CN110252409B - Photocatalyst for removing nitric oxide and preparation method thereof - Google Patents
Photocatalyst for removing nitric oxide and preparation method thereof Download PDFInfo
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- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims abstract description 218
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 222
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 96
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 70
- 239000010439 graphite Substances 0.000 claims abstract description 70
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims abstract description 69
- 239000011773 ferrous fumarate Substances 0.000 claims abstract description 69
- 229960000225 ferrous fumarate Drugs 0.000 claims abstract description 69
- 235000002332 ferrous fumarate Nutrition 0.000 claims abstract description 69
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 53
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 35
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910001447 ferric ion Inorganic materials 0.000 claims abstract description 31
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 31
- -1 fumaric acid radical Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 235000019441 ethanol Nutrition 0.000 claims description 79
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 39
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 15
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims description 14
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 abstract description 31
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 31
- 230000003647 oxidation Effects 0.000 abstract description 19
- 238000007254 oxidation reaction Methods 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 abstract description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000001530 fumaric acid Substances 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 241001311547 Patina Species 0.000 description 29
- 239000002245 particle Substances 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 9
- 238000003915 air pollution Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 150000002829 nitrogen Chemical class 0.000 description 6
- 238000005215 recombination Methods 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- 238000004887 air purification Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses a photocatalyst for removing nitric oxide and a preparation method thereof, wherein the photocatalyst mainly comprises the following components: the carbon nitride-based carbon material comprises a ferrous fumarate ethanol solution, ferric acetylacetonate, sodium hydroxide and graphite carbon nitride, wherein the molar ratio of ferrous ions, ferric ions and hydroxyl in the ferrous fumarate ethanol solution, the ferric acetylacetonate and the sodium hydroxide is 1-4: 1: 2-6, and the solid-to-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution is 1: 0.5-4 mg/mL. According to the invention, the graphite carbon nitride material is modified, and the fumaric acid radical green rust and acetylacetone radical green rust-doped material is synthesized at normal temperature and loaded on the graphite carbon nitride material, so that the photocatalytic performance of the catalyst nitric oxide is effectively improved, the removal amount of nitric oxide is increased, the generation amount of nitrogen dioxide is remarkably reduced, and the problem of secondary pollution caused by the generation of nitrogen dioxide in the traditional nitric oxide catalytic oxidation process is solved.
Description
Technical Field
The invention belongs to the field of gas pollution purification, and particularly relates to a photocatalyst for removing nitric oxide and a preparation method thereof.
Background
Nitrogen oxides are one of the main atmospheric pollutants, are not only easy to induce ecological environmental problems, but also can cause direct harm to human health. Nitrogen oxides mainly include nitrogen monoxide and nitrogen dioxide. The nitrogen monoxide can react with ozone molecules in the atmosphere to form an ozone cavity, so that the shielding effect of the atmosphere on ultraviolet rays is weakened. The existing removal method of nitric oxide mainly comprises a catalytic reduction method, a plasma method and an oxidation absorption method. The catalytic reduction method has the problems of low denitration efficiency, high temperature requirement, easy poisoning of the catalyst and the like. The plasma method has the problems of high equipment price, limited operation conditions, high operation cost and the like. The oxidation absorption method has the problems of high generation rate of nitrogen dioxide, low denitrification index and secondary pollution caused by untimely recovery of nitrate and nitrite.
In recent years, semiconductor photocatalytic oxidation technology has attracted attention because of its simple operation process, low equipment requirements, and normal temperature operation characteristics. The catalytic oxidation of nitric oxide under visible light irradiation conditions using graphite carbon nitride as a photocatalyst has become a hot point of research in recent years. However, the graphite carbon nitride has high electron band gap energy, a photocatalytic window is narrow, the transfer efficiency of photo-generated electrons and oxygen generated under the illumination condition is low, the photo-generated electrons and photo-generated holes are easy to recombine, the nitrogen monoxide oxidation efficiency is low, and the specific gravity of the nitrogen monoxide gas converted into the nitrogen dioxide gas is high. Considering that nitrogen dioxide is more toxic and more ecologically hazardous than nitric oxide, the yield of nitrogen dioxide during oxidation should be minimized.
