CN105214637A - A kind of metatitanic acid cesium silicate photochemical catalyst and its preparation method and application - Google Patents

A kind of metatitanic acid cesium silicate photochemical catalyst and its preparation method and application Download PDF

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CN105214637A
CN105214637A CN201510461114.0A CN201510461114A CN105214637A CN 105214637 A CN105214637 A CN 105214637A CN 201510461114 A CN201510461114 A CN 201510461114A CN 105214637 A CN105214637 A CN 105214637A
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cesium
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tio
metatitanic acid
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CN105214637B (en
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乔学斌
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Nanjing Tongli Crystal Materials Research Institute Co., Ltd.
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Jiangsu Normal University
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Abstract

The invention discloses a kind of metatitanic acid cesium silicate photochemical catalyst and its preparation method and application, this metatitanic acid cesium silicate photochemical catalyst chemical formula is CsSi 2tiO 6.5its pattern is irregular particle shape or form of spherical particles, and high temperature solid-state method, sol-gel process can be adopted to prepare, production cost is low, equipment requirement is simple, and the metatitanic acid cesium silicate photochemical catalyst good dispersion of preparation, uniform granularity, chemical stability be good, have very strong light absorption, has the effect of decomposing harmful chemical under the irradiation of ultraviolet light, and repetition stability is good, there is potential applications well prospect.

Description

A kind of metatitanic acid cesium silicate photochemical catalyst and its preparation method and application
Technical field
The present invention relates to one and can realize ultraviolet light photocatalysis material, preparation method and application, particularly relate to a kind of metatitanic acid cesium silicate photochemical catalyst and its preparation method and application, belong to inorganic field of photocatalytic material.
Background technology
At present, along with the development of human society, the prosperity day by day that science and technology is economic, the mankind have enjoyed comfortable life, but taste the bitter pill that living environment constantly worsens, and the deterioration of ecological environment more and more governs the sustainable development of future society.In various environmental pollution, the most generally, main and what have the greatest impact is chemical contamination.Thus; effectively controlling and administering various chemical pollutant to the destruction forming the most basic water resource, soil and the atmospheric environment of human survival is emphasis in comprehensive environmental improvement, and exploitation can be the key of environmental protection practical technique innoxious for various chemical pollutant.Because efficiency is low, pollutant can not be thoroughly innoxious, easily produces secondary pollution; Only can process specific pollutant; Or energy consumption is high, be not suitable for the existence of the aspect drawbacks such as large-scale promotion, thus, exploitation be efficient, low energy consumption, applied widely and have the chemical pollutant clearance technique of deep oxidation ability to be the target that green technology is pursued always.Photocatalysis technology is exactly the emerging green technology progressively grown up from 20 century 70s.
Within 1972, Fujishima and Honda finds at irradiated TiO 2on can continue the redox reaction of water occurs, from then on start the large quantity research to semiconductor light-catalyst.Light-catalyzed reaction produces electron-hole by semiconductor particle absorb photons and causes.After inorganic semiconductor is subject to being greater than the photon irradiation of energy gap energy, electronics transits to empty conduction band from valence band, defines photohole in valence band, light induced electron is defined at conduction band, electronics has reproducibility, and hole has oxidisability, and organic pollution is finally decomposed into CO 2and H 2the innocuous substances such as O.
In many metal oxide semiconductors, TiO 2be the maximum of research, but its energy gap is 3.2 electron-volts, corresponding light wave absorbing wavelength is 387.5 nanometers, and light absorption is only limitted to ultra-violet (UV) band, TiO 2the light induced electron and the hole that produce after illumination is penetrated easily compound again, or by metastable state surperficial capture and lose activity.Therefore photocatalysis effect can be improved by research novel inorganic photochemical catalyst.
In prior art, patent CN103170323A reports titanate photocatalyst A 2tiO 4and preparation method thereof, patent CN103599772A reports a kind of titanate nanotube composite photocatalyst and its preparation method and application simultaneously, obtains the CdS/ titanate nanotube composite photo-catalyst of one dimension tubular structure.On these report bases about titanate photocatalyst, we have studied a kind of novel metatitanic acid cesium silicate photochemical catalyst CsSi 2tiO 6.5, this compound has excellent ultraviolet light response photocatalysis performance, and its preparation method and application is so far not reported.
Summary of the invention
For above-mentioned existing technical problem, the invention provides a kind of preparation technology simple, production cost is low, simultaneously metatitanic acid cesium silicate photochemical catalyst that can realize ultraviolet light photocatalysis and its preparation method and application.
For achieving the above object, the invention provides a kind of metatitanic acid cesium silicate photochemical catalyst, chemical formula is CsSi 2tiO 6.5, its pattern is irregular particle shape or form of spherical particles.
The present invention provides again a kind of preparation method of above-mentioned metatitanic acid cesium silicate photochemical catalyst, adopts high temperature solid-state method, comprises following concrete steps:
(1) by chemical formula CsSi 2tiO 6.5in the stoichiometric proportion of each element, take respectively containing cesium ion Cs +compound, containing silicon ion Si 4+compound, containing titanium ion Ti 4+compound, grind and mix;
(2) by the precalcining 1 ~ 2 time in air atmosphere of step (1) gains, calcining heat is 200 ~ 600 DEG C, and calcination time is 2 ~ 10 hours;
(3) naturally cooled by step (2) gains, to grind and after mixing, then calcine in air atmosphere, calcining heat is 600 ~ 900 DEG C, and calcination time is 2 ~ 15 hours;
(4) step (3) gains are cooled naturally, obtain metatitanic acid cesium silicate material C sSi 2tiO 6.5.
Further, described containing cesium ion Cs +compound be one in cesium oxide, cesium carbonate, caesium bicarbonate, cesium nitrate; Described contains silicon ion Si 4+compound be one in silica and silicic acid; Described contains titanium ion Ti 4+compound be titanium dioxide.
Further, the precalcining temperature of step (2) is 300 ~ 600 DEG C, and calcination time is 3 ~ 10 hours; The calcining heat of step (3) is 600 ~ 850 DEG C, and calcination time is 3 ~ 12 hours.
The present invention reoffers a kind of preparation method of above-mentioned metatitanic acid cesium silicate photochemical catalyst, adopts sol-gel process, comprises following concrete steps:
(A) by chemical formula CsSi 2tiO 6.5in the stoichiometric proportion of each element, take respectively containing cesium ion Cs +compound, containing silicon ion Si 4+compound, containing titanium ion Ti 4+compound; First will containing cesium ion Cs +compound be dissolved in deionized water or dilute nitric acid solution, obtain clear solution, then press 0.5 ~ 2.0 times of metal cation mole amount and add complexing agent citric acid or oxalic acid; Secondly will containing silicon ion Si 4+compound dilute nitric acid dissolution, add absolute ethyl alcohol simultaneously, and dilute by deionized water; Again will containing titanium ion Ti 4+compound add glacial acetic acid solution, under the temperature conditions of 50 ~ 100 DEG C, add thermal agitation, until complete hydrolysis; Finally obtain the mixed liquor of each raw material;
(B) each raw material mixed liquor that step (A) obtains slowly is mixed, continue stirring after 1 ~ 2 hour, leave standstill, dry, obtain fluffy presoma;
(C) the precursor powder that step (B) obtains is placed in crucible, prior in Muffle furnace, calcines 2 ~ 3 times in air atmosphere, calcining heat is 200 ~ 650 DEG C, and calcination time 2 ~ 13 hours, then naturally cools to room temperature, obtains metatitanic acid cesium silicate material C sSi 2tiO 6.5.
Further, described containing cesium ion Cs +compound be one in cesium oxide, cesium carbonate, caesium bicarbonate, cesium nitrate; Described contains silicon ion Si 4+compound be ethyl orthosilicate; Described contains titanium ion Ti 4+compound be one in butyl titanate and tetraisopropyl titanate.
Further, the calcining heat of step (C) is 300 ~ 600 DEG C, and calcination time is 3 ~ 12 hours.
The present invention also provides a kind of above-mentioned metatitanic acid cesium silicate photochemical catalyst as the application of inorganic catalysis material.
Compared with prior art, metatitanic acid cesium silicate photochemical catalyst CsSi prepared by technical solution of the present invention 2tiO 6.5not only can realize ultraviolet light photocatalysis effect, also possess following advantage:
1, the present invention prepares metatitanic acid cesium silicate photochemical catalyst CsSi 2tiO 6.5production method be calcine obtained in air atmosphere, firing temperature is lower, and preparation technology is simple, and being easy to operation, is potential catalysis material.
2, the metatitanic acid cesium silicate photochemical catalyst CsSi for preparing of the present invention 2tiO 6.5can band gap narrower, under UV-irradiation, this photochemical catalyst can high efficiency photocatalysis degradation of methylene blue, has good photocatalytic activity.
3, the present invention prepares metatitanic acid cesium silicate photochemical catalyst CsSi 2tiO 6.5raw materials abundance, cheap, and energy resource consumption is low, environmentally friendly, the metatitanic acid cesium silicate properties of catalyst of synthesis is stablized.
Accompanying drawing explanation
Fig. 1 is that the embodiment of the present invention 1 prepares sample CsSi 2tiO 6.5x-ray powder diffraction pattern;
Fig. 2 is that the embodiment of the present invention 1 prepares sample CsSi 2tiO 6.5sEM figure;
Fig. 3 is that the embodiment of the present invention 1 prepares sample CsSi 2tiO 6.5uV-Vis diffuse reflection spectroscopy figure;
Fig. 4 is that the embodiment of the present invention 1 prepares sample CsSi 2tiO 6.5to the degradation curve figure of organic dyestuff methylene blue under the ultraviolet light different light time;
Fig. 5 is that the embodiment of the present invention 1 prepares sample CsSi 2tiO 6.5the kinetic curve figure of degradating organic dye methylene blue;
Fig. 6 is that the embodiment of the present invention 5 prepares sample CsSi 2tiO 6.5x-ray powder diffraction pattern;
Fig. 7 is that the embodiment of the present invention 5 prepares sample CsSi 2tiO 6.5sEM figure;
Fig. 8 is that the embodiment of the present invention 5 prepares sample CsSi 2tiO 6.5uV-Vis diffuse reflection spectroscopy figure;
Fig. 9 is that the embodiment of the present invention 5 prepares sample CsSi 2tiO 6.5to the degradation curve figure of organic dyestuff methylene blue under the ultraviolet light different light time;
Figure 10 is that the embodiment of the present invention 5 prepares sample CsSi 2tiO 6.5the kinetic curve figure of degradating organic dye methylene blue.
Detailed description of the invention
Below in conjunction with drawings and Examples, the invention will be further described.
Metatitanic acid cesium silicate photochemical catalyst chemical formula of the present invention is CsSi 2tiO 6.5, solid phase method, sol-gel process can be adopted to prepare, and specific implementation method is as follows.
Embodiment 1:
High temperature solid-state method is adopted to prepare CsSi 2tiO 6.5, namely using as the various oxide of raw material or carbonate according to the metering of target constitutional chemistry than mixing, then to synthesize in air atmosphere at ambient pressure.
First, according to chemical formula CsSi 2tiO 6.5, take cesium oxide Cs respectively 2o:1.41 gram, silica SiO 2: 1.2 grams, titanium dioxide TiO 2: 0.8 gram, grind and mix in agate mortar, select air atmosphere first time calcining, temperature is 300 DEG C, and calcination time is 3 hours, is then chilled to room temperature, takes out sample.Then, by front step sample, fully ground and mixed is even again, and calcine in air atmosphere, calcining heat is 600 DEG C, and calcination time is 10 hours, is cooled to room temperature, takes out sample.Finally, be placed in Muffle furnace after fully being ground by front step sample and calcine in air, calcining heat is 850 DEG C, and calcination time is 12 hours, is then chilled to room temperature, takes out sample, namely obtains metatitanic acid cesium silicate CsSi 2tiO 6.5powder.
See accompanying drawing 1, the present embodiment 1 prepares the X-ray powder diffraction figure of sample, and XRD test result shows, prepared metatitanic acid cesium silicate CsSi 2tiO 6.5for monophase materials, exist without any other dephasign, and degree of crystallinity is better.
See accompanying drawing 2, the present embodiment 1 prepares the SEM figure of sample, and this material crystalline is functional, even particle size distribution, and average grain diameter is at 2 microns.
