CN116351417B - Preparation method of composite nano catalytic material for removing nitrogen oxides in atmospheric environment - Google Patents
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- 239000002131 composite material Substances 0.000 title claims abstract description 80
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 138
- 239000010949 copper Substances 0.000 claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 23
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 20
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000012018 catalyst precursor Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 36
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 31
- 150000001879 copper Chemical class 0.000 claims description 25
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012716 precipitator Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 5
- 238000004090 dissolution Methods 0.000 claims 1
- 238000010907 mechanical stirring Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 7
- XCBKGJWOCHSAMS-UHFFFAOYSA-L copper;dichlorocopper Chemical compound [Cu].Cl[Cu]Cl XCBKGJWOCHSAMS-UHFFFAOYSA-L 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- APTUIUORLSQNEF-UHFFFAOYSA-N dicopper tetranitrate Chemical compound [Cu++].[Cu++].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O APTUIUORLSQNEF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- VEMHQNXVHVAHDN-UHFFFAOYSA-J [Cu+2].[Cu+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Cu+2].[Cu+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VEMHQNXVHVAHDN-UHFFFAOYSA-J 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Health & Medical Sciences (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a preparation method of a composite nano catalytic material for removing nitrogen oxides in the atmosphere, belonging to the technical field of catalytic material preparation and environmental protection for pollution gas prevention. The invention takes titanyl sulfate as a titanium source, realizes uniform mixing with copper ions by the characteristic of being soluble in water, realizes the preparation of a copper composite titanium oxide precursor by adjusting Ph, and prepares the nano copper-copper ion doped titanium dioxide composite nano catalytic material by controlling the amount of hydrogen peroxide, the introduction of secondary copper ions and the control of a reducing agent. The composite catalyst prepared by the invention is a nano copper@copper ion doped titanium dioxide composite structure, has a large specific surface area (132.5 m 2/g) and rich high-activity catalytic sites, and has more efficient catalytic conversion activity (84%) of NOx than pure titanium dioxide at the outdoor normal temperature, thereby realizing the function of removing nitrogen oxides in the atmospheric environment.
Description
Technical Field
The invention belongs to the field of catalytic material preparation and environmental protection for pollution gas prevention and control, and in particular relates to a preparation method of a composite nano catalytic material for removing nitrogen oxides in the atmosphere.
Background
With the deep advancement of industrialization and town, the massive consumption of fossil energy increases the emission of harmful gases such as nitrogen oxides and the like, and serious environmental problems are generated. The excessive emission of nitrogen oxides not only directly produces strong stimulation and harm to skin and respiratory systems, but also participates in the formation of acid rain, photochemical smog, ozone and haze, and indirectly causes harm to the environment. At the same time, nitrogen oxides are also one of the important precursors for the formation of secondary aerosols. Therefore, how to reduce the nitrogen oxide content in the atmosphere becomes a key issue for environmental pollution control. At present, the problem is mainly alleviated by controlling the emission amount of nitrogen oxides from the source, such as reducing the nitrogen oxides emitted in the industrial production process by using control technologies such as selective catalytic reduction, high-temperature/catalytic combustion or low-temperature condensation. While enhancing source emissions reduction, there is an urgent need to actively develop suitable new technology to treat NOx that has been emitted to the atmosphere.
Disclosure of Invention
The invention aims to provide a preparation method of a composite nano catalytic material for removing nitrogen oxides in the atmosphere.
In order to achieve the above purpose, the invention adopts the following technical scheme:
Step 1: mixing titanyl sulfate and soluble copper salt according to 100: adding the mixture into water in a molar ratio of 1-20 in turn to dissolve the mixture to obtain a mixed solution with the concentration of the titanyl sulfate of 10-150 g/L;
Step 2: adding an alkaline solution precipitator into the mixed solution, regulating the Ph value to 8-9, centrifuging the precipitate, and washing with water to obtain a Cu@Cu 2+/TiO2 composite catalyst precursor;
Step 3: taking a Cu@Cu 2+/TiO2 composite catalyst precursor and hydrogen peroxide, wherein the molar ratio of Ti atoms to hydrogen peroxide in the Cu@Cu 2+/TiO2 composite catalyst precursor is 1:1-2, and then mixing the mixture according to the molar ratio of Ti atoms to soluble copper salt in the Cu@Cu 2+/TiO2 composite catalyst precursor of 1-10:1, adding an aqueous solution of soluble copper salt into the catalyst, mixing and dispersing to obtain a mixed solution with the concentration of a Cu@Cu 2+/TiO2 composite catalyst precursor of 10-100g/L, and then transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction;
Step 4: after the reaction is finished, removing a product from the hydrothermal reaction kettle, centrifuging a precipitate, and washing with water, wherein the molar ratio of copper atoms to a reducing agent is 1:1-2 adding a reducing agent into the mixture, heating the mixture to 100 ℃, and then preserving the heat for 2-4 hours to obtain the nano copper-copper ion doped titanium dioxide composite nano catalytic material.
