CN102698727A - Method for preparing supported TiO2 photocatalyst with high thermal stability - Google Patents
Method for preparing supported TiO2 photocatalyst with high thermal stability Download PDFInfo
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- CN102698727A CN102698727A CN2012101577892A CN201210157789A CN102698727A CN 102698727 A CN102698727 A CN 102698727A CN 2012101577892 A CN2012101577892 A CN 2012101577892A CN 201210157789 A CN201210157789 A CN 201210157789A CN 102698727 A CN102698727 A CN 102698727A
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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 the 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 that makes
2Catalysis material has big specific area, less crystallite dimension and comparatively stable phase structure; It is a kind of green light catalyst that can efficiently, stably handle organic pollution; Be mainly used in environmental improvement, like purified treatment such as waste water, sewage, indoor and outdoor gaseous contamination, antibacterial and deodourings.
Background technology
TiO
2With its photocatalytic activity height, non-toxic inexpensive, conduction band valence band current potential is suitable, photoetch property is little, plurality of advantages such as stability height, non-secondary pollution, becomes the multiphase photocatalysis hot research fields.In recent years, development and progress along with photochemistry and technology utilize TiO
2Multiphase photocatalysis is eliminated in the environment and is polluted; Pollutant is decomposed and is converted into innocuous substance; Deep purifying processing to sewage, air has higher usefulness, has become the most deep semiconductor of photocatalysis field research and environmental area and has used one of photochemical catalyst the most widely.Although TiO
2Photochemical catalyst has many advantages in environmental improvement, but the issues limit of its low photocatalysis efficiency and difficult Separation and Recovery its large-scale application in the environmental improvement field.
TiO
2Photocatalysis efficiency depend on it self character to a great extent, like crystal type, crystallite dimension, specific area, degree of crystallinity etc.Common anatase phase TiO
2Have higher photocatalytic activity, in addition, contain a certain proportion of anatase and mix TiO mutually with rutile
2Also has higher photocatalytic activity; Less crystallite dimension helps improving the separation of photo-generated carrier, and then reduces the recombination probability in light induced electron-hole; Bigger specific area can provide more chain carrier, and helps the absorption of contaminant molecule; Higher degree of crystallinity can reduce the complex centre in light induced electron-hole.But obtain to have simultaneously the TiO of above good characteristic
2Catalysis material has certain difficulty.
Usually, has nano-TiO than bigger serface
2Be prone under lower synthesis temperature, obtain, but its corresponding lower degree of crystallinity influences its photocatalytic activity inevitably.In order to improve its degree of crystallinity, then need at high temperature further calcining, but have the Detitanium-ore-type TiO of comparatively superior photocatalysis performance
2Nanocrystalline because the restriction of heat-treated temperature; Usually just begin to the rutile inversion of phases at 500 ℃-600 ℃; And be accompanied by sharply the reducing of increase and reunion, specific area of crystal grain; Cause the reduction of photocatalytic activity, after 800 ℃ of calcinings, be converted into the rutile phase mostly, this has also greatly influenced anatase TiO
2Nanocrystalline at photocatalysis decontamination, deodorizing sterilizing etc. such as Application for Field such as antibiotic property domestic ceramicses.At present, in order to improve TiO
2In the time of degree of crystallinity, suppress the transformation of its crystal formation and keep its specific area, usually at TiO
2In mix some anion, metal cation or use other metal oxide etc. as stabilizing agent, but the adding of these materials generally can influence TiO
2Itself structure and performance are used thereby influence it widely.Therefore, a kind of simple, supported titanium of exploitation with bigger serface, little crystallite dimension and stable phase structure
2The preparation method of photochemical catalyst is to the TiO of preparation high heat stability
2Nanocrystalline having great importance.
Patent 201210143682.2 provides a kind of preparation acidifying to peel off vermiculite load TiO
2The method of photochemical catalyst, it is carrier that this method is peeled off the vermiculite lamella with the acidifying of cheapness, with TiO
2Photochemical catalyst is carried on the laminar surface that vermiculite is peeled off in acidifying, has reached absorption-photocatalysis integrated processing organic pollution and has been easy to separate and recycle the purpose of catalyst.On this basis, the present invention selects for use and has heat endurance, big specific area, surface preferably and be rich in the acidifying of silicon oh group and peel off vermiculite as being TiO
2Carrier, titanium is peeled off the reinforced ratio of vermiculite with acidifying when using photocatalytic activity more excellent, and regulates the pH value in the Preparation of Catalyst condition, makes Si-O-Ti chemical bond inhibition TiO in the loaded catalyst that synthesizes through the original position hydrothermal method
2Crystal transfer in heat treatment process, thus TiO improved
2Heat endurance.
Up to the present, do not see that using acidifying to peel off the vermiculite lamella is TiO
2Preparing carriers bigger serface, high thermal stability supported titanium
2The relevant report of photochemical catalyst.
Summary of the invention
The objective of the invention is to, a kind of supported titanium for preparing high thermal stability is provided
2The method of photochemical catalyst, this method adopts simple hydrothermal synthesis method, and peeling off the vermiculite lamella with the acidifying of cheapness is carrier, with TiO
2Photochemical catalyst is carried on the laminar surface that vermiculite is peeled off in acidifying, evenly and the load of regular ground spongy and the ternary mixed crystal phase TiO of one deck with obvious pore structure
2Stratum granulosum.This method simple possible, with low cost, the loaded nano TiO of acquisition
2Photochemical catalyst has big, abundant pore structure of less crystallite dimension, specific area and high heat endurance; And has a higher photocatalytic activity; Can be widely used in environmental improvement, like purified treatment such as waste water, sewage, indoor and outdoor gaseous contamination, antibacterial and deodourings.
A kind of supported titanium for preparing high thermal stability of the present invention
2The method of photochemical catalyst, carry out according to the following steps:
A, vermiculite is crossed 300 mesh sieves; By mass fraction be 20%-40% join 1-3mol/L phosphoric acid, sulfuric acid, hydrochloric acid or salpeter solution in, the reaction 6-12h after, filtered water is washed till neutrality; And with filter cake at temperature 50-120 ℃ of dry 4-12h, obtain acidifying and peel off vermiculite through grinding;
B, vermiculite is peeled off in step a acidifying be dispersed in the 50-80mL deionized water, and add 0.03-0.05mol hydrochloric acid, cool to 0-10 ℃;
C, be 1 with tetra-n-butyl titanate or tetraisopropyl titanate 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 under temperature 0-10 ℃, continue to stir 1-5h, obtain translucent collosol suspension liquid;
The pH value of d, the ammoniacal liquor that uses 1-5mol/L, NaOH or the translucent collosol suspension liquid of potassium hydroxide solution regulating step c is 0.5-2, transfers to then in the agitated reactor, at temperature 120-200 ℃ of following hydro-thermal reaction 5-50h;
After e, the reaction end, reactant and extremely neutral with ethanol and deionized water washing is taken out in cooling naturally under the normal temperature, behind temperature 50-80 ℃ of following vacuum drying 5-20h, pulverizes, and can obtain the supported titanium of high thermal stability
2Photochemical catalyst.
To peel off vermiculite be a kind of peel off fully, lamellar structure that the silicon hydroxyl is rich on the surface in acidifying among the step a.
The supported titanium of the high thermal stability that obtains through this method
2In the photochemical catalyst, TiO
2For anatase, rutile and brockite ternary are mixed crystalline phase.
The supported titanium of the high thermal stability that obtains through this method
2The used carrier of photochemical catalyst is that the 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 that obtains through this method
2The photochemical catalyst specific area is bigger, is 200-300m
2/ g, crystallite dimension is 6-9nm.
A kind of supported titanium for preparing high thermal stability of the present invention
2The method of photochemical catalyst, the advantage of this method is: (1) used carrier is that vermiculite is peeled off in acidifying, and vermiculite is a kind of natural clay of laminar silicate mineral, and reserves enrich, draw materials easy, cheap in China, and therefore preparation cost of the present invention is lower; (2) preparation method's simple possible.
The supported titanium of the high thermal stability that obtains through preparation method of the present invention
2The advantage of photochemical catalyst is: (1) has meso-hole structure, bigger specific area, good adsorption performance, has increased the contact probability of organic pollutant molecule and photochemical catalyst and effectively reacts; (2) TiO
2Orderly mode of loading at the carrier layer outer surface has improved TiO
2To the utilization rate of light, help the carrying out of light-catalyzed reaction; (3) have less crystallite dimension, and under higher temperature, still can keep stable crystalline phase.Behind calcining 3-5h under temperature 500-900 ℃, specific area is 120-280m
2/ g, crystallite dimension is 7-23nm.
The supported titanium of the high thermal stability that obtains through the method for the invention
2Photochemical catalyst content of anatase, rutile and three kinds of crystalline phases of brockite in the sample under different calcining heats through relatively, is calcined this loaded catalyst, TiO in temperature below 700 ℃
2In the content of three kinds of crystalline phases remain unchanged basically, but when calcining heat was elevated to 700 ℃ of temperature, brockite crystal transfer wherein was complete, a part is transformed into the anatase phase, another part changes the rutile phase into; Along with the further rising of temperature, when 800 ℃ of temperature, a spot of anatase changes to rutile, and 85.9% when causing the anatase phase content from 700 ℃ of temperature drops to 80.1%, and correspondingly, rutile content increases to some extent; When temperature rose to 900 ℃, the part anatase changed to rutile, made the rutile phase content be increased to 48.5%.This shows this supported titanium
2The temperature that brockite changes fully in the photochemical catalyst is 700 ℃, and anatase is 800 ℃ to the initial temperature that rutile changes, and is calcining down for 900 ℃ up to temperature, and anatase still is main crystalline phase, than common TiO
2The crystal transfer temperature improved about 300 ℃, and have higher photocatalytic activity.See table 1:
Table 1
Remarks: Ti-V representes the high thermal stability supported titanium
2Photochemical catalyst; Ti-V-500 representes the heat endurance supported titanium
2The sample of photochemical catalyst after 500 ℃ of calcinings of temperature, other sample similarly.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram of the present invention's sample under different calcining heats, and wherein (a) (b) is 500 ℃ for not calcining, (c) is 600 ℃, (d) is 700 ℃, (e) is 800 ℃, (f) is 900 ℃ of X-ray diffraction spectrograms of calcining back sample down; * be: anatase, ◆ be rutile, ● be brockite; Can know the supported titanium of this high thermal stability by figure
2Photochemical catalyst is that anatase, rutile and brockite ternary are mixed crystalline phase; Mainly be the anatase phase wherein, and contain a spot of rutile and brockite mutually, when calcining heat is elevated to 700 ℃; The diffraction maximum of brockite phase disappears, and explains that crystal transfer has taken place whole brockites; In the time of 800 ℃, the characteristic diffraction peak intensity of anatase is bigger, the peak is more sharp-pointed; Simultaneously, the characteristic diffraction of rutile phase also strengthens to some extent, has explained that a spot of anatase changes to rutile; Along with the further rising of temperature, in the time of 900 ℃, the characteristic diffraction of rutile obviously strengthens, and the characteristic diffraction of anatase obviously weakens, and this declaratives anatase has been transformed into rutile, but wherein anatase still is 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) (b) is 500 ℃ for not calcining, (c) is the X-ray diffraction spectrogram of the sample after the calcining under 700 ℃; * be: anatase, ◆ be rutile, ● be brockite; Can know by 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 wherein the diffraction maximum of rutile phase and anatase mutually with the comparing of brockite phase, the intensity increase is more obvious, 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 all are transformed into rutile fully; This shows, without the TiO of load
2Photochemical catalyst in, anatase mutually with brockite in opposite directions the initial temperature that changes mutually of rutile be 500 ℃, change complete in the time of 700 ℃.
Fig. 3 is N of the present invention
2The adsorption-desorption curve map shows that this photochemical catalyst has abundant meso-hole structure.
Fig. 4 is sem photograph of the present invention and transmission electron microscope picture, and wherein (a) is sem photograph, (b) is transmission electron microscope picture.Make discovery from observation, as the acidifying of carrier peel off on the vermiculite lamella evenly and the load of regular ground spongy and the TiO of one deck with obvious pore structure
2Stratum granulosum.
