CN103691472A - Preparation method of nitrogen-doped titanium dioxide mesoporous visible light photocatalyst - Google Patents
Preparation method of nitrogen-doped titanium dioxide mesoporous visible light photocatalyst Download PDFInfo
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- CN103691472A CN103691472A CN201310736377.9A CN201310736377A CN103691472A CN 103691472 A CN103691472 A CN 103691472A CN 201310736377 A CN201310736377 A CN 201310736377A CN 103691472 A CN103691472 A CN 103691472A
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Abstract
The invention discloses a preparation method of a nitrogen-doped titanium dioxide mesoporous visible light photocatalyst, and belongs to the field of novel materials. The preparation method is mainly characterized by comprising the following steps: preparing a compound titanium silicon oxide by taking titanium alkoxide and tetraethoxysilane as main raw materials and inorganic acid as a hydrolysis catalyst according to a sol-gel method, drying, grinding and sieving the compound oxide, and performing high-temperature calcinations to remove organic matters from gel; nitriding calcined powder in flowing ammonia gas at 850-950 DEG C, cooling to room temperature, washing through an alkaline solution, and dissolving silicon dioxide and excess nitrogen to obtain the nitrogen-doped titanium dioxide mesoporous visible light photocatalyst. The nitrogen-doped titanium dioxide mesoporous visible light photocatalyst is an agglomerate formed by nitrogen-doped titanium dioxide with the mesoporous and crystal particle sizes less than 10 nm, the specific surface area is more than 150 m<2>/g, and the spectral response range is expanded to the wavelength of 600 nm.
Description
Technical field
The preparation method who the present invention relates to the mesoporous visible light-responded photochemical catalyst of nitrogen-doped titanium dioxide, belongs to field of new.
Technical background
Nano titanium oxide is a kind of very effective photochemical catalyst, but also exist can only absorb ultraviolet light, to shortcomings such as the visible ray of sunshine accounting 40% can not utilize.The nonmetalloids such as nitrogen replace after the oxygen in titanium dioxide, the photoresponse scope of titanium dioxide can be extended to visible region by ultraviolet light, and show visible light catalysis activity.At present the method for the nitrogen-doping of report mainly contain titania surface nitrogen treatment (Asahi R, Morikawa T, Ohwaki T,
s degree Celsius of ien degree Celsius of e of et al., 2001,293,269-271), utilize ammonia and nano titanium oxide at 500-600 degree Celsius of gas-solid reaction, nitrogen partly replaces after oxygen, obtains the titanium dioxide of nitrogen doping.While containing ammonium radical ion in the titanium dioxide of preparation, in air, heat, also can obtain light yellow nitrogen-doped titanium dioxide (Kis degree Celsius of h H, Ma degree Celsius of yk W.
degree Celsius hemPhys degree Celsius of hem, 2002,3,399-400).But because nitrogen anion not too easily mixes the lattice of titanium oxide with " replacement " form, so how to realize Effective Doping, just become a key issue in research.Mechanochemistry mixing (high-energy ball milling) processing (Yin S, Yamaki H, Komatsu M,
mater. degree Celsius of hem. of et al. J., 2003,13:2996-3001.), the processing of introducing ammonium salt (Yin S, Yamaki H, Komatsu M,
mater. degree Celsius of hem. of et al. J., 2003,13:2996-3001. Sato S.
degree Celsius hem. Phys. Lett., 1986,123:126-128.), TiN annealing in process (Morikawa T, Asahi R, Ohwaki T,
et al. Jpn. J. Appl. Phys., 2001,40:561-563) etc.
Utilize that gas-solid reaction or titanium dioxide are mixed to be prepared nitrogen-doped titanium dioxide degree with ammonium salt heat treatment and be faced with some problems, gas-solid reaction temperature is low, short nitrogen content of time absorptivity low, catalyst visible region is little, only visible ray is had to weak response.Raising nitriding temperature, prolongation nitridation time may cause that nitrogenize is excessive, it by titanium dioxide nitrogenize, is the titanium nitride that there is no photocatalytic activity, as [methods of preparing nano-sized nitride by inorganic double salt aminolysis such as high Lian, Zhang Qinghong, Chinese invention patent number: ZL200410015915.6] show, in the time of 700 degrees Celsius, titanium dioxide just may be transformed into titanium nitride (detecting with XRD) completely.In addition, because nitriding temperature is high, the reaction time is long, titanium dioxide must inevitably be grown up, and nano titanium oxide gas-solid reaction is difficult to obtain the nitrogen-doped titanium dioxide visible light catalyst of high-specific surface area, ultra-fine grain.
Summary of the invention
The object of the invention is to implement like this: it is that to utilize titanium alkoxide and ethyl orthosilicate be primary raw material, employing inorganic acid is hydrolyst, with sol-gal process, prepare Ti-Si composite oxide, composite oxides drying, pulverize and sieve after, high-temperature calcination, in ammonia, nitrogenize makes titanium dioxide nitrating.Composite granule after nitrating, after aqueous slkali washing, dissolves silica wherein, obtains the mesoporous visible-light photocatalysis material of required nitrogen-doped titanium dioxide.This material is less than by mesoporous and crystallite dimension the aggregate that the nitrating titanium dioxide of 10 nanometers is constructed, and its specific area is greater than 150m
2more than/g.
Concrete enforcement can be divided into three and walk greatly:
The first step is prepared Ti-Si composite oxide; The nitrogenize of second step composite oxides; Composite oxides after the 3rd step aqueous slkali washing crystallization, thus the nitrating titanium dioxide mesoporous material with visible light photocatalysis characteristic obtained.Now details are as follows respectively:
One, the preparation of Ti-Si composite oxide
By bistep hydrolysis, can effectively control the texture of Ti-Si composite oxide.The mentioned titanium alkoxide of the present invention can be tetraethyl titanate, isopropyl titanate or butyl titanate.At present, in the alkoxide of domestic titanium, butyl titanate is easy to get.Because the hydrolysis rate of ethyl orthosilicate is than titanium alkoxide slow (while especially being used butyl titanate), thus to obtain the uniform composite granule of component should allow ethyl orthosilicate first partial hydrolysis obtain colloidal sol.
Concrete preparation technology is: the ethanolic solution of the ethyl orthosilicate that is first 1:1 by volume ratio is in 50-70 degree Celsius of hydrolysis, make colloidal sol, the ethanolic solution of the titanium alkoxide that is then 1:1 by volume ratio joins in above-mentioned colloidal sol, progressively add again the ethanolic solution of 0.1M dilute sulfuric acid to make the hydrolysis of alkoxide of titanium, obtain complex sol, complex sol is gelation at room temperature.The ratio of two kinds of solution of adjusting can obtain the composite oxides of different titanium silicon ratios.The titanium silicon of composite oxides provided by the invention is 1:19 to 1:1 than excursion.Specifically consist of: TiO
219SiO
2, TiO
29SiO
2, TiO
24SiO
2, TiO
23SiO
2, TiO
2siO
2deng 5 kinds.
Under mixed sols room temperature, gelation time is with titanium silicon than relevant, and when titanium silicon ratio is 4:1, gel process can complete in 1h; Titanium silicon is than when the 1:19, and gelation time needs just complete for 3 weeks, under room temperature gelation required time from 1 hour to several weeks not etc.
It is crucial that two-step method prepares in the process of silicon dioxide and titanium dioxide composite oxides that the presoma hydrolytic process of titanium and silicon controls.The hydrolysis rate of ethyl orthosilicate can be accelerated by rising temperature, 50-70 degree Celsius of backflow 1-2 hour for example, with the ethanolic solution of 0.1M dilute sulfuric acid as hydrolyst, silicon is controlled at 1:1 with the ratio of the amount of substance of water, (Ti+Si): the H that adds the total amount of water to remain in whole process
2the ratio of O=1:2, reaction water is that the form with 0.1M dilute sulfuric acid ethanolic solution progressively adds.
Two, the nitrogenize of composite oxides
Plural gel, in 120-150 degree Celsius of vacuum drying, is calcined 2 hours for 600 degrees Celsius in grinding and sieving, air.The composite oxides of cooling rear weighing certain mass, nitrogenize in the ammonia that flows in tube furnace, the range of flow of ammonia is 100-2000 ml/min, and nitriding temperature scope is 850-950 degree Celsius, and nitriding temperature scope 2-5 hour, makes titanium dioxide nitrogenize.
Titanium silicon is during higher than 1:1, and under so high nitriding temperature, the titanium dioxide Partial Conversion in composite oxides is titanium nitride, in follow-up alkaline cleaning procedure, titanium nitride is still more stable, contains the titanium nitride of photocatalytic activity in product, titanium silicon than multi-control at 1:3 or lower.
In the composite granule of titania/silica, utilize the network limits of silica to be used for suppressing the Fast Growth of titania in nitridation process, through high-temperature calcination, can obtain the composite granule of crystalline state titanium dioxide and indefiniteness silica.
In composite granule, dioxide-containing silica is high can suppress titanium dioxide crystallization, TiO in composite oxides after 600 degrees Celsius of calcinings
2with impalpable structure, exist.SiO after gel
2/ TiO
2in composite granule, due to SiO
2network stops transporting of titanium in calcination process, and mass transport process is difficult to carry out.When 850 degrees Celsius or above temperature nitrogen treatment, titanium dioxide crystallization is Anatase, after crystallization, titanium dioxide density becomes large, volume contraction, makes to use more reaction channel in composite oxides, and it is favourable with reacting of titanium dioxide that ammonia, ammonia are decomposed to the nitrogen substance producing.
Three, the composite oxides after aqueous slkali washing nitrogenize
Composite granule after nitrogenize, containing nitrogen-doped titanium dioxide, silica, because nitridation reaction temperature is high, nitrogen doping is abundant, hindered the grain growth of titanium dioxide due to the network of silica, so the titania of nitrogen doping is tiny especially simultaneously.By chemical method, dissolve the silica in composite granule, can obtain mesoporous nitrogen-doped titanium dioxide.Alternative chemical substance has highly basic and hydrofluoric acid.But the fluorine ion in hydrofluoric acid and Ti
4+form [TiF
6]
2-complex ion, also makes titanium dioxide be partly dissolved when result makes to dissolve silica, therefore not ideal enough.
Select the highly basic such as NaOH or potassium hydroxide effectively to dissolve silica and can not make titanium dioxide dissolve.Its reaction expression is:
2ROH + SiO
2 → R
2SiO
3 + H
2O
(R
+for Na
+, K
+ion)
The R generating
2siO
3for the metasilicate of monovalent ion, soluble in water, by washing, remove.The rate of removing of silica depends on concentration, reaction temperature and the time of the strong base solution of use.General alkali cleaning condition is 2-5M strong base solution 20-60 degree Celsius of alkali cleaning 12-72 hour at temperature.The condition of optimizing is that the concentration of aqueous slkali is that 5M, reaction temperature are that 60 degrees Celsius, reaction time are 20 hours.The prolongation reaction time can be removed more silica, makes the powder of gained have higher porosity and larger specific area.But overlong time can make titanium dioxide aggregate size diminish, and be difficult for by the method for filtering, separating from liquid phase.So it is important selecting the suitable reaction time.For example, after the alkali cleaning time is 72 hours, the size reduction of aggregation, part granule is only 100-200 nanometer, by the method for filtering, is difficult to make it separated and reclaim.And through alkali cleaning in 20 hours, it is little that aggregate size changes, size is several microns, and alkali cleaning can dissolve 91% SiO in 24 hours
2.
beneficial effect
The outstanding feature that the invention provides the mesoporous visible-light photocatalyst preparation method of nitrogen-doped titanium dioxide is:
1. the nitrogen-doped titanium dioxide of preparation is Anatase, and crystallite dimension is less than 10nm.
2. mesoporous pore-size distribution is narrow, is 2-8 nanometer, and most probable aperture is 5 nanometers, has good heat endurance.
3. have higher absorptivity and visible light absorption region, wavelength can be expanded to 600 nanometers.
Specific area high, be greater than 150m
2/ g.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) photo of the mesoporous visible light catalyst of nitrogen-doped titanium dioxide.Consist of TiO
23SiO
2the composite oxides flow velocity of recording a demerit be 900 degrees Celsius of nitrogenize of ammonia 5 hours of 1000 ml/min, 60 degrees Celsius by the soaking with sodium hydroxide of 5M after 12 hours, washes, dry.
Fig. 2 is saturating high-resolution radio sub-microscope (TEM) photo of the mesoporous visible light catalyst of nitrogen-doped titanium dioxide.Consist of TiO
23SiO
2the composite oxides flow velocity of recording a demerit be 900 degrees Celsius of nitrogenize of ammonia 5 hours of 1000 ml/min, 60 degrees Celsius by the soaking with sodium hydroxide of 5M after 12 hours, washes, dry.
Fig. 3 is the Raman spectrogram of the mesoporous visible light catalyst of nitrogen-doped titanium dioxide.Consist of TiO
23SiO
2composite oxides and consist of TiO
24SiO
2the composite oxides flow velocity of recording a demerit be 900 degrees Celsius of nitrogenize of ammonia 5 hours of 1000 ml/min, 60 degrees Celsius by the soaking with sodium hydroxide of 5M after 12 hours, washes, dry.
Fig. 4 is the UV-vis DRS spectrum of the mesoporous visible light catalyst of nitrogen-doped titanium dioxide.Listed titanium dioxide; The nano titanium dioxide powder of nitrogenize; Consist of TiO
23SiO
2composite oxides through flow velocity, be 900 degrees Celsius of nitrogenize of ammonia 5 hours of 1000 ml/min, 60 degrees Celsius by the soaking with sodium hydroxide of 5M after 12 hours, washes, the dry nitrogen-doped titanium dioxide mesoporous photocatalytic agent obtaining; Consist of TiO
2siO
2the composite oxides flow velocity of recording a demerit be 900 degrees Celsius of nitrogenize of ammonia 5 hours of 1000 ml/min, 60 degrees Celsius by the soaking with sodium hydroxide of 5M after 12 hours, washes, the dry nitrogen-doped titanium dioxide mesoporous photocatalytic agent obtaining.
Fig. 5 is the graph of pore diameter distribution of the mesoporous visible light catalyst of nitrogen-doped titanium dioxide.Consist of TiO
23SiO
2the composite oxides flow velocity of recording a demerit be 900 degrees Celsius of nitrogenize of ammonia 5 hours of 1000 ml/min, 60 degrees Celsius by the soaking with sodium hydroxide of 5M after 12 hours, washes, dry.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
embodiment 1
The ethanolic solution of the ethyl orthosilicate that is 1:1 toward volume ratio adds the ethanolic solution of 0.1M hydrochloric acid, and making silicon and the ratio of the amount of substance of water is 1:1, and 70 degrees Celsius are refluxed 1 hour, are cooled to room temperature.Then adding volume ratio is the ethanolic solution of the butyl titanate of 1:1, and the ratio that makes Ti/Si amount of substance is 1:3.Progressively add the ethanolic solution of 0.1M hydrochloric acid, the amount of substance that makes water is the twice of the amount of substance sum of titanium and silicon again.After 12 hours, form gel.Be dried, pulverize, sieve, calcine two hours for 600 degrees Celsius.2 grams of cooling rear weighings, are placed in tube furnace, and flow velocity is in the mobile ammonia of 1000 ml/min, 900 degrees Celsius of nitrogenize 5 hours, cool to room temperature in nitrogen protection.Take 2 grams, be placed in 60 degrees Celsius of washings of 5.0M sodium hydroxide solution 12 hours, wash rear 110 degrees Celsius of oven dry.Its transmission electron microscope photo as shown in Figure 1, is the titanium dioxide of doping compared with dark colour particle, and the hole of light color is mesoporous; Its high-resolution-ration transmission electric-lens photo as shown in Figure 2, Raman spectrum as shown in Figure 3,148.5 degrees Celsius of m
-1the titanium dioxide that is about 8nm corresponding to crystallite dimension.The absorption spectrum of diffuse reflection pattern is as TiO in Fig. 4
2-xn
xshown in (embodiment 1), it absorbs the TiO obviously obtaining compared with its gas-solid reaction of titanium dioxide powder
2-xn
xstronger, be yellowish-brown, the scope of absorption spectrum is wider (extending to 600nm) also, pore-size distribution as shown in Figure 5, most probable aperture 5.5nm, specific area 238.6m
2/ g, 0.38 degree Celsius of m
3/ g.
embodiment 2
The ethanolic solution of the ethyl orthosilicate that is 1:2 toward volume ratio adds the ethanolic solution of 0.1M hydrochloric acid, and making silicon and the ratio of the amount of substance of water is 1:1, and 70 degrees Celsius are refluxed 1 hour, are cooled to room temperature.Then adding volume ratio is the ethanolic solution of the butyl titanate of 1:2, and the ratio that makes Ti/Si amount of substance is 1:1.Progressively add the ethanolic solution of 0.1M hydrochloric acid, the amount of substance that makes water is the twice of the amount of substance sum of titanium and silicon again.After 24 hours, form gel.Be dried, pulverize, sieve, calcine two hours for 600 degrees Celsius.2 grams of cooling rear weighings, are placed in tube furnace, and flow velocity is in the mobile ammonia of 1000 ml/min, 900 degrees Celsius of nitrogenize 5 hours, cool to room temperature in nitrogen protection.Take 2 grams, be placed in 60 degrees Celsius of washings of 5.0M sodium hydroxide solution 24 hours, wash rear 110 degrees Celsius of oven dry.The absorption spectrum of diffuse reflection pattern is as TiO in Fig. 4
2-xn
xshown in (embodiment 2), it absorbs the TiO obviously obtaining compared with its gas-solid reaction of titanium dioxide powder
2-xn
xstronger, be dark brown, the scope of absorption spectrum is wider (extending to 800nm) also.
embodiment 3
The ethanolic solution of the ethyl orthosilicate that is 1:2 toward volume ratio adds the ethanolic solution of 0.1M hydrochloric acid, and making silicon and the ratio of the amount of substance of water is 1:1, and 70 degrees Celsius are refluxed 1 hour, are cooled to room temperature.Then adding volume ratio is the ethanolic solution of the butyl titanate of 1:2, and the ratio that makes Ti/Si amount of substance is 1:4.Progressively add the ethanolic solution of 0.1M hydrochloric acid, the amount of substance that makes water is the twice of the amount of substance sum of titanium and silicon again.After 24 hours, form gel.Be dried, pulverize, sieve, calcine two hours for 600 degrees Celsius.2 grams of cooling rear weighings, are placed in tube furnace, and flow velocity is in the mobile ammonia of 1000 ml/min, 900 degrees Celsius of nitrogenize 2 hours, cool to room temperature in nitrogen protection.Take 2 grams, be placed in 60 degrees Celsius of washings of 5.0M sodium hydroxide solution 24 hours, wash rear 110 degrees Celsius of oven dry.Raman spectrum as shown in Figure 3,152.1 degrees Celsius of m
-1the titanium dioxide that is about 5nm corresponding to crystallite dimension.
Claims (6)
1. the preparation method of the mesoporous visible-light photocatalyst of nitrogen-doped titanium dioxide, by Ti-Si composite oxide through techniques such as the nitrogenize of ammonia solution and aqueous slkali washings, it is characterized in that: (1) prepares Ti-Si composite oxide by sol-gel process, wherein the amount of substance of silicon is more than or equal to the amount of substance of titanium; (2) composite oxides through vacuum drying, pulverize, sieve and calcine after, high-temperature ammonolysis makes the nitrogenize of titanium dioxide part; (3) composite granule after nitrogenize, after aqueous slkali washing, dissolves silica and excess nitrogen wherein, obtains being less than by mesoporous and crystallite dimension the aggregate that the nitrogen-doped titanium dioxide of 10nm is constructed, and specific area is greater than 150m
2/ g.
2. by preparation method claimed in claim 1, it is characterized in that regulating the ratio of the ethanolic solution of ethyl orthosilicate and the ethanolic solution of titanium alkoxide can obtain the composite oxides of different titanium silicon ratios, titanium silicon is (Ti/Si ratio) 1:19 to 1:1 than excursion; After mixing with ethanol with 0.1M dilute sulfuric acid, make hydrolyst and the water of hydrolysis needs is provided.
3. by preparation method claimed in claim 1, it is characterized in that after the vacuum drying of gelation composite oxides, xerogel, in 500～600 degrees Celsius of insulations high-temperature calcination in 2 hours, is removed organic matter, moisture content and more nitridation reaction passage is provided.
4. by preparation method claimed in claim 1, it is characterized in that the composite oxides nitrogenize in mobile ammonia after calcining, 100 milliliters of-2000 ml/min of flow velocity of ammonia, nitriding temperature 850-950 degree Celsius, nitridation time is 2-5 hour.
5. by preparation method claimed in claim 1, it is characterized in that the aqueous slkali adopting is NaOH or potassium hydroxide, concentration is 1.0-5.0M, 20～60 degrees Celsius of processing of wash temperature some hours, reaction time is 12-72 hour, and the alkali cleaning condition of optimization is 60 degrees Celsius of alkali cleanings 20 hours.
6. by preparation method claimed in claim 1, it is characterized in that the specific area of the mesoporous catalyst that obtains is greater than 150m
2/ g, titanium dioxide are that Anatase crystallite dimension is less than 10nm, catalyst that the response wave length of light is extended to the nitrogen-doped titanium dioxide that 600nm and absorptivity obtain compared with the gas-solid nitridation reaction of nano-titanium oxide is higher.
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| CN108134104A (en) * | 2017-12-26 | 2018-06-08 | 成都新柯力化工科技有限公司 | Composite catalyst carrier for fuel cell and preparation method and application thereof |
| CN108607596A (en) * | 2018-05-11 | 2018-10-02 | 东华大学 | A kind of Composite Pt/TiO with visible photocatalysis water hydrogen manufacturing performance2-xNxCatalyst and its preparation and application |
| CN110694630A (en) * | 2019-10-24 | 2020-01-17 | 吉林师范大学 | Preparation method of divalent nickel ion doped modified titanium dioxide (nickel-titanium dioxide) visible light photocatalyst |
| CN115805094A (en) * | 2022-12-01 | 2023-03-17 | 珠海市派特尔科技股份有限公司 | Antibacterial agent with photocatalytic degradation and antibacterial properties and preparation method thereof |
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| CN108607596A (en) * | 2018-05-11 | 2018-10-02 | 东华大学 | A kind of Composite Pt/TiO with visible photocatalysis water hydrogen manufacturing performance2-xNxCatalyst and its preparation and application |
| CN110694630A (en) * | 2019-10-24 | 2020-01-17 | 吉林师范大学 | Preparation method of divalent nickel ion doped modified titanium dioxide (nickel-titanium dioxide) visible light photocatalyst |
| CN115805094A (en) * | 2022-12-01 | 2023-03-17 | 珠海市派特尔科技股份有限公司 | Antibacterial agent with photocatalytic degradation and antibacterial properties and preparation method thereof |
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Application publication date: 20140402 |