (10-15): (1-2), most preferably the molar ratio is 1:13: 1.
Preferably, the Eu (NO)3)3And the molar volume ratio of the exhaust water is 1 mmol: (50-100) mL.
Preferably, the method comprises the following steps:
weighing Eu (NO)3)3·6H2O、NaNO3HMT dissolved in exhaust water and N introduced2Purifying the reaction solution, carrying out hydrothermal reaction at 90 ℃ for 12h, cooling at room temperature after the reaction is stopped, carrying out suction filtration, washing the exhaust water and absolute ethyl alcohol for multiple times, and drying at 40 ℃ under vacuum to obtain the catalyst.
The application of the invention, the Eu (NO)3)3The preparation method comprises the following steps:
europium oxide and concentrated nitric acid are mixed according to the mass-volume ratio (1-5) g: heating and refluxing 5mL of the mixture in a 70-85 ℃ water bath for 2-5 hours, performing rotary evaporation until the pH value is 3-4, and drying and crystallizing to obtain the crystal;
preferably, the method comprises the following steps:
weighing europium oxide (Eu)2O3) About 3.0g of the solution was put into a 50mL round-bottomed flask, 10mL of water and 5.0mL of concentrated nitric acid were added thereto, and the mixture was stirred in a water bath at about 80 ℃ and heated under reflux for 3 hours. And after the solution is clarified, carrying out rotary evaporation by using a rotary evaporator until solid is separated out, then adding 10mL of deionized water, and repeating the rotary evaporation for 7-8 times until the pH value of the solution at the last time is 3-4. Drying and crystallizing under infrared lamp to obtain Eu (NO)3)3·6H2O。
The application provided by the invention realizes the MoO under mild conditions by utilizing the antenna effect4 2ˉFluorescence detection of ions, it was found that trace MoO could be judged by fluorescence change in a short time4 2ˉIs present. Provides a mild, simple and effective method for detecting molybdate radicals in aqueous solution.
Therefore, the invention also provides a detection agent which is nitrate type layered europium hydroxide NO3 ˉ-LEuH. The detection agent is preferably used for detecting molybdate.
The detection agent of the present invention is nitrate type layered europium hydroxide NO3 ˉ-LEuH is prepared as follows:
eu (NO)3)3And NaNO3Hexamethylenetetramine (HMT) according to (0.5-1): (5-20): (1-5), dissolving in exhaust water after mixing according to the molar ratio, carrying out hydrothermal reaction at 80-95 ℃ for 10-15h, and carrying out vacuum drying to obtain the catalyst; preferably, the molar ratio is 1: (10-15): (1-2), most preferably the molar ratio is 1:13: 1.
Preferably, the Eu (NO)3)3And the molar volume ratio of the exhaust water is 1 mmol: (50-100) mL.
Preferably, the method comprises the following steps:
weighing Eu (NO)3)3·6H2O、NaNO3HMT dissolved in exhaust water and N introduced2Purifying the reaction solution, carrying out hydrothermal reaction at 90 ℃ for 12h, cooling at room temperature after the reaction is stopped, carrying out suction filtration, washing the exhaust water and absolute ethyl alcohol for multiple times, and drying at 40 ℃ under vacuum to obtain the catalyst.
The detection agent of the present invention, the Eu (NO)3)3The preparation method comprises the following steps:
europium oxide and concentrated nitric acid are mixed according to the mass-volume ratio (1-5) g: heating and refluxing 5mL of the mixture in a 70-85 ℃ water bath for 2-5 hours, performing rotary evaporation until the pH value is 3-4, and drying and crystallizing to obtain the crystal;
preferably, the method comprises the following steps:
weighing europium oxide (Eu)2O3) About 3.0g of the solution was put into a 50mL round-bottomed flask, 10mL of water and 5.0mL of concentrated nitric acid were added thereto, and the mixture was stirred in a water bath at about 80 ℃ and heated under reflux for 3 hours. After the solution is clarified, the solution is evaporated by a rotary evaporator until solid is separated outThen 10mL of deionized water is added, and the spinning is repeated for 7-8 times until the pH value of the solution in the last time is 3-4. Drying and crystallizing under infrared lamp to obtain Eu (NO)3)3·6H2O。
The detection agent provided by the invention realizes the purpose of MoO detection under mild conditions4 2ˉDetection of ions found that trace MoO can be judged by fluorescence change in a short time4 2ˉIs present.