In order to verify this metatitanic acid cesium silicate CsSi 2tiO 6.5the characteristic of photochemical catalyst, takes 100 milligrams of CsSi 2tiO 6.5, by pulverizing means such as ball mills, particle diameter is diminished, uses 500 watts of mercury lamps as light source, degrade 250 milliliters, the methylene blue solution of 10 mg/litre.Within every 15 minutes, get a sample, illumination, after two hours, will sample centrifugal, get its supernatant, measure the absorbance of methylene blue solution with ultraviolet-visible spectrophotometer in wavelength 664-666 nanometers.According to Lambert-Beer's law, calculate the clearance of methylene blue solution.
See accompanying drawing 3, sample CsSi prepared by the present embodiment 1 2tiO 6.5uV-Vis diffuse reflection spectroscopy figure, as can be seen from the figure, the shearing wavelength of this sample is 394 nanometers, in UV light region.
See accompanying drawing 4, sample CsSi prepared by the present embodiment 1 2tiO 6.5degradation curve to organic dyestuff methylene blue under the different UV Light time.As can be seen from the figure, the degradation rate of this sample photocatalytic degradation methylene blue reaches 79.94% in 340 minutes, and the pure phase CsSi prepared is described 2tiO 6.5material has certain photocatalytic activity.
See accompanying drawing 5, sample CsSi prepared by the present embodiment 1 2tiO 6.5the kinetic curve figure of degradating organic dye methylene blue, as can be seen from the figure, the apparent kinetics speed constant of this sample photocatalytic degradation methylene blue is 0.00554 minute -1.
Embodiment 2:
Still high temperature solid-state method is adopted, first according to chemical formula CsSi 2tiO 6.5, take cesium carbonate Cs respectively 2cO 3: 1.63 grams, silicic acid H 2siO 3: 1.56 grams, titanium dioxide TiO 2: 0.8 gram, grind and mix in agate mortar, select air atmosphere first time calcining, temperature is 350 DEG C, and calcination time is 3 hours, is then chilled to room temperature, takes out sample.Then, by front step sample, fully ground and mixed is even again, and calcine in air atmosphere, calcining heat is 500 DEG C, and calcination time is 4 hours, is cooled to room temperature, takes out sample.Finally, be placed in Muffle furnace after fully being ground by front step sample and calcine in air, calcining heat is 600 DEG C, and calcination time is 3 hours, is then chilled to room temperature, takes out sample, namely obtains metatitanic acid cesium silicate CsSi 2tiO 6.5powder, and by pulverizing means such as ball mills, particle diameter is diminished, be convenient to follow-up test.
During characteristic test, take 100 milligrams of photochemical catalyst CsSi 2tiO 6.5, use 500 watts of mercury lamps as light source, degrade 250 milliliters, the methylene blue solution of 10 mg/litre.Within every 15 minutes, get a sample, illumination, after two hours, will sample centrifugal, get its supernatant, measure the absorbance of methylene blue solution with ultraviolet-visible spectrophotometer in wavelength 664-666 nanometers.According to Lambert-Beer's law, calculate the clearance of methylene blue solution.Known, the CsSi that the present embodiment is obtained 2tiO 6.5primary structure pattern performance, luminescent properties similar to embodiment 1, also demonstrate that this metatitanic acid cesium silicate photochemical catalyst can be applied as inorganic catalysis material.
Embodiment 3:
Still high temperature solid-state method is adopted, first according to chemical formula CsSi 2tiO 6.5, take caesium bicarbonate CsHCO respectively 3: 1.94 grams, silica SiO 2: 1.2 grams, titanium dioxide TiO 2: 0.8 gram, grind and mix in agate mortar, select air atmosphere first time calcining, temperature is 400 DEG C, and calcination time is 5 hours, is then chilled to room temperature, takes out sample.Then, by front step sample, fully ground and mixed is even again, and calcine in air atmosphere, calcining heat is 600 DEG C, and calcination time is 6 hours, is cooled to room temperature, takes out sample.Finally, be placed in Muffle furnace after fully being ground by front step sample and calcine in air, calcining heat is 800 DEG C, and calcination time is 10 hours, is then chilled to room temperature, takes out sample, namely obtains metatitanic acid cesium silicate CsSi 2tiO 6.5powder, and by pulverizing means such as ball mills, particle diameter is diminished, be convenient to follow-up test.
During photo-catalysis capability test, take 100 milligrams of photochemical catalyst CsSi 2tiO 6.5, use 500 watts of mercury lamps as light source, degrade 250 milliliters, the methylene blue solution of 10 mg/litre.Within every 15 minutes, get a sample, illumination, after two hours, will sample centrifugal, get its supernatant, measure the absorbance of methylene blue solution with ultraviolet-visible spectrophotometer in wavelength 664-666 nanometers.According to Lambert-Beer's law, calculate the clearance of methylene blue solution.Known, the CsSi that the present embodiment is obtained 2tiO 6.5primary structure pattern performance, luminescent properties similar to embodiment 1, also demonstrate that this metatitanic acid cesium silicate photochemical catalyst can be applied as inorganic catalysis material.
Embodiment 4:
Again adopt high temperature solid-state method, first according to chemical formula CsSi 2tiO 6.5, take cesium carbonate Cs respectively 2cO 3: 1.63 grams, silica SiO 2: 1.2 grams, titanium dioxide TiO 2: 0.8 gram, grind and mix in agate mortar, select air atmosphere first time calcining, temperature is 450 DEG C, and calcination time is 8 hours, is chilled to room temperature, takes out sample.Then, by front step sample, fully ground and mixed is even again, and calcine in air atmosphere, calcining heat is 550 DEG C, and calcination time is 9 hours, is cooled to room temperature, takes out sample.Finally, be placed in Muffle furnace after fully being ground by front step sample and calcine in air, calcining heat is 750 DEG C, and calcination time is 11 hours, is then chilled to room temperature, takes out sample, namely obtains metatitanic acid cesium silicate CsSi 2tiO 6.5powder, and by pulverizing means such as ball mills, particle diameter is diminished, be convenient to follow-up test.
During experiment, take 100 milligrams of photochemical catalysts, use 500 watts of mercury lamps as light source, degrade 250 milliliters, the methylene blue solution of 10 mg/litre.Within every 15 minutes, get a sample, illumination, after two hours, will sample centrifugal, get its supernatant, measure the absorbance of methylene blue solution with ultraviolet-visible spectrophotometer in wavelength 664-666 nanometers.According to Lambert-Beer's law, calculate the clearance of methylene blue solution.Known, the CsSi that the present embodiment is obtained 2tiO 6.5primary structure pattern performance, luminescent properties similar to embodiment 1.
Embodiment 5:
Prepared by employing sol-gel process, according to chemical formula CsSi 2tiO 6.5, take cesium nitrate CsNO respectively 3: 1.95 grams, ethyl orthosilicate Si (OC 2h 5) 4: 1.05 grams, butyl titanate: 3.41 grams, oxalic acid H 2c 2o 4-2H 2o:0.46 gram.First, cesium nitrate is dissolved in deionized water, obtains clear solution, then 0.5 times that presses metal cation mole amount is added the stirring of complexing agent oxalic acid; Secondly ethyl orthosilicate dust technology is gone to dissolve, add a certain amount of absolute ethyl alcohol simultaneously, and dilute by deionized water; Again butyl titanate is added appropriate glacial acetic acid solution, add thermal agitation, until complete hydrolysis; Then, by the mixed liquor mix and blend of each raw material formed vitreosol, then leave standstill, dry after obtain fluffy presoma.
Calcined in air atmosphere by presoma, calcining heat is 300 DEG C, and calcination time is 3 hours, is then cooled to room temperature, takes out sample; By the raw material of first time calcining, fully mixed grinding is even again, and in air atmosphere, carry out second time calcining, calcining heat 500 DEG C, calcination time 5 hours, is then chilled to room temperature, takes out sample; Be placed in Muffle furnace after finally it again fully being ground, calcine in air atmosphere, calcining heat is 600 DEG C, and calcination time is 12 hours, selects air atmosphere to calcine, is chilled to room temperature, take out sample, namely obtain CsSi 2tiO 6.5powder.
See accompanying drawing 6, the present embodiment 5 prepares the X-ray powder diffraction pattern of sample, and XRD test result shows, and adopts the CsSi that sol-gel process is obtained 2tiO 6.5for monophase materials, the impurity thing without any other exists mutually.
See accompanying drawing 7, the present embodiment 5 prepares the SEM figure of sample, and this material crystalline is functional, even particle size distribution, and average grain diameter is at 50 ran, and the material particle size that grain diameter prepared by visible sol-gal process is prepared than high temperature solid-state method is much smaller.
See accompanying drawing 8, the present embodiment 5 prepares sample CsSi 2tiO 6.5uV-Vis diffuse reflection spectroscopy figure, as can be seen from the figure, the shearing wavelength of this sample is 397 nanometers, in UV light region.
During photocatalysis characteristic experiment, take 100 milligrams of photochemical catalyst CsSi 2tiO 6.5powder, uses 500 watts of mercury lamps as light source, degrade 250 milliliters, the methylene blue solution of 10 mg/litre.Within every 15 minutes, get a sample, illumination, after two hours, will sample centrifugal, get its supernatant, measure the absorbance of methylene blue solution with ultraviolet-visible spectrophotometer in wavelength 664-666 nanometers.According to Lambert-Beer's law, calculate the clearance of methylene blue solution.
See accompanying drawing 9, the present embodiment 5 prepares sample CsSi 2tiO 6.5degradation curve to organic dyestuff methylene blue under the different UV Light time.As can be seen from the figure, the degradation rate of this sample photocatalytic degradation methylene blue reaches 88.39% in 260 minutes, and the pure phase CsSi prepared is described 2tiO 6.5material has certain photocatalytic activity.
See accompanying drawing 10, the present embodiment 5 prepares sample CsSi 2tiO 6.5the kinetic curve figure of degradating organic dye methylene blue, as can be seen from the figure, the apparent kinetics speed constant of this sample photocatalytic degradation methylene blue is 0.00853 minute -1.
Embodiment 6:
Prepared by employing sol-gel process, according to chemical formula CsSi 2tiO 6.5, take cesium oxide Cs respectively 2o:1.41 gram, ethyl orthosilicate Si (OC 2h 5) 4: 1.05 grams, tetraisopropyl titanate: 2.85 grams, oxalic acid H 2c 2o 4-2H 2o:0.91 gram; First cesium oxide is dissolved in dust technology, obtains clear solution, then 1.0 times that press metal cation mole amount are added the stirring of complexing agent oxalic acid; Secondly ethyl orthosilicate dust technology is gone to dissolve, add a certain amount of absolute ethyl alcohol simultaneously, and dilute by deionized water; Again tetraisopropyl titanate is added appropriate glacial acetic acid solution, adds thermal agitation, until complete hydrolysis, by the mixed liquor mix and blend of each raw material formed vitreosol, then leave standstill, dry after obtain fluffy presoma.
Calcined in air atmosphere by presoma, calcining heat is 350 DEG C, and calcination time is 5 hours, is then cooled to room temperature, takes out sample; By the raw material of first time calcining, fully mixed grinding is even again, and in air atmosphere, carry out second time calcining, calcining heat 400 DEG C, calcination time 6 hours, is then chilled to room temperature, takes out sample; Be placed in Muffle furnace after finally it again fully being ground, calcine in air atmosphere, calcining heat is 500 DEG C, and calcination time is 10 hours, selects air atmosphere to calcine, is chilled to room temperature, take out sample, namely obtain titanate CsSi 2tiO 6.5powder.
During photocatalysis characteristic checking, 100 milligrams of photochemical catalysts can be taken, use 500 watts of mercury lamps as light source, degrade 250 milliliters, the methylene blue solution of 10 mg/litre.Within every 15 minutes, get a sample, illumination, after two hours, will sample centrifugal, get its supernatant, measure the absorbance of methylene blue solution with ultraviolet-visible spectrophotometer in wavelength 664-666 nanometers.According to Lambert-Beer's law, calculate the clearance of methylene blue solution.
Through observation, CsSi prepared by the present embodiment 2tiO 6.5the primary structure of powder, can realize ultraviolet light photocatalysis effect, similar to embodiment 5 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 7:
Or adopt sol-gel process preparation, according to chemical formula CsSi 2tiO 6.5, take cesium carbonate Cs respectively 2cO 3: 1.63 grams, ethyl orthosilicate Si (OC 2h 5) 4: 1.05 grams, butyl titanate: 3.41 grams, oxalic acid H 2c 2o 4-2H 2o:1.36 gram; First cesium carbonate is dissolved in dust technology, obtains clear solution, then 1.5 times that press metal cation mole amount are added the stirring of complexing agent oxalic acid; Secondly ethyl orthosilicate dust technology is gone to dissolve, add a certain amount of absolute ethyl alcohol simultaneously, and dilute by deionized water; Again butyl titanate is added appropriate glacial acetic acid solution, add thermal agitation, until complete hydrolysis; By the mixed liquor mix and blend of each raw material formed vitreosol, then leave standstill, dry after obtain fluffy presoma.
Calcined in air atmosphere by presoma, calcining heat is 400 DEG C, and calcination time is 5 hours, is then cooled to room temperature, takes out sample; By the raw material of first time calcining, fully mixed grinding is even again, and in air atmosphere, carry out second time calcining, calcining heat 500 DEG C, calcination time 8 hours, is then chilled to room temperature, takes out sample; Be placed in Muffle furnace after finally it again fully being ground, calcine in air atmosphere, calcining heat is 550 DEG C, and calcination time is 11 hours, selects air atmosphere to calcine, is chilled to room temperature, take out sample, namely obtain CsSi 2tiO 6.5powder.
During photocatalysis characteristic checking, take 100 milligrams of photochemical catalysts, use 500 watts of mercury lamps as light source, degrade 250 milliliters, the methylene blue solution of 10 mg/litre.Within every 15 minutes, get a sample, illumination, after two hours, will sample centrifugal, get its supernatant, measure the absorbance of methylene blue solution with ultraviolet-visible spectrophotometer in wavelength 664-666 nanometers.According to Lambert-Beer's law, calculate the clearance of methylene blue solution.
Result of the test shows, CsSi prepared by the present embodiment 2tiO 6.5the primary structure of powder, can realize ultraviolet light photocatalysis effect, similar to embodiment 5 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
Embodiment 8:
Or adopt sol-gel process preparation, according to chemical formula CsSi 2tiO 6.5, take cesium nitrate CsNO respectively 3: 1.95 grams, ethyl orthosilicate Si (OC 2h 5) 4: 1.05 grams, butyl titanate: 3.41 grams, oxalic acid H 2c 2o 4-2H 2o:1.81 gram; First cesium carbonate is dissolved in dust technology, obtains clear solution, then 2 times that press metal cation mole amount are added the stirring of complexing agent oxalic acid; Secondly ethyl orthosilicate dust technology is gone to dissolve, add a certain amount of absolute ethyl alcohol simultaneously, and dilute by deionized water; Again butyl titanate is added appropriate glacial acetic acid solution, add thermal agitation, until complete hydrolysis; By the mixed liquor mix and blend of each raw material formed vitreosol, then leave standstill, dry after obtain fluffy presoma.
Calcined in air atmosphere by presoma, calcining heat is 350 DEG C, and calcination time is 6 hours, is then cooled to room temperature, takes out sample; By the raw material of first time calcining, fully mixed grinding is even again, and in air atmosphere, carry out second time calcining, calcining heat 420 DEG C, calcination time 7 hours, is then chilled to room temperature, takes out sample; Be placed in Muffle furnace after finally it again fully being ground, calcine in air atmosphere, calcining heat is 580 DEG C, and calcination time is 9 hours, selects air atmosphere to calcine, is chilled to room temperature, take out sample, namely obtain CsSi 2tiO 6.5powder.
During photocatalysis characteristic checking, take 100 milligrams of photochemical catalysts, use 500 watts of mercury lamps as light source, degrade 250 milliliters, the methylene blue solution of 10 mg/litre.Within every 15 minutes, get a sample, illumination, after two hours, will sample centrifugal, get its supernatant, measure the absorbance of methylene blue solution with ultraviolet-visible spectrophotometer in wavelength 664-666 nanometers.According to Lambert-Beer's law, calculate the clearance of methylene blue solution.
Through observation, CsSi prepared by the present embodiment 2tiO 6.5the primary structure of powder, similar to embodiment 5 with the kinetic curve of degradation of methylene blue to the degradation rate of methylene blue.
To sum up, the chemical formula that prepared by each embodiment is CsSi 2tiO 6.5photochemical catalyst, confirm to have excellent ultraviolet light response photocatalysis performance through test, preparation technology is simple, is easy to operation.

Claims (8)

1. a metatitanic acid cesium silicate photochemical catalyst, is characterized in that, chemical formula is CsSi 2tiO 6.5, its pattern is irregular particle shape or form of spherical particles.
2. a preparation method for a kind of metatitanic acid cesium silicate photochemical catalyst as claimed in claim 1, is characterized in that, adopts high temperature solid-state method, comprises following concrete steps:
By chemical formula CsSi 2tiO 6.5in the stoichiometric proportion of each element, take respectively containing cesium ion Cs +compound, containing silicon ion Si 4+compound, containing titanium ion Ti 4+compound, grind and mix;
By the precalcining 1 ~ 2 time in air atmosphere of step (1) gains, calcining heat is 200 ~ 600 DEG C, and calcination time is 2 ~ 10 hours;
Naturally cooled by step (2) gains, to grind and after mixing, then calcine in air atmosphere, calcining heat is 600 ~ 900 DEG C, and calcination time is 2 ~ 15 hours;
Step (3) gains are cooled naturally, obtains metatitanic acid cesium silicate material C sSi 2tiO 6.5.
3. the preparation method of a kind of metatitanic acid cesium silicate photochemical catalyst according to claim 2, is characterized in that: described contains cesium ion Cs +compound be one in cesium oxide, cesium carbonate, caesium bicarbonate, cesium nitrate; Described contains silicon ion Si 4+compound be one in silica and silicic acid; Described contains titanium ion Ti 4+compound be titanium dioxide.
4. the preparation method of a kind of metatitanic acid cesium silicate photochemical catalyst according to Claims 2 or 3, is characterized in that: the precalcining temperature of step (2) is 300 ~ 600 DEG C, and calcination time is 3 ~ 10 hours; The calcining heat of step (3) is 600 ~ 850 DEG C, and calcination time is 3 ~ 12 hours.
5. a preparation method for a kind of metatitanic acid cesium silicate photochemical catalyst as claimed in claim 1, is characterized in that, adopts sol-gel process, comprises following concrete steps:
(A) by chemical formula CsSi 2tiO 6.5in the stoichiometric proportion of each element, take respectively containing cesium ion Cs +compound, containing silicon ion Si 4+compound, containing titanium ion Ti 4+compound; First will containing cesium ion Cs +compound be dissolved in deionized water or dilute nitric acid solution, obtain clear solution, then press 0.5 ~ 2.0 times of metal cation mole amount and add complexing agent citric acid or oxalic acid; Secondly will containing silicon ion Si 4+compound dilute nitric acid dissolution, add absolute ethyl alcohol simultaneously, and dilute by deionized water; Again will containing titanium ion Ti 4+compound add glacial acetic acid solution, under the temperature conditions of 50 ~ 100 DEG C, add thermal agitation, until complete hydrolysis; Finally obtain the mixed liquor of each raw material;
(B) each raw material mixed liquor that step (A) obtains slowly is mixed, continue stirring after 1 ~ 2 hour, leave standstill, dry, obtain fluffy presoma;
(C) the precursor powder that step (B) obtains is placed in crucible, prior in Muffle furnace, calcines 2 ~ 3 times in air atmosphere, calcining heat is 200 ~ 650 DEG C, and calcination time 2 ~ 13 hours, then naturally cools to room temperature, obtains metatitanic acid cesium silicate material C sSi 2tiO 6.5.
6. the preparation method of a kind of metatitanic acid cesium silicate photochemical catalyst according to claim 5, is characterized in that, described contains cesium ion Cs +compound be one in cesium oxide, cesium carbonate, caesium bicarbonate, cesium nitrate; Described contains silicon ion Si 4+compound be ethyl orthosilicate; Described contains titanium ion Ti 4+compound be one in butyl titanate and tetraisopropyl titanate.
7. the preparation method of a kind of metatitanic acid cesium silicate photochemical catalyst according to claim 5 or 6, is characterized in that, the calcining heat of step (C) is 300 ~ 600 DEG C, and calcination time is 3 ~ 12 hours.
8. an a kind of metatitanic acid cesium silicate photochemical catalyst as claimed in claim 1 is as the application of inorganic catalysis material.
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