CN111562230B - Method for measuring dye content in dye/metal organic framework composite material - Google Patents
Method for measuring dye content in dye/metal organic framework composite material Download PDFInfo
- Publication number
- CN111562230B CN111562230B CN202010419073.XA CN202010419073A CN111562230B CN 111562230 B CN111562230 B CN 111562230B CN 202010419073 A CN202010419073 A CN 202010419073A CN 111562230 B CN111562230 B CN 111562230B
- Authority
- CN
- China
- Prior art keywords
- dye
- mof
- ultraviolet absorption
- content
- residual liquid
- 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
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000010521 absorption reaction Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000012088 reference solution Substances 0.000 claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 32
- 239000012621 metal-organic framework Substances 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 abstract description 8
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography 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
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention discloses a method for measuring the dye content in a dye/metal organic framework composite material, which mainly comprises the following steps: 1. in-situ synthesizing dye @ MOF, and acquiring an ultraviolet absorption spectrum of the reaction residual liquid; 2. obtaining a reference solution R with the same position as the ultraviolet absorption peak of the reaction residual liquid in the step 1; 3. drawing a standard relation curve; 4. obtaining the concentration of Dye in the reaction residual liquid in the step 1; 5. and calculating the content of Dye in the Dye @ MOF composite material and the proportion of the Dye in the Dye @ MOF. The method has the advantages that the whole process is simple, the operability is strong, the characteristic that the ultraviolet absorption spectrum of Dye changes under the high-temperature condition in the process of preparing the Dye @ MOF material by the in-situ method is fully considered, the method can be used for reasonably characterizing the content of the Dye in the Dye @ MOF, and further the luminescence property of the MOF composite luminescent material prepared by the in-situ synthesis method is accurately characterized.
Description
Technical Field
The invention belongs to the technical field of material testing, and particularly relates to a method for measuring the content of a Dye in a Dye/metal organic framework composite material, in particular to a method for measuring the content of Dye in Dye @ MOF.
Background
Metal-organic frameworks (MOFs), also known as coordination polymers, are a class of crystalline materials with an infinite network structure of one, two, and three dimensions formed by self-assembly of organic ligands and Metal centers. Combines the rigidity of inorganic materials with the flexibility of organic materials. So that the material has huge development potential and attractive development prospect in the aspect of modern material research.
At present, the composite luminescent material prepared based on the metal organic framework attracts people's extensive attention, and compared with the traditional luminescent material, the composite luminescent material has incomparable advantages in aspects of properties, synthesis and composition. In terms of properties, when coordinated, metal ions of the MOF composite luminescent material have a preferential coordination geometrical configuration, and coordination with organic ligands with specific shapes can form MOF structures with predictable structures; in the aspect of synthesis, the MOF composite luminescent material has mild reaction conditions, for example, the temperature of a hydrothermal method is generally 60-120 ℃, and the MOF composite luminescent material can be assisted by methods such as microwave, ultrasound and the like, so that the reaction time can be obviously shortened; in terms of composition, the MOF composite luminescent material has two performances of an organic material and an inorganic material, so that the diversity of luminescent forms is increased.
The luminous performance of the MOF composite luminous material mainly comes from ligand luminescence, charge transfer luminescence, object luminescence, metal ion luminescence and the like. For the MOF composite luminescent material with the luminous object, the concentration of the luminous object can greatly influence the luminous performance of the composite material. After the MOF composite luminescent material is prepared in a large scale, the content of an object needs to be measured under the condition that the luminescent property of the MOF composite luminescent material is not influenced, so that the luminescent property of the MOF composite luminescent material is accurately characterized.
When Dye @ MOF is prepared by an activated adsorption method, MOF is prepared by high-temperature heating, then an MOF material is placed in a Dye solution with known content at normal temperature to adsorb Dye in a pore passage of the MOF, a reaction residual liquid can be obtained by filtering the Dye @ MOF material, the content of the unreacted Dye in the reaction residual liquid can be determined by measuring the ultraviolet absorption intensity of the Dye in the reaction residual liquid, so that the content of the Dye in the Dye @ MOF is calculated according to the known content of the Dye, and the luminescence property of the composite luminescent material is further characterized.
However, the method is not suitable for characterizing the luminescence property of the MOF composite luminescent material prepared by an in-situ synthesis method, mainly because a precursor solution composed of Dye and MOF components needs to be heated at high temperature at the same time to react to obtain Dye @ MOF, and because of the existence of a heating process aiming at Dye, the position of an ultraviolet absorption peak of the Dye in a reaction residual solution can be changed, so that the situation that the position of the ultraviolet absorption peak of the Dye in the precursor solution is different, the content of the Dye in the Dye @ MOF cannot be directly determined according to the change of the intensity of the ultraviolet absorption peak of the Dye in a reaction residual solution, and finally the problem of inaccurate characterization of the luminescence property of the material is caused.
Disclosure of Invention
The invention aims to solve the defects in the prior art, provides a method for measuring the Dye content in a Dye/metal organic framework composite material, considers the characteristic that the ultraviolet absorption spectrum of Dye changes under the high-temperature condition in the process of preparing the Dye @ MOF material by an in-situ synthesis method, and can reasonably represent the Dye content after improvement.
The technical scheme of the invention is as follows: the invention discloses a method for measuring the dye content in a dye/metal organic framework composite material, which comprises the following steps:
(1) In-situ synthesis of Dye @ MOF (Dye refers to a Dye molecule, MOF refers to a metal organic framework), acquisition of an ultraviolet absorption spectrum of a reaction raffinate: preparing a precursor solution containing MOF components and Dye, and simultaneously recording the total volume of the precursor solution as VmL and the initial content of the Dye as a mg/mL; heating the precursor solution at high temperature to obtain a dye @ MOF material, filtering the dye @ MOF material to obtain a reaction residual solution, testing and drawing an ultraviolet absorption spectrogram of the reaction residual solution, and simultaneously recording the mass of the obtained dye @ MOF as M mg;
(2) Obtaining a reference solution R with the same position of the ultraviolet absorption peak of the reaction residual liquid in the step (1): adjusting solutes, selecting different partial MOF components and Dye to form a plurality of groups of new precursor solutions, and performing the same technological process as that of the step (1) in-situ synthesis of the Dye @ MOF material to obtain a reference solution R with the same position of the ultraviolet absorption peak of the reaction residual liquid in the step (1);
(3) Drawing a standard relation curve: adjusting the Dye concentration in the reference solution R to obtain the corresponding ultraviolet absorption intensity value of the reference solution R, and drawing a standard relation curve of the ultraviolet absorption intensity and the Dye concentration by taking the Dye concentration as an X axis and the ultraviolet absorption intensity of the reference solution R as a Y axis;
(4) Obtaining the Dye concentration in the reaction residual liquid in the step (1): determining the concentration of Dye in the reaction residual liquid to be b mg/mL according to the ultraviolet absorption spectrum intensity of the reaction residual liquid obtained in the step (1) by using the standard relation curve obtained in the step (3);
(5) Calculating the content of Dye in the Dye @ MOF composite material as follows:
V×(a-b) (1)
the ratio of Dye in Dye @ MOF is:
further, in the step (1), the Dye and the MOF are reacted after being simultaneously heated at high temperature to obtain the Dye @ MOF, and the reaction product Dye @ MOF does not exist in the reaction residual liquid.
Further, the solute in step (2) is adjusted by selecting different portions of MOF components and Dye materials to form multiple groups of new precursor solutions, except for selecting precursor solutions containing all MOF components and Dye materials, and the material types and content ratios of MOF components and Dye materials are not changed.
The shift of the ultraviolet absorption peak is due to the change of Dye due to heating denaturation, and the change of the absorption peak intensity is still determined by the concentration of Dye in the solution, so that only whether the ultraviolet absorption peak position is consistent or not is considered when solute adjustment is performed, and the influence factor of the intensity of the absorption peak position is not considered.
Selecting different partial MOF components and Dye to form a plurality of groups of new precursor solutions, and obtaining a reference solution with the same position as the ultraviolet absorption peak of the reaction residual liquid after the same technological process of in-situ synthesis of the Dye @ MOF material; since the concentration of Dye in the reference solution is known and Dye @ MOF is not synthesized, i.e., the concentration of Dye in the reference solution is unchanged; therefore, as long as the peak positions and peak intensities of the ultraviolet absorption spectra of Dye in the reference solution and the reaction raffinate are consistent, the Dye concentration of the reference solution is also consistent with the Dye concentration in the reaction raffinate; the Dye content in Dye @ MOF prepared by the in situ method can be finally obtained from the difference between the initial Dye content and the Dye content in the reaction raffinate.
The invention has the beneficial effects that:
the method disclosed by the invention is simple, the characteristic that the ultraviolet absorption spectrum of Dye changes under the high-temperature condition in the process of preparing the Dye @ MOF material by an in-situ method is fully considered, a reference solution with the same position as the ultraviolet absorption peak of the Dye in the reaction residual liquid is selected to further draw a relation curve of the ultraviolet absorption intensity and the concentration of the heated Dye, and finally the concentration of the Dye in the residual liquid after the Dye @ MOF is synthesized in situ is determined through the relation curve.
Drawings
FIG. 1 is a schematic flow diagram of a method for measuring dye content in a dye/metal organic framework composite;
FIG. 2 is a diagram showing an ultraviolet absorption spectrum of a reaction raffinate obtained in the first example;
FIG. 3 shows the solutes RhB, rhB + Zn obtained in example one 2+ Ultraviolet absorption spectra of solutions of RhB + BDC, rhB + TED, and RhB + BDC + TED;
FIG. 4 is a graph of the concentration of RhB as a function of the intensity of UV absorption for the solute RhB + BDC in example one.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, steps or conditions of the present invention may be made without departing from the spirit of the invention.
Example one
1. Preparation of MOF-containing Components (BDC + TED + Zn) 2+ ) And a precursor solution of RhB, simultaneously recording that the volume V of the precursor solution is 10mL, the initial content a of RhB is 0.5mg/mL, obtaining a RhB @ MOF composite material after high-temperature heating (namely utilizing an in-situ synthesis method), filtering the RhB @ MOF composite material to obtain a reaction residual liquid, testing and drawing an ultraviolet absorption spectrogram of the reaction residual liquid, as shown in figure 2, and simultaneously recording the mass M of the obtained RhB @ MOF to be 5mg;
2. respectively preparing solutes of RhB + BDC + TED, rhB + BDC, rhB and RhB + Zn 2+ After the precursor solution undergoes the same technological process as that of the preparation of the RhB @ MOF material by in-situ synthesis in the step 1, ultraviolet absorption spectrograms of the five solutions are tested and drawn, and the peak position of the ultraviolet absorption spectrogram of the RhB + BDC solution is basically consistent with that of the residual liquid of the reaction of the RhB @ MOF mixed solution as can be seen from figure 3;
3. selecting a RhB + BDC solution as a reference solution R, and adjusting the Dye concentration (0.1-1 mg/mL) in the RhB + BDC solution to obtain a relation curve of the ultraviolet absorption intensity and the solute concentration of the RhB + BDC solution, wherein the relation curve is shown in figure 4;
4. and (3) comparing the relation curve drawn in the step (3) to obtain a concentration value b of Dye in the reaction raffinate of 0.479mg/mL, wherein the content of Dye adsorbed into the MOF is Vx (a-b) =0.213mg, and finally calculating the proportion of RhB in RhB @ MOF according to the following formula:
the foregoing illustrates and describes the principles, general features, and advantages of the present invention. However, the above description is only an example of the present invention, the technical features of the present invention are not limited thereto, and any other embodiments that can be obtained by those skilled in the art without departing from the technical solution of the present invention should be covered by the claims of the present invention.
Claims (2)
1. A method for measuring the dye content in a dye/metal organic framework composite material is characterized by comprising the following steps:
(1) Preparing a precursor solution containing MOF components and Dye, and simultaneously recording the total volume of the precursor solution as VmL and the initial content of the Dye as a mg/mL; heating the precursor solution at high temperature to obtain a dye @ MOF material, simultaneously recording the mass of the obtained dye @ MOF as M mg, filtering out the dye @ MOF material to obtain a reaction residual liquid, and testing and drawing an ultraviolet absorption spectrogram of the reaction residual liquid;
(2) Adjusting solute, selecting different partial MOF components and Dye to form a plurality of groups of new precursor solutions, and performing the same technological process as that in the step (1) of in-situ synthesis of the Dye @ MOF material to obtain a reference solution R with the same position of the ultraviolet absorption peak of the reaction residual liquid in the step (1);
(3) Adjusting the Dye concentration in the reference solution R to obtain the corresponding ultraviolet absorption intensity value of the reference solution R, and drawing a standard relation curve of the ultraviolet absorption intensity and the Dye concentration by taking the Dye concentration as an X axis and the ultraviolet absorption intensity of the reference solution R as a Y axis;
(4) Determining the concentration of Dye in the reaction residual liquid to be b mg/mL according to the ultraviolet absorption spectrum intensity of the reaction residual liquid obtained in the step (1) by using the standard relation curve obtained in the step (3);
(5) The content of Dye in the Dye @ MOF composite material is calculated as follows:
V×(a-b) (1)
the ratio of Dye in Dye @ MOF is:
the solute adjustment in the step (2) is to select different partial MOF components and Dye materials to form a plurality of groups of new precursor solutions, the condition that the precursor solutions containing all the MOF components and the Dye materials are selected to form the precursor solutions is not included, and the material types and the content ratios of the MOF components and the Dye materials are not changed.