The invention also provides a method for detecting molybdate radical, which uses the detection agent of any one of the technical schemes;
specifically, the method comprises the following steps:
the nitrate type layered europium hydroxide NO3 ˉMixing LEuH with the liquid to be detected, and adsorbing for 0.25-6h to obtain an adsorption product; carrying out infrared detection and/or fluorescence excitation on the obtained adsorption product to obtain the product;
preferably, the adsorption time is 0.5 to 6 h.
In the method of the present invention, the wavelength of the infrared detection is preferably 500-.
The method of the invention preferably employs fluorescence excitation; preferably, the excitation wavelength of the fluorescence excitation is 250-500nm, preferably 250-450 nm; and/or an emission wavelength of 550-750nm, preferably 619 nm.
In the method of the present invention, preferably, molybdate exists in the liquid to be detected, and nitrate type layered europium hydroxide NO exists in the liquid to be detected3 ˉ-the mass concentration ratio of LEuH to the molybdate is (0.1-10) g: (50-200) ppm;
more preferably, the mass concentration ratio is (0.1-5) g: (50-150) ppm.
Preferably, the content of molybdate radicals in the liquid to be detected is not less than 100 ppm.
Specifically, the method comprises the following steps:
nitrate radical type layered europium hydroxide NO3 ˉMixing LEuH with the liquid to be detected, adsorbing for 0.25-6h, centrifuging, washing, and drying to obtain an adsorption product(ii) a Carrying out fluorescence excitation on the obtained adsorption product to obtain the fluorescent material;
preferably, the method comprises the following steps:
(1) nitrate radical type layered europium hydroxide NO3 ˉ-LEuH determining the fluorescence excitation and/or the infrared spectrum, obtaining first data;
(2) nitrate radical type layered europium hydroxide NO3 ˉMixing LEuH and liquid to be detected, adsorbing for 0.25-6h, centrifuging, washing and drying to obtain an adsorption product, and measuring fluorescence excitation and/or infrared spectrum of the adsorption product according to the same conditions in the step (1) to obtain second data;
(3) and comparing the first data with the second data to obtain the target.
In the method of the present invention, the first data and the second data may be selected from any one of an excitation spectrum, an infrared spectrum, a peak intensity in an excitation spectrum, or a peak intensity in an infrared spectrum.
The method of the invention comprises the following steps:
preferably, the first data are the nitrate type layered europium hydroxide NO3 ˉ-peak intensity of LEuH at 260nm in the excitation spectrum of fluorescence excitation;
the second data is the peak intensity of the adsorption product of the step (2) at 260nm in the excitation spectrum of fluorescence excitation under the same conditions of the step (1);
and judging that the molybdate radical exists if the second data is larger than the first data.
In the method of the present invention, the centrifugation, washing and drying may be performed by a conventional method in the art, and as a preferred technical scheme:
wherein the centrifugation condition is centrifugation at room temperature at 10000 rpm for 1 minute.
The washing is carried out by adopting a method of deionized water washing once at room temperature and ethanol washing once.
The drying is carried out at 40 ℃.
The current methods for detecting molybdate include color development, spectrophotometry and ion chromatography, but the complicated operation, ionic interference and harsh and limited conditions limit the development of these methods.
The method for detecting molybdate ions in aqueous solution provided by the invention adopts layered rare earth hydroxide as a detection agent for the first time, under the condition of normal temperature, due to the antenna effect between molybdate ions and rare earth elements, the existence of molybdate ions can be detected through the change of fluorescence intensity, and trace MoO can be judged through the change of fluorescence in a short time4 2ˉIs present. It was verified that a molybdate solution with a concentration of 100ppm could be detected within 30 minutes using 0.1g of the detection agent.
The invention is to detect MoO in aqueous solution4 ˉProvides a mild, simple and effective method. The method provides a new idea for detecting molybdate radicals, and also plays a promoting role in the application of optical materials in the fields of industry, medicine and the like.
