CN115870011B - Nanometer catalyst for efficiently degrading ammonia pollutants and application method thereof - Google Patents
Nanometer catalyst for efficiently degrading ammonia pollutants and application method thereof Download PDFInfo
- Publication number
- CN115870011B CN115870011B CN202211302177.8A CN202211302177A CN115870011B CN 115870011 B CN115870011 B CN 115870011B CN 202211302177 A CN202211302177 A CN 202211302177A CN 115870011 B CN115870011 B CN 115870011B
- Authority
- CN
- China
- Prior art keywords
- solution
- ammonia
- pollutants
- degrading
- degrading ammonia
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 55
- 230000000593 degrading effect Effects 0.000 title claims abstract description 31
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 23
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title abstract description 18
- 239000003054 catalyst Substances 0.000 title description 14
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 54
- 239000000084 colloidal system Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 239000007983 Tris buffer Substances 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical group Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 38
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 30
- 229960003638 dopamine Drugs 0.000 abstract description 15
- 239000004408 titanium dioxide Substances 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 102000001554 Hemoglobins Human genes 0.000 description 2
- 108010054147 Hemoglobins Proteins 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007954 hypoxia Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 231100001240 inorganic pollutant Toxicity 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009323 psychological health Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a nano catalyst for efficiently degrading ammonia pollutants and an application method thereof; the zirconium oxide and titanium dioxide composite oxide prepared by the invention can well adsorb and catalyze and oxidize and degrade ammonia, the transfer capacity of photo-generated carriers and the collection efficiency of visible light can be obviously improved through the synergistic effect of dopamine and the composite oxide, the light absorbing capacity is enhanced, the generated electron-hole pairs are increased, and the generated hydroxyl free radicals and superoxide anion free radicals are more, so that excellent photocatalytic activity is generated, and more ammonia can be rapidly catalyzed and degraded; the method has the advantages of mild reaction conditions, low energy consumption, environment-friendly raw materials, no pollution to the environment and environment-friendly chemical requirements.
Description
Technical Field
The invention relates to the technical field of photocatalytic degradation of ammonia gas, in particular to a nano catalyst for efficiently degrading ammonia gas pollutants and an application method thereof.
Background
The malodorous gas is used as a sensory public hazard, which not only causes serious damage to physical and psychological health of people, but also causes bad influence to ecological environment, the ammonia gas is used as one of malodorous gas, has stimulation and corrosion effects on the upper respiratory tract of human body or animals, can enter blood through alveoli to combine with hemoglobin to destroy the oxygen transportation function of the hemoglobin, and causes organism to generate tissue hypoxia, thereby reducing the resistance of organism, endangering animal and human health and life, and in addition, the ammonia gas can be attached to dust and migrate to farther places, can cause acidification of soil and water after sedimentation, causes eutrophication of an ecological system, has destructive effect on ecological environment and seriously pollutes environment.
When the indoor environment air ammonia is mainly derived from additives such as high-alkali concrete expanding agent and urea-containing concrete antifreezing agent added in concrete in construction, the additives containing ammonia substances are reduced to ammonia gas in a wall body along with the change of environmental factors such as humidity, temperature and the like, and the ammonia gas is slowly released from the wall body, so that the ammonia gas in the indoor air is polluted, in general, a house containing urea antifreezing agent is used, the ammonia release in the wall body is completely required for about 10-32 years, and the ammonia in the indoor air can also come from artificial pollution such as decorative material additives, brightening agents and the like, so that the human health is closely related to the indoor air quality condition.