In combination with the above problems, it is critical to develop a photocatalyst for removing nitric oxide efficiently based on the photocatalytic properties of graphitic carbon nitride.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a photocatalyst for removing nitric oxide.
The second technical problem to be solved by the invention is to provide a preparation method of the photocatalyst for removing nitric oxide.
The technical scheme is as follows: in order to solve the technical problems, the invention adopts the following technical scheme: a photocatalyst for removing nitric oxide, the photocatalyst being made essentially of: the iron chloride-containing carbon nitride-based carbon material comprises a ferrous fumarate ethanol solution, ferric acetylacetonate, sodium hydroxide and graphite carbon nitride, wherein the molar ratio of ferrous ions, ferric ions and hydroxyl in the ferrous fumarate ethanol solution, the ferric acetylacetonate and the sodium hydroxide is 1-4: 1: 2-6, and the solid-to-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution is 1: 0.5-4 mg/mL.
Wherein the molar ratio of the ferrous ions, the ferric ions and the hydroxyl ions is 2-3: 1: 3-5, and the solid-to-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution is 1: 1-3 mg/mL.
The invention also provides a preparation method of the photocatalyst for removing nitric oxide, which comprises the following steps:
1) weighing ferrous fumarate, ferric acetylacetonate powder and sodium hydroxide according to the molar ratio of ferrous ions, ferric ions and hydroxyl ions of 1-4: 1: 2-6 respectively;
2) mixing ferrous fumarate into absolute ethyl alcohol according to the solid-liquid ratio of 1: 5-10 mmol/mL, continuously stirring under a sealed condition until the ferrous fumarate is completely dissolved in the absolute ethyl alcohol, and preparing to obtain a ferrous fumarate ethyl alcohol solution;
3) weighing the graphite carbon nitride according to the solid-to-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution of 1: 0.5-4 mg/mL, mixing the graphite carbon nitride with the ferrous fumarate ethanol solution, and continuously and uniformly stirring under a sealed condition to obtain a graphite carbon nitride loaded ferrous ethanol solution;
4) mixing a corresponding amount of ferric acetylacetonate into anisole with the same volume, and continuously stirring under a sealed condition until the ferric acetylacetonate is completely dissolved in the anisole to prepare ferric acetylacetonate anisole solution;
5) mixing a corresponding amount of sodium hydroxide into absolute ethyl alcohol, continuously stirring under a sealed condition until the sodium hydroxide is completely dissolved in the ethyl alcohol, and preparing a sodium hydroxide ethanol solution;
6) mixing the carbon nitride graphite loaded ferrous ethanol solution, the ferric acetylacetonate anisole solution and the sodium hydroxide ethanol solution, fully stirring under a sealed condition, centrifuging, drying in vacuum, and grinding to obtain the photocatalyst for removing the nitric oxide.
The stirring speed in the step 2) is 20-60 rpm, if the rotating speed is lower than 20rmp, the dissolving time of the ferrous fumarate is increased, anhydrous ethanol volatile gas is easy to accumulate in the container, and the ethanol volatilization amount is increased when the container is opened, so that air pollution is caused. If the rotating speed is higher than 60rmp, the rotating speed is too high, the stirrer rubs with the ethanol solution to generate cavity bubbles, anhydrous ethanol volatile gas is easy to accumulate in the container, the ethanol volatile amount is increased when the container is opened, and air pollution is caused.
The stirring speed in the step 3) is 20-60 rpm, if the speed is lower than 20rmp, the loading time of the graphite carbon nitride and the ferrous fumarate is increased, so that the ferrous ions are not favorably and uniformly loaded on the graphite carbon nitride, the anhydrous ethanol volatile gas is easy to accumulate in the container, the ethanol volatile amount is increased when the container is opened, and air pollution is caused. If the rotating speed is higher than 60rmp, the rotating speed is too high, the stirrer rubs with the solution to generate cavity bubbles, so that ferrous ions are uniformly and unevenly loaded on the graphite carbon nitride, anhydrous ethanol volatile gas is accumulated in the container, the ethanol volatile amount is increased when the container is opened, and air pollution is caused.
