CN101844806A - Method for ethylene diamine tetraacetic acid (EDTA)-assisted hydrothermal synthesis of nanometer porous titanium dioxide(TiO2) - Google Patents
Method for ethylene diamine tetraacetic acid (EDTA)-assisted hydrothermal synthesis of nanometer porous titanium dioxide(TiO2) Download PDFInfo
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- CN101844806A CN101844806A CN 201010197848 CN201010197848A CN101844806A CN 101844806 A CN101844806 A CN 101844806A CN 201010197848 CN201010197848 CN 201010197848 CN 201010197848 A CN201010197848 A CN 201010197848A CN 101844806 A CN101844806 A CN 101844806A
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Abstract
The invention discloses a method for ethylene diamine tetraacetic acid (EDTA)-assisted hydrothermal synthesis of nanometer porous titanium dioxide (TiO2). The method comprises the following: 1, a step of preparing precursor solution, in which sodium ethylene diamine tetracetate and aqueous solution of titanium trichloride are added into deionized water and the mixture is uniformly stirred and then stood until the mixed solution is flocculent to give the precursor solution; 2, a step of performing a hydrothermal reaction, in which the precursor solution is put into an oven and heated to 115 to 125 DEG C to be aged for 20 and 28 hours to give aged products; and 3, a step of post-treatment, in which the ageing products are cooled to 58 to 62 DEG C and poured into deionized water to be washed until the pH value of the solution is 7.0, the solution is filtered, and filter residues are dried to give the nanometer porous TiO2. The method has the advantages of simple preparation process, low energy consumption, high practicability, low material and equipment cost and the like and is suitable for mass production of anatase TiO2.
Description
Technical field
The invention belongs to nanoporous TiO
2Preparation field, particularly a kind of disodium ethylene diamine tetraacetate assisted hydrothermal synthesis of nanometer porous TiO
2Method.
Background technology
TiO
2Be a kind of highly effective photocatalyst, be widely used in the purifying of sky G﹠W, synthetic method has hydrothermal method, sol-gel method, sputtering method etc.The titanium dioxide that these methods are synthesized need be calcined mostly just has good crystal formation, and under high-temperature calcination, the degree of crystallinity of titanium dioxide has improved, but change has also taken place in its trickle structure, for example, the hole of mesoporous TiO 2 subsides easily, and specific surface area diminishes; Nano-titania particle can be reunited in the incinerating process, and therefore the photocatalysis performance of the titanium dioxide after the calcining all can be subjected to certain influence.Anatase titania is owing to greater band gap (3.2eV), and in the ultraviolet region excellent catalytic effect, therefore synthetic a kind of nanoporous high-specific surface area, the pure anatase phase titanium dioxide that photocatalysis performance is good have important practical value.
Summary of the invention
For the shortcoming and deficiency that remedy prior art, primary and foremost purpose of the present invention is to provide a kind of disodium ethylene diamine tetraacetate (EDTA-Na
2) assisted hydrothermal synthesis of nanometer porous TiO
2Method; This method technology is simple, cost is low.
Second purpose of the present invention is to provide the nanoporous TiO of method for preparing
2, this nanoporous TiO
2Have high specific surface area, the mesoporous microstructure of excellence and good photocatalysis performance.
Purpose of the present invention is achieved through the following technical solutions: a kind of disodium ethylene diamine tetraacetate assisted hydrothermal synthesis of nanometer porous TiO
2Method, comprise following operation steps:
(1) configuration precursor aqueous solution: the aqueous solution that is 15.0～20.0% titanous chloride to sodium ethylene diamine tetracetate and mass percent concentration joins in the deionized water, the pH of the aqueous solution of described titanous chloride is 1～1.5, leave standstill after stirring, be flocculence to solution, obtain precursor aqueous solution; The mass percent concentration of sodium ethylene diamine tetracetate is 3.45%～9.68% in the described precursor aqueous solution, and the mass percent concentration of titanous chloride is 6.77%～7.45%;
(2) hydro-thermal reaction: place baking oven to be warming up to 115～125 ℃ precursor aqueous solution, ageing 20～28 hours obtains the ageing product;
(3) subsequent disposal: the ageing product is cooled to 58～62 ℃, pours in the deionized water of 78～82 ℃ of temperature and wash, be neutral, with the filter residue oven dry, obtain nanoporous TiO after the filtration until pH
2
The described time of leaving standstill of step (1) is 15～30 minutes.
The described oven dry of step (3) is to dry in 115～125 ℃ of baking ovens.
A kind of nanoporous TiO according to method for preparing
2
Above-mentioned nanoporous TiO
2Be a kind of Photodegradation catalyst, can be widely used in the photocatalysis to degrade organic matter field.
The relative prior art of the present invention has following advantage and beneficial effect: (1) the present invention adopts direct hydrothermal method to synthesize nanoporous TiO
2, synthetic used raw material is easy to get, and the aqueous solution of titanous chloride and sodium ethylene diamine tetracetate all are the reagent of using always, synthetic method is simple, the reaction conditions gentleness, use be hydro-thermal reaction under the lesser temps, product is handled convenient, and product is washed, dried and get final product; (2) titanium dioxide that obtains of the present invention has pure anatase octahedrite phase, need not calcine, and the titanium dioxide specific surface area that obtains is big, and good photocatalytic is arranged; (3) the synthetic titanium dioxide that obtains of the present invention has vesicular structure, and mean pore size has high specific surface area between 2～4nm, and specific surface area is at 94.85m
2/ g～216.45m
2Between/the g; Advantage such as (4) the inventive method has that preparation technology is simple, energy consumption is low, the cost of practical, raw material and equipment is lower is suitable for the scale operation of anatase phase titanium dioxide.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the embodiment of the invention 1～5 products obtained therefrom, wherein a is the x-ray diffraction pattern of embodiment 1 products obtained therefrom, b is the x-ray diffraction pattern of embodiment 2 products obtained therefroms, c is the x-ray diffraction pattern of embodiment 3 products obtained therefroms, d is the x-ray diffraction pattern of embodiment 4 products obtained therefroms, and e is the x-ray diffraction pattern of embodiment 5 products obtained therefroms.
Fig. 2 is the sem photograph of embodiment 1 products obtained therefrom.
Fig. 3 is the sem photograph of embodiment 3 products obtained therefroms.
Fig. 4 is the sem photograph of embodiment 5 products obtained therefroms.
Fig. 5 is embodiment 3 products obtained therefrom isothermal nitrogen adsorption line charts.
Fig. 6 is embodiment 3 products obtained therefrom pore size distribution line charts.
The lab diagram of the photocatalytic degraded tropeolin-D of all embodiment 1～5 products obtained therefroms of Fig. 7, wherein a is the photocatalysis performance figure of embodiment 1 products obtained therefrom, b is the photocatalysis performance figure of embodiment 2 products obtained therefroms, c is the photocatalysis performance figure of embodiment 3 products obtained therefroms, d is the photocatalysis performance figure of embodiment 4 products obtained therefroms, and e is the photocatalysis performance figure of embodiment 5 products obtained therefroms.
Embodiment
Below in conjunction with concrete example and accompanying drawing the present invention is done further detailed narration, but implementation method of the present invention is flexible, is not limited only to this routine described concrete operations mode.
Embodiment 1
(1) configuration precursor aqueous solution: the aqueous solution that is 18.0% titanous chloride to sodium ethylene diamine tetracetate and mass percent concentration joins in the deionized water, the pH of the aqueous solution of described titanous chloride is 1, pour into after mechanical stirring is even and left standstill in the tetrafluoroethylene reactor 15 minutes, be flocculence to solution, obtain precursor aqueous solution; The mass percent concentration of sodium ethylene diamine tetracetate is 3.45% in the described precursor aqueous solution, and the mass percent concentration of titanous chloride is 7.45%;
(2) hydro-thermal reaction: place baking oven to be warming up to 120 ℃ precursor aqueous solution, ageing 24 hours obtains the ageing product;
(3) subsequent disposal: the ageing product is cooled to 60 ℃, pours in the deionized water of 80 ℃ of temperature and wash, be neutral, after the filtration filter residue is dried in 120 ℃ of baking ovens, obtain anatase octahedrite nanoporous TiO until pH
2Gained anatase octahedrite nanoporous TiO
2Specific surface area be 94.85m
2/ g, pore volume are 0.0778cm
3/ g, mean pore size is 3.3nm.The x-ray diffraction pattern of products obtained therefrom is shown in Fig. 1 (a), and sem photograph as shown in Figure 2.
Embodiment 2
(1) configuration precursor aqueous solution: the aqueous solution that is 15.0% titanous chloride to sodium ethylene diamine tetracetate and mass percent concentration joins in the deionized water, the pH of the aqueous solution of described titanous chloride is 1.5, pour into after mechanical stirring is even and left standstill in the tetrafluoroethylene reactor 30 minutes, be flocculence to solution, obtain precursor aqueous solution; The mass percent concentration of sodium ethylene diamine tetracetate is 5.08% in the described precursor aqueous solution, and the mass percent concentration of titanous chloride is 7.32%;
(2) hydro-thermal reaction: place baking oven to be warming up to 115 ℃ precursor aqueous solution, ageing 28 hours obtains the ageing product;
(3) subsequent disposal: the ageing product is cooled to 58 ℃, pours in the deionized water of 78 ℃ of temperature and wash, be neutral, after the filtration filter residue is dried in 125 ℃ of baking ovens, obtain anatase octahedrite nanoporous TiO until pH
2Gained anatase octahedrite nanoporous TiO
2Specific surface area be 184.18m
2/ g, pore volume are 0.1230cm
3/ g, mean pore size is 2.8nm.The x-ray diffraction pattern of products obtained therefrom is shown in Fig. 1 (b).
Embodiment 3
(1) configuration precursor aqueous solution: the aqueous solution that is 20.0% titanous chloride to sodium ethylene diamine tetracetate and mass percent concentration joins in the deionized water, the pH of the aqueous solution of described titanous chloride is 1.2, pour into after mechanical stirring is even and left standstill in the tetrafluoroethylene reactor 15 minutes, be flocculence to solution, obtain precursor aqueous solution; The mass percent concentration of sodium ethylene diamine tetracetate is 6.67% in the described precursor aqueous solution, and the mass percent concentration of titanous chloride is 7.20%;
(2) hydro-thermal reaction: place baking oven to be warming up to 125 ℃ precursor aqueous solution, ageing 20 hours obtains the ageing product;
(3) subsequent disposal: the ageing product is cooled to 62 ℃, pours in the deionized water of 82 ℃ of temperature and wash, be neutral, after the filtration filter residue is dried in 115 ℃ of baking ovens, obtain anatase octahedrite nanoporous TiO until pH
2Gained anatase octahedrite nanoporous TiO
2Specific surface area be 196.24m
2/ g, pore volume are 0.1349cm
3/ g, mean pore size is 2.8nm.The sem photograph of product as shown in Figure 3.The x-ray diffraction pattern of products obtained therefrom shown in Fig. 1 (c), sem photograph as shown in Figure 3, the isothermal nitrogen adsorption line chart as shown in Figure 5, the pore size distribution line chart is as shown in Figure 6.Fig. 5 nitrogen adsorption as can be seen has a tangible hysteresis loop, is typical mesoporous material, and Fig. 6 is the product pore size distribution curve that embodiment 3 obtains, and pore size distribution is between 2～4nm.
Embodiment 4
(1) configuration precursor aqueous solution: the aqueous solution that is 19.0% titanous chloride to sodium ethylene diamine tetracetate and mass percent concentration joins in the deionized water, the pH of the aqueous solution of described titanous chloride is 1.1, pour into after mechanical stirring is even and left standstill in the tetrafluoroethylene reactor 20 minutes, be flocculence to solution, obtain precursor aqueous solution; The mass percent concentration of sodium ethylene diamine tetracetate is 8.20% in the described precursor aqueous solution, and the mass percent concentration of titanous chloride is 7.08%;
(2) hydro-thermal reaction: place baking oven to be warming up to 118 ℃ precursor aqueous solution, ageing 26 hours obtains the ageing product;
(3) subsequent disposal: the ageing product is cooled to 61 ℃, pours in the deionized water of 79 ℃ of temperature and wash, be neutral, after the filtration filter residue is dried in 119 ℃ of baking ovens, obtain anatase octahedrite nanoporous TiO until pH
2Gained anatase octahedrite nanoporous TiO
2Specific surface area be 200.63m
2/ g, pore volume are 0.1415cm
3/ g, mean pore size is 2.8nm.The x-ray diffraction pattern of products obtained therefrom is shown in Fig. 1 (d).
(1) configuration precursor aqueous solution: the aqueous solution that is 16.0% titanous chloride to sodium ethylene diamine tetracetate and mass percent concentration joins in the deionized water, the pH of the aqueous solution of described titanous chloride is 1.5, pour into after mechanical stirring is even and left standstill in the tetrafluoroethylene reactor 25 minutes, be flocculence to solution, obtain precursor aqueous solution; The mass percent concentration of sodium ethylene diamine tetracetate is 9.68% in the described precursor aqueous solution, and the mass percent concentration of titanous chloride is 6.97%;
(2) hydro-thermal reaction: place baking oven to be warming up to 123 ℃ precursor aqueous solution, ageing 22 hours obtains the ageing product;
(3) subsequent disposal: the ageing product is cooled to 59 ℃, pours in the deionized water of 81 ℃ of temperature and wash, be neutral, after the filtration filter residue is dried in 120 ℃ of baking ovens, obtain anatase octahedrite nanoporous TiO until pH
2Gained anatase octahedrite nanoporous TiO
2Specific surface area be 216.45m
2/ g, pore volume are 0.2134cm
3/ g, mean pore size is 3.9nm.The x-ray diffraction pattern of products obtained therefrom is shown in Fig. 1 (e), and sem photograph as shown in Figure 4.
The synthetic sample all is an anatase titania as seen from Figure 1.
As can be seen along with the increase of sodium ethylene diamine tetracetate concentration, synthesize the TiO that obtains from Fig. 2, Fig. 3, Fig. 4
2Microparticle is more and more littler, piles up between particle to form vesicular structure; Fig. 2 sees is to assemble a spot of small-particle on the titanium dioxide of bulk, and Fig. 3 is that the bigger titanium dioxide of particle flocks together, and can see that in Fig. 4 the inside a large amount of short grained titanium dioxide flocks together.
Embodiment 6: gained nanoporous TiO of the present invention
2Photocatalysis performance test
Measure a series of 200mL1 * 10 respectively
-4The methyl orange solution of mol/L, pour in the silica glass device of photoreactor, taking by weighing each 0.05g of titanium dioxide that embodiment 1, embodiment 2, embodiment 3, embodiment 4 and embodiment 5 make respectively adds in the silica glass device of reactor, with the 300W high voltage mercury lamp is light source, and light path is a 3cm irradiation silica glass device.Need magnetic agitation and cooling circulating water in the photocatalytic degradation process, every 10min takes a sample once in the process of illumination, and the solution centrifugal after the taking-up separates wavelength 460nm place on spectrophotometer, back and measures.
Fig. 7 as can be seen, the increase of sodium ethylene diamine tetracetate concentration in the building-up process, photocatalysis performance is also just good more, but along with the amount of sodium ethylene diamine tetracetate increases, the washing process of product is also just difficult more, and residual sodium ethylene diamine tetracetate is difficult to washes clean, therefore, select the proportioning of embodiment 3, the washing of product is easy, and the photochemical catalysis effect might as well.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (4)
1. disodium ethylene diamine tetraacetate assisted hydrothermal synthesis of nanometer porous TiO
2Method, it is characterized in that comprising following operation steps:
(1) configuration precursor aqueous solution: the aqueous solution that is 15.0～20.0% titanous chloride to sodium ethylene diamine tetracetate and mass percent concentration joins in the deionized water, the pH of the aqueous solution of described titanous chloride is 1～1.5, leave standstill after stirring, be flocculence to solution, obtain precursor aqueous solution; The mass percent concentration of sodium ethylene diamine tetracetate is 3.45%～9.68% in the described precursor aqueous solution, and the mass percent concentration of titanous chloride is 6.77%～7.45%;
(2) hydro-thermal reaction: place baking oven to be warming up to 115～125 ℃ precursor aqueous solution, ageing 20～28 hours obtains the ageing product;
(3) subsequent disposal: the ageing product is cooled to 58～62 ℃, pours in the deionized water of 78～82 ℃ of temperature and wash, be neutral, with the filter residue oven dry, obtain nanoporous TiO after the filtration until pH
2
2. a kind of disodium ethylene diamine tetraacetate assisted hydrothermal synthesis of nanometer porous TiO according to claim 1
2Method, it is characterized in that: the described time of leaving standstill of step (1) is 15～30 minutes.
3. a kind of disodium ethylene diamine tetraacetate assisted hydrothermal synthesis of nanometer porous TiO according to claim 1
2Method, it is characterized in that: the described oven dry of step (3) is to dry in 115～125 ℃ of baking ovens.
4. nanoporous TiO according to each described method preparation of claim 1～3
2
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502810A (en) * | 2011-11-01 | 2012-06-20 | 南京林业大学 | Method for preparing porous nano TiO2 |
| CN104118906A (en) * | 2014-08-05 | 2014-10-29 | 苏州巨联环保科研有限公司 | Method for preparing porous titanium dioxide by polymer-assisted deposition |
| CN105618022A (en) * | 2016-01-12 | 2016-06-01 | 遵义医学院 | Preparation method of high-activity mesoporous hydrated titanium oxide powder |
| CN111439781A (en) * | 2020-03-31 | 2020-07-24 | 广西金茂钛业有限公司 | Method for producing high-purity electronic titanium dioxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4999181A (en) * | 1987-11-25 | 1991-03-12 | U.S. Philips Corporation | Method of manufacturing titanium dioxide powder |
| US6399540B1 (en) * | 1999-08-12 | 2002-06-04 | Sumitomo Chemical Co., Ltd. | Porous titania, catalyst comprising the porous titania |
| CN1865155A (en) * | 2006-04-06 | 2006-11-22 | 深圳清华大学研究院 | Method for synthesizing soluble titanium dioxide nano crystal in low temperature |
-
2010
- 2010-06-09 CN CN201010197848XA patent/CN101844806B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4999181A (en) * | 1987-11-25 | 1991-03-12 | U.S. Philips Corporation | Method of manufacturing titanium dioxide powder |
| US6399540B1 (en) * | 1999-08-12 | 2002-06-04 | Sumitomo Chemical Co., Ltd. | Porous titania, catalyst comprising the porous titania |
| CN1865155A (en) * | 2006-04-06 | 2006-11-22 | 深圳清华大学研究院 | Method for synthesizing soluble titanium dioxide nano crystal in low temperature |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502810A (en) * | 2011-11-01 | 2012-06-20 | 南京林业大学 | Method for preparing porous nano TiO2 |
| CN102502810B (en) * | 2011-11-01 | 2013-12-18 | 南京林业大学 | Method for preparing porous nano TiO2 |
| CN104118906A (en) * | 2014-08-05 | 2014-10-29 | 苏州巨联环保科研有限公司 | Method for preparing porous titanium dioxide by polymer-assisted deposition |
| CN104118906B (en) * | 2014-08-05 | 2016-06-29 | 苏州巨联环保科研有限公司 | A kind of method that polymer assistant depositing prepares poriferous titanium dioxide |
| CN105618022A (en) * | 2016-01-12 | 2016-06-01 | 遵义医学院 | Preparation method of high-activity mesoporous hydrated titanium oxide powder |
| CN105618022B (en) * | 2016-01-12 | 2018-09-18 | 遵义医学院 | A kind of mesoporous hydrous titanium oxide raw powder's production technology of high activity |
| CN111439781A (en) * | 2020-03-31 | 2020-07-24 | 广西金茂钛业有限公司 | Method for producing high-purity electronic titanium dioxide |
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