At present, the traditional ammonia gas treatment technology comprises ventilation, physical adsorption, selective catalysis, photocatalysis and the like, the physical adsorption generally depends on the adsorptivity of activated carbon or modified activated carbon to remove harmful substances in the air, and most types of activated carbon have the defects of pollutant removal selectivity, small adsorption capacity, secondary pollution caused by easy desorption after adsorption saturation, poor pollutant removal effect on low concentration and the like; the selective catalytic technology can use various catalyst metals, and the metal oxide can completely remove the ammonia by oxidizing the ammonia, but the catalytic oxidation is carried out at a very high temperature, so that the effective removal of the gaseous ammonia at room temperature cannot be realized. The photocatalytic degradation technology is a clean, efficient and economic new method, can utilize light energy at room temperature to generate hydroxyl free radicals and superoxide anion free radicals with strong oxidizing ability, and can almost catalyze and degrade most of organic and inorganic pollutants in the air into inorganic micromolecular substances. The main advantages of the photocatalytic technique are: mild reaction condition, less secondary pollution, low energy consumption, simple equipment and the like. Titanium dioxide has high photocatalytic activity, and is widely available, nontoxic and harmless, so that the titanium dioxide is widely applied to photocatalytic degradation of pollutants. However, the forbidden bandwidth of the single TiO 2 is 3.2eV, the transition energy corresponds to the ultraviolet light part in sunlight, the light source utilization rate is not high, and the photo-generated electrons and holes are easy to be combined, so that the light quantum efficiency is low; in addition, the common TiO 2 has large specific surface area and more available catalytic active sites, but the nano ion has high surface energy, is easy to aggregate and reduces the catalytic activity.
CN 103170321A discloses a titanium dioxide catalyst for photocatalytic purification of ammonia gas, a preparation method and use thereof, the method comprising the steps of: (1) Uniformly mixing an organic compound of titanium, an HF solution and water to obtain a mixed solution; (2) transferring the mixed solution into a reaction kettle for reaction; (3) And washing and drying the reaction product to obtain the titanium dioxide catalyst for purifying ammonia by photocatalysis. According to the invention, HF is used as a surface structure guiding agent, an organic compound of titanium is used as a titanium source, titanium dioxide with exposed (001) crystal face is prepared by a hydrothermal synthesis method, and compared with a catalyst without the HF as the structure guiding agent, the catalytic performance of the catalyst with the HF as the structure guiding agent is obviously improved, and the catalyst is superior to that of a commercial catalyst P25. However, the catalyst prepared by the method can only catalyze and oxidize ammonia under the condition of ultraviolet irradiation, and the effect of catalyzing and oxidizing ammonia under visible light is poor.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to solve the problem that the nano TiO 2 photodegradation catalyst in the prior art cannot effectively perform photocatalytic degradation of ammonia under the condition of visible light.
In order to achieve the aim, the invention provides the nano catalyst with high ammonia gas degradation efficiency, simple preparation process and high stability, and the photoresponse range of the catalyst can be expanded to visible light in sunlight.
In order to achieve the above object, the present invention adopts the following technical scheme:
a preparation method of a nano catalyst for efficiently degrading ammonia pollutants comprises the following steps:
s1, mixing absolute ethyl alcohol and tetrabutyl titanate to obtain a solution A;
S2, mixing a precipitator and water to obtain a solution B, adding the solution A into the solution B, and then adding an organic acid and an inhibitor to form a colloid solution;
S3, adding a zirconium source into the colloid solution, performing hydrothermal reaction, and cooling after the reaction is finished to obtain a mixed solution;
S4, adding the Tris solution of dopamine hydrochloride into the mixed solution, uniformly mixing, filtering, collecting a filter cake, washing with water, and drying to obtain the nano catalyst for efficiently degrading ammonia pollutants.
Preferably, the preparation method of the nano catalyst for efficiently degrading ammonia pollutants comprises the following steps:
S1, mixing absolute ethyl alcohol and tetrabutyl titanate at 20-40 ℃ to obtain a solution A;
s2, mixing a precipitator and water to obtain a solution B, dropwise adding the solution A into the solution B, stirring at 400-600rpm for reaction for 0.5-1h after the dropwise addition is completed, and then adding an organic acid and an inhibitor to form a colloid solution;
S3, adding a zirconium source into the colloid solution, then placing the colloid solution into an autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction at 100-150 ℃ for 4-6 hours, and cooling to 20-40 ℃ after the reaction is finished to obtain a mixed solution;
S4, adding a Tris solution of dopamine hydrochloride into the mixed solution, reacting for 10-20 hours, filtering, collecting a filter cake, washing for 2-3 times, and finally drying in a drying oven at 60-80 ℃ for 10-12 hours to obtain the nano catalyst for efficiently degrading ammonia pollutants.
