CN104772148A - Preparation method of perovskite type air purification photocatalyst - Google Patents
Preparation method of perovskite type air purification photocatalyst Download PDFInfo
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- CN104772148A CN104772148A CN201510157859.8A CN201510157859A CN104772148A CN 104772148 A CN104772148 A CN 104772148A CN 201510157859 A CN201510157859 A CN 201510157859A CN 104772148 A CN104772148 A CN 104772148A
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- titanium hydroxide
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Abstract
The invention discloses a preparation method of a perovskite type air purification photocatalyst. The method comprises the steps of feeding a dilute sulfuric acid solution into titanium hydroxide emulsion according to the molar ratio of titanium hydroxide to sulfuric acid being 1: (0.005-0.100), evenly stirring, and oscillating for 10-60 minutes in ultrasonic waves to obtain acidified emulsion; feeding perovskite type substances into the prepared acidified titanium hydroxide emulsion in a stirring state, wherein the mass ratio of titanium hydroxide to perovskite type substances is equal to 1: (0.01-0.30); oscillating for 10-60 minutes in ultrasonic waves, then centrifugally washing, pouring away supernatant liquor after centrifugally washing, calcining the precipitate at the temperature of 150-350 DEG C, and carrying out heat preservation for 2-10 hours to obtain the perovskite type air purification photocatalyst. According to the preparation method, the perovskite type substances are introduced into anatase titanium dioxide nano materials, so that the photocatalyst can be expanded into a visible light area from an ultraviolet light area by a spectrum, the photocatalyst can produce laser within the range of visible light, electron-hole pairs can be produced, and the utilization rate of sunlight is improved; the preparation method is widely applied to the industrial production of the photocatalyst for an air purifier.
Description
Technical field
The invention belongs to technical field of air purification, particularly a kind of preparation method of Ca-Ti ore type purification of air photochemical catalyst.
Background technology
After entering 2l century, people are more and more stronger for the consciousness of environmental protection, and this environmental consciousness is not only embodied in residing natural environment aspect, are also like this to the environment of oneself life; At present, the peculiar smell of the new house such as fitted up in living environment, the new car of buying and more and more outstanding environmental pollution, bring harm to the health of people and life; Decreasing pollution as far as possible, the living environment creating a green safety becomes the target of people's pursuit.
Now widely used TiO
2the organic pollution that catalysis material can be degraded in air at normal temperatures and pressures efficiently, good stability, catalytic efficiency is high, is a kind of ideal photochemical catalyst; But nano-TiO in the market
2product is nano-TiO mainly
2powder dispersion, these systems carry out surface modification owing to employing various high molecular organic dispersion stabilizer to it, and mostly less stable and photocatalysis performance significantly decline.
What is more important, TiO
2extinction frequency band narrow, the band-gap energy Eg ≈ 3.2Ev of anatase, only under the photon excitation of wavelength X≤387.5nm, could produce electron-hole pair (e
--h
+), mainly use the ultraviolet light of 387. 5 below nm, this part light radiation only accounts for about 4 % of light radiation total amount to ground; Therefore all adopt artificial light source at present, energy consumption is higher, if can scope be utilized to expand to visible ray the spectrum of photochemical catalyst, then equipment investment and operating cost can be made greatly to reduce.
Summary of the invention
Technical problem to be solved by this invention is, overcome the shortcoming of prior art, a kind of preparation method of Ca-Ti ore type purification of air photochemical catalyst is provided, Ca-Ti ore type material is introduced anatase titania nano material, what make photochemical catalyst can expand to visible region with spectrum from ultraviolet region, makes it can produce optical excitation in visible-range, produces electron-hole pair, improve the utilization rate of sunlight, can be widely used in the industrial production of air purifier photochemical catalyst.
In order to solve above technical problem, the invention provides a kind of preparation method of Ca-Ti ore type purification of air photochemical catalyst, comprising the steps:
titanium hydroxide in molar ratio in titanium hydroxide emulsion: sulfuric acid is that 1:0.005-0.100 adds dilution heat of sulfuric acid, shakes 10-60 minute after stirring in ultrasonic wave, obtained acidifying emulsion; Dilution heat of sulfuric acid is distilled water by volume: sulfuric acid is 2-10:1 preparation; Titanium hydroxide emulsion is prepared as follows: ammoniacal liquor is added Ti (SO
4)
2in solution, generate the flocculent deposit of white-amorphous and carry out filtering, wash rear making beating and obtain;
under stirring, Ca-Ti ore type material is added in obtained acidifying titanium hydroxide emulsion, the quality of titanium hydroxide and the mass ratio of Ca-Ti ore type material are 1:0.01-0.30, shake 10-60 minute in ultrasonic wave after, carry out centrifuge washing, supernatant is outwelled after centrifuge washing, and by sediment at 150-350 DEG C of sintering soak 2-10 hour, obtained Ca-Ti ore type purification of air photochemical catalyst;
The molecular formula of Ca-Ti ore type material is AB
1-xc
xo
3, wherein the value of dopant ratio x is 0 to 1, and its preparation method comprises the following steps:
When the value of x is 0, with the nitrate of metal element A, B for raw material presoma is dissolved in the water, wherein the mol ratio of the nitrate of metal element A, B is M
a=M
b, obtain mixing salt solution, first dry 6-10 hour at 100-150 DEG C, at 550-750 DEG C, after high-temperature calcination 1-4 hour, obtain Ca-Ti ore type substance A BO subsequently
3;
When the value of x is not 0, with the nitrate of metal element A, B, C for raw material presoma is dissolved in the water, wherein the mol ratio of the nitrate of metal element A, B, C is M
a=M
b+ M
c, obtain mixing salt solution, first dry 6-10 hour at 100-150 DEG C, at 550-750 DEG C, after high-temperature calcination 1-4 hour, obtain Ca-Ti ore type substance A B subsequently
1-xc
xo
3.
As the preferred method of the present invention:
Further, the preparation method of aforesaid Ca-Ti ore type purification of air photochemical catalyst:
Elements A is the one in alkaline earth element, rare earth element or transition elements;
Element B is the one in transition elements;
Elements C is the one in transition elements.
The preparation method of aforesaid Ca-Ti ore type purification of air photochemical catalyst:
Elements A is the one in Sr, La, Nd, Gd, Ca, Cd, Pb;
Element B is the one in Zr, Ti, V, Cr, Mn, Fe, Co;
Elements C is the one in Y, Ga, Cu.
The invention has the beneficial effects as follows: the preparation method of the Ca-Ti ore type purification of air photochemical catalyst designed by the present invention, the photochemical catalyst prepared is compared with traditional photocatalyst catalyst, Ca-Ti ore type material is introduced anatase titania nano material by the present invention, what make photochemical catalyst can expand to visible region with spectrum from ultraviolet region, make it can produce optical excitation in visible-range, produce electron-hole pair, improve the utilization rate of sunlight, obtain beyond thought technique effect, PARA FORMALDEHYDE PRILLS(91,95), acetaldehyde, volatile organic solvent, the organic pollutions such as polycyclic aromatic hydrocarbon have good removal effect, embody increasing superiority, can be used in the industrial production of air purifier photochemical catalyst.
Detailed description of the invention
embodiment 1
Present embodiments provide a kind of preparation method of Ca-Ti ore type purification of air photochemical catalyst, with the nitrate of lanthanum, iron for raw material presoma is dissolved in the water, get the iron nitrate solution Homogeneous phase mixing that lanthanum nitrate hexahydrate that 100mL concentration is 0.1mol/L and 100mL concentration are 0.1mol/L, drying 8 hours at 100 DEG C, carry out calcining in 3 hours subsequently at 700 DEG C after, obtain Ca-Ti ore type material LaFeO
3;
Titanium hydroxide in molar ratio in titanium hydroxide emulsion: sulfuric acid is that 1:0.005 adds dilution heat of sulfuric acid, shakes 60 minutes after stirring in ultrasonic wave, obtained acidifying emulsion; Dilution heat of sulfuric acid is distilled water by volume: sulfuric acid is 2:1 preparation; Titanium hydroxide emulsion is prepared as follows: ammoniacal liquor is added Ti (SO
4)
2in solution, generate the flocculent deposit of white-amorphous and carry out filtering, wash rear making beating and obtain;
Under stirring, be that 1:0.03 adds Ca-Ti ore type material by the mass ratio of titanium hydroxide quality and Ca-Ti ore type material in obtained acidifying titanium hydroxide emulsion, shake in ultrasonic wave after 60 minutes, carry out centrifuge washing, supernatant is outwelled after centrifuge washing, and by sediment sintering soak 3 hours at 350 DEG C, obtained LaFeO
3/ TiO
2composite photo-catalyst.
embodiment 2
Present embodiments provide a kind of preparation method of Ca-Ti ore type purification of air photochemical catalyst, with the nitrate of lanthanum, iron, copper for raw material presoma is dissolved in the water, get lanthanum nitrate hexahydrate that 100mL concentration is 0.1mol/L, copper nitrate solution Homogeneous phase mixing that iron nitrate solution that 95mL concentration is 0.1mol/L and 5mL concentration are 0.1mol/L, 110 DEG C of dryings 7 hours, carry out calcining in 4 hours subsequently at 600 DEG C after, obtain Ca-Ti ore type material LaFe
0.95cu
0.05o
3;
Titanium hydroxide in molar ratio in titanium hydroxide emulsion: sulfuric acid is that 1:0.01 adds dilution heat of sulfuric acid, shakes 40 minutes after stirring in ultrasonic wave, obtained acidifying emulsion; Dilution heat of sulfuric acid is distilled water by volume: sulfuric acid is 4:1 preparation; Titanium hydroxide emulsion is prepared as follows: ammoniacal liquor is added Ti (SO
4)
2in solution, generate the flocculent deposit of white-amorphous and carry out filtering, wash rear making beating and obtain;
Under stirring, be that 1:0.08 adds Ca-Ti ore type material by the mass ratio of titanium hydroxide and Ca-Ti ore type material in obtained acidifying titanium hydroxide emulsion, shake in ultrasonic wave after 60 minutes, carry out centrifuge washing, supernatant is outwelled after centrifuge washing, and by sediment sintering soak 7 hours at 250 DEG C, obtained LaFe
0.95cu
0.05o
3/ TiO
2composite photo-catalyst.
embodiment 3
Present embodiments provide a kind of preparation method of Ca-Ti ore type purification of air photochemical catalyst, with the nitrate of strontium, zirconium, yttrium for raw material presoma is dissolved in the water, get strontium nitrate solution that 100mL concentration is 0.1mol/L, yttrium nitrate solution Homogeneous phase mixing that zirconium nitrate solution that 95mL concentration is 0.1mol/L and 5mL concentration are 0.1mol/L, drying 7 hours at 120 DEG C, after carrying out calcining in 4 hours at 650 DEG C subsequently, obtain Ca-Ti ore type material SrZr
0.95y
0.05o
3;
Titanium hydroxide in molar ratio in titanium hydroxide emulsion: sulfuric acid is that 1:0.05 adds dilution heat of sulfuric acid, shakes 20 minutes after stirring in ultrasonic wave, obtained acidifying emulsion; Dilution heat of sulfuric acid is distilled water by volume: sulfuric acid is 6:1 preparation; Titanium hydroxide emulsion is prepared as follows: ammoniacal liquor is added Ti (SO
4)
2in solution, generate the flocculent deposit of white-amorphous and carry out filtering, wash rear making beating and obtain;
Under stirring, be that 1:0.2 adds Ca-Ti ore type material by the mass ratio of titanium hydroxide and Ca-Ti ore type material in obtained acidifying titanium hydroxide emulsion, shake in ultrasonic wave after 50 minutes, carry out centrifuge washing, supernatant is outwelled after centrifuge washing, and by sediment sintering soak 6 hours at 300 DEG C, obtained SrZr
0.95y
0.05o
3/ TiO
2composite photo-catalyst.
embodiment 4
Present embodiments provide a kind of preparation method of Ca-Ti ore type purification of air photochemical catalyst, with the nitrate of calcium, zirconium, gallium for raw material presoma is dissolved in the water, get calcium nitrate solution that 100mL concentration is 0.1mol/L, gallium nitrate solution Homogeneous phase mixing that zirconium nitrate solution that 90mL concentration is 0.1mol/L and 10mL concentration are 0.1mol/L, 130 DEG C of dryings 6 hours, after carrying out calcining in 2 hours at 750 DEG C subsequently, obtain Ca-Ti ore type substance C aZr
0.90ga
0.10o
3;
Titanium hydroxide in molar ratio in titanium hydroxide emulsion: sulfuric acid is that 1:0.05 adds dilution heat of sulfuric acid, shakes 20 minutes after stirring in ultrasonic wave, obtained acidifying emulsion; Dilution heat of sulfuric acid is distilled water by volume: sulfuric acid is 8:1 preparation; Titanium hydroxide emulsion is prepared as follows: ammoniacal liquor is added Ti (SO
4)
2in solution, generate the flocculent deposit of white-amorphous and carry out filtering, wash rear making beating and obtain;
Under stirring, be that 1:0.1 adds Ca-Ti ore type material by the mass ratio of titanium hydroxide and Ca-Ti ore type material in obtained acidifying titanium hydroxide emulsion, shake in ultrasonic wave after 60 minutes, carry out centrifuge washing, supernatant is outwelled after centrifuge washing, and by sediment sintering soak 8 hours at 200 DEG C, obtained CaZr
0.90ga
0.10o
3/ TiO
2composite photo-catalyst.
comparative example 1
Titanium hydroxide in molar ratio in titanium hydroxide emulsion: sulfuric acid is that 1:0.005 adds dilution heat of sulfuric acid, shakes 60 minutes after stirring in ultrasonic wave, obtained acidifying emulsion; Dilution heat of sulfuric acid is distilled water by volume: sulfuric acid is 2:1 preparation; Titanium hydroxide emulsion is prepared as follows: ammoniacal liquor is added Ti (SO
4)
2in solution, generate the flocculent deposit of white-amorphous and carry out filtering, wash rear making beating and obtain.
After obtained acidifying titanium hydroxide emulsion shake 60 minutes in ultrasonic wave, carry out centrifuge washing, after centrifuge washing, outwell supernatant, and by sediment 350 DEG C of sintering soak 3 hours, obtain TiO
2photochemical catalyst.
the clean-up effect of table 1 Ca-Ti ore type purification of air photochemical catalyst
In embodiment 1-3, the purification of air performance of gained photochemical catalyst detects according to GBT 23761-2009, adopt the purification of air performance of ultraviolet source and visible light source test gained photochemical catalyst respectively, FID detection reaction device is utilized to export acetaldehyde concentration, the acetaldehyde degradation experimental result of the purification of air photochemical catalyst of the Ca-Ti ore type purification of air photochemical catalyst that table 1 obtains for embodiment 1-3 and comparative example 1 preparation;
Can obviously be found out by table 1, compared with traditional photocatalyst catalyst, Ca-Ti ore type material is introduced anatase titania nano material by the present invention, develop novel photochemical catalyst, the utilized spectrum of photochemical catalyst is expanded to visible region from ultraviolet region, improve the utilization rate of sunlight, embodied increasing superiority, can be used in the industrial production of air purifier photochemical catalyst.
Above embodiment is only and technological thought of the present invention is described, can not limit protection scope of the present invention with this, and every technological thought proposed according to the present invention, any change that technical scheme basis is done, all falls within scope.
Claims (3)
1. a preparation method for Ca-Ti ore type purification of air photochemical catalyst, is characterized in that, comprises the steps:
titanium hydroxide in molar ratio in titanium hydroxide emulsion: sulfuric acid is that 1:0.005-0.100 adds dilution heat of sulfuric acid, shakes 10-60 minute after stirring in ultrasonic wave, obtained acidifying emulsion; Described dilution heat of sulfuric acid distilled water by volume: sulfuric acid is 2-10:1 preparation; Described titanium hydroxide emulsion is prepared as follows: ammoniacal liquor is added Ti (SO
4)
2in solution, generate the flocculent deposit of white-amorphous and carry out filtering, wash rear making beating and obtain;
under stirring, Ca-Ti ore type material is added in obtained acidifying titanium hydroxide emulsion, the quality of titanium hydroxide and the mass ratio of Ca-Ti ore type material are 1:0.01-0.30, shake 10-60 minute in ultrasonic wave after, carry out centrifuge washing, supernatant is outwelled after centrifuge washing, and by sediment at 150-350 DEG C of sintering soak 2-10 hour, obtained Ca-Ti ore type purification of air photochemical catalyst;
The molecular formula of described Ca-Ti ore type material is AB
1-xc
xo
3, wherein the value of dopant ratio x is 0 to 1, and its preparation method comprises the following steps:
When the value of x is 0, with the nitrate of metal element A, B for raw material presoma is dissolved in the water, wherein the mol ratio of the nitrate of metal element A, B is M
a=M
b, obtain mixing salt solution, first dry 6-10 hour at 100-150 DEG C, at 550-750 DEG C, after high-temperature calcination 1-4 hour, obtain Ca-Ti ore type substance A BO subsequently
3;
When the value of x is not 0, with the nitrate of metal element A, B, C for raw material presoma is dissolved in the water, wherein the mol ratio of the nitrate of metal element A, B, C is M
a=M
b+ M
c, obtain mixing salt solution, first dry 6-10 hour at 100-150 DEG C, at 550-750 DEG C, after high-temperature calcination 1-4 hour, obtain Ca-Ti ore type substance A B subsequently
1-xc
xo
3.
2. the preparation method of Ca-Ti ore type purification of air photochemical catalyst according to claim 1, is characterized in that:
Described elements A is the one in alkaline earth element, rare earth element or transition elements;
Described element B is the one in transition elements;
Described Elements C is the one in transition elements.
3. the preparation method of Ca-Ti ore type purification of air photochemical catalyst according to claim 1 and 2, is characterized in that:
Described elements A is the one in Sr, La, Nd, Gd, Ca, Cd, Pb;
Described element B is the one in Zr, Ti, V, Cr, Mn, Fe, Co;
Described Elements C is the one in Y, Ga, Cu.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109046365A (en) * | 2018-07-11 | 2018-12-21 | 江苏师范大学 | A kind of perovskite-like structure vanadium titanate catalysis material and its preparation and application |
| CN114345124A (en) * | 2022-01-14 | 2022-04-15 | 黎新安 | Air purifying agent capable of rapidly degrading formaldehyde and preparation method thereof |
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Cited By (3)
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|---|---|---|---|---|
| CN109046365A (en) * | 2018-07-11 | 2018-12-21 | 江苏师范大学 | A kind of perovskite-like structure vanadium titanate catalysis material and its preparation and application |
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| CN114345124B (en) * | 2022-01-14 | 2023-11-03 | 广东九田环保科技有限公司 | Air purifying agent capable of rapidly degrading formaldehyde and preparation method thereof |
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Application publication date: 20150715 |