Fig. 5 calcines gained sample and pure TiO for the present invention under different temperatures
2Calcine the photocatalytic degradation speed constant comparison diagram of gained sample down for 500 ℃ in temperature to methylene blue; Can know the supported titanium under the different calcining heats by figure
2Photochemical catalyst all has the pure TiO that calcines down than 500 ℃
2Higher photocatalytic activity.
The specific embodiment
A, vermiculite being crossed 300 mesh sieves, is 20% to join in the phosphoric acid solution of 1mol/L by mass fraction, and behind the reaction 12h, filtered water is washed till neutrality, and with filter cake at 50 ℃ of dry 12h of temperature, obtain acidifying and peel off vermiculite through grinding;
B, vermiculite is peeled off in step a acidifying be dispersed in the 50mL deionized water, and add 0.03mol hydrochloric acid, cool to 0 ℃;
C, be to mix at 1: 10 in molar ratio with tetra-n-butyl titanate and alcohol solvent; 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, obtain translucent collosol suspension liquid at 0 ℃ of following stirring 2h that continues of temperature;
The pH value of the translucent collosol suspension liquid of ammonia spirit regulating step c of d, use 2mol/L is 0.5, transfers to then in the agitated reactor, at 120 ℃ of following hydro-thermal reaction 36h of temperature;
After e, the reaction end, reactant and extremely neutral with ethanol and deionized water washing is taken out in cooling naturally under the normal temperature, behind 50 ℃ of following vacuum drying 12h of temperature, pulverizes, and can obtain the supported titanium of high thermal stability
2Photochemical catalyst.
With 100mL concentration is that the methylene blue solution of 10ppm is the degraded object, and (back TiO converts to take by weighing the 20mg photochemical catalyst
2Amount) add wherein, dark space stirring and adsorbing 30min is a light source with the 300W xenon lamp, carries out the photocatalytic degradation reaction of methylene.Every get 5mL appearance at a distance from 10min, supernatant liquor is got in centrifugation, according to its absorbance change calculations methylene blue degradation rate, and assesses its photocatalytic activity through ultraviolet-visible spectrophotometer.
The supported titanium of the high thermal stability that present embodiment obtains
2The photochemical catalyst specific area is bigger, is 230m
2/ g, crystallite dimension is 8nm, behind calcining 3h under temperature 500-900 ℃, specific area is 120-225m
2/ g, crystallite dimension is 9-23nm; Has higher phase transformation stability; Brockite wherein anatase in opposite directions changes mutually completely with rutile that temperature is 700 ℃, and the anatase initial temperature that changes mutually of rutile in opposite directions is 800 ℃, up to 900 ℃ of temperature lower calcinations; Anatase still is main crystalline phase, than common TiO
2The crystal transfer temperature improved about 300 ℃, and have higher photocatalytic activity.
A, vermiculite being crossed 300 mesh sieves, is 25% to join in the sulfuric acid solution of 1.5mol/L by mass fraction, and behind the reaction 10h, filtered water is washed till neutrality, and with filter cake at 60 ℃ of dry 10h of temperature, obtain acidifying and peel off vermiculite through grinding;
B, vermiculite is peeled off in step a acidifying be dispersed in the 60mL deionized water, and add 0.04mol hydrochloric acid, cool to 2 ℃;
C, tetraisopropyl titanate and n-butanol solvent are 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 tetraisopropyl titanate and acidifying is 26mmol/g; And, obtain translucent collosol suspension liquid at 2 ℃ of following stirring 3h that continue of temperature;
The pH value of the translucent collosol suspension liquid of sodium hydroxide solution regulating step c of d, use 3mol/L is 1, transfers to then in the agitated reactor, at 140 ℃ of following hydro-thermal reaction 30h of temperature;
After e, the reaction end, reactant and extremely neutral with ethanol and deionized water washing is taken out in cooling naturally under the normal temperature, behind 60 ℃ of following vacuum drying 10h of temperature, pulverizes, and can obtain the supported titanium of high thermal stability
2Photochemical catalyst.
Assess its photocatalytic activity with experiment condition identical among the embodiment 1.