Further preferably, the preparation method of the nano catalyst for efficiently degrading ammonia pollutants comprises the following steps:
s1, mixing 15-20mL of absolute ethyl alcohol with 6-10mL of tetrabutyl titanate at the temperature of 20-40 ℃ to obtain a solution A;
S2, mixing 2-4g of precipitant and 20-30g of water to obtain a solution B, dropwise adding the solution A into the solution B, stirring at a rotating speed of 400-600rpm for reaction for 0.5-1h after the dropwise adding is finished, and adding 1-2g of organic acid and 1-2g of inhibitor to form a colloid solution;
s3, adding 3-5g of zirconium source into the colloid solution, then placing the colloid solution into an autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction at 100-150 ℃ for 4-6h, and cooling to 20-40 ℃ after the reaction is finished to obtain a mixed solution;
S4, adding 20-30mL of Tris solution of dopamine hydrochloride into the mixed solution, reacting for 10-20h, filtering, collecting a filter cake, washing for 2-3 times, and finally drying in a drying oven at 60-80 ℃ for 10-12h to obtain the nano catalyst for efficiently degrading ammonia pollutants.
Preferably, the precipitant in the step S2 is one or two or more of urea, ammonia water, sodium hydroxide aqueous solution and potassium hydroxide aqueous solution;
preferably, the drop acceleration in the step S2 is 1-2 drops/second;
Preferably, the organic acid in the step S2 is one or two or more of citric acid, tartaric acid, acetic acid and glycolic acid;
preferably, the inhibitor in the step S2 is one or two or more of polyethylene glycol, stearic acid alcohol, diethanolamine and ethanol; a further preferred inhibitor is polyethylene glycol; the addition of inhibitors can prevent colloidal agglomeration.
Preferably, in the step S2, the ultrasonic time is 1-1.5h, the ultrasonic power is 550-800W, and the ultrasonic frequency is 28-40 kHz.
Preferably, the zirconium source in the step S3 is one or two or more of zirconium oxychloride, zirconium nitrate, zirconium sulfate and zirconium acetate; a further preferred zirconium source is zirconium oxychloride.
Preferably, the concentration of the Tris solution of dopamine hydrochloride in the step S4 is 20-30wt% and the pH value is 8.5-8.6.
The zirconia and titania composite oxide is prepared by combining a sol method and a hydrothermal method, and the prepared zirconia and titania composite oxide has the advantages of uniform metal element distribution, large specific surface area and strong ultraviolet aging resistance; the introduction of zirconium serving as a metal element can cause larger lattice defects, so that the storage of lattice oxygen is improved; the zirconia and titanium dioxide composite oxide has strong oxidizing property and strong adsorption and catalytic oxidation capability to ammonia gas; the pi conjugated system in the dopamine molecule has high visible light capturing efficiency and electron-hole separation capability, and the dopamine can enhance the binding force between contact materials, improve the stability of a photocatalyst, and simultaneously is an electron donor, so that the separation of electrons and holes can be improved. The inventor finds that the synergistic effect of dopamine, zirconia and titanium dioxide composite oxide can obviously improve the transfer capability of photo-generated carriers and the collection efficiency of visible light, enhance the light absorption capability, increase the generated electron-hole pairs, generate more hydroxyl free radicals and superoxide anion free radicals, generate excellent photocatalytic activity and can rapidly catalyze and degrade more ammonia.
The invention also provides application of the nano catalyst for efficiently degrading ammonia pollutants in photocatalytic degradation of indoor ammonia under visible light.
Compared with the prior art, the invention has the beneficial effects that:
1. The method has the advantages of mild reaction conditions, low energy consumption, environment-friendly raw materials, no pollution to the environment and environment-friendly chemical requirements.
2. The invention uses dopamine, can improve the photocatalytic activity of the catalyst while enhancing the binding force between materials, widens the light capturing efficiency of visible light, and improves the light source utilization rate.
