CN110465259B - Hierarchical porous TiO2Material, preparation method and application of material in protein adsorption - Google Patents
Hierarchical porous TiO2Material, preparation method and application of material in protein adsorption Download PDFInfo
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Abstract
The invention belongs to the field of hierarchical porous metal oxide materials, and particularly relates to hierarchical porous TiO2A material, a preparation method and application thereof in protein adsorption. The hierarchical porous TiO2The material takes a triblock copolymer and a biomass material plant tanning agent as a double template, takes nontoxic and low-price soluble inorganic metal salt of titanium as a metal source, carries out mild self-assembly under the condition of no need of high-temperature hydrothermal, promotes the conversion of crystal form, and finally forms the product with the specific surface area of 32-142 m through calcination2(g) hierarchical porous TiO with the pore diameter ranging from 1.8 nm to 94nm2A material. The invention provides a synthetic route for preparing hierarchical porous TiO, which is simple to operate and low in cost2The material has larger specific surface area and abundant pore structures, can effectively adsorb protein biomacromolecules, and has good adsorption effect on protein substances in tanning softening wastewater.
Description
Technical Field
The invention belongs to the field of hierarchical porous metal oxide materials, and particularly relates to hierarchical porous TiO2A material, a preparation method and application thereof in protein adsorption.
Background
With the development of biotechnology, proteomics is widely applied in the fields of biomedicine, genetic diagnosis, etc., and the separation and purification of proteins are the prerequisite for the fine study of proteins. The adsorption method is a common method for separating and purifying protein by virtue of simple operation and low cost. Therefore, designing an adsorbing material capable of effectively adsorbing proteins is of great significance for the separation and purification of proteins.
In recent years, the development of chemistry and material science is vigorous, wherein porous materials are widely applied to the fields of adsorption, catalysts, solar energy systems, nano sensors and the like by virtue of the rich porosity and adjustable pore structures. According to the definition of International Union of Pure and Applied Chemistry (IUPAC), porous materials are divided into micropores (the aperture is less than 2nm), mesopores (the aperture is 2-50 nm) and macropores (the aperture is more than 50nm), wherein the mesopores and the macropores with larger pore sizes can realize effective adsorption and separation of protein biomacromolecules. However, the pore size of the mesoporous material synthesized at present is mostly about 6nm, which is not enough to provide a channel for transferring protein mass, and the synthesis process of the mesoporous material with larger pore size (pore size >10nm) is more complicated, and the synthesis raw material is expensive; the synthetic macroporous material is used for adsorbing biomacromolecules, but the simple macroporous structure has the defects of low specific surface area, easy collapse of a pore structure and the like. Therefore, the two pore structures are skillfully compounded, on one hand, the macroporous structure can promote the mass transfer of biomacromolecules, and on the other hand, the mesoporous material can improve the specific surface area of the material.
Titanium dioxide (TiO)2) Is a semiconductor material with excellent performance, has no toxicity and biocompatibility, and is widely applied to the field of biomedicine. The template method is the most commonly used method for preparing hierarchical porous TiO2Materials, but the currently reported hierarchical porous TiO2The preparation method of the material mostly needs harsh hydrothermal conditions and a template agent with higher price, and is not beneficial to large-scale production. Therefore, the method for synthesizing the hierarchical porous TiO with simple preparation conditions and low cost is developed2The new method of the material has practical significance for adsorbing and separating biomacromolecules.
Disclosure of Invention
The invention provides hierarchical porous TiO2Material, preparation method and application thereof in protein adsorption, hierarchical porous TiO2The material has simple preparation conditions and low cost, and the larger specific surface area and rich pore structures of the material can effectively adsorb protein biomacromolecules and simultaneously has good adsorption effect on protein substances in the actual tanning softening wastewater。
The first purpose of the invention is to provide hierarchical porous TiO2The preparation method of the material comprises the steps of mixing an ethanol solution of a triblock copolymer with an aqueous solution of a biomass material plant tanning agent to form a double template, mixing the double template with soluble inorganic metal salt of titanium, and stirring at room temperature for 3-6 hours to form metal TiO2Performing aging, drying and calcining on the prepolymer solution to finally prepare the hierarchical pore TiO2A material.
Preferably, the hierarchical porous TiO is2The preparation method of the material comprises the following steps of aging at 35-45 ℃ for 24-96 hours, and drying at 50-70 ℃ for 24-48 hours; the calcining condition is 550-650 ℃ for 240-360 min.
Preferably, the hierarchical porous TiO is2The preparation method of the material comprises the steps of mixing an ethanol solution of the triblock copolymer with an aqueous solution of a biomass material plant tanning agent, and stirring for 15-25 min to obtain the double-template.
Preferably, the hierarchical porous TiO is2The preparation method of the material comprises the following steps:
s1, dissolving the triblock copolymer in absolute ethyl alcohol to obtain an ethanol solution of the triblock copolymer; dissolving a biomass material plant tanning agent in distilled water to obtain an aqueous solution of the biomass material plant tanning agent; mixing an ethanol solution of the triblock copolymer with an aqueous solution of a biomass material plant tanning agent at room temperature to obtain a double template;
s2, adding inorganic metal salt of titanium into the double templates of S1, stirring for 3-6 h at room temperature to form metal TiO2A prepolymer solution;
s3, metal TiO2The prepolymer solution is treated in two stages of aging and drying to promote crystal form transformation;
s4, placing the dried crystal in a muffle furnace for calcining to obtain hierarchical porous TiO2A material.
Preferably, the hierarchical porous TiO is2The preparation method of the material, S1, the triblock copolymer is Pluronic (Pluronic) series copolymer which is mainly composed of polyoxyethylene-polyoxypropylene-polyoxyethylene(PEO-PPO-PEO) triblock; pluronic P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer), Pluronic F127 or Pluronic F108 were specifically selected, the building blocks of these three polymers being identical, but the number of PEO and PPO chains being different.
Preferably, the hierarchical porous TiO is2The preparation method of the material, in S1, the biomass material plant tanning agent is one of a Madecassia tannin extract (BA tannin extract), a larch tannin extract and myricetin.
Preferably, the hierarchical porous TiO is2In the preparation method of the material, in S2, the soluble inorganic metal salt of titanium is one of titanium sulfate and titanium chloride.
Preferably, the hierarchical porous TiO is2The preparation method of the material comprises the following steps of S1-S2, wherein the molar ratio of triblock copolymer to biomass material plant tanning agent to soluble inorganic metal salt of titanium is 0.005-0.01: 0.01 to 0.09: 0.1 to 0.9.
The second purpose of the invention is to provide a hierarchical porous TiO prepared by the method2Material, hierarchical porous TiO2The specific surface area of the material is 32-142 m2The pore diameter is 1.8-100 nm.
The third purpose of the invention is to provide the hierarchical porous TiO prepared by the method2The material is applied to adsorbing lysozyme, bovine serum albumin or bovine hemoglobin.
The fourth purpose of the invention is to provide the hierarchical porous TiO prepared by the method2The application of the material in absorbing protein substances in tanning softening wastewater.
Compared with the prior art, the hierarchical porous TiO provided by the invention2The material, the preparation method and the application thereof in protein adsorption have at least the following beneficial effects:
1. the biomass material plant tanning agent is combined with the traditional template triblock copolymer for preparing the mesoporous material to be used as a double template, and the hierarchical pore TiO with the micropore-mesopore-macropore structure is prepared by a simple one-pot synthesis method2A material.
2. The invention adopts soluble inorganic metal salt of titanium as a metal source, and avoids the problems of high price and high toxicity of common organic alkoxide of titanium and titanium oxychloride.
3. The prepared hierarchical porous TiO2The material can effectively adsorb lysozyme, bovine serum albumin and bovine hemoglobin, the adsorption capacities of the material can respectively reach 42.1-42.9 mg/g, 26.2-26.9 mg/g and 160.1-165.7 mg/g, the material has certain adsorption capacity on protein substances in actual tanning softening wastewater, and the absorbance of the protein substances in the wastewater after adsorption is obviously reduced.
Drawings
FIG. 1 is a diagram of example 1 for synthesizing hierarchical porous TiO2A TEM spectrum of the material;
FIG. 2 Synthesis of hierarchical porous TiO according to example 22XRD spectrum of the material;
FIG. 3 Synthesis of hierarchical porous TiO according to example 32Nitrogen adsorption and desorption isotherms and pore size distribution maps of the material;
FIG. 3A is a hierarchical porous TiO2Pore size distribution plot of solid material, FIG. 3B is a hierarchical pore TiO2A nitrogen adsorption and desorption isotherm of a solid material;
FIG. 4 Synthesis of hierarchical porous TiO according to example 42SEM spectra of the material;
FIG. 5 Synthesis of hierarchical porous TiO according to example 12The adsorption effect of the material on lysozyme is shown;
FIG. 6 Synthesis of hierarchical porous TiO according to example 12The adsorption effect of the material on bovine serum albumin is shown;
FIG. 7 is a diagram of the synthesis of hierarchical porous TiO according to example 12The adsorption effect of the material on protein substances in tannery softening wastewater is shown.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention to be implemented, the present invention will be further described with reference to the following specific embodiments and accompanying drawings. The following examples, as well as test methods not specifically identified in the summary of the invention, were conducted according to methods and conditions conventional in the art.
The experimental methods and the detection methods described in the following examples are, unless otherwise specified, conventional methods or conditions recommended by the respective reagent manufacturers; the reagents and materials are commercially available, unless otherwise specified. In the following examples, the tannery softening wastewater used was supplied from cowhide tanning Co., Ltd of North east China
Example 1
Hierarchical porous TiO2The preparation method of the material comprises the following steps:
weighing 1.00g triblock copolymer P123(Pluronic P123) and dissolving in 20mL ethanol solution, weighing 1.1638g BA extract (Marina Acacia extract) and dissolving in 30mL distilled water, mixing ethanol solution of Pluronic P123 and water solution of BA extract, stirring under air for 20min, adding 2.29g Ti (SO)4)2Stirring for 3h, transferring the solution into a culture dish, aging in a 40 deg.C oven for 48h, transferring into a 60 deg.C oven, and drying for 24h to promote metal TiO2Self-assembly, drying the TiO2Transferring the crystal solid of the organic template compound into a corundum crucible, and calcining at 550 ℃ for 240min in a muffle furnace to obtain hierarchical porous TiO2A solid material.
Example 1 synthetic hierarchical porous TiO2The TEM spectrum of (a) is shown in fig. 1, from which it can be clearly observed that the sample synthesized in example 1 has porous structures of different sizes distributed relatively uniformly (light-colored part of fig. 1). These pore structures are, on the one hand, relatively large pores formed by the interparticle polymerization and stacking, and, on the other hand, relatively small mesoporous structures formed in the pore walls after the triblock copolymer is calcined.
Example 2
The hierarchical porous TiO provided in this example2The process for the solid material was essentially the same as in example 1, except that the muffle calcination temperature was 650 ℃. Example 2 synthetic hierarchical porous TiO2The XRD pattern of the solid material is shown in fig. 2, from which it can be seen that the XRD pattern of the synthesized sample of example 2 has a sharp and distinct diffraction peak at 25.3 ° 2 θ, corresponding to anatase TiO2(101) Crystal face, proving that the synthesized hierarchical pore TiO2The crystallinity is higher; in thatWeak diffraction peaks at 38.1 °, 48.1 °, 53.9 °, 55.1 °, 62.5 °, 68.7 °, 70.3 ° and 75.1 ° 2 θ, respectively, corresponding to anatase TiO2The (004), (200), (105), (211), (204), (116), (220) and (215) crystal planes of (c).
Example 3
The hierarchical porous TiO provided in this example2The process of solid material is the same as in example 2, with the difference that the amount of BA tannin extract is 1.9397 g. Example 3 synthetic hierarchical porous TiO2The pore size distribution of the solid material is shown in FIG. 3A, and FIG. 3B is a hierarchical pore TiO2And (3) adsorbing and desorbing an isotherm by using nitrogen as a solid material. As can be seen from the figure, the hierarchical porous TiO synthesized in example 32The isotherms of (A) belong to the typical class IV isotherms and have H3 type hysteresis loops, which are caused by the capillary condensation phenomenon of nitrogen molecules in mesopores, and prove that the synthesized hierarchical pore TiO is2The mesoporous structure exists in the solid material sample, and the relative pressure is lower (p/p)0<0.05) the adsorption capacity increased sharply, demonstrating the existence of a microporous structure in the synthesized sample. Pore size distribution diagram demonstrating TiO synthesized in example 32Both microporous and mesoporous structures exist.
Example 4
The hierarchical porous TiO provided in this example2The process of solid material is substantially the same as example 2, with the difference that the amount of BA tannin extract is 0.3879 g. Example 4 synthetic hierarchical porous TiO2The SEM spectrum of the solid material is shown in FIG. 4, from which it can be seen that the hierarchical porous TiO synthesized in example 42Solid materials with pore structures of different sizes prove that TiO with hierarchical pore structures2Successfully synthesized by the invention.
The hierarchical porous TiO synthesized in examples 1 to 4 above2The material is subjected to SEM, TEM, XRD, nitrogen adsorption and desorption isotherm and pore size distribution analysis, and XRD spectrogram proves that anatase TiO is successfully prepared2The crystal, nitrogen adsorption and desorption isotherm and the pore size distribution diagram prove that the synthesized TiO2The material has a mesoporous structure, and the average mesoporous aperture size is 15-25 nThe m, SEM and TEM spectra prove that the synthesized TiO2The material presents a macroporous structure. A series of structural characterization means prove that the method can successfully prepare TiO with a hierarchical pore structure2A material.
Example 5
Weighing 0.005mol triblock copolymer Pluronic F127 in 20mL ethanol solution, weighing 0.01mol larch tannin extract in 30mL distilled water, mixing ethanol solution of Pluronic F127 and water solution of larch tannin extract, stirring under air for 20min, adding 0.9mol TiCl4Stirring for 6h, transferring the solution into a culture dish, aging in a 35 ℃ oven for 96h, transferring into a 50 ℃ oven, and drying for 48h to promote metal TiO2Self-assembly, drying the TiO2Transferring the crystal solid of the organic template compound into a corundum crucible, and calcining the corundum crucible in a muffle furnace at the high temperature of 600 ℃ for 360min to obtain hierarchical porous TiO2A solid material.
Example 6
Weighing 0.01mol triblock copolymer Pluronic F108 and dissolving in 20mL ethanol solution, weighing 0.05mol myricetin and dissolving in 30mL distilled water, mixing ethanol solution of Pluronic F108 and myricetin water solution, stirring under air for 25min, and adding 0.5mol Ti (SO)4)2Stirring for 4h, transferring the solution into a culture dish, aging in a 45 deg.C oven for 24h, transferring to a 70 deg.C oven, and drying for 36h to promote metal TiO2Self-assembly, drying the TiO2Transferring the crystal solid of the organic template compound into a corundum crucible, and calcining the corundum crucible in a muffle furnace at the high temperature of 550 ℃ for 360min to obtain hierarchical porous TiO2A solid material.
Example 7
Weighing 0.007mol of triblock copolymer P123 and dissolving in 20mL of ethanol solution, weighing 0.05mol of BA tannin extract and dissolving in 30mL of distilled water, mixing the ethanol solution of P123 and the aqueous solution of BA tannin extract, stirring for 15min under air, and adding 0.1mol of Ti (SO)4)2Stirring for 4h, transferring the solution into a culture dish, aging in a 40 deg.C oven for 24h, transferring into a 50 deg.C oven, and drying for 24h to promote metal TiO2Self-assembly ofDried TiO2Transferring the organic template compound solid into a corundum crucible, and calcining at 550 ℃ for 240min in a muffle furnace to obtain hierarchical porous TiO2A solid material.
In addition, the hierarchical pore TiO prepared by the invention2The solid material was subjected to adsorption application experiments:
1) the hierarchical porous TiO synthesized by the above embodiment of the invention2The solid material was subjected to a lysozyme adsorption experiment:
the 500 mu g/mL lysozyme solution is prepared by utilizing the PBS buffer solution with the pH value of 5, and the hierarchical pore TiO synthesized in the example 1 is weighed20.2g of the material was mixed with 20mL of the above lysozyme solution to make TiO2Solid material adsorbing protein, FIG. 5 is the synthesis of hierarchical porous TiO according to example 12The adsorption effect of the material on lysozyme is shown in the figure, when the lysozyme is adsorbed for 720min, the adsorption rate of the lysozyme is 95.8%, and the adsorption capacity is 42.5 mg/g. In addition, we take the hierarchical porous TiO of examples 2-72The results of lysozyme adsorption experiments by referring to the method show that the adsorption capacities of the lysozyme in examples 2 to 7 are 42.5mg/g, 42.9mg/g, 42.7mg/g, 42.8mg/g and 42.1mg/g respectively after 720min of adsorption.
2) The hierarchical porous TiO synthesized by the above embodiment of the invention2The solid material was subjected to bovine serum albumin adsorption experiments:
PBS buffer solution with pH of 4.5 is utilized to prepare bovine serum albumin solution with 500 mug/mL, and the hierarchical pore TiO synthesized in the embodiment 1 is weighed2Mixing 0.2g of the material with 20mL of the above bovine serum albumin solution to obtain TiO2Solid material adsorbing protein, FIG. 6 is the synthesis of hierarchical porous TiO according to example 12The adsorption effect of the material on bovine serum albumin is shown in the figure, and after 720min of adsorption, the adsorption rate of the bovine serum albumin is 62%, and the adsorption capacity is 26.2 mg/g. In addition, we take the hierarchical porous TiO of examples 2-72The results of the bovine serum albumin adsorption experiments carried out according to the method show that the adsorption capacities of the bovine serum albumin in examples 2 to 7 are 26.4mg/g, 26.3mg/g, 26.9mg/g, 26.5mg/g, 26.2mg/g and 26.9mg/g respectively after 720min of adsorption.
3) The bovine hemoglobin solution of 500. mu.g/mL was prepared using PBS buffer solution of pH 4.5, and the hierarchical pore TiO synthesized in example 1 was weighed2Mixing 0.2g of the material with 20mL of the above bovine serum albumin solution to obtain TiO2The solid material adsorbs protein for 360min, the adsorption rate of the bovine hemoglobin reaches 100%, and the adsorption capacity is 163.9 mg/g. In addition, we take the hierarchical porous TiO of examples 2-72The results of the bovine serum albumin adsorption experiments carried out according to the method show that the adsorption capacities of the bovine serum albumin in examples 2 to 7 are 160.1mg/g, 165.7mg/g, 163.0mg/g, 165.1mg/g, 162.4mg/g and 162.5mg/g respectively after 360min of adsorption.
4) For the hierarchical porous TiO synthesized in the above example 1 of the present invention2The solid material is subjected to an adsorption experiment of protein substances in tannery softening wastewater:
filtering tannery softening wastewater to remove filter residues, taking 20mL of filtrate for later use, and weighing the hierarchical pore TiO synthesized in example 120.2g of the material was placed in 20mL of the tannery softening wastewater after filtration for 6 hours, and as can be seen from FIG. 7, the maximum absorption wavelength of the protein in the softening wastewater was 602nm, and the absorbance of the protein substances in the tannery softening wastewater after adsorption (taking the absorbance value at the maximum absorption wavelength) was reduced from 2.1Abs before adsorption to 1.6 Abs. Because the protein substances in the tanning softening wastewater are mainly absorbed at the wavelength, the reduction of the absorbance before and after the adsorption experiment can be reflected qualitatively: through the hierarchical pore TiO2After the adsorption of the material, the content of protein substances in the tanning softening wastewater is reduced.
It should be noted that when the following claims refer to numerical ranges, it should be understood that both ends of each numerical range and any number between the two ends can be selected, and the preferred embodiments of the present invention are described for the sake of avoiding redundancy, but those skilled in the art may make other changes and modifications to these embodiments once they learn the basic inventive concept. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (6)
1. Hierarchical porous TiO2The preparation method of the material is characterized in that ethanol solution of triblock copolymer and water solution of biomass material plant tanning agent are mixed to form double templates, the double templates are mixed with soluble inorganic metal salt of titanium, and stirring is carried out at room temperature for 3-6 hours to form metal TiO2Performing aging, drying and calcining on the prepolymer solution to finally prepare the hierarchical pore TiO2A material;
the triblock copolymer is Pluronic P123, Pluronic F127 or Pluronic F108;
the biomass material plant tanning agent is a Mazhan acacia tannin extract, a larch tannin extract or myricetin;
hierarchical porous TiO2The preparation method of the material comprises the following steps:
s1, dissolving the triblock copolymer in absolute ethyl alcohol to obtain an ethanol solution of the triblock copolymer; dissolving a biomass material plant tanning agent in distilled water to obtain an aqueous solution of the biomass material plant tanning agent; mixing an ethanol solution of the triblock copolymer with an aqueous solution of a biomass material plant tanning agent at room temperature to obtain a double template;
s2, adding soluble inorganic metal salt of titanium into the double templates of S1, stirring for 3-6 h at room temperature to form metal TiO2A prepolymer solution; the molar ratio of the triblock copolymer to the biomass material plant tanning agent to the soluble inorganic metal salt of titanium is 0.005-0.01: 0.01-0.09: 0.1 to 0.9;
s3, metal TiO2The prepolymer solution is treated in two stages of aging and drying to promote crystal form transformation;
s4, placing the dried crystal in a muffle furnace to be calcined for 240-360 min at 550-650 ℃ to obtain hierarchical-pore TiO2A material.
2. Root of herbaceous plantThe hierarchical porous TiO of claim 12The preparation method of the material is characterized in that the aging condition is aging at 35-45 ℃ for 24-96 h, and the drying condition is drying at 50-70 ℃ for 24-48 h.
3. The hierarchical porous TiO of claim 12The preparation method of the material is characterized in that in S2, the soluble inorganic metal salt of titanium is one of titanium sulfate and titanium chloride.
4. Hierarchical porous TiO prepared by the method according to any one of claims 1 to 32Material characterized by a hierarchical porous TiO2The specific surface area of the material is 32-142 m/g, and the pore diameter is in the range of 1.8-100 nm.
5. The hierarchical porous TiO of claim 42The material is applied to adsorbing lysozyme, bovine serum albumin or bovine hemoglobin.
6. The hierarchical porous TiO of claim 42The application of the material in absorbing protein substances in tanning softening wastewater.
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