The stirring speed in the step 4) is 20-60 rpm, if the rotating speed is lower than 20rmp, the dissolving time of iron acetylacetonate is increased, anisole volatile gas is easy to accumulate in the container, and the anisole volatile amount is increased when the container is opened, so that air pollution is caused. If the rotating speed is higher than 60rmp, the rotating speed is too high, the stirrer rubs with the anisole solution to generate cavity bubbles, and anisole volatile gas is easy to accumulate in the container, so that the anisole volatile amount is increased when the container is opened, and air pollution is caused.
The stirring speed in the step 5) is 20-60 rpm, the rotating speed is lower than 20rmp, the dissolving time of sodium hydroxide is increased, anhydrous ethanol volatile gas is easy to accumulate in the container, and the ethanol volatile amount is increased when the container is opened, so that air pollution is caused. If the rotating speed is higher than 60rmp, the rotating speed is too high, the stirrer rubs with the ethanol solution to generate cavity bubbles, anhydrous ethanol volatile gas is easy to accumulate in the container, the ethanol volatile amount is increased when the container is opened, and air pollution is caused.
And 6), the centrifugal speed in the step 6) is 6000-12000 rpm, and if the centrifugal speed is lower than 6000rpm, the centrifugal force is small, and the flocculated precipitate and the liquid are not completely separated. If the heart rate is higher than 12000rpm, the centrifugal force is too large, the solid climbs along the pipe wall and the pipe orifice of the centrifugal pipe, and the solid is easy to return to the liquid during solid-liquid separation to form turbid liquid.
And 6), sieving with a 200-400-mesh sieve after grinding, wherein if the sieving mesh number is less than 200 meshes, the sieving effect of the sample powder is poor, the specific surface area of the sample powder is reduced, and the carbon monoxide and nitrogen removal experiment is directly influenced. If the number of the sieved meshes is more than 400 meshes, the sieved sample is easy to agglomerate, so that the specific surface area of the sample powder is easy to reduce, and the carbon monoxide and nitrogen removal experiment is directly influenced.
The working principle of the invention is as follows: in the preparation process of the catalyst, the mixture of the carbon nitride graphite loaded ferrous ethanol solution, the ferric acetylacetonate anisole solution and the sodium hydroxide ethanol solution can induce the formation of the fumarate-doped patina and the acetylacetonate-doped patina and promote the patina material to be fully loaded on the surface of the carbon nitride graphite particles and in the cracks and cavities of the particles. The loading of the fumarate radical mixed with the green rust and the acetyl acetonate radical mixed with the green rust can reduce the electronic band gap energy (eV) of the graphite carbon nitride and strengthen the excitation and activation performance of the catalyst under the condition of visible light irradiation. In the photocatalysis process, the fumarate radical-doped patina and the acetylacetonate radical-doped patina material can pass through Fe2+/Fe3+The ion pair effect accelerates the transfer of the photo-generated electrons to oxygen molecules, reduces the recombination probability of the photo-generated electrons and the photo-generated holes, and strengthens the catalytic oxidation effect of the photo-generated holes, thereby promoting the conversion of more nitric oxide to inorganic nitrogen salt (nitrite and nitrate) and reducing the generation of nitrogen dioxide gas in the oxidation process. Meanwhile, the patina material has a double-layer space structure. The molecular structures of the fumarate radical and the acetylacetone radical enable the layer spacing of the microstructure of the fumarate radical-doped patina and the acetylacetone radical-doped patina to be larger, the specific surface of the patina material is enlarged, and the active sites are increased. During photocatalytic oxidation, a significant portion of the nitric oxide and oxygen is first adsorbed onto the patina particles, which shortens the photoproduction electron transfer distance. The surface of the patina particles is composed of nitrogen oxideThe inorganic nitrogen salt and part of the nitrogen dioxide generated by the chemical reaction can further migrate to the patina particle layer and be fixed between the molecular structures of the fumarate and the acetylacetonate. The timely migration of the inorganic nitrogen salt and part of the nitrogen dioxide enables active sites on the surface of the patina particles to be reactivated and continuously participate in the processes of adsorption, oxidation and transfer of nitric oxide pollutants.