The supported titanium of the high thermal stability that present embodiment obtains
2The photochemical catalyst specific area is bigger, is 250m
2/ g, crystallite dimension is 7.5nm, behind calcining 4h under temperature 500-900 ℃, specific area is 130-240m
2/ g, crystallite dimension is 8-20nm; Has higher phase transformation stability; Brockite wherein anatase in opposite directions changes mutually completely with rutile that temperature is 700 ℃, and the anatase initial temperature that changes mutually of rutile in opposite directions is 800 ℃, up to 900 ℃ of temperature lower calcinations; Anatase still is main crystalline phase, than common TiO
2The crystal transfer temperature improved about 300 ℃, and have higher photocatalytic activity.
Embodiment 3
A, vermiculite being crossed 300 mesh sieves, is 30% to join in the hydrochloric acid solution of 2mol/L by mass fraction, and behind the reaction 8h, filtered water is washed till neutrality, and with filter cake at 70 ℃ of dry 8h of temperature, obtain acidifying and peel off vermiculite through grinding;
B, vermiculite is peeled off in step a acidifying be dispersed in the 70mL deionized water, and add 0.05mol hydrochloric acid, cool to 5 ℃;
C, be to mix at 1: 30 in molar ratio with tetra-n-butyl titanate and isoamyl alcohol solvent; 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, obtain translucent collosol suspension liquid at 5 ℃ of following stirring 4h that continue of temperature;
The pH value of the translucent collosol suspension liquid of potassium hydroxide solution regulating step c of d, use 4mol/L is 1.5, transfers to then in the agitated reactor, at 160 ℃ of following hydro-thermal reaction 28h of temperature;
After e, the reaction end, reactant and extremely neutral with ethanol and deionized water washing is taken out in cooling naturally under the normal temperature, behind 70 ℃ of following vacuum drying 8h of temperature, pulverizes, and can obtain the supported titanium of high thermal stability
2Photochemical catalyst.
Assess its photocatalytic activity with experiment condition identical among the embodiment 1.
The supported titanium of the high thermal stability that present embodiment obtains
2The photochemical catalyst specific area is bigger, is 260m
2/ g, crystallite dimension is 7nm, behind calcining 3.5h under temperature 500-900 ℃, specific area is 150-250m
2/ g, crystallite dimension is 7-18nm; Has higher phase transformation stability; Brockite wherein anatase in opposite directions changes mutually completely with rutile that temperature is 700 ℃, and the anatase initial temperature that changes mutually of rutile in opposite directions is 800 ℃, up to 900 ℃ of temperature lower calcinations; Anatase still is main crystalline phase, than common TiO
2The crystal transfer temperature improved about 300 ℃, and have higher photocatalytic activity.
Embodiment 4
A, vermiculite being crossed 300 mesh sieves, is 35% to join in the salpeter solution of 2.5mol/L by mass fraction, and behind the reaction 7h, filtered water is washed till neutrality, and with filter cake at 80 ℃ of dry 6h of temperature, obtain acidifying and peel off vermiculite through grinding;
B, vermiculite is peeled off in step a acidifying be dispersed in the 80mL deionized water, and add 0.04mol hydrochloric acid, cool to 8 ℃;
C, be to mix at 1: 40 in molar ratio with tetraisopropyl titanate and isopropanol solvent; 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, obtain translucent collosol suspension liquid at 8 ℃ of following stirring 5h that continue of temperature;
The pH value of the translucent collosol suspension liquid of sodium hydroxide solution regulating step c of d, use 5mol/L is 0.5, transfers to then in the agitated reactor, at 180 ℃ of following hydro-thermal reaction 24h of temperature;
After e, the reaction end, reactant and extremely neutral with ethanol and deionized water washing is taken out in cooling naturally under the normal temperature, behind 70 ℃ of following vacuum drying 10h of temperature, pulverizes, and can obtain the supported titanium of high thermal stability
2Photochemical catalyst.
Assess its photocatalytic activity with experiment condition identical among the embodiment 1.
The supported titanium of the high thermal stability that present embodiment obtains
2The photochemical catalyst specific area is bigger, is 255m
2/ g, crystallite dimension is 7.5nm, behind calcining 4h under temperature 500-900 ℃, specific area is 140-245m
2/ g, crystallite dimension is 7-19nm; Has higher phase transformation stability; Brockite wherein anatase in opposite directions changes mutually completely with rutile that temperature is 700 ℃, and the anatase initial temperature that changes mutually of rutile in opposite directions is 800 ℃, up to 900 ℃ of temperature lower calcinations; Anatase still is main crystalline phase, than common TiO
2The crystal transfer temperature improved about 300 ℃, and have higher photocatalytic activity.
Embodiment 5
A, vermiculite being crossed 300 mesh sieves, is 40% to join in the hydrochloric acid solution of 3mol/L by mass fraction, and behind the reaction 6h, filtered water is washed till neutrality, and with filter cake at 100 ℃ of dry 4h of temperature, obtain acidifying and peel off vermiculite through grinding;
B, vermiculite is peeled off in step a acidifying be dispersed in the 60mL deionized water, and add 0.04mol hydrochloric acid, cool to 10 ℃;
C, be to mix at 1: 20 in molar ratio with tetra-n-butyl titanate and isoamyl alcohol agent; 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, obtain translucent collosol suspension liquid at 10 ℃ of following stirring 5h that continue of temperature;
The pH value of the translucent collosol suspension liquid of sodium hydroxide solution regulating step c of d, use 5mol/L is 0.5, transfers to then in the agitated reactor, at 200 ℃ of following hydro-thermal reaction 20h of temperature;
After e, the reaction end, reactant and extremely neutral with ethanol and deionized water washing is taken out in cooling naturally under the normal temperature, behind 60 ℃ of following vacuum drying 20h of temperature, pulverizes, and can obtain the supported titanium of high thermal stability
2Photochemical catalyst.
Assess its photocatalytic activity with experiment condition identical among the embodiment 1.
The supported titanium of the high thermal stability that present embodiment obtains
2The photochemical catalyst specific area is bigger, is 240m
2/ g, crystallite dimension is 8nm, behind calcining 2.5h under temperature 500-900 ℃, specific area is 125-230m
2/ g, crystallite dimension is 8-21nm; Has higher phase transformation stability; Brockite wherein anatase in opposite directions changes mutually completely with rutile that temperature is 700 ℃, and the anatase initial temperature that changes mutually of rutile in opposite directions is 800 ℃, up to 900 ℃ of temperature lower calcinations; Anatase still is main crystalline phase, than common TiO
2The crystal transfer temperature improved about 300 ℃, and have higher photocatalytic activity.
Embodiment 6 (contrasts pure TiO
2Photochemical catalyst)
0.04mol hydrochloric acid is joined in the 50mL deionized water, cool to 3 ℃; With tetra-n-butyl titanate and alcohol solvent is to mix at 1: 20 in molar ratio, joins in the acid solution, and this reactant is being formed vitreosol at 3 ℃ after continuing down to stir 3h; Using the pH value of this colloidal sol of sodium hydroxide solution adjusting of 5mol/L is 0.5, transfers to then in the agitated reactor, at 180 ℃ of following hydro-thermal reaction 24h of temperature; After reaction finished, cooling was naturally taken out reactant, and with deionized water and washing with alcohol, is pulverized behind 60 ℃ of vacuum drying 8h under the normal temperature, makes pure TiO
2Nano material.
Get the pure TiO suitable with each sample load capacity
2, assess its photocatalytic activity with experiment condition identical among the embodiment 1.
The pure TiO that present embodiment obtains
2The photochemical catalyst specific area is 130m
2/ g, crystallite dimension is 9nm, after 500 ℃ of temperature were calcined 3h down, specific area was 65.2m
2/ g, crystallite dimension is 12.5nm; Phase transformation stability is lower, wherein anatase mutually with brockite in opposite directions the initial temperature that changes mutually of rutile be 500 ℃, change fully in the time of 700 ℃, its photocatalytic activity is relatively low.
Claims (5)
1. supported titanium for preparing high thermal stability
2The method of photochemical catalyst is characterized in that following these steps to carrying out:
A, vermiculite is crossed 300 mesh sieves; By mass fraction be 20%-40% join 1-3mol/L phosphoric acid, sulfuric acid, hydrochloric acid or salpeter solution in, the reaction 6-12h after, filtered water is washed till neutrality; And with filter cake at temperature 50-120 ℃ of dry 4-12h, obtain acidifying and peel off vermiculite through grinding;
B, vermiculite is peeled off in step a acidifying be dispersed in the 50-80mL deionized water, and add 0.03-0.05mol hydrochloric acid, cool to 0-10 ℃;
C, be 1 with tetra-n-butyl titanate or tetraisopropyl titanate 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 under temperature 0-10 ℃, continue to stir 1-5h, obtain translucent collosol suspension liquid;
The pH value of d, the ammoniacal liquor that uses 1-5mol/L, NaOH or the translucent collosol suspension liquid of potassium hydroxide solution regulating step c is 0.5-2, transfers to then in the agitated reactor, at temperature 120-200 ℃ of following hydro-thermal reaction 5-50h;
After e, the reaction end, reactant and extremely neutral with ethanol and deionized water washing is taken out in cooling naturally under the normal temperature, behind temperature 50-80 ℃ of following vacuum drying 5-20h, pulverizes, and can obtain the supported titanium of high thermal stability
2Photochemical catalyst.
2. method according to claim 1 is characterized in that it is a kind of peel off fully, lamellar structure that the silicon hydroxyl is rich on the surface that vermiculite is peeled off in acidifying among the step a.
3. method according to claim 1 is characterized in that the supported titanium through the high thermal stability of this method acquisition
2In the photochemical catalyst, TiO
2For anatase, rutile and brockite ternary are mixed crystalline phase.
4. method according to claim 1 is characterized in that the supported titanium through the high thermal stability of this method acquisition
2The used carrier of photochemical catalyst is that the 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 through the high thermal stability of this method acquisition
2The photochemical catalyst specific area is 200-300m
2/ g, crystallite dimension is 6-9nm.
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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 |
| CN105887157A (en) * | 2016-05-13 | 2016-08-24 | 中环清新人工环境工程技术(北京)有限责任公司 | Preparation method of honeycomb shaped nanometer material capable of purifying air |
| CN108097226A (en) * | 2017-12-15 | 2018-06-01 | 沈阳理工大学 | A kind of preparation method with the perlite particle of light catalytic purifying |
| CN112705185A (en) * | 2020-12-29 | 2021-04-27 | 四川建筑职业技术学院 | Preparation method of quartz sand/titanium dioxide composite catalyst |
| CN114368782A (en) * | 2022-01-27 | 2022-04-19 | 南京信息工程大学 | Titanium dioxide-feldspar composite material and preparation method and application thereof |
| CN115028198A (en) * | 2022-06-14 | 2022-09-09 | 安徽迪诺环保新材料科技有限公司 | Production method of titanium dioxide and photocatalytic self-cleaning ceramic |
| CN116477660A (en) * | 2023-05-16 | 2023-07-25 | 塔里木大学 | Process for preparing stable anatase titanium dioxide and stable anatase titanium dioxide |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104383906A (en) * | 2014-11-10 | 2015-03-04 | 沈阳理工大学 | Method for preparing porous strontium titanate photocatalyst |
| CN105887157A (en) * | 2016-05-13 | 2016-08-24 | 中环清新人工环境工程技术(北京)有限责任公司 | Preparation method of honeycomb shaped nanometer material capable of purifying air |
| CN105887157B (en) * | 2016-05-13 | 2017-05-31 | 中环清新人工环境工程技术(北京)有限责任公司 | A kind of preparation method that can be used for the cellular nano material of purification of air |
| CN108097226A (en) * | 2017-12-15 | 2018-06-01 | 沈阳理工大学 | A kind of preparation method with the perlite particle of light catalytic purifying |
| CN112705185A (en) * | 2020-12-29 | 2021-04-27 | 四川建筑职业技术学院 | Preparation method of quartz sand/titanium dioxide composite catalyst |
| CN114368782A (en) * | 2022-01-27 | 2022-04-19 | 南京信息工程大学 | Titanium dioxide-feldspar composite material and preparation method and application thereof |
| CN115028198A (en) * | 2022-06-14 | 2022-09-09 | 安徽迪诺环保新材料科技有限公司 | Production method of titanium dioxide and photocatalytic self-cleaning ceramic |
| CN116477660A (en) * | 2023-05-16 | 2023-07-25 | 塔里木大学 | Process for preparing stable anatase titanium dioxide and stable anatase titanium dioxide |
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