CN1762828A - Mesoporous nanopowder titanium dioxide bionic synthesis method - Google Patents
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Abstract
The bionic process of synthesizing mesoporous nanometer TiO2 powder belongs to the field of nanometer material technology. Biological surfactant is fermented in water solution and emulsified to form emulsion A; inorganic solution containing Ti ion is dropped into emulsion A to obtain solution B; the pH value of solution B is regulated to 7-9 to obtain emulsion C; and the precipitate is water washed, alcohol washed, calcined at 300-600 deg.c in a calcining furnace for 1-2 hr to eliminate biological surfactant template and obtain anatase-type mesoporous nanometer TiO2 powder, and further heated at 600-700 deg.c for 1-2 hr to obtain rutile-type mesoporous nanometer TiO2 powder. The present invention synthesizes mesoporous nanometer TiO2 powder by using the cheap natural biological surfactant and the mineralizing deposition process and has simple technological process, low cost and no pollution, and the product has spherical form, narrow size diameter distribution, high dispersivity and high activity.
Description
Technical field
The present invention relates to a kind of low-cost high reactivity mesoporous nano powder body TiO
2Biomimetic synthesis method, belong to technical field of nano material.
Background technology
The mesoporous TiO of nano level
2Nontoxic because of having, chemistry and Heat stability is good, good electrical property and special photocatalysis performance and absorption property, and be widely used in the photocatalyst of high-concentration hardly-degradable technology for treating industrial waste water, also can be used for solar cell material and catalytic material, also can be used for the high-performance electronic pottery.Studies have shown that the nano-TiO of biomimetic method preparation
2, the particle radius narrowly distributing does not have and reunites, and the particle mean size of anatase octahedrite is 8-20nm, and BET is up to 280m
2/ g, active high, just can become the rutile particles that particle diameter is the 25-100nm scope fully mutually at 700 ℃, no matter be anatase octahedrite or rutile, structure hole is all arranged on the particle, its mesoporous mean sizes is 3-15nm, sees transmission electron microscope photo Fig. 3 and Fig. 4.TiO with meso-hole structure
2Active height by the nanometer package technique, can be expanded its wavelength response range, improves solar energy utilization ratio, develops to have high quantum production rate, can be by visible light in the solar spectrum even infrared ray excited high efficiency semiconductor catalyzer.Present preparation method has sol-gel method, chemical precipitation method, hydrothermal method, template etc., but the TiO of existing method preparation
2Particle agglomeration is serious, and is active low, complicated process of preparation and cost height, and effect is relatively poor, is difficult to apply.Therefore how to prepare low-cost highly active mesoporous TiO
2Nano-powder is a new problem of this area.
Summary of the invention
In order to solve the problems referred to above that prior art exists, the invention provides a kind of mesoporous nano powder body TiO
2Biomimetic synthesis method, make highly active mesoporous TiO with lower cost
2Nano powder.
The present invention utilizes the natural biological tensio-active agent to be template, with the raw material that contains Ti, carries out the biomineralization deposition under mild conditions, and the bionic nano assembling forms organic-inorganic composite material, removes organic formwork at last, makes highly active mesoporous TiO
2Nano powder.
Mesoporous nano powder body TiO of the present invention
2Biomimetic synthesis method, step is as follows:
(1) with bio-surfactant in the aqueous solution, fermenting under the normal temperature and pressure, form the ball silk yeast water solution of bio-surfactant, add sugared auxiliary agent 0-0.1g/L, stir room temperature emulsification 20-60 minute.Form the emulsion A of micelle-forming concentration.
Bio-surfactant is synthetic by carrying out the self-assembly template, utilizes himself peculiar circle or elliptical erythrocyte structure, forms the emulsion A of micelle-forming concentration.The circle of emulsion or elliptical erythrocyte structure are referring to microphotograph Fig. 1.
(2) under the effect of magnetic agitation, will contain Ti
4+Inorganic solution, the rate of addition that drips by per minute 2-10 is added in the above-mentioned emulsion liquid A, allows Ti
4+Can fully be adsorbed onto on the negatively charged ion group of biologically active agent cell surface TiO
2Content is controlled at 50-120g/L (TiO
2Content is for containing Ti
4+Inorganic salt solution convert), after the normal temperature lower magnetic force stirs 0.5-1 hour, must solution B.
Examine under a microscope inorganic salt positively charged ion Ti
4+Be adsorbed on the situation on the cell walls, microphotograph is referring to Fig. 2.
(3) speed of under the room temperature ammoniacal liquor being dripped by per minute 1-5 is added drop-wise in the above-mentioned B solution, regulates PH=7-9, continues to stir 2-3h, allows the abundant mineralising of cellularstructure of bio-surfactant precipitate, and obtains emulsion C.
(4) emulsion C is left standstill 1-2h, with throw out washing 2 times, alcohol is washed 2 times, removes NH then
4+And Cl
-And H
2O.
(5) will wash and the throw out of alcohol after washing at 60-80 ℃ of dry 2-3h, again dried throw out is heat-treated, in calcining furnace, be warmed up to 300-600 ℃, remove the bio-surfactant template with speed less than 10 ℃/min, behind the insulation 1-2h, promptly obtain mesoporous anatase TiO
2Nano-powder (XRD figure is composed as shown in Figure 5) obtains mesoporous rutile TiO behind 600-700 ℃ of insulation 1-2h
2Nano-powder (XRD figure is composed as shown in Figure 6).
The raw material of the above-mentioned Ti of containing is selected from one of titanium sulfate, chloric acid titanium, Titanium Nitrate, citric acid titanium, titanium hydroxide or titanium oxide or combination.
Bio-surfactant is that contract ammonia system, phosphatide system, fatty acid series, protein of glycolipid system, acyl group is one of tensio-active agent or combination, and add-on is 1-10 a times of its micelle-forming concentration.
Above-mentioned glycolipid is that bio-surfactant is generally rhamnolipid, marine alga glycolipid, sophorolipid etc., and sophorolipid is that ball silk yeast or candiyeast produce when cultivating in glucose and normal paraffin or longer chain fatty acid; The acyl group ammonia that contracts is that bio-surfactant is generally the product by microbial culture such as Bacillus subtilus; Phosphatide is that bio-surfactant is generally Yelkin TTS or by phosphatide of sulphur bacteria fermentation culture etc.; The fatty acid series bio-surfactant is generally and covers mycolic acid or the acid of mould spore etc.; Protein is that bio-surfactant is generally gelatin or with the condenses of collagenic protein hydrolysate and arginine reaction etc.
Adopt the inventive method, gordian technique is when removing the bio-surfactant template, the subsiding of formed meso-hole structure, and reactant concn is high more, and mesoporous ball wall is thick more, and vice versa.The thermal treatment heat-up rate of removing biological template should be controlled＜10 ℃/min.In addition, the kind of bio-surfactant and consumption have significant effects to the formation of meso-hole structure and the size shape in hole.
Compared with prior art, the excellent results of the inventive method just is to use cheap natural biological tensio-active agent, utilizes biological nanometer multilayer vesicle structure and mineralising deposition process, synthesising mesoporous TiO under the condition of gentleness
2Nano powder, particle is subsphaeroidal, and particle size distribution range is narrow, and dispersion effect is good, and active high, preparation technology is simple, and cost is low, and is pollution-free.Anatase octahedrite TiO
2Particle mean size be 8-20nm, its mesoporous mean sizes is 3-15nm, specific surface area (BET) is up to 280m
2/ g, the difficult for biological degradation oxygen-consumption (COD) of photocatalytic degradation high-concentration hardly-degradable paper waste has reduced by 80.3%, and percent of decolourization reaches 99%.Mesoporous anatase just can become the mesoporous rutile of nano level mutually at 650 ℃, and the degree of crystallinity of 700 ℃ of rutile is 99.95%, and particle size is 25-100nm, and specific surface area (BET) is up to 112m
2/ g.Cost is about below 50% of additive method.The mesoporous TiO of this nano level
2Can be used for photocatalyst, solar cell, electronic ceramics, matrix material, ultraviolet shielded material of nanometer assembled material, high-concentration hardly-degradable trade effluent etc.
Description of drawings
Fig. 1 is that glycolipid is the optical microscope photograph (400 times) of the circular or oval ball silk yeast cell structure of bio-surfactant sophorolipid emulsion among the embodiment 2.
Fig. 2 is inorganic salt positively charged ion Ti among the embodiment 2
4+Be adsorbed on the optical microscope photograph (400 times) on the sophorolipid ball silk yeast cells wall.
Fig. 3 is the transmission electron microscope photo (270,000 times) of anatase octahedrite after 500 ℃ of calcinings among the embodiment 2.
Fig. 4 is the transmission electron microscope photo (100,000 times) of rutile after 700 ℃ of calcinings among the embodiment 2.
Fig. 5 is the X ray diffracting spectrum of anatase octahedrite after 500 ℃ of calcinings among the embodiment 2, and ordinate zou is a diffracted intensity, and X-coordinate is a diffraction angle.
Fig. 6 is the X ray diffracting spectrum of rutile after 700 ℃ of calcinings among the embodiment 2, and ordinate zou is a diffracted intensity, and X-coordinate is a diffraction angle.
Embodiment
Embodiment 1.
With the glycolipid of the 6.7g/L (micelle-forming concentration) of 150ml be bio-surfactant sophorolipid ball silk yeast water solution at room temperature sugaring 0.5g stir, emulsification 20 minutes, obtain emulsion A, then, with the Ti (SO of the 0.4mol/L of 50ml
4)
2Solution is added drop-wise among the emulsion A with the speed of 10 of per minutes, continues magnetic agitation 30 minutes, allows Ti
4+Can be adsorbed on fully in the nanometer vesicle structure of biomass cells.Slowly drip 1mol/L ammoniacal liquor with 5 speed of per minute, until PH=7, continue magnetic agitation 2h, allow cellularstructure part mineralising deposition, leave standstill 2h then, high speed centrifugation separates, washing, alcohol wash each twice, remove SO
4 2-And NH
4 +And H
2O.At last with throw out in loft drier 80 ℃ the oven dry 2h after, with the heat-up rate of 5 ℃/min,, divide other mesoporous anatase and mesoporous rutile respectively at 400 ℃ and 700 ℃ of thermal treatment 2h.Its anatase octahedrite TiO
2Particle size be 10-25nm, its mesoporous mean sizes is 3-11nm, BET is up to 220m
2/ g.The particle size of rutile is 52-120nm, and BET is up to 62m
2/ g.
Embodiment 2.
With the glycolipid of the 6.7g/L (micelle-forming concentration) of 100ml is bio-surfactant sophorolipid ball silk yeast water solution sugaring 0.5g at room temperature, and the emulsion A. of stirring and emulsifying after 20 minutes is with the 0.5mol/L TiCl of 50ml
4Solution is added drop-wise among the emulsion A with the speed of 10 of per minutes, continues magnetic agitation 30 minutes, allows Ti
4+Can be adsorbed on fully in the nanometer vesicle structure of biomass cells.Slowly drip 1mol/L ammoniacal liquor with 5 speed of per minute, until PH=7, continue magnetic agitation 2h, allow the abundant mineralising deposition of cellularstructure, leave standstill 2h then, high speed centrifugation separates, washing, alcohol wash each twice, remove Cl
-And NH
4 +And H
2O.At last with throw out in loft drier behind 80 ℃ of oven dry 2h, with the heat-up rate of 5 ℃/min, respectively at 500 ℃ and 700 ℃ of thermal treatment 2h, respectively must mesoporous anatase and mesoporous rutile.Its anatase octahedrite TiO
2Particle mean size be 8-20nm, its mesoporous mean sizes is 3-15nm, BET is up to 280m
2/ g, the particle mean size of rutile is 25-100nm, BET is up to 112m
2/ g.
Embodiment 3.
As described in embodiment 1, different is that heat treated heat-up rate is 10 ℃/min, and thermal treatment temp is 450 ℃ and 750 ℃.Its anatase octahedrite TiO
2Particle size be 12-31nm, its mesoporous mean sizes is 5-13nm, BET is up to 180m
2/ g.The particle size of rutile is 62-110nm, and BET is up to 56m
2/ g.
Embodiment 4.
As described in embodiment 2, different is that heat treated heat-up rate is 10 ℃/min, and thermal treatment temp is 450 ℃ and 750 ℃.Its anatase octahedrite TiO
2Particle mean size be 8-25nm, its mesoporous mean sizes is 4-10nm, BET is up to 250m
2/ g, the particle mean size 29-110nm of rutile, BET is up to 102m
2/ g.
Embodiment 5.
As described in embodiment 2, different is that bio-surfactant is that phosphatide is bio-surfactant Yelkin TTS, and its concentration is 0.0014g/L, but not sugaring.Its anatase octahedrite TiO
2Particle mean size be 18-70nm, its mesoporous mean sizes is 3-10nm,, the particle mean size of rutile is 85-180nm.
Embodiment 6. is as described in the embodiment 1, and different is that bio-surfactant is the acid of mould spore.
Embodiment 7. is as described in the embodiment 1, and different is that bio-surfactant is a gelatin.
Claims (7)
1. mesoporous nano powder body TiO
2Biomimetic synthesis method, it is characterized in that step is as follows:
(1) with bio-surfactant in the aqueous solution, fermenting under the normal temperature and pressure, form the ball silk yeast water solution of bio-surfactant, add sugared auxiliary agent 0-0.1g/L, stir, room temperature emulsification 20-60 minute forms the emulsion A of micelle-forming concentration;
(2) under the effect of magnetic agitation, will contain Ti
4+Inorganic solution, the rate of addition that drips by per minute 2-10 is added in the above-mentioned emulsion liquid A, allows Ti
4+Can fully be adsorbed onto on the negatively charged ion group of biologically active agent cell surface TiO
2Content is controlled at 50～120g/L, and the normal temperature lower magnetic force stirred after 0.5～1 hour, got solution B;
(3) speed of under the room temperature ammoniacal liquor being dripped by per minute 1-5 is added drop-wise in the above-mentioned B solution, regulates PH=7-9, continues to stir 2-3h, allows the abundant mineralising of cellularstructure of bio-surfactant precipitate, and obtains emulsion C;
(4) emulsion C is left standstill 1-2h, with throw out washing 2 times, alcohol is washed 2 times, removes NH respectively then
4+And Cl
-Or H
2O;
(5) will wash and the throw out of alcohol after washing at 60-80 ℃ of dry 2-3h, again dried throw out is heat-treated, in calcining furnace, be warmed up to 300-600 ℃, remove the bio-surfactant template with speed less than 10 ℃/min, behind the insulation 1-2h, promptly obtain mesoporous anatase TiO
2Nano-powder obtains mesoporous rutile TiO behind 600-700 ℃ of insulation 1-2h
2Nano-powder.
2. mesoporous nano powder body TiO as claimed in claim 1
2Biomimetic synthesis method, it is characterized in that, the raw material of the described Ti of containing be selected from one of titanium sulfate, chloric acid titanium, Titanium Nitrate, citric acid titanium, titanium hydroxide or titanium oxide or the combination.
3. mesoporous nano powder body TiO as claimed in claim 1
2Biomimetic synthesis method, it is characterized in that described bio-surfactant is that contract ammonia system, phosphatide system, fatty acid series, protein of glycolipid system, acyl group is one of tensio-active agent or combination, add-on is 1-10 a times of its micelle-forming concentration.
4. mesoporous nano powder body TiO as claimed in claim 1
2Biomimetic synthesis method, it is characterized in that described glycolipid is that bio-surfactant is rhamnolipid, marine alga glycolipid or sophorolipid, wherein sophorolipid is that ball silk yeast or candiyeast produce when cultivating in glucose and normal paraffin or longer chain fatty acid.
5. mesoporous nano powder body TiO as claimed in claim 1
2Biomimetic synthesis method, it is characterized in that described phosphatide is that bio-surfactant is a Yelkin TTS or by the phosphatide of sulphur bacteria fermentation culture.
6. mesoporous nano powder body TiO as claimed in claim 1
2Biomimetic synthesis method, it is characterized in that described fatty acid series bio-surfactant is for covering mycolic acid or the acid of mould spore.
7. mesoporous nano powder body TiO as claimed in claim 1
2Biomimetic synthesis method, it is characterized in that described protein is that bio-surfactant is a gelatin or with the condenses of collagenic protein hydrolysate and arginine reaction.
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