Of course, not all of the advantages described above need to be achieved at the same time in the practice of any one product or method of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows the detection reagent NO3 ˉLEuH 100ppm MoO in 20ml4 2-The XRD patterns of the adsorption products obtained after the adsorption products are respectively stirred for 0.25, 0.5, 1, 3, 6 and 12 hours in the aqueous solution; wherein a-f correspond to adsorption time of 0.25-12h respectively;
FIG. 2 shows the detection reagent NO3 ˉLEuH 100ppm MoO in 20ml4 2-Stirring the mixture in the aqueous solution for 0.25, 0.5, 1, 3, 6 and 12 hours respectively to obtain an infrared spectrum of an adsorption product; wherein a-f are respectively adsorbed correspondinglyThe time is 0.25 to 12 hours; (g) is MoO4 2-An own infrared spectrum;
FIG. 3 shows the detection reagent NO3 ˉLEuH 100ppm MoO in 20ml4 2-And (3) stirring the mixture in the aqueous solution for 0, 0.25, 0.5, 1, 3, 6 and 12 hours respectively to obtain a fluorescence excitation spectrum (A) and an emission spectrum (B) of the adsorption product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example provides a detection agent, which is nitrate type layered europium hydroxide NO3 ˉ-LEuH。
Specifically, the preparation process is as follows:
(1) weighing europium oxide (Eu)2O3) About 3.0g of the solution was put into a 50mL round-bottomed flask, 10mL of water and 5.0mL of concentrated nitric acid were added thereto, and the mixture was stirred in a water bath at about 80 ℃ and heated under reflux for 3 hours. And after the solution is clarified, carrying out rotary evaporation by using a rotary evaporator until solid is separated out, then adding 10mL of deionized water, and repeating the rotary evaporation for 7-8 times until the pH value of the solution at the last time is about 3-4. Drying and crystallizing under infrared lamp to obtain Eu (NO)3)3·6H2And O is standby.
(2) Eu (NO)3)3·6H2O(1mmol)、NaNO3(13mmol) and HMT (1mmol) were dissolved in 80mL of exhaust water and N was added2Purifying the reaction solution, transferring the reaction solution into a 100mL reaction kettle, carrying out hydrothermal reaction at 90 ℃ for 12h, cooling at room temperature after the reaction is stopped, carrying out suction filtration, washing the exhaust water and absolute ethyl alcohol for multiple times, and drying at 40 ℃ under vacuum to obtain NO3 ￣-LEuH。
Preferably, the detection agent provided in this embodiment is used to detect molybdate.
Example 2
The embodiment provides a method for detecting molybdate radicals, which comprises the following specific steps:
(1) 0.1g of NO obtained in example 1 was added at room temperature3 ￣LEuH 20ml MoO 100ppm4 2-Stirring the mixture in the aqueous solution for 0.5h, centrifuging, washing and drying to obtain an adsorption product.
(2) Performing fluorescence excitation on the adsorption product obtained in the step (1) between 250 and 500nm, and performing infrared spectrum measurement between 500 and 4000 nm.
XRD scanning is carried out on the adsorption product obtained in the step (1), and the obtained result is shown as the attached figure 1 (b).
The result obtained in step (2) is shown in FIG. 2 (b).
Example 3
This example provides a method for detecting molybdate, which differs from example 2 only in that the stirring time in step (1) is 0.25 h.
The results are shown in (a) of FIGS. 1 and 2.
Example 4
This example provides a method for detecting molybdate, which differs from example 2 only in that the stirring time in step (1) is 1 h.
The results are shown in (c) of FIGS. 1 and 2.
Example 5
This example provides a method for detecting molybdate, which differs from example 2 only in that the stirring time in step (1) is 3 hours.
The results are shown in (d) of FIGS. 1 and 2.
Example 6
This example provides a method for detecting molybdate, which differs from example 2 only in that the stirring time in step (1) is 6 h.
The results are shown in (e) of FIGS. 1 and 2.
Example 7
This example provides a method for detecting molybdate, which differs from example 2 only in that the stirring time in step (1) is 12 h.
The results are shown in (f) of FIGS. 1 and 2.