The soluble copper salt is one or a mixture of any proportion of copper chloride, copper sulfate and copper nitrate.
The step 1 is to add the titanyl sulfate and the soluble copper salt into water with the temperature of 35 ℃ to 40 ℃ in sequence, and mechanically stir and dissolve the titanyl sulfate and the soluble copper salt.
The alkaline solution precipitant in the step 2 is ammonia water or sodium hydroxide.
The hydrothermal reaction temperature in the step 3 is 120 ℃, and the hydrothermal reaction time is 3-6 hours.
The reducing agent in the step 4 is sodium borohydride.
The invention takes titanyl sulfate as a titanium source, realizes uniform mixing with copper ions by the characteristic of being soluble in water, realizes the preparation of a copper composite titanium oxide precursor by adjusting Ph, and prepares the nano copper-copper ion doped titanium dioxide composite nano catalytic material by controlling the amount of hydrogen peroxide, the introduction of secondary copper ions and the control of a reducing agent. The composite catalyst prepared by the invention is a nano copper@copper ion doped titanium dioxide composite structure, has a large specific surface area (132.5 m 2/g) and rich high-activity catalytic sites, and has more efficient catalytic conversion activity (84%) of NOx than pure titanium dioxide at the outdoor normal temperature, thereby realizing the function of removing nitrogen oxides in the atmospheric environment.
Drawings
FIG. 1 is a transmission electron microscope of the nano copper-copper ion doped titanium dioxide composite nano catalytic material prepared by the invention.
Fig. 2 is an adsorption-desorption isotherm and a pore size distribution line of the nano copper-copper ion doped titanium dioxide composite nano catalytic material N 2 prepared by the invention.
FIG. 3 is a graph showing the comparison of NO purification curves of the nano copper-copper ion doped titanium dioxide composite nano catalytic material prepared by the invention under visible light.
Detailed Description
The present invention will be further described in detail with reference to examples.
Example 1
Step 1: mixing titanyl sulfate and soluble copper salt copper chloride according to a ratio of 100:5, sequentially adding the mixture into water at 35 ℃ in a molar ratio, and mechanically stirring and dissolving to obtain a mixed solution with the concentration of the titanyl sulfate of 13 g/L;
step 2: adding ammonia water as a precipitator into the mixed solution, adjusting Ph value to 8, centrifuging the precipitate, and washing with water to obtain a Cu@Cu 2+/TiO2 composite catalyst precursor;
Step 3: taking a Cu@Cu 2+/TiO2 composite catalyst precursor and hydrogen peroxide, wherein the molar ratio of Ti atoms to hydrogen peroxide in the Cu@Cu 2+/TiO2 composite catalyst precursor is 1:1, and then mixing the mixture according to the molar ratio of Ti atoms to soluble copper salt in the Cu@Cu 2+/TiO2 composite catalyst precursor of 3:1 adding a water solution of soluble copper salt into the catalyst, mixing and dispersing to obtain a mixed solution with the concentration of a Cu@Cu 2+/TiO2 composite catalyst precursor of 50g/L, and then transferring the mixed solution into a hydrothermal reaction kettle to carry out hydrothermal reaction for 3 hours at 120 ℃;
Step 4: after the reaction is finished, removing a product from the hydrothermal reaction kettle, centrifuging a precipitate, and washing with water, wherein the molar ratio of copper atoms to a reducing agent is 1:1 adding reducing agent sodium borohydride into the mixture, heating the mixture to 100 ℃, and then preserving the heat for 2 hours to obtain the nano copper-copper ion doped titanium dioxide composite nano catalytic material.
Example 2
Step 1: mixing titanyl sulfate and soluble copper salt copper sulfate according to the weight ratio of 100: adding the mixture into water at 38 ℃ in turn according to the molar ratio of 10, and mechanically stirring and dissolving to obtain a mixed solution with the concentration of the titanyl sulfate of 10 g/L;
Step 2: adding sodium hydroxide into the mixed solution as a precipitator, adjusting Ph value to 8, centrifuging the precipitate, and washing with water to obtain a Cu@Cu 2+/TiO2 composite catalyst precursor;
step 3: taking a Cu@Cu 2+/TiO2 composite catalyst precursor and hydrogen peroxide, wherein the molar ratio of Ti atoms to hydrogen peroxide in the Cu@Cu 2+/TiO2 composite catalyst precursor is 1:1.8, and then mixing the mixture according to the molar ratio of Ti atoms to soluble copper salt in the Cu@Cu 2+/TiO2 composite catalyst precursor of 8:1, adding an aqueous solution of soluble copper salt into the catalyst, mixing and dispersing to obtain a mixed solution with the concentration of Cu@Cu 2+/TiO2 composite catalyst precursor of 80g/L, and then transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction at 120 ℃ for 5 hours;
step 4: after the reaction is finished, removing a product from the hydrothermal reaction kettle, centrifuging a precipitate, and washing with water, wherein the molar ratio of copper atoms to a reducing agent is 1:2 adding reducing agent sodium borohydride into the mixture, heating the mixture to 100 ℃, and preserving the heat for 3 hours to obtain the nano copper-copper ion doped titanium dioxide composite nano catalytic material.
Example 3
Step 1: mixing titanyl sulfate and soluble copper salt copper nitrate according to the weight ratio of 100: sequentially adding the mixture into water at 40 ℃ according to the molar ratio of 15, and mechanically stirring and dissolving to obtain a mixed solution with the concentration of titanyl sulfate of 15 g/L;
step 2: adding ammonia water as a precipitator into the mixed solution, adjusting Ph value to 8, centrifuging the precipitate, and washing with water to obtain a Cu@Cu 2+/TiO2 composite catalyst precursor;
Step 3: taking a Cu@Cu 2+/TiO2 composite catalyst precursor and hydrogen peroxide, wherein the molar ratio of Ti atoms to hydrogen peroxide in the Cu@Cu 2+/TiO2 composite catalyst precursor is 1:1.5, and then mixing the mixture according to the molar ratio of Ti atoms to soluble copper salt in the Cu@Cu 2+/TiO2 composite catalyst precursor of 1:1 adding water solution of soluble copper salt into the catalyst, mixing and dispersing to obtain mixed solution with Cu@Cu 2+/TiO2 composite catalyst precursor concentration of 30g/L, and then transferring the mixed solution into a hydrothermal reaction kettle to carry out hydrothermal reaction for 4 hours at 120 ℃;
Step 4: after the reaction is finished, removing a product from the hydrothermal reaction kettle, centrifuging a precipitate, and washing with water, wherein the molar ratio of copper atoms to a reducing agent is 1:1.5 adding reducing agent sodium borohydride into the mixture, heating the mixture to 100 ℃ and then preserving the heat for 4 hours to obtain the nano copper-copper ion doped titanium dioxide composite nano catalytic material.
Example 4
Step 1: mixing titanyl sulfate and soluble copper salt copper chloride according to a ratio of 100:8, sequentially adding the mixture into water at 36 ℃ in a molar ratio, and mechanically stirring and dissolving to obtain a mixed solution with the concentration of the titanyl sulfate of 12 g/L;
Step 2: adding sodium hydroxide into the mixed solution as a precipitator, adjusting Ph value to 8.5, centrifuging the precipitate, and washing with water to obtain a Cu@Cu 2+/TiO2 composite catalyst precursor;
Step 3: taking a Cu@Cu 2+/TiO2 composite catalyst precursor and hydrogen peroxide, wherein the molar ratio of Ti atoms to hydrogen peroxide in the Cu@Cu 2+/TiO2 composite catalyst precursor is 1:2, and then mixing the mixture according to the molar ratio of Ti atoms to soluble copper salt in the Cu@Cu 2+/TiO2 composite catalyst precursor of 5:1, adding an aqueous solution of soluble copper salt into the catalyst, mixing and dispersing to obtain a mixed solution with the concentration of a Cu@Cu 2+/TiO2 composite catalyst precursor of 100g/L, and then transferring the mixed solution into a hydrothermal reaction kettle to carry out hydrothermal reaction for 6 hours at 120 ℃;
step 4: after the reaction is finished, removing a product from the hydrothermal reaction kettle, centrifuging a precipitate, and washing with water, wherein the molar ratio of copper atoms to a reducing agent is 1:1.2 adding reducing agent sodium borohydride into the mixture, heating the mixture to 100 ℃ and then preserving the heat for 4 hours to obtain the nano copper-copper ion doped titanium dioxide composite nano catalytic material.
Example 5
Step 1: mixing titanyl sulfate, soluble copper salt copper chloride and copper sulfate according to a ratio of 100: sequentially adding the molar ratio of 18 into water at 39 ℃ and mechanically stirring and dissolving to obtain a mixed solution with the concentration of titanyl sulfate of 14 g/L;
Step 2: adding ammonia water as a precipitator into the mixed solution, adjusting Ph value to 9, centrifuging the precipitate, and washing with water to obtain a Cu@Cu 2+/TiO2 composite catalyst precursor;
Step 3: taking a Cu@Cu 2+/TiO2 composite catalyst precursor and hydrogen peroxide, wherein the molar ratio of Ti atoms to hydrogen peroxide in the Cu@Cu 2+/TiO2 composite catalyst precursor is 1:1.6, and then mixing the mixture according to the molar ratio of Ti atoms to soluble copper salt in the Cu@Cu 2+/TiO2 composite catalyst precursor of 10:1 adding water solution of soluble copper salt into the catalyst, mixing and dispersing to obtain mixed solution with the concentration of Cu@Cu 2+/TiO2 composite catalyst precursor of 10g/L, and then transferring the mixed solution into a hydrothermal reaction kettle to carry out hydrothermal reaction for 4 hours at 120 ℃;
Step 4: after the reaction is finished, removing a product from the hydrothermal reaction kettle, centrifuging a precipitate, and washing with water, wherein the molar ratio of copper atoms to a reducing agent is 1:1.8 adding reducing agent sodium borohydride into the mixture, heating the mixture to 100 ℃, and preserving the heat for 2 hours to obtain the nano copper-copper ion doped titanium dioxide composite nano catalytic material.
Example 6
Step 1: mixing titanyl sulfate, soluble copper salt copper chloride, copper sulfate and copper nitrate according to a ratio of 100:13 are added into water with the temperature of 37 ℃ in sequence, and are mechanically stirred and dissolved to obtain a mixed solution with the concentration of the titanyl sulfate of 11 g/L;
Step 2: adding sodium hydroxide into the mixed solution as a precipitator, adjusting Ph value to 9, centrifuging the precipitate, and washing with water to obtain a Cu@Cu 2+/TiO2 composite catalyst precursor;
Step 3: taking a Cu@Cu 2+/TiO2 composite catalyst precursor and hydrogen peroxide, wherein the molar ratio of Ti atoms to hydrogen peroxide in the Cu@Cu 2+/TiO2 composite catalyst precursor is 1:1.3, and then mixing the mixture according to the molar ratio of Ti atoms to soluble copper salt in the Cu@Cu 2+/TiO2 composite catalyst precursor of 2:1, adding an aqueous solution of soluble copper salt into the catalyst, mixing and dispersing to obtain a mixed solution with the concentration of Cu@Cu 2+/TiO2 composite catalyst precursor of 60g/L, and then transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction at 120 ℃ for 6 hours;
Step 4: after the reaction is finished, removing a product from the hydrothermal reaction kettle, centrifuging a precipitate, and washing with water, wherein the molar ratio of copper atoms to a reducing agent is 1:1.5 adding reducing agent sodium borohydride into the mixture, heating the mixture to 100 ℃, and preserving the heat for 3 hours to obtain the nano copper-copper ion doped titanium dioxide composite nano catalytic material.