2. The method for measuring the Dye content in the Dye/metal organic framework composite material according to claim 1, wherein in the step (1), the Dye and the MOF are reacted after being heated at high temperature simultaneously to obtain the Dye @ MOF, and the reaction product Dye @ MOF does not exist in the reaction residual liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010419073.XA CN111562230B (en) | 2020-05-18 | 2020-05-18 | Method for measuring dye content in dye/metal organic framework composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010419073.XA CN111562230B (en) | 2020-05-18 | 2020-05-18 | Method for measuring dye content in dye/metal organic framework composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111562230A CN111562230A (en) | 2020-08-21 |
| CN111562230B true CN111562230B (en) | 2022-12-20 |
Family
ID=72074857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010419073.XA Active CN111562230B (en) | 2020-05-18 | 2020-05-18 | Method for measuring dye content in dye/metal organic framework composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111562230B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080160620A1 (en) * | 2006-12-28 | 2008-07-03 | United Technologies Corporation | Method for quantitatively determining the dye content in dyed oils |
| JP5083179B2 (en) * | 2008-11-12 | 2012-11-28 | 住友電気工業株式会社 | Method for preparing calibration curve for quantitative analysis by infrared spectroscopy and quantitative method by infrared spectroscopy |
| CN103740361B (en) * | 2013-12-24 | 2015-04-15 | 浙江大学 | Dye/metal-organic framework composite material for white light emission and preparation method thereof |
| CN109585887B (en) * | 2018-12-05 | 2022-02-01 | 福建师范大学 | Dye @ metal organic framework material and preparation method and application thereof |
| CN109821574B (en) * | 2019-02-18 | 2021-07-30 | 河海大学 | Europium-based metal organic framework material Eu-MOF, preparation method thereof and Congo red dye photocatalytic degradation method |
| CN110698681B (en) * | 2019-09-04 | 2021-07-16 | 四川师范大学 | Preparation and application of double-emission dye-coated lanthanide metal organic framework |
| CN110560004A (en) * | 2019-09-19 | 2019-12-13 | 西北师范大学 | Eu-MOF complex, synthesis thereof and application of Eu-MOF complex in adsorption of organic dye in wastewater |
-
2020
- 2020-05-18 CN CN202010419073.XA patent/CN111562230B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111562230A (en) | 2020-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pan et al. | In situ rapid preparation of homochiral metal-organic framework coated column for open tubular capillary electrochromatography | |
| CN111253586B (en) | Cadmium-based metal-organic framework material and preparation method and application thereof | |
| He et al. | Engineering of amino microporous organic network on zeolitic imidazolate framework-67 derived nitrogen-doped carbon for efficient magnetic extraction of plant growth regulators | |
| CN110658280A (en) | Method for detecting bisphenol compounds based on magnetic metal organic framework composite material | |
| CN110229349A (en) | A kind of zeolite imidazole metalloid organic framework materials and its preparation method and application | |
| CN113372394B (en) | Dual-core host-guest supermolecule and preparation method and application thereof | |
| CN107349805A (en) | A kind of preparation method of the crystal films of ZIF 8 | |
| CN106866988A (en) | A kind of layer column type metal-organic framework material as well as preparation method and application thereof | |
| CN111562230B (en) | Method for measuring dye content in dye/metal organic framework composite material | |
| Yin et al. | A metal-organic framework@ hydrogen-bond framework as a matrix for MALDI-TOF-MS analysis of small molecules | |
| Choi et al. | Synthesis of o-carborane-functionalized metal–organic frameworks through ligand exchanges for aggregation-induced emission in the solid state | |
| Yu et al. | Structure, assembly mechanism and magnetic properties of heterometallic dodecanuclear nanoclusters Dy III4 M II8 (M= Ni, Co) | |
| van Albada et al. | Fluctuations between square-planar and tetrahedral coordination geometry with bis (2-benzimidazolyl) alkane ligands. Synthesis, spectroscopic properties and X-ray crystal structure of four representative examples | |
| CN113637178B (en) | Preparation method of metal-organic framework composite material IL @ ZIF-67 | |
| CN113292690B (en) | Phenoxazine two-dimensional covalent organic framework material and preparation method and application thereof | |
| CN112480423A (en) | Metal organic framework complex of semi-rigid tricarboxylic acid, preparation method and application thereof | |
| Kumar et al. | Synthesis, characterization and X-ray structural studies of three hybrid inorganic–organic compounds: Silver (I)-, lead (II)-and tris (phenanthroline) copper (II)-2, 6-naphthalenedisulfonate (2, 6-nds) | |
| CN109406476B (en) | Method for detecting antibiotics in drinking water | |
| CN111072988A (en) | Preparation and application of MOFs (metal-organic frameworks) based on lanthanide metal and tetraphenylethylene group | |
| CN103819494B (en) | 1-H-benzotriazole acetic acid-Yin (I) title complex and preparation method | |
| Ma et al. | Multi-component hybrid films based on covalent post-synthetic functionalization of silicon chip using both ZIF-90 and lanthanide complexes for luminescence tuning | |
| CN114605656A (en) | Preparation method and application of neodymium-based metal organic framework material Nd-MOF | |
| Wang et al. | A ratiometric fluorescent probe based on UiO-66-TCPP for selective and visual detection of quercetin in food | |
| CN107790100B (en) | Preparation method of SBA-15 with specific phosphate group coordination to lanthanum element | |
| CN117285720B (en) | Rare earth luminous coordination polymer 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 |