CN116351417A - Preparation method of composite nano catalytic material for removing nitrogen oxides in atmospheric environment - Google Patents
Preparation method of composite nano catalytic material for removing nitrogen oxides in atmospheric environment Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 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
- 239000010949 copper Substances 0.000 claims abstract description 52
- 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 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 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 18
- 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
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 44
- 239000012018 catalyst precursor Substances 0.000 claims description 41
- 239000011259 mixed solution Substances 0.000 claims description 34
- 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
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 9
- 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
- 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
- 239000003054 catalyst Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002243 precursor Substances 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
- 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
- 238000003825 pressing Methods 0.000 description 4
- 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
- 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
- 238000000696 nitrogen adsorption--desorption isotherm Methods 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
- 238000001338 self-assembly Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
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- 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
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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
- 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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- B01D2255/207—Transition metals
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- B01D2255/207—Transition metals
- B01D2255/20761—Copper
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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, and has a large specific surface area (132.5 m) 2 Per g) and abundant high-activity catalytic sites, and has higher activity than pure titanium dioxide at room temperatureThe catalyst has high NOx catalytic conversion activity (84%), 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 Cu@Cu 2+ /TiO 2 Compounding a catalyst precursor;
step 3: taking Cu@Cu 2+ /TiO 2 The compound catalyst precursor and hydrogen peroxide are mixed according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to hydrogen peroxide in the composite catalyst precursor is 1:1-2, then according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to soluble copper salt in the composite catalyst precursor is 1-10:1 into itAdding water solution of soluble copper salt, mixing and dispersing to obtain Cu@Cu 2+ /TiO 2 The concentration of the compound catalyst precursor is 10-100g/L of the mixed solution, and then the mixed solution is moved 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, and has a large specific surface area (132.5 m) 2 And/g) and abundant high-activity catalytic sites, has more efficient catalytic conversion activity (84%) of NOx than pure titanium dioxide at room temperature outdoors, 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 shows a nano copper-copper ion doped II prepared by the methodTitanium oxide composite nano catalytic material N 2 Adsorption-desorption isotherms and pore size distribution lines thereof.
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 Cu@Cu 2+ /TiO 2 Compounding a catalyst precursor;
step 3: taking Cu@Cu 2+ /TiO 2 The compound catalyst precursor and hydrogen peroxide are mixed according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to hydrogen peroxide in the composite catalyst precursor is 1:1, then according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to soluble copper salt in the composite catalyst precursor is 3:1 adding water solution of soluble copper salt into the mixture, mixing and dispersing the mixture to obtain Cu@Cu 2+ /TiO 2 The concentration of the precursor of the composite catalyst is 50g/L of the mixed solution, and then the mixed solution is moved 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 Cu@Cu 2+ /TiO 2 Compounding a catalyst precursor;
step 3: taking Cu@Cu 2+ /TiO 2 The compound catalyst precursor and hydrogen peroxide are mixed according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to hydrogen peroxide in the composite catalyst precursor is 1:1.8 mixing, then pressing Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to soluble copper salt in the composite catalyst precursor is 8:1 adding water solution of soluble copper salt into the mixture, mixing and dispersing the mixture to obtain Cu@Cu 2+ /TiO 2 The concentration of the compound catalyst precursor is 80g/L of mixed solution, and then the mixed solution is moved 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 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 Cu@Cu 2+ /TiO 2 Compounding a catalyst precursor;
step 3: taking Cu@Cu 2+ /TiO 2 The compound catalyst precursor and hydrogen peroxide are mixed according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to hydrogen peroxide in the composite catalyst precursor is 1:1.5 mixing, and then pressing Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to soluble copper salt in the composite catalyst precursor is 1:1 adding water solution of soluble copper salt into the mixture, mixing and dispersing the mixture to obtain Cu@Cu 2+ /TiO 2 The mixed solution with the concentration of the precursor of the composite catalyst being 30g/L is transferred intoCarrying out hydrothermal reaction for 4 hours at 120 ℃ in a hydrothermal reaction kettle;
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 Cu@Cu 2+ /TiO 2 Compounding a catalyst precursor;
step 3: taking Cu@Cu 2+ /TiO 2 The compound catalyst precursor and hydrogen peroxide are mixed according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to hydrogen peroxide in the composite catalyst precursor is 1:2, then mixing according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to soluble copper salt in the composite catalyst precursor is 5:1 adding water solution of soluble copper salt into the mixture, mixing and dispersing the mixture to obtain Cu@Cu 2+ /TiO 2 The concentration of the precursor of the composite catalyst is 100g/L of the mixed solution, and then the mixed solution is moved 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 Cu@Cu 2+ /TiO 2 Compounding a catalyst precursor;
step 3: taking Cu@Cu 2+ /TiO 2 The compound catalyst precursor and hydrogen peroxide are mixed according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to hydrogen peroxide in the composite catalyst precursor is 1:1.6 mixing, and then pressing Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to soluble copper salt in the composite catalyst precursor is 10:1 adding water solution of soluble copper salt into the mixture, mixing and dispersing the mixture to obtain Cu@Cu 2+ /TiO 2 The concentration of the compound catalyst precursor is 10g/L of mixed solution, and then the mixed solution is moved 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 Cu@Cu 2+ /TiO 2 Compounding a catalyst precursor;
step 3: taking Cu@Cu 2+ /TiO 2 The compound catalyst precursor and hydrogen peroxide are mixed according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to hydrogen peroxide in the composite catalyst precursor is 1:1.3 mixing, then pressing Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to soluble copper salt in the composite catalyst precursor is 2:1 adding water solution of soluble copper salt into the mixture, mixing and dispersing the mixture to obtain Cu@Cu 2+ /TiO 2 The concentration of the precursor of the composite catalyst is 60g/LMixing the solutions, 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 1:1.5 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 Cu@Cu 2+ /TiO 2 Compounding a catalyst precursor;
step 3: taking Cu@Cu 2+ /TiO 2 The compound catalyst precursor and hydrogen peroxide are mixed according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to hydrogen peroxide in the composite catalyst precursor is 1:1.2, then according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to soluble copper salt in the composite catalyst precursor is 6:1 adding water solution of soluble copper salt into the mixture, mixing and dispersing the mixture to obtain Cu@Cu 2+ /TiO 2 The concentration of the compound catalyst precursor is 70g/L of mixed solution, and then the mixed solution is moved 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.