In summary of examples 2 to 7, it can be seen from FIG. 1 that the interlayer spacing of the adsorbed product did not change much with time (from 0.25h to 6h), indicating that only a small amount of adsorbed ions entered the interlayer or adsorbed on the surface of the laminate, but that the interlayer spacing was changed when the adsorption time reached 12h, indicating that molybdic acid and ions had successfully entered the interlayer and replaced nitrate. But still a peak with an interlayer spacing of 0.83nm was present indicating that the exchange of nitrate ions was not complete.
From the IR spectrum of FIG. 2, it can be seen that when the adsorption time reaches 0.5h, the Mo-O vibration at 839nm begins to appear, and the Mo-O vibration becomes more and more obvious with the change of time.
As can be seen from the fluorescence diagram of FIG. 3 (A is fluorescence excitation spectrum, B is emission spectrum), the broadband peak generated by molybdate at 260nm becomes obvious and enhanced gradually in the excitation spectrum of fluorescence with the increase of time within 0.25-12h and the emission wavelength is set to be 614nm, which shows that molybdate ions gradually increase and energy transfer occurs with rare earth ions with the change of time.
In the emission spectrum, to prove NO3 ￣Sensitivity of LEuH to molybdic acid, in fig. 3, a broadband peak of molybdate was found in the excitation spectrum when the adsorption time was 0.5 hours, and the fluorescence intensity of the emission spectrum also significantly increased, which demonstrates that the presence of molybdate could be detected on the fluorescence spectrum at 0.5 hours, which fully demonstrates the sensitivity of the antenna effect.
That is, the detection agent provided by the invention can detect the existence of molybdate with the concentration of 100ppm within 0.5h by adopting the adsorbent with the lowest detection limit of 0.1g obtained by the detection method.
Also, as will be appreciated by those skilled in the art, in NO3 ￣-LEuH and MoO4 2-The mass concentration ratio of (A) to (B) is 0.1 g: the presence of molybdate was already well detected at 100ppmIn that, NO is increased3 ￣In the case of higher quantities of LEuH or molybdate, the presence of molybdate must be detected well.
By means of NO3 ￣-LEuH vs. MoO4 2-The fluorescence selectivity of the ions was determined by performing a series of adsorption experiments using nitrate as the starting material. The results show that the ultra-high sensitivity of the antenna effect makes the results of its lowest detection limit good, which is also the case in the art for qualitatively performing MoO4 2-Ion detection takes an important step.
Example 8
The embodiment provides a method for detecting molybdate radicals, which comprises the following specific steps:
(1) NO obtained in example 13 ˉ-performing fluorescence excitation on LEuH between 250 and 500nm, and performing infrared spectrum measurement between 500 and 4000mn to obtain a first fluorescence excitation spectrum, a first fluorescence emission spectrum and a first infrared spectrum;
(2) 0.1g of NO obtained in example 1 was added at room temperature3 ￣Adding LEuH into 20ml of the aqueous solution to be detected, stirring for 0.5h, centrifuging, washing, and drying to obtain an adsorption product.
(3) And (3) performing fluorescence excitation on the adsorption product obtained in the step (2) under the same condition as in the step (1), and performing infrared spectrum measurement to obtain a second fluorescence excitation spectrum, a second fluorescence emission spectrum and a second infrared spectrum.
(4) And (4) comparing the second fluorescence excitation spectrum, the second fluorescence emission spectrum and the second infrared spectrum obtained in the step (3) with the first fluorescence excitation spectrum, the first fluorescence emission spectrum and the first infrared spectrum, and judging whether the aqueous solution to be detected has molybdate radicals.
Examples 9 to 12
Examples 9-12 each provide a method for detecting molybdate, which differs from example 8 in that,
step (2) preparation of NO from example 13 ￣-LeuH 0.5g, 1g, 3g, 5g, respectively.
As will be appreciated by those skilled in the art, the presence of molybdate was already well detected under the detection conditions of example 8, and must be well detected under the detection conditions of examples 9-12.
Example 13
The embodiment provides a method for detecting molybdate radicals, which comprises the following specific steps:
(1) NO obtained in example 13 —Fluorescence excitation is carried out on LEuH between 250 and 500nm to obtain first fluorescence intensity at 260 nm;
(2) 0.1g of NO obtained in example 1 was added at room temperature3 ￣Adding LEuH into 20ml of the aqueous solution to be detected, stirring for 0.5h, centrifuging, washing, and drying to obtain an adsorption product.
(3) And (3) performing fluorescence excitation on the adsorption product obtained in the step (2) under the same condition of the step (1) to obtain a second fluorescence intensity at 260 nm.
(4) Comparing the first fluorescence intensity and the second fluorescence intensity:
if the first fluorescence intensity is greater than or equal to the second fluorescence intensity, judging that the aqueous solution to be detected does not contain molybdate radicals;
and if the first fluorescence intensity is smaller than the second fluorescence intensity, judging that the aqueous solution to be detected contains molybdate.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (12)
1. Application of nitrate type layered europium hydroxide in detection of molybdate, and nitrate type layered europium hydroxide NO3 --LEuH is prepared as follows:
eu (NO)3)3And NaNO3Hexamethylenetetramine according to (0).5-1): (5-20): (1-5), dissolving in exhaust water, carrying out hydrothermal reaction at 80-95 ℃ for 10-15h, and carrying out vacuum drying to obtain the catalyst.
2. Use according to claim 1, characterized in that the nitrate-type layered europium hydroxide is adsorbed in a molybdate-containing solution to give an adsorption product, which is detected by fluorescence and/or infrared spectroscopy.
3. A method for detecting molybdate radical is characterized in that nitrate radical type layered europium hydroxide NO is used3 --LeuH as a detection agent;
mixing the detection agent with the liquid to be detected, and adsorbing for 0.25-6h to obtain an adsorption product; carrying out infrared detection and/or fluorescence excitation on the obtained adsorption product to obtain the product;
said nitrate type layered europium hydroxide NO3 --LEuH is prepared as follows:
eu (NO)3)3And NaNO3Hexamethylenetetramine according to (0.5-1): (5-20): (1-5), dissolving in exhaust water, carrying out hydrothermal reaction at 80-95 ℃ for 10-15h, and carrying out vacuum drying to obtain the catalyst.
4. The process according to claim 3, characterized in that the adsorption time is between 0.5 and 6 h.
5. The method as claimed in claim 3, wherein the wavelength of the infrared detection is 500-2500 nm.
6. The method as claimed in claim 3, wherein the wavelength of the infrared detection is 800-900 nm.
7. The method according to claim 3, wherein the excitation wavelength of the fluorescence excitation is 250-500 nm;
and/or an emission wavelength of 550-750 nm.
8. The method according to claim 3, wherein the excitation wavelength of the fluorescence excitation is 250-450 nm.
9. Method according to claim 3, characterized in that molybdate is present in the liquid to be examined, the nitrate type layered europium hydroxide NO3 —The mass concentration ratio of LEuH to the molybdate radical is (0.1-10) g: (50-200) ppm.
10. The method of claim 3, wherein said nitrate type layered europium hydroxide NO3 —The mass concentration ratio of LEuH to the molybdate radical is (0.1-5) g: (50-150) ppm.
11. The method according to claim 3, wherein the liquid to be detected contains molybdate in a range of not less than 100 ppm.
