CN1692979A - Photocatalyst used for purifying organic pollutants and its prepn. method - Google Patents
Photocatalyst used for purifying organic pollutants and its prepn. method Download PDFInfo
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- CN1692979A CN1692979A CN 200510013230 CN200510013230A CN1692979A CN 1692979 A CN1692979 A CN 1692979A CN 200510013230 CN200510013230 CN 200510013230 CN 200510013230 A CN200510013230 A CN 200510013230A CN 1692979 A CN1692979 A CN 1692979A
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Abstract
A photocatalyst for removing organic pollutants is prepared through pretreating sepiolite particles, depositing a layer of CdS nanocrystals on the surface of sepiolite particle, and depositing a layer of Tio2 nanocrystals. Under the irrediation of visual light, the pollutants in the water can be degradated into Co2 and H2O by it.
Description
Technical field
The invention belongs to the photocatalytic oxidation degradation of organic pollution, the method for purification, proposed a kind of photochemical catalyst that is used for eliminating organic pollutant and preparation method thereof especially.
Background technology
Sepiolite is by the slice-group growth fibre structure of class talcum stratiform, has passage on the sepiolite direction consistent with the fiber extending direction, and therefore, sepiolite has bigger specific area, through being often used as the carrier of adsorbent and catalyst., more much bigger in the length of machine direction than common nano-particle material size on average at 2.6 μ m, be easy to from aqueous phase separation, but the no photocatalytic activity of sepiolite itself.
Nano-TiO
2Be use now very wide photochemical catalyst, but nanometer powder TiO
2Be difficult for separating from aqueous phase, and pure TiO
2Ultraviolet light can only be absorbed, visible light can not be absorbed, low to the visible spectrum utilization rate in the sunshine.The nanocrystalline visible light absorbing of CdS has photocatalytic activity, but unstable, have the photoetch problem, and the semiconductor band gap can be lower.Also can take at large area substrates surface-coated nanometer film photochemical catalyst, but the nanometer film catalyst has and adheres to shortcoming insecure, that the effective catalyst amount is few, photocatalysis efficiency is low.
There are some researches show at present the nano-tube/CdS semiconductor is coupled to colloid TiO
2The surface can make the absorption spectrum of coupling rear catalyst expand to red light district, has enlarged TiO
2Excitation spectrum.But colloid TiO
2Catalyst granules is too thin, is difficult to separate, and also inconvenient in use.In addition, since CdS at TiO
2Outer surface, still can not effectively suppress the photoetch of CdS.
So, seek that a kind of photocatalytic activity to be arranged, visible light is had absorption, is easy to from the catalyst of aqueous phase separation be to need at present the problem that solves.
Summary of the invention
According to the problem that present needs solve, be carrier with the sepiolite, utilize the advantage that its granularity is big, easily separated, specific area is big.The present invention proposes a kind of composite photo-catalyst and preparation method.
The structure of catalyst of the present invention is three layers, deposits the nanocrystalline thick 30～600nm of one deck CdS earlier on the sepiolite particle surface, again in CdS surface deposition one deck TiO
2Nanocrystalline; But TiO
2The thickness of layer is 30～500nm.Visible light can be seen through, shine the CdS layer.
Because TiO
2Protective effect, photoetch does not take place in CdS, and can also absorb visible light, has further improved the sunshine utilization rate.
A kind of preparation method who is used for the photochemical catalyst of eliminating organic pollutant of the present invention comprises the steps:
1) preliminary treatment of sepiolite: with the sepiolite hydrochloric acid preliminary treatment of pulverizing, acid treatment is filtered till adding the no bubble generation of acid again, and after being washed to neutrality and not having the chlorion existence, suction strainer, oven dry after screening, obtain the sepiolite of 2～10 μ m granularities;
2) CdS-loaded:
Earlier by the required solution of following proportional arrangement: the quality with sepiolite is 1 calculating: select for use
Cadmium nitrate is 0.3～0.6 times of sepiolite;
Potassium hydroxide is 2.4～3 times of sepiolite;
Thiocarbamide is 1.2～1.8 times of sepiolite;
Ammonium nitrate is 8～15 times of sepiolite;
Ammonium chloride is 0.1～0.5 times of sepiolite;
Sepiolite is joined in the above-mentioned solution, and what add that ammoniacal liquor is stirred to the pH value is adjusted to 9.3～9.9, and depositing temperature is at 55～90 ℃, and sedimentation time is 4～10h; Cooling is then filtered, and washing is blotted; Obtain the sepiolite after CdS-loaded;
3) load TiO
2:
With above-mentioned sepiolite after CdS-loaded, add ethanol solution, the mass ratio of ethanol and sepiolite is 17～24: 1; Stir under the room temperature, add the liquid butyl titanate then, the mass ratio of butyl titanate and sepiolite is 1.9～2.5: 1; Continue to stir 0.5～1.0h, follow ultrasonic dispersion and continue to add thermal agitation after 20～40 minutes again, be evaporated completely substantially until absolute ethyl alcohol;
Sample is put into the constant device of maintenance humidity, behind 24～30h, sample is joined in the deionized water mix strongly with red fuming nitric acid (RFNA) again, the mass ratio of red fuming nitric acid (RFNA) and sepiolite is 0.3～0.45: 1, add thermal agitation at 75～90 ℃, all evaporate up to most water; Suction filtration, filter cake are put baking oven inner drying 10～15h of 100 ℃～110 ℃ into, put into 480 ℃～510 ℃ high temperature furnace again and calcine 8～12h, spend deionised water behind the taking-up sample, and suction filtration until the filtrate clarification, obtains the outer TiO that is
2The carrier photochemical catalyst.
The effect of photochemical catalyst of the present invention: under catalyst of the present invention and radiation of visible light, organic pollution in the water such as environmental hormone phthalate ester, dyestuff, agricultural chemicals, surfactant etc. can be degraded to inorganic molecules such as carbon dioxide, water, and water body is purified.
The specific embodiment
Embodiment 1
The preparation photochemical catalyst
Process one: meerschaum pretreatment.
Concentrated hydrochloric acid with 37% is made into 4～6% diluted hydrochloric acid aqueous solution.Weighing 100g sepiolite is put in the large beaker of 1000mL, adds 200mL distilled water and stirs.Add above-mentioned dilute hydrochloric acid solution to destroy carbonate, have bubble to emit, show that hydrochloric acid has reacted with carbonate to emit CO
2Gas, so repeated treatments till no longer producing gas after the hydrochloric acid adding, makes solution acidity pH ≈ 4 for several times.Standing over night, the sucking-off clear liquid with distilled water washing, suction filtration, is removed calcium, chlorion, until using AgNO then
3Solution detects in the filtrate till the no white precipitate.Last filter cake is at 110 ℃ of oven dry 2h down, solid abrasive, pulverize stand-by.
Process two: CdS-loaded.
Get the sepiolite 5g of above-mentioned acid treatment, add 25mL distilled water furnishing pasty state.
Cadmium nitrate, potassium hydroxide, thiocarbamide are made into the aqueous solution of 0.02M, 0.5M and 0.2M respectively.The mixed solution that ammonium chloride and ammonium nitrate is made into content again and is 0.04M and 1.4M is standby.
The 500mL potassium hydroxide solution is slowly poured in the 500mL cadmium nitrate solution, stirred.Add the mixed solution of 500mL ammonium chloride and ammonium nitrate, the solution of 500mL thiocarbamide more successively, stir and obtain water white mixed liquor.Add the sepiolite of furnishing pasty state this moment, constantly stir.Transferring pH with ammoniacal liquor then is 9.7, and places 80 ℃ water bath with thermostatic control, and deposition reaction 5h in deposition process, transfers pH to remain unchanged with ammoniacal liquor.
Deposition reaction is cooled to room temperature after finishing, and filters, and is washed till neutrality with distilled water, after blotting, dries in 80 ℃ baking oven.
Process three: load TiO
2
The above-mentioned sepiolite after CdS-loaded of weighing 10g places the beaker of 400mL, adds the 200g ethanol solution, and the room temperature lower magnetic force stirs.Then, add the liquid butyl titanate of 22mL, continue to stir 30min.After following ultrasonic dispersion 20min, continue to add thermal agitation again and be evaporated completely substantially until absolute ethyl alcohol.The sample of doing is placed in the 250mL beaker, beaker is put in the 1.0L beaker with cover that water is housed left standstill a night again, and keep humidity constant.Second day, sample joined in the 375mL deionized water mix strongly with the 2.5mL red fuming nitric acid (RFNA), under 80 ℃, add thermal agitation again, till most water all evaporates.Suction filtration omits wet sample, filter cake is put into 105 ℃ baking oven inner drying 10h.Take out the sample dried, put in 500 ℃ the high temperature furnace and calcine 12h.Take out behind the sample with the deionized water washing powder that vibrates strongly, suction filtration is clarified until filtrate then.
The catalyst inner layer that this method is made is a sepiolite, and the intermediate layer is CdS, and skin is TiO
2, thickness is respectively 3.1 μ m, 152nm, 106nm.