Example 7
Step 1: mixing titanyl sulfate and soluble copper salt copper nitrate according to the weight ratio of 100: sequentially adding the molar ratio of 20 into water at 40 ℃ and mechanically stirring and dissolving to obtain a mixed solution with the concentration of titanyl sulfate of 15 g/L;
step 2: adding ammonia water as a precipitator into the mixed solution, adjusting Ph value to 8, centrifuging the precipitate, and washing with water to obtain a Cu@Cu 2+/TiO2 composite catalyst precursor;
Step 3: taking a Cu@Cu 2+/TiO2 composite catalyst precursor and hydrogen peroxide, wherein the molar ratio of Ti atoms to hydrogen peroxide in the Cu@Cu 2+/TiO2 composite catalyst precursor is 1:1.2, and then mixing the mixture according to the molar ratio of Ti atoms to soluble copper salt in the Cu@Cu 2+/TiO2 composite catalyst precursor of 6:1, adding an aqueous solution of soluble copper salt into the catalyst, mixing and dispersing to obtain a mixed solution with the concentration of a Cu@Cu 2+/TiO2 composite catalyst precursor of 70g/L, and then transferring the mixed solution into a hydrothermal reaction kettle to carry out hydrothermal reaction for 5 hours at 120 ℃;
step 4: after the reaction is finished, removing a product from the hydrothermal reaction kettle, centrifuging a precipitate, and washing with water, wherein the molar ratio of copper atoms to a reducing agent is 1:2 adding reducing agent sodium borohydride into the mixture, heating the mixture to 100 ℃, and preserving the heat for 4 hours to obtain the nano copper-copper ion doped titanium dioxide composite nano catalytic material.
It can be seen from fig. 1 that the cu@cu 2+/TiO2 composite catalyst is a core-shell self-assembled structure as a whole, and the titanium dioxide shell layer is embedded with small nano particles. The composite catalyst has the whole size of sphere with the diameter of 150-200nm, the thickness of a shell layer is about 25nm, and the shell layer consists of titanium dioxide with the thickness of about 10nm and nano copper with the thickness of about 3-5 nm.
From FIG. 2, it can be seen that the Cu@Cu 2+/TiO2 composite catalyst has a good mesoporous structure and a large specific surface area, and the specific surface area is 132.5m 2/g.
From fig. 3, it can be seen that the cu@cu 2+/TiO2 composite catalyst has high NOx catalytic conversion activity of 84%, and the activity is relatively stable, and the activity is not significantly attenuated within 26 minutes.
Claims (6)
1. The preparation method of the composite nano catalytic material for removing nitrogen oxides in the atmosphere is characterized by comprising the following steps:
Step 1: mixing titanyl sulfate and soluble copper salt according to 100: adding the mixture into water in a molar ratio of 1-20 in turn to dissolve the mixture to obtain a mixed solution with the concentration of the titanyl sulfate of 10-150 g/L;
Step 2: adding an alkaline solution precipitator into the mixed solution, regulating the pH value to 8-9, centrifuging the precipitate, and washing with water to obtain a Cu@Cu 2+/TiO2 composite catalyst precursor;
Step 3: taking a Cu@Cu 2+/TiO2 composite catalyst precursor and hydrogen peroxide, wherein the molar ratio of Ti atoms to hydrogen peroxide in the Cu@Cu 2+/TiO2 composite catalyst precursor is 1:1-2, and then mixing the mixture according to the molar ratio of Ti atoms to soluble copper salt in the Cu@Cu 2+/TiO2 composite catalyst precursor of 1-10:1, adding an aqueous solution of soluble copper salt into the catalyst, mixing and dispersing to obtain a mixed solution with the concentration of Cu@Cu 2+/TiO2 composite catalyst precursor of 10-100g/L, and then transferring the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction;
Step 4: after the reaction is finished, removing a product from the hydrothermal reaction kettle, centrifuging a precipitate, and washing with water, wherein the molar ratio of copper atoms to a reducing agent is 1:1-2 adding a reducing agent into the mixture, heating the mixture to 100 ℃, and then preserving the heat for 2-4 hours to obtain the nano copper-copper ion doped titanium dioxide composite nano catalytic material.
2. The method for preparing the composite nano catalytic material for removing nitrogen oxides in the atmosphere according to claim 1, wherein the soluble copper salt is one or a mixture of any proportion of copper chloride, copper sulfate and copper nitrate.
3. The method for preparing the composite nano catalytic material for removing nitrogen oxides in the atmosphere according to claim 1, wherein the step 1 is to sequentially add titanyl sulfate and soluble copper salt into water at 35-40 ℃ for mechanical stirring and dissolution.
4. The method for preparing the composite nano catalytic material for removing nitrogen oxides in the atmosphere according to claim 1, wherein the alkaline solution precipitant in the step 2 is ammonia water or sodium hydroxide.
5. The method for preparing the composite nano catalytic material for removing nitrogen oxides in the atmosphere according to claim 1, wherein the hydrothermal reaction temperature in the step 3 is 120 ℃ and the hydrothermal reaction time is 3-6 hours.
6. The method for preparing a composite nano-catalytic material for removing nitrogen oxides in the atmosphere according to claim 1, wherein the reducing agent of step 4 is sodium borohydride.
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