CN114231271B - Preparation method of europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material - Google Patents
Preparation method of europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material Download PDFInfo
- Publication number
- CN114231271B CN114231271B CN202111522740.8A CN202111522740A CN114231271B CN 114231271 B CN114231271 B CN 114231271B CN 202111522740 A CN202111522740 A CN 202111522740A CN 114231271 B CN114231271 B CN 114231271B
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- iii
- ordered mesoporous
- mesoporous carbon
- complex
- 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
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000001301 oxygen Substances 0.000 title claims abstract description 68
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000011540 sensing material Substances 0.000 title claims abstract description 29
- 230000003287 optical effect Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 title claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 92
- 239000000203 mixture Substances 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000007789 sealing Methods 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 16
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 239000011877 solvent mixture Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- MNXMBMNXSPNINS-UHFFFAOYSA-N 1,10-phenanthroline-5,6-diamine Chemical compound C1=CC=C2C(N)=C(N)C3=CC=CN=C3C2=N1 MNXMBMNXSPNINS-UHFFFAOYSA-N 0.000 claims description 7
- ORYSFKVWQQMDAX-UHFFFAOYSA-N 1-ethylindole-2,3-dione Chemical compound C1=CC=C2N(CC)C(=O)C(=O)C2=C1 ORYSFKVWQQMDAX-UHFFFAOYSA-N 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000000523 sample Substances 0.000 abstract description 20
- 238000001514 detection method Methods 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 239000003755 preservative agent Substances 0.000 description 21
- 230000002335 preservative effect Effects 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052693 Europium Inorganic materials 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000027734 detection of oxygen Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- -1 mesoporous carbon nitrides Chemical class 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
-
- 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"
- G01N2021/6432—Quenching
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Luminescent Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a preparation method of europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material, which prepares Eu-containing carbon nitride by ordered mesoporous carbon nitride 3+ Europium (III) complex-ordered mesoporous carbon nitride prepared by mixing complex solutions omg‑ C 3 N 4 ) Is provided. When O exists in the environment 2 When the molecule is used, the fluorescence emission of the Eu (III) complex probe molecule can be strongly quenched by the oxygen molecule, so that the oxygen concentration sensitivity detection is realized. The response time is 8s, the reduction time is 12s, the sensitivity reaches 2.56, and the simple, rapid and high-sensitivity detection of the oxygen content can be realized.
Description
Technical Field
The invention belongs to the technical field of novel functional materials and oxygen sensing detection, and particularly relates to a preparation method of an europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material.
Background
The real-time measurement of the concentration of oxygen molecules has very important significance for the research fields of environmental monitoring, medical diagnosis, chemical analysis and the like. A common method of measuring the concentration of oxygen molecules is amperometric. This method is realized based on the fact that an oxygen electrode can measure the diffusion rate of oxygen to the anode, which is limited by the stability of the electrode surface, and thus the measured data stability is not high. The optical oxygen sensor material is formed based on the quenching behavior of oxygen to the excited state of the luminescent molecule used, has the characteristics of high sensitivity and high selectivity, and has become an important direction in the research field of oxygen sensing in recent years. The working principle is that oxygen molecules in an object to be detected enter a pore canal of a carrier and collide with luminescent probe molecules which are highly sensitive to oxygen, the luminescent probe molecules are subjected to fluorescence quenching, the luminous intensity is weakened, and after oxygen is removed, the luminescent molecules emit light again. By utilizing the characteristic of sensitivity to oxygen concentration, the detection of the oxygen concentration is realized through the change of the fluorescence intensity of the luminescent probe molecules.
The primary problem of the optical oxygen sensing material is to design and synthesize the luminescent probe molecule. Long-term studies have found that probes with longer decay times are more suitable for oxygen sensing. Among them, luminescent metal complexes are used for development and application of optical oxygen sensing due to their relatively long fluorescence lifetime, absorption in the visible region, large Stokes shift and photostability. Of this class of complexes, more currently studied are Ru (II), os (II) and Ir (II). It was found that the fluorescence emission of the above-mentioned ions in the liquid state can be strongly quenched by oxygen molecules. The earliest reported ruthenium-based oxygen sensor was a water-soluble complex Ru (bpy) 3 Cl 2 . In the next twenty years, modification and functional expansion are carried out on the basis of the complex, and a series of Ru complexes are developed. The polypyridine complex of Ru (II) is deactivated by thermal radiation easily occurring in its luminescence excited state, thereby limiting its further application.
