CN109896576B - Bacterial cellulose membrane/molecular imprinting adsorption material and preparation method and application thereof - Google Patents
Bacterial cellulose membrane/molecular imprinting adsorption material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a bacterial cellulose membrane/molecular imprinting adsorption material and a preparation method and application thereof, wherein a layer of polydopamine is polymerized and coated on fibers of the bacterial cellulose membrane in situ, and then in-situ mineralization is carried out on the fibers, specifically, by utilizing the adhesiveness of the polydopamine, nano titanium dioxide is prepared by adopting a sol-gel method and is adhered to the surface of the polydopamine, a cross-linking agent and imprinting molecules are added for cross-linking polymerization to obtain the bacterial cellulose membrane polymerized with the imprinting molecules, and template molecules are eluted in an acid solution to obtain three-dimensional holes specifically combined with organic molecules such as o-cresol, m-cresol, p-cresol and the like. The structure has high selectivity and high adsorbability to the imprinted molecules, and can accurately adsorb organic pollutant molecules in wastewater, thereby achieving the purpose of removing specific organic pollutants.
Description
Technical Field
The invention belongs to the field of adsorption materials for organic pollutants, and particularly relates to a bacterial cellulose membrane/molecular imprinting adsorption material, and a preparation method and application thereof.
Background
Due to the rapid development of the field of petrochemical industry, the types and the contents of various pollutants in industrial sewage are increased rapidly. The phenolic compounds belong to organic pollutants with strong toxicity and are widely used in the industries of petrifaction, printing and dyeing, pesticides and the like. Due to the discharge of industrial sewage, surface water is extremely easy to be polluted by phenolic compounds, o-cresol, m-cresol and p-cresol are pollutants with higher content in the phenolic compounds, methyl derivatives of phenol are teratogenic and carcinogenic, and the toxicity of the methyl derivatives of phenol is increased along with the increase of the substitution degree on aromatic rings.
At present, there are three main industrial methods for treating phenol-containing wastewater: physical, chemical, biological methods. The physical method mainly utilizes the physical properties of phenolic substances to achieve the removal purpose, such as: solubility, volatility, and the like. And can be simply classified into four types, i.e., an adsorption method, an extraction method, a liquid membrane method, and a gas stripping method. The chemical method mainly utilizes the chemical properties of phenolic substances to achieve the purpose of removing, and mainly comprises a precipitation method, an oxidation method, an electrolysis method, a photocatalysis method and the like. The biochemical method is to utilize some microorganisms or enzymes with specific catalytic degradation of phenolic compounds to achieve the purpose of removing the phenolic compounds, and mainly comprises an activated sludge method, a biofilm method, a biological contact oxidation method and the like.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a bacterial cellulose membrane/molecular imprinting adsorption material, and the bacterial cellulose membrane/molecular imprinting adsorption material is applied to removing phenolic pollutants, and the preparation method specifically comprises the following steps:
step 1: adding dopamine hydrochloride into deionized water to completely dissolve the dopamine hydrochloride, adding a bacterial cellulose film (BC) after complete dissolution, performing ultrasonic treatment at low temperature, continuously adding trihydroxymethyl aminomethane, adjusting the pH value of the mixed solution, placing the mixed solution in a low-temperature environment to perform ultrasonic treatment continuously to assist diffusion, placing the mixed solution in a shaking incubator after the ultrasonic treatment is finished to perform in-situ polymerization to obtain a bacterial cellulose/polydopamine composite film (BC/PDA), and repeatedly performing ultrasonic cleaning on the film by using the deionized water until the cleaned water becomes clear;
step 2: adding ammonium fluotitanate into deionized water to completely dissolve the ammonium fluotitanate, and then adding the cleaned bacterial cellulose/polydopamine into the deionized waterThe composite membrane is placed in a low-temperature environment for ultrasonic treatment, boric acid is added into the composite membrane, the composite membrane is continuously placed in the low-temperature environment for ultrasonic treatment, then the composite membrane is placed in a shaking incubator for prepolymerization, and after prepolymerization is finished, the composite membrane is continuously placed in a constant-temperature environment for static polymerization to obtain a bacterial cellulose/polydopamine/titanium dioxide composite membrane (BC/PDA/TiO)2) Repeatedly ultrasonically cleaning the membrane by using deionized water until the cleaned water becomes clear;
and step 3: dissolving the imprinted molecules in absolute ethyl alcohol, adding 3-aminopropyltriethoxysilane and tetraethyl orthosilicate, and then placing the mixture in a low-temperature environment for ultrasonic treatment to assist dissolution to obtain a mixed solution;
and 4, step 4: adding the bacterial cellulose/polydopamine/titanium dioxide composite membrane cleaned in the step 2 into the mixed solution prepared in the step 3, carrying out ultrasonic treatment in a low-temperature environment, adding ammonia water after the ultrasonic treatment is finished, and carrying out cross-linking polymerization under a static condition to obtain a bacterial cellulose membrane polymerized with imprinted molecules;
and 5: and (4) soaking the bacterial cellulose membrane polymerized with the imprinted molecules obtained in the step (4) in an acid solution, continuously washing with methanol after soaking is finished, and then freeze-drying to finally obtain the bacterial cellulose membrane/molecular imprinted adsorbent material (MIBCM).
As an optimization scheme: in the step 1, the bacterial cellulose film (BC) is a bacterial cellulose film generated by culturing and fermenting acetobacter xylinum, the thickness of the bacterial cellulose film is 0.5-2mm, the concentration of the dissolved dopamine hydrochloride in deionized water is 1-2g/L, the action of trihydroxymethyl aminomethane is taken as a neutralizer, the pH value of the solution is 7.8-8.5, the temperature set in a shaking culture box is 5-50 ℃, the rotating speed is 180r/min, and the time of in-situ polymerization in the shaking culture box is 12-24 hours.
As a further optimization scheme: in the step 2, the concentration of the dissolved ammonium fluotitanate in the deionized water is 100mM, the concentration of the added boric acid is 300mM, the temperature set in the shaking incubator is 5-50 ℃, the rotating speed is 150-180r/min, the time of prepolymerization in the shaking incubator is 30min, the temperature of static polymerization is 5-50 ℃, and the time is 3 h.
As a further optimization scheme: in the step 3, the imprinted molecules are one or more of ortho-phenol, m-cresol, p-cresol, catechol and bisphenol A in any combination, the content of the imprinted molecules is 1-2mmol/50mL, the content of 3-aminopropyl triethoxysilane is 0.5mL/50mL, and the content of tetraethyl orthosilicate is 2mL/50 mL.
As a further optimization scheme: the concentration of ammonia in step 4 was 0.5mL/50 mL.
As a further optimization scheme: the acid solution in the step 5 is a mixed solution of acetic acid and methanol in a volume ratio of 1: 9.
Has the advantages that: the prepared bacterial cellulose membrane/molecular imprinting adsorption material has adjustable pore diameter, and is beneficial to the diffusion and adsorption of organic pollutant molecules; the adsorbent has the advantages of large specific surface area, multiple adsorption sites, strong specific adsorption capacity, high adsorbability and high selectivity on phenolic organic molecules, can perform repeated adsorption and desorption processes, and has high material reuse rate.
Drawings
FIG. 1 is a schematic diagram of the preparation process of the bacterial cellulose membrane/molecularly imprinted adsorbent material of the present invention;
FIG. 2 is a scanning electron micrograph of 4 film species in steps of the invention,
wherein: fig. 2(a) is a scanning electron microscope image of a bacterial cellulose film, fig. 2(b) is a scanning electron microscope image of a bacterial cellulose/polydopamine composite film, fig. 2(c) is a scanning electron microscope image of a bacterial cellulose/polydopamine/titanium dioxide composite film, and fig. 2(d) is a scanning electron microscope image of a bacterial cellulose film/molecularly imprinted adsorbent material;
FIG. 3 is a comparative infrared spectrum of 4 membrane materials at various steps of the invention;
FIG. 4 is a comparative XRD pattern of 4 membrane species at various steps of the invention;
FIG. 5 is a comparative XPS spectrum of 4 membrane species for each step of the present invention;
FIG. 6 is a graph showing the adsorption kinetics of o-cresol by the bacterial cellulose membrane/molecular imprinting adsorbing material of the invention,
wherein: FIG. 6(a) is a first test graph, and FIG. 6(b) is a second test graph;
FIG. 7 is a graph showing the adsorption kinetics of paracresol by the bacterial cellulose membrane/molecular imprinting adsorption material of the present invention,
wherein: FIG. 7(a) is a first time test chart, and FIG. 7(b) is a second time test chart;
FIG. 8 is a comparison of the reproducibility of the adsorption of p-o-cresol and p-cresol with the bacterial cellulose membrane/molecularly imprinted adsorbent material of the present invention;
FIG. 9 is a comparison of selective adsorption capacities of the bacterial cellulose membrane/molecularly imprinted adsorbent material of the invention for different contaminants,
wherein: FIG. 9(a) is a schematic diagram showing the selective adsorption capacity of the bacterial cellulose membrane/molecular imprinting adsorbent material of the present invention for o-cresol, FIG. 9(b) is a schematic diagram showing the selective adsorption capacity of the bacterial cellulose membrane/molecular imprinting adsorbent material of the present invention for o-cresol, FIG. 9(c) is a schematic diagram showing the selective adsorption capacity of a template-free molecule for o-cresol and p-cresol, and FIG. 9(d) is a schematic diagram showing the comparison of the selective adsorption capacities of FIGS. 9(a), 9(b) and 9 (c).
Detailed Description
The present invention is further illustrated by the following figures and specific examples, which are to be understood as illustrative only and not as limiting the scope of the invention, which is to be given the full breadth of the appended claims and any and all equivalent modifications thereof which may occur to those skilled in the art upon reading the present specification.
As shown in the preparation flow chart of fig. 1, the principle of the invention is as follows: the method comprises the steps of firstly coating a layer of polydopamine on fibers of a bacterial cellulose membrane in an in-situ polymerization manner, then carrying out in-situ mineralization on the fibers, specifically preparing nano titanium dioxide by utilizing the adhesion of the polydopamine through a sol-gel method, adhering the nano titanium dioxide on the surface of the polydopamine, then adding a cross-linking agent and imprinted molecules for cross-linking polymerization to obtain the bacterial cellulose membrane polymerized with the imprinted molecules, and eluting template molecules in an acid solution to obtain three-dimensional cavities specifically combined with organic molecules such as o-cresol, m-cresol, p-cresol and the like. The structure has high selectivity and high adsorbability to the imprinted molecules, and can accurately adsorb organic pollutant molecules in wastewater, thereby achieving the purpose of removing specific organic pollutants.
Example 1:
step 1: dissolving 0.1g of dopamine hydrochloride in 50mL of deionized water, adding a bacterial cellulose film with the area of 20 multiplied by 20mm and the thickness of 0.5mm, wherein the shape of the bacterial cellulose film is as shown in figure 2(a), carrying out ultrasonic treatment for 30min at low temperature, then adding 0.18g of tris (hydroxymethyl) aminomethane, adjusting the pH value to be 7.8-8.5, and then carrying out ultrasonic treatment for 30min at low temperature to fully diffuse small molecular monomers into the film. Then, the membrane is placed into a shaking incubator, the temperature is set to be 30 ℃, the rotating speed is 150rpm, and dopamine is polymerized on the surface and inside of the fine cellulose membrane in situ to obtain the bacterial cellulose/polydopamine composite membrane, as shown in fig. 2(b), wherein the fiber diameter is 100-500 nm. And repeatedly ultrasonically cleaning the obtained bacterial cellulose/polydopamine composite membrane by using deionized water until the cleaned water is clear and has no obvious visible impurities.
Step 2: fully dissolving 0.927g of boric acid in 50mL of deionized water, adding a bacterial cellulose/polydopamine composite membrane, performing ultrasonic treatment at low temperature, then adding 0.198g of ammonium fluotitanate, performing ultrasonic treatment at low temperature for 30min, then placing the mixture into a shaking incubator, setting the temperature at 30 ℃ and the rotating speed at 150rpm, and performing prepolymerization. And then carrying out static polymerization at 50 ℃ to obtain the bacterial cellulose/polydopamine/titanium dioxide composite membrane, wherein as shown in figure 2(c), the fiber is coated with a layer of granular structure with the diameter of 200-500nm, and the ultrasonic cleaning is repeated by using deionized water until the cleaned water is clear and has no obvious visible impurities.
And step 3: 0.108g of o-cresol was added to 50mL of anhydrous ethanol, 0.2mL of 3-aminopropyltriethoxysilane and 0.8mL of tetraethyl orthosilicate were added, and then the mixture was subjected to ultrasonic treatment at low temperature for 30min to be thoroughly mixed and dissolved.
And 4, step 4: and (3) adding the bacterial cellulose/polydopamine/titanium dioxide composite membrane obtained in the step (2), performing ultrasonic treatment for 30min at low temperature, adding 0.5mL of ammonia water, and performing cross-linking polymerization for 16 hours under a static condition to obtain the bacterial cellulose membrane polymerized with the imprinted molecules.
And 5: the resulting bacterial cellulose membrane with the imprinted molecules polymerized was washed with acetic acid: fully soaking the mixture with the methanol volume ratio of 1:9 for 24 hours, eluting the imprinted molecules, taking out, continuously washing the mixture with methanol, and freeze-drying to obtain the bacterial cellulose membrane/molecular imprinted adsorption material, wherein the material has a larger specific surface area and more adsorption sites as shown in fig. 2 (d). FIGS. 3, 4 and 5 are 4 membrane species in steps of the invention, respectively: the comparison infrared spectra of the bacterial cellulose film, the bacterial cellulose/polydopamine composite film, the bacterial cellulose/polydopamine/titanium dioxide composite film and the bacterial cellulose film/molecular imprinting adsorption material, the comparison XRD spectra and the comparison XPS spectra are obtained according to the consistency and the step-by-step performance of absorption wavelengths, the material disclosed by the invention is superior in the specificity of absorbing phenolic substances, and the point is verified in fig. 9.
Example 2:
the bacterial cellulose film added in the step 1 is a bacterial cellulose film with the thickness of 1mm, and the rest steps are the same as the step 1.
Example 3:
the bacterial cellulose film added in the step 1 is a bacterial cellulose film with the thickness of 2mm, and the rest steps are the same as the step 1.
Example 4
The static polymerization temperature in step 2 was 5 ℃ and the rest of the procedure was the same as in example 3.
Example 5
The static polymerization temperature in step 2 was 35 ℃ and the rest of the procedure was the same as in example 3.
Example 6
The time for the cross-linking polymerization in step 4 was 20 hours, and the rest of the procedure was the same as in example 3.
Example 7
The amount of o-cresol added in step 3 was 0.216g, and the rest of the procedure was the same as in example 6.
Example 8
In step 3, o-cresol was changed to m-cresol, and the amount of m-cresol added was 0.108g, and the rest of the procedure was the same as in example 6.
Example 9
In step 3, o-cresol was changed to p-cresol, and the soaking time in step 5 was 12 hours, and the rest of the procedure was the same as in example 1.
The bacterial cellulose membrane used by the invention has adjustable aperture, the aperture is 50nm-5um, compared with other materials, the bacterial cellulose membrane has larger specific surface area, the prepared adsorbing material has more adsorption sites, the controllable aperture is also beneficial to the diffusion and adsorption of organic pollutant molecules, the obtained adsorbing material has extremely high specific adsorption capacity, figures 6 and 7 respectively describe the trend of the adsorption kinetics curve of the material of the invention to o-cresol and p-cresol, which shows that the material has high adsorption and high selectivity to organic molecules such as o-cresol and p-cresol, and the comparison schematic diagram of the repeated performance of the bacterial cellulose membrane/molecular imprinting adsorbing material to o-cresol and p-cresol is shown in figure 8, the adsorption performance is stable and not reduced, and the repeated adsorption and desorption process can be carried out theoretically, namely the material can be reused. FIG. 9 is a comparison of selective adsorption capacities of bacterial cellulose membranes/molecularly imprinted adsorbent materials of the invention for different contaminants, wherein: FIG. 9(c) is a graph showing the selective adsorption capacities of p-o-cresol and p-cresol in the absence of templating molecules as a comparative example, and FIG. 9(d) is a graph showing a comparison of the selective adsorption capacities of FIGS. 9(a), 9(b) and 9(c), and it can be seen from FIG. 9(d) that the adsorbent of the present invention is superior to the comparative example in terms of adsorption of phenolic substances.
The bacterial cellulose is a kind of cellulose obtained by culturing and fermenting microorganisms, has the same molecular structure unit with natural cellulose generated by plants or seaweeds, but has a plurality of unique properties, does not contain lignin, pectin, hemicellulose and other associated products compared with the plant cellulose, and has high crystallinity; the fibers of the bacterial cellulose are formed by combining microfibers with diameters of 3-4 nanometers into fiber bundles with the thickness of 40-60 nanometers, and are mutually interwoven to form a developed hyperfine network structure; the elastic modulus is several times to more than ten times of that of common plant fibers, and the fiber has high tensile strength and good hydrophilicity. The molecular imprinting technology is a technology rapidly developed in recent years, and the principle is as follows: multiple action points are formed when the imprinted molecules are contacted with the polymer monomers, the action is memorized in the polymerization process, and after the imprinted molecules are removed, cavities with the multiple action points, which are matched with the spatial configuration of the imprinted molecules, are formed in the polymer, and the cavities have extremely high selective recognition characteristics on the imprinted molecules and the like. The molecular imprinting technology is combined with the bacterial cellulose, and the hyperfine grid structure of the bacterial cellulose has extremely high specific surface area, so that the pore-forming of an imprinting combination site with high density can be facilitated.
Claims (7)
1. A preparation method of a bacterial cellulose membrane/molecular imprinting adsorption material is characterized by comprising the following steps:
step 1: adding dopamine hydrochloride into deionized water, adding a bacterial cellulose film after complete dissolution, performing ultrasonic treatment at low temperature, continuously adding trihydroxymethyl aminomethane, adjusting the pH value of the mixed solution, placing the mixed solution in a low-temperature environment, continuously performing ultrasonic treatment to assist diffusion, placing the mixed solution into a shaking incubator after ultrasonic treatment for in-situ polymerization to obtain a bacterial cellulose/polydopamine composite film, and repeatedly performing ultrasonic cleaning on the film by using deionized water until the cleaned water becomes clear;
step 2: adding ammonium fluotitanate into deionized water to completely dissolve the ammonium fluotitanate, adding the cleaned bacterial cellulose/polydopamine composite membrane into the deionized water, placing the composite membrane into a low-temperature environment for ultrasonic treatment, adding boric acid into the composite membrane, continuing to place the composite membrane into the low-temperature environment for ultrasonic treatment, then placing the composite membrane into a shaking incubator for prepolymerization, continuing to place the composite membrane into a constant-temperature environment for static polymerization after prepolymerization is finished, obtaining a bacterial cellulose/polydopamine/titanium dioxide composite membrane, and repeatedly performing ultrasonic cleaning on the composite membrane by using deionized water until the cleaned water becomes clear;
and step 3: dissolving the imprinted molecules in absolute ethyl alcohol, adding 3-aminopropyltriethoxysilane and tetraethyl orthosilicate, and then placing the mixture in a low-temperature environment for ultrasonic treatment to assist dissolution to obtain a mixed solution;
the imprinted molecule is one or more of o-cresol, m-cresol, p-cresol, catechol and bisphenol A in any combination, the content of the imprinted molecule is 1-2mmol/50mL, the content of the 3-aminopropyltriethoxysilane is 0.5mL/50mL, and the content of tetraethyl orthosilicate is 2mL/50 mL;
and 4, step 4: adding the bacterial cellulose/polydopamine/titanium dioxide composite membrane cleaned in the step 2 into the mixed solution prepared in the step 3, carrying out ultrasonic treatment in a low-temperature environment, adding ammonia water after the ultrasonic treatment is finished, and carrying out cross-linking polymerization under a static condition to obtain a bacterial cellulose membrane polymerized with imprinted molecules;
and 5: and (4) soaking the bacterial cellulose membrane polymerized with the imprinted molecules obtained in the step (4) in an acid solution, continuously washing with methanol after soaking is finished, and then freeze-drying the bacterial cellulose membrane/molecularly imprinted adsorption material to finally obtain the bacterial cellulose membrane/molecularly imprinted adsorption material.
2. The method for preparing a bacterial cellulose membrane/molecular imprinting adsorption material according to claim 1, wherein: in the step 1, the bacterial cellulose film is a bacterial cellulose film generated by culturing and fermenting acetobacter xylinum, the thickness of the bacterial cellulose film is 0.5-2mm, the concentration of the dissolved dopamine hydrochloride in deionized water is 1-2g/L, the action of the trihydroxymethyl aminomethane is taken as a neutralizer, the pH value of the solution is 7.8-8.5, the temperature of the shaking culture box is 5-50 ℃, the rotating speed is 150-180r/min, and the time of in-situ polymerization in the shaking culture box is 12-24 hours.
3. The method for preparing a bacterial cellulose membrane/molecular imprinting adsorption material according to claim 1, wherein: in the step 2, the concentration of the ammonium fluotitanate after being dissolved in the deionized water is 100mM, the concentration of the added boric acid is 300mM, the temperature set in the shaking incubator is 5-50 ℃, the rotating speed is 150-180r/min, the time of prepolymerization in the shaking incubator is 30min, the temperature of static polymerization is 5-50 ℃, and the time is 3 h.
4. The method for preparing a bacterial cellulose membrane/molecular imprinting adsorption material according to claim 1, wherein: the concentration of the ammonia water in the step 4 is 0.5mL/50 mL.
5. The method for preparing a bacterial cellulose membrane/molecular imprinting adsorption material according to claim 1, wherein: in the step 5, the acid solution is a mixed solution of acetic acid and methanol in a volume ratio of 1: 9.
6. A bacterial cellulose membrane/molecular imprinting material, characterized by: a method of preparing a bacterial cellulose membrane/molecular imprinting absorbent material according to any one of claims 1 to 5.
7. Use of a bacterial cellulose membrane/molecularly imprinted adsorbent material, characterized in that: a bacterial cellulose membrane/molecular imprinting material according to claim 6, for use in the removal of phenolic contaminants.
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| CN106362805A (en) * | 2016-08-26 | 2017-02-01 | 湖南大学 | Titanium dioxide/graphene/molecularly imprinted composite material and preparation method and application thereof |
| CN107469653A (en) * | 2017-08-16 | 2017-12-15 | 江苏大学 | A kind of synthetic method for the molecularly imprinted composite membrane for being enriched with and separating Norfloxacin |
| CN108816058A (en) * | 2018-06-27 | 2018-11-16 | 江苏大学 | A kind of rheum emodin molecular engram titanium dioxide nano-particle composite membrane and the preparation method and application thereof |
| CN109216048A (en) * | 2018-08-14 | 2019-01-15 | 南京理工大学 | Flexible electrode and preparation method thereof based on bacteria cellulose film |
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|---|---|---|---|---|
| CN106362805A (en) * | 2016-08-26 | 2017-02-01 | 湖南大学 | Titanium dioxide/graphene/molecularly imprinted composite material and preparation method and application thereof |
| CN107469653A (en) * | 2017-08-16 | 2017-12-15 | 江苏大学 | A kind of synthetic method for the molecularly imprinted composite membrane for being enriched with and separating Norfloxacin |
| CN108816058A (en) * | 2018-06-27 | 2018-11-16 | 江苏大学 | A kind of rheum emodin molecular engram titanium dioxide nano-particle composite membrane and the preparation method and application thereof |
| CN109216048A (en) * | 2018-08-14 | 2019-01-15 | 南京理工大学 | Flexible electrode and preparation method thereof based on bacteria cellulose film |
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