CN107213877B - Synthetic method of imprinted mesoporous material with high selectivity to bisphenol A - Google Patents
Synthetic method of imprinted mesoporous material with high selectivity to bisphenol A Download PDFInfo
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Abstract
The invention provides a synthesis method of imprinted mesoporous material with high selectivity to bisphenol A, which comprises the following steps: (1) uniformly mixing template molecule bisphenol A and a functional monomer to obtain a pre-acting solution; (2) dissolving hexadecyl trimethoxy ammonium bromide in water, adjusting the pH value to 10.5-11.5 by using a sodium hydroxide solution, and stirring for 50-70 minutes; adding tetraethoxysilane into the solution, and stirring for 20-40 minutes; adding the pre-acting solution into the solution, and stirring for 140 minutes; carrying out hydrothermal crystallization on the mixture to obtain a mixture; (3) and drying the mixture, and removing template molecule bisphenol A. The invention is easy to implement; the obtained imprinted mesoporous material has high selectivity to bisphenol A, large adsorption capacity, and good recycling performance and reproducibility.
Description
Technical Field
The invention belongs to the technical field of molecular imprinting, and mainly relates to a method for synthesizing a molecularly imprinted mesoporous material.
Background
Bisphenol A (BPA) is one of industrial raw materials widely used in the world, and is mainly used for producing various high polymer materials and fine chemical products. Currently, bisphenol a has been detected in water, sediments, soil, atmospheric environment and in organisms. Bisphenol A belongs to a low-toxicity chemical and is also an environmental estrogen; trace or even trace amounts of bisphenol a can adversely affect the physiological condition, reproductive system and fetal development of animals and can produce a wide range of adverse effects on the endocrine, reproductive and nervous systems of the organism. The domestic and foreign governments have taken continuous measures against the safety of bisphenol A in the consumption field, including limiting the reduction of the amount of bisphenol A used and prohibiting it from being used in the production of partial products such as infant milk products. Therefore, the development of a novel adsorbent having high selectivity for bisphenol a has been a hot point of research.
In 1994, selergren first reported the use of molecularly imprinted polymers as adsorbents in national phase extraction, after which the molecularly imprinted-solid phase extraction technique developed rapidly. The molecularly imprinted polymer has a memory effect on target molecules, and can identify the target molecules in complex samples with high selectivity. The research results show that the molecularly imprinted polymer serving as the national phase extraction adsorbent has the advantages of high selectivity, strong binding force, reusability and low cost.
In the prior art, a magnetic molecularly imprinted polymer is prepared by taking a magnetic material as a carrier. However, the partially imprinted sites of the magnetic molecularly imprinted polymer are embedded in the bulk of the polymer, resulting in incomplete elution of the template molecules. In addition, the molecular engram polymer in the prior art has obviously lower selective adsorption and adsorption capacity to bisphenol A in aqueous phase.
Therefore, it is necessary to develop a method for preparing a molecularly imprinted material with high selectivity to bisphenol A and large adsorption capacity.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a synthesis method of a mesoporous material with high selectivity imprinting on bisphenol A; the prepared imprinted mesoporous material has high selectivity to bisphenol A and large adsorption capacity.
In order to solve the problems, the invention is realized according to the following technical scheme:
a synthetic method of imprinted mesoporous material with high selectivity to bisphenol A comprises the following steps:
(1) mixing template molecule bisphenol A and functional monomer, stirring for 100-140 min to obtain pre-acting solution;
(2) dissolving Cetyl Trimethoxy Ammonium Bromide (CTAB) in water, adjusting pH to 10.5-11.5 with sodium hydroxide solution, and stirring for 50-70 min; adding Tetraethoxysilane (TEOS) into the solution, and stirring for 20-40 minutes; adding the pre-acting solution into the solution, and stirring for 140 minutes; carrying out hydrothermal crystallization on the mixture to obtain a mixture;
(3) and drying the mixture, and removing template molecule bisphenol A.
Preferably, the steps (1) to (3) are carried out at a temperature of 35 to 45 ℃.
It is particularly preferred that the steps (1) to (3) are carried out at a temperature of 40 ℃. The present inventors found that the reaction efficiency of each step can be improved when the reaction temperature is 40 ℃.
Preferably, the preparation method of the functional monomer comprises the following steps: dissolving 2-mercapto-4-methyl-5-thiazole acetic acid (MMTA) and KH-570 in ethanol, adjusting pH to 7.5-8.5 with triethylamine solution, and stirring at 35-45 deg.C for 50-70 min to obtain functional monomer.
Particularly preferably, the preparation method of the functional monomer comprises the following steps: dissolving 2-mercapto-4-methyl-5-thiazole acetic acid (MMTA) and KH-570 in ethanol, adjusting pH to 8 with triethylamine solution, and stirring at 40 deg.C for 60 min to obtain functional monomer.
Preferably, the molar ratio of the 2-mercapto-4-methyl-5-thiazoleacetic acid (MMTA) to the KH-570 is 1-2: 1-2.
Particularly preferably, the molar ratio of the 2-mercapto-4-methyl-5-thiazoleacetic acid (MMTA) to KH-570 is 1: 1.
Preferably, the mol volume ratio L of the 2-mercapto-4-methyl-5-thiazole acetic acid (MMTA) to the ethanol is 1: 4.5-5.5.
Particularly preferably, the mol volume ratio L of the 2-mercapto-4-methyl-5-thiazole acetic acid (MMTA) to the ethanol is 1: 5.
Preferably, the step (1) comprises mixing template molecule bisphenol A and functional monomer, and stirring vigorously for 2 hours to obtain a pre-action solution. The violent stirring is carried out at the rotation speed of 150-; can further form hydrogen bond and pi-pi interaction between template molecule bisphenol A and functional monomer.
Preferably, the step (2) comprises dissolving Cetyl Trimethoxy Ammonium Bromide (CTAB) in water at 40 deg.C, adjusting pH to 11 with sodium hydroxide solution, and stirring for 60 min; adding tetraethoxysilane into the solution drop by drop, and stirring for 30 minutes; dropwise adding the pre-acting solution into the solution, and stirring for 120 minutes; carrying out hydrothermal crystallization on the product to obtain the product.
Preferably, the mole ratio of the template molecule bisphenol A to the functional monomer is 1: 4.5-5.5.
Particularly preferably, the mole ratio of the template molecule bisphenol A to the functional monomer is 1: 5.
Preferably, the mole ratio of the template molecules bisphenol A, hexadecyl trimethoxy ammonium bromide (CTAB) and Tetraethoxysilane (TEOS) is 1: 2.5-3.0: 21.6-26.4.
Particularly preferably, the template molecules bisphenol A, cetyltrimethoxy ammonium bromide (CTAB) and tetraethyl orthosilicate (TEOS) are present in a molar ratio of 1: 2.74: 24.
Preferably, the mass volume ratio g to ml of the hexadecyl trimethoxy ammonium bromide (CTAB) and the water is 1: 35-45.
Particularly preferably, the mass volume ratio g: ml of the hexadecyl trimethoxy ammonium bromide (CTAB) and the water is 1: 40.
Preferably, the water in step (2) is deionized water.
Preferably, the molar concentration of the sodium hydroxide solution is 8-12 mol/L.
Particularly preferably, the molar concentration of the sodium hydroxide solution is 10 mol/L.
Preferably, the hydrothermal crystallization is performed at a temperature of 80-90 ℃ for 70-74 hours.
Particularly preferably, the hydrothermal crystallization is performed at a temperature of 85 ℃ for 72 hours.
Preferably, the step of removing template molecule bisphenol A is a Soxhlet extraction with a mixed solution of hydrochloric acid and ethanol.
Preferably, the soxhlet extraction time is 88 to 104 hours.
Particularly preferably, the soxhlet extraction time is 96 hours.
Preferably, the volume ratio of the hydrochloric acid to the ethanol is 1: 8.1-9.9.
Particularly preferably, the volume ratio of the hydrochloric acid to the ethanol is 1: 9.
The invention has the following beneficial effects:
1. the imprinted mesoporous material prepared by the invention has the appearance of a highly ordered and tightly arranged hexagonal pore structure, and the particles are distributed more uniformly; the average pore diameter of the imprinted mesoporous material is 3.6nm, and the pore volume is 1.58cm3g-1。
2. At a pH value of 6.5, the imprinted mesoporous material has the maximum adsorption amount on bisphenol A. When the concentration of the bisphenol A solution is 700mg/L, the imprinted mesoporous material can reach saturated adsorption balance, and the adsorption capacity is 88.6 mg/g; therefore, the imprinted mesoporous material prepared by the invention has large adsorption capacity.
3. The imprinted mesoporous material prepared by the invention has selective imprinted sites for bisphenol A, and has good selective recognition capability for bisphenol A.
4. After the imprinted mesoporous Materials (MIPs) prepared by the method are repeatedly used for 5 times, the recovery rate can be kept above 98.0%, and the imprinted mesoporous Materials (MIPs) have better recycling performance.
5. The imprinted mesoporous Materials (MIPs) prepared by the method have good reproducibility. At different times, when 5 batches of imprinted mesoporous Materials (MIPs) synthesized by the technical scheme of the invention are used for adsorption tests, the Relative Standard Deviation (RSD) of the adsorption amount of the 5 batches of imprinted mesoporous Materials (MIPs) to the bisphenol a is only 1.1%.
Drawings
FIG. 1 is a synthetic route diagram of the present invention;
FIG. 2 is an infrared spectrum before and after Soxhlet extraction of the imprinted mesoporous Material (MIPs) prepared in example 1 of the present invention;
FIG. 3 is a small angle XRD diffractogram of imprinted mesoporous Materials (MIPs) prepared in example 1 of the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) image of imprinted mesoporous Materials (MIPs) prepared in example 1 of the present invention;
FIG. 5 is a perspective electron microscope (TEM) image of imprinted mesoporous Materials (MIPs) prepared in example 1 of the present invention;
FIG. 6 is a nitrogen adsorption and desorption graph of imprinted mesoporous Materials (MIPs) prepared in example 1 of the present invention;
FIG. 7 is a distribution diagram of the pore size of imprinted mesoporous Materials (MIPs) prepared in example 1 of the present invention;
FIG. 8 is a graph showing the effect of pH on the adsorption amount of imprinted mesoporous Materials (MIPs) prepared in example 1 of the present invention;
FIG. 9 is an adsorption graph of imprinted mesoporous Materials (MIPs) prepared in example 1 of the present invention;
FIG. 10 is a graph showing the adsorption kinetics of imprinted mesoporous Materials (MIPs) prepared in example 1 of the present invention;
fig. 11 is a data diagram of a repetitive experiment of imprinted mesoporous Materials (MIPs) prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples:
example 1:
1) preparation of functional monomer:
in a 10ml flask, 1.0mmol of 2-mercapto-4-methyl-5-thiazoleacetic acid (MMTA) and 1.0mmol of KH-570 were dissolved in 5ml of ethanol, and the pH of the solution was adjusted to 8 with triethylamine. Stirring for 2 hours at the temperature of 40 ℃; obtaining light yellow liquid as functional monomer, and sealing and storing the light yellow liquid.
2) Preparation of imprinted mesoporous material with high selectivity to bisphenol a:
(1) 0.25mol of template molecule bisphenol A and 1.0mmol of functional monomer are mixed and stirred vigorously for 2 hours under the condition that the temperature of water bath is 40 ℃, and thus, a pre-acting solution is obtained.
(2) Under the condition that the water bath temperature is 40 ℃, 1.0g of hexadecyl trimethoxy ammonium bromide (CTAB) is dissolved in 40mL of deionized water, the pH value is adjusted to 11.0 by 10mol/L of sodium hydroxide solution, and the mixture is stirred for 1 hour. 5.2g of tetraethyl orthosilicate (TEOS) was added dropwise to the solution, and stirred for 30 minutes; dropwise adding the pre-acting solution into the solution, and stirring for 2 hours; transferring the mixture into a hydrothermal reaction kettle, and carrying out hydrothermal crystallization for 72 hours at the temperature of 85 ℃ to obtain a mixture.
(3) After the mixture is filtered and dried, a mixed solution of hydrochloric acid and ethanol with the volume ratio of 1: 9 is used for Soxhlet extraction for 96 hours at the water bath temperature of 40 ℃, template molecule bisphenol A is removed, hexadecyl trimethoxy ammonium bromide (CTAB) is also removed, and the obtained product is dried to obtain the imprinted mesoporous Material (MIPs).
Attached:
1) synthetic roadmaps, see fig. 1;
2) experimental reagents and instruments, see tables 1 and 2.
TABLE 1 test reagents
TABLE 2 Experimental instruments
| Laboratory apparatus | Model number | Manufacturer of the product |
| Electric mechanical stirrer | JJ-1A | Experimental instrument factory for Jiangsu Jincheng Guosheng |
| Water bath pot | HH-S11 | SHANGHAI YUE FUNG INSTRUMENT Co.,Ltd. |
| Soxhlet extractor | HH-S11 | SHANGHAI YUE FUNG INSTRUMENT Co.,Ltd. |
| Analytical balance | OOS | SARTORIUS STEDIM BIOTECH GmbH |
| Electric heating blowing dry box | DGG-9070DA2 | Shanghai Sensin laboratory instruments Ltd |
| Infrared spectrometer | DRX-400 | Varian corporation, USA |
| Nitrogen adsorption instrument | ASAP-2020 | Micromeritics, USA |
| X-ray diffractometer | D8Advance | Bruker, Germany |
| Transmission electron microscope analyzer | JEM-2100HR | JEOL Ltd |
| Field emission scanning electron microscope | ZEISS Ultra55 | German Carl Zeiss Co |
| Constant temperature oscillator | THZ82 | Jiangsu Taicang laboratory plant |
| High-speed centrifugal machine | TG16-W | Guangzhou Guangyi scientific instruments Co Ltd |
| Ultrasonic instrument | SK250H | Shanghai accessible ultrasonic instruments Ltd |
| Micro high-speed centrifugal machine | TG16-W | Changshan instrument centrifuge instruments Ltd |
Structural characterization of the imprinted material prepared in example 1:
A. and (3) infrared spectrum characterization:
1040cm, as can be seen in FIG. 2-1、960cm-1、791cm-1The three absorption peaks are characteristic peaks of the mesoporous material (silicon-based material). Imprinted mesoporous Materials (MIPs) before Soxhlet extraction are 2800-3000cm-1The region presents sharp absorption peaks representing symmetric and asymmetric oscillations of C-H due to the presence of the porogen cetyltrimethoxy ammonium bromide (CTAB). After soxhlet extraction with ethanol and hydrochloric acid (9: 1 ═ V/V), the C-H characteristic absorption peak disappeared, indicating that CTAB had eluted cleanly. Imprinting mesoporous Materials (MIPs) before and after elution are 1640cm-1The absorption peak is the stretching vibration absorption peak of C ═ O, which shows that the functional monomer has successfully participated in the mesoporous materialAnd (3) synthesizing the skeleton.
B. Small angle XRD characterization:
as can be seen from FIG. 3, three distinct characteristic peaks are (100), (110) and (200) crystal planes respectively, and the characterization result of small-angle XRD shows that the imprinted mesoporous Material (MIPs) has a characteristic structure of highly ordered MCM-41 mesopores.
C. Characterization by an electron microscope:
as can be seen from fig. 4, the synthesized imprinted mesoporous Material (MIPs) has a more uniform particle distribution.
As can be seen from fig. 5, the imprinted mesoporous Materials (MIPs) have a highly ordered and closely arranged morphology of hexagonal pore structures.
D. And (3) nitrogen adsorption and desorption characterization:
the pore diameter and the pore volume of the imprinted mesoporous Materials (MIPs) are measured by a nitrogen adsorption and desorption experiment.
As shown in fig. 6, the nitrogen adsorption-desorption isotherm of the imprinted mesoporous Material (MIPs) is an IV-type curve, which is a typical nitrogen adsorption-desorption isotherm of the mesoporous material. The specific surface area of the material is calculated to be 960.5m by adopting a Bnmauer-Enunett-Teller (BET) method2g-1Pore volume of 1.58cm3g-1The numerical value shows that the imprinted mesoporous Material (MIPs) has larger specific surface area and pore volume, and is beneficial to the mass distribution and reabsorption process of imprinted sites.
As can be seen from FIG. 7, the imprinted mesoporous Materials (MIPs) have uniform pore size distribution, concentrated and sharp peak-shaped distribution, mainly concentrated between 3.4 nm and 3.9nm, which proves that the materials have high order. The average pore diameter of the material is 3.6nm obtained by a Barrett-Joyner-Halenda (BJH) method.
Experiment for examining adsorption property of blotting material prepared in example 1:
in order to examine the adsorption performance of the imprinted material, two physical quantities, namely adsorption quantity and adsorption rate, can be used for characterization. The adsorption capacity reflects the adsorption capacity of the adsorbent for a certain concentration of the substrate, and is a very important thermodynamic parameter.
The adsorption amount is calculated by the following equation (1-1):
Q＝(CO-Ct)V/M (1-1)
wherein Q represents the adsorption amount (mg/g) at time t;
CO-initial concentration of the substance to be adsorbed (mg/L);
Ct-concentration of the substance to be adsorbed at time t (mg/L);
m-mass of adsorbent (mg);
v-volume of reaction solution (mL).
Influence of ph value on adsorption performance a of imprinted mesoporous Materials (MIPs):
the adsorption effect of the imprinted mesoporous Materials (MIPs) on target molecule bisphenol A under different pH values (pH is 5-8) is explored. Adding 10mg of imprinted mesoporous Materials (MIPs) into bisphenol A solutions with different pH conditions (pH 5-8), the volume of which is 3mL and the concentration of which is 200mg/L, shaking at room temperature for 4h, centrifuging, and detecting the concentration of bisphenol A in the filtrate by using high performance liquid chromatography. Substituting the obtained product into a formula 1-1 to calculate the adsorption capacity of the imprinted mesoporous Materials (MIPs), thereby obtaining the influence of pH on the adsorption capacity.
As shown in fig. 8, when the pH of the curve of the adsorption amount of the imprinted mesoporous Materials (MIPs) along with the change of pH is 5.5-6.5, the adsorption amount of the imprinted mesoporous Materials (MIPs) increases with the increase of pH, which is probably because the pi electron cloud density of negative electrons on the aromatic ring is reduced due to the too strong acidity, so that the pi-pi interaction between rings is weakened, and the adsorption amount is reduced. At pH 6.5 to 8, as the basicity of the solution increases, the hydroxyl groups in bisphenol a and the carboxyl groups of the functional monomer are deprotonated, resulting in a decrease in the intermolecular hydrogen bonding force, further resulting in a decrease in the amount of adsorption. Therefore, when the pH is 6.5, the interaction force between the template molecule bisphenol a and the functional monomer is strongest, and the corresponding adsorption amount is maximized. The maximum adsorption was 15.6 mg/g.
B. Measurement of saturated adsorption curve:
respectively adding 10mg of imprinted mesoporous Materials (MIPs), non-imprinted mesoporous materials (NIPs) and mesoporous materials (MCM-41) into a series of bisphenol A solutions with the concentration of 50-1000mg/L and the pH value of 6.5 and the volume of 10mL, shaking for 4h, performing centrifugal separation, detecting the concentration of bisphenol A in filtrate by using a high performance liquid chromatograph, and substituting the concentration into a formula 1-1 to respectively calculate the adsorption capacity of the imprinted mesoporous Materials (MIPs), the non-imprinted mesoporous materials (NIPs) and the mesoporous materials (MCM-41).
As shown in fig. 9, adsorption curves of imprinted mesoporous Materials (MIPs), non-imprinted mesoporous materials (NIPs) and mesoporous materials (MCM-41) in a series of bisphenol a solutions with a concentration of 50-1000 mg/L; imprinted mesoporous Materials (MIPs) exhibit greater adsorption capacity than non-imprinted mesoporous materials (NIPs) and mesoporous materials (MCM-41). The imprinted mesoporous Materials (MIPs) reach saturated adsorption balance when the concentration of a bisphenol A solution is 700mg/L, and the adsorption capacity is 88.6 mg/g. The adsorption capacity of non-imprinted mesoporous materials (NIPs) and the adsorption capacity of mesoporous materials (MCM-41) are 39.3mg/g and 30.2mg/g respectively under the same concentration of bisphenol A solution. The maximum adsorption capacity of the imprinted mesoporous Materials (MIPs) indicates that the imprinting effect increases the specific surface area and the pore volume of the mesoporous materials. The method is beneficial to increasing the contact chance and action time of bisphenol A molecules and imprinted holes in the polymer, and the adsorption of imprinted mesoporous Materials (MIPs) to bisphenol A is enhanced.
Attached:
1) the synthesis method of non-imprinted mesoporous materials (NIPs) comprises the following steps: the method is basically the same as the synthesis method of imprinted mesoporous Materials (MIPs), and the only difference is that template molecule bisphenol A is not added in the step (1).
2) The synthesis method of the mesoporous material (MCM-41) comprises the following steps: dissolving 1.0g of hexadecyl trimethoxy ammonium bromide (CTAB) in 40mL of deionized water, stirring for 1 hour at the temperature of 40 ℃, and adjusting the pH to 11.0 by using 10mol/L Na0H solution; stirring for 1.0 hour, dropwise adding 5.2g of ethyl orthosilicate, stirring for 24 hours, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal crystallization for 72 hours at the temperature of 85 ℃, carrying out suction filtration and drying on a product, and then adding hydrochloric acid: soxhlet extracting with mixed solution of ethanol (v: v ═ 1: 9) for 7 days, removing Cetyl Trimethoxy Ammonium Bromide (CTAB), and drying the obtained product to obtain mesoporous material (MCM-41).
C. Adsorption kinetics experiment:
10mg of imprinted mesoporous Material (MIPs) is added into 3mL of bisphenol A solution with the concentration of 60mg/L and 800mg/L, the pH value of 6.5 and the volume of room temperature shaking. And (3) centrifuging and separating solids every 5 minutes, detecting the concentration of the bisphenol A in the filtrate by using a high performance liquid chromatograph, substituting the concentration into a formula 1-1 to calculate the adsorption amount of the imprinted mesoporous Materials (MIPs) to the bisphenol A, and further researching the dynamic situation of the MIPs.
Fig. 10 shows that the adsorption power curve of the imprinted mesoporous Material (MIPs) is the result of the kinetic adsorption experiment of the imprinted mesoporous Material (MIPs). Two bisphenol A solutions with different concentrations are selected in the experiment, and the concentrations are respectively 60mg/L and 800 mg/L. The pH of the solution was 6.5, and the time for the adsorption to reach equilibrium increased with the increase of the concentration of bisphenol A in the solution, 15 min and 25min respectively. It can be seen that the adsorption kinetic time of the imprinted mesoporous Material (MIPs) prepared in example 1 is much faster than that of the common molecularly imprinted material, and the imprinted mesoporous material has a large pore size and a large specific surface area.
D. Selective analysis of imprinted mesoporous Materials (MIPs):
selective experiments of imprinted mesoporous Materials (MIPs) using 4-cinnamyl phenol, bisphenol F, catechol and phenol as structural analogs. Preparing a solution of bisphenol A, 4-cinnamyl phenol, bisphenol F and catechol with the molar concentration of 0.6mmol/L, and respectively adding 10mg of imprinted mesoporous Materials (MIPs) and non-imprinted mesoporous materials (NIPs) into the solution with the volume of 10 mL. After shaking for 4h at room temperature, separating imprinted mesoporous Materials (MIPs) and non-imprinted mesoporous materials (NIPs) by a centrifugal method, detecting the concentrations of bisphenol A, 4-cinnamyl phenol, bisphenol F, catechol and phenol by a college liquid chromatography, and substituting the concentrations into a formula 1-1 to calculate the adsorption amounts of the imprinted mesoporous Materials (MIPs) and the non-imprinted mesoporous materials (NIPs). The relative selectivity coefficients of the imprinted mesoporous Materials (MIPs) and the non-imprinted mesoporous materials (NIPs) for the five compounds are shown in table 3.
K represents the partition coefficient, RIFRepresenting the relative influence factor, the calculation formula is as follows:
K＝Q/Ce，
RIF＝RMPs/KNIPs。
wherein Q is the adsorption capacity of imprinted mesoporous Materials (MIPs) or non-imprinted mesoporous materials (NIPs) to template molecules or analogues thereof;
ce is the remaining concentration of template molecules or analogues thereof in the adsorbed solution;
KMIPsis the partition coefficient of imprinted mesoporous Materials (MIPs); kNIPsPartition coefficients of non-imprinted mesoporous materials (NIPs).
TABLE 3 relative selectivity coefficients of imprinted mesoporous Materials (MIPs) and non-imprinted mesoporous materials (NIPs) for five compounds
As can be seen from Table 3-1, the relative imprinting factors varied from 1.06 to 3.20, which indicates that MIPs have a better selective recognition ability for bisphenol A and have selective imprinting sites for BPA. KNIPsThe results indicate that the NIPs are not specifically selective for the adsorption of BPA because there are no imprinted sites that selectively recognize BPA.
E. Repeated adsorption and reproduction performance research of imprinted mesoporous Materials (MIPs):
in order to examine reusability of imprinted mesoporous Materials (MIPs), 10mg of imprinted mesoporous Materials (MIPs) are added into a bisphenol A solution with the volume of 3mL and the concentration of 200mg/L, pH value of 6.5, the mixture is shaken for 25min at room temperature and centrifuged, the imprinted mesoporous Materials (MIPs) are eluted and separated by hydrochloric acid with the volume of 2mL, the concentration of bisphenol A in filtrate is detected by high performance liquid chromatography, and the recovery rate is calculated. Washing the imprinted mesoporous Material (MIPs) for a plurality of times by deionized water, and drying the imprinted mesoporous material for the next use. The imprinted mesoporous Materials (MIPs) are recycled for 5 times.
Fig. 11 shows that after the imprinted mesoporous Materials (MIPs) are reused for 5 times, the adsorption amount is reduced to a certain extent with the increase of the number of times of recycling, but the recovery rate of the imprinted mesoporous Materials (MIPs) can be maintained above 98.0%, which indicates that the materials have better recycling performance.
To test the reproducibility of MIPs, adsorption experiments were performed using 5 batches of imprinted mesoporous Materials (MIPs) synthesized at different times using the synthesis method of example 1. The experimental data are shown in Table 4.
TABLE 4 reproducibility test of imprinted mesoporous Materials (MIPs)
Table 4 shows the adsorption amount of bisphenol a for 5 batches of imprinted mesoporous Materials (MIPs). According to the data, the Relative Standard Deviation (RSD) of the adsorption amount of bisphenol a of 5 batches of imprinted mesoporous Materials (MIPs) was calculated to be 1.1%, which proves that the imprinted mesoporous Materials (MIPs) prepared in example 1 have very good reproducibility.
F. Actual sample adsorption experiment:
selecting water of a myrica rubra water plant in a high-brightness area of Guangdong Foshan as a sample solution, and testing the adsorption capacity of an actual sample of the imprinted mesoporous Material (MIPs). The sample solution was first filtered through a 0.45 micron filter to remove solid impurities. The content of bisphenol A in the sample is measured by college liquid chromatography, and is 0.031 mg/L. 20mg, 40mg, 60mg, 80mg and 100mg of imprinted mesoporous Materials (MIPs) are respectively added into a sample solution with the volume of 30ml, the mixture is shaken for 4 hours at room temperature, the imprinted mesoporous Materials (MIPs) are centrifugally separated, the concentration of bisphenol a in the filtrate is measured by a high performance liquid chromatography, the concentration is substituted into a formula 1-1 to calculate the adsorption capacity of the imprinted mesoporous Materials (MIPs), and the experimental results are shown in table 5.
TABLE 5 adsorptivity of imprinted mesoporous Materials (MIPs) to actual samples in different amounts
As shown in Table 5, adsorption studies were performed on actual samples by adding different amounts of imprinted mesoporous Materials (MIPs), and when 120mg of imprinted mesoporous Materials (MIPs) were added, the concentration of BPA was reduced to 0.008mg/L, which is lower than the national emission standard (GB5749-2006, 0.01 mg/L). Therefore, the amount of MIPs required for treating water in a waxberry water plant is about 4.0 g/L.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention will still fall within the scope of the technical solution of the present invention without departing from the content of the technical solution of the present invention.
Claims (4)
1. A synthetic method of imprinted mesoporous material with high selectivity to bisphenol A is characterized by comprising the following steps:
(1) mixing template molecule bisphenol A and functional monomer, stirring for 100-140 min to obtain pre-acting solution; the mole ratio of template molecule bisphenol A to functional monomer is 1: 4.5-5.5;
the preparation method of the functional monomer comprises the following steps: dissolving 2-mercapto-4-methyl-5-thiazoleacetic acid and KH-570 in ethanol, adjusting pH value to 7.5-8.5 with triethylamine solution, and stirring at 35-45 deg.C for 50-70 min to obtain functional monomer; the molar ratio of the 2-mercapto-4-methyl-5-thiazoleacetic acid to the KH-570 is 1-2: 1-2; the mol ratio of the 2-mercapto-4-methyl-5-thiazole acetic acid to the ethanol is as follows: l is 1: 4.5-5.5;
(2) dissolving hexadecyl trimethoxy ammonium bromide in water, adjusting the pH value to 10.5-11.5 by using a sodium hydroxide solution, and stirring for 50-70 minutes; adding tetraethoxysilane into the solution, and stirring for 20-40 minutes; adding the pre-acting solution into the solution, and stirring for 140 minutes; carrying out hydrothermal crystallization on the mixture, wherein the hydrothermal crystallization is carried out for 70-74 hours at the temperature of 80-90 ℃ to obtain a mixture;
(3) drying the mixture, and removing template molecule bisphenol A, wherein the step of removing template molecule bisphenol A is to perform Soxhlet extraction for 88 to 104 hours by using a mixed solution of hydrochloric acid and ethanol, and the volume ratio of the hydrochloric acid to the ethanol is 1: 8.1-9.9.
2. The method for synthesizing imprinted mesoporous material with high selectivity to bisphenol a according to claim 1, wherein the mole ratio of template molecules bisphenol a, hexadecyl trimethoxy ammonium bromide and ethyl orthosilicate is 1: 2.5-3.0: 21.6-26.4.
3. The method for synthesizing imprinted mesoporous material with high selectivity to bisphenol A according to claim 2, wherein the mass-to-volume ratio of cetyl trimethoxy ammonium bromide to water is g: the ml ratio is 1: 35-45.
4. The method for synthesizing imprinted mesoporous material with high selectivity to bisphenol A according to claim 1, wherein the steps (1) to (3) are performed at a temperature of 35-45 ℃.
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