12. A method according to any of claims 3-11, characterized by the steps of:
(1) the nitrate type layered europium hydroxide NO3 --LEuH determining the fluorescence excitation and/or the infrared spectrum, obtaining first data;
(2) the nitrate type layered europium hydroxide NO3 -Mixing LEuH and the liquid to be detected, adsorbing for 0.25-6h, centrifuging, washing and drying to obtain an adsorption product, and measuring fluorescence excitation and/or infrared spectrum of the adsorption product according to the same conditions in the step (1) to obtain second data;
(3) comparing the first data with the second data to obtain the second data;
the first data is the nitrate type layered europium hydroxide NO3 —The peak intensity of LEuH at 260nm in the excitation spectrum of fluorescence excitation;
the second data is the peak intensity of the adsorbed product of step (2) at 260nm in the excitation spectrum of fluorescence excitation under the same conditions as in step (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910651677.4A CN110346339B (en) | 2019-07-18 | 2019-07-18 | Application of nitrate type layered europium hydroxide in detection of molybdate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910651677.4A CN110346339B (en) | 2019-07-18 | 2019-07-18 | Application of nitrate type layered europium hydroxide in detection of molybdate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110346339A CN110346339A (en) | 2019-10-18 |
| CN110346339B true CN110346339B (en) | 2022-04-05 |
Family
ID=68179220
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910651677.4A Active CN110346339B (en) | 2019-07-18 | 2019-07-18 | Application of nitrate type layered europium hydroxide in detection of molybdate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110346339B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497545B (en) * | 2016-09-18 | 2018-10-09 | 北京师范大学 | Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs and its synthetic method |
-
2019
- 2019-07-18 CN CN201910651677.4A patent/CN110346339B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110346339A (en) | 2019-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112898965B (en) | Preparation and use method of ratiometric fluorescent probe for visual differential detection | |
| Zhang et al. | A bifunctional 3D Tb-based metal–organic framework for sensing and removal of antibiotics in aqueous medium | |
| Leyden et al. | Fourier transform infrared spectrometry, carbon-13 nuclear magnetic resonance spectrometry, and photoacoustic spectroscopy of a silica-immobilized ligand | |
| CN109705839B (en) | Terpyridine derivative functionalized rare earth europium mesoporous hybrid luminescent material and preparation method and application thereof | |
| CN113444261A (en) | Microporous zinc coordination polymer for detecting nitro explosives | |
| CN105115947B (en) | A kind of graphene quantum dot sensor and its application in terms of trinitrophenol is detected | |
| CN110346339B (en) | Application of nitrate type layered europium hydroxide in detection of molybdate | |
| CN109970990B (en) | Terbium coordination polymer and preparation method and application thereof | |
| CN106582492B (en) | A kind of heavy metal containing wastewater treatment ZrO2And its preparation method and application | |
| Ilibi et al. | Luminescent hybrid materials based on covalent attachment of Eu (III)-tris (bipyridinedicarboxylate) in the mesoporous silica host MCM-41 | |
| CN111729664A (en) | Supported nano zinc oxide and preparation and application thereof | |
| CN108913122B (en) | Cyanide ion supramolecular sensor and synthesis and application thereof in fluorescence recognition of cyanide | |
| Zhai et al. | Selective enrichment of trace copper (II) from biological and natural water samples by SPE using ion‐imprinted polymer | |
| CN105964281A (en) | Preparation method and application of flaky alkali type copper chloride catalyst | |
| CN114235771B (en) | Sensing detection method for heavy metal mercury ion detection | |
| KR20120136913A (en) | Chemosensor for cyanide sensing using bisindole anchored mesoporous silica nanoparticles | |
| EP4073066A2 (en) | Lanthanide compounds for luminescence "turn-on" detection | |
| CN114891030A (en) | Europium complex time-resolved fluorescent material and preparation method thereof | |
| JP6561411B2 (en) | photocatalyst | |
| CN108048078B (en) | Fluorescent dual-response hollow mesoporous material and preparation method and application thereof | |
| CN108409675B (en) | Application of 2, 3-diaminophenazine salt as sensor in recognition of cyanide ions in pure water | |
| CN106732638A (en) | A kind of photochemical catalyst Fe2O3‑WO3And preparation method thereof | |
| CN113493473A (en) | High-efficiency red-light europium complex luminescent material and preparation method and application thereof | |
| Duan et al. | Detecting Structural Environments of Carboxyl Groups in Dissolved Natural Organic Molecules | |
| CN114409876B (en) | Polymer for identifying cadmium and zinc bimetallic ions, and preparation method, application and analysis method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220318 Address after: 100875, 19, Xinjie street, Haidian District, Beijing Applicant after: BEIJING NORMAL University Address before: Building 6, Hengqin creative Valley, 1889 Huandao East Road, Hengqin New District, Zhuhai City, Guangdong Province, 519031 Applicant before: BNU-BUCM HENGQIN INNOVATION INSTITUTE OF SCIENCE AND TECHNOLOGY Applicant before: Beijing Normal University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |