CN103230776B - A kind of Lamellar hydroxide composite material and preparation method thereof - Google Patents
A kind of Lamellar hydroxide composite material and preparation method thereof Download PDFInfo
- Publication number
- CN103230776B CN103230776B CN201310150638.9A CN201310150638A CN103230776B CN 103230776 B CN103230776 B CN 103230776B CN 201310150638 A CN201310150638 A CN 201310150638A CN 103230776 B CN103230776 B CN 103230776B
- Authority
- CN
- China
- Prior art keywords
- hydroxide
- composite material
- stratiform
- crown ether
- lamellar
- 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.)
- Expired - Fee Related
Links
Abstract
The invention provides a kind of stratiform rare-earth hydroxide composite, be obtained by reacting by stratiform rare-earth hydroxide and crown ether-like carboxylic acid derivates.Compared with prior art, the present invention is the composite of stratiform rare-earth hydroxide and crown ether compound, first, has the advantages such as high-specific surface area, porous and the high stability that stratiform rare-earth hydroxide has, can absorbing heavy metal ions in water; Secondly, also there is the flexibility of organic macrocycle crown ether compound and guest ions is had to the feature of high selectivity, therefore Lamellar hydroxide composite material of the present invention can overcome both respective defects, plays advantage, and heavy metal ion has good adsorption capacity and selective.
Description
Technical field
The invention belongs to new material and water pollutions inorganic agent technical field, particularly relate to a kind of Lamellar hydroxide composite material and preparation method thereof.
Background technology
China has a large population, water resource lacks, and water resources ownership per capita is only 1/4 of world average level, is one of 13 poor-water states in the world.Along with the fast development of industrial or agricultural economy, the discharge capacity of waste water increases day by day, industrial wastewater complicated component and containing a large amount of available resource, wherein the significant damage that causes environment with the features of pollution of himself of heavy metal ion and be subject to the attention of height.In order to be separated and the heavy metal ion in enrichment waste water, realize the double effects of resource reclaim and environmental protection, about the research of Adsorption of Heavy Metal Ions material obtains extensive concern day by day.
Layered double hydroxide (LDH) and stratiform rare-earth hydroxide (LRH) are extremely important anionic type laminated materials, different anions is introduced LDH and LRH that interlayer can obtain organic anion intercalation, this type of material has extensive use in the storage of optics, catalysis, biomolecule, the field such as drug delivery and release, bio-sensing, sewage disposal, electrochemical sensing.
The hydroxide with hydrotalcite layered structure that layered double hydroxide is made up of bivalent metal ion and trivalent metal ion, also known as mixed metal hydroxides, layered double hydroxide has shepardite lamellar structure, laminate due to trivalent metal ion isomorphous substitution bivalent metal ion with positive charge, electric charge and the laminate positive charge of the object anion that interlayer can exchange balance, layered double hydroxide is made to be electroneutral, layered double hydroxide has larger anion-exchange capacity (AEC, 2 ~ 3mep/g), acceptant object anion, therefore can be used in adsorbed water body with the metal of anion form existence and organic pollution, but selective to guest molecule of this type of material shortage, limit range of application.
Stratiform rare-earth hydroxide is the novel inorganic stratiform functional material that a class has layer structure, its main body is made up of the hydroxide of rare earth metal, there is the structure similar with layered double hydroxide, also there is the Modulatory character of interlayer object anion species and quantity, but yet there are no the relevant report for adsorbent.
Organic/inorganic composite material recently rises and extremely potential research field in materials chemistry, it is combined by synergy organifying compound and inorganic matter in nanometer range, with the double grading of organic compounds and inorganic matter, combination property is better than each one-component, be the study hotspot of technical field of material chemistry in recent years, receive much concern always.
The present invention considers layered hydroxide and the macrocyclic compound crown ether with molecular recognition properties to be compounded to form composite.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of Lamellar hydroxide composite material and preparation method thereof, and this composite heavy metal ion has good adsorption capacity and selective.
The invention provides a kind of Lamellar hydroxide composite material, be obtained by reacting by stratiform rare-earth hydroxide and crown ether-like carboxylic acid derivates.
Preferably, described crown ether-like carboxylic acid derivates is tetraazacrown ether carboxylic acid derivates or diaza crown ether carboxylic acid derivates.
Preferably, layered rare-earth hydroxide is stratiform gadolinium hydroxide, stratiform yttrium hydroxide, stratiform europium hydroxide or stratiform terbium hydroxide.
Preferably, the interlayer anion of layered rare-earth hydroxide is univalent anion.
Preferably, the interlayer anion of layered rare-earth hydroxide is nitrate ion or chlorion.
Present invention also offers a kind of preparation method of Lamellar hydroxide composite material, comprising:
A) stratiform rare-earth hydroxide, crown ether-like carboxylic acid derivates, water are mixed with alkali metal hydroxide, reaction, obtains Lamellar hydroxide composite material.
Preferably, described steps A) be specially:
Crown ether-like carboxylic acid derivates, water are mixed with alkali metal hydroxide, then adds stratiform rare-earth hydroxide, stirring reaction, obtain Lamellar hydroxide composite material.
Preferably, the mol ratio of described crown ether-like carboxylic acid derivates and stratiform rare-earth hydroxide is (0.5 ~ 1): 1.
Preferably, the mol ratio of described crown ether-like carboxylic acid derivates and alkali metal hydroxide is 1:(5 ~ 8).
Preferably, described alkali metal hydroxide is NaOH and/or potassium hydroxide.
The invention provides a kind of Lamellar hydroxide composite material, be obtained by reacting by stratiform rare-earth hydroxide and crown ether-like carboxylic acid derivates.Compared with prior art, the present invention is the composite of stratiform rare-earth hydroxide and crown ether compound, first, has the advantages such as high-specific surface area, porous and the high stability that stratiform rare-earth hydroxide has, can absorbing heavy metal ions in water; Secondly, also there is the flexibility of organic macrocycle crown ether compound and guest ions is had to the feature of high selectivity, therefore Lamellar hydroxide composite material of the present invention can overcome both respective defects, plays advantage, and heavy metal ion has good adsorption capacity and selective.
Experimental result shows, Lamellar hydroxide composite material of the present invention is to Ag
+adsorbance can reach 0.14mmol/g.
Accompanying drawing explanation
The X-ray diffractogram of the Lamellar hydroxide composite material that Fig. 1 is the embodiment of the present invention 1, prepare in embodiment 2 and embodiment 3;
The infrared spectrogram of the Lamellar hydroxide composite material that Fig. 2 is the embodiment of the present invention 1, prepare in embodiment 2 and embodiment 3;
Fig. 3 is the X-ray diffractogram of the Lamellar hydroxide composite material after the Lamellar hydroxide composite material for preparing in the embodiment of the present invention 2 and embodiment 4 are adsorbed.
Detailed description of the invention
The invention provides a kind of Lamellar hydroxide composite material, be obtained by reacting by stratiform rare-earth hydroxide and crown ether-like carboxylic acid derivates.
Wherein, layered rare-earth hydroxide is stratiform rare-earth hydroxide well known to those skilled in the art, there is no special restriction, the rare-earth hydroxide of stratiform described in the present invention is preferably stratiform gadolinium hydroxide, stratiform yttrium hydroxide, stratiform europium hydroxide or stratiform terbium hydroxide, is more preferably stratiform gadolinium hydroxide.
To be a class fill by positively charged metal hydroxides nitride layer and interlayer the pillared layered compound that exchangeable anions forms to stratiform rare-earth hydroxide, wherein, the interlayer anion of stratiform rare-earth hydroxide of the present invention is preferably univalent anion, is more preferably nitrate ion or chlorion.By electrostatic or hydrogen bond action between interlayer anion and laminate, this more weak interaction force makes interlayer anion have interchangeability, desired anion can be introduced interlayer by ion-exchange method and obtain required layered hydroxide.
Stratiform rare-earth hydroxide has excellent ion-exchange performance, and has the advantages such as high-specific surface area, porous and stability, the heavy metal ion in adsorbable water.
Described crown ether-like carboxylic acid derivates is crown ether-like carboxylic acid derivates well known to those skilled in the art, there is no special restriction, the carboxylic acid derivates of crown ether-like described in the present invention is preferably tetraazacrown ether carboxylic acid derivates or diaza crown ether carboxylic acid derivates, is more preferably 4,7,13,16-tetra-carboxyethyl-1,10-dioxy-4,7,13,16-tetraazacyclododecane octadecane.
Organic macrocycle crown ether compound has high selectivity to guest molecule, the Lamellar hydroxide composite material that itself and stratiform rare-earth hydroxide are obtained by reacting can in conjunction with the advantage of stratiform rare-earth hydroxide and crown ether compound, overcome respective defect, thus obtain heavy metal ion and have better adsorption capacity and optionally composite.
Present invention also offers the preparation method of above-mentioned Lamellar hydroxide composite material, comprising: A) stratiform rare-earth hydroxide, crown ether-like carboxylic acid derivates, water are mixed with alkali metal hydroxide, reaction, obtains Lamellar hydroxide composite material.
The all raw materials of the present invention, do not have special restriction to its source, commercially purchase or homemade.Layered rare-earth hydroxide and crown ether-like carboxylic acid derivates all same as above, do not repeat them here.
The preparation method of layered rare-earth hydroxide and crown ether-like carboxylic acid derivates all adopts method well known to those skilled in the art to be prepared, and there is no special restriction.
The present invention is under the effect of alkali metal hydroxide, stratiform rare-earth hydroxide, crown ether-like carboxylic acid derivates are mixed with water, react, wherein said alkali metal hydroxide is hydroxide well known to those skilled in the art, there is no special restriction, in the present invention, be preferably NaOH or potassium hydroxide.
Alkali metal hydroxide can make the deprotonation of crown ether-like carboxylic acid derivates, forms anion and then can exchange with the anion in layered hydroxide.
The process that stratiform rare-earth hydroxide, crown ether-like carboxylic acid derivates, water mix with alkali metal hydroxide is specially by the present invention: first crown ether-like carboxylic acid derivates, water are mixed with alkali metal hydroxide, this step can make the first deprotonation of crown ether-like carboxylic acid derivates form anion, and then adds stratiform rare-earth hydroxide again.
According to the present invention, the mol ratio of described crown ether-like carboxylic acid derivates and alkali metal hydroxide is 1:(5 ~ 8), be preferably 1:(6 ~ 7), this ratio can make the deprotonation of crown ether-like carboxylic acid derivates maximum ratio, and then obtains more anion.
The mol ratio of described crown ether-like carboxylic acid derivates and stratiform rare-earth hydroxide is (0.5 ~ 1): 1, is more preferably (0.7 ~ 1): 1.
After being mixed by above-mentioned raw materials in the present invention, react, described reaction is ion-exchange reactions, and the anion that the interlayer anion of stratiform rare-earth hydroxide and the deprotonation of crown ether-like carboxylic acid derivates are formed exchanges.Described reaction is preferably at room temperature stirred and is reacted; The time of described reaction is preferably 20 ~ 26h, is more preferably 22 ~ 24h.
Experimental result shows, Lamellar hydroxide composite material of the present invention is to Ag
+adsorbance can reach 0.14mmol/g.
The preparation process of Lamellar hydroxide composite material of the present invention is simple, mild condition, and crown ether compound inserts stratiform rare-earth hydroxide interlayer as guest molecule by ion-exchange first, the development for lamellar compound and macrocyclic compound opens a new research direction.
In order to further illustrate the present invention, below in conjunction with embodiment, Lamellar hydroxide composite material provided by the invention and preparation method thereof is described in detail.
Reagent used in following examples is commercially available.
Embodiment 1
1.1 by 2gGd
2o
3be dissolved in the nitric acid of 20ml1:1, through heating evaporation, condensing crystallizing obtains Gd (NO
3)
36H
2o.
1.2 by 0.451g(1mmol) Gd (NO that obtains in 1.1
3)
36H
2o, 1.105g(13mmol) NaNO
3with 0.140g(1mmol) hexamethylenetetramine mixes, and adds the water of 80ml through pump-down process, and logical nitrogen 5min, is heated to 90 DEG C of hydro-thermal reaction 12h, suction filtration, washes 3 times, obtain white powder stratiform gadolinium hydroxide and NO
3 --LGdH.
1.3 by after water-soluble for 16.0gNaOH 200ml solution; be placed in 500ml tri-mouthfuls of round-bottomed flasks; add 13.5ml ethylenediamine; water-bath temperature control is at 40 DEG C ~ 50 DEG C; add 80.0g paratoluensulfonyl chloride (TsCl) under stirring condition in batches, after Keep agitation 4h, add 50ml ethanol; be heated to 90 DEG C; stop reaction after backflow 5min, be cooled to room temperature, suction filtration; product distillation washing three times; dry rear ethyl alcohol recrystallization, suction filtration obtains white needle-like crystals, is N; N '-two p-toluenesulfonyl ethylenediamine (A), reaction equation is as follows:
1.4 add the N obtained in 33.3g1.3 in 250ml round-bottomed flask, N '-two p-toluenesulfonyl ethylenediamine (A), 18.0g anhydrous K
2cO
3and 40mlN, dinethylformamide (DMF), adds 11.9ml2 under magnetic agitation, 2 '-dichlorodiethyl ether; oil bath temperature control, at 170 DEG C, adds hot reflux 10h, is cooled to room temperature, puts into the freezing 20h of environment of 5 DEG C; suction filtration, filter cake respectively washes twice with acetone and water successively, and the DMF drying rear heat is recrystallized to obtain white crystal; be 4,7,13; 16-tetra-p-toluenesulfonyl-1,10-dioxy-4,7; 13,16-tetra-azepine-18 hat-6(B), reaction equation is as follows:
1.5 add obtain in 15g1.4 4 in 100ml round-bottomed flask; 7; 13; 16-tetra-p-toluenesulfonyl-1; 10-dioxy-4; 7,13,16-tetra-azepine-18 hat-6(B) and the 40ml concentrated sulfuric acid; three day three night of stirring reaction under the condition of 100 DEG C of oil baths; reactant liquor is transferred in 500ml conical flask afterwards, with about NaOH solution adjust ph to 12, filters while hot; the a small amount of chloroform of solid washs; repeatedly fully extract with a large amount of chloroform after cleaning solution and filtrate merge, merge organic phase, add appropriate anhydrous Na
2sO
4drying, placed two days later and filtered Na
2sO
4, revolve and steam filtrate, obtain white solid, placing normal heptane two days later and to be recrystallized to obtain white needle-like crystals, is 1,10-dioxy-4,7,13,16-tetra-azepine-18-hat-6(L), reaction equation is as follows:
1.6 add 0.52g(2mmol in 25ml round-bottomed flask) 1, the 10-dioxy-4,7 that obtains in 1.5,13,16-tetra-azepine-18-hat-6(L) and 8ml absolute ethyl alcohol, stir and make it dissolve completely, add 2.7ml acrylonitrile again, add hot reflux 24h, clear yellow viscous thing (L1) after revolving steaming, can be obtained; In L1, add 30ml hydrochloric acid solution (mass ratio of hydrochloric acid and water is 2:1), add hot reflux 24h, after stopping reaction, heating solvent flashing, separates out a large amount of crystal, cold filtration, drying at room temperature, obtains clear crystal, is 4,7,13,16-tetra-carboxyethyl-1,10-dioxy-4,7,13,16-tetraazacyclododecane octadecane (L2), reaction equation is as follows:
1.7 by 0.05g(0.076mmol) 4,7,13,16-tetra-carboxyethyl-1,10-dioxy-4,7,13, the 16-tetraazacyclododecane octadecanes that obtain in 1.6,80ml distilled water mixes with 0.532mmol NaOH, then adds the NO obtained in 0.10g1.2
3-LGdH, the pH value of solution is about 9.38, stirring at room temperature 24h, suction filtration, and vacuum drying obtains Lamellar hydroxide composite material.
