CN102614828B - Cysteine modified sba-15 mesoporous material and preparation method thereof - Google Patents
Cysteine modified sba-15 mesoporous material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a cysteine modified SBA-15 mesoporous material and a preparation method thereof. Hydrogen of hydroxy on the surface of SBA-15 is functionalized by a group which is shown in the specification of the invention, and therefore the cysteine modified SBA-15 mesoporous material is obtained. According to the invention, since cysteine is introduced to a sulfydryl functional group,Hg(II) can be absorbed efficiently and quickly with high selectivity.
Description
Technical field
The invention belongs to mesoporous material chemical modification field, relate to and a kind ofly novel Hg (II) being had efficiently, fast and the mesoporous material of the surface modification of high selectivity absorption, be specifically related to modified SBA-15 mesoporous material of a kind of cysteine and preparation method thereof.
Background technology
In recent years, environmental pollution is violent day by day, and the discharging of heavy metal ion has caused serious harm to the mankind and other biological, wherein, and Hg
2+The harm that (Hg (II)) causes environment is especially big, belongs to the hypertoxic heavy metal that can put aside in human body and animal tissue.Inorganic mercury in the polluted-water can change the bigger organic mercury of toxicity under microbial action, organic mercury causes the serious harm nervous system except meeting, also can cause various types of gene mutations.Hg (II) high volatility, toxicity are big, bioaccumulation is strong, in addition industrial mercurous discarded object complicated component.Prior art often adopts the Hg (II) in the absorption method removal water, and the sorbing material that adopts then is the core of this technology.
Mesoporous material is the material of class aperture porous road structure in 2～50nm scope, it has very high specific area, regular and adjustable aperture, bigger pore volume and surface are easy to carry out advantages such as chemical modification, and it is widely used and potential using value at aspects such as catalysis, biology, medicine, separation.
In recent years, the research of relevant mesoporous sorbent material had become a very active problem, wherein had the mesoporous material of efficient absorption to obtain certain achievement to Hg (II).As people such as Dai (Sheng Dai et al., Angew.Chem.1999,111,1314-1318) utilize a kind of " imprint surface " technology to improve the adsorptive selectivity of mesoporous material, people (Genhua Wu et al. such as Wu afterwards effectively, Analytica Chimica Acta, 582 (2007), 304 – 310) again with in its application and the selective absorption to Hg (II), adsorption capacity reaches 0.2mmol/g, but the preparation cost height of these class methods, and material regeneration is general.
In addition, prior art has also that open employing is inorganic, organo-functional group carries out adsorption capacity and the adsorptive selectivity that modification handles to improve mesoporous material to mesoporous material; CN1136960C discloses a kind of mercapto functional group MCM-48 mesopore molecular sieve and can be used for adsorbing mercury ion; CN102009983A discloses a kind of sulfhydryl modified SBA-15 molecular sieve and is used for the absorption mercury ion.People such as Liu (A.M.Liu et al., Chem.Commun., 2000,1145 – 1146) synthesized the Hg of mercapto-functionalized SBA-15 (II) efficient selective absorption has been arranged, people such as Zhang (Lingxia Zhang et al., Chem.Commun., 2003,210 – 211) the organic-inorganic compound mesoporous material that has prepared the thioether functionalization by coprecipitation reaches the adsorption capacity of 2700mg/g to Hg (II).
Yet existing have than the material modified of high adsorption capacity how to carry out modification by organic mercaptan/ether, phosphino-etc. to Hg (II) mostly, inevitably has certain toxicity, and adsorption process may cause secondary pollution after finishing.
Summary of the invention
In the face of the problems referred to above that prior art exists, the inventor have recognized the need to provide a kind of eco-friendly, can efficiently, fast, optionally adsorb the sorbing material of Hg (II).At this, the inventor recognizes that eco-friendly cysteine contains sulfydryl, can introduce cysteine existing SBA-15 mesoporous material is carried out the modification processing, be expected to improve adsorption capacity and the adsorptive selectivity of the Hg of SBA-15 (II), and cysteine is a kind of common amino acid in the organism, it can may not cause the secondary pollution of water quality as existing thioether/alcohol, thereby Environmental compatibility is good.
Based on above-mentioned cognition, through inventor's research with keen determination, the invention provides the modified SBA-15 mesoporous material of a kind of cysteine, wherein, the hydrogen on the hydroxyl on SBA-15 surface is by group
Functionalization, the formation chemical formula is
The modified SBA-15 mesoporous material of cysteine, wherein, x be 0,1 or 2, n greater than 1.
The present invention provides the sulfydryl functional group by introducing cysteine, can realize efficient, quick, the high absorption of selecting to Hg (II).And, to compare with existing mercapto-functionalized SBA-15, cysteine is a kind of common amino acid in the organism, it can may not cause the secondary pollution of water quality as existing thioether/alcohol, thereby Environmental compatibility is good.
The modified SBA-15 mesoporous material of cysteine provided by the invention, to Hg (II) show efficiently, selective absorption fast, will aspect the waste water treatment of heavy metal ions application promise in clinical practice arranged.
For example, in pH was 0.5～7.5 scope, the modified SBA-15 mesoporous material of cysteine provided by the invention can reach more than 90% high adsorption capacity to the adsorption rate of Hg (II).
Again for example, be that the modified SBA-15 mesoporous material of cysteine provided by the invention is more than 90% to the adsorption rate of Hg (II), and does not adsorb Pd, Cu or Cd ion basically under 1.5 the situation at pH, adsorptive selectivity is good.
On the other hand, the present invention also provides a kind of method for preparing the modified SBA-15 mesoporous material of above-mentioned cysteine, comprising: comprising:
Steps A: according to following formula SBA-15 and 3-aminopropyl triethoxysilane are dissolved in the toluene, reflux more than 12 hours, get NH
2-SBA-15,
Step B: according to following formula with the NH that makes
2-SBA-15 got the modified SBA-15 mesoporous material of described cysteine in 12～48 hours with cysteine reaction under 85～120 ℃ under the catalysis of catalyst dicyclohexylcarbodiimide and 4-dimethylamino naphthyridine,
In the present invention, in steps A, the rate of charge of SBA-15 and 3-aminopropyl triethoxysilane can be 1g:1mL～1g:5mL.
Again, in the present invention, in step B, used reaction dissolvent can be N, dinethylformamide.The mol ratio of catalyst dicyclohexylcarbodiimide and 4-dimethylamino naphthyridine can be 1:1～32:1.
Preferably, in steps A, used SBA-15 can be the SBA-15 through the boiling water activation.
Again, preferably, in steps A, described steps A and/or step B can carry out under nitrogen atmosphere protection.
Preparation method's raw material of the present invention is simple, cost is low and technological process is simple, the controllability height, and good reproducibility, Environmental compatibility is good, is fit to large-scale production, has fabulous application prospect.
Description of drawings
Fig. 1 is the synthetic route schematic diagram of the modified SBA-15 mesoporous material of cysteine of the present invention;
Fig. 2 is the vertical direction TEM(transmission electron microscope of an example of the modified SBA-15 mesoporous material of cysteine of the present invention) figure;
Fig. 3 is the horizontal direction TEM(transmission electron microscope of an example of the modified SBA-15 mesoporous material of cysteine of the present invention) figure;
Fig. 4 is the infrared spectrogram of an example of the modified SBA-15 mesoporous material of cysteine of the present invention;
Fig. 5 illustrates pH to the influence of the modified SBA-15 mesoporous material absorption Hg of cysteine of the present invention (II);
Fig. 6 illustrates adsorption time to the influence of the modified SBA-15 mesoporous material absorption Hg of cysteine of the present invention (II);
Fig. 7 illustrates the adsorbent consumption to the influence of the modified SBA-15 mesoporous material absorption Hg of cysteine of the present invention (II);
Fig. 8 illustrates initial concentration to the influence of the modified SBA-15 mesoporous material absorption Hg of cysteine of the present invention (II).
The specific embodiment
With reference to Figure of description, and further specify the present invention with the following embodiments, should be understood that Figure of description and following embodiment only are used for explanation the present invention, and unrestricted the present invention.
The SBA-15 that the present invention adopts can adopt commercially available, perhaps with reference to existing document (for example, with reference to J.Am.Chem.Soc., 120 (24), 1998,6025) preparation.For example, referring to Fig. 1, be the synthetic SBA-15 of raw material hydro-thermal method with triblock copolymer surfactant P123 and TEOS (ethyl orthosilicate):
Take by weighing triblock copolymer surfactant P123, it is dissolved in hydrochloric acid and the deionized water, this mixed solution placed 35-45 ℃ stirred in water bath to the solution clarification, slowly add TEOS (ethyl orthosilicate), continue to stir 10-30 minutes, after left standstill 24 hours or stirred 24 hours, P123:TEOS:HCl (2M): H wherein
2O=2:4.25:60:15 (mass ratio).Hydrothermal treatment consists is 24-48 hours under 80-100 ℃ of conditions, cooling back is with deionized water filtration washing repeatedly, the gained powder is after 80-100 ℃ of dry processing, place in the Muffle furnace, slowly be warming up to 500-550 ℃ and calcine 4-6 hours to remove surfactant, obtain white mesoporous material SBA-15.
The above-mentioned SBA-15 that makes is activated 2-3 hours in boiling water, filter, drying, standby.
Then SBA-15 and the APTES (3-aminopropyl triethoxysilane) of activation are mixed with 1g:1mL-1g:5mL ratio and are dissolved in the solvent (for example dried toluene) time back flow reaction more than 12 hours, with dried solvent (for example toluene) repeatedly filtration washing get NH
2-SBA-15 powder.When adopting toluene as reaction dissolvent, reflux temperature is about 110 ℃.This reaction is preferably carried out under inert gas atmosphere (for example but atmosphere) protection, but should be understood that and be not limited to this.
At last by above-mentioned NH
2-SBA-15 powder mixes with cysteine 0.5:1-2.7:1 (mass ratio), DCC (dicyclohexylcarbodiimide) and DMAP (4-dimethylamino naphthyridine) press 1:1-32:1 (mol ratio) and add, make solvent with dry DMF (dimethyl formamide), refluxed 12-48 hours down at 85-120 ℃, suction filtration, with dry DMF, absolute ethyl alcohol, deionized water washing, drying can obtain the modified SBA-15 mesoporous material of cysteine of the present invention successively.This reaction is preferably carried out under inert gas atmosphere (for example blanket of nitrogen) protection, but should be understood that and be not limited to this.At this, this reaction adopts DMF as solvent, is not limited to this but should understand available solvent equally.
The product that finally obtains is that hydrogen on the hydroxyl on SBA-15 surface is by group
Functionalization.Should understand in this functionalization group, can contain or not contain unhydrolysed ethyoxyl, namely, x can be 0,1 or 2.When x=0, be appreciated that 1 this functionalization group is combined (for example referring to the example shown in Fig. 1) with 3 hydroxyls on SBA-15 surface; When x=1, be appreciated that 2 hydroxyls in 1 this functionalization group and SBA-15 surface are combined, and keep a unhydrolysed ethyoxyl; When x=1, be appreciated that 1 hydroxyl in 1 this functionalization group and SBA-15 surface is combined, and keep two unhydrolysed ethyoxyls.
Prepare
Can contain a plurality of functional groups that contain sulfydryl, namely in the formula, n is greater than 1.In view of there is great amount of hydroxy group on the SBA-15 surface, it will be appreciated by those skilled in the art that the rate of charge according to reaction, can make n and be the material greater than 1 arbitrary value.
Referring to Fig. 2 and 3, it illustrates vertical direction and the horizontal direction TEM(transmission electron microscope of an example of the modified SBA-15 mesoporous material of cysteine of invention) figure.As seen from the figure, the modified SBA-15 mesoporous material of cysteine of the present invention, the duct is six sides and arranges in order.
Material of the present invention is carried out Staticadsorption experiment results, investigate its adsorption capacity under different pH, adsorption time, adsorbent consumption, adsorbate initial concentration condition.
Referring to Fig. 5～8, it illustrates an example of the present invention and (presses cysteine: NH
2-SBA-15:DCC:DMAP mass ratio is that 1:2:1.7:2 prepares the gained material) under different pH, adsorption time, adsorbent consumption, adsorbate initial concentration condition, carry out Staticadsorption experiment results.
(1) the material of pH adsorbs Hg (II) influence: acidity condition has very significant effects to Staticadsorption experiment, measures metal ion solution absorption front and back change in concentration by regulating different pH values back, and the research acidity condition is to the influence of absorption property.Hg (II) solution of getting the about 10 μ g/ml of 20ml concentration respectively with pipette is in clean beaker, with the HNO of variable concentrations
3And NH
3H
2O regulates pH respectively between 0.5-9.5, the mesoporous material that takes by weighing the cysteine modification of about 20mg is then put into the solution that has mixed up, and stirring and adsorbing 1 hour leaves standstill, by 0.22 micron membrane filtration, filtrate is detected by inductive coupling plasma emission spectrograph (ICP-AES).Between 0.5-7.5, the material adsorption efficiency is higher as can be seen from Figure 5, and adsorption efficiency can reach more than 90%, pH〉7.5 o'clock, mercury forms precipitation influence absorption.In pH8.5-9.5 scope, adsorption rate begins to descend gradually, drops to 70% during pH9.5.
(2) adsorption time adsorbs Hg (II) influence to material: be (it is the same that other test treatment steps) under 2.5 the situation in pH value, investigate adsorption time to the influence of static state absorption, the result as shown in Figure 6, reach the maximum adsorption capacity time less than five minutes, along with the time increases, adsorbance also increases thereupon, but increase trend is not obvious, compare with existing bibliographical information, as seen this material has the characteristics of quick absorption.
(3) the adsorbent consumption adsorbs Hg (II) influence to material: be 2.5 at pH, Hg (II) concentration is that 10 μ g/ml adsorption times are under the condition of 1h, investigate the modified mesoporous material consumption to the influence of absorption, experimental result as shown in Figure 7, after material usage arrived 5mg, adsorbance reached maximum, adsorption capacity is 43.5mg/g to the maximum when solution concentration is 60mg/L, continuing increases the adsorbent consumption, and adsorbance reduces gradually, and visible material has efficient absorption characteristics.
(4) adsorbent solution concentration is adsorbed Hg (II) influence to material: be 2.5 at pH, it is under the condition of 1h for the 5mg adsorption time that Hg (II) concentration is respectively 5-80 μ g/ml adsorbent consumptions, investigate initial concentration of solution to the influence of absorption, experimental result as shown in Figure 8, increase with initial concentration solution, adsorbance also increases gradually, and as seen this material has higher adsorption capacity, can realize the efficient absorption of Hg (II).
(5) material is tested Hg (II) selective absorption: be that 1.5, Hg (II) concentration is 10 μ g/ml in the pH value, add Pb, Cu, the Cd ion of asking to join one concentration simultaneously, stirring and adsorbing 1h leaves standstill, and filters; Detect absorption rear filtrate and preceding each ion concentration of solution of absorption respectively with ICP-AES; To investigate this material to the selective absorption of Hg (II), the result is as shown in table 1:
Table 1
As can be seen from Table 1, this material has good absorption to Hg, to other metal ions do not adsorb or adsorbance seldom, as seen this material has the characteristics to the selective absorption of Hg (II).
The invention has the beneficial effects as follows that what the mesoporous material modification was adopted is cysteine, free from environmental pollution, and Hg (II) is had good selective absorption, adsorption capacity is compared other mesoporous material and is improved a lot, and can realize absorption fast.
Further for example following examples are to illustrate the present invention better in the present invention, and should understand following embodiment only is exemplary and unrestricted the present invention.
Embodiment 1:
Taking by weighing 4.0g triblock copolymer surfactant P123, to be dissolved in 120mL concentration be in 2mol/L hydrochloric acid and the 30mL deionized water, this mixed solution placed 38 ℃ stirred in water bath to the solution clarification, slowly add TEOS, continue to stir 10min, after left standstill 24 hours.Hydrothermal treatment consists is 24 hours under 100 ℃ of conditions, cooling back is with deionized water filtration washing repeatedly, and the gained powder places in the Muffle furnace after 100 ℃ of dry processing, slowly be warming up to 550 ℃ and calcine 5 hours to remove surfactant, obtain white mesoporous material SBA-15;
The SBA-15 that obtains is activated 3 hours in boiling water, filter drying; Get above-mentioned product 2.2g and 5mL APTES and be dissolved in the dried toluene of 250mL 110 ℃ of back flow reaction 20 hours under nitrogen atmosphere, with dried toluene, absolute ethyl alcohol repeatedly filtration washing get powder; Take by weighing above-mentioned dry powder 3.9g at last, cysteine 2.0g, DCC:3.4g, DMAP:2.0g, make solvent under nitrogen atmosphere with the dry DMF of 250mL (dimethyl formamide), 120 ℃ were refluxed suction filtration 48 hours, with dry DMF, absolute ethyl alcohol, deionized water washing, drying gets final product successively.The gained target product is carried out Hg (II) Staticadsorption experiment by above-mentioned Study on adsorption properties method.
Embodiment 2:
Taking by weighing 4.0g triblock copolymer surfactant P123, to be dissolved in 120mL concentration be in 2mol/L hydrochloric acid and the 30mL deionized water, this mixed solution placed 38 ℃ stirred in water bath to the solution clarification, slowly adds TEOS, continues to stir 24 hours.Hydrothermal treatment consists is 24 hours under 100 ℃ of conditions, cooling back is with deionized water filtration washing repeatedly, and the gained powder places in the Muffle furnace after 100 ℃ of dry processing, slowly be warming up to 550 ℃ and calcine 5 hours to remove surfactant, obtain white mesoporous material SBA-15;
The SBA-15 that obtains is activated 3 hours in boiling water, filter drying; Get above-mentioned product 1g and 5mL APTES and be dissolved in the dried toluene of 100mL 110 ℃ of back flow reaction 20 hours under nitrogen atmosphere, with dried toluene repeatedly filtration washing get powder; Take by weighing above-mentioned powder 2.0g at last, cysteine 1.0g, DCC:2.02g, DMAP:0.12g, make solvent under nitrogen atmosphere with the dry DMF of 200mL (dimethyl formamide), 85 ℃ were refluxed suction filtration 12 hours, with dry DMF, absolute ethyl alcohol, deionized water washing, drying gets final product successively.
Embodiment 3:
Taking by weighing 4.0g triblock copolymer surfactant P123, to be dissolved in 120mL concentration be in 2mol/L hydrochloric acid and the 30mL deionized water, this mixed solution placed 38 ℃ stirred in water bath to the solution clarification, slowly adds TEOS, stirred 24 hours.Hydrothermal treatment consists is 24 hours under 100 ℃ of conditions, cooling back is with deionized water filtration washing repeatedly, and the gained powder places in the Muffle furnace after 100 ℃ of dry processing, slowly be warming up to 550 ℃ and calcine 5 hours to remove surfactant, obtain white mesoporous material SBA-15;
The SBA-15 that obtains is activated 3 hours in boiling water, filter drying; Get above-mentioned product 1.5g and 8mL APTES and be dissolved in the dried toluene of 150mL 110 ℃ of back flow reaction 20 hours under nitrogen atmosphere, with dried toluene repeatedly filtration washing get powder; Take by weighing above-mentioned powder 1.6g at last, cysteine 0.8g, DCC:0.8g, DMAP:0.015g, make solvent under nitrogen atmosphere with the dry DMF of 160mL (dimethyl formamide), 120 ℃ were refluxed suction filtration 48 hours, with dry DMF, absolute ethyl alcohol, deionized water washing, drying gets final product successively.
Industrial applicability: the invention provides the good modified SBA-15 mesoporous material of cysteine of a kind of novel environmental compatibility, Hg (II) is had good selective absorption, adsorption capacity is compared other mesoporous material and is improved a lot, and can realize absorption fast.In addition, preparation is simple, cost is low, be fit to large-scale production for method of the present invention.
Claims (10)
1. the modified SBA-15 mesoporous material of cysteine is characterized in that the hydrogen on the hydroxyl on SBA-15 surface is by group
Functionalization, the formation chemical formula is
The modified SBA-15 mesoporous material of cysteine, wherein, x be 0,1 or 2, n greater than 1.
2. the modified SBA-15 mesoporous material of cysteine according to claim 1 is characterized in that, in pH was 0.5～7.5 scope, the modified SBA-15 mesoporous material of described cysteine was more than 90% to the adsorption rate of Hg (II).
3. the modified SBA-15 mesoporous material of cysteine according to claim 1 and 2, it is characterized in that, be that the modified SBA-15 mesoporous material of described cysteine is more than 90% to the adsorption rate of Hg (II), and does not adsorb Pd, Cu or Cd ion basically under 1.5 the situation at pH.
4. a method for preparing the modified SBA-15 mesoporous material of each described cysteine in the claim 1～3 is characterized in that, comprising:
Steps A: according to following formula SBA-15 and 3-aminopropyl triethoxysilane are dissolved in the toluene, reflux more than 12 hours, get NH
2-SBA-15,
Step B: according to following formula with the NH that makes
2-SBA-15 got the modified SBA-15 mesoporous material of described cysteine in 12～48 hours with cysteine reaction under 85～120 ℃ under the catalysis of catalyst dicyclohexylcarbodiimide and 4-dimethylamino naphthyridine,
5. method according to claim 4 is characterized in that, in steps A, the rate of charge of SBA-15 and 3-aminopropyl triethoxysilane is 1g:1mL～1g:5mL.
6. method according to claim 4 is characterized in that, in step B, and NH
2The mass ratio that feeds intake of-SBA-15 and cysteine is 0.5:1～2.7:1.
7. method according to claim 6 is characterized in that, in step B, used reaction dissolvent is N, dinethylformamide.
8. method according to claim 6 is characterized in that, in step B, the mol ratio of catalyst dicyclohexylcarbodiimide and 4-dimethylamino naphthyridine is 1:1～32:1.
9. method according to claim 6 is characterized in that, in steps A, used SBA-15 is the SBA-15 through the boiling water activation.
10. according to each described method in the claim 4～9, it is characterized in that described steps A and/or step B carry out under nitrogen atmosphere protection.
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| CN103599758A (en) * | 2013-10-29 | 2014-02-26 | 江苏大学 | Preparation method and application of amine aldehyde resin-mesoporous material compound |
| CN103752275B (en) * | 2013-12-27 | 2015-08-19 | 中国科学院上海硅酸盐研究所 | SBA-15 mesoporous material of modification and its preparation method and application |
| CN104226238B (en) * | 2014-09-15 | 2016-09-14 | 淮阴师范学院 | Ni2+the preparation of adsorbent and adsorption method thereof |
| CN105126766B (en) * | 2015-08-21 | 2017-12-08 | 中国科学院上海硅酸盐研究所 | A kind of preparation method of simple and quick absorption Hg (II) cysteine-modifying silicon-based mesoporous material |
| CN106745008A (en) * | 2016-12-01 | 2017-05-31 | 东莞市佳乾新材料科技有限公司 | A kind of ordered mesoporous materials of modified SBA 15 for adsorbing lithium and preparation method thereof |
| CN106925225B (en) * | 2017-03-17 | 2020-11-03 | 北京中能环科技术发展有限公司 | Histidine functionalized mesoporous molecular sieve adsorbent and application thereof in wastewater treatment |
| CN110385113A (en) * | 2018-04-17 | 2019-10-29 | 中国科学院大连化学物理研究所 | Penicillamine is the copper ion chelating adsorbent of ligand and its preparation and application |
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