CN113830824A - Method for preparing anatase {001} surface with high exposure rate through microwave synthesis, product and application - Google Patents
Method for preparing anatase {001} surface with high exposure rate through microwave synthesis, product and application Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 74
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000000137 annealing Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 229910010342 TiF4 Inorganic materials 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 12
- 230000006378 damage Effects 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 230000006872 improvement Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 6
- 235000012501 ammonium carbonate Nutrition 0.000 description 6
- 239000001099 ammonium carbonate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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Abstract
The invention discloses a method for preparing an anatase {001} surface with high exposure rate by microwave synthesis, which comprises the following steps: s1, mixing a titanium source and a crystal face treating agent, adding a solvent to form a mixed liquid, fully mixing the mixed liquid, and putting the mixed liquid into a microwave synthesizer for microwave synthesis; s2 the liquid obtained by microwave synthesis in step S1 is washed thoroughly and dried to obtain an anatase {001} surface carrier precursor, and the precursor is annealed to obtain an anatase {001} surface with a high exposure. The invention also discloses a corresponding product and application. According to the invention, ammonium salt containing carbonate radical is used as a crystal face treating agent instead of hydrofluoric acid, so that the damage to the environment is greatly reduced while the high exposure rate is ensured; by adopting the microwave synthesis method, the raw materials are mixed more uniformly, the reaction time is greatly shortened, the production period of the carrier is reduced, the obtained anatase {001} crystal face exposure rate is high, the impurities are less, the performance is excellent, the anatase {001} crystal face exposure rate can be further used as a good carrier of the SCR catalyst, and the application range is wider.
Description
Technical Field
The invention belongs to the technical field of SCR catalyst carrier preparation, and particularly relates to a method for preparing an anatase {001} surface SCR catalyst carrier with high exposure rate by using a non-hydrofluoric acid treating agent based on microwave synthesis, a product and application.
Background
Energy and environmental problems are basic conditions for survival and development all over the world, and with the continuous development of economic demand, the utilization and development of fossil fuels are rapidly increased, which brings about various serious pollution problems, wherein the emission of NOx is one of the main sources causing atmospheric pollution, acid rain and greenhouse effect. Currently, the mainstream technology for industrial NOx emission control is Selective Catalytic Reduction (SCR). The selective oxidation-reduction reaction is simply referred to as SCR reaction, that is, in a certain temperature range (usually 100-500 ℃), under the action of a catalyst, a reducing agent is NH3Or CO (NH)2)2Selectively removing NO as pollutant gas in flue gasxReduction to non-toxic N2And simultaneously generating water.
Wherein NH3The SCR (ammonia selective catalytic reduction) technology is the most effective post-combustion control technology for removing nitrogen oxides in the flue gas of a fixed source, and the preparation of a catalyst carrier is a key link of the SCR technology and determines the efficiency and the economy of an SCR system. Supports of general interest include TiO2、Al2O3AC, ZSM-5, etc., wherein anatase TiO2The carrier has a high specific surface area, so that the active ingredient can be highly dispersed on the surface, which contributes to the improvement of the catalytic activity of the catalyst. For anatase TiO2The nano crystal has different crystal faces showing different activities, and the average surface energy sequence is as follows: 001} (0.90J/m)2）>{100}（0.53 J/m2）>{101}（0.44 J/m2). Most available TiO are based on the principle of minimum surface energy2Nanocrystals consist primarily of the thermodynamically stable 101 crystal plane, rather than the more reactive 001 crystal plane. At present, the synthesis time of an anatase {001} crystal face carrier is long, the exposure rate is low, in the preparation method of the anatase {001} crystal face with high exposure rate, hydrofluoric acid is mostly adopted as a crystal face end capping agent, and the hydrofluoric acid is used as a substance with high toxicity and strong corrosivity, which violates the green chemical rule. Therefore, a new preparation method needs to be researched to solve the technical problems of long synthesis time, low exposure rate and great harm of crystal face treating agents to the environment of the anatase {001} crystal face carrier.
Disclosure of Invention
Aiming at one or more of the defects or the improvement requirements of the prior art, the invention provides a method for preparing an anatase {001} face with high exposure rate by microwave synthesis, a product and an application thereof, and solves the technical problems of long synthesis time of an anatase {001} crystal face carrier, low exposure rate and great harm of a crystal face treating agent to the environment by adopting a microwave synthesis method and an ammonium carbonate treating agent.
To achieve the above object, according to one aspect of the present invention, there is provided a method for preparing an anatase {001} face with high exposure rate by microwave synthesis, comprising the steps of:
s1, mixing a titanium source and a crystal face treating agent, adding a solvent to form a mixed liquid, fully mixing the mixed liquid, and putting the mixed liquid into a microwave synthesizer for microwave synthesis;
s2 washing the liquid obtained by microwave synthesis in S1, drying to obtain anatase {001} surface carrier precursor, and annealing the precursor to obtain the anatase {001} surface SCR catalyst carrier with high exposure rate.
As a further improvement of the invention, in step S1, the titanium source is TiF4Powder, wherein the crystal face treating agent is (NH)4)2CO3Powder, and the titanium source andthe mass ratio of the crystal face treating agent is (8-10): (3-5).
As a further improvement of the present invention, in step S1, the solvent is a mixture of absolute ethyl alcohol and deionized water; the mass-volume ratio of the titanium source, the crystal face treating agent and the absolute ethyl alcohol is (8-10): (3-5): (20-30); the mass volume ratio of the titanium source, the crystal face treating agent and the deionized water is (8-10): (3-5): (15-25).
As a further improvement of the invention, in step S1, the temperature range of the microwave synthesis is 150-250 ℃.
As a further improvement of the invention, in step S2, the annealing treatment is carried out in a muffle furnace at a temperature range of 400-600 ℃.
According to a second aspect of the present invention, there is provided a microwave synthetically produced high exposure anatase {001} surface produced by the process comprising the steps of:
s1, mixing a titanium source and a crystal face treating agent, adding a solvent to form a mixed liquid, fully mixing the mixed liquid, and putting the mixed liquid into a microwave synthesizer for microwave synthesis;
s2 washing the liquid obtained by microwave synthesis in S1, drying to obtain anatase {001} surface carrier precursor, and annealing the precursor to obtain the anatase {001} surface SCR catalyst carrier with high exposure rate.
As a further improvement of the invention, in step S1, the titanium source is TiF4Powder, wherein the crystal face treating agent is (NH)4)2CO3And powder, wherein the mass ratio of the titanium source to the crystal face treating agent is (8-10): (3-5).
As a further improvement of the present invention, in step S1, the solvent is a mixture of absolute ethyl alcohol and deionized water; the mass-volume ratio of the titanium source, the crystal face treating agent and the absolute ethyl alcohol is (8-10): (3-5): (20-30); the mass volume ratio of the titanium source, the crystal face treating agent and the deionized water is (8-10): (3-5): (15-25).
As a further improvement of the invention, in step S1, the temperature range of the microwave synthesis is 150 ℃ to 250 ℃; in step S2, the annealing treatment is performed in a muffle furnace at a temperature range of 400 ℃ to 600 ℃.
According to a third aspect of the invention, the application of the high-exposure anatase {001} surface prepared by microwave synthesis as an SCR catalyst carrier is provided.
TiF is adopted based on microwave synthesis method at present4The synthesis of high exposure anatase 001-plane supports with ammonium carbonate has not been investigated. Carbonate as a novel nontoxic crystal face end capping agent can well replace hydrofluoric acid, and the microwave synthesis method has the advantages of short reaction time, uniform reaction and the like.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) according to the method for preparing the anatase {001} surface with the high exposure rate through microwave synthesis, the simple and easily-obtained crystal face end capping agent ammonium carbonate is used for replacing the traditional hydrofluoric acid end capping agent, so that the anatase (001) crystal face exposure rate is ensured, and meanwhile, the green chemical concept is also met; the microwave synthesis method is adopted to replace a general hydrothermal synthesis method, the reaction is more uniform, the reaction time is shorter, only 1/48 of the hydrothermal synthesis method is consumed, and the production period of the anatase (001) crystal face carrier is greatly shortened. Solves the technical problems of long synthesis time, low exposure rate and great harm of crystal face treating agent to the environment of the anatase {001} crystal face carrier in the prior art.
(2) According to the method for preparing the anatase {001} surface with the high exposure rate through microwave synthesis, through annealing treatment at 400-600 ℃, on one hand, further exposure of an anatase (001) crystal surface is promoted, on the other hand, the phenomenon that the exposure rate of the crystal surface is reduced due to overhigh temperature is prevented, and the activity of the (001) crystal surface is reduced; the microwave synthesis temperature is controlled to be 150-250 ℃, so that the formation of a {001} crystal face is facilitated. If the temperature is too low, the effect of the crystal face end capping agent is incomplete, so that the {001} crystal face is incomplete; too high a temperature increases the reaction pressure, prevents crystal face formation, and is accompanied by decomposition of a small amount of the capping agent, which is unfavorable for {001} crystal face formation.
(3) The method for preparing the anatase {001} surface with the high exposure rate through microwave synthesis is based on the method for preparing the anatase {001} surface with the high exposure rate through microwave synthesis, is convenient to operate, short in production period, good in anatase {001} crystal face exposure effect, wide in application range and suitable for industrial production.
Drawings
FIG. 1 is a flow chart of a method for preparing anatase 001 surface with high exposure rate by microwave synthesis according to an embodiment of the present invention;
FIG. 2 is a TEM image of example 1 of the present invention;
FIG. 3 is a TEM image of example 2 of the present invention;
FIG. 4 is a TEM image of example 3 of the present invention;
FIG. 5 is a TEM image of example 4 of the present invention;
FIG. 6 is a TEM image of example 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
FIG. 1 is a flow chart of a method for preparing anatase 001 surface with high exposure rate by microwave synthesis according to an embodiment of the present invention; as shown in the figure, the method for preparing the anatase {001} surface with high exposure rate by microwave synthesis is carried out according to the following steps:
s1, mixing a titanium source and a crystal face treating agent, adding a solvent to form a mixed liquid, fully mixing the mixed liquid, and putting the mixed liquid into a microwave synthesizer for microwave synthesis;
s2 the liquid obtained by microwave synthesis in step S1 is washed thoroughly and dried to obtain an anatase {001} surface carrier precursor, and the precursor is annealed to obtain an anatase {001} surface with a high exposure.
In step S1, the titanium source is TiF4Powder, crystal face treating agent is (NH)4)2CO3Powder, and source and crystal planes of titaniumThe mass ratio of the treating agent is preferably (8-10): (3-5); the solvent is a mixture of absolute ethyl alcohol and deionized water, and the mass volume ratio of the titanium source, the crystal face treating agent and the absolute ethyl alcohol is (8-10): (3-5): (20-30); the mass volume ratio of the titanium source, the crystal face treating agent and the deionized water is (8-10): (3-5): (20-30); the titanium source, the crystal face treating agent and the solvent are preferably mixed by a magnetic stirrer. The invention controls TiF4And (NH)4)2CO3The mass ratio of (8-10): (3-5), the effect of the crystal face end capping agent is fully exerted, and the crystal face exposure rate of {001} is improved. If a crystal face capping agent (NH)4)2CO3If too much, the crystal face is locally accumulated after being formed, and the shape is irregular; if a crystal face capping agent (NH)4)2CO3If the amount is too small, the crystal plane is inverted toward the {101} crystal plane, and the {001} crystal plane exposure rate is lowered.
Furthermore, the temperature range of microwave synthesis is preferably 150-250 ℃, and the microwave synthesis temperature is controlled to be 150-250 ℃, so that the formation of a {001} crystal face is facilitated. If the synthesis temperature is lower than 150 ℃, the crystal face end capping agent has incomplete action, so that the {001} crystal face is incomplete; if the synthesis temperature is higher than 250 ℃, the reaction pressure is increased, the crystal face formation is hindered, and the {001} crystal face formation is not favored along with the decomposition of a small amount of the end capping agent.
In step S2, the annealing process is performed in a muffle furnace at a temperature range of 400 ℃ to 600 ℃. Compared with the traditional annealing temperature range of 300-650 ℃, the annealing treatment at 400-600 ℃ is adopted, and the temperature is lower than 400 ℃, so that the crystal face of {001} is incomplete, and the exposure rate is reduced; on the other hand, the damage of the original formed {001} crystal face can be accelerated by preventing the temperature from being higher than 600 ℃, the exposure rate is reduced, and the activity of the {001} crystal face is reduced.
In order to better understand the preparation method and the carrier preparation effect of the present embodiment, the following description will be further made with reference to specific examples.
The method for preparing the anatase {001} surface with high exposure rate by microwave synthesis comprises the following steps:
(1) weighing 2.4-3.0 parts ofTiF4And 0.9-1.5 parts of ammonium carbonate, and dissolving in 15-25 parts of deionized water and 20-30 parts of absolute ethyl alcohol to form a solution;
(2) stably stirring the solution prepared in the step (1) at 30 ℃ by using a magnetic stirrer, putting the solution into a microwave synthesizer, and performing microwave synthesis for 25 minutes at 150-250 ℃;
(3) and (3) fully washing and drying the reaction solution after microwave synthesis, and then annealing for 3-5 hours at 400-600 ℃ in a muffle furnace to obtain the required anatase (001) crystal face carrier with high exposure rate.
Example 1
The method for preparing the anatase {001} surface with high exposure rate by microwave synthesis in the embodiment comprises the following steps:
(1) 2.4g of TiF are weighed4And 0.9g of (NH)4)2CO3Dissolving the mixture in 15ml of deionized water and 20ml of absolute ethyl alcohol to form a solution;
(2) stably stirring the solution prepared in the step (1) at 30 ℃ by using a magnetic stirrer, putting the solution into a microwave synthesizer, and performing microwave synthesis for 25 minutes at 150 ℃;
(3) the reaction solution after microwave synthesis was sufficiently washed and dried, and then annealed at 400 ℃ for 3 hours in a muffle furnace.
And (3) carrying out transmission electron microscope analysis (TEM) on the prepared anatase carrier, and observing the morphology of an anatase (001) crystal face, wherein the specific operation before observation is as follows: firstly, grinding a carrier sample into powder, and then putting the powder into ethanol for ultrasonic treatment for 20 min to obtain a white suspension. And then, dropwise adding a small amount of suspension on the carbon film copper net and drying the carbon film copper net to complete sample preparation. The TEM results are shown in fig. 1, and it can be seen that the anatase (001) crystal plane in a plate shape has partially appeared, but the exposure rate may be less than 50% due to the lower reaction temperature and annealing temperature.
Example 2
The method for preparing the anatase {001} surface with high exposure rate by microwave synthesis in the embodiment comprises the following steps:
(1) 2.7g of TiF are weighed4And 1.2g of (NH)4)2CO3Dissolving the mixture in 20ml of deionized water and 25ml of absolute ethyl alcohol to form a solution;
(2) stably stirring the solution prepared in the step (1) at 30 ℃ by using a magnetic stirrer, putting the solution into a microwave synthesizer, and performing microwave synthesis for 25 minutes at 200 ℃;
(3) the reaction solution after microwave synthesis was sufficiently washed and dried, and then annealed at 500 ℃ for 4 hours in a muffle furnace.
The obtained anatase carrier is subjected to Transmission Electron Microscope (TEM) analysis, and TEM results are shown in FIG. 2, so that more flaky anatase (001) crystal faces can be obviously seen, the size is about 80-100 nm, the exposure rate is about 70%, and the synthesis effect is better under the conditions.
Example 3
The method for preparing the anatase {001} surface with high exposure rate by microwave synthesis in the embodiment comprises the following steps:
(1) 3.0g of TiF are weighed4And 1.5g of (NH)4)2CO3Dissolving the mixture in 25ml of deionized water and 30ml of absolute ethyl alcohol to form a solution;
(2) stably stirring the solution prepared in the step (1) at 30 ℃ by using a magnetic stirrer, putting the solution into a microwave synthesizer, and performing microwave synthesis for 25 minutes at 250 ℃;
(3) the reaction solution after microwave synthesis was sufficiently washed and dried, and then annealed at 600 ℃ for 5 hours in a muffle furnace.
When the anatase carrier is subjected to Transmission Electron Microscope (TEM), as shown in FIG. 3, the sheet structure is nearly half, the size is about 120-200nm, and it is not easy to see that part of the sheet structure is being transformed into other irregular shapes, so the reaction temperature and annealing temperature are higher, which is not favorable for the formation of (001) crystal plane.
Example 4
The method for preparing the anatase {001} surface with high exposure rate by microwave synthesis in the embodiment comprises the following steps:
(1) 3.0g of TiF are weighed4And 0.9g of (NH)4)2CO3Dissolved in 20ml of deionized water and 25ml of deionized waterForming a solution in water and ethanol;
(2) stably stirring the solution prepared in the step (1) at 30 ℃ by using a magnetic stirrer, putting the solution into a microwave synthesizer, and performing microwave synthesis for 25 minutes at 200 ℃;
(3) the reaction solution after microwave synthesis was sufficiently washed and dried, and then annealed at 500 ℃ for 4 hours in a muffle furnace.
When the obtained anatase carrier was subjected to Transmission Electron Microscopy (TEM) analysis and the TEM result is shown in FIG. 4, it was found that in the case of a small amount of ammonium carbonate, although a (001) sheet structure was present, the effect was not good and the exposure rate was lower than that of the other examples.
Example 5
The method for preparing the anatase {001} surface with high exposure rate by microwave synthesis in the embodiment comprises the following steps:
(1) 2.4g of TiF are weighed4And 1.5g of (NH)4)2CO3Dissolving the mixture in 20ml of deionized water and 25ml of absolute ethyl alcohol to form a solution;
(2) stably stirring the solution prepared in the step (1) at 30 ℃ by using a magnetic stirrer, putting the solution into a microwave synthesizer, and performing microwave synthesis for 25 minutes at 250 ℃;
(3) the reaction solution after microwave synthesis was sufficiently washed and dried, and then annealed at 500 ℃ for 4 hours in a muffle furnace.
The anatase carrier obtained was analyzed by Transmission Electron Microscopy (TEM), and as a result of TEM, as shown in FIG. 5, the crystal face of the plate-like (001) was more distinct, and the exposure was about 50%.
In view of the above 5 examples, it can be seen that the effect of example 2 is optimal, and that ammonium carbonate, a crystal face treatment agent, either in small amounts or in excess, is detrimental to the formation of the (001) crystal face.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for preparing anatase (001) face with high exposure rate by microwave synthesis is characterized by comprising the following steps:
s1, mixing a titanium source and a crystal face treating agent, adding a solvent to form a mixed liquid, fully mixing the mixed liquid, and putting the mixed liquid into a microwave synthesizer for microwave synthesis;
s2 the liquid obtained by microwave synthesis in step S1 is washed thoroughly and dried to obtain an anatase {001} surface carrier precursor, and the precursor is annealed to obtain an anatase {001} surface with a high exposure.
2. The method for preparing anatase {001} face with high exposure rate by microwave synthesis according to claim 1 wherein the titanium source is TiF in step S14Powder, wherein the crystal face treating agent is (NH)4)2CO3And powder, wherein the mass ratio of the titanium source to the crystal face treating agent is (8-10): (3-5).
3. The method for preparing anatase {001} face with high exposure rate by microwave synthesis according to claim 1 or 2 wherein the solvent is a mixture of absolute ethyl alcohol and deionized water in step S1; the mass-volume ratio of the titanium source, the crystal face treating agent and the absolute ethyl alcohol is (8-10): (3-5): (20-30); the mass volume ratio of the titanium source, the crystal face treating agent and the deionized water is (8-10): (3-5): (15-25).
4. The method for preparing anatase {001} face with high exposure rate by microwave synthesis according to claim 1 or 2, wherein the temperature range of microwave synthesis in step S1 is 150 ℃ to 250 ℃.
5. The method for preparing anatase {001} face with high exposure rate by microwave synthesis according to claim 1 or 2 wherein the annealing treatment is performed in a muffle furnace at a temperature range of 400 ℃ to 600 ℃ in step S2.
6. A high-exposure anatase {001} surface prepared by microwave synthesis is characterized by being prepared according to the following steps:
s1, mixing a titanium source and a crystal face treating agent, adding a solvent to form a mixed liquid, fully mixing the mixed liquid, and putting the mixed liquid into a microwave synthesizer for microwave synthesis;
s2 the liquid obtained by microwave synthesis in step S1 is washed thoroughly and dried to obtain an anatase {001} surface carrier precursor, and the precursor is annealed to obtain an anatase {001} surface with a high exposure.
7. The microwave synthetically produced anatase {001} surface with high exposure according to claim 6 wherein in step S1 the source of titanium is TiF4Powder, wherein the crystal face treating agent is (NH)4)2CO3And powder, wherein the mass ratio of the titanium source to the crystal face treating agent is (8-10): (3-5).
8. The microwave synthetically prepared anatase {001} surface with high exposure rate according to claim 6 or 7 wherein the solvent is a mixture of absolute ethyl alcohol and deionized water in step S1; the mass-volume ratio of the titanium source, the crystal face treating agent and the absolute ethyl alcohol is (8-10): (3-5): (20-30); the mass volume ratio of the titanium source, the crystal face treating agent and the deionized water is (8-10): (3-5): (15-25).
9. The microwave synthetically prepared anatase {001} surface with high exposure rate according to claim 6 or 7 wherein the microwave synthesis temperature is in the range of 150 ℃ to 250 ℃ in step S1; in step S2, the annealing treatment is performed in a muffle furnace at a temperature range of 400 ℃ to 600 ℃.
10. Use of a high-exposure anatase {001} plane produced by microwave synthesis according to any one of claims 6 to 9 as a support for SCR catalysts.
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