Embodiment 2
The preparation photochemical catalyst
Process one: with embodiment 1.
Process two: CdS-loaded.
Get the sepiolite 5g of above-mentioned acid treatment, add 25mL distilled water furnishing pasty state.
Cadmium nitrate, potassium hydroxide, thiocarbamide are made into the aqueous solution of 0.02M, 0.5M and 0.2M respectively.The mixed solution that ammonium chloride and ammonium nitrate is made into content again and is 0.04M and 1.4M is standby.
The 700mL potassium hydroxide solution is slowly poured in the 700mL cadmium nitrate solution, stirred.Add the mixed solution of 700mL ammonium chloride and ammonium nitrate, the solution of 700mL thiocarbamide more successively, stir and obtain water white mixed liquor.Add the sepiolite of furnishing pasty state this moment, constantly stir.Transferring pH with ammoniacal liquor then is 9.9, and places 55 ℃ water bath with thermostatic control, and deposition reaction 10h in deposition process, transfers pH to remain unchanged with ammoniacal liquor.
Deposition reaction is cooled to room temperature after finishing, and filters, and is washed till neutrality with distilled water, after blotting, dries in 90 ℃ baking oven.
Process three: load TiO
2
The above-mentioned sepiolite after CdS-loaded of weighing 10g places the beaker of 400mL, adds the 200g ethanol solution, and the room temperature lower magnetic force stirs.Then, add the liquid butyl titanate of 22mL, continue to stir 30min.After following ultrasonic dispersion 40min, continue to add thermal agitation again and be evaporated completely substantially until absolute ethyl alcohol.The sample of doing is placed in the 250mL beaker, beaker is put in the 1.0L beaker with cover that water is housed left standstill a night again, and keep humidity constant.Second day, sample joined in the 375mL deionized water mix strongly with the 2.5mL red fuming nitric acid (RFNA), under 75 ℃, add thermal agitation again, till most water all evaporates.Suction filtration omits wet sample, filter cake is put into 110 ℃ baking oven inner drying 15h.Take out the sample dried, put in 510 ℃ the high temperature furnace and calcine 10h.Take out behind the sample with the deionized water washing powder that vibrates strongly, suction filtration is clarified until filtrate then.
The catalyst inner layer that this method is made is a sepiolite, and the intermediate layer is CdS, and skin is TiO
2, thickness is respectively 3.1 μ m, 280nm, 136nm.
Embodiment 3
The preparation photochemical catalyst
Process one: with embodiment 1.
Process two: CdS-loaded.
Get the sepiolite 5g of above-mentioned acid treatment, add 25mL distilled water furnishing pasty state.
Cadmium nitrate, potassium hydroxide, thiocarbamide are made into the aqueous solution of 0.02M, 0.5M and 0.2M respectively.The mixed solution that ammonium chloride and ammonium nitrate is made into content again and is 0.04M and 1.4M is standby.
The 700mL potassium hydroxide solution is slowly poured in the 700mL cadmium nitrate solution, stirred.Add the mixed solution of 700mL ammonium chloride and ammonium nitrate, the solution of 700mL thiocarbamide more successively, stir and obtain water white mixed liquor.Add the sepiolite of furnishing pasty state this moment, constantly stir.Transferring pH with ammoniacal liquor then is 9.3, and places 90 ℃ water bath with thermostatic control, and deposition reaction 4h in deposition process, transfers pH to remain unchanged with ammoniacal liquor.
Deposition reaction is cooled to room temperature after finishing, and filters, and is washed till neutrality with distilled water, after blotting, dries in 60 ℃ baking oven.
Process three: load TiO
2
The above-mentioned sepiolite after CdS-loaded of weighing 10g places the beaker of 400mL, adds the 250g ethanol solution, and the room temperature lower magnetic force stirs.Then, add the liquid butyl titanate of 27mL, continue to stir 50min.After following ultrasonic dispersion 35min, continue to add thermal agitation again and be evaporated completely substantially until absolute ethyl alcohol.The sample of doing is placed in the 250mL beaker, beaker is put in the 1.0L beaker with cover that water is housed left standstill a night again, and keep humidity constant.Second day, sample joined in the 375mL deionized water mix strongly with the 3.0mL red fuming nitric acid (RFNA), under 90 ℃, add thermal agitation again, till most water all evaporates.Suction filtration omits wet sample, filter cake is put into 100 ℃ baking oven inner drying 12h.Take out the sample dried, put in 480 ℃ the high temperature furnace and calcine 8h.Take out behind the sample with the deionized water washing powder that vibrates strongly, suction filtration is clarified until filtrate then.