Has the advantages that: the preparation method has the advantages of simple preparation operation process and low equipment requirement, and can be directly popularized in a commercial mode. According to the invention, the graphite carbon nitride material is modified, and the fumaric acid radical green rust and acetylacetone radical green rust-doped material is synthesized at normal temperature and loaded on the graphite carbon nitride material, so that the photocatalytic performance of the catalyst nitric oxide is effectively improved, the removal amount of nitric oxide is increased, the generation amount of nitrogen dioxide is remarkably reduced, and the problem of secondary pollution caused by the generation of nitrogen dioxide in the traditional nitric oxide catalytic oxidation process is solved to a certain extent. The invention provides a new idea for removing the nitric oxide.
Drawings
FIG. 1 is a flow chart illustrating the preparation of the photocatalyst for removing nitric oxide according to the present invention.
Detailed Description
The invention is further described below with reference to the figures and examples.
Fig. 1 shows a flow chart of a method for preparing a photocatalyst for removing nitric oxide. The reactions of the examples of the present invention were all carried out at normal temperature.
Example 1 Effect of ferrous ion, ferric ion, hydroxyl mole ratio on the photocatalytic Performance of nitric oxide
Preparation of a first group of nitric oxide photocatalysts: ferrous fumarate, ferric acetylacetonate powder and sodium hydroxide are respectively weighed according to the mole ratio of ferrous ions, ferric ions and hydroxide radicals of 1:3, 1.5: 1:3, 1.8: 1:3, 2: 1:3, 2.5: 1:3, 3:1:3, 3.2: 1:3, 3.5: 1:3 and 4:1: 3. Mixing ferrous fumarate into absolute ethanol according to the solid-liquid ratio of 1: 5mmol/mL, and continuously stirring at the rotating speed of 20rpm under a sealed condition until the ferrous fumarate is completely dissolved in the ethanol to prepare a ferrous fumarate ethanol solution. Weighing the graphite carbon nitride according to the solid-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution of 1: 1mg/mL, mixing the graphite carbon nitride with the ferrous fumarate ethanol solution, and continuously and uniformly stirring at the rotating speed of 20rpm under a sealed condition to obtain the graphite carbon nitride loaded ferrous ethanol solution. And (3) mixing a corresponding amount of ferric acetylacetonate into anisole with the same volume, and continuously stirring at the rotating speed of 20rpm under a sealed condition until the ferric acetylacetonate is completely dissolved in the anisole to prepare the ferric acetylacetonate anisole solution. And (3) mixing a corresponding amount of sodium hydroxide into absolute ethyl alcohol, and continuously stirring at a rotating speed of 20rpm under a sealed condition until the sodium hydroxide is completely dissolved in the ethyl alcohol to prepare a sodium hydroxide ethyl alcohol solution. Mixing the carbon nitride graphite loaded ferrous ethanol solution, the ferric acetylacetonate anisole solution and the sodium hydroxide ethanol solution, fully stirring under a sealed condition, centrifuging at the rotating speed of 6000rmp, drying in vacuum, grinding, and sieving with a 200-mesh sieve to obtain the photocatalyst for removing the nitric oxide.
