CN101711975B - Method for preparing iron ion imprinted silica gel - Google Patents
Method for preparing iron ion imprinted silica gel Download PDFInfo
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- CN101711975B CN101711975B CN2009101127598A CN200910112759A CN101711975B CN 101711975 B CN101711975 B CN 101711975B CN 2009101127598 A CN2009101127598 A CN 2009101127598A CN 200910112759 A CN200910112759 A CN 200910112759A CN 101711975 B CN101711975 B CN 101711975B
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Abstract
The invention discloses a method for preparing an iron ion imprinted silica gel, which relates to an imprinted silica gel. The method for preparing the iron ion imprinted silica gel comprises the following steps of: soaking a silica gel in acid solution, washing the silica gel until the silica gel is neutral, and drying the silica gel to obtain an activated silica gel; putting a salt containing iron ions into a solvent, heating and stirring the salt and the solvent until the solid is dissolved to obtain a mixture; adding mercapto-propyl silane into the mixture, and heating, stirring and refluxing the mixture; adding the activated silica gel into the mixture, and heating, stirring and refluxing the mixture continuously to obtain a crude product of the iron ion imprinted silica gel; filtering the crude product, washing the crude product with a solvent until no impurity is detected, then soaking the crude product with an acid until no iron ion imprinted silica gel is detected, and finally washing the iron ion imprinted silica gel until the iron ion imprinted silica gel is neutral; and drying the iron ion imprinted silica gel to obtain a final product. In the method, the mercapto-propyl silane is used as a functional monomer, and a synthesis technique of molecular engram is utilized. The preparation process is simple and convenient, and is easy to operate, the obtained iron ion imprinted silica gel has high adsorption capacity and certain adsorption selection performance of the iron ions, and the synthesized iron ion imprinted silica gel can be filled to form a small solid phase extraction column which is used for the selective extraction of the iron ions in a water sample.
Description
Technical field
The present invention relates to a kind of imprinted silica gel, especially relating to a kind of is template with the iron ion, iron ion is had the preparation method of the iron ion imprinted silica gel of certain selection absorption property in the silica gel surface preparation.
Background technology
Iron is material common in the water, also is the trace element of needed by human, and general content is to the health did not influence.But for the underground water that contains higher irony, can produce special color, peculiar smell and muddiness, be difficult to drink ([1] Li Yuan, Qi Chen continent, Ou Guorong etc., PLA's preventive medicine magazine, 2003,21 (1): 30).Iron in the ocean is to the growth of phytoplankton in addition, the level of primary productivity has crucial influence even becomes " the restricted factor " ([2] Martin J.H., Fitzwater S.E., Gordon M., Global Biogeochem.Cycl., 1990,4:5), up-to-date achievement in research shows that the iron in the coastal seawater may play conclusive effect to the kind composition of phytoplankton, and then to comprising nitrogen, phosphorus, silicon produces far-reaching influence ([3] Hutchins D.A. in the Biogeochemistry behavior of other interior elements, Ditullio G.R., Zhang Y., et.al, LimnolOceaorg, 1998,43 (6): 103).Therefore the content of accurately measuring iron ion in the water sample is significant.But the content of iron is extremely low in the general water sample, concentration is 0.05～2.0nmol/L ([4] Wu J.F. as in the seawater, Boyle E.A., AnalyticaChimica Acta, 1998,367:18.), this has exceeded the detection range of general instrument, and the mensuration of iron ion is seriously disturbed in complicated substrate meeting in the while sample, therefore before carrying out Instrument measuring, must adopt suitable means that water sample is carried out preliminary treatment, to reach the purpose of removing interference and enrichment.
At present, measuring the pre-treating method that iron ion is commonly used in the water is that ([5] Zheng build ion-exchange, Wei Junfu, Zhao Kongyin etc., Tianjin University of Technology's journal, 2009,28 (2): 5; [6] Lv Ming, Tang Lu, metallurgical analysis, 2008,28 (3): 75; [7] occupy red virtue, physical and chemical inspection-chemical fascicle, 2004,40 (11): 660), this method utilizes cationic ion-exchange resin by separation and the enrichment of ion exchange realization to iron ion, but it has enrichment to other ion equally, can't realize the selective enrichment to iron ion.Therefore, must develop new enrichment material, realize selective enrichment iron ion.
Summary of the invention
The present invention aims to provide a kind of preparation method of iron ion imprinted silica gel.
Technical scheme of the present invention is to be template with the iron ion, and mercapto propyl trimethoxy or mercaptopropyltriethoxysilane are function monomer, is solvent with methyl alcohol or ethanol, and the technology of preparing of utilizing molecular engram is at the synthetic ion imprinted polymer layer in silica gel surface.Preparation-obtained iron ion imprinted silica gel can carry out selective enrichment to ferric ion (Fe (III)).
Process route of the present invention is:
Wherein, Acid is acid.
The present invention includes following steps:
1) activation of silica gel: silica gel is soaked with acid solution, is washed with water to neutrality again, dry activated silica gel, stand-by;
2) preparation iron ion imprinted silica gel: the salt that will contain iron ion places solvent, and heating is stirred to the solid dissolving, gets mixture, add the mercapto propyl silane in mixture, the heating stirring and refluxing adds activated silica gel then, continue the heating stirring and refluxing, get the iron ion imprinted silica gel head product;
3) post processing of iron ion imprinted silica gel: gained iron ion imprinted silica gel head product is filtered, detect with solvent wash to free from admixture, do not detect to there being iron ion imprinted silica gel with acid soak then, wash iron ion imprinted silica gel at last with water to neutral, oven dry gets the end product iron ion imprinted silica gel.
In step 1), the particle diameter of described silica gel is preferably 30～300 orders, described acid can be hydrochloric acid, sulfuric acid or nitric acid etc., the molar concentration of described acid solution is preferably 1～10mol/L, the consumption of silica gel and acid is preferably every gram silica gel and adds 5～20ml acid, the time of described immersion is preferably 0.5～10h, the most handy ultra-pure water of described water, and the temperature of described oven dry is preferably 40～120 ℃.
In step 2) in, the described salt that contains iron ion can be iron chloride, ferric sulfate or ferric acetate etc., described solvent can adopt methyl alcohol or ethanolic solution, the consumption of described salt that contains iron ion and solvent is preferably the salt that every gram contains iron ion and adds 20～50ml solvent, the amount of described adding mercapto propyl silane is preferably 1 with the mol ratio that contains the salt of iron ion: (1～5), the temperature of described heating stirring and refluxing is preferably 60～80 ℃, the time of heating stirring and refluxing is preferably 0.5～5.0h, the consumption of described adding activated silica gel is preferably 1～2 times of mercapto propyl silane, and the time of described continuation heating stirring and refluxing is preferably 6～48h.
In step 3), described solvent is preferably methyl alcohol or ethanol etc., the molar concentration of described acid is preferably 0.5～5.0mol/L, described acid is preferably hydrochloric acid, nitric acid or acetic acid etc., the most handy ultra-pure water of described water, the temperature of described oven dry is preferably 60～80 ℃, and the time of oven dry is preferably 1.0～12.0h.
The present invention is a function monomer with the mercapto propyl silane first, and utilizes the synthetic technology of molecular engram to prepare the ion blotting silica gel of iron ion for template.Preparation process is easy, easy to operate, prepared iron ion imprinted silica gel has higher adsorption capacity and certain adsorptive selectivity energy to iron ion, the iron ion imprinted silica gel that is synthesized can be loaded into solid phase extraction column, be applied to the selective extraction of iron ion in the water sample.
Description of drawings
Fig. 1 is the infrared spectrogram of the embodiment of the invention 2 iron ion imprinted silica gels.In Fig. 1, abscissa is wave number Wavenumber (cm
-1), ordinate is light transmittance %Transmittance; 3466.44 belong to hydroxyl with the absworption peak at 1092.05 places, 2925.39,2847.5 and 795.23 absworption peak belongs to methyl and methylene, 2353.20 absworption peak belongs to carbon dioxide, and 1640.89 absworption peak belongs to sulfydryl.
Fig. 2 is the influences of the embodiment of the invention 4 different duration of oscillations to iron ion imprinted silica gel absorption iron ion.In Fig. 2, abscissa is duration of oscillation (min), and ordinate is adsorbance (mg/g); ◆ be iron ion imprinted silica gel, ■ is non-imprinted silica gel.
Fig. 3 is the influences of the embodiment of the invention 5 different iron ion initial concentrations to the iron ion imprinted silica gel absorption property.In Fig. 3, abscissa is iron concentration (mg/L), and ordinate is adsorbance (mg/g); ■ is an iron ion imprinted silica gel, ◆ be non-imprinted silica gel.
The specific embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1:1) activation of silica gel: getting particle diameter is 30 order silica gel 1.0g, is the sulfuric acid solution immersion 0.5h of 1.0mol/L with 5.0mL concentration, and extremely neutral with the ultra-pure water washing then, 40 ℃ of oven dry are stand-by.2) preparation of iron ion imprinted silica gel: take by weighing 0.38g ferric sulfate and place the 7.6mL ethanolic solution, heating is stirred to the solid dissolving.In above-mentioned mixture, add the mercaptopropyltriethoxysilane of 0.26g, and under 60 ℃ of conditions, heat stirring and refluxing 0.5h, add the 0.26g activated silica gel then, continue heating stirring and refluxing 6h.3) post processing of iron ion imprinted silica gel: above-mentioned iron ion imprinted silica gel is filtered, wash to free from admixture with ethanol and detect, do not detect to there being iron ion with the 0.5mol/L nitric acid dousing then.Extremely neutral with ultra-pure water washing iron ion imprinted silica gel at last, dry 1.0h down at 60 ℃ and get end product.
Embodiment 2: the activation of silica gel: getting particle diameter is 200 order silica gel 50g, is the hydrochloric acid solution immersion 5.0h of 5.0mol/L with 500mL concentration, and extremely neutral with the ultra-pure water washing then, 80 ℃ of oven dry are stand-by.The preparation of iron ion imprinted silica gel: take by weighing 3.41gFeCl
36H
2O places the 120mL methanol solution, and heating is stirred to the solid dissolving.In above-mentioned mixture, add the mercaptopropyl trimethoxysilane of 6.81g, and under 70 ℃ of conditions, heat stirring and refluxing 2.0h, add the 9g activated silica gel then, continue heating stirring and refluxing 24h.The post processing of iron ion imprinted silica gel: above-mentioned imprinted silica gel is filtered, detect, be dipped to no iron ion with 5.0mol/L hydrochloric acid then and detect with methanol wash to free from admixture.Extremely neutral with ultra-pure water washing IIP at last, dry 6.0h down at 70 ℃ and get end product.Fig. 1 is the infrared spectrogram of embodiment 2 gained iron ion imprinted silica gels.
Embodiment 3: the activation of silica gel: getting particle diameter is 300 order silica gel 100g, is the salpeter solution immersion 10h of 10.0mol/L with 2000mL concentration, and extremely neutral with the ultra-pure water washing then, 120 ℃ of oven dry are stand-by.The preparation of iron ion imprinted silica gel: take by weighing the 8.0g ferric acetate and place the 400mL methanol solution, heating is stirred to the solid dissolving.In above-mentioned mixture, add the mercaptopropyl trimethoxysilane of 29.1g, and under 80 ℃ of conditions, heat stirring and refluxing 5.0h, add the 58.2g activated silica gel then, continue heating stirring and refluxing 48h.The post processing of iron ion imprinted silica gel: with above-mentioned iron ion imprinted silica gel filtered through silica gel, wash to free from admixture with ethanol and to detect, be dipped to no iron ion with the 2.0mol/L acetum then and detect.Extremely neutral with ultra-pure water washing iron ion imprinted silica gel at last, dry 12.0h down at 80 ℃ and get end product.
Embodiment 4: take by weighing a series ofly by each 100mg of iron ion imprinted silica gel that embodiment 2 synthesizes, add 20mL 2.0mg/LFeCl
3Solution, vibrate with 200r/min at 25 ℃, investigate of the influence of different duration of oscillations to iron ion imprinted silica gel absorption iron ion, the mensuration of iron ion adopts luxuriant and rich with fragrance alloxazine spectrophotometric determination method ([1] Li Yuan in the solution, the Qi Chen continent, Ou Guorong etc., PLA's preventive medicine magazine, 2003,21 (1): 30; [8] Gong Xia, Liu Shujuan, Luo Mingbiao etc., modern surveying and laboratory room managing, 2007,1:18).Prepare non-imprinted silica gel simultaneously, its preparation process and each amount of substance such as embodiment 2, but do not add iron ion.The same with above-mentioned iron ion imprinted silica gel process, investigate of the influence of different duration of oscillations to non-imprinted silica gel absorption iron ion, its result is as shown in Figure 2.
Embodiment 5: take by weighing a series ofly by each 100mg of iron ion imprinted silica gel that embodiment 2 synthesizes, add 20mL variable concentrations FeCl
3Solution, 25 ℃ with 200r/min vibration 60min, investigate variable concentrations FeCl
3To the influence of iron ion imprinted silica gel absorption iron ion, the mensuration of iron ion adopts luxuriant and rich with fragrance alloxazine spectrophotometric determination method (([1] Li Yuan, Qi Chen continent, Ou Guorong etc., PLA's preventive medicine magazine, 2003,21 (1): 30 in the solution; [8] Gong Xia, Liu Shujuan, Luo Mingbiao etc., modern surveying and laboratory room managing, 2007,1:18).Investigate variable concentrations FeCl simultaneously
3To the influence of non-imprinted silica gel absorption iron ion, its result as shown in Figure 3.
Embodiment 6: take by weighing by embodiment 2 synthesizes iron ion imprinted silica gel and each 100mg of non-imprinted silica gel, add respectively and contain (55.93ng/mL) 20mL of iron ion (87.08ng/mL) and non-imprinted silica gel (Mn (II)), at 25 ℃ with 200r/min vibration 60min, investigate iron ion imprinted silica gel and non-imprinted silica gel selection absorption property to iron ion, iron ion in the solution and non-imprinted silica gel (Mn (II)) are measured with inductivity coupled plasma mass spectrometry (ICP-MS), and its end product iron ion imprinted silica gel is as shown in table 1 to the selection absorption property of iron ion and non-imprinted silica gel (Mn (II)) hybrid metal ion.
Table 1
Embodiment 7: take by weighing a series of by each 100mg of iron ion imprinted silica gel that embodiment 2 synthesizes, pack into and make the SPE pillar in SPE (SPE) blank pipe, investigate synthetic iron ion imprinted silica gel to the rate of recovery of mark-on iron ion in the actual water sample, water sample comprises running water and seawater, iron ion imprinted silica gel is as shown in table 2 to the different recovery of standard addition of actual water sample as a result for it, does not wherein add timestamp, used volume of water sample 1.0L, when adding scalar and being 1.0ng/mL, used volume of water sample 1.0L; When adding scalar and being 5.0ng/mL, used volume of water sample 0.1L.Going up sample flow velocity 5.0mL/min in the experiment, is that the hydrochloric acid of 2.0mol/L carries out wash-out with 2.0mL concentration, and flow velocity is 3.0mL/min.The mensuration of iron ion adopts luxuriant and rich with fragrance alloxazine spectrophotometric determination method ([1] Li Yuan, Qi Chen continent, Ou Guorong etc., PLA's preventive medicine magazine, 2003,21 (1): 30 in the eluent; [8] Gong Xia, Liu Shujuan, Luo Mingbiao etc., modern surveying and laboratory room managing, 2007,1:18).
Table 2
Claims (10)
1. the preparation method of iron ion imprinted silica gel is characterized in that may further comprise the steps:
1) activation of silica gel: silica gel is soaked with acid solution, is washed with water to neutrality again, dry activated silica gel, stand-by;
2) preparation iron ion imprinted silica gel: the salt that will contain iron ion places solvent, heating is stirred to the solid dissolving, get mixture, in mixture, add the mercapto propyl silane, the heating stirring and refluxing adds activated silica gel then, continues the heating stirring and refluxing, get the iron ion imprinted silica gel head product, described mercapto propyl silane is mercaptopropyl trimethoxysilane or mercaptopropyltriethoxysilane;
3) post processing of iron ion imprinted silica gel: gained iron ion imprinted silica gel head product is filtered, detect with solvent wash to free from admixture, do not detect to there being iron ion imprinted silica gel with acid soak then, wash iron ion imprinted silica gel at last with water to neutral, oven dry gets the end product iron ion imprinted silica gel.
2. the preparation method of iron ion imprinted silica gel as claimed in claim 1 is characterized in that in step 1), and the particle diameter of described silica gel is 30～300 orders.
3. the preparation method of iron ion imprinted silica gel as claimed in claim 1 is characterized in that in step 1), and described acid is hydrochloric acid, sulfuric acid or nitric acid, and the molar concentration of described acid solution is 1～10mol/L.
4. the preparation method of iron ion imprinted silica gel as claimed in claim 1 is characterized in that in step 1), and described silica gel is that every gram silica gel adds 5～20ml acid with the consumption of acid.
5. the preparation method of iron ion imprinted silica gel as claimed in claim 1 is characterized in that in step 1), and the time of described immersion is 0.5～10h, described water ultra-pure water, and the temperature of described oven dry is 40～120 ℃.
6. the preparation method of iron ion imprinted silica gel as claimed in claim 1 is characterized in that in step 2) in, the described salt that contains iron ion is iron chloride, ferric sulfate or ferric acetate; Described solvent is methyl alcohol or ethanolic solution.
7. the preparation method of iron ion imprinted silica gel as claimed in claim 1, it is characterized in that in step 2) in, the consumption of described salt that contains iron ion and solvent is that the salt that every gram contains iron ion adds 20～50ml solvent, and the amount of described adding mercapto propyl silane is 1: 1～5 with the mol ratio that contains the salt of iron ion.
8. the preparation method of iron ion imprinted silica gel as claimed in claim 1 is characterized in that in step 2) in, the temperature of described heating stirring and refluxing is 60～80 ℃, the time of heating stirring and refluxing is 0.5～5.0h.
9. the preparation method of iron ion imprinted silica gel as claimed in claim 1 is characterized in that in step 2) in, the consumption of described adding activated silica gel is 1～2 times of mercapto propyl silane; The time of described continuation heating stirring and refluxing is 6～48h.
10. the preparation method of iron ion imprinted silica gel as claimed in claim 1, it is characterized in that in step 3), described solvent is methyl alcohol or ethanol, the molar concentration of described acid is 0.5～5.0mol/L, described acid is hydrochloric acid, nitric acid or acetic acid, described water is ultra-pure water, and the temperature of described oven dry is 60～80 ℃, and the time of oven dry is 1.0～12.0h.
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| CN102389775A (en) * | 2011-07-27 | 2012-03-28 | 河南师范大学 | azo violet functionalized silicon gel and preparation method thereof, and method for purifying water by using azo violet functionalized silicon gel |
| CN103055831A (en) * | 2011-10-20 | 2013-04-24 | 中国科学院兰州化学物理研究所 | Preparation method of inorganic core-shell type quercetin molecularly imprinted polymer microsphere |
| CN106979930B (en) * | 2017-05-23 | 2018-04-24 | 中国科学院地质与地球物理研究所 | A kind of method of free iron content in quantitative analysis Soil/Sediment Samples |
| CN107649101B (en) * | 2017-09-29 | 2019-09-10 | 湖南大学 | Mercapto-functionalized titania molecule trace composite material and its aqueous phase preparation method and application |
| CN110407976B (en) * | 2018-04-27 | 2020-08-21 | 中国科学院过程工程研究所 | Iron ion imprinted polymer and preparation method and application thereof |
| CN115814761A (en) * | 2022-12-20 | 2023-03-21 | 江苏海普功能材料有限公司 | Iron-containing feed liquid aluminum ion removal imprinted adsorption material and preparation method thereof |
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| 徐伟箭等.基于硅胶表面修饰的分子印迹技术研究进展.《应用化学》.2003,第20卷(第10期),919-923. * |
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