Lanthanide metal complexes are an extremely attractive class of compounds that are widely used in the laser and luminescent fields due to their high emission quantum yields, long fluorescence lifetimes and sharp emission peaks, and as probe molecules for microwells and biological materials. Recently, light emitting properties of europium (III) complexes grafted on a stable substrate have been systematically studied and attempts have been made to use europium (III) complexes as optical oxygen sensing materials.
Disclosure of Invention
The invention aims to provide a preparation method of europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material comprises the following steps:
firstly, preparing ordered mesoporous carbon nitride;
second step, eu (III) complex Eu (N-DPIQ) (TTA) 3 Is synthesized by (1);
third step, assembling the oxygen sensing material
The ordered mesoporous carbon nitride is weighed and dissolved in a 1, 2-dichloroethane/ethanol solvent mixture, the solvent mixture ratio is 50/50 (w/w), and the mass ratio of the ordered mesoporous carbon nitride to the solvent mixture is 1:100;
eu (N-DPIQ) (TTA) is added thereto 3 ,Eu(N-DPIQ)(TTA) 3 And (3) centrifugally stirring for 30min, collecting the mixture into an evaporation dish, and drying the mixture under the protection of nitrogen to obtain the Eu (III) complex-ordered mesoporous carbon nitride photochemical oxygen sensing material.
As a further scheme of the invention, the preparation method of the ordered mesoporous carbon nitride comprises the following steps:
heating carbon tetrachloride and melamine in a water bath to 50-70 ℃ and stirring until the carbon tetrachloride and the melamine are completely dissolved, dropwise adding the mixture onto SBA-15 at a mass ratio of 3:1, 3:2 or 1:1, fully soaking the mixture after ultrasonic dispersion, adding the mixture into an oil bath at 90 ℃ for condensation reflux for 6-8 hours, wherein the mass ratio of the SBA-15 to the carbon tetrachloride is 1:6;
oven drying at 70-90deg.C for 24 hr to obtain brown solid, grinding, and collecting N 2 Calcining in atmosphere, at N 2 At a flow rate of 300ml/min, the temperature is raised from room temperature to 500-600 ℃ at a heating rate of 5 ℃/min and maintained for 5 hours, and after the temperature is lowered to room temperature at 5 ℃/min, black solid is obtained and ground.
As a further scheme of the invention, the washing method after grinding the black solid is as follows: ultrasonic washing with ethanol, oscillating and washing with HF 40% by mass for several times, stirring and washing with deionized water for several times, and washing with 4mol.L -1 NH of (C) 4 And (3) performing HF vibration washing for a plurality of times, and finally performing centrifugal washing by using ethanol, and then drying for 2-5 hours in a vacuum furnace at 70-90 ℃ to obtain the ordered mesoporous carbon nitride.
As a further aspect of the present invention, the method for synthesizing the Eu (III) complex in the second step comprises the steps of:
s1, weighing alpha-thenoyl trifluoroacetone and N-DPIQ, and dissolving in ethanol, wherein the mol ratio of HTTA to N-DPIQ is 3:1, a step of;
s2, dropwise adding sodium hydroxide solution, and stopping adding when the pH value of the solution measured by a pH meter is between 6.5 and 7.1;
s3, then adding EuCl 3 ·6H 2 O aqueous solution, heating the mixture to 70-90 ℃ under the water bath heating condition;
s4, stirring at 60r/min after sealing, and cooling and crystallizing the obtained mixture after 1-3 h;
s5, washing with ethanol for 3-5 times, and filtering and collecting a product by using filter paper with the pore diameter of 20 microns;
s6, taking ethanol as a solvent, heating in a water bath after sealing, and recrystallizing after complete dissolution to obtain Eu (N-DPIQ) (TTA) 3 Namely Eu (III) complexes.
As a further scheme of the invention, the preparation method of the N-DPIQ comprises the following steps:
1, 10-phenanthroline-5, 6-diamine is weighed and added into methanol to be fully and uniformly stirred, and then 1-ethylindole-2, 3-dione is added, wherein the molar ratio of 1, 10-phenanthroline-5, 6-diamine to 1-ethylindole-2, 3-dione is 1.2:1, a step of;
reflux the obtained mixed solution at 70-90 ℃ under the protection of nitrogen, and reacting to room temperature to form suspension;
standing until the mixture is cooled to room temperature, layering, filtering the upper suspension by using filter paper with the diameter of 20 mu m, placing the upper suspension in a glass evaporation dish, washing the upper suspension by using ethanol, and drying the upper suspension in vacuum;
placing the obtained crude product in a beaker, adding ethanol, sealing, heating and stirring in a water bath at 40-60 ℃ until the crude product is completely dissolved, cooling at room temperature, and recrystallizing to obtain N-DPIQ.
The invention has the beneficial effects that:
(1) The invention successfully prepares a novel photochemical oxygen sensing material, firstly applies the ordered mesoporous carbon nitride to an optical oxygen sensor, enriches the choice of materials, and solves the problem that the organic groups introduced by the silicon-based mesoporous material are unevenly distributed, and occupy the pore space to reduce the pore volume;
(2) The photochemical sensor prepared by the invention is used for detecting the oxygen content, and has the advantages of short response time, low detection limit, wide linear range and good stability; the response time of the invention is 8s, the reduction time is 12s, the sensitivity reaches 2.56, and the simple, rapid and high-sensitivity detection of the oxygen content can be realized;
(3) The amino functional group on the surface of the carbon nitride is utilized to form firm bonding with the Eu (III) complex probe molecule, so that the structural form of the Eu (III) complex molecule group can be stabilized when the Eu (III) complex probe molecule is subjected to quenching reaction with oxygen molecules, and the physical and chemical properties of the surface of the Eu (III) complex molecule group are stable;
(4) The invention utilizes the limiting field effect of the nanometer pore cavity to reduce the loss of Eu (III) complex probe molecules and the structural deformation of the molecule groups in the reaction process, thereby improving the oxygen sensing reaction activity, high selectivity and stability, and the ordered mesoporous carbon nitride carrier not only can well disperse nanometer particles, but also can promote the activation of probe molecules.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic view of an oxygen sensing characteristic test device according to an embodiment of the present invention;
FIG. 2 is a Stern-Volmer plot for photochemical oxygen sensing materials at various oxygen concentrations based on examples 1 through 3;
FIG. 3 is a graph from 100% N 2 To 100% O 2 The photo-response time at 610nm of the photochemical oxygen sensing material in examples 1 to 3 under periodic cycling.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material comprises the following steps:
first, preparation of ordered mesoporous carbon nitride nanomaterial
3g of carbon tetrachloride and 2g of melamine are added into a 50ml beaker, heated to 60 ℃ in a water bath, stirred at a magnetic stirring speed of 50r/min until the mixture is completely dissolved, then added dropwise onto 0.5g of SBA-15, dispersed for 30min by ultrasound, fully immersed, condensed in an oil bath at 90 ℃ and refluxed for 6h. And (5) sealing and punching the preservative film, and then putting the preservative film into a 70 ℃ oven for drying for 24 hours to obtain brown solid. Grinding and then placing in N 2 Roasting in a protected tube furnace, and calcining in N 2 At a flow rate of 300ml/min, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min and keeping for 5 hours, taking out the material after cooling to room temperature at 5 ℃/min, grinding the obtained black solid, firstly washing with 500ml of ethanol at 60HZ by ultrasonic for 1 time, washing with 200ml of HF with a mass fraction of 40% by vibration for two times, washing with deionized water for three times by stirring, and then washing with NH 4 HF(4mol·L -1 ) 200ml of the mixture is washed twice by shaking, and finally, the mixture is centrifugally washed by ethanol and then is dried for 2 hours in a vacuum furnace at 80 ℃ to obtain ordered mesoporous carbon nitride expressed as omg -C 3 N 4 ;
Second step, ligand synthesis
1, 10-phenanthroline-5, 6-diamine (0.7516 g,3.6 mmol) was weighed into a 250mL beaker and added to 80mL methanol, after stirring thoroughly, 1-ethylindole-2, 3-dione (0.525 g,3 mmol) was added. The resulting mixture was refluxed at 80 ℃ under nitrogen protection and reacted for a certain period of time until the beaker formed a suspension at room temperature. After allowing the mixture to stand until it cooled to room temperature, delamination occurred, the upper suspension was filtered off with a filter paper of 20 μm, and then placed in a glass evaporation dish, washed with ethanol, and dried in vacuo. Placing the obtained crude product in a beaker, adding 200ml of ethanol, sealing a preservative film, heating and stirring in a water bath at 50 ℃ until the preservative film is completely dissolved, and placing the product at room temperature for cooling and recrystallizing after the preservative film is replaced to obtain a required product (N-DPIQ);
third step, synthesis of Eu (III) complex
(1) Weigh (0.067 g,0.3 mmol) α -thenoyltrifluoroacetone (HTTA) and (0.035 g,0.1 mmol) N-DPIQ into a 50ml beaker;
(2) weighing 10mL of ethanol, pouring the ethanol into the container, and stirring the mixture until the ethanol is completely dissolved;
(3) dropwise adding sodium hydroxide solution, and stopping adding when the pH value of the solution measured by a pH meter is between 6.95 and 7.05;
(4) then 3ml of EuCl was added 3 ·6H 2 O aqueous solution, heating the mixture to 80 ℃ under the water bath heating condition;
(5) stirring under magnetic force of 60r/min after sealing the preservative film, and cooling and crystallizing the obtained mixture after 1 h;
(6) washing with 100ml ethanol three times, and filtering with filter paper with pore size of 20 μm to collect the product;
(7) taking ethanol as a solvent, sealing a preservative film, heating in a water bath, and recrystallizing after complete dissolution to obtain an Eu (III) complex;
fourth step, assembling the oxygen sensing material
1g of ordered mesoporous carbon nitride was weighed out and dissolved in a solvent mixture of 1, 2-dichloroethane/ethanol in a ratio of 50/50 (w/w). After stirring the solvent mixture, 0.4wt.% Eu (N-DPIQ) (TTA) was added to the solution relative to the ordered mesoporous carbon nitride 3 . Centrifugally stirring for 30min, collecting in an evaporation dish, and drying under nitrogen. Obtaining the photochemical oxygen sensing material of Eu (III) complex-ordered mesoporous carbon nitride.
Example 2
The preparation method of the europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material comprises the following steps:
first, preparation of ordered mesoporous carbon nitride nanomaterial
3g of carbon tetrachloride and 2g of melamine are added into a 50ml beaker, heated to 50 ℃ in a water bath, stirred at a magnetic stirring speed of 50r/min until the mixture is completely dissolved, then added dropwise onto 0.5g of SBA-15, dispersed for 30min by ultrasound, fully immersed, condensed in an oil bath at 90 ℃ and refluxed for 7h. And (3) sealing and punching the preservative film, and then putting the preservative film into an oven at 80 ℃ for drying for 24 hours to obtain brown solid. Grinding and then placing in N 2 Roasting in a protected tube furnace, and calcining in N 2 At a flow rate of 300ml/min, heating from room temperature to 550deg.C at a heating rate of 5deg.C/min and maintaining for 5 hr, cooling to room temperature at 5deg.C/min, taking out the material, grinding the obtained black solid, and ultrasonic washing with 500ml ethanol at 60HZ for 1 timeWashing with 200ml HF (40%) by mass fraction, shaking twice, washing with deionized water three times, and washing with NH 4 HF (4 mol.L-1)) 200ml, washing twice with shaking, centrifuging with ethanol, and drying in a vacuum furnace at 80deg.C for 2 hr to obtain ordered mesoporous carbon nitride.
Second step, ligand synthesis
1, 10-phenanthroline-5, 6-diamine (0.7516 g,3.6 mmol) was weighed into a 250mL beaker and added to 80mL methanol, after stirring thoroughly, 1-ethylindole-2, 3-dione (0.525 g,3 mmol) was added. The resulting mixture was refluxed at 80 ℃ under nitrogen protection and reacted for a certain period of time until the beaker formed a suspension at room temperature. After allowing the mixture to stand until it cooled to room temperature, delamination occurred, the upper suspension was filtered off with a filter paper of 20 μm, and then placed in a glass evaporation dish, washed with ethanol, and dried in vacuo. Placing the obtained crude product in a beaker, adding 200ml of ethanol, sealing a preservative film, heating and stirring in a water bath at 50 ℃ until the preservative film is completely dissolved, placing the product at room temperature after replacing the preservative film, cooling and recrystallizing to obtain the required product (N-DPIQ).
Third step, synthesis of Eu (III) complex
(1) (0.067 g,0.3 mmol) HTTA and (0.035 g,0.1 mmol) N-DPIQ were weighed into a 50ml beaker;
(2) weighing 10mL of ethanol, pouring the ethanol into the container, and stirring the mixture until the ethanol is completely dissolved;
(3) the sodium hydroxide solution is added dropwise, and the addition is stopped when the pH value of the solution measured by the pH meter is between 6.95 and 7.05.
(4) Then 3ml of EuCl was added 3 ·6H 2 O aqueous solution, heating the mixture to 80 ℃ under the water bath heating condition;
(5) stirring under magnetic force of 60r/min after sealing the preservative film, and cooling and crystallizing the obtained mixture after 1 h;
(6) washing with 100ml ethanol three times, and filtering with filter paper with pore size of 20 μm to collect the product;
(7) ethanol is used as a solvent, the preservative film is sealed and then heated in water bath, and the Eu (III) complex is obtained by recrystallization after complete dissolution.
Fourth step, assembling the oxygen sensing material
1g of ordered mesoporous carbon nitride was weighed out and dissolved in a solvent mixture of 1, 2-dichloroethane/ethanol in a ratio of 50/50 (w/w). After stirring the solvent mixture, 0.6wt.% Eu (N-DPIQ) (TTA) was added to the solution relative to the ordered mesoporous carbon nitride 3 . Centrifugally stirring for 30min, collecting in an evaporation dish, and drying under nitrogen. Obtaining the photochemical oxygen sensing material of Eu (III) complex-ordered mesoporous carbon nitride.
Example 3
The preparation method of the europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material comprises the following steps:
first, preparation of ordered mesoporous carbon nitride nanomaterial
3g of carbon tetrachloride and 2g of melamine are added into a 50ml beaker, heated to 70 ℃ in a water bath, stirred at a magnetic stirring speed of 50r/min until the mixture is completely dissolved, then added dropwise onto 0.5g of SBA-15, dispersed for 30min by ultrasound, fully immersed, condensed in an oil bath at 90 ℃ and refluxed for 8h. And (5) sealing and punching the preservative film, and then putting the preservative film into a 90 ℃ oven for drying for 24 hours to obtain brown solid. Grinding, calcining in a tube furnace under protection of N2, and calcining in N 2 At a flow rate of 300ml/min, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min and maintaining for 5 hours, cooling to room temperature at 5 ℃/min, taking out the material, grinding the obtained black solid, firstly ultrasonically washing with 500ml of ethanol and 60HZ for 1 time, washing with 200ml of HF (40%) with a mass fraction of 200ml for two times by shaking, stirring with deionized water for three times, and then washing with NH 4 HF (4 mol.L-1)) 200ml, washing twice with shaking, centrifuging with ethanol, and drying in a vacuum furnace at 80deg.C for 2 hr to obtain ordered mesoporous carbon nitride.
Second step, ligand synthesis
1, 10-phenanthroline-5, 6-diamine (0.7516 g,3.6 mmol) was weighed into a 250mL beaker and added to 80mL methanol, after stirring thoroughly, 1-ethylindole-2, 3-dione (0.525 g,3 mmol) was added. The resulting mixture was refluxed at 80 ℃ under nitrogen protection and reacted for a certain period of time until the beaker formed a suspension at room temperature. After allowing the mixture to stand until it cooled to room temperature, delamination occurred, the upper suspension was filtered off with a filter paper of 20 μm, and then placed in a glass evaporation dish, washed with ethanol, and dried in vacuo. Placing the obtained crude product in a beaker, adding 200ml of ethanol, sealing a preservative film, heating and stirring in a water bath at 50 ℃ until the preservative film is completely dissolved, placing the product at room temperature after replacing the preservative film, cooling and recrystallizing to obtain the required product (N-DPIQ).
Third step, synthesis of Eu (III) complex
(1) (0.067 g,0.3 mmol) HTTA and (0.035 g,0.1 mmol) N-DPIQ were weighed into a 50ml beaker;
(2) weighing 10mL of ethanol, pouring the ethanol into the container, and stirring the mixture until the ethanol is completely dissolved;
(3) dropwise adding sodium hydroxide solution, and stopping adding when the pH value of the solution measured by a pH meter is between 6.95 and 7.05;
(4) then 3ml of EuCl was added 3 ·6H 2 O aqueous solution, heating the mixture to 80 ℃ under the water bath heating condition;
(5) stirring under magnetic force of 60r/min after sealing the preservative film, and cooling and crystallizing the obtained mixture after 1 h;
(6) washing with 100ml ethanol three times, and filtering with filter paper with pore size of 20 μm to collect the product;
(7) taking ethanol as a solvent, sealing a preservative film, heating in a water bath, and recrystallizing after complete dissolution to obtain an Eu (III) complex;
fourth step, assembling the oxygen sensing material
1g of ordered mesoporous carbon nitride was weighed out and dissolved in a solvent mixture of 1, 2-dichloroethane/ethanol in a ratio of 50/50 (w/w). After stirring the solvent mixture, 0.8wt.% Eu (N-DPIQ) (TTA) was added to the solution relative to the ordered mesoporous carbon nitride 3 . Centrifugally stirring for 30min, collecting in an evaporation dish, and drying under nitrogen. Obtaining the photochemical oxygen sensing material of Eu (III) complex-ordered mesoporous carbon nitride.