Preparation of a second group of nitric oxide photocatalysts: ferrous fumarate, ferric acetylacetonate powder and sodium hydroxide are respectively weighed according to the mole ratio of ferrous ions, ferric ions and hydroxide radicals of 3:1: 2, 3:1: 2.5, 3:1: 2.8, 3:1:3, 3:1: 4, 3:1: 5, 3:1: 5.2, 3:1: 5.5 and 3:1: 6. Mixing ferrous fumarate into absolute ethanol according to the solid-liquid ratio of 1: 7.5mmol/mL, continuously stirring at 40rpm under a sealed condition until the ferrous fumarate is completely dissolved in the ethanol, and preparing to obtain a ferrous fumarate ethanol solution. Weighing the graphite carbon nitride according to the solid-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution of 1: 1mg/mL, mixing the graphite carbon nitride with the ferrous fumarate ethanol solution, and continuously and uniformly stirring at the rotating speed of 40rpm under a sealed condition to obtain the graphite carbon nitride loaded ferrous ethanol solution. And (3) mixing a corresponding amount of ferric acetylacetonate into anisole with the same volume, and continuously stirring at the rotating speed of 40rpm under a sealed condition until the ferric acetylacetonate is completely dissolved in the anisole to prepare the ferric acetylacetonate anisole solution. And (3) mixing a corresponding amount of sodium hydroxide into absolute ethyl alcohol, and continuously stirring at a rotating speed of 40rpm under a sealed condition until the sodium hydroxide is completely dissolved in the ethyl alcohol to prepare a sodium hydroxide ethanol solution. Mixing the carbon nitride graphite loaded ferrous ethanol solution, the ferric acetylacetonate anisole solution and the sodium hydroxide ethanol solution, fully stirring under a sealed condition, centrifuging at the rotating speed of 9000rmp, drying in vacuum, grinding, and sieving with a 300-mesh sieve to obtain the photocatalyst for removing nitric oxide.
And (3) testing the performance of the nitric oxide photocatalyst: the performance test of the nitric oxide photocatalyst is carried out according to the international standard BS ISO 22197-1: 2016, Fine ceramics (advanced ceramics, advanced technical ceramics) -Test method for air purification performance of chemical catalytic materials-Part 1: removal of nitric oxide was performed, and the amount of nitric oxide removed (μmol) and the amount of nitrogen dioxide generated (μmol) and the percentage of the amount of nitrogen dioxide generated and the amount of nitric oxide removed in the standard were selected as the monitoring and evaluation indexes, and the test results are shown in Table 1.
TABLE 1 influence of ferrous ion, ferric ion, hydroxyl mole ratio on the photocatalyst Performance of nitric oxide
As can be seen from Table 1, for the first group of nitric oxide photocatalysts, when the molar ratio of ferrous ions, ferric ions and hydroxyl is lower than 2: 1:3 (e.g., the molar ratio of ferrous ions, ferric ions and hydroxyl is 1.8: 1:3, 1.5: 1:3, 1:3 and lower ratios not listed in Table 1), the relative amount of ferrous fumarate is less, the surface loading of the graphite carbon nitride particles in the graphite carbon nitride loaded ferrous ethanol solution is less, the amount of green rust material generated is reduced, and Fe is reduced2+/Fe3+The action of ion pairs on accelerating the transfer of photo-generated electrons to oxygen molecules is weakened, the recombination probability of the photo-generated electrons and the photo-generated holes is increased, and the nitric oxide oxidation rate is increased along with the moleThe ratio decreases gradually. Meanwhile, the reduction of the green rust product weakens the adsorption effect of nitrogen oxide and oxygen, and photoproduction electrons cannot be effectively transferred to oxygen molecules, so that the percentage ratio of the generation amount of nitrogen dioxide to the removal amount of nitric oxide is higher than 44%, and the generation amount and the removal amount of nitric oxide gradually increase along with the reduction of the molar ratio; when the molar ratio of ferrous ions, ferric ions and hydroxide radicals is 2-3: 1:3, the relative addition amount of ferrous fumarate is proper, the green rust doped with butenedioic acid radicals and the green rust doped with acetylacetone radicals can be effectively loaded on the surface of the graphite carbon nitride particles, and Fe2+/Fe3+The ion pair effect is obvious, in the photocatalytic oxidation process, nitric oxide and oxygen are effectively adsorbed on patina particles, and inorganic nitrogen salt and part of nitrogen dioxide migrate in time, so that the removal amount of the nitric oxide is higher than 26 mu mol, and the generation amount of the nitrogen dioxide is lower than 8.5 mu mol; when the molar ratio of ferrous ions, ferric ions and hydroxyl ions is higher than 3:1:3 (for example, in table 1, the molar ratio of ferrous ions, ferric ions and hydroxyl ions is 3.2: 1:3, 3.5: 1:3, 4:1: 3 and higher ratios not listed in table 1), the relative addition amount of the ferrous fumarate is too high, the effective active sites on the surface of the patina are reduced, and too much ferrous ions shield the catalytic oxidation effect of photogenerated holes on the nitric oxide. Meanwhile, excessive ferrous ions and photo-generated electrons compete for oxygen, so that the recombination probability of the photo-generated electrons and photo-generated holes is increased, the removal amount of nitric oxide is gradually reduced along with the further increase of the molar ratio, and the percentage of the generation amount of nitrogen dioxide and the removal amount of nitric oxide is remarkably improved along with the further increase of the molar ratio. Therefore, in summary, the benefit and the cost are combined, and when the molar ratio of the ferrous ions to the ferric ions to the hydroxyl is 2-3: 1:3, the performance of the nitric oxide photocatalyst is most favorably improved.
As can be seen from Table 1, for the second group of nitric oxide photocatalysts, when the molar ratio of ferrous ions, ferric ions and hydroxyl ions is lower than 3:1:3 (as shown in Table 1, the molar ratio of ferrous ions, ferric ions and hydroxyl ions is 3:1: 2.8, 3:1: 2.5, 3:1: 2 and lower ratios not listed in Table 1), the relative addition amount of ferric acetylacetonate is less, the effective active sites on the surface of the patina are reduced, and the relative addition amount of ferric acetylacetonate is less than that of the effective active sites on the surface of the patinaExcessive ferrous ions shield the catalytic oxidation effect of photoproduction holes on nitric oxide and compete for oxygen with photoproduction electrons, so that the recombination probability of the photoproduction electrons and the photoproduction holes is increased, the removal amount of nitric oxide is gradually reduced along with the reduction of the molar ratio, and the percentage of the generation amount of nitrogen dioxide and the removal amount of nitric oxide is increased along with the reduction of the molar ratio; when the molar ratio of ferrous ions, ferric ions and hydroxyl ions is equal to 3:1: 3-5, the relative addition amount of the iron acetylacetonate is appropriate, the butenedioic acid radical-doped patina and the acetylacetone radical-doped patina can be effectively loaded on the surface of the graphite carbon nitride particles, and Fe2+/Fe3 +The ion pair effect is obvious, in the photocatalytic oxidation process, nitric oxide and oxygen are effectively adsorbed on the patina particles, and inorganic nitrogen salt and part of nitrogen dioxide migrate to the interior of the patina particles in time, so that the removal amount of the nitric oxide is higher than 29 mu mol, and the generation amount of the nitrogen dioxide is lower than 8.2 mu mol; when the molar ratio of ferrous ions, ferric ions and hydroxyl ions is higher than 3:1: 5 (as shown in Table 1, the molar ratio of ferrous ions, ferric ions and hydroxyl ions is 3:1: 5.2, 3:1: 5.5, 3:1: 6 and higher ratios not listed in Table 1), the relative addition amount of ferric acetylacetonate is too high, the generation amount of magnetic iron material is increased, the generation amount of amorphous patina material is reduced, and Fe is more than 12+/Fe3+The ion pair has the advantages that the effect of accelerating the transfer of the photo-generated electrons to the oxygen molecules is weakened, the recombination probability of the photo-generated electrons and the photo-generated holes is increased, the adsorption effect of the nitrogen oxide and the oxygen is weakened, the photo-generated electrons cannot be effectively transferred to the oxygen molecules, the removal amount of the nitrogen oxide is gradually reduced along with the further increase of the molar ratio, and the percentage of the generation amount of the nitrogen dioxide and the removal amount of the nitrogen oxide is remarkably improved along with the further increase of the molar ratio. Therefore, in summary, the efficiency and the cost are combined, and when the molar ratio of the ferrous ions to the ferric ions to the hydroxyl ions is equal to 3:1: 3-5, the performance of the nitric oxide photocatalyst is most favorably improved.
