CN103908979A - Supported nano TiO2 catalyst and preparation method thereof - Google Patents
Supported nano TiO2 catalyst and preparation method thereof Download PDFInfo
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- CN103908979A CN103908979A CN201410142954.6A CN201410142954A CN103908979A CN 103908979 A CN103908979 A CN 103908979A CN 201410142954 A CN201410142954 A CN 201410142954A CN 103908979 A CN103908979 A CN 103908979A
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Abstract
The invention discloses a supported nano TiO2 catalyst and a preparation method of the supported nano TiO2 catalyst. The preparation method comprises the following steps: firstly carrying out certain pretreatment on bacterial cellulose prepared by a dynamic fermentation method, by utilizing rich polyhydroxyl groups and a directionally-distributed water molecule layer on the surface of the bacterial cellulose, enabling the titanium dioxide precursor comprising chlorate, sulfate and organic complex and the like to be directionally hydrolyzed on the surface of the bacterial cellulose by a hydrothermal method, and finally preparing the supported nano TiO2 catalyst by dewatering. The supported nano TiO2 catalyst prepared by the invention has the advantages that the preparation process is simple, the cost is low, the reaction condition is mild, the shape of a product is controllable and the specific surface area is large and the like, and can be widely applied in the fields such as photocatalysis, optical devices and proton exchange membrane fuel cells.
Description
Technical field
The invention belongs to new type water thermal synthesis field, be specifically related to a kind of loaded nano TiO
2catalysts and its preparation method.
Background technology
Nano-metal-oxide catalyst has very large specific area, due to small-size effect, skin effect, quantum size effect and macro quanta tunnel effect etc., show physics, the chemistry and biology characteristic of the not available novelty of conventional material, there is good performance and application in fields such as solar energy conversion, battery, catalysis, sensings, thereby studied widely.
In various nano-metal-oxide catalyst, TiO
2there is highlight catalytic active, biological and chemical inertia, the feature such as resistance to corrosion is strong, therefore, TiO
2be considered to very promising material and be used to basis and real application research.Nano-TiO
2the preparation method of catalyst mainly produces by salting liquid or organic coordination compound presoma.Conventional method is divided into coprecipitation, sol-gel process, hydrothermal synthesis method etc.But conventional method exists the easy inactivation of catalyst, easily cohesion, the difficult shortcoming reclaiming.Catalyst immobilization is prepared to loaded nano TiO
2catalyst both can solve a difficult problem for separation and recovery of catalyst, can also overcome suspended phase poor catalyst stability and easy poisoning shortcoming, was also the desirable approach that the various functions of application of active component and carrier combine to design catalytic reactor.Loaded nano TiO
2the carrier of catalyst, conventional have glass cloth, active carbon, refractory brick, the grains of sand, hollow glass bead, pottery, a silica gel etc.Adopt examples of such carriers to carry out the fixing of catalyst, can cause suction-operated and the extinction Efficiency Decreasing of catalyst, thereby reduce catalyst activity.
Summary of the invention:
The object of the present invention is to provide a kind of support type to receive TiO
2catalysts and its preparation method.
The technical solution that realizes the object of the invention is: described loaded nano TiO
2catalyst as biological template, slowly adds TiO 2 precursor with bacteria cellulose under water inhibitor and precipitating reagent effect, by hydrothermal synthesis method, specifically comprises the following steps:
The first step, will join heat treated in aqueous slkali after the rinsing of hygrometric state bacteria cellulose, then neutralizes with acid solution, then with deionized water washing until neutral;
Second step, the ethanolic solution that first step products therefrom is placed in respectively to variable concentrations soaks, and removes the unordered water on bacteria cellulose surface by exchange of solvent, last isolated by filtration;
The 3rd step, joins the bacteria cellulose of second step gained in solvent, then adds water inhibitor and precipitating reagent, more slowly adds TiO 2 precursor, constantly stirs;
The 4th step, is uniformly dispersed ultrasonic the mixed solution of the 3rd step, then is placed in hydrothermal reaction kettle, puts at baking oven 120-200 ℃ temperature and reacts;
The 5th step, after reaction finishes, filters products therefrom, washs respectively for several times by absolute ethyl alcohol and deionized water, finally product is dried and obtains loaded nano TiO
2catalyst.
Wherein, in the first step, aqueous slkali is one or more the mixing in NaOH, potassium hydroxide, sodium carbonate, and aqueous slkali mass concentration is 1%-4%.Rinsing hydrogen peroxide mass concentration 1 ‰-10 ‰ used.
In ethanolic solution in second step, ethanol volumetric concentration from 50% to 90% progressively increases (progressively removing the unordered water on bacteria cellulose surface).
In the 3rd step, reaction dissolvent is deionized water and alcohol mixed solution.
In the 3rd step, water inhibitor is selected acetylacetone,2,4-pentanedione (effect of water inhibitor is the fast hydrolyzing that prevents presoma); Precipitating reagent is selected the one in urea, NaOH, ammoniacal liquor, potassium hydroxide, and preferably (effect of precipitating reagent is in order to make nano-TiO for urea or ammoniacal liquor
2evenly be attached to bacteria cellulose surface); TiO 2 precursor is selected the one in titanium chloride, titanium sulfate, butyl titanate, preferably butyl titanate.
Preferably 150～200 ℃ of reaction temperatures in the 4th step, the reaction time is 12-48h.
Number of times with deionized water washing in the 5th step is 1-5 time, with the number of times that ethanolic solution washs be 1-3 time, baking temperature is 60-120 ℃.
Principle explanation:
In bacteria cellulose-water system, exist oriented alignment water molecule layer, under the effect due to hydrogen bond, make fiber surface be wrapped in the water molecule layer of an oriented alignment forming to several hydrones at the fiber surface of polyhydroxy group.Can form certain transition zone in oriented alignment water molecule layer outside, in this layer, hydrone to disordered state transition, and is the unordered water that large quantity of moisture forms in transition zone outside by ordered state.For this reason, by exchange of solvent method, remove unordered water and the transition zone water of fiber surface, retaining the orderly water molecule layer under the effect of fiber surface hydroxyl.On this basis, presoma is joined in the mixed solution system containing bacteria cellulose, presoma is under the orderly water effect of fiber surface, directed hydrolysis forms hydroxide aggregation, in the intermolecular dehydration of the hydrothermal synthesizing condition generation aggregation of HTHP, and generate nano-metal-oxide, nano particle with fiber surface hydroxyl active force under oriented alignment.
The present invention compared with prior art, its remarkable advantage is: (1) adopts dynamic bacteria cellulose is biological template, utilize its surface containing abundant polyhydroxy group and the water molecule layer of oriented alignment, forerunner's physical efficiency is hydrolyzed at surface orientation, make its catalyst can be dispersed in uniformly bacteria cellulose surface, effectively avoided the generation of agglomeration.(2) bacteria cellulose has ultra-fine tridimensional network, has high-specific surface area, can regulate and control the features such as size, and the catalyst pattern that makes take bacteria cellulose as masterplate is controlled, performance is efficient.(3) bacteria cellulose material, as a kind of new bio synthetic material, has unique bioaffinity and degradability, high retentiveness, and the loaded catalyst preparing easily reclaims, environmental protection.
Accompanying drawing explanation
Fig. 1 is bacteria cellulose load TiO in example 1
2the XRD figure of catalyst.
Fig. 2 is bacteria cellulose load TiO in example 1
2the transmission electron microscope picture of catalyst.
Fig. 3 is bacteria cellulose load TiO in example 1
2the photocatalysis performance figure of catalyst.
The specific embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Bacteria cellulose (Bacterialcellulose, BC) refer under different condition, by synthetic cellulosic general designation such as certain microorganism in acetic acid Pseudomonas (Acetobacter), Agrobacterium (Agrobacterium), rhizobium (Rhizobium) and Sarcina (Sarcina) etc.The bacteria cellulose the present invention relates to is to obtain according to the described method preparation of document (Effectof additionofsodiumalginateonbacterialcelluloseproductionby Acetobacterxylinum, JInd MicrobiolBiotechnol (2007) 34:483 – 489).
The present invention uses bacteria cellulose masterplate legal system for nano-TiO
2catalyst, comprises the following steps:
The first step, will after the rinsing of hygrometric state bacteria cellulose crude product, join 100 ℃ of heating stir process 12h in aqueous slkali, then neutralize with acid solution, then with deionized water washing until neutral; Alkaline solution is one or more the mixed solution in NaOH, potassium hydroxide, sodium acid carbonate, saleratus, alkaline concentration is 1%-4%, in order to bleach bacteria cellulose crude product, can add a small amount of hydrogenperoxide steam generator, wherein the quality solubility of hydrogen peroxide is 1 ‰-10 ‰.
Second step, the ethanolic solution that the bacteria cellulose that the first step is obtained is placed in variable concentrations soaks, then ethanol volumetric concentration is progressively increased to 90% from 50%, (being respectively 50%, 60%, 70%, 80%, 90%) is by exchange of solvent effect, remove the unordered water on bacteria cellulose surface, last centrifugation goes out bacteria cellulose.
The 3rd step, as solvent, adds the bacteria cellulose after centrifugal with the ethanolic solution of volumetric concentration 90%-99%, then adds water inhibitor and precipitating reagent, more slowly adds TiO 2 precursor, constantly stirs.Wherein water inhibitor is 1-3ml acetylacetone,2,4-pentanedione, and precipitating reagent is the one in urea, ammoniacal liquor, NaOH, potassium hydroxide, and TiO 2 precursor is selected the one in titanium chloride, titanium sulfate, butyl titanate.
The 4th step, is uniformly dispersed ultrasonic the mixed solution of the 3rd step, then is placed in hydrothermal reaction kettle, puts into 150 ℃-200 ℃ reaction 12h-48h of baking oven.
The 5th step, by product isolated by filtration, then washs 3-5 time respectively by absolute ethyl alcohol and deionized water after reaction finishes, and finally product is placed in to the natural drying 12h of normal temperature, finally puts into 60 ℃ of dry 12h of baking oven and obtains loaded nano TiO
2catalyst.
Embodiment 1
The first step, with joining in 1% NaOH aqueous slkali 100 ℃ of heating stir process 12h after 1 ‰ hydrogen peroxide rinsings, then neutralizes hygrometric state bacteria cellulose crude product with acetum, then with deionized water washing until neutral;
Second step, it is that 50% solution soaks that the bacteria cellulose that the first step is obtained is placed in ethanol volumetric concentration, then progressively increases finally to 90% of ratio of ethanol in solution, by exchange of solvent effect, remove the unordered water on bacteria cellulose surface, last centrifugation goes out bacteria cellulose.
The 3rd step,, adds the bacteria cellulose after centrifugal and stirs as solvent with 99% ethanolic solution, adds 1ml acetylacetone,2,4-pentanedione, then adds 1g urea, finally slowly adds the butyl titanate of 5ml, and last mixed liquor at room temperature stirs 30min.
The 4th step, is uniformly dispersed ultrasonic the mixed solution of the 3rd step, then is placed in hydrothermal reaction kettle, puts into 200 ℃ of reaction 24h of baking oven.
The 5th step, by product isolated by filtration, then washs respectively 3 times by absolute ethyl alcohol and deionized water after reaction finishes, and finally product is placed in to the natural drying 12h of normal temperature, finally puts into 120 ℃ of dry 12h of baking oven.Finally obtain loaded nano TiO
2catalyst.
As Fig. 1,, there is 2 θ=25.3 °, the spectrum peak of 38.2 °, 48.0 °, 54.4 °, 62.8 ° in the XRD of bacterial cellulose loaded nanometer TiO2 figure, by with Detitanium-ore-type TiO
2the comparison of diffraction maximum position, confirms that the nano particle of preparing is anatase type tio2.(101) of corresponding TiO2 respectively, (004), (200), (105) and (204) diffraction maximum.
As Fig. 2, bacterial cellulose loaded nanometer TiO
2tEM figure, as can be seen from the figure the bacteria cellulose surface uniform of tridimensional network has covered nano-TiO
2particle.
As Fig. 3, bacterial cellulose loaded nanometer TiO
2with business P25 catalyst photo-catalytic degradation of methyl-orange catalytic performance comparison diagram, as can be seen from the figure bacterial cellulose loaded nanometer catalyst TiO under ultra violet lamp
2catalytic activity be better than P25.
Embodiment 2
The first step, with joining in 2% NaOH aqueous slkali 100 ℃ of heating stir process 12h after 2 ‰ hydrogen peroxide rinsings, then neutralizes hygrometric state bacteria cellulose crude product with acetum, then with deionized water washing until neutral;
Second step, it is that 50% solution soaks that the bacteria cellulose that the first step is obtained is placed in ethanol volumetric concentration, then progressively increases finally to 90% of ratio of ethanol in solution, by exchange of solvent effect, remove the unordered water on bacteria cellulose surface, last centrifugation goes out bacteria cellulose.
The 3rd step,, adds the bacteria cellulose after centrifugal and stirs as solvent with 95% ethanolic solution.Add 1ml acetylacetone,2,4-pentanedione, then add the ammonia spirit of 5ml mass fraction 28%, finally slowly add 8ml butyl titanate, last mixed liquor at room temperature stirs 30min.
The 4th step, is uniformly dispersed ultrasonic the mixed solution of the 3rd step, then is placed in hydrothermal reaction kettle, puts into 120 ℃ of reaction 12h of baking oven.
The 5th step, by product isolated by filtration, then washs respectively 3 times by absolute ethyl alcohol and deionized water after reaction finishes, and finally product is placed in to the natural drying 12h of normal temperature, finally puts into 100 ℃ of dry 12h of baking oven.Finally obtain loaded nano TiO
2catalyst.
Embodiment 3
The first step, with joining in 1% NaOH aqueous slkali 100 ℃ of heating stir process 12h after 5 ‰ hydrogen peroxide rinsings, then neutralizes hygrometric state bacteria cellulose crude product with acetum, then with deionized water washing until neutral;
Second step, it is that 50% solution soaks that the bacteria cellulose that the first step is obtained is placed in ethanol volumetric concentration, then progressively increases finally to 90% of ratio of ethanol in solution, by exchange of solvent effect, remove the unordered water on bacteria cellulose surface, last centrifugation goes out bacteria cellulose.
The 3rd step,, adds the bacteria cellulose after centrifugal and stirs as solvent with 90% ethanolic solution.Add 2ml acetylacetone,2,4-pentanedione, then add 1.2g urea, finally slowly add 10ml butyl titanate, last mixed liquor at room temperature stirs 30min.
The 4th step, is uniformly dispersed ultrasonic the mixed solution of the 3rd step, then is placed in hydrothermal reaction kettle, puts into 200 ℃ of reaction 12h of baking oven.
The 5th step, by product isolated by filtration, then washs respectively 3 times by absolute ethyl alcohol and deionized water after reaction finishes, and finally product is placed in to the natural drying 12h of normal temperature, finally puts into 60 ℃ of dry 12h of baking oven.Finally obtain loaded nano TiO
2catalyst.
Embodiment 4
The first step, with joining in 2% NaOH aqueous slkali 100 ℃ of heating stir process 12h after 5 ‰ hydrogen peroxide rinsings, then neutralizes hygrometric state bacteria cellulose crude product with acetum, then with deionized water washing until neutral;
Second step, it is that 50% solution soaks that the bacteria cellulose that the first step is obtained is placed in ethanol volumetric concentration, then progressively increases finally to 90% of ratio of ethanol in solution, by exchange of solvent effect, remove the unordered water on bacteria cellulose surface, last centrifugation goes out bacteria cellulose.
The 3rd step,, adds the bacteria cellulose after centrifugal and stirs as solvent with 99% ethanolic solution, adds 1ml acetylacetone,2,4-pentanedione, then adds 0.2gNaOH, slowly adds 5mlTiCl
4, last mixed liquor at room temperature stirs 30min.
The 4th step, is uniformly dispersed ultrasonic the mixed solution of the 3rd step, then is placed in hydrothermal reaction kettle, puts into 180 ℃ of reaction 24h of baking oven.
The 5th step, by product isolated by filtration, then washs respectively 3 times by absolute ethyl alcohol and deionized water after reaction finishes, and finally product is placed in to the natural drying 12h of normal temperature, finally puts into 60 ℃ of dry 12h of baking oven.Finally obtain loaded nano TiO
2catalyst.
Execute example 5
The first step, with joining in 4% NaOH aqueous slkali 100 ℃ of heating stir process 12h after 8 ‰ hydrogen peroxide rinsings, then neutralizes hygrometric state bacteria cellulose crude product with acetum, then with deionized water washing until neutral;
Second step, it is that 50% solution soaks that the bacteria cellulose that the first step is obtained is placed in ethanol volumetric concentration, then progressively increases finally to 90% of ratio of ethanol in solution, by exchange of solvent effect, remove the unordered water on bacteria cellulose surface, last centrifugation goes out bacteria cellulose.
The 3rd step,, adds the bacteria cellulose after centrifugal and stirs as solvent with 90% ethanolic solution, adds 2ml acetylacetone,2,4-pentanedione, adds 0.5gKOH, more slowly adds 10mlTiCl
4.Last mixed liquor at room temperature stirs 30min.
The 4th step, is uniformly dispersed ultrasonic the mixed solution of the 3rd step, then is placed in hydrothermal reaction kettle, puts into 200 ℃ of reaction 12h of baking oven.
The 5th step, by product isolated by filtration, then washs respectively 3 times by absolute ethyl alcohol and deionized water after reaction finishes, and finally product is placed in to the natural drying 12h of normal temperature, finally puts into 60 ℃ of dry 12h of baking oven.Finally obtain loaded nano TiO
2catalyst.
Embodiment 6
The first step, with joining in 4% potassium hydroxide aqueous slkali 100 ℃ of heating stir process 12h after 10 ‰ hydrogen peroxide rinsings, then neutralizes hygrometric state bacteria cellulose crude product with acetum, then with deionized water washing until neutral;
Second step, it is that 50% solution soaks that the bacteria cellulose that the first step is obtained is placed in ethanol volumetric concentration, then progressively increases finally to 90% of ratio of ethanol in solution, by exchange of solvent effect, remove the unordered water on bacteria cellulose surface, last centrifugation goes out bacteria cellulose.
The 3rd step,, adds the bacteria cellulose after centrifugal and stirs as solvent with 95% ethanolic solution, adds 1ml acetylacetone,2,4-pentanedione, then adds 1g urea, slowly adds 0.5gTi (SO
4)
29H
2o, last mixed liquor at room temperature stirs 30min.
The 4th step, is placed in hydrothermal reaction kettle the mixed solution of the 3rd step, puts into 200 ℃ of reaction 24h of baking oven.
The 5th step, by product isolated by filtration, then washs respectively 3 times by absolute ethyl alcohol and deionized water after reaction finishes, and finally product is placed in to the natural drying 12h of normal temperature, finally puts into 60 ℃ of dry 12h of baking oven.Finally obtain loaded nano TiO
2catalyst.
Embodiment 7
The first step, with joining in 4% sodium carbonate aqueous slkali 100 ℃ of heating stir process 12h after 8 ‰ hydrogen peroxide rinsings, then neutralizes hygrometric state bacteria cellulose crude product with acetum, then with deionized water washing until neutral;
Second step, it is that 50% solution soaks that the bacteria cellulose that the first step is obtained is placed in ethanol volumetric concentration, then progressively increases finally to 90% of ratio of ethanol in solution, by exchange of solvent effect, remove the unordered water on bacteria cellulose surface, last centrifugation goes out bacteria cellulose.
The 3rd step,, adds the bacteria cellulose after centrifugal and stirs as solvent with 90% ethanolic solution, add 3ml acetylacetone,2,4-pentanedione, add the ammonia spirit of 5ml mass fraction 20% again, slowly add 1gTi (SO4) 29H2O, last mixed liquor at room temperature stirs 30min.
The 4th step, ultrasonic the mixed solution of the 3rd step dispersion, is placed in hydrothermal reaction kettle, puts into 150 ℃ of reaction 24h of baking oven.
The 5th step, by product isolated by filtration, then washs respectively 3 times by absolute ethyl alcohol and deionized water after reaction finishes, and finally product is placed in to the natural drying 12h of normal temperature, finally puts into 60 ℃ of dry 12h of baking oven.Finally obtain loaded nano TiO
2catalyst.
Claims (9)
1. a loaded nano TiO
2catalyst, is characterized in that: described loaded nano TiO
2catalyst as biological template, slowly adds TiO 2 precursor with bacteria cellulose under water inhibitor and precipitating reagent effect, is prepared and is obtained by hydro-thermal method.
2. loaded nano TiO according to claim 1
2catalyst, is characterized in that: described loaded nano TiO
2the preparation method of catalyst comprises the following steps:
The first step, will join heat treated in aqueous slkali after the rinsing of hygrometric state bacteria cellulose, then neutralizes with acid solution, then with deionized water washing until neutral;
Second step, the ethanolic solution that first step products therefrom is placed in respectively to variable concentrations soaks, and removes the unordered water on bacteria cellulose surface by exchange of solvent, last isolated by filtration;
The 3rd step, joins the bacteria cellulose of second step gained in solvent, then adds water inhibitor and precipitating reagent, more slowly adds TiO 2 precursor, constantly stirs;
The 4th step, is uniformly dispersed ultrasonic the mixed solution of the 3rd step, then is placed in hydrothermal reaction kettle, puts at baking oven 120-200 ℃ temperature and reacts;
The 5th step, after reaction finishes, filters products therefrom, washs respectively for several times by absolute ethyl alcohol and deionized water, finally product is dried and obtains loaded nano TiO
2catalyst.
3. loaded nano TiO according to claim 2
2catalyst, is characterized in that: in the first step, aqueous slkali is one or more the mixing in NaOH, potassium hydroxide, sodium carbonate, and aqueous slkali mass concentration is 1%-4%.
4. loaded nano TiO according to claim 2
2catalyst, is characterized in that: in the ethanolic solution in second step, ethanol volumetric concentration from 50% to 90% progressively increases.
5. loaded nano TiO according to claim 2
2catalyst, is characterized in that: in the 3rd step, reaction dissolvent is deionized water and alcohol mixed solution.
6. loaded nano TiO according to claim 2
2catalyst, is characterized in that: in the 3rd step, water inhibitor is selected acetylacetone,2,4-pentanedione; Precipitating reagent is selected the one in urea, NaOH, ammoniacal liquor, potassium hydroxide; TiO 2 precursor is selected the one in titanium chloride, titanium sulfate, butyl titanate.
7. loaded nano TiO according to claim 6
2catalyst, is characterized in that: precipitating reagent is selected urea or ammoniacal liquor; Presoma is selected butyl titanate.
8. loaded nano TiO according to claim 2
2catalyst, is characterized in that: in the 4th step, reaction temperature is 150～200 ℃, and the reaction time is 12-48h.
9. loaded nano TiO according to claim 2
2catalyst, is characterized in that: the number of times with deionized water washing in the 5th step is 1-5 time, with the number of times that ethanolic solution washs be 1-3 time, baking temperature is 60-120 ℃.
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| CN105110433A (en) * | 2015-09-09 | 2015-12-02 | 洛阳理工学院 | Photocatalysis-based drinking water disinfection device and disinfection technique |
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| CN105854953A (en) * | 2016-04-21 | 2016-08-17 | 海南大学 | Preparation method of bacterial cellulose/bismuth tungstate thin film and bacterial cellulose/bismuth tungstate thin film and application |
| CN105883914A (en) * | 2014-11-11 | 2016-08-24 | 天津科技大学 | Method for preparing titanium dioxide nano-tubes |
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| CN108751739B (en) * | 2018-06-05 | 2021-06-15 | 青岛科技大学 | TiO22Nanorod and spike-shaped rod bundle staggered array film and preparation method thereof |
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Application publication date: 20140709 |