Example 4
Detection of oxygen content
The oxygen sensing characteristic of the photochemical oxygen sensing material is realized by an oxygen sensing characteristic testing device, as shown in fig. 1, wherein the oxygen sensing characteristic testing device comprises a flowmeter, a gas mixing device, an excitation light source, a sample cell, a signal collector and a signal output device. The specific test method is as follows:
firstly, fixing a photochemical oxygen sensing material sample on a sample frame in a sample cell, wherein the sample cell is provided with two quartz windows which are at right angles to each other, and the flow rates of nitrogen and oxygen are controlled by two rotameters;
the luminescence spectrum of the test sample under the pure nitrogen condition is then tested under the condition of different oxygen concentrations in sequence, the result after fitting the experimental data is shown in figure 2, the oxygen content is controlled by the rotameter, meanwhile, the light response time of the sample to oxygen is recorded, and the working curve is drawn, and the result is shown in figure 3.
The invention synthesizes a novel Eu (N-DPIQ) (TTA) 3 Oxygen sensitive Eu (III) complexes, and introduced into ordered mesoporous carbon nitrides by coupling wall loading, expressed as Eu (N-DPIQ) (TTA) 3 / omg- C 3 N 4 . The surface of the ordered mesoporous carbon nitride contains amino functional groups, can form firm bonding with Eu (III) complex probe molecules, and can stabilize the structural form of the complex molecule groups when undergoing quenching reaction with oxygen molecules; the three-dimensional ordered mesoporous nano structure can effectively promote mass transfer, adsorption and reaction processes of Eu (III) complex probe molecules and oxygen molecules, and reduce loss of Eu (III) complex molecules and structural deformation of molecular groups in the reaction process by utilizing the limiting field effect of nano pore cavities, so that the oxygen sensing reaction activity is improved, the selectivity and the stability are high, the sensitivity of an oxygen sensing material is improved, and the response time is shortened.
The foregoing detailed description of the invention has been presented for purposes of illustration and description, but is not intended to limit the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (4)
1. The preparation method of the europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material is characterized by comprising the following steps of:
firstly, preparing ordered mesoporous carbon nitride;
second step, eu (III) complex Eu (N-DPIQ) (TTA) 3 Is synthesized by (1);
third step, assembling the oxygen sensing material
The ordered mesoporous carbon nitride is weighed and dissolved in a 1, 2-dichloroethane/ethanol solvent mixture, the solvent mixture ratio is 50/50 (w/w), and the mass ratio of the ordered mesoporous carbon nitride to the solvent mixture is 1:100;
eu (N-DPIQ) (TTA) is added thereto 3 ,Eu(N-DPIQ)(TTA) 3 0.4 to 0.8 weight percent of ordered mesoporous carbon nitride is centrifugally stirred for 30min and then is collected into an evaporation dish, and is dried under the protection of nitrogen, so that Eu (III) complex-ordered mesoporous carbon nitride photochemical oxygen sensing material is obtained;
the preparation method of the ordered mesoporous carbon nitride comprises the following steps:
heating carbon tetrachloride and melamine in a water bath to 50-70 ℃ and stirring until the carbon tetrachloride and the melamine are completely dissolved, dropwise adding the mixture onto SBA-15 at a mass ratio of 3:1, 3:2 or 1:1, fully soaking the mixture after ultrasonic dispersion, and adding the mixture into an oil bath at 90 ℃ to condense and reflux for 6-8h at a mass ratio of 1:6;
oven drying at 70-90deg.C for 24 hr to obtain brown solid, grinding, and collecting N 2 Calcining in atmosphere, at N 2 Under the condition of 300ml/min of flow rate, the temperature is raised to 500-600 ℃ from room temperature at a heating rate of 5 ℃/min and kept for 5 hours, and black solid is obtained and ground after the temperature is lowered to room temperature at 5 ℃/min;
the washing method after grinding the black solid comprises the following steps: ultrasonic washing with ethanol, oscillating and washing with HF 40% by mass for several times, stirring and washing with deionized water for several times, and washing with 4mol.L -1 NH of (C) 4 And (3) performing HF vibration washing for a plurality of times, and finally performing centrifugal washing by using ethanol, and then drying for 2-5 hours in a vacuum furnace at 70-90 ℃ to obtain the ordered mesoporous carbon nitride.
