CN103861623A - Method for preparing Bi3Ti2O8F photocatalyst/adsorbent - Google Patents

Method for preparing Bi3Ti2O8F photocatalyst/adsorbent Download PDF

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CN103861623A
CN103861623A CN201410057454.2A CN201410057454A CN103861623A CN 103861623 A CN103861623 A CN 103861623A CN 201410057454 A CN201410057454 A CN 201410057454A CN 103861623 A CN103861623 A CN 103861623A
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suspension
preparation
adsorbent
photochemical catalyst
titanium
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黄靖云
王威
叶志镇
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention provides a method for preparing a Bi3Ti2O8F photocatalyst/adsorbent. The method comprises the following steps: dissolving a titanium source in deionized water or an acetic acid solution, thereby obtaining a titanium source solution; adding Bi(NO3)3.5H2O into the titanium source solution, and stirring to form a suspension; adding NaF into the suspension, and stirring until the NaF is dissolved; regulating the pH value of the suspension by an NaOH solution and an HNO3 solution till the suspension is alkaline; keeping the temperature of 100-200 DEG C for 4-10 hours, and naturally cooling; centrifugally washing cooling liquid in the step, and drying for 12 hours to obtain the Bi3Ti2O8F. According to the method, the tetragonal phase Bi3Ti2O8F powder with high adsorptive property and ultraviolet/visible light catalytic performance is prepared, is high in purity, has extremely high adsorptive property on organic pollutants, can be used for performing catalytic degradation on organic dyestuffs and can be repeatedly utilized, the preparation raw materials adopted by the preparation method are common reagents, low in price and readily available, the preparation process is simple, and the preparation period is short.

Description

Bi 3ti 2o 8the preparation method of F photochemical catalyst/adsorbent
Technical field
The preparation method who the present invention relates to a kind of photochemical catalyst, is specifically related to Bi 3ti 2o 8the preparation method of F photochemical catalyst/adsorbent and the application aspect organic pollutant degradation thereof.
Background technology
The discharge of trade effluent and sanitary wastewater has caused serious threat to the mankind's living environment, and particularly the residual of the hardly degraded organic substance such as agricultural chemicals, dyestuff brought injury to human health.
At present, sewage disposal mainly contains two kinds of means, the one, physisorphtion, as active carbon, zeolite molecular sieve, clay etc. have stronger adsorption capacity to pollutant, and scrubbing speed is fast, but really degradation of contaminant of absorption method can only play transferance, and adsorbent can not reuse, thereby limit the extensive utilization of absorption method; Be exactly the photocatalytic degradation method of photochemical catalyst in addition, TiO 2because cheap, nontoxic, stable advantage is widely used as photochemical catalyst, but due to the restriction (3.2ev) of energy gap, only can absorb 4% of sunshine, therefore limit its practice, in order to improve the utilization to sunshine, found one both energy-efficient, the stability visible light catalyst that cost is low again becomes the focus of current research, at present, constantly there is new catalyst to be synthesized out, as BiVO 4, BiWO 6, Ag 3pO 4, SrTiO 3, BiOI etc., but they or efficiency are low, or easily the problem such as photodissociation still can not obtain actual utilization at present.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of photochemical catalyst/adsorbent B i 3ti 2o 8the preparation method of F, can prepare the Tetragonal Bi that has strong absorption property and ultraviolet/visible light catalytic performance concurrently 3ti 2o 8f catalyst fines.
The technical scheme that technical solution problem of the present invention adopts is:
Bi 3ti 2o 8the preparation method of F photochemical catalyst/adsorbent, comprises the following steps:
(1) the titanium source of certain amount of substance is dissolved in to deionized water or acetic acid solution, obtains titanium source solution;
(2) in the solution of titanium source, add Bi (NO 3) 35H 2o, is stirred to the white suspension that forms homogeneous;
(3) in suspension, add NaF, be stirred to NaF and dissolve completely;
(4) with certain density NaOH solution and HNO 3the pH value of the suspension of solution regulating step (3) gained is alkalescence;
(5) alkaline suspension liquid of step (4) gained is placed in to water heating kettle, naturally cools to room temperature keep 4～10h at 100～200 DEG C after;
(6), by centrifugal the cooling fluid of step (5) gained, respectively wash after three times the Bi of dry 12h at 60 DEG C with deionized water and absolute ethyl alcohol 3ti 2o 8f photochemical catalyst.
In adopting technique scheme, the present invention is further technical scheme below can also adopting or combine and adopting:
Described titanium source is organic titanium or inorganic titanium, and described organic titanium is selected from butyl titanate, isopropyl titanate, and the one in titanyl sulfate, described inorganic titanium is selected from titanium tetrachloride, the one of titanium tetrafluoride.
Bi (the NO adding in described step (2) 3) 35H 2o is 1:1.5 with the ratio of the amount of substance in titanium source.
The NaF adding in described step (3) is 1:10～1:30 with the ratio of the amount of substance in titanium source.
In described step (4), the pH value of the suspension of gained is 8.5～10.5, is preferably 9.0～9.5, and under lasting 1h stirs, pH value remains unchanged.
Adopt automatic physical adsorption appearance to the Bi making 3ti 2o 8f photochemical catalyst/sample of sorbent carry out specific area measuring, result as shown in Figure 1, from the data of Fig. 1, can find out that making sample has larger specific area, contain mesoporous in a large number, organic pollution is had to very strong adsorption capacity, and it is approximately 100 times of P25 to the adsorption capacity of RhB.
Adopt phase structure and the crystal property of X-ray diffractometer to sample to analyze, analysis result as shown in Figure 2, as can be seen from Figure 2, is prepared the XRD collection of illustrative plates peak position (full curve on Fig. 2 top) and thing phase Bi of sample 3ti 2o 8the standard diffracting spectrum (the discrete vertical line of Fig. 2 downside) of F overlaps completely, peak this coincidence of strong basis, and the strong difference in part peak comes from the preferential growth of crystal.Therefore the sample of preparation belongs to the Bi of tetragonal 3ti 2o 8f, the bright and sharp interpret sample crystallinity of diffraction maximum is good, and without assorted peak, the purity of interpret sample is high.
Adopt field emission scanning electron microscope the microscopic appearance of sample is carried out to electromicroscopic photograph collection, the electromicroscopic photograph of sample as shown in Figure 3, as can be seen from Figure 3, Bi 3ti 2o 8f photochemical catalyst is made up of a large amount of spherical particles uniformly, and without agglomeration, each chondritic is made up of interconnected nanometer sheet, and it is a large amount of mesoporous that this structure has formed material, has improved the adsorption capacity of material.
To the Bi making 3ti 2o 8the absorption property of F photochemical catalyst and the mensuration of Photocatalytic Degradation Property: sample thief 0.02g, being placed in simulation organic pollution, to be respectively concentration be 20 μ M, volume is in 100ml rhodamine B (RhB) aqueous solution or the malachite green aqueous solution, Xe lamp taking ultraviolet source as 300W, visible light source is that the Xe lamp that adds the 300W of 420nm optical filter (cut-off of wavelength X < 420nm light) irradiates, and Fig. 5 is Bi 3ti 2o 8f photochemical catalyst is adsorbed in degraded pictorial diagram to RhB's, adopts the concentration of measurement of ultraviolet-visible spectrophotometer residual organic matter after a period of time, and Fig. 4 b is Bi 3ti 2o 8f photochemical catalyst/adsorbent is the degraded time history plot to RhB in the RhB aqueous solution under visible ray, Fig. 4 a is P25 degraded time history plot to RhB in the RhB aqueous solution under similarity condition, can find out the Bi that the present invention is prepared from the contrast of Fig. 4 a and Fig. 4 b 3ti 2o 8f photochemical catalyst/adsorbent, along with the growth of time, strengthens the palliating degradation degree of RhB, and P25 does not vary widely.
The invention has the beneficial effects as follows: by preparation method of the present invention, prepared the Bi that has strong absorption property and ultraviolet/visible light catalytic performance concurrently 3ti 2o 8f powder, the present invention, by hydro-thermal method, has synthesized Tetragonal Bi for the first time 3ti 2o 8f catalyst fines, Bi 3ti 2o 8f photochemical catalyst has good dispersiveness in water, difficult reunion, synthetic catalyst is made up of homodisperse nanoscale three-dimensional structure orbicule, and there is higher purity, at assessment and analysis absorption property and the catalytic performance of this catalyst, result has shown the dual property that it is excellent, can adsorb effectively rapidly organic pollution, again can efficient catalytic degradating organic dye, catalyst can be reused, the Bi that the present invention is prepared 3ti 2o 8the existing good clean-up effect of F, can reach again scrubbing effect fast, has broad application prospects; And the raw materials that preparation method of the present invention adopts, comprises titanium source, deionized water, acetic acid solution, Bi (NO 3) 35H 2o, NaF, alkali lye and nitric acid are common agents, cheap and easy to get, and preparation technology is simple, and manufacturing cycle is short, the Bi of preparation 3ti 2o 8f photochemical catalyst purity is high.
Brief description of the drawings
Fig. 1 is the prepared Bi of the present invention 3ti 2o 8f photochemical catalyst and P25 character contrast table.
Fig. 2 is the prepared Bi of the present invention 3ti 2o 8the XRD collection of illustrative plates of F photochemical catalyst.
Fig. 3 is the prepared Bi of the present invention 3ti 2o 8the high resolution scanning photo of F photochemical catalyst.
Fig. 4 a be P25 under visible ray to waste water from dyestuff in the degraded time history plot of RhB.
Fig. 4 b is the prepared Bi of the present invention 3ti 2o 8f photochemical catalyst under visible ray to waste water from dyestuff in the degraded time history plot of RhB.
Fig. 5 is the prepared Bi of the present invention 3ti 2o 8f photochemical catalyst is to the absorption of RhB and degraded pictorial diagram.
Detailed description of the invention
Embodiment 1
0.1ml titanyl sulfate is dissolved in the acetic acid solution of 35ml (volume ratio, acetic acid: water=1:6), adds 0.832g Bi (NO after stirring 30min 3) 35H 2o, continues to be stirred to the suspension that makes solution become white homogeneous, in suspension, adds NaF 0.72～2.16g, is stirred to NaF and all dissolves, with certain density NaOH solution and HNO 3solution regulates pH of suspension value in 8.5～10.5 scopes, and continue to stir in 1h and ensure that pH value stabilization is constant, alkaline suspension liquid is loaded in 50ml water heating kettle, keep 4～10h at 100～200 DEG C after, naturally cool to room temperature, finally use after the each centrifuge washing of deionized water and absolute ethyl alcohol three times, at 60 DEG C, after dry 12h, obtain Bi 3ti 2o 8f photochemical catalyst/adsorbent.
Embodiment 2
0.1ml isopropyl titanate is dissolved in the acetic acid solution of 35ml (acetic acid: water=1:6), adds 0.832g Bi (NO after stirring 30min 3) 35H 2o, continues to be stirred to the suspension that makes solution become white homogeneous, in suspension, adds NaF 0.72～2.16g, is stirred to NaF and all dissolves, with certain density NaOH solution and HNO 3solution regulates pH of suspension value in 8.5～10.5 scopes, and in lasting 1h, pH value stabilization is constant, alkaline suspension liquid is loaded in 50ml water heating kettle, keep 4～10h at 100～200 DEG C after, naturally cool to room temperature, finally use after the each centrifuge washing of deionized water and absolute ethyl alcohol three times, at 60 DEG C, after dry 12h, obtain Bi 3ti 2o 8f photochemical catalyst/adsorbent.
Embodiment 3
0.1ml butyl titanate is dissolved in the acetic acid solution of 35ml (acetic acid: water=1:6), adds 0.832g Bi (NO after stirring 30min 3) 35H 2o, continues to be stirred to the suspension that makes solution become white homogeneous, in suspension, adds NaF 0.72～2.16g, is stirred to NaF and all dissolves, with certain density NaOH solution and HNO 3solution regulates pH of suspension value in 8.5～10.5 scopes, and in lasting 1h, pH value stabilization is constant, alkaline suspension liquid is loaded in 50ml water heating kettle, keep 4～10h at 100～200 DEG C after, naturally cool to room temperature, finally use after the each centrifuge washing of deionized water and absolute ethyl alcohol three times, at 60 DEG C, after dry 12h, obtain Bi 3ti 2o 8f photochemical catalyst/adsorbent.
Embodiment 4
0.1ml titanium tetrafluoride is dissolved in the deionized water of 35ml, after stirring 30min, adds 0.832g Bi (NO 3) 35H 2o, continues to be stirred to the suspension that makes solution become white homogeneous, in suspension, adds NaF0.72～2.16g, is stirred to NaF and all dissolves, with certain density NaOH solution and HNO 3solution regulates pH of suspension value in 9.0～9.5 scopes, and in lasting 1h, pH value stabilization is constant, alkaline suspension liquid is loaded in 50ml water heating kettle, keep 4～10h at 100～200 DEG C after, naturally cool to room temperature, finally use after the each centrifuge washing of deionized water and absolute ethyl alcohol three times, at 60 DEG C, after dry 12h, obtain Bi 3ti 2o 8f photochemical catalyst/adsorbent.
Embodiment 5
0.08g titanium tetrafluoride is dissolved in the deionized water of 35ml, after stirring 30min, adds 0.832g Bi (NO 3) 35H 2o, continues to be stirred to the suspension that makes solution become white homogeneous, in suspension, adds NaF0.72～2.16g, is stirred to NaF and all dissolves, with certain density NaOH solution and HNO 3solution regulates pH of suspension value in 9.0～9.5 scopes, and in lasting 1h, pH value stabilization is constant, alkaline suspension liquid is loaded in 50ml water heating kettle, keep 4～10h at 100～200 DEG C after, naturally cool to room temperature, finally use after the each centrifuge washing of deionized water and absolute ethyl alcohol three times, at 60 DEG C, after dry 12h, obtain Bi 3ti 2o 8f photochemical catalyst/adsorbent.
Adopt automatic physical adsorption appearance to the Bi making 3ti 2o 8f photochemical catalyst/sample of sorbent carry out specific area measuring, result as shown in Figure 1, from the data of Fig. 1, can find out that making sample has larger specific area, contain mesoporous in a large number, organic pollution is had to very strong adsorption capacity, and it is approximately 100 times of P25 to the adsorption capacity of RhB.
Adopt phase structure and the crystal property of X-ray diffractometer to sample to analyze, analysis result as shown in Figure 2, as can be seen from Figure 2, is prepared the XRD collection of illustrative plates peak position (full curve on Fig. 2 top) and thing phase Bi of sample 3ti 2o 8the standard diffracting spectrum (the discrete vertical line of Fig. 2 downside) of F overlaps completely, peak this coincidence of strong basis, and the strong difference in part peak comes from the preferential growth of crystal.Therefore the sample of preparation belongs to the Bi of tetragonal 3ti 2o 8f, the bright and sharp interpret sample crystallinity of diffraction maximum is good, and without assorted peak, the purity of interpret sample is high.
Adopt field emission scanning electron microscope the microscopic appearance of sample is carried out to electromicroscopic photograph collection, the electromicroscopic photograph of sample as shown in Figure 3, as can be seen from Figure 3, Bi 3ti 2o 8f photochemical catalyst is made up of a large amount of spherical particles uniformly, and without agglomeration, each chondritic is made up of interconnected nanometer sheet, and it is a large amount of mesoporous that this structure has formed material, has improved the adsorption capacity of material.
To the Bi making 3ti 2o 8the absorption property of F photochemical catalyst and the mensuration of Photocatalytic Degradation Property: sample thief 0.02g, being placed in simulation organic pollution, to be respectively concentration be 20 μ M, volume is in 100ml rhodamine B (RhB) aqueous solution, Xe lamp taking visible light source as the 300W that adds 420nm optical filter (cut-off of wavelength X < 420nm light) irradiates, and Fig. 5 is Bi 3ti 2o 8f photochemical catalyst is adsorbed in degraded pictorial diagram to RhB's, adopts the concentration of measurement of ultraviolet-visible spectrophotometer residual organic matter after a period of time, and Fig. 4 b is Bi 3ti 2o 8f photochemical catalyst/adsorbent is the degraded time history plot to RhB in the RhB aqueous solution under visible ray, Fig. 4 a is P25 degraded time history plot to RhB in the RhB aqueous solution under similarity condition, can find out the Bi that the present invention is prepared from the contrast of Fig. 4 a and Fig. 4 b 3ti 2o 8f photochemical catalyst/adsorbent, along with the growth of time, strengthens the palliating degradation degree of RhB, and P25 does not vary widely.

Claims (6)

1.Bi 3ti 2o 8the preparation method of F photochemical catalyst/adsorbent, is characterized in that: described preparation method comprises the following steps:
(1) the titanium source of certain amount of substance is dissolved in to deionized water or acetic acid solution, stirs to obtain titanium source solution;
(2) in the solution of titanium source, add Bi (NO 3) 35H 2o, is stirred to the white suspension that forms homogeneous;
(3) in suspension, add NaF, be stirred to NaF and dissolve completely;
(4) with certain density NaOH solution and HNO 3the pH value of the suspension of solution regulating step (3) gained is alkalescence;
(5) alkaline suspension liquid of step (4) gained is placed in to water heating kettle, naturally cools to room temperature keep 4～10h at 100～200 DEG C after;
(6), by centrifugal the cooling fluid of step (5) gained, respectively wash after three times the Bi of dry 12h at 60 DEG C with deionized water and absolute ethyl alcohol 3ti 2o 8f photochemical catalyst.
2. Bi as claimed in claim 1 3ti 2o 8the preparation method of F photochemical catalyst/adsorbent, is characterized in that: described titanium source is organic titanium or inorganic titanium, and described organic titanium is selected from butyl titanate, isopropyl titanate, and the one in titanyl sulfate, described inorganic titanium is selected from titanium tetrachloride, the one of titanium tetrafluoride.
3. Bi as claimed in claim 1 3ti 2o 8the preparation method of F photochemical catalyst/adsorbent, is characterized in that: the Bi (NO adding in described step (2) 3) 35H 2o is 1:1.5 with the ratio of the amount of substance in titanium source.
4. Bi as claimed in claim 1 3ti 2o 8the preparation method of F photochemical catalyst/adsorbent, is characterized in that: the NaF adding in described step (3) is 1:10～1:30 with the ratio of the amount of substance in titanium source.
5. Bi as claimed in claim 1 3ti 2o 8the preparation method of F photochemical catalyst/adsorbent, is characterized in that: in described step (4), the pH value of the suspension of gained is 8.5～10.5, is preferably 9.0～9.5, and under lasting 1h stirs, pH value remains unchanged.
6. the made Bi of preparation method of any one in claim 1-5 3ti 2o 8the application of F photochemical catalyst/adsorbent aspect organic pollutant degradation.
CN201410057454.2A 2014-02-20 2014-02-20 Method for preparing Bi3Ti2O8F photocatalyst/adsorbent Pending CN103861623A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110890554A (en) * 2019-11-29 2020-03-17 扬州大学 High-power flexible single-enzyme glucose fuel cell and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001070396A2 (en) * 2000-03-22 2001-09-27 Speer Samuel E Photolytic and photocatalytic reaction enhancement device
CN101219813A (en) * 2008-01-24 2008-07-16 浙江大学 Iron doped sodium-bismuth titanate multiferroics and method for producing the same
CN102319576A (en) * 2011-07-08 2012-01-18 山东大学 Fluoride photocatalytic material and preparation method thereof
CN102941106A (en) * 2012-11-22 2013-02-27 上海师范大学 Preparation method of C60/Bi2Tio4F2 composite photocatalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001070396A2 (en) * 2000-03-22 2001-09-27 Speer Samuel E Photolytic and photocatalytic reaction enhancement device
CN101219813A (en) * 2008-01-24 2008-07-16 浙江大学 Iron doped sodium-bismuth titanate multiferroics and method for producing the same
CN102319576A (en) * 2011-07-08 2012-01-18 山东大学 Fluoride photocatalytic material and preparation method thereof
CN102941106A (en) * 2012-11-22 2013-02-27 上海师范大学 Preparation method of C60/Bi2Tio4F2 composite photocatalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110890554A (en) * 2019-11-29 2020-03-17 扬州大学 High-power flexible single-enzyme glucose fuel cell and preparation method thereof

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Application publication date: 20140618