3. The zirconia and titania composite oxide prepared by the method can be used as a strong oxidant, and can efficiently adsorb and degrade ammonia.
4. The nano catalyst for efficiently degrading ammonia gas has high degradation rate and high degradation speed.
Detailed Description
The invention will be described in further detail with reference to specific examples. The procedures, conditions, experimental methods, etc. for carrying out the present invention are common general knowledge and knowledge in the art, except for the following specific references, and the present invention is not particularly limited.
For the sake of brevity, the articles used in the examples below are commercially available products unless otherwise specified, and the methods used are conventional methods unless otherwise specified.
Example 1
A preparation method of a nano catalyst for efficiently degrading ammonia pollutants comprises the following steps:
S1, mixing 15mL of absolute ethyl alcohol with 9mL of tetrabutyl titanate at the temperature of 30 ℃ to obtain a solution A;
s2, mixing 3g of urea and 30g of water to obtain a solution B, dropwise adding the solution A into the solution B at a speed of 1 drop/second, stirring at a rotating speed of 50rpm for reaction for 1h after the dropwise adding is finished, and adding 1.5g of citric acid and 1g of polyethylene glycol 400 to form a colloid solution;
S3, adding 4g of zirconium oxychloride into the colloid solution, placing the mixture into an autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction at 120 ℃ for 5 hours, and cooling to 30 ℃ after the reaction is finished to obtain a mixed solution;
S4, adding 30mL of 30wt% dopamine hydrochloride Tris solution into the mixed solution, reacting for 12 hours, filtering, collecting a filter cake, washing with water for 3 times, and finally drying in a drying oven at 80 ℃ for 12 hours to obtain the nano catalyst for efficiently degrading ammonia pollutants.
Comparative example 1
A method for preparing a nano catalyst for degrading ammonia pollutants, which comprises the following steps:
S1, mixing 15mL of absolute ethyl alcohol with 9mL of tetrabutyl titanate at the temperature of 30 ℃ to obtain a solution A;
s2, mixing 3g of urea and 30g of water to obtain a solution B, dropwise adding the solution A into the solution B at a speed of 1 drop/second, stirring at a rotating speed of 50rpm for reaction for 1h after the dropwise adding is finished, and adding 1.5g of citric acid and 1g of polyethylene glycol 400 to form a colloid solution;
S3, adding 4g of zirconium oxychloride into the colloid solution, placing the mixture into an autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction at 120 ℃ for 5 hours, and cooling to 30 ℃ after the reaction is finished to obtain a mixed solution;
And S4, standing the mixed solution for 2 hours, and then roasting at 400 ℃ for 3 hours to obtain the nano catalyst for degrading the ammonia pollutant.
Comparative example 2
A method for preparing a nano catalyst for degrading ammonia pollutants, which comprises the following steps:
S1, mixing 15mL of absolute ethyl alcohol with 9mL of tetrabutyl titanate at the temperature of 30 ℃ to obtain a solution A;
s2, mixing 3g of urea and 30g of water to obtain a solution B, dropwise adding the solution A into the solution B at a speed of 1 drop/second, stirring at a rotating speed of 50rpm for reaction for 1h after the dropwise adding is finished, and adding 1.5g of citric acid and 1g of polyethylene glycol 400 to form a colloid solution;
S3, adding 30mL of 30wt% dopamine hydrochloride Tris solution into the colloid solution, reacting for 12 hours, filtering, collecting a filter cake, washing with water for 3 times, and finally drying in a drying oven at 80 ℃ for 12 hours to obtain the nano catalyst for degrading ammonia pollutants.
Comparative example 3
One type of nanocatalyst for degrading ammonia gas contaminants is commercially available nano TiO 2.
Test example 1
And (3) testing the degradation rate of ammonia under ultraviolet light: uniformly scattering 10g of experiment sample plates of the catalyst of the embodiment 1 and the comparative examples 1-3 in the temperature of 25 ℃ and the humidity of 50% RH, placing the experiment sample plates in an experiment cabin, sealing the cabin, wherein the area of the sample plates is 0.06m 2, the thickness is 1.0ram, and the size in the experiment cabin is 3 cubic meters; adding ammonia gas with the flow rate of 80mL/min from a sample injection hole of the experimental cabin for 90s, then opening a fan to mix the gas in the experimental cabin uniformly, closing the fan after 15min, measuring the concentration of the ammonia gas in the experimental cabin as the initial concentration of the ammonia gas, and starting an irradiation light source of the experimental cabin, wherein the irradiation light source is an ultraviolet light source with the wavelength of 254 nm. In the test process, detecting the concentration of ammonia in the experiment cabin for 1 time every 20min, starting a fan 15min before detection, closing the fan during detection, wherein a control group is 4 blank glass plates, the flow of ammonia is controlled by a D07 series ammonia flowmeter manufactured by Beijing Qixing Hua Chuan electronic Co., ltd, and the concentration of ammonia is detected by a HYCA-1 ammonia detector manufactured by Toguan City Weituo instruments Co., ltd, wherein the detection limit is as follows: the sensitivity is 0.01ppm and the degradation rate of ammonia is calculated as follows: degradation rate= (initial ammonia concentration-post-degradation ammonia concentration)/initial ammonia concentration x 100%, test results are shown in table 1:
Table 1: ammonia degradation rate test result table of nano catalyst under ultraviolet light
From the experimental data in table 1, it can be seen that the nano catalyst for efficiently degrading ammonia pollutants in the invention has a good effect of degrading ammonia under ultraviolet light, ammonia can be completely degraded in 90min, while the difference between the embodiment 1 and other comparative examples is that zirconium oxide, titanium dioxide and dopamine are added, the possible reasons are that the zirconium oxide and titanium dioxide composite oxide has strong oxidizing property, can well adsorb and catalyze and degrade ammonia, while the dopamine can enhance the binding force between contact materials, improve the stability of the photocatalyst, and simultaneously is an electron donor, can improve the separation of electrons and holes, and the synergy of the three can obviously improve the transfer capability of photo-generated carriers and the collection efficiency of visible light, enhance the light absorbing capability, increase the generated electron-hole pairs, generate more hydroxyl free radicals and superoxide anion free radicals, thereby generating excellent photocatalytic activity and rapidly catalyzing and degrading more ammonia.
Test example 2
And (3) testing the ammonia degradation rate under visible light: the irradiation light source in test example 1 was changed to a visible light source, the visible light was obtained by filtering off ultraviolet light from a xenon lamp, the wavelength of the visible light was 420-800nm, the other test steps were the same as in test example 1, and the test results are shown in table 2:
Table 2: ammonia degradation rate test result table of nano catalyst under visible light
From the experimental data in table 2, it can be seen that the nano catalyst for efficiently degrading ammonia prepared in example 1 has a good effect of degrading ammonia under visible light, and may be because dopamine realizes pi-pi energy level transition under visible light, excited electrons transfer from HOMO orbitals of dopamine to LUMO orbitals, which generate a large number of photo-generated holes injected from HOMO orbitals of dopamine, on one hand, zirconium oxide generates photo-generated electrons and holes by absorbing visible light, since the conduction band potential of zirconium oxide is higher than LUMO of dopamine, this induces photo-generated electrons to transfer from LUMO of dopamine to conduction band of zirconium oxide, then photo-generated electrons continue to transfer to electric field of titania, under the internal electric field formed by titania and zirconia, resulting in cascade-driven charge separation and transfer, in addition, because of complete connection between dopamine and titania, LUMO electrons from dopamine transfer directly into conduction band of titania, while photo-generated holes on semiconductor valence band of titania and zirconia transfer to HOMO of dopamine, resulting in effective separation of photo-generated electrons and holes, which convert oxygen into more oxygen-generated oxygen radicals, and more rapidly degrading hydroxyl groups on the surface of titania.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (5)
1. A nanocatalyst for degrading ammonia gas contaminants, comprising the steps of:
s1, mixing 15-20mL of absolute ethyl alcohol with 6-10mL of tetrabutyl titanate at the temperature of 20-40 ℃ to obtain a solution A;
S2, mixing 2-4g of precipitant and 20-30g of water to obtain a solution B, dropwise adding the solution A into the solution B, stirring at a rotating speed of 400-600rpm for reaction for 0.5-1h after the dropwise adding is finished, and adding 1-2g of organic acid and 1-2g of inhibitor to form a colloid solution;
s3, adding 3-5g of zirconium source into the colloid solution, then placing the colloid solution into an autoclave with a polytetrafluoroethylene lining, performing hydrothermal reaction at 100-150 ℃ for 4-6h, and cooling to 20-40 ℃ after the reaction is finished to obtain a mixed solution;
S4, adding 20-30mL of Tris solution of dopamine hydrochloride into the mixed solution, reacting for 10-20h, filtering, collecting a filter cake, washing for 2-3 times, and finally drying in a drying oven at 60-80 ℃ for 10-12h to obtain the nano catalyst for degrading ammonia pollutants;
The zirconium source is zirconium oxychloride.
2.A nanocatalyst for degrading ammonia gas contaminants according to claim 1 wherein: the precipitant in the step S2 is one or two or more of urea, ammonia water, sodium hydroxide aqueous solution and potassium hydroxide aqueous solution.
3. A nanocatalyst for degrading ammonia gas contaminants according to claim 1 wherein: the organic acid in the step S2 is one or two or more of citric acid, tartaric acid, acetic acid and glycolic acid.
4. A nanocatalyst for degrading ammonia gas contaminants according to claim 1 wherein: the inhibitor in the step S2 is one or two or more of polyethylene glycol, stearic acid alcohol, diethanolamine and ethanol.
5. The application of the nano catalyst for degrading ammonia pollutants in the room of photocatalytic degradation of ammonia under visible light as set forth in any one of claims 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211302177.8A CN115870011B (en) | 2022-10-24 | 2022-10-24 | Nanometer catalyst for efficiently degrading ammonia pollutants and application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211302177.8A CN115870011B (en) | 2022-10-24 | 2022-10-24 | Nanometer catalyst for efficiently degrading ammonia pollutants and application method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115870011A CN115870011A (en) | 2023-03-31 |
| CN115870011B true CN115870011B (en) | 2024-05-28 |
Family
ID=85758872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211302177.8A Active CN115870011B (en) | 2022-10-24 | 2022-10-24 | Nanometer catalyst for efficiently degrading ammonia pollutants and application method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115870011B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739064B (en) * | 2022-11-22 | 2024-09-24 | 仙居县蔚徕新材料科技有限公司 | Nanometer material for ultraviolet light catalytic degradation and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389784A (en) * | 2011-09-20 | 2012-03-28 | 同济大学 | Method for preparing nano high-efficiency TiO2-ZrO2 composite photocatalyst |
| CN107670664A (en) * | 2017-10-31 | 2018-02-09 | 云南健牛生物科技有限公司 | Titanic oxide composite photochemical catalyst system prepares and its application |
| CN109319877A (en) * | 2018-11-13 | 2019-02-12 | 吉林师范大学 | A method of utilizing zirconium oxide/dioxide composite nanofiber material processing organic wastewater |
| CN111604043A (en) * | 2020-04-28 | 2020-09-01 | 山东科技大学 | Inorganic nonmetallic mineral composite material loaded with titanium dioxide layer and preparation method |
| CN112973798A (en) * | 2021-02-10 | 2021-06-18 | 深圳大学 | Photocatalytic material and preparation method and application thereof |
| CN114388713A (en) * | 2020-10-16 | 2022-04-22 | Tcl科技集团股份有限公司 | Electron transport material, preparation method thereof and photoelectric device |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100935512B1 (en) * | 2008-05-15 | 2010-01-06 | 경북대학교 산학협력단 | Manufacturing method of TiO2 photocatalyst and TiO2 photocatalyst manufactured by the same |
-
2022
- 2022-10-24 CN CN202211302177.8A patent/CN115870011B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389784A (en) * | 2011-09-20 | 2012-03-28 | 同济大学 | Method for preparing nano high-efficiency TiO2-ZrO2 composite photocatalyst |
| CN107670664A (en) * | 2017-10-31 | 2018-02-09 | 云南健牛生物科技有限公司 | Titanic oxide composite photochemical catalyst system prepares and its application |
| CN109319877A (en) * | 2018-11-13 | 2019-02-12 | 吉林师范大学 | A method of utilizing zirconium oxide/dioxide composite nanofiber material processing organic wastewater |
| CN111604043A (en) * | 2020-04-28 | 2020-09-01 | 山东科技大学 | Inorganic nonmetallic mineral composite material loaded with titanium dioxide layer and preparation method |
| CN114388713A (en) * | 2020-10-16 | 2022-04-22 | Tcl科技集团股份有限公司 | Electron transport material, preparation method thereof and photoelectric device |
| CN112973798A (en) * | 2021-02-10 | 2021-06-18 | 深圳大学 | Photocatalytic material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Visible-light-driven photocatalytic performance of nitrogen-doped Ti1-xZrxO2 solid solution;Bifen Gao等;《Materials Research Bulletin》;20121116;第48卷;第587-594页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115870011A (en) | 2023-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105498478B (en) | A kind of method and device of gas phase photolysis-liquid phase photochemical catalytic oxidation purifying volatile organic matter | |
| CN108970613A (en) | A kind of titanium dioxide composite photocatalyst and the preparation method and application thereof that FeOOH is modified | |
| CN105597528A (en) | Waste gas purification device and process | |
| CN108786788B (en) | Method for removing dioxin and NO in flue gasxCatalyst, preparation method and application | |
| CN106944092A (en) | A kind of Fe MnO with efficient photo-thermal concerted catalysis purifying VOCs2The preparation method of catalyst | |
| WO2022047813A1 (en) | Organic wastewater treatment method based on multi-element co-doped tio2 nano photocatalytic material | |
| CN115870011B (en) | Nanometer catalyst for efficiently degrading ammonia pollutants and application method thereof | |
| CN104096465B (en) | Formaldehyde decomposition solution of a kind of pollen carbon nanometer and preparation method thereof | |
| CN103357395B (en) | Lanthanide-doped nanotube TiO 2the preparation method of composite photo-catalyst and the application in VOCs administers thereof | |
| CN106861392A (en) | A kind of nitrogen oxide removal process based on catalytic oxidation of hydrogen peroxide | |
| CN113083277A (en) | Preparation method and application of nano ZnO rich in oxygen vacancy for photocatalytic reduction of hexavalent uranium | |
| CN113731402B (en) | Catalyst and preparation method and application thereof | |
| CN111841565B (en) | Normal-temperature ozone-removing catalytic material | |
| CN102698734B (en) | Amorphous tantalic acid photocatalyst for decomposing benzene pollutants and preparation method for amorphous tantalic acid photocatalyst | |
| CN206566726U (en) | One kind spraying exhaust gas purification and treatment device | |
| CN115193473B (en) | Catalyst for oxidizing methyl mercaptan by ozone, preparation method and application thereof | |
| CN115739064B (en) | Nanometer material for ultraviolet light catalytic degradation and preparation method thereof | |
| CN104353354A (en) | Method for purifying air by combining electrochemical degradation with photocatalysis technique | |
| CN110332631A (en) | A kind of novel photocatalyst air purifier | |
| CN115845921A (en) | Preparation and application of bimetallic organic framework material Ce-MIL-88B (Fe) photocatalyst | |
| CN212492406U (en) | Photocatalyst organic waste gas treatment equipment | |
| CN110038546B (en) | Nano composite material for photocatalysis and preparation method and application thereof | |
| CN113441001A (en) | Application of composite photocatalytic material in photocatalytic degradation of formaldehyde | |
| CN208018333U (en) | A kind of UV photocatalysis exhaust air deodorization device | |
| CN113398737A (en) | Waste gas treatment method for refuse transfer station |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |