CN103230776A - Lamellar hydroxide composite material and preparation method thereof - Google Patents
Lamellar hydroxide composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a lamellar rare earth hydroxide composite material. The lamellar rare earth hydroxide composite material is prepared by carrying out a reaction on lamellar rare earth hydroxide and crown ether carboxylic acid derivatives. In comparison with the prior art, the lamellar hydroxide composite material is compounded from the lamellar rare earth hydroxide and a crown ether compound. Firstly, the lamellar rare earth hydroxide composite material has the advantages of high specific surface area, porosity and high stability of the lamellar rare earth hydroxide, so that heavy metal ion in water can be absorbed; and secondly, the lamellar rare earth hydroxide composite material has the characteristics of softness and high selectivity to object ions of the organic macrocyclic crown ether compound. Thus, the lamellar rare earth hydroxide composite material can overcome the defects and develop the advantages, and has high adsorption capacity and selectivity to heavy metal ions.
Description
Technical field
The invention belongs to new material and water and pollute the inorganic agent technical field, relate in particular to a kind of layered hydroxide composite and preparation method thereof.
Background technology
China has a large population, water resource lacks, and water resources ownership per capita is 1/4 of world average level only, is one of 13 poor-water states in the world.Along with the industrial or agricultural rapid economy development, discharged waste water increases day by day, industrial wastewater complicated component and contain a large amount of available resources, the wherein significant damage that environment caused with himself features of pollution of heavy metal ion and be subjected to the attention of height.For separate with enrichment waste water in heavy metal ion, realize that resource reclaims the double effects with environmental protection, the research of relevant 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 the LRH that interlayer can obtain the organic anion intercalation, and this type of material has extensive use in fields such as storage, drug delivery and the release of optics, catalysis, biomolecule, bio-sensing, sewage disposal, electrochemical sensings.
The hydroxide with hydrotalcite layered structure that layered double hydroxide is made up of bivalent metal ion and trivalent metal ion claims mixed metal hydroxides again; Layered double hydroxide has the shepardite lamellar structure, laminate is owing to trivalent metal ion isomorphous substitution bivalent metal ion has positive charge, the electric charge of the object anion that interlayer can exchange and laminate positive charge balance, make layered double hydroxide be electroneutral, layered double hydroxide has bigger anion-exchange capacity (AEC, 2～3mep/g), acceptant object anion, therefore can be used to the metal and the organic pollution that exist with the anion form in the adsorbed water body, but this type of material shortage is selective to guest molecule, has limited range of application.
The stratiform rare-earth hydroxide is the novel inorganic stratiform functional material that a class has layer structure, its main body is made of the hydroxide of rare earth metal, have and the similar structure of layered double hydroxide, also have the Modulatory character of interlayer object anion species and quantity, but yet there are no the relevant report for adsorbent.
Organic/inorganic composite material is the research field of rising and have development potentiality in the materials chemistry recently, it is to combine by synergy organifying compound and inorganic matter in nanometer range, double grading with organic compounds and inorganic matter, combination property is better than each one-component, be the research focus in materials chemistry field in recent years, receive much concern always.
The present invention considers layered hydroxide and the macrocyclic compound crown ether with molecular recognition characteristic are 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 layered hydroxide composite and preparation method thereof, and this composite has better adsorption capability with selective to heavy metal ion.
The invention provides a kind of layered hydroxide composite, obtained by stratiform rare-earth hydroxide and the reaction of crown ether-like carboxylic acid derivates.
Preferably, described crown ether-like carboxylic acid derivates is four Azacrown ether containing 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.
The present invention also provides a kind of preparation method of layered hydroxide composite, comprising:
A) stratiform rare-earth hydroxide, crown ether-like carboxylic acid derivates, water are mixed with alkali metal hydroxide, reaction obtains the layered hydroxide composite.
Preferably, described steps A) be specially:
Crown ether-like carboxylic acid derivates, water are mixed with alkali metal hydroxide, add the stratiform rare-earth hydroxide again, stirring reaction obtains the layered hydroxide composite.
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 layered hydroxide composite, obtained by stratiform rare-earth hydroxide and the reaction of 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, at first, has the advantages such as high-specific surface area, porous and high stability that the stratiform rare-earth hydroxide has, can absorbing heavy metal ions in water; Secondly, the flexibility that also has the organic macrocycle crown ether compound reaches the characteristics that the object ion had high selectivity, therefore layered hydroxide composite of the present invention can overcome both defectives separately, and the performance advantage has better adsorption capability with selective to heavy metal ion.
Experimental result shows that layered hydroxide composite of the present invention is to Ag
+Adsorbance can reach 0.14mmol/g.
Description of drawings
Fig. 1 be the embodiment of the invention 1, embodiment 2 with embodiment 3 in the X-ray diffractogram of the layered hydroxide composite for preparing;
Fig. 2 be the embodiment of the invention 1, embodiment 2 with embodiment 3 in the infrared spectrogram of the layered hydroxide composite for preparing;
Fig. 3 is the X-ray diffractogram of the layered hydroxide composite of the layered hydroxide composite for preparing in the embodiment of the invention 2 after adsorbing with embodiment 4.
The specific embodiment
The invention provides a kind of layered hydroxide composite, obtained by stratiform rare-earth hydroxide and the reaction of crown ether-like carboxylic acid derivates.
Wherein, layered rare-earth hydroxide is that stratiform rare-earth hydroxide well known to those skilled in the art gets final product, 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, more preferably stratiform gadolinium hydroxide.
The stratiform rare-earth hydroxide is that a class is filled the layer stylolitization compound that commutative anion constitutes by positively charged metal hydroxides thing layer and interlayer, wherein, the interlayer anion of stratiform rare-earth hydroxide of the present invention is preferably univalent anion, more preferably nitrate ion or chlorion.By static or hydrogen bond action, this more weak interaction force makes interlayer anion have interchangeability between interlayer anion and laminate, the target anion can be introduced interlayer by ion-exchange method and obtain required layered hydroxide.
The stratiform rare-earth hydroxide has good ion-exchange performance, and has advantages such as high-specific surface area, porous and stability, the heavy metal ion in the adsorbable water.
Described crown ether-like carboxylic acid derivates is that crown ether-like carboxylic acid derivates well known to those skilled in the art gets final product, there is no special restriction, the carboxylic acid derivates of crown ether-like described in the present invention is preferably four Azacrown ether containing carboxylic acid derivates or diaza crown ether carboxylic acid derivates, and more preferably 4,7,13,16-tetracarboxylic acid ethyl-1,10-dioxy-4,7,13,16-tetraazacyclododecane octadecane.
The organic macrocycle crown ether compound has high selectivity to guest molecule, the layered hydroxide composite that itself and the reaction of stratiform rare-earth hydroxide obtain can be in conjunction with the advantage of stratiform rare-earth hydroxide and crown ether compound, overcome defective separately, thereby obtain that heavy metal ion is had better adsorption capacity and composite optionally.
The present invention also provides the preparation method of above-mentioned layered hydroxide composite, comprising: A) stratiform rare-earth hydroxide, crown ether-like carboxylic acid derivates, water are mixed with alkali metal hydroxide, reaction obtains the layered hydroxide composite.
All raw materials of the present invention do not have special restriction to its source, buy in market or homemadely all can.Layered rare-earth hydroxide and crown ether-like carboxylic acid derivates are 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 gets final product, 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 that hydroxide well known to those skilled in the art gets final product, there is no special restriction, be preferably NaOH or potassium hydroxide among the present invention.
Alkali metal hydroxide can make the deprotonation of crown ether-like carboxylic acid derivates, form anion so that can with layered hydroxide in anion exchange.
The present invention is specially the process that stratiform rare-earth hydroxide, crown ether-like carboxylic acid derivates, water mix with alkali metal hydroxide: at first crown ether-like carboxylic acid derivates, water are mixed with alkali metal hydroxide, this step can make the deprotonation of crown ether-like carboxylic acid derivates elder generation form anion, and then adds the 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, more preferably (0.7～1): 1.
