CN102764666B - Nitrogen and cerium co-doped titanium dioxide hollow sphere photo-catalyst and preparation method thereof - Google Patents
Nitrogen and cerium co-doped titanium dioxide hollow sphere photo-catalyst and preparation method thereof Download PDFInfo
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- CN102764666B CN102764666B CN201210235525.4A CN201210235525A CN102764666B CN 102764666 B CN102764666 B CN 102764666B CN 201210235525 A CN201210235525 A CN 201210235525A CN 102764666 B CN102764666 B CN 102764666B
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Abstract
The invention discloses a nitrogen and cerium co-doped titanium dioxide hollow sphere photo-catalyst and a preparation method thereof. The hollow sphere photo-catalyst is controllable in wall thickness and good in monodispersity, the diameter of hollow spheres is 300 to 500 nanometers, the wall thickness is 10 to 50 nanometers, and the photo-catalyst has high photo-catalytic efficiency for simulated organic rhodamine B pollutant in water. The method comprises the following steps of: preparing silicon dioxide microspheres by using an in-situ hydrolysis technology, coating a layer of nitrogen and cerium co-doped titanium dioxide on the surface of the silicon dioxide microspheres, removing the silicon dioxide template by using a method of corroding with a corrosive, and finally obtaining the nitrogen and cerium co-doped titanium dioxide photo-catalyst material. The nitrogen and cerium co-doped titanium dioxide hollow sphere photo-catalyst prepared by using the method is uniform in granularity distribution, large in specific surface area and high photo-catalytic reaction efficiency.
Description
Technical field
The invention belongs to industrial chemicals photochemical catalyst preparing technical field, relate to a kind of nano-hollow ball catalysis material, be specifically related to a kind of nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst, the invention still further relates to the preparation method of this catalyst.
Background technology
Photocatalysis technology is the emerging green technology progressively growing up from 20 century 70s, it utilizes conductor oxidate material can be subject to the characteristic of activation, oxidation Decomposition organic matter, reducing heavy metal ion, kill bacteria and elimination peculiar smell effectively at the condition lower surface of illumination.In numerous catalysis materials, TiO
2nontoxic, harmless, the non-corrosiveness that have due to self, can Reusability, can be by organic matter permineralization Cheng Shui and inorganic ions, the features such as non-secondary pollution, there are traditional high temperature, the incomparable tempting glamour of conventional catalyst, have broad prospect of application in environmental contaminants process field.
In recent years, for effectively improving TiO
2the light-catalyzed reaction efficiency of photocatalyst material and expand its application at visible light wave range, researchers adopt several different methods to prepare titania-based photocatalysis composite.Wherein, titanium dioxide nonmetal and metal-doped is one of emphasis of titanium dioxide optical catalyst investigation of materials in recent years.Nonmetal and metal can use and prevent the compound of electronics and hole as electron capture center, thereby improves the reaction efficiency of catalyst, can play again the effect that reduces titanium dioxide energy gap simultaneously, expands the object that it uses at visible region.
Summary of the invention
The object of this invention is to provide a kind of nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst, change the molecular structure of titanium dioxide, improve the performance of titanium dioxide, make the wave band that excites of titanium dioxide, expand to visible region from ultraviolet region, as long as light wave is below 800nm, without ultraviolet light, just can there is excitation to it, and performance greatly strengthens, decomposing formaldehyde, benzene, ammonia, organic volatile etc., to people's basis and the harmful gas of environment, have improved antibacterial deodorizing ability quickly and efficiently, utilize powder to can be made into the dispersion liquid of various concentration simultaneously.
Another object of the present invention is to provide the preparation method that a kind of nitrogen cerium is mixed titanium dioxide hollow ball photochemical catalyst altogether.
The technical solution adopted in the present invention is, a kind of nitrogen cerium is mixed titanium dioxide hollow ball photochemical catalyst altogether, and the diameter of hollow ball is 300 ~ 500nm, and wall thickness is 10 ~ 50nm.
Another technical scheme of the present invention is, a kind of nitrogen cerium is mixed the preparation method of titanium dioxide hollow ball photochemical catalyst altogether, the hollow ball photochemical catalyst preparing, and the diameter of hollow ball is 300 ~ 500nm, wall thickness is 10 ~ 50nm;
Specifically implement according to following steps:
Step 1: absolute ethyl alcohol is dissolved in to deionized water and obtains the ethanol solution that quality-volumetric concentration is 0.27gL, ethyl orthosilicate is joined in ethanol solution, the volume ratio of ethyl orthosilicate and ethanol solution is 9:175, magnetic agitation, then under stirring, be the ammoniacal liquor of 25wt% to adding mass concentration in mixed solution, the volume ratio of mixed solution and ammoniacal liquor is 184:9, continue stirring reaction 10h, centrifugation is also cleaned 3 times successively by absolute ethyl alcohol and deionized water, in 80 ℃ of baking ovens, is dried and obtains lily silicon-dioxide powdery;
Step 2: be that 16gL-160g/L takes the silicon-dioxide powdery that step 1 makes and is scattered in absolute ethyl alcohol according to quality-volumetric concentration, ultrasonic dispersion 30min, be labeled as solution A, be that 0.003g/L-0.077g/L takes butyl titanate and joins in absolute ethyl alcohol according to quality-volumetric concentration, be labeled as solution B, then under stirring, solution B is joined in solution A and mixed, add ammonium nitrate and cerous nitrate simultaneously, continue to stir 1 ~ 3h, and ageing 3h;
Step 3: get the mixed liquor obtaining after step 2 ageing and join with in teflon-lined water heating kettle, carry out hydro-thermal reaction, after finishing, reaction naturally cools to room temperature, obtain a milky white liquid, by this white liquid centrifugation, and wash respectively 3 times with deionized water and absolute ethyl alcohol, finally gained solid product is put into dry 12 hours of the vacuum drying chamber of 60 ~ 80 ℃, obtain white powder;
Step 4: be 1/30g/L according to quality-volumetric concentration, taking the white powder that step 3 makes is scattered in deionized water, add corrosive agent and corrode 8h under stirring, by deionized water centrifuge washing 3 times of remaining solid product, and dry 12 hours of the vacuum drying chamber of putting into 80 ℃, make nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst.
Feature of the present invention is also,
In step 2 wherein, the mass ratio of ammonium nitrate and mixed solution is 1.25 × 10
-4-3.64 × 10
-4: 1, the mass ratio of cerous nitrate and mixed solution is 4.55 × 10
-4-0.001:1.
Hydro-thermal reaction in step 3 wherein, reaction temperature is 120-200 ℃, 30 ~ 90 minutes reaction time.
In step 4 wherein, the mass ratio of corrosive agent and white powder is 0.4:1.
Corrosive agent in step 4 wherein adopts the one in NaOH or sodium borohydride, or the mixture of two kinds.
The invention has the beneficial effects as follows: process of the present invention is simple, is suitable for large-scale production, and the raw material such as ethyl orthosilicate and butyl titanate using is easy to get, pollution-free.The product particle size homogeneous that the present invention is prepared, pattern is regular, and nitrogen cerium is mixed altogether titanium dioxide hollow ball photochemical catalyst and had higher light-catalyzed reaction efficiency.
Accompanying drawing explanation
Fig. 1 is the X ray diffracting spectrum that the prepared nitrogen cerium of the embodiment of the present invention 1 is mixed titanium dioxide hollow ball altogether;
Fig. 2 is that the prepared nitrogen cerium of the embodiment of the present invention 2 is mixed titanium dioxide hollow ball transmission electron microscope photo altogether;
Fig. 3 is the degradation curve that the prepared nitrogen cerium of the embodiment of the present invention 4 is mixed rhodamine B in titanium dioxide hollow ball photochemical catalyst removal water body altogether.
The specific embodiment
18mL ethyl orthosilicate is joined in the mixed solution of 260mL absolute ethyl alcohol and 90mL deionized water, and magnetic agitation.Then under stirring, in mixed liquor, add 18mL ammoniacal liquor (25wt%), continue stirring reaction 10h.Centrifugation is also cleaned 3 times successively by absolute ethyl alcohol and deionized water.Finally in 80 ℃ of baking ovens, be dried and obtain lily silicon-dioxide powdery.Take prepared silicon-dioxide powdery 0.5g and be scattered in 65mL absolute ethyl alcohol, ultrasonic dispersion 30min, is labeled as solution A, then takes 0.5g butyl titanate and join in 10mL absolute ethyl alcohol, is labeled as solution B.Then under stirring, solution B is joined in solution A, add the ammonium nitrate of 20mg and the cerous nitrate of 20mg simultaneously, continue to stir 1h, and ageing 3h.Get the mixed liquor 50mL of gained after ageing and join with in teflon-lined water heating kettle, and be placed in many flux of MDS-10 type closed microwave chem workstation and carry out hydro-thermal reaction, reaction temperature is 160 ℃, 60 minutes reaction time.After finishing, reaction naturally cools to room temperature, obtain a milky white liquid, by this white liquid centrifugation, and wash respectively for several times with deionized water and absolute ethyl alcohol, the vacuum drying chamber of finally gained solid product being put into 60 ℃ is dried 12 hours, obtains white powder.Taking the prepared white powder 0.5g of step 3 powder is scattered in 15mL deionized water, add 0.2g corrosive agent and corrode 8h under stirring, by deionized water centrifuge washing several for remaining solid product, and dry 12 hours of the vacuum drying chamber of putting into 80 ℃, finally make nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst.Fig. 1 is the XRD collection of illustrative plates that prepared nitrogen cerium is mixed titanium dioxide hollow ball photochemical catalyst altogether, as can be seen from the figure, the diffraction maximum that nitrogen cerium is mixed titanium dioxide does not altogether have the diffraction maximum of unadulterated titanium dioxide sharp-pointed, and there is diffraction peaks broadening, illustrate because the introducing of nitrogen cerium has caused diminishing of titanium dioxide granule size.
18mL ethyl orthosilicate is joined in the mixed solution of 260mL absolute ethyl alcohol and 90mL deionized water, and magnetic agitation.Then under stirring, in mixed liquor, add 18mL ammoniacal liquor (25wt%), continue stirring reaction 10h.Centrifugation is also cleaned 3 times successively by absolute ethyl alcohol and deionized water.Finally in 80 ℃ of baking ovens, be dried and obtain lily silicon-dioxide powdery.Take prepared silicon-dioxide powdery 0.5g and be scattered in 65mL absolute ethyl alcohol, ultrasonic dispersion 30min, is labeled as solution A, then takes 0.5g butyl titanate and join in 10mL absolute ethyl alcohol, is labeled as solution B.Then under stirring, solution B is joined in solution A, add the ammonium nitrate of 20mg and the cerous nitrate of 40mg simultaneously, continue to stir 1h, and ageing 3h.Get the mixed liquor 50mL of gained after ageing and join with in teflon-lined water heating kettle, and be placed in many flux of MDS-10 type closed microwave chem workstation and carry out hydro-thermal reaction, reaction temperature is 200 ℃, 60 minutes reaction time.After finishing, reaction naturally cools to room temperature, obtain a milky white liquid, by this white liquid centrifugation, and wash respectively for several times with deionized water and absolute ethyl alcohol, the vacuum drying chamber of finally gained solid product being put into 60 ℃ is dried 12 hours, obtains white powder.Taking the prepared white powder 0.5g of step 3 powder is scattered in 15mL deionized water, add 0.2g corrosive agent and corrode 8h under stirring, by deionized water centrifuge washing several for remaining solid product, and dry 12 hours of the vacuum drying chamber of putting into 80 ℃, finally make nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst.Fig. 2 is the transmission electron microscope photo that prepared nitrogen cerium is mixed titanium dioxide hollow ball photochemical catalyst altogether.As can be seen from the figure, the prepared titanium dioxide hollow ball photochemical catalyst of mixing is altogether monodispersed hollow ball, and diameter is about 400nm, wall thickness 10～30nm, and pattern is regular, size homogeneous, and silica is corroded completely.
18mL ethyl orthosilicate is joined in the mixed solution of 260mL absolute ethyl alcohol and 90mL deionized water, and magnetic agitation.Then under stirring, in mixed liquor, add 18mL ammoniacal liquor (25wt%), continue stirring reaction 10h.Centrifugation is also cleaned 3 times successively by absolute ethyl alcohol and deionized water.Finally in 80 ℃ of baking ovens, be dried and obtain lily silicon-dioxide powdery.Take prepared silicon-dioxide powdery 0.1g and be scattered in 30mL absolute ethyl alcohol, ultrasonic dispersion 30min, is labeled as solution A, then takes 1.0g butyl titanate and join in 10mL absolute ethyl alcohol, is labeled as solution B.Then under stirring, solution B is joined in solution A, add the ammonium nitrate of 5mg and the cerous nitrate of 40mg simultaneously, continue to stir 1h, and ageing 3h.Get the mixed liquor 50mL of gained after ageing and join with in teflon-lined water heating kettle, and be placed in many flux of MDS-10 type closed microwave chem workstation and carry out hydro-thermal reaction, reaction temperature is 120 ℃, 30 minutes reaction time.After finishing, reaction naturally cools to room temperature, obtain a milky white liquid, by this white liquid centrifugation, and wash respectively for several times with deionized water and absolute ethyl alcohol, the vacuum drying chamber of finally gained solid product being put into 60 ℃ is dried 12 hours, obtains white powder.Taking the prepared white powder 0.5g of step 3 powder is scattered in 15mL deionized water, add 0.2g corrosive agent and corrode 8h under stirring, by deionized water centrifuge washing several for remaining solid product, and dry 12 hours of the vacuum drying chamber of putting into 80 ℃, finally make nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst.
18mL ethyl orthosilicate is joined in the mixed solution of 260mL absolute ethyl alcohol and 90mL deionized water, and magnetic agitation.Then under stirring, in mixed liquor, add 18mL ammoniacal liquor (25wt%), continue stirring reaction 10h.Centrifugation is also cleaned 3 times successively by absolute ethyl alcohol and deionized water.Finally in 80 ℃ of baking ovens, be dried and obtain lily silicon-dioxide powdery.Take prepared silicon-dioxide powdery 1.0g and be scattered in 100mL absolute ethyl alcohol, ultrasonic dispersion 30min, is labeled as solution A, then takes 0.1g butyl titanate and join in 10mL absolute ethyl alcohol, is labeled as solution B.Then under stirring, solution B is joined in solution A, add the ammonium nitrate of 40mg and the cerous nitrate of 5mg simultaneously, continue to stir 3h, and ageing 3h.Get the mixed liquor 50mL of gained after ageing and join with in teflon-lined water heating kettle, and be placed in many flux of MDS-10 type closed microwave chem workstation and carry out hydro-thermal reaction, reaction temperature is 200 ℃, 90 minutes reaction time.After finishing, reaction naturally cools to room temperature, obtain a milky white liquid, by this white liquid centrifugation, and wash respectively for several times with deionized water and absolute ethyl alcohol, the vacuum drying chamber of finally gained solid product being put into 80 ℃ is dried 12 hours, obtains white powder.Taking the prepared white powder 0.5g of step 3 powder is scattered in 15mL deionized water, add 0.2g corrosive agent and corrode 8h under stirring, by deionized water centrifuge washing several for remaining solid product, and dry 12 hours of the vacuum drying chamber of putting into 80 ℃, finally make nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst.Fig. 3 is the degradation curve that prepared nitrogen cerium is mixed rhodamine B in titanium dioxide hollow ball photochemical catalyst removal water body altogether.Can obviously find out that from degradation curve the nitrogen cerium of preparation mixes altogether titanium dioxide hollow ball photochemical catalyst rhodamine B water body is had to higher degradation efficiency.
Claims (1)
1. nitrogen cerium is mixed a preparation method for titanium dioxide hollow ball photochemical catalyst altogether, it is characterized in that, specifically implements according to following steps:
18mL ethyl orthosilicate is joined in the mixed solution of 260mL absolute ethyl alcohol and 90mL deionized water, and magnetic agitation, then under stirring, in mixed liquor, add 18mL ammoniacal liquor, continue stirring reaction 10h, centrifugation is also cleaned 3 times successively by absolute ethyl alcohol and deionized water, finally in 80 ℃ of baking ovens, be dried and obtain lily silicon-dioxide powdery, taking prepared silicon-dioxide powdery 0.5g is scattered in 65mL absolute ethyl alcohol, ultrasonic dispersion 30min, be labeled as solution A, taking 0.5g butyl titanate joins in 10mL absolute ethyl alcohol again, be labeled as solution B, then under stirring, solution B is joined in solution A, add the ammonium nitrate of 20mg and the cerous nitrate of 20mg simultaneously, continue to stir 1h, and ageing 3h, getting the mixed liquor 50mL of gained after ageing joins with in teflon-lined water heating kettle, and be placed in many flux of MDS-10 type closed microwave chem workstation and carry out hydro-thermal reaction, reaction temperature is 160 ℃, 60 minutes reaction time, after finishing, reaction naturally cools to room temperature, obtain a milky white liquid, by this white liquid centrifugation, and wash respectively for several times with deionized water and absolute ethyl alcohol, the vacuum drying chamber of finally gained solid product being put into 60 ℃ is dried 12 hours, obtain white powder, taking the white powder 0.5g powder making is scattered in 15mL deionized water, add 0.2g corrosive agent and corrode 8h under stirring, by deionized water centrifuge washing several for remaining solid product, and the vacuum drying chamber of putting into 80 ℃ is dried 12 hours, finally make nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst,
Or, specifically implement according to following steps:
18mL ethyl orthosilicate is joined in the mixed solution of 260mL absolute ethyl alcohol and 90mL deionized water, and magnetic agitation, then under stirring, in mixed liquor, add 18mL ammoniacal liquor, continue stirring reaction 10h, centrifugation is also cleaned 3 times successively by absolute ethyl alcohol and deionized water, finally in 80 ℃ of baking ovens, be dried and obtain lily silicon-dioxide powdery, taking prepared silicon-dioxide powdery 0.5g is scattered in 65mL absolute ethyl alcohol, ultrasonic dispersion 30min, be labeled as solution A, taking 0.5g butyl titanate joins in 10mL absolute ethyl alcohol again, be labeled as solution B, then under stirring, solution B is joined in solution A, add the ammonium nitrate of 20mg and the cerous nitrate of 40mg simultaneously, continue to stir 1h, and ageing 3h, getting the mixed liquor 50mL of gained after ageing joins with in teflon-lined water heating kettle, and be placed in many flux of MDS-10 type closed microwave chem workstation and carry out hydro-thermal reaction, reaction temperature is 200 ℃, 60 minutes reaction time, after finishing, reaction naturally cools to room temperature, obtain a milky white liquid, by this white liquid centrifugation, and wash respectively for several times with deionized water and absolute ethyl alcohol, the vacuum drying chamber of finally gained solid product being put into 60 ℃ is dried 12 hours, obtain white powder, taking the white powder 0.5g powder making is scattered in 15mL deionized water, add 0.2g corrosive agent and corrode 8h under stirring, by deionized water centrifuge washing several for remaining solid product, and the vacuum drying chamber of putting into 80 ℃ is dried 12 hours, finally make nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst,
Or, specifically implement according to following steps:
18mL ethyl orthosilicate is joined in the mixed solution of 260mL absolute ethyl alcohol and 90mL deionized water, and magnetic agitation, then under stirring, in mixed liquor, add 18mL ammoniacal liquor, continue stirring reaction 10h, centrifugation is also cleaned 3 times successively by absolute ethyl alcohol and deionized water, finally in 80 ℃ of baking ovens, be dried and obtain lily silicon-dioxide powdery, taking prepared silicon-dioxide powdery 0.1g is scattered in 30mL absolute ethyl alcohol, ultrasonic dispersion 30min, be labeled as solution A, taking 1.0g butyl titanate joins in 10mL absolute ethyl alcohol again, be labeled as solution B, then under stirring, solution B is joined in solution A, add the ammonium nitrate of 5mg and the cerous nitrate of 40mg simultaneously, continue to stir 1h, and ageing 3h, getting the mixed liquor 50mL of gained after ageing joins with in teflon-lined water heating kettle, and be placed in many flux of MDS-10 type closed microwave chem workstation and carry out hydro-thermal reaction, reaction temperature is 120 ℃, 30 minutes reaction time, after finishing, reaction naturally cools to room temperature, obtain a milky white liquid, by this white liquid centrifugation, and wash respectively for several times with deionized water and absolute ethyl alcohol, the vacuum drying chamber of finally gained solid product being put into 60 ℃ is dried 12 hours, obtain white powder, taking the white powder 0.5g powder making is scattered in 15mL deionized water, add 0.2g corrosive agent and corrode 8h under stirring, by deionized water centrifuge washing several for remaining solid product, and the vacuum drying chamber of putting into 80 ℃ is dried 12 hours, finally make nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst,
Or, specifically implement according to following steps:
18mL ethyl orthosilicate is joined in the mixed solution of 260mL absolute ethyl alcohol and 90mL deionized water, and magnetic agitation, then under stirring, in mixed liquor, add 18mL ammoniacal liquor, continue stirring reaction 10h, centrifugation is also cleaned 3 times successively by absolute ethyl alcohol and deionized water, finally in 80 ℃ of baking ovens, be dried and obtain lily silicon-dioxide powdery, taking prepared silicon-dioxide powdery 1.0g is scattered in 100mL absolute ethyl alcohol, ultrasonic dispersion 30min, be labeled as solution A, taking 0.1g butyl titanate joins in 10mL absolute ethyl alcohol again, be labeled as solution B, then under stirring, solution B is joined in solution A, add the ammonium nitrate of 40mg and the cerous nitrate of 5mg simultaneously, continue to stir 3h, and ageing 3h, getting the mixed liquor 50mL of gained after ageing joins with in teflon-lined water heating kettle, and be placed in many flux of MDS-10 type closed microwave chem workstation and carry out hydro-thermal reaction, reaction temperature is 200 ℃, 90 minutes reaction time, after finishing, reaction naturally cools to room temperature, obtain a milky white liquid, by this white liquid centrifugation, and wash respectively for several times with deionized water and absolute ethyl alcohol, the vacuum drying chamber of finally gained solid product being put into 80 ℃ is dried 12 hours, obtain white powder, taking the white powder 0.5g powder making is scattered in 15mL deionized water, add 0.2g corrosive agent and corrode 8h under stirring, by deionized water centrifuge washing several for remaining solid product, and the vacuum drying chamber of putting into 80 ℃ is dried 12 hours, finally make nitrogen cerium and mix altogether titanium dioxide hollow ball photochemical catalyst.
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| CN106179442A (en) * | 2016-07-04 | 2016-12-07 | 河海大学 | A kind of cerium and nitrogen co-doped titanium dioxide optical catalyst and its preparation method and application |
| CN106582657B (en) * | 2016-12-21 | 2019-01-15 | 郑州师范学院 | A kind of TiO2- M-B cooperative photocatalysis agent and its preparation method and application |
| CN111282565A (en) * | 2020-03-24 | 2020-06-16 | 清华大学盐城环境工程技术研发中心 | MnCeOxPreparation method and application of catalyst |
| CN114570348B (en) * | 2022-03-02 | 2024-03-12 | 济南大学 | Titanium dioxide-based nano composite photocatalyst for photocatalytic degradation by irradiation of visible light and application thereof |
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| CN101941736A (en) * | 2010-10-21 | 2011-01-12 | 北京科技大学 | Preparation method of echinoid titanium dioxide microspheres in single/double layer cavity structure |
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| CN101941736A (en) * | 2010-10-21 | 2011-01-12 | 北京科技大学 | Preparation method of echinoid titanium dioxide microspheres in single/double layer cavity structure |
Non-Patent Citations (2)
| Title |
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| "Preparation of cerium and nitrogen co-doped titania hollow spheres with enhanced visible light photocatalytic performance";Chao Wang et al;《Powder Technology》;20110326;第210卷;第2节 * |
| Chao Wang et al."Preparation of cerium and nitrogen co-doped titania hollow spheres with enhanced visible light photocatalytic performance".《Powder Technology》.2011,第210卷第2节. |
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