As can be seen from FIG. 1, cu@Cu 2+ /TiO 2 The composite catalyst is in a core-shell self-assembly structure as a whole, and the titanium dioxide shell 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 is about 10nmTitanium oxide and nano copper with a wavelength of about 3-5 nm.
From FIG. 2, it can be seen that Cu@Cu 2+ /TiO 2 The composite catalyst has good mesoporous structure and large specific surface area, and the specific surface area is 132.5m 2 /g。
From FIG. 3, it can be seen that Cu@Cu 2+ /TiO 2 The composite catalyst has high NOx catalytic conversion activity of 84%, and the activity is relatively stable, and the activity is not obviously 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 Cu@Cu 2+ /TiO 2 Compounding a catalyst precursor;
step 3: taking Cu@Cu 2+ /TiO 2 The compound catalyst precursor and hydrogen peroxide are mixed according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to hydrogen peroxide in the composite catalyst precursor is 1:1-2, then according to Cu@Cu 2+ /TiO 2 The molar ratio of Ti atoms to soluble copper salt in the composite catalyst precursor is 1-10:1 adding water solution of soluble copper salt into the mixture, mixing and dispersing the mixture to obtain Cu@Cu 2+ /TiO 2 The concentration of the compound catalyst precursor is 10-100g/L of the mixed solution, and then the mixed solution is moved 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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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103212416A (en) * | 2013-05-09 | 2013-07-24 | 中国科学院新疆理化技术研究所 | Preparation method of titanium dioxide coated nano-copper with core-shell structure |
| US20150273440A1 (en) * | 2012-09-19 | 2015-10-01 | Shin-Etsu Chemical Co., Ltd. | Visible light-responsive photocatalytic nanoparticle dispersion liquid, method for producing same, and member having photocatalytic thin film on surface |
| CN106466604A (en) * | 2016-11-22 | 2017-03-01 | 安徽理工大学 | A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof |
| CN108079990A (en) * | 2017-12-12 | 2018-05-29 | 南京邮电大学 | A kind of coated by titanium dioxide copper nanocomposite and its preparation method and application |
| US20180161762A1 (en) * | 2016-12-13 | 2018-06-14 | King Abdulaziz University | Composite hollow particle, a method for making thereof, and a method for producing hydrogen gas |
| WO2018122569A1 (en) * | 2016-12-30 | 2018-07-05 | The Hong Kong University Of Science And Technology | Core-shell nanoparticle catalysts |
| CN109865514A (en) * | 2019-03-26 | 2019-06-11 | 武汉工程大学 | A kind of preparation method of copper/titanic oxide composite photochemical catalyst material |
| CN112371105A (en) * | 2020-11-26 | 2021-02-19 | 陕西科技大学 | Niobium pentoxide/titanium dioxide composite photocatalyst and preparation method and application thereof |
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150273440A1 (en) * | 2012-09-19 | 2015-10-01 | Shin-Etsu Chemical Co., Ltd. | Visible light-responsive photocatalytic nanoparticle dispersion liquid, method for producing same, and member having photocatalytic thin film on surface |
| CN103212416A (en) * | 2013-05-09 | 2013-07-24 | 中国科学院新疆理化技术研究所 | Preparation method of titanium dioxide coated nano-copper with core-shell structure |
| CN106466604A (en) * | 2016-11-22 | 2017-03-01 | 安徽理工大学 | A kind of Cu2O/TiO2Composite photocatalyst material and preparation method thereof |
| US20180161762A1 (en) * | 2016-12-13 | 2018-06-14 | King Abdulaziz University | Composite hollow particle, a method for making thereof, and a method for producing hydrogen gas |
| WO2018122569A1 (en) * | 2016-12-30 | 2018-07-05 | The Hong Kong University Of Science And Technology | Core-shell nanoparticle catalysts |
| CN108079990A (en) * | 2017-12-12 | 2018-05-29 | 南京邮电大学 | A kind of coated by titanium dioxide copper nanocomposite and its preparation method and application |
| CN109865514A (en) * | 2019-03-26 | 2019-06-11 | 武汉工程大学 | A kind of preparation method of copper/titanic oxide composite photochemical catalyst material |
| CN112371105A (en) * | 2020-11-26 | 2021-02-19 | 陕西科技大学 | Niobium pentoxide/titanium dioxide composite photocatalyst and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| JIALI ZHANG ET AL: ""Novel CuO@TiO2 Core–Shell Nanostructure Catalyst for Selective Catalytic Reduction of NOx with NH3"", 《CATALYSIS LETTERS》, vol. 151, 7 January 2021 (2021-01-07) * |
| 张佳丽: ""铜基催化剂的制备及其NH3-SCR催化性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 02, 15 February 2022 (2022-02-15) * |
| 曹瑞雪等: ""核壳结构Al2O3-TiO2脱硝催化剂的制备及性能研究"", 《化学研究与应用》, vol. 34, 30 April 2022 (2022-04-30) * |
| 马东等: ""Cu2O@TiO2核壳异质结的制备及其光催化性能研究 "", 《淮北师范大学学报（自然科学版）》, no. 1, 31 March 2017 (2017-03-31) * |
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