Example 2 Effect of graphitic carbon nitride and ferrous fumarate EtOH solution solid-liquid ratio on the photocatalyst Performance of nitric oxide
Preparation of nitric oxide photocatalyst: ferrous fumarate, ferric acetylacetonate powder and sodium hydroxide are respectively weighed according to the molar ratio of ferrous ions, ferric ions and hydroxide radicals of 3:1: 5. Mixing ferrous fumarate into absolute ethanol according to the solid-liquid ratio of 1: 10mmol/mL, and continuously stirring at the rotating speed of 60rpm under a sealed condition until the ferrous fumarate is completely dissolved in the ethanol to prepare a ferrous fumarate ethanol solution. Respectively weighing the graphite carbon nitride according to the solid-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution of 1:0.5 mg/mL, 1: 0.7mg/mL, 1: 0.9mg/mL, 1: 1mg/mL, 1: 2mg/mL, 1: 3mg/mL, 1: 3.2mg/mL, 1: 3.5mg/mL and 1: 4mg/mL, mixing the graphite carbon nitride with the ferrous fumarate ethanol solution, and continuously stirring the mixture uniformly at the rotating speed of 60rpm under the sealed condition to obtain the graphite carbon nitride loaded ferrous alcohol solution. And (3) mixing a corresponding amount of ferric acetylacetonate into anisole with the same volume, and continuously stirring at the rotating speed of 60rpm under a sealed condition until the ferric acetylacetonate is completely dissolved in the anisole to prepare the ferric acetylacetonate anisole solution. And (3) mixing a corresponding amount of sodium hydroxide into absolute ethyl alcohol, and continuously stirring at the rotating speed of 60rpm under a sealed condition until the sodium hydroxide is completely dissolved in the ethyl alcohol to prepare a sodium hydroxide ethyl alcohol solution. Mixing the carbon nitride graphite loaded ferrous ethanol solution, the ferric acetylacetonate anisole solution and the sodium hydroxide ethanol solution, fully stirring under a sealed condition, centrifuging at the rotating speed of 12000rmp, drying in vacuum, grinding and sieving by a 400-mesh sieve to obtain the photocatalyst for removing the nitric oxide.
And (3) testing the performance of the nitric oxide photocatalyst: the performance test of the nitric oxide photocatalyst is carried out according to the international standard BS ISO 22197-1: 2016, Fine ceramics (advanced ceramics, advanced technical ceramics) -Test method for air purification performance of chemical catalytic materials-Part 1: removal of nitric oxide is performed, the Removal amount of nitric oxide (mu mol) and the generation amount of nitrogen dioxide (mu mol) in the standard and the percentage of the generation amount of nitrogen dioxide and the Removal amount of nitric oxide are selected as monitoring and evaluating indexes, and the test results are shown in Table 2.
TABLE 2 influence of graphitic carbon nitride and ferrous fumarate ethanolic solid-liquid ratio on the photocatalyst performance of nitric oxide
As can be seen from Table 2, when the solid-liquid ratio of the graphitic carbon nitride to the ethanol solution of ferrous fumarate is less than 1: 1mg/mL (as shown in Table 2, the solid-liquid ratio of the graphitic carbon nitride to the ethanol solution of ferrous fumarate is 1: 0.9mg/mL, 1: 0.7mg/mL, 1:0.5 mg/mL and lower ratios not listed in Table 2), the loading of the fumarate-doped patina and the acetylacetonate-doped patina on the surface of the graphitic carbon nitride particles, in the cracks and in the cavities of the particles during the preparation of the catalyst is insufficient, the reduction of the electronic band gap energy (eV) of the graphitic carbon nitride is less, the activation performance of the catalyst under visible light irradiation is limited, and the Fe is not enhanced2 +/Fe3+The ion pair has the advantages that the effect of accelerating the transfer of the photo-generated electrons to oxygen molecules is weakened, the recombination probability of the