Utilize X-ray diffractometer to the stratiform gadolinium hydroxide obtained in 1.2 and NO
3 -the Lamellar hydroxide composite material obtained in-LGdH and 1.7 is analyzed, and obtains its X-ray diffractogram as shown in Figure 1, and unit is nm, and wherein, a is the stratiform gadolinium hydroxide obtained in 1.2, and b is the Lamellar hydroxide composite material obtained in 1.7.As shown in Figure 1, compared with stratiform gadolinium hydroxide, the interlamellar spacing of Lamellar hydroxide composite material expands 1.50 ~ 1.52nm to by original 0.82nm, and the interlamellar spacing disappearance that nitrate ion intercalation is corresponding, there is the Series diffractive peak of about 1.50nm, 0.76nm, 0.51nm, 0.38nm and 0.32nm in Figure 1b, d
basal=1.50nm, illustrates that 4,7,13,16-tetra-carboxyethyl-1,10-dioxy-4,7,13,16-tetraazacyclododecane octadecane successfully exchanges to interlayer, and the diffraction maximum of Lamellar hydroxide composite material is all comparatively sharp-pointed, shows that it has higher degree of crystallinity.
Utilize infrared spectrometer to the stratiform gadolinium hydroxide obtained in 1.2 and NO
3 -the Lamellar hydroxide composite material obtained in crown ether-like carboxylic acid derivates 4,7,13,16-tetra-carboxyethyl-1,10-dioxy-4,7,13, the 16-tetraazacyclododecane octadecane obtained in-LGdH, 1.6 and 1.7 is analyzed, and obtains its infrared spectrogram, as shown in Figure 2.Wherein a is the stratiform gadolinium hydroxide obtained in 1.2, and b is the Lamellar hydroxide composite material obtained in 1.7, and e is crown ether-like carboxylic acid derivates 4,7,13,16-tetra-carboxyethyl-1,10-dioxy-4,7,13, the 16-tetraazacyclododecane octadecane obtained in 1.6.1384cm in Fig. 2 a
-1place is NO
3 -characteristic absorption, formed after Lamellar hydroxide composite material and disappear, illustrate that ion-exchange is complete.Fig. 2 e is at 1737cm
-1with 1412cm
-1place to be absorbed as in crown ether-like carboxylic acid derivates C=O absorption of vibrations in-COOH, in Lamellar hydroxide composite material, move to 1559cm respectively
-1with 1404cm
-1, illustrate that the carboxyl in crown ether-like carboxylic acid derivates is with carboxylate form's intercalation of deprotonation; 1194cm in Fig. 2 e
-1, 1132cm
-1place is the absorption of crown ether cycle C-N and C-O-C, and in Lamellar hydroxide composite material, red shift is to 1115cm
-1and 1050cm
-1place, illustrates that crown ether-like carboxylic acid derivates and laminate and intermediary water molecule are had an effect; 588cm
-1place is the absorption of M-O in laminate, illustrates and defines Lamellar hydroxide composite material.
Embodiment 2
By 0.075g(0.11mmol) 4,7,13,16-tetra-carboxyethyl-1,10-dioxy-4,7,13, the 16-tetraazacyclododecane octadecanes that obtain in 1.6,80ml distilled water mixes with 0.77mmol NaOH, then adds the NO obtained in 0.10g1.2
3 --LGdH, the pH value of solution is about 9.38, stirring at room temperature 24h, suction filtration, and vacuum drying obtains Lamellar hydroxide composite material.
Utilize X-ray diffractometer to obtain Lamellar hydroxide composite material analysis in embodiment 2, obtain its X-ray diffractogram as shown in Figure 1, wherein c is the Lamellar hydroxide composite material obtained in embodiment 2.
Utilize infrared spectrometer to analyze the Lamellar hydroxide composite material obtained in embodiment 2, obtain its infrared spectrogram, as shown in Figure 2.Wherein c is the Lamellar hydroxide composite material obtained in 1.7.
Embodiment 3
By 0.1g(0.15mmol) 4,7,13,16-tetra-carboxyethyl-1,10-dioxy-4,7,13, the 16-tetraazacyclododecane octadecanes that obtain in 1.6,80ml distilled water mixes with 1.05mmol NaOH, then adds the NO obtained in 0.10g1.2
3-LGdH, the pH value of solution is about 9.38, stirring at room temperature 24h, suction filtration, and vacuum drying obtains Lamellar hydroxide composite material.
Utilize X-ray diffractometer to obtain Lamellar hydroxide composite material analysis in embodiment 3, obtain its X-ray diffractogram as shown in Figure 1, wherein d is the Lamellar hydroxide composite material obtained in embodiment 2.
Utilize infrared spectrometer to analyze the Lamellar hydroxide composite material obtained in embodiment 3, obtain its infrared spectrogram, as shown in Figure 2.Wherein d is the Lamellar hydroxide composite material obtained in 1.7.
Embodiment 4
Be the AgNO of 10mmol/L by the Lamellar hydroxide composite material obtained in 0.05g embodiment 2 and 5ml total concentration
3(colourless), Pd (NO
3)
2, Cd (NO
3)
2, Cr (NO
3)
3mixed liquor (light blue) mixing of four kinds of materials, sealing, leaves standstill 3 days, daytime rocks once every 2 ~ 3h, and after absorption, mixed liquor becomes brown, gets supernatant after centrifugal, dilution, utilization is electrically coupled plasma emission spectrometer (ICP) and tests its concentration, and test result is in table 1; The 60 DEG C of vacuum drying of solid after absorption, utilize X-ray diffractometer to test it.
The adsorption capacity of table 1 Lamellar hydroxide composite material heavy metal ion and distribution coefficient
As shown in Table 1, the adsorption capacity of Lamellar hydroxide composite material heavy metal ion and selecting sequence are: Ag
+>>Pb
2+>Cr
3+>Cd
2+, to Ag
+suction-operated best, distribution coefficient K
dbe more than 40 times of other ions, the selective difference of Lamellar hydroxide composite material to different metal ion is described.
Utilize X-ray diffractometer to analyze Lamellar hydroxide composite material before and after absorption in embodiment 4, obtain its X-ray diffractogram, as shown in Figure 3, wherein b is Lamellar hydroxide composite material before absorption, and b ' is Lamellar hydroxide composite material after absorption.As shown in Figure 3, after absorption, Lamellar hydroxide composite material interlamellar spacing becomes large, may be because metal ion enters interlayer, with crown ether cycle and side chain carboxyl group coordination, the polycomplexation zoarium of formation makes interlayer region become large, and then makes interlamellar spacing become large, in addition, the complexing of metal ion and crown ether-like carboxylic acid derivates, also can weaken the electrostatic interaction of crown ether-like carboxylic acid derivates and laminate, increases interlamellar spacing.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a Lamellar hydroxide composite material, is characterized in that, is obtained by reacting by stratiform rare-earth hydroxide and crown ether-like carboxylic acid derivates; The mol ratio of described crown ether-like carboxylic acid derivates and stratiform rare-earth hydroxide is (0.5 ~ 1): 1.
2. Lamellar hydroxide composite material according to claim 1, is characterized in that, described crown ether-like carboxylic acid derivates is tetraazacrown ether carboxylic acid derivates or diaza crown ether carboxylic acid derivates.
3. Lamellar hydroxide composite material according to claim 1, is characterized in that, layered rare-earth hydroxide is stratiform gadolinium hydroxide, stratiform yttrium hydroxide, stratiform europium hydroxide or stratiform terbium hydroxide.
4. Lamellar hydroxide composite material according to claim 1, is characterized in that, the interlayer anion of layered rare-earth hydroxide is univalent anion.
5. Lamellar hydroxide composite material according to claim 1, is characterized in that, the interlayer anion of layered rare-earth hydroxide is nitrate ion or chlorion.
6. a preparation method for Lamellar hydroxide composite material, is characterized in that, comprising:
A) stratiform rare-earth hydroxide, crown ether-like carboxylic acid derivates, water are mixed with alkali metal hydroxide, reaction, obtains Lamellar hydroxide composite material.
7. preparation method according to claim 6, is characterized in that, described steps A) be specially:
Crown ether-like carboxylic acid derivates, water are mixed with alkali metal hydroxide, then adds stratiform rare-earth hydroxide, stirring reaction, obtain Lamellar hydroxide composite material.
8. preparation method according to claim 6, is characterized in that, the mol ratio of described crown ether-like carboxylic acid derivates and stratiform rare-earth hydroxide is (0.5 ~ 1): 1.
9. preparation method according to claim 6, is characterized in that, the mol ratio of described crown ether-like carboxylic acid derivates and alkali metal hydroxide is 1:(5 ~ 8).
10. preparation method according to claim 6, is characterized in that, described alkali metal hydroxide is NaOH and/or potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310150638.9A CN103230776B (en) | 2013-04-26 | 2013-04-26 | A kind of Lamellar hydroxide composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310150638.9A CN103230776B (en) | 2013-04-26 | 2013-04-26 | A kind of Lamellar hydroxide composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103230776A CN103230776A (en) | 2013-08-07 |
| CN103230776B true CN103230776B (en) | 2016-01-20 |
Family
ID=48878884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310150638.9A Expired - Fee Related CN103230776B (en) | 2013-04-26 | 2013-04-26 | A kind of Lamellar hydroxide composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103230776B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119905B (en) * | 2014-06-26 | 2015-10-28 | 北京师范大学 | O-coumaric acid-LEuH complex body and synthetic method thereof |
| CN104119904B (en) * | 2014-06-26 | 2015-10-28 | 北京师范大学 | P-coumaric acid-LEuH complex body and synthetic method thereof |
| CN104151368B (en) * | 2014-08-06 | 2016-05-04 | 北京师范大学 | A kind of Rare Earth Europium Complex and synthetic method thereof |
| CN104151367B (en) * | 2014-08-06 | 2016-05-04 | 北京师范大学 | A kind of Rare Earth Lanthanum complex and synthetic method thereof |
| CN104263350B (en) * | 2014-08-21 | 2016-05-04 | 北京师范大学 | HPTS/OS-LEuH complex and synthetic method thereof |
| CN104267006B (en) * | 2014-08-21 | 2016-06-01 | 北京师范大学 | O-coumaric acid-LTbH complex body and synthetic method thereof |
| CN106673111B (en) * | 2017-01-10 | 2020-09-08 | 苏州大学 | Method for treating wastewater containing selenate |
| CN106947461B (en) * | 2017-04-25 | 2019-09-17 | 宁波大学 | A kind of crown ether-like rare earth photochromic material and preparation method thereof |
| CN107570106B (en) * | 2017-10-17 | 2020-02-14 | 西南大学 | Iron-manganese layered double hydroxide, preparation method and application |
| CN109233830B (en) * | 2018-10-17 | 2020-10-16 | 北京师范大学 | Trimesic acid-LEuH complex and synthesis method thereof |
| CN115052837A (en) * | 2020-02-17 | 2022-09-13 | 国立研究开发法人科学技术振兴机构 | Layered double hydroxide electronic compound and method for producing same |
| CN112717886A (en) * | 2020-12-10 | 2021-04-30 | 中国科学院江西稀土研究院 | Rare earth element adsorbent and preparation method and application thereof |
| CN113463129B (en) * | 2021-06-30 | 2022-07-29 | 中国石油大学(华东) | Preparation and application of carboxyl intercalation nickel-iron-lithium layered hydroxide electrocatalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225917A (en) * | 2011-04-18 | 2011-10-26 | 北京师范大学 | Preparation method of organic/layered double hydroxide (LDH) complex |
| CN102565421A (en) * | 2011-12-27 | 2012-07-11 | 北京师范大学 | Tyrosine radical/LRH complex for amino acid detection and synthesis method of the complex |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5116587A (en) * | 1990-01-18 | 1992-05-26 | Board Of Trustees Operating Michigan State University | Layered double hydroxide sorbents for the removal of sox from flue gas resulting from coal combustion |
| CN102584739A (en) * | 2011-12-21 | 2012-07-18 | 北京师范大学 | Carboxyl benzyl replaced nitrogen dioxide crown ether derivative and synthesizing method thereof |
-
2013
- 2013-04-26 CN CN201310150638.9A patent/CN103230776B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225917A (en) * | 2011-04-18 | 2011-10-26 | 北京师范大学 | Preparation method of organic/layered double hydroxide (LDH) complex |
| CN102565421A (en) * | 2011-12-27 | 2012-07-11 | 北京师范大学 | Tyrosine radical/LRH complex for amino acid detection and synthesis method of the complex |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103230776A (en) | 2013-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103230776B (en) | A kind of Lamellar hydroxide composite material and preparation method thereof | |
| Wu et al. | Highly selective separation of rare earth elements by Zn-BTC metal–organic framework/nanoporous graphene via in situ green synthesis | |
| CN102911194B (en) | Preparation method of nano rare earth carboxylic acid coordination polymer and application thereof | |
| JP2001122877A (en) | Cucurbituril derivative, method for preparing the same, and use | |
| CN103816872B (en) | Magnetic hydroxyl oximate shitosan and preparation method thereof | |
| CN103586006A (en) | Method of aminopyridine modified resin for adsorbing rhodium octanoate dimer and metal ions | |
| CN105218765A (en) | A kind of Preparation method and use of photoresponse intelligence trace mesoporous material | |
| Zhou et al. | A multifunctional nanocage-based MOF with tri-and tetranuclear zinc cluster secondary building units | |
| CN104707563A (en) | Magnetically modified hydrotalcite as well as preparation method and application thereof | |
| Chai et al. | Five Mesoporous Lanthanide Metal–Organic Frameworks: Syntheses, Structures, and Fluorescence Sensing of Fe3+, Cr2O72–, and H2O2 and Electrochemical Sensing of Trinitrophenol | |
| Wu et al. | Porphyrin-based hydrogen-bonded organic framework for visible light driven photocatalytic removal of U (VI) from real low-level radioactive wastewater | |
| CN105289576A (en) | Preparation method of ZnAl-LDO-coated Nb2O5 photocatalysis material | |
| CN102225917A (en) | Preparation method of organic/layered double hydroxide (LDH) complex | |
| CN101555253B (en) | Ruthenium polypyridyl complex inducing DNA to condense, preparation method and application thereof | |
| CN108722445A (en) | A kind of ultra-thin BiOX based solid solution photochemical catalyst and its preparation method and application | |
| CN107572564A (en) | A kind of wheat head shape porous magnesia and preparation method thereof | |
| CN105017295A (en) | Novel near-infrared luminescence 8-hydroxyquinoline-type rare earth ytterbium complex tetramer crystal and preparation method thereof | |
| CN109675521B (en) | Graphene oxide-gadolinium hydroxide composite material, preparation method and application thereof | |
| CN106315609A (en) | Preparation method of one-step method microporous/mesoporous composite molecular sieve with framework doped with rare earth in complexing mode | |
| CN104151368B (en) | A kind of Rare Earth Europium Complex and synthetic method thereof | |
| CN102616901B (en) | Preparation of magnetic cucurbituril and application of magnetic cucurbituril in removing HA (humic acid) pollutants from drinking source water | |
| CN102350297B (en) | Adsorbent, preparation method and application thereof | |
| CN114891030A (en) | Europium complex time-resolved fluorescent material and preparation method thereof | |
| CN114835909A (en) | Dysprosium-based single-ion magnet supermolecular frame with high stability and photostimulation responsiveness and synthesis method thereof | |
| CN104004508A (en) | Preparation method of conductive mixed metal polymer film material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20190426 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |