CN102698727B - Method for preparing supported TiO2 photocatalyst with high thermal stability - Google Patents
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Abstract
The invention relates to a method for preparing supported TiO2 photocatalyst with high thermal stability. By the adoption of a simple hydrothermal synthesis method, and the low-cost acidified stripped vermiculite flake layer is used as the carrier, the TiO2 photocatalyst is supported on the surface of the acidified stripped vermiculite flake layer, and one layer of sponge-shaped ternary mixed-crystal-phase TiO2 particles with obvious pore structures is supported regularly and orderly. The method is simple and practical and has low cost. The supported TiO2 photocatalyst prepared by adopting the method has small grain size, large specific surface area, abundant pore structures, high thermal stability and high photocatalytic activity, can be widely applied to the environmental governance such as the pollution prevention, bacteria resistance, deodorization and purification of waste water, sewage and indoor and outdoor gases.
Description
Technical field
The invention belongs to environment functional material preparing technical field, be specifically related to a kind of supported titanium of high thermal stability
2the preparation method of photochemical catalyst, the supported titanium making
2catalysis material has large specific area, less crystallite dimension and comparatively stable phase structure, it is a kind of green light catalyst that can efficiently, stably process organic pollution, be mainly used in environmental improvement, as purified treatment such as waste water, sewage, indoor and outdoor gaseous contamination, antibacterial and deodourings.
Background technology
TiO
2, non-toxic inexpensive high with its photocatalytic activity, the plurality of advantages such as conduction band valence band current potential is suitable, photoetch is little, stability is high, non-secondary pollution, become the study hotspot in multiphase photocatalysis field.In recent years, development and progress along with photochemistry and technology, utilize TiO
2multiphase photocatalysis is eliminated in environment and is polluted, pollutant is decomposed and be converted into innocuous substance, the deep purifying of sewage, air is processed and had higher usefulness, become one of photochemical catalyst that the most deep semiconductor of photocatalysis field research and environmental area be most widely used.Although TiO
2photochemical catalyst has many advantages in environmental improvement, but its low photocatalysis efficiency has limited its large-scale application in environmental improvement field with the problem of difficult separated recovery.
TiO
2photocatalysis efficiency depend on to a great extent it self character, as crystal type, crystallite dimension, specific area, degree of crystallinity etc.Common Anatase TiO
2there is higher photocatalytic activity, in addition, contain the TiO that a certain proportion of anatase and rutile mix phase
2also there is higher photocatalytic activity; Less crystallite dimension is conducive to improve the separation of photo-generated carrier, and then reduces the recombination probability in light induced electron-hole; Larger specific area can provide more chain carrier, and is conducive to the absorption of contaminant molecule; Higher degree of crystallinity can reduce the complex centre in light induced electron-hole.But obtain the TiO simultaneously with above good characteristic
2catalysis material has certain difficulty.
Conventionally, there is the nano-TiO compared with bigger serface
2easily under lower synthesis temperature, obtain, but its corresponding lower degree of crystallinity inevitably affects its photocatalytic activity.In order to improve its degree of crystallinity, need at high temperature further to calcine, but there is the Detitanium-ore-type TiO of comparatively superior photocatalysis performance
2the nanocrystalline restriction due to heat-treated temperature, conventionally at 500 ℃-600 ℃, just start to transform to Rutile Type, and be accompanied by sharply reducing of the increase of crystal grain and reunion, specific area, cause the reduction of photocatalytic activity, 800 ℃ of calcinings, be mostly converted into afterwards Rutile Type, this has also greatly affected anatase TiO
2nanocrystalline at photocatalysis decontamination, deodorizing sterilizing etc. such as the application in the fields such as antibiotic property domestic ceramics.At present, in order to improve TiO
2in the time of degree of crystallinity, suppress the transformation of its crystal formation and maintain its specific area, conventionally at TiO
2some anion of middle doping, metal cation or use other metal oxide etc. as stabilizing agent, but adding generally of these materials can affect TiO
2itself structure and performance, apply widely thereby affect it.Therefore, develop a kind of simple, supported titanium with bigger serface, little crystallite dimension and stable phase structure
2the preparation method of photochemical catalyst, to preparing the TiO of high heat stability
2nanocrystalline having great importance.
Patent 201210143682.2 provides a kind of and has prepared acidifying and peel off vermiculite load TiO
2the method of photochemical catalyst, the method be take cheap acidifying and is peeled off vermiculite lamella as carrier, by TiO
2photocatalyst is peeled off the layer surface of vermiculite in acidifying, reached absorption-photocatalysis integrated processing organic pollution and be easy to object separated and recycling catalyst.On this basis, the present invention select there is good heat endurance, the acidifying of large specific area, the siliceous oh group of rich surface peels off vermiculite as being TiO
2carrier, while using photocatalytic activity more excellent, titanium is peeled off the feed ratio of vermiculite with acidifying, and regulates the pH value in catalyst preparation condition, makes by Si-O-Ti chemical bond inhibition TiO in the synthetic loaded catalyst of Situ Hydrothermal method
2crystal transfer in heat treatment process, thus TiO improved
2heat endurance.
Up to the present, have no and use acidifying to peel off vermiculite lamella for TiO
2carrier is prepared bigger serface, high thermal stability supported titanium
2the relevant report of photochemical catalyst.
Summary of the invention
The object of the invention is to, a kind of supported titanium of preparing high thermal stability is provided
2the method of photochemical catalyst, the method adopts simple hydrothermal synthesis method, and the cheap acidifying of take is peeled off vermiculite lamella as carrier, by TiO
2photocatalyst is peeled off the layer surface of vermiculite in acidifying, evenly and the load of regular ground one deck spongy and there is the ternary mixed crystal phase TiO of obvious pore structure
2stratum granulosum.The method simple possible, with low cost, the loaded nano TiO of acquisition
2photochemical catalyst has compared with large, the abundant pore structure of little crystallite dimension, specific area and high heat endurance, and there is higher photocatalytic activity, can be widely used in environmental improvement, as purified treatment such as waste water, sewage, indoor and outdoor gaseous contamination, antibacterial and deodourings.
A kind of supported titanium of preparing high thermal stability of the present invention
2the method of photochemical catalyst, carry out according to the following steps:
A, vermiculite is crossed to 300 mesh sieves, by mass fraction be 20%-40% join 1-3mol/L phosphoric acid, sulfuric acid, hydrochloric acid or salpeter solution in, reaction 6-12h after, filtered water is washed till neutrality, and by filter cake at temperature 50-120 ℃ of dry 4-12h, through grinding, obtain acidifying and peel off vermiculite;
B, step a acidifying is peeled off to vermiculite be dispersed in 50-80mL deionized water, and add 0.03-0.05mol hydrochloric acid, cool to 0-10 ℃;
C, by tetra-n-butyl titanate or tetraisopropyl titanate, be 1 in molar ratio with ethanol, isopropyl alcohol, isoamyl alcohol or n-butanol solvent: 10-1: 40 mix, joining step b contains acidifying and peels off in the acid solution of vermiculite, the ratio that vermiculite is peeled off in regulation and control tetra-n-butyl titanate or tetraisopropyl titanate and acidifying is 25-30mmol/g, and at temperature 0-10 ℃, continue to stir 1-5h, obtain translucent collosol suspension liquid;
The pH value of ammoniacal liquor, NaOH or the translucent collosol suspension liquid of potassium hydroxide solution regulating step c of d, use 1-5mol/L is 0.5-2, then transfers in reactor hydro-thermal reaction 5-50h at temperature 120-200 ℃;
After e, reaction finish, naturally cooling under normal temperature, take out reactant and wash to neutral by ethanol and deionized water, at temperature 50-80 ℃, after vacuum drying 5-20h, pulverize, can obtain the supported titanium of high thermal stability
2photochemical catalyst.
In step a, the lamellar structure that vermiculite is a kind of that peel off completely, siliceous hydroxyl of rich surface is peeled off in acidifying.
The supported titanium of the high thermal stability obtaining by the method
2in photochemical catalyst, TiO
2for anatase, rutile and brockite ternary multiphase.
The supported titanium of the high thermal stability obtaining by the method
2photochemical catalyst carrier used is that vermiculite lamella is peeled off in acidifying, on this lamella evenly and the load of regular ground the spongy mesoporous TiO of one deck
2stratum granulosum.
The supported titanium of the high thermal stability obtaining by the method
2photochemical catalyst specific area is larger, is 200-300m
2/ g, crystallite dimension is 6-9nm.
A kind of supported titanium of preparing high thermal stability of the present invention
2the method of photochemical catalyst, the advantage of the method is: (1) carrier used is that vermiculite is peeled off in acidifying, therefore vermiculite is a kind of natural clay of laminar silicate mineral, and in China, reserves enrich, draw materials easy, cheap, and preparation cost of the present invention is lower; (2) preparation method's simple possible.
The supported titanium of the high thermal stability obtaining by preparation method of the present invention
2the advantage of photochemical catalyst is: (1) has meso-hole structure, larger specific area, good absorption property, has increased organic pollutant molecule with the contact probability of photochemical catalyst and has effectively reacted; (2) TiO
2orderly mode of loading at carrier layer outer surface, has improved TiO
2utilization rate to light, is conducive to the carrying out of light-catalyzed reaction; (3) there is less crystallite dimension, and still can keep stable crystalline phase at higher temperature.At temperature 500-900 ℃, calcine after 3-5h, specific area is 120-280m
2/ g, crystallite dimension is 7-23nm.
The supported titanium of the high thermal stability obtaining by the method for the invention
2photochemical catalyst content of anatase, rutile and three kinds of crystalline phases of brockite in sample under different calcining heats, by relatively, at 700 ℃ of following these loaded catalysts of calcining of temperature, TiO
2in the content of three kinds of crystalline phases substantially remain unchanged, but when calcining heat is elevated to 700 ℃ of temperature, brockite crystal transfer is wherein complete, a part is transformed into Anatase, another part changes Rutile Type into; Along with the further rising of temperature, when 800 ℃ of temperature, a small amount of anatase changes to rutile, and 85.9% while causing Anatase content from 700 ℃ of temperature drops to 80.1%, and correspondingly, rutile content increases to some extent; When temperature rises to 900 ℃, part anatase changes to rutile, makes Rutile Type content be increased to 48.5%.As can be seen here, this supported titanium
2the temperature that in photochemical catalyst, brockite changes is completely 700 ℃, and the initial temperature that anatase changes to rutile is 800 ℃, and up to calcining at 900 ℃ of temperature, anatase is still main crystalline phase, than common TiO
2crystal transfer temperature improved 300 ℃ of left and right, and there is higher photocatalytic activity.In Table 1:
Table 1
Remarks: Ti-V represents high thermal stability supported titanium
2photochemical catalyst; Ti-V-500 represents heat endurance supported titanium
2the sample of photochemical catalyst after 500 ℃ of calcinings of temperature, other sample similarly.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of the present invention's sample under different calcining heats, and wherein (a), for not calcining, (b) is 500 ℃, (c) be 600 ℃, (d) being 700 ℃, is (e) 800 ℃, is (f) the X-ray diffraction spectrogram of the rear sample of calcining at 900 ℃; * be: anatase, ◆ be rutile, ● be brockite; As seen from the figure, the supported titanium of this high thermal stability
2photochemical catalyst is anatase, rutile and brockite ternary multiphase, be wherein mainly Anatase, and contain a small amount of rutile and brookite, when calcining heat is elevated to 700 ℃, the diffraction maximum of brookite disappears, and illustrates that crystal transfer has occurred whole brockites; In the time of 800 ℃, the characteristic diffraction peak intensity of anatase is larger, peak is more sharp-pointed; Meanwhile, the feature diffraction of Rutile Type also strengthens to some extent, illustrates that a small amount of anatase changes to rutile; Along with the further rising of temperature, in the time of 900 ℃, the feature diffraction of rutile obviously strengthens, and the feature diffraction of anatase obviously weakens, and this declaratives anatase has been transformed into rutile, but wherein anatase is still main crystalline phase.
Fig. 2 is obtained pure TiO by comparative example 6 of the present invention
2the X-ray diffraction spectrogram of sample under different calcining heats, wherein (a), for not calcining, (b) is 500 ℃, is (c) the X-ray diffraction spectrogram of the sample after calcining at 700 ℃; * be: anatase, ◆ be rutile, ● be brockite; As seen from the figure, in the time of 500 ℃, calcine resulting TiO
2the diffraction peak intensity of powder all increases to some extent, show that its degree of crystallinity increases, but comparing of the diffraction maximum of Rutile Type and Anatase and brookite wherein, strength increase is more obvious, and this declaratives anatase and brockite crystal formation all change to rutile; When calcining heat is elevated to 700 ℃, the characteristic diffraction peak of remaining rutile only in the diffraction of gained sample, this explanation anatase and brockite are all transformed into rutile completely; As can be seen here, without the TiO of load
2photochemical catalyst in, the initial temperature that Anatase and brookite change to Rutile Type is 500 ℃, in the time of 700 ℃, changes completely.
Fig. 3 is N of the present invention
2adsorption-desorption curve map, shows that this photochemical catalyst has abundant meso-hole structure.
Fig. 4 is scanning electron microscope (SEM) photograph of the present invention and transmission electron microscope picture, and wherein (a) is scanning electron microscope (SEM) photograph, is (b) transmission electron microscope picture.Make discovery from observation, as the acidifying of carrier peel off on vermiculite lamella evenly and the load of regular ground one deck spongy and there is the TiO of obvious pore structure
2stratum granulosum.
Fig. 5 is that the present invention calcines gained sample and pure TiO under different temperatures
2at 500 ℃ of temperature, calcine the rate of photocatalytic oxidation constant comparison diagram of gained sample to methylene blue; As seen from the figure, the supported titanium under different calcining heats
2photochemical catalyst all has than the pure TiO of calcining at 500 ℃
2higher photocatalytic activity.
The specific embodiment
A, vermiculite being crossed to 300 mesh sieves, is 20% to join in the phosphoric acid solution of 1mol/L by mass fraction, and after reaction 12h, filtered water is washed till neutrality, and by filter cake at the dry 12h of temperature 50 C, through grinding, obtain acidifying and peel off vermiculite;
B, step a acidifying is peeled off to vermiculite be dispersed in 50mL deionized water, and add 0.03mol hydrochloric acid, cool to 0 ℃;
C, by tetra-n-butyl titanate and alcohol solvent, be to mix at 1: 10 in molar ratio, joining step b contains acidifying and peels off in the acid solution of vermiculite, the ratio that vermiculite is peeled off in regulation and control tetra-n-butyl titanate and acidifying is 25mmol/g, and at 0 ℃ of temperature, continue to stir 2h, obtain translucent collosol suspension liquid;
D, to use the pH value of the translucent collosol suspension liquid of ammonia spirit regulating step c of 2mol/L be 0.5, then transfers in reactor hydro-thermal reaction 36h at 120 ℃ of temperature;
After e, reaction finish, naturally cooling under normal temperature, take out reactant and wash to neutral by ethanol and deionized water, under temperature 50 C, after vacuum drying 12h, pulverize, can obtain the supported titanium of high thermal stability
2photochemical catalyst.
The methylene blue solution that the 100mL concentration of take is 10ppm is degraded object, takes 20mg photochemical catalyst (TiO after converting
2amount) add wherein, dark space stirring and adsorbing 30min, take 300W xenon lamp as light source, carries out the photocatalytic degradation reaction of methylene.Every 10min, get 5mL sample, supernatant liquor is got in centrifugation, by ultraviolet-visible spectrophotometer, according to its absorbance change calculations methylene blue degradation rate, and assesses its photocatalytic activity.
The supported titanium of the high thermal stability that the present embodiment obtains
2photochemical catalyst specific area is larger, is 230m
2/ g, crystallite dimension is 8nm, at temperature 500-900 ℃, calcines after 3h, specific area is 120-225m
2/ g, crystallite dimension is 9-23nm; There is higher phase transformation stability, it is 700 ℃ that brookite wherein changes temperature completely to anatase and Rutile Type, and the initial temperature that Anatase changes to Rutile Type is 800 ℃, up to 900 ℃ of temperature lower calcinations, anatase is still main crystalline phase, than common TiO
2crystal transfer temperature improved 300 ℃ of left and right, and there is higher photocatalytic activity.
A, vermiculite being crossed to 300 mesh sieves, is 25% to join in the sulfuric acid solution of 1.5mol/L by mass fraction, and after reaction 10h, filtered water is washed till neutrality, and by filter cake at the dry 10h of temperature 60 C, through grinding, obtain acidifying and peel off vermiculite;
B, step a acidifying is peeled off to vermiculite be dispersed in 60mL deionized water, and add 0.04mol hydrochloric acid, cool to 2 ℃;
C, tetraisopropyl titanate are to mix at 1: 20 with n-butanol solvent in molar ratio, joining step b contains acidifying and peels off in the acid solution of vermiculite, the ratio that vermiculite is peeled off in regulation and control tetraisopropyl titanate and acidifying is 26mmol/g, and at 2 ℃ of temperature, continue to stir 3h, obtain translucent collosol suspension liquid;
D, to use the pH value of the translucent collosol suspension liquid of sodium hydroxide solution regulating step c of 3mol/L be 1, then transfers in reactor hydro-thermal reaction 30h at 140 ℃ of temperature;
After e, reaction finish, naturally cooling under normal temperature, take out reactant and wash to neutral by ethanol and deionized water, under temperature 60 C, after vacuum drying 10h, pulverize, can obtain the supported titanium of high thermal stability
2photochemical catalyst.
With experiment condition identical in embodiment 1, assess its photocatalytic activity.
The supported titanium of the high thermal stability that the present embodiment obtains
2photochemical catalyst specific area is larger, is 250m
2/ g, crystallite dimension is 7.5nm, at temperature 500-900 ℃, calcines after 4h, specific area is 130-240m
2/ g, crystallite dimension is 8-20nm; There is higher phase transformation stability, it is 700 ℃ that brookite wherein changes temperature completely to anatase and Rutile Type, and the initial temperature that Anatase changes to Rutile Type is 800 ℃, up to 900 ℃ of temperature lower calcinations, anatase is still main crystalline phase, than common TiO
2crystal transfer temperature improved 300 ℃ of left and right, and there is higher photocatalytic activity.
Embodiment 3
A, vermiculite being crossed to 300 mesh sieves, is 30% to join in the hydrochloric acid solution of 2mol/L by mass fraction, and after reaction 8h, filtered water is washed till neutrality, and by filter cake at the dry 8h of temperature 70 C, through grinding, obtain acidifying and peel off vermiculite;
B, step a acidifying is peeled off to vermiculite be dispersed in 70mL deionized water, and add 0.05mol hydrochloric acid, cool to 5 ℃;
C, by tetra-n-butyl titanate and isoamyl alcohol solvent, be to mix at 1: 30 in molar ratio, joining step b contains acidifying and peels off in the acid solution of vermiculite, the ratio that vermiculite is peeled off in regulation and control tetra-n-butyl titanate and acidifying is 28mmol/g, and at 5 ℃ of temperature, continue to stir 4h, obtain translucent collosol suspension liquid;
D, to use the pH value of the translucent collosol suspension liquid of potassium hydroxide solution regulating step c of 4mol/L be 1.5, then transfers in reactor hydro-thermal reaction 28h at 160 ℃ of temperature;
After e, reaction finish, naturally cooling under normal temperature, take out reactant and wash to neutral by ethanol and deionized water, under temperature 70 C, after vacuum drying 8h, pulverize, can obtain the supported titanium of high thermal stability
2photochemical catalyst.
With experiment condition identical in embodiment 1, assess its photocatalytic activity.
The supported titanium of the high thermal stability that the present embodiment obtains
2photochemical catalyst specific area is larger, is 260m
2/ g, crystallite dimension is 7nm, at temperature 500-900 ℃, calcines after 3.5h, specific area is 150-250m
2/ g, crystallite dimension is 7-18nm; There is higher phase transformation stability, it is 700 ℃ that brookite wherein changes temperature completely to anatase and Rutile Type, and the initial temperature that Anatase changes to Rutile Type is 800 ℃, up to 900 ℃ of temperature lower calcinations, anatase is still main crystalline phase, than common TiO
2crystal transfer temperature improved 300 ℃ of left and right, and there is higher photocatalytic activity.
Embodiment 4
A, vermiculite being crossed to 300 mesh sieves, is 35% to join in the salpeter solution of 2.5mol/L by mass fraction, and after reaction 7h, filtered water is washed till neutrality, and by filter cake at 80 ℃ of dry 6h of temperature, through grinding, obtain acidifying and peel off vermiculite;
B, step a acidifying is peeled off to vermiculite be dispersed in 80mL deionized water, and add 0.04mol hydrochloric acid, cool to 8 ℃;
C, by tetraisopropyl titanate and isopropanol solvent, be to mix at 1: 40 in molar ratio, joining step b contains acidifying and peels off in the acid solution of vermiculite, the ratio that vermiculite is peeled off in regulation and control tetraisopropyl titanate and acidifying is 30mmol/g, and at 8 ℃ of temperature, continue to stir 5h, obtain translucent collosol suspension liquid;
D, to use the pH value of the translucent collosol suspension liquid of sodium hydroxide solution regulating step c of 5mol/L be 0.5, then transfers in reactor hydro-thermal reaction 24h at 180 ℃ of temperature;
After e, reaction finish, naturally cooling under normal temperature, take out reactant and wash to neutral by ethanol and deionized water, under temperature 70 C, after vacuum drying 10h, pulverize, can obtain the supported titanium of high thermal stability
2photochemical catalyst.
With experiment condition identical in embodiment 1, assess its photocatalytic activity.
The supported titanium of the high thermal stability that the present embodiment obtains
2photochemical catalyst specific area is larger, is 255m
2/ g, crystallite dimension is 7.5nm, at temperature 500-900 ℃, calcines after 4h, specific area is 140-245m
2/ g, crystallite dimension is 7-19nm; There is higher phase transformation stability, it is 700 ℃ that brookite wherein changes temperature completely to anatase and Rutile Type, and the initial temperature that Anatase changes to Rutile Type is 800 ℃, up to 900 ℃ of temperature lower calcinations, anatase is still main crystalline phase, than common TiO
2crystal transfer temperature improved 300 ℃ of left and right, and there is higher photocatalytic activity.
Embodiment 5
A, vermiculite being crossed to 300 mesh sieves, is 40% to join in the hydrochloric acid solution of 3mol/L by mass fraction, and after reaction 6h, filtered water is washed till neutrality, and by filter cake at 100 ℃ of dry 4h of temperature, through grinding, obtain acidifying and peel off vermiculite;
B, step a acidifying is peeled off to vermiculite be dispersed in 60mL deionized water, and add 0.04mol hydrochloric acid, cool to 10 ℃;
C, by tetra-n-butyl titanate and isoamyl alcohol agent, be to mix at 1: 20 in molar ratio, joining step b contains acidifying and peels off in the acid solution of vermiculite, the ratio that vermiculite is peeled off in regulation and control tetra-n-butyl titanate and acidifying is 29mmol/g, and at 10 ℃ of temperature, continue to stir 5h, obtain translucent collosol suspension liquid;
D, to use the pH value of the translucent collosol suspension liquid of sodium hydroxide solution regulating step c of 5mol/L be 0.5, then transfers in reactor hydro-thermal reaction 20h at 200 ℃ of temperature;
After e, reaction finish, naturally cooling under normal temperature, take out reactant and wash to neutral by ethanol and deionized water, under temperature 60 C, after vacuum drying 20h, pulverize, can obtain the supported titanium of high thermal stability
2photochemical catalyst.
With experiment condition identical in embodiment 1, assess its photocatalytic activity.
The supported titanium of the high thermal stability that the present embodiment obtains
2photochemical catalyst specific area is larger, is 240m
2/ g, crystallite dimension is 8nm, at temperature 500-900 ℃, calcines after 2.5h, specific area is 125-230m
2/ g, crystallite dimension is 8-21nm; There is higher phase transformation stability, it is 700 ℃ that brookite wherein changes temperature completely to anatase and Rutile Type, and the initial temperature that Anatase changes to Rutile Type is 800 ℃, up to 900 ℃ of temperature lower calcinations, anatase is still main crystalline phase, than common TiO
2crystal transfer temperature improved 300 ℃ of left and right, and there is higher photocatalytic activity.
Embodiment 6 (contrasts pure TiO
2photochemical catalyst)
0.04mol hydrochloric acid is joined in 50mL deionized water, cool to 3 ℃; By tetra-n-butyl titanate and alcohol solvent, be to mix at 1: 20 in molar ratio, join in acid solution, this reactant is continued at 3 ℃ after stirring 3h, form vitreosol; Using the sodium hydroxide solution of 5mol/L to regulate the pH value of this colloidal sol is 0.5, then transfers in reactor hydro-thermal reaction 24h at 180 ℃ of temperature; After reaction finishes, naturally cooling under normal temperature, take out reactant, and with deionized water and ethanol washing, after 60 ℃ of vacuum drying 8h, pulverize, make pure TiO
2nano material.
Get the pure TiO suitable with each sample load capacity
2, with experiment condition identical in embodiment 1, assess its photocatalytic activity.
The pure TiO that the present embodiment obtains
2photochemical catalyst specific area is 130m
2/ g, crystallite dimension is 9nm, at 500 ℃ of temperature, calcines after 3h, specific area is 65.2m
2/ g, crystallite dimension is 12.5nm; Phase transformation stability is lower, and the initial temperature that wherein Anatase and brookite change to Rutile Type is 500 ℃, in the time of 700 ℃, changes completely, and its photocatalytic activity is relatively low.
Claims (5)
1. a supported titanium of preparing high thermal stability
2the method of photochemical catalyst, is characterized in that following these steps to carrying out:
A, vermiculite is crossed to 300 mesh sieves, by mass fraction be 20%-40% join 1-3mol/L phosphoric acid, sulfuric acid, hydrochloric acid or salpeter solution in, reaction 6-12h after, filtered water is washed till neutrality, and by filter cake at temperature 50-120 ℃ of dry 4-12h, through grinding, obtain acidifying and peel off vermiculite;
B, step a acidifying is peeled off to vermiculite be dispersed in 50-80mL deionized water, and add 0.03-0.05mol hydrochloric acid, cool to 0-10 ℃;
C, by tetra-n-butyl titanate or tetraisopropyl titanate, be 1 in molar ratio with ethanol, isopropyl alcohol, isoamyl alcohol or n-butanol solvent: 10-1: 40 mix, joining step b contains acidifying and peels off in the acid solution of vermiculite, the ratio that vermiculite is peeled off in regulation and control tetra-n-butyl titanate or tetraisopropyl titanate and acidifying is 25-30mmol/g, and at temperature 0-10 ℃, continue to stir 1-5h, obtain translucent collosol suspension liquid;
The pH value of ammoniacal liquor, NaOH or the translucent collosol suspension liquid of potassium hydroxide solution regulating step c of d, use 1-5mo1/L is 0.5-2, then transfers in reactor hydro-thermal reaction 5-50h at temperature 120-200 ℃;
After e, reaction finish, naturally cooling under normal temperature, take out reactant and wash to neutral by ethanol and deionized water, at temperature 50-80 ℃, after vacuum drying 5-20h, pulverize, can obtain the supported titanium of high thermal stability
2photochemical catalyst.
2. method according to claim 1, is characterized in that acidifying in step a peels off the lamellar structure that vermiculite is a kind of that peel off completely, siliceous hydroxyl of rich surface.
3. method according to claim 1, is characterized in that the supported titanium of the high thermal stability that obtains by the method
2in photochemical catalyst, TiO
2for anatase, rutile and brockite ternary multiphase.
4. method according to claim 1, is characterized in that the supported titanium of the high thermal stability that obtains by the method
2photochemical catalyst carrier used is that vermiculite lamella is peeled off in acidifying, on this lamella evenly and the load of regular ground the spongy mesoporous TiO of one deck
2stratum granulosum.
5. method according to claim 1, is characterized in that the supported titanium of the high thermal stability that obtains by the method
2photochemical catalyst specific area is 230-260m
2/ g, crystallite dimension is 7-8nm.
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| CN104383906A (en) * | 2014-11-10 | 2015-03-04 | 沈阳理工大学 | Method for preparing porous strontium titanate photocatalyst |
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