CN110465259A - Multi-stage porous TiO2Material, preparation method and its application in adsorbed proteins - Google Patents

Multi-stage porous TiO2Material, preparation method and its application in adsorbed proteins Download PDF

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CN110465259A
CN110465259A CN201910876925.5A CN201910876925A CN110465259A CN 110465259 A CN110465259 A CN 110465259A CN 201910876925 A CN201910876925 A CN 201910876925A CN 110465259 A CN110465259 A CN 110465259A
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porous tio
tio
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titanium
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CN110465259B (en
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强涛涛
宋云颖
朱润桐
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Shaanxi University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents

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Abstract

The invention belongs to multi-stage porous metal oxide materials fields, and in particular to a kind of multi-stage porous TiO2Material, preparation method and its application in adsorbed proteins.The multi-stage porous TiO2Material is using triblock copolymer and a kind of biological material vegetable tanning agent as " double-template ", using the soluble inorganic metal salt of nontoxic, low price titanium as source metal, mild carry out self assembly under conditions of being not necessarily to high temperature hydro-thermal, the conversion for promoting crystal form, forming specific surface area size eventually by calcining is 32~142m2/ g, multi-stage porous TiO of the pore diameter range in 1.8~94nm2Material.The present invention provides a kind of synthetic routes easy to operate, at low cost to prepare multi-stage porous TiO2Material, biggish specific surface area and pore structure abundant can effective adsorbed proteins class large biological molecule, while there is good suction-operated to the protein matter in Bating Process of Leather Making waste water.

Description

Multi-stage porous TiO2Material, preparation method and its application in adsorbed proteins
Technical field
The invention belongs to multi-stage porous metal oxide materials fields, and in particular to a kind of multi-stage porous TiO2Material, preparation side Method and its application in adsorbed proteins.
Background technique
With the development of biotechnology, proteomics is widely used in the fields such as biological medicine, gene diagnosis, and The isolation and purification of protein is the prerequisite of protein scrutiny.Absorption method easy to operate, at low cost is formed by its For the common method of protein separation.Therefore, design it is a kind of can effective adsorbed proteins adsorbent material to protein Isolate and purify and be of great significance.
In recent years, chemistry flourishes with material science, and wherein porous material is by its porosity abundant and adjustable Pore structure and be widely used in the fields such as absorption, catalyst, solar energy system and nano-sensor.According to it is international purely with answer With the definition of chemical combined meeting (IUPAC), porous material is divided into micropore (aperture < 2nm), mesoporous (2~50nm of aperture) and macropore (aperture > 50nm), wherein the mesoporous and large pore material with larger pore size may be implemented to protein-based large biological molecule Effectively absorption and separation.But the aperture size of the mesoporous material synthesized at present is mostly 6nm or so, is not enough to provide albumen The channel of matter mass transfer, and the synthesis process of the mesoporous material with larger pore size (aperture > 10nm) is complex, synthesis Expensive raw material price；The report that synthesis large pore material is used to adsorb large biological molecule is more, and still, simple macroporous structure is deposited again The disadvantages of specific surface area is low, cellular structure is easily collapsed.Therefore, on the one hand big by two kinds of pore structures cleverly compound method Pore structure can promote the mass transfer of large biological molecule, and the specific surface area of material can be improved in one side mesoporous material.
Titanium dioxide (TiO2) it is a kind of semiconductor material haveing excellent performance, there is non-toxic and biocompatibility, it is wide General is applied to field of biomedicine.Template is most common to prepare multi-stage porous TiO2Material, but the multistage reported at present Hole TiO2Material preparation method needs the harsh higher template of hydrothermal condition and price mostly, is unfavorable for large-scale life It produces.Therefore it is simple, at low cost for synthesizing multi-stage porous TiO to develop a kind of preparation condition2The new method of material, to adsorbing separation Large biological molecule has practical significance.
Summary of the invention
The present invention provides a kind of multi-stage porous TiO2Material, preparation method and its application in adsorbed proteins, it is multistage Hole TiO2Material preparation condition is simple, at low cost, and biggish specific surface area can be adsorbed effectively with pore structure abundant Protein-based large biological molecule, while there is good suction-operated to the protein matter in practical Bating Process of Leather Making waste water.
The first purpose of the invention is to provide a kind of multi-stage porous TiO2The preparation method of material, by triblock copolymer Ethanol solution is mixed with the aqueous solution of biological material vegetable tanning agent as double-template, by the soluble inorganic of double-template and titanium gold Belong to salt mixing, 3~6h is stirred at room temperature, forms metal TiO2Prepolymer solution, then by ageing, drying and calcination step, most Obtained multi-stage porous TiO eventually2Material.
Preferably, above-mentioned multi-stage porous TiO2The preparation method of material, aging condition are 35~45 DEG C of 24~96h of ageing, are done Dry condition is 50~70 DEG C of dry 24~48h；The condition of calcining is 550~650 DEG C of 240~360min of calcining.
Preferably, above-mentioned multi-stage porous TiO2The preparation method of material, by the ethanol solution and biomass of triblock copolymer 15~25min is stirred after the aqueous solution mixing of Materials Plant tanning agent, obtains double-template.
Preferably, above-mentioned multi-stage porous TiO2The preparation method of material, comprising the following steps:
Triblock copolymer is dissolved in dehydrated alcohol by S1, obtains the ethanol solution of triblock copolymer；By biomass Materials Plant tanning agent is dissolved in distilled water, obtains the aqueous solution of biological material vegetable tanning agent；By the second of triblock copolymer Double-template is obtained after the aqueous solution mixed at room temperature of alcoholic solution and biological material vegetable tanning agent；
S2 the inorganic metal salt of titanium is added in the double-template of S1, and 3~6h is stirred at room temperature, and forms metal TiO2Performed polymer Solution；
S3, metal TiO2Aged and dry two phase process of prepolymer solution, promote crystal habit transformation；
Crystal after drying is placed in Muffle furnace and calcines by S4, obtains multi-stage porous TiO2Material.
Preferably, above-mentioned multi-stage porous TiO2The preparation method of material, in S1, the triblock copolymer is pluronic (Pluronic) series copolymer, the series copolymer is mainly by polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO- PEO) three block is constituted；Being specifically chosen Pluronic P123, (polyethylene oxide-polypropylene oxide-polyethylene oxide three block is total Polymers), Pluronic F127 or Pluronic F108, the structural unit of these three polymer be it is identical, but PEO chain and The number of PPO chain is different.
Preferably, above-mentioned multi-stage porous TiO2The preparation method of material, in S1, the biological material vegetable tanning agent is horse Account for one of yearning between lovers tannin extract (BA tannin extract), larch extract, Baybery tannin.
Preferably, above-mentioned multi-stage porous TiO2The preparation method of material, in S2, the soluble inorganic metal salt of the titanium is sulphur One of sour titanium, titanium chloride.
Preferably, above-mentioned multi-stage porous TiO2The preparation method of material, in S1~S2, triblock copolymer, biological material Vegetable tanning agent, titanium soluble inorganic metal salt molar ratio be 0.005~0.01:0.01~0.09:0.1~0.9.
A second object of the present invention is to provide a kind of multi-stage porous TiO of above method preparation2Material, multi-stage porous TiO2Material Material specific surface area is 32~142m2/ g, pore diameter range is in 1.8~100nm.
Third object of the present invention is to provide a kind of multi-stage porous TiO of above method preparation2Material absorption lysozyme, Application in bovine serum albumin or bovine hemoglobin.
Fourth object of the present invention is to provide a kind of multi-stage porous TiO of above method preparation2Material is adsorbing The application of protein matter in Bating Process of Leather Making waste water.
Compared with prior art, a kind of multi-stage porous TiO provided by the invention2Material, preparation method and its in adhesion protein Application in matter, at least has the advantages that
1. being made in conjunction with traditional template triblock copolymer for preparing mesoporous material using biological material vegetable tanning agent For double-template, prepared by simple one-pot synthesis method with micropore-mesopore-macroporous structure multi-stage porous TiO2Material.
2. the present invention uses the soluble inorganic metal salt of titanium for source metal, organic alkoxide, the chlorine of common titanium are avoided The problem that price existing for titanium oxide is high, toxicity is big.
Multi-stage porous TiO obtained by 3.2Material can effectively adsorb lysozyme, bovine serum albumin, bovine hemoglobin, Adsorption capacity is respectively up to 42.1~42.9mg/g, 26.2~26.9mg/g, 160.1~165.7mg/g, to practical Bating Process of Leather Making Protein matter in waste water has certain adsorption capacity, and the absorbance of protein matter is substantially reduced in waste water after absorption.
Detailed description of the invention
Fig. 1 is that embodiment 1 synthesizes multi-stage porous TiO2The TEM spectrogram of material；
Fig. 2 is that embodiment 2 synthesizes multi-stage porous TiO2The XRD spectra of material；
Fig. 3 is that embodiment 3 synthesizes multi-stage porous TiO2The nitrogen adsorption desorption isotherm and pore size distribution figure of material；
Fig. 3 A is multi-stage porous TiO2The pore size distribution figure of solid material, Fig. 3 B are multi-stage porous TiO2Solid material nitrogen is inhaled Attached desorption isotherm；
Fig. 4 is that embodiment 4 synthesizes multi-stage porous TiO2The SEM spectrogram of material；
Fig. 5 is that embodiment 1 synthesizes multi-stage porous TiO2The adsorption effect figure of the material to lysozyme；
Fig. 6 is that embodiment 1 synthesizes multi-stage porous TiO2The adsorption effect figure of the material to bovine serum albumin；
Fig. 7 is that embodiment 1 synthesizes multi-stage porous TiO2The adsorption effect figure of the material to Bating Process of Leather Making waste water protein matter.
Specific embodiment
In order to enable those skilled in the art to more fully understand, technical solution of the present invention is practiced, below with reference to specific The invention will be further described for embodiment and attached drawing.Actual conditions are not specified in following embodiments and foregoing invention content Test method, according to conventional methods in the art with condition carry out.
Experimental method and detection method described in following each embodiments, unless otherwise specified, be conventional method or by According to condition proposed by each reagent manufacturer；The reagent and material are commercially available on the market unless otherwise specified.Under It states in embodiment test, Bating Process of Leather Making waste water used is provided by Hebei Dongming Leather Tannery Co., Ltd.
Embodiment 1
A kind of multi-stage porous TiO2The preparation method of material, comprising the following steps:
It weighs 1.00g triblock copolymer P123 (Pluronic P123) to be dissolved in 20mL ethanol solution, weigh 1.1638g BA tannin extract (Acacia mangiumwilld tannin extract) is dissolved in 30mL distilled water, by the ethanol solution and BA of Pluronic P123 The aqueous solution of tannin extract mixes, and 2.29g Ti (SO is added after 20min is stirred under air4)2, continue to stir 3h, then turn solution It moves in culture dish, is transferred to drying in 60 DEG C of baking ovens after ageing 48h in 40 DEG C of baking ovens and for 24 hours, promotes metal TiO2Self assembly, By the TiO after drying2/ organic formwork compound crystal solid is transferred in corundum crucible, 550 DEG C of high-temperature calcinations in Muffle furnace 240min obtains multi-stage porous TiO2Solid material.
The multi-stage porous TiO that embodiment 1 synthesizes2TEM spectrogram as shown in Figure 1, can clearly observe implementation from figure There is the porous structure (Fig. 1 light-colored part) for being distributed relatively uniform different sizes in the sample that example 1 synthesizes.These pore structures On the one hand it is the biggish hole due to polymerization accumulation and generation between particle, is on the other hand after triblock copolymer is calcined in hole Wall generates lesser meso-hole structure.
Embodiment 2
Multi-stage porous TiO provided in this embodiment2The method of solid material is substantially the same manner as Example 1, and difference is horse Not furnace calcination temperature is 650 DEG C.The multi-stage porous TiO that embodiment 2 synthesizes2The XRD spectra of solid material is as shown in Fig. 2, from figure As can be seen that the XRD spectra of 2 synthetic sample of embodiment has a sharp and apparent diffraction maximum at 2 θ=25.3 °, correspond to Anatase TiO2(101) crystal face, it was demonstrated that synthesized multi-stage porous TiO2Crystallinity with higher；In 2 θ=38.1 °, 48.1 °, There is weaker diffraction maximum at 53.9 °, 55.1 °, 62.5 °, 68.7 °, 70.3 ° and 75.1 °, corresponds respectively to anatase TiO2 (004), (200), (105), (211), (204), (116), (220) and (215) crystal face.
Embodiment 3
Multi-stage porous TiO provided in this embodiment2The method of solid material is same as Example 2, and difference is BA tannin extract It is dosage is 1.9397g.The multi-stage porous TiO that embodiment 3 synthesizes2The pore size distribution figure of solid material is as shown in Figure 3A, figure 3B is multi-stage porous TiO2Solid material nitrogen adsorption desorption isotherm.It can be seen from the figure that the multi-stage porous that embodiment 3 synthesizes TiO2Thermoisopleth belong to typical IV class thermoisopleth and there is H3 type hysteresis loop, this be by nitrogen molecule in mesoporous Caused by capillary condensation phenomenon, it was demonstrated that synthesized multi-stage porous TiO2There are meso-hole structures in solid material sample, while (p/p under lower relative pressure0< 0.05) adsorption capacity sharply increases under, it was demonstrated that there are microcellular structures for synthesized sample.Hole Size distribution plot proves the TiO that embodiment 3 synthesizes2Exist simultaneously micropore and meso-hole structure.
Embodiment 4
Multi-stage porous TiO provided in this embodiment2The method of solid material is substantially the same manner as Example 2, and difference is BA The dosage of tannin extract is 0.3879g.The multi-stage porous TiO that embodiment 4 synthesizes2The SEM spectrogram of solid material is as shown in figure 4, from figure As can be seen that the multi-stage porous TiO synthesized in embodiment 42Solid material has the pore structure of different sizes, it was demonstrated that multi-stage porous The TiO of structure2Successfully synthesize through the invention.
It should be noted that the multi-stage porous TiO that above-described embodiment 1~4 synthesizes2Material has carried out SEM, TEM, XRD, nitrogen Gas adsorption/desorption isotherms, pore size distribution analysis, XRD spectra proof have been successfully prepared anatase TiO2Crystal, nitrogen are inhaled Attached desorption isotherm and pore size distribution figure prove synthesized TiO2Material has meso-hole structure, and average mesopore aperture size Size is that 15~25nm, SEM and TEM spectrogram prove synthesized TiO2There are macroporous structures for material.A series of structural characterization Means prove that the TiO with hierarchical porous structure can successfully be prepared by this method2Material.
Embodiment 5
It weighs 0.005mol triblock copolymer Pluronic F127 to be dissolved in 20mL ethanol solution, weighs 0.01mol Larch extract is dissolved in 30mL distilled water, and the aqueous solution of the ethanol solution of Pluronic F127 and larch extract is mixed It closes, 0.9mol TiCl is added after 20min is stirred under air4, continue to stir 6h, then solution is transferred in culture dish, in It is transferred in 50 DEG C of baking ovens dry 48h after being aged 96h in 35 DEG C of baking ovens, promotes metal TiO2Self assembly, by the TiO after drying2/ Organic formwork compound crystal solid is transferred in corundum crucible, and 600 DEG C of high-temperature calcination 360min, obtain multistage in Muffle furnace Hole TiO2Solid material.
Embodiment 6
It weighs 0.01mol triblock copolymer Pluronic F108 to be dissolved in 20mL ethanol solution, weighs 0.05mol Baybery tannin is dissolved in 30mL distilled water, and the aqueous solution of the ethanol solution of Pluronic F108 and Baybery tannin is mixed, in 0.5mol Ti (SO is added after stirring 25min under air4)2, continue to stir 4h, then solution is transferred in culture dish, in 45 It is aged in DEG C baking oven and is transferred in 70 DEG C of baking ovens dry 36h afterwards for 24 hours, promote metal TiO2Self assembly, by the TiO after drying2/ have Machine template composite crystalline solids are transferred in corundum crucible, and 550 DEG C of high-temperature calcination 360min, obtain multi-stage porous in Muffle furnace TiO2Solid material.
Embodiment 7
It weighs 0.007mol triblock copolymer P123 to be dissolved in 20mL ethanol solution, it is molten to weigh 0.05mol BA tannin extract Solution mixes the aqueous solution of the ethanol solution of P123 and BA tannin extract in 30mL distilled water, is added after stirring 15min under air 0.1mol Ti(SO4)2, continue to stir 4h, then solution be transferred in culture dish, is aged in 40 DEG C of baking ovens and shifts afterwards for 24 hours Into 50 DEG C of baking ovens, drying for 24 hours, promotes metal TiO2Self assembly, by the TiO after drying2/ organic formwork composite solids are transferred to In corundum crucible, 550 DEG C of high-temperature calcination 240min in Muffle furnace obtain multi-stage porous TiO2Solid material.
In addition to this, the multi-stage porous TiO that we are also prepared the present invention2Solid material has carried out adsorption applications reality It tests:
1) to the multi-stage porous TiO of the above embodiment of the present invention synthesis2Solid material has carried out lysozyme adsorption experiment:
Using the lysozyme soln of the pH 500 μ g/mL of PBS buffer preparation for being 5, the multistage of the synthesis of embodiment 1 is weighed Hole TiO2Material 0.2g is mixed with the above-mentioned lysozyme soln of 20mL, makes TiO2Solid material adsorbed proteins, Fig. 5 are the conjunction of embodiment 1 At multi-stage porous TiO2Material is to the adsorption effect figure of lysozyme, and after adsorbing 720min, the adsorption rate of lysozyme is 95.8%, inhales Attached capacity is 42.5mg/g.In addition, the multi-stage porous TiO of our Examples 2~72Material, and bacteriolyze is carried out referring to the above method Enzyme adsorption experiment, the results show that after adsorbing 720min, the adsorption capacity of 2~7 lysozyme of embodiment be respectively 42.5mg/g, 42.9mg/g、42.9mg/g、42.7mg/g、42.8mg/g、42.1mg/g。
2) to the multi-stage porous TiO of the above embodiment of the present invention synthesis2Solid material has carried out bovine serum albumin adsorption experiment:
Using the bovine serum albumen solution of the pH 500 μ g/mL of PBS buffer preparation for being 4.5, the synthesis of embodiment 1 is weighed Multi-stage porous TiO2Material 0.2g is mixed with the above-mentioned bovine serum albumen solution of 20mL, makes TiO2Solid material adsorbed proteins, Fig. 6 Multi-stage porous TiO is synthesized for embodiment 12Material is to the adsorption effect figure of bovine serum albumin, after adsorbing 720min, bovine serum albumin Adsorption rate be 62%, adsorption capacity 26.2mg/g.In addition, the multi-stage porous TiO of our Examples 2~72Material, and join Bovine serum albumin adsorption experiment is carried out according to the above method, the results show that after adsorbing 720min, 2~7 bovine serum albumin of embodiment Adsorption capacity be respectively 26.4mg/g, 26.3mg/g, 26.9mg/g, 26.5mg/g, 26.2mg/g, 26.9mg/g.
3) using the bovine hemoglobin solution of the pH 500 μ g/mL of PBS buffer preparation for being 4.5, the conjunction of embodiment 1 is weighed At multi-stage porous TiO2Material 0.2g is mixed with the above-mentioned bovine serum albumen solution of 20mL, makes TiO2Solid material adsorbed proteins 360min, the adsorption rate of bovine hemoglobin reach 100%, adsorption capacity 163.9mg/g.In addition, our Examples 2~7 Multi-stage porous TiO2Material, and bovine serum albumin adsorption experiment is carried out referring to the above method, the results show that as absorption 360min Afterwards, the adsorption capacity of 2~7 bovine serum albumin of embodiment is respectively 160.1mg/g, 165.7mg/g, 163.0mg/g, 165.1mg/ g、162.4mg/g、162.5mg/g。
4) the multi-stage porous TiO that the above embodiment of the present invention 1 is synthesized2Solid material has carried out albumen in Bating Process of Leather Making waste water The adsorption experiment of substance:
Bating Process of Leather Making waste water filtering is removed into filter residue, takes 20mL filtrate spare, weighs the multi-stage porous synthesized in embodiment 1 TiO2Material 0.2g is placed in 6h in the above-mentioned filtered Bating Process of Leather Making waste water of 20mL, from figure 7 it can be seen that egg in softening waste water The a length of 602nm of the maximum absorption wave of white matter, the absorbance of protein material (takes maximum absorption wave in Bating Process of Leather Making waste water after absorption The absorbance value of strong point) from the 2.1Abs before absorption it is reduced to 1.6Abs.Due to the protein matter master in Bating Process of Leather Making waste water It will be in the wavelength absorption, so the reduction of absorbance qualitative can reflect before and after adsorption experiment: by multi-stage porous TiO2Material After absorption, the protein matter content in Bating Process of Leather Making waste water is reduced.
It should be noted that involved in claims of the present invention when numberical range, it is thus understood that each numberical range Any one numerical value can be selected between two endpoints and two endpoints, repeat in order to prevent, the present invention describes preferably Embodiment, once a person skilled in the art knows basic creative concepts, then can make in addition to these embodiments Change and modification.So it includes preferred embodiment and the institute for falling into the scope of the invention that the following claims are intended to be interpreted as Have altered and modifies.Obviously, various changes and modifications can be made to the invention without departing from this hair by those skilled in the art Bright spirit and scope.In this way, if these modifications and changes of the present invention belongs to the claims in the present invention and its equivalent technologies Within the scope of, then the present invention is also intended to include these modifications and variations.

Claims (10)

1. a kind of multi-stage porous TiO2The preparation method of material, which is characterized in that by the ethanol solution and biomass of triblock copolymer The aqueous solution mixing of Materials Plant tanning agent is used as double-template, double-template is mixed with the soluble inorganic metal salt of titanium, room temperature is stirred 3~6h is mixed, metal TiO is formed2Multi-stage porous TiO is finally made then by ageing, drying and calcination step in prepolymer solution2 Material.
2. multi-stage porous TiO according to claim 12The preparation method of material, which is characterized in that aging condition is 35~45 DEG C ageing 24~96h, dry condition is 50~70 DEG C of dry 24~48h；The condition of calcining be 550~650 DEG C calcining 240~ 360min。
3. multi-stage porous TiO according to claim 12The preparation method of material, which comprises the following steps:
Triblock copolymer is dissolved in dehydrated alcohol by S1, obtains the ethanol solution of triblock copolymer；By biological material Vegetable tanning agent is dissolved in distilled water, obtains the aqueous solution of biological material vegetable tanning agent；The ethyl alcohol of triblock copolymer is molten Double-template is obtained after the aqueous solution mixed at room temperature of liquid and biological material vegetable tanning agent；
S2 the soluble inorganic metal salt of titanium is added in the double-template of S1, and 3~6h is stirred at room temperature, and forms metal TiO2Performed polymer Solution；
S3, metal TiO2Aged and dry two phase process of prepolymer solution, promote crystal habit transformation；
Crystal after drying is placed in Muffle furnace and calcines by S4, obtains multi-stage porous TiO2Material.
4. multi-stage porous TiO according to claim 32The preparation method of material, which is characterized in that in S1, the three block Copolymer is pluronic series copolymer, is made of polyoxyethylene-poly-oxypropylene polyoxyethylene three block.
5. multi-stage porous TiO according to claim 32The preparation method of material, which is characterized in that in S1, the biomass Materials Plant tanning agent is one of Acacia mangiumwilld tannin extract, larch extract, Baybery tannin.
6. multi-stage porous TiO according to claim 32The preparation method of material, which is characterized in that in S2, the titanium it is solvable Property inorganic metal salt be one of titanium sulfate, titanium chloride.
7. multi-stage porous TiO according to claim 32The preparation method of material, which is characterized in that in S1~S2, three block is total Polymers, biological material vegetable tanning agent, titanium soluble inorganic metal salt molar ratio be 0.005~0.01:0.01~ 0.09:0.1~0.9.
8. the multi-stage porous TiO of any method preparation according to claim 1~72Material, which is characterized in that multi-stage porous TiO2 Material specific surface area is 32~142m2/ g, pore diameter range is in 1.8~100nm.
9. multi-stage porous TiO according to claim 82Material is in absorption lysozyme, bovine serum albumin or bovine hemoglobin Application.
10. multi-stage porous TiO according to claim 82Protein matter of the material in absorption Bating Process of Leather Making waste water is answered With.
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