The catalyst inner layer that this method is made is a sepiolite, and the intermediate layer is CdS, and skin is TiO
2, thickness is respectively 3.1 μ m, 158nm, 186nm.
Embodiment 4
The photocatalytic degradation reaction.
Adopt the dispersed with stirring system, intermittently carry out light-catalyzed reaction, reaction unit is the vertical Pyrex glass reaction bottle of volume 120mL, magnetic agitation, light source is halogen lamp (cuts away ultraviolet light with optical filter and utilize visible light), and the carried catalyst that weighing 0.4g embodiment 1 makes joins in the aqueous solution that contains 100mg/L environmental hormone diethyl phthalate that the deionized water with 110mL is mixed with, lucifuge stirs 30min, makes absorption evenly.Start the halogen lamp irradiation simultaneously in stirring afterwards, behind the reaction 10h, the catalyst post analysis is isolated in sampling, and diethyl phthalate has been degraded 90%.
Embodiment 5
The photocatalytic degradation reaction.
Adopt the dispersed with stirring system, intermittently carry out light-catalyzed reaction, reaction unit is the vertical Pyrex glass reaction bottle of volume 120mL, magnetic agitation, light source is halogen lamp (cuts away ultraviolet light with optical filter and utilize visible light), the carried catalyst that weighing 0.6g embodiment 1 makes, and the deionized water that joins with 110mL is mixed with in the aqueous solution that contains 30mg/L dyestuff methylene blue, lucifuge stirs 40min, makes absorption evenly.Start the halogen lamp irradiation simultaneously in stirring afterwards, behind the reaction 9h, the catalyst post analysis is isolated in sampling, and the dyestuff methylene blue has been degraded 93%.
Embodiment 6
The photocatalytic degradation reaction.
Adopt the dispersed with stirring system, intermittently carry out light-catalyzed reaction, reaction unit is the vertical Pyrex glass reaction bottle of volume 120mL, magnetic agitation, light source is halogen lamp (cuts away ultraviolet light with optical filter and utilize visible light), and the carried catalyst that weighing 0.4g embodiment 2 makes joins in the aqueous solution that contains 50mg/L environmental hormone diethyl phthalate that the deionized water with 110mL is mixed with, lucifuge stirs 20min, makes absorption evenly.Start the halogen lamp irradiation simultaneously in stirring afterwards, behind the reaction 10h, the catalyst post analysis is isolated in sampling, and diethyl phthalate has been degraded 93%.
Embodiment 7
The photocatalytic degradation reaction.
Adopt the dispersed with stirring system, intermittently carry out light-catalyzed reaction, reaction unit is the vertical Pyrex glass reaction bottle of volume 120mL, magnetic agitation, light source is halogen lamp (cuts away ultraviolet light with optical filter and utilize visible light), and the carried catalyst that weighing 0.4g embodiment 3 makes joins in the aqueous solution that contains 200mg/L environmental hormone diethyl phthalate that the deionized water with 110mL is mixed with, lucifuge stirs 40min, makes absorption evenly.Start the halogen lamp irradiation simultaneously in stirring afterwards, behind the reaction 15h, the catalyst post analysis is isolated in sampling, and diethyl phthalate has been degraded 80%.
The present invention is not limited to the technology described in the embodiment; its description is illustrative; and it is nonrestrictive; authority of the present invention is limited by claim; based on present technique field personnel according to the present invention can change, technology related to the present invention that method such as reorganization obtains, all within protection scope of the present invention.
Claims (3)
1. photochemical catalyst that is used for eliminating organic pollutant, the structure of catalyst is three layers, it is characterized in that at 2～10 μ m sepiolite particle surface deposition one deck CdS nanocrystallinely, thick 30～600nm is at CdS surface deposition one deck TiO
2Nanocrystalline; TiO
2The thickness of layer is 30～500nm.
2. a preparation method who is used for the photochemical catalyst of eliminating organic pollutant comprises the steps:
1) preliminary treatment of sepiolite: with the sepiolite hydrochloric acid preliminary treatment of pulverizing, acid treatment is filtered till adding the no bubble generation of acid again, and after being washed to neutrality and not having the chlorion existence, suction strainer, oven dry after screening, obtain the sepiolite of 2～10 μ m granularities;
2) CdS-loaded:
Earlier by the required solution of following proportional arrangement: the quality with sepiolite is 1 calculating: select for use
Cadmium nitrate is 0.3～0.6 times of sepiolite;
Potassium hydroxide is 2.4～3 times of sepiolite;
Thiocarbamide is 1.2～1.8 times of sepiolite;
Ammonium nitrate is 8～15 times of sepiolite;
Ammonium chloride is 0.1～0.5 times of sepiolite;
Sepiolite is joined in the above-mentioned solution, and what add that ammoniacal liquor is stirred to the pH value is adjusted to 9.3～9.9, and depositing temperature is at 55～90 ℃, and sedimentation time is 4～10h; Cooling is then filtered, and washing is blotted; Obtain the sepiolite after CdS-loaded;
3) load TiO
2:
With above-mentioned sepiolite after CdS-loaded, add ethanol solution, the mass ratio of ethanol and sepiolite is 17～24: 1; Stir under the room temperature, add the liquid butyl titanate then, the mass ratio of butyl titanate and sepiolite is 1.9～2.5: 1; Continue to stir 0.5～1.0h, follow ultrasonic dispersion and continue to add thermal agitation after 20～40 minutes again, be evaporated completely substantially until absolute ethyl alcohol;
Sample is put into the constant device of maintenance humidity, behind 24～30h, sample is joined in the deionized water mix strongly with red fuming nitric acid (RFNA) again, the mass ratio of red fuming nitric acid (RFNA) and sepiolite is 0.3～0.45: 1, add thermal agitation at 75～90 ℃, all evaporate up to most water; Suction filtration, filter cake are put baking oven inner drying 10～15h of 100 ℃～110 ℃ into, put into 480 ℃～510 ℃ high temperature furnace again and calcine 8～12h, spend deionised water behind the taking-up sample, and suction filtration until the filtrate clarification, obtains the outer TiO that is
2The carrier photochemical catalyst.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976439A (en) * | 2012-12-11 | 2013-03-20 | 常州大学 | Method for degrading organic chloride in wastewater through cadmium titanate photocatalyst |
| CN103468049A (en) * | 2013-09-30 | 2013-12-25 | 四川嘉宝莉涂料有限公司 | Formaldehyde-removing coating with absorption function and decomposition function and preparation method thereof |
| CN103521206A (en) * | 2013-09-30 | 2014-01-22 | 四川嘉宝莉涂料有限公司 | Synthetic method of sepiolite/nano TiO2 composite material |
| CN103521207A (en) * | 2013-09-30 | 2014-01-22 | 四川嘉宝莉涂料有限公司 | Method for sepiolite/nano TiO2 in situ synthesis and doping modification |
| CN103736500A (en) * | 2013-12-23 | 2014-04-23 | 清华大学 | Titanium dioxide/cadmium sulfide/titanium dioxide composite film and application thereof |
| CN107362813A (en) * | 2017-09-05 | 2017-11-21 | 云南大学 | The preparation method and purposes of a kind of cadmium sulfide/bismuth oxyiodide heterojunction photocatalyst |
-
2005
- 2005-03-23 CN CN 200510013230 patent/CN1692979A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976439A (en) * | 2012-12-11 | 2013-03-20 | 常州大学 | Method for degrading organic chloride in wastewater through cadmium titanate photocatalyst |
| CN103468049A (en) * | 2013-09-30 | 2013-12-25 | 四川嘉宝莉涂料有限公司 | Formaldehyde-removing coating with absorption function and decomposition function and preparation method thereof |
| CN103521206A (en) * | 2013-09-30 | 2014-01-22 | 四川嘉宝莉涂料有限公司 | Synthetic method of sepiolite/nano TiO2 composite material |
| CN103521207A (en) * | 2013-09-30 | 2014-01-22 | 四川嘉宝莉涂料有限公司 | Method for sepiolite/nano TiO2 in situ synthesis and doping modification |
| CN103521207B (en) * | 2013-09-30 | 2016-04-06 | 四川嘉宝莉涂料有限公司 | The method of a kind of sepiolite/nano TiO 2 fabricated in situ, doping vario-property |
| CN103736500A (en) * | 2013-12-23 | 2014-04-23 | 清华大学 | Titanium dioxide/cadmium sulfide/titanium dioxide composite film and application thereof |
| CN103736500B (en) * | 2013-12-23 | 2016-06-15 | 清华大学 | A kind of Titanium dioxide/cadmium sulfide/titanium dioxide composite film and application thereof |
| CN107362813A (en) * | 2017-09-05 | 2017-11-21 | 云南大学 | The preparation method and purposes of a kind of cadmium sulfide/bismuth oxyiodide heterojunction photocatalyst |
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