With after the above-mentioned raw materials mixing, react among the present invention, 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 form exchanges.Described reaction is preferably at room temperature stirred and is reacted; The time of described reaction is preferably 20～26h, more preferably 22～24h.
Experimental result shows that layered hydroxide composite of the present invention is to Ag
+Adsorbance can reach 0.14mmol/g.
The preparation process of layered hydroxide composite 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, for a new research direction has been opened up in the development of lamellar compound and macrocyclic compound.
In order to further specify the present invention, below in conjunction with embodiment layered hydroxide composite provided by the invention and preparation method thereof is described in detail.
Used reagent is commercially available in following examples.
Embodiment 1
1.1 with 2g Gd
2O
3Be dissolved in the nitric acid of 20ml1:1, through heating evaporation, condensing crystallizing obtains Gd (NO
3)
36H
2O.
1.2 with 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 80ml through the water of pump-down process, and logical nitrogen 5min is heated to 90 ℃ of hydro-thermal reaction 12h, and suction filtration is washed 3 times, and obtaining white powder stratiform gadolinium hydroxide is NO
3 --LGdH.
1.3 after the water-soluble solution of 16.0g NaOH usefulness 200ml; place three mouthfuls of round-bottomed flasks of 500ml; add the 13.5ml ethylenediamine; the water-bath temperature control is at 40 ℃～50 ℃; add 80.0g paratoluensulfonyl chloride (TsCl) under the stirring condition in batches, after continuing to stir 4h, add 50ml ethanol; heat temperature raising to 90 ℃; stop reaction behind the backflow 5min, be cooled to room temperature, suction filtration; product is given a baby a bath on the third day after its birth inferior with distilled water; dry the back and use ethyl alcohol recrystallization, suction filtration gets white needle-like crystals, is N; N '-two p-toluenesulfonyl ethylenediamine (A), reaction equation is as follows:
1.4 in the 250ml round-bottomed flask, add the N that obtains among the 33.3g1.3, N '-two p-toluenesulfonyl ethylenediamine (A), 18.0g anhydrous K
2CO
3And 40ml N, dinethylformamide (DMF) adds 11.9ml2 under the magnetic agitation, 2 '-dichlorodiethyl ether; the oil bath temperature control adds hot reflux 10h at 170 ℃, is cooled to room temperature, puts into 5 ℃ the freezing 20h of environment; suction filtration, filter cake respectively wash twice with acetone and water successively, dry the back with hot DMF be recrystallized white crystal; be 4,7,13; 16-four p-toluenesulfonyls-1,10-dioxy-4,7; hat-6(B), reaction equation is as follows for 13,16-, four azepines-18:
1.5 in the 100ml round-bottomed flask, add obtain among the 15g1.4 4; 7; 13; 16-four p-toluenesulfonyls-1; 10-dioxy-4; 7,13,16-, four azepines-18 hat-6(B) and the 40ml concentrated sulfuric acid; three days three nights of stirring reaction under the condition of 100 ℃ of oil baths; afterwards reactant liquor is transferred in the 500ml conical flask, regulates about pH value to 12 with NaOH solution, filter while hot; solid washs with a small amount of chloroform; cleaning solution and filtrate merge the back with the repeatedly fully extraction of a large amount of chloroforms, merge organic phase, add an amount of anhydrous Na
2SO
4Drying is placed and is removed by filter Na two days later
2SO
4, revolve and steam filtrate, obtain white solid, place two days later normal heptane be recrystallized white needle-like crystals, be 1,10-dioxy-4,7,13, hat-6(L), reaction equation is as follows for 16-four azepines-18-:
1.6 in the 25ml round-bottomed flask, add 0.52g(2mmol) obtain in 1.5 1,10-dioxy-4,7,13,16-, four azepines-18-hat-6(L) and 8ml absolute ethyl alcohol stir it are dissolved fully, add the 2.7ml acrylonitrile again, add hot reflux 24h, can get yellow dope (L1) after revolving steaming; In L1, add 30ml hydrochloric acid solution (mass ratio of hydrochloric acid and water is 2:1), add hot reflux 24h, after stopping to react, the heated volatile solvent is separated out a large amount of crystal, cold filtration, drying at room temperature gets clear crystal, is 4,7,13,16-tetracarboxylic acid ethyl-1,10-dioxy-4,7,13,16-tetraazacyclododecane octadecane (L2), reaction equation is as follows:
1.7 with 0.05g(0.076mmol) obtain in 1.6 4,7,13,16-tetracarboxylic acid ethyl-1,10-dioxy-4,7,13,16-tetraazacyclododecane octadecane, 80ml distilled water mix with 0.532mmol NaOH, add the NO that obtains among the 0.10g1.2 again
3-LGdH, the pH value of solution is about 9.38, stirring at room 24h, suction filtration, vacuum drying obtains the layered hydroxide composite.
Utilizing X-ray diffractometer is NO to the stratiform gadolinium hydroxide that obtains in 1.2
3 -The layered hydroxide composite that obtains among-the 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 that obtains in 1.2, and b is the layered hydroxide composite that obtains in 1.7.As shown in Figure 1, compare with stratiform gadolinium hydroxide, the interlamellar spacing of layered hydroxide composite expands 1.50～1.52nm to by original 0.82nm, and the corresponding interlamellar spacing of nitrate ion intercalation disappears, the serial diffraction maximum that about 1.50nm, 0.76nm, 0.51nm, 0.38nm and 0.32nm in Fig. 1 b, have occurred, d
Basal=1.50nm illustrates 4,7,13,16-tetracarboxylic acid ethyl-1,10-dioxy-4,7,13, and 16-tetraazacyclododecane octadecane successfully exchanges to interlayer, and the diffraction maximum of layered hydroxide composite is all more sharp-pointed, shows that it has higher degree of crystallinity.
Utilizing infrared spectrometer is NO to the stratiform gadolinium hydroxide that obtains in 1.2
3 -The crown ether-like carboxylic acid derivates 4,7,13 that obtains among-the LGdH, 1.6,16-tetracarboxylic acid ethyl-1,10-dioxy-4,7,13, the layered hydroxide composite that obtains in the 16-tetraazacyclododecane octadecane and 1.7 is analyzed, and obtains its infrared spectrogram, as shown in Figure 2.Wherein a is the stratiform gadolinium hydroxide that obtains in 1.2, and b is the layered hydroxide composite that obtains in 1.7, and e is the crown ether-like carboxylic acid derivates 4,7,13 that obtains in 1.6,16-tetracarboxylic acid ethyl-1,10-dioxy-4,7,13,16-tetraazacyclododecane octadecane.1384cm among Fig. 2 a
-1The place is NO
3 -Characteristic absorption, disappear after forming the layered hydroxide composite, illustrate that ion-exchange is complete.Fig. 2 e is at 1737cm
-1With 1412cm
-1C=O absorption of vibrations among being absorbed as in the crown ether-like carboxylic acid derivates of place-COOH moves to 1559cm respectively in the layered hydroxide composite
-1With 1404cm
-1, illustrate that carboxyl in the crown ether-like carboxylic acid derivates is with the carboxylate radical form intercalation of deprotonation; 1194cm among Fig. 2 e
-1, 1132cm
-1The place is the absorption of crown ether cycle C-N and C-O-C, and red shift is to 1115cm in the layered hydroxide composite
-1And 1050cm
-1The place illustrates that crown ether-like carboxylic acid derivates and laminate and intermediary water molecule have an effect; 588cm
-1The place illustrates to have formed the layered hydroxide composite for the absorption of M-O in the laminate.
Embodiment 2
With 0.075g(0.11mmol) obtain in 1.6 4,7,13,16-tetracarboxylic acid ethyl-1,10-dioxy-4,7,13,16-tetraazacyclododecane octadecane, 80ml distilled water mix with 0.77mmol NaOH, add the NO that obtains among the 0.10g1.2 again
3 --LGdH, the pH value of solution is about 9.38, stirring at room 24h, suction filtration, vacuum drying obtains the layered hydroxide composite.