2. The method for preparing an optical oxygen sensor material of europium (III) complex-ordered mesoporous carbon nitride according to claim 1, wherein the method for synthesizing the Eu (III) complex in the second step comprises the steps of:
s1, weighing alpha-thenoyl trifluoroacetone and N-DPIQ, and dissolving in ethanol, wherein the mol ratio of HTTA to N-DPIQ is 3:1, a step of;
s2, dropwise adding sodium hydroxide solution, and stopping adding when the pH value of the solution measured by a pH meter is between 6.5 and 7.1;
s3, then adding EuCl 3 ·6H 2 O aqueous solution, heating the mixture to 70-90 ℃ under the water bath heating condition;
s4, stirring at 60r/min after sealing, and cooling and crystallizing the obtained mixture after 1-3 h;
s5, washing with ethanol for 3-5 times, and filtering and collecting a product by using filter paper with the pore diameter of 20 microns;
s6, taking ethanol as a solvent, heating in a water bath after sealing, and recrystallizing after complete dissolution to obtain Eu (N-DPIQ) (TTA) 3 Namely Eu (III) complexes.
3. The method for preparing the europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material according to claim 2, wherein the preparation method of N-DPIQ is as follows:
1, 10-phenanthroline-5, 6-diamine is weighed and added into methanol to be fully and uniformly stirred, and then 1-ethylindole-2, 3-dione is added, wherein the molar ratio of 1, 10-phenanthroline-5, 6-diamine to 1-ethylindole-2, 3-dione is 1.2:1, a step of;
reflux the obtained mixed solution at 70-90 ℃ under the protection of nitrogen, and reacting to room temperature to form suspension;
standing until the mixture is cooled to room temperature, layering, filtering the upper suspension by using filter paper with the diameter of 20 mu m, placing the upper suspension in a glass evaporation dish, washing the upper suspension by using ethanol, and drying the upper suspension in vacuum;
placing the obtained crude product in a beaker, adding ethanol, sealing, heating and stirring in a water bath at 40-60 ℃ until the crude product is completely dissolved, cooling at room temperature, and recrystallizing to obtain N-DPIQ.
4. An optical oxygen sensor material based on europium (III) complexes prepared by the preparation method according to any one of claims 1 to 3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111522740.8A CN114231271B (en) | 2021-12-13 | 2021-12-13 | Preparation method of europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111522740.8A CN114231271B (en) | 2021-12-13 | 2021-12-13 | Preparation method of europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114231271A CN114231271A (en) | 2022-03-25 |
CN114231271B true CN114231271B (en) | 2023-06-23 |
Family
ID=80755484
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111522740.8A Active CN114231271B (en) | 2021-12-13 | 2021-12-13 | Preparation method of europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114231271B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008126799A1 (en) * | 2007-04-05 | 2008-10-23 | National Institute For Materials Science | Mesoporous carbon nitride material and process for producing the same |
WO2018220474A1 (en) * | 2017-06-01 | 2018-12-06 | Sabic Global Technologies B.V. | Synthesis of nitrogen rich 2d mesoporous carbon nitride with rod shaped morphology and tunable pore diameters |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101717629B (en) * | 2009-07-06 | 2012-11-14 | 中国科学院长春光学精密机械与物理研究所 | Optical oxygen sensing composite material and preparation method thereof |
BR102016006005B1 (en) * | 2016-03-18 | 2022-11-16 | Universidade Estadual De Campinas - Unicamp | HIERARCHICALLY NANOSTRUCTURED NANOPARTICLE FOR WHITE LIGHT EMISSION AND USE |
CN105879829A (en) * | 2016-04-29 | 2016-08-24 | 江苏大学 | Preparation method of ordered mesoporous carbon nitride and application thereof |
CN107045010B (en) * | 2017-01-19 | 2019-03-15 | 济南大学 | The preparation method of optical electro-chemistry sensor based on the mesoporous carbonitride of stannic disulfide- |
CN108761095B (en) * | 2018-07-27 | 2021-03-19 | 济南大学 | Preparation method and application of photoelectrochemical immunosensor based on tin dioxide/tin disulfide/mesoporous carbon nitride |
CN109337679A (en) * | 2018-11-07 | 2019-02-15 | 广州大学 | A kind of g-C of europium doping3N4Base semiconductor material and preparation method thereof |
CN113247869B (en) * | 2021-05-19 | 2024-04-05 | 东南大学 | Preparation method of carbon nitride material, carbon nitride material prepared by preparation method and application of carbon nitride material |
-
2021
- 2021-12-13 CN CN202111522740.8A patent/CN114231271B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2008126799A1 (en) * | 2007-04-05 | 2008-10-23 | National Institute For Materials Science | Mesoporous carbon nitride material and process for producing the same |
WO2018220474A1 (en) * | 2017-06-01 | 2018-12-06 | Sabic Global Technologies B.V. | Synthesis of nitrogen rich 2d mesoporous carbon nitride with rod shaped morphology and tunable pore diameters |
Also Published As
Publication number | Publication date |
---|---|
CN114231271A (en) | 2022-03-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Li et al. | Recent progress in fluorescent probes for metal ion detection | |
CN103694269B (en) | A kind of compound and Synthesis and applications thereof detecting secondary amine | |
CN107245334B (en) | A kind of water soluble polymer fluoresceins fluorescence probe and preparation method thereof detecting mercury ion | |
CN106084873B (en) | A kind of efficiently near-infrared fluorescent material and its biologic applications | |
Shi et al. | Tunable photoluminescence properties of fluorescein in a layered double hydroxide matrix and its application in sensors | |
CN109438722A (en) | Based on manganese base luminescent metal organic framework material and its preparation method and application | |
CN101935529A (en) | Multifunctional nano-composite having up-conversion luminescence, oxygen sensing and biological connectivity and preparation method thereof | |
CN114231271B (en) | Preparation method of europium (III) complex-ordered mesoporous carbon nitride optical oxygen sensing material | |
CN110330444A (en) | A kind of fluorescent chemicals and preparation method and its application as test paper type detection probe for the detection of isocyanates substance | |
CN112079892B (en) | Preparation method and application of carbon quantum dot doped rare earth ratio type fluorescent probe | |
CN111848671B (en) | Nitrosonoyl peroxide anion ratio far infrared fluorescent probe, preparation method and application | |
CN109233547B (en) | Oxygen concentration response high-molecular photoluminescence coating and preparation and application thereof | |
CN106749356B (en) | A kind of rare earth luminous metal organic frame new material of recyclable regenerative type of highly selective detection trace TNT | |
CN102731479A (en) | Organic ligand, rare earth organic fluorescent probe material thereof and preparation method thereof | |
CN110498930A (en) | A kind of preparation method and applications of Lanthanide Coordination Polymers nano material | |
CN110283330A (en) | Based on zinc-base luminescent metal organic framework material and its preparation method and application | |
CN113340862B (en) | Fluorescent molecular sensor, preparation method thereof and detection method of trace uranyl ions in water | |
CN109369527A (en) | A kind of preparation and its oxygen Application in Sensing of pure organic room temperature phosphorimetry compound containing selenium | |
US20040062683A1 (en) | Sensitive single-layer sensing device of covalently attached luminescent indicator on glass surface for measuring the concentration of analytes | |
CN110669350B (en) | Piperidyl BODIPY red-light fluorescent dye and preparation method and application thereof | |
Spangler et al. | Luminescent chemical and physical sensors based on lanthanide complexes | |
Liu et al. | Cyanine dye-assembled composite upconversion nanoparticles for the sensing and cell imaging of nitrite based on a single particle imaging method | |
CN108048078B (en) | Fluorescent dual-response hollow mesoporous material and preparation method and application thereof | |
Zhang et al. | Temperature and oxygen sensing properties of Ru (II) covalently-grafted sol–gel derived ormosil hybrid materials | |
CN113121566B (en) | Pyrene derivative fluorescent molecule and preparation method and application 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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20240122 Address after: 230000 Anhui Hefei high tech Zone Innovation Industrial Park two phase J2 District C block 18 floor. Patentee after: HEFEI LONGTUTEM INFORMATION TECHNOLOGY Co.,Ltd. Country or region after: China Address before: 238000 No. 1 Bantang Road, Chaohu Economic Development Zone, Chaohu City, Anhui Province Patentee before: CHAOHU University Country or region before: China |