Utilize X-ray diffractometer to analyze obtaining the layered hydroxide composite among the embodiment 2, obtain its X-ray diffractogram as shown in Figure 1, wherein the layered hydroxide composite of c for obtaining among the embodiment 2.
Utilize infrared spectrometer that the layered hydroxide composite that obtains among the embodiment 2 is analyzed, obtain its infrared spectrogram, as shown in Figure 2.Wherein c is the layered hydroxide composite that obtains in 1.7.
Embodiment 3
With 0.1g(0.15mmol) obtain in 1.6 4,7,13,16-tetracarboxylic acid ethyl-1,10-dioxy-4,7,13,16-tetraazacyclododecane octadecane, 80ml distilled water mix with 1.05mmol NaOH, add the NO that obtains among the 0.10g1.2 again
3-LGdH, the pH value of solution is about 9.38, stirring at room 24h, suction filtration, vacuum drying obtains the layered hydroxide composite.
Utilize X-ray diffractometer to analyze obtaining the layered hydroxide composite among the embodiment 3, obtain its X-ray diffractogram as shown in Figure 1, wherein the layered hydroxide composite of d for obtaining among the embodiment 2.
Utilize infrared spectrometer that the layered hydroxide composite that obtains among the embodiment 3 is analyzed, obtain its infrared spectrogram, as shown in Figure 2.Wherein d is the layered hydroxide composite that obtains in 1.7.
Embodiment 4
Be the AgNO of 10mmol/L with the layered hydroxide composite and the 5ml total concentration that obtain among the 0.05g embodiment 2
3(colourless), Pd (NO
3)
2, Cd (NO
3)
2, Cr (NO
3)
3The mixed liquor of four kinds of materials (light blue) mixes, and sealing was left standstill 3 days, rock once every 2～3h daytime, and absorption back mixed liquor becomes brown, gets supernatant after centrifugal, dilution utilizes electric coupling plasma emission spectrometer (ICP) to test its concentration, and test result sees Table 1; 60 ℃ of vacuum drying of solid after the absorption utilize X-ray diffractometer that it is tested.
Table 1 layered hydroxide composite is to adsorption capacity and the distribution coefficient of heavy metal ion
As shown in Table 1, the layered hydroxide composite to adsorption capacity and the selecting sequence of heavy metal ion is: Ag
+Pb
2+Cr
3+Cd
2+, to Ag
+Suction-operated best, distribution coefficient K
dBe more than 40 times of other ions, illustrate that the layered hydroxide composite is to the selective difference of different metal ion.
Utilize X-ray diffractometer that layered hydroxide composite before and after the absorption among the embodiment 4 is analyzed, obtain its X-ray diffractogram, as shown in Figure 3, wherein b is the preceding layered hydroxide composite of absorption, and b ' is absorption back layered hydroxide composite.As shown in Figure 3, absorption back layered hydroxide composite interlamellar spacing becomes big, 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 big, and then makes interlamellar spacing become big, 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 only is preferred embodiment of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 layered hydroxide composite is characterized in that, is obtained by stratiform rare-earth hydroxide and the reaction of crown ether-like carboxylic acid derivates.
2. layered hydroxide composite according to claim 1 is characterized in that, described crown ether-like carboxylic acid derivates is four Azacrown ether containing carboxylic acid derivates or diaza crown ether carboxylic acid derivates.
3. layered hydroxide composite 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. layered hydroxide composite according to claim 1 is characterized in that, the interlayer anion of layered rare-earth hydroxide is univalent anion.
5. layered hydroxide composite according to claim 1 is characterized in that, the interlayer anion of layered rare-earth hydroxide is nitrate ion or chlorion.
6. the preparation method of a layered hydroxide composite 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 the layered hydroxide composite.
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, add the stratiform rare-earth hydroxide again, stirring reaction obtains the layered hydroxide composite.
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.
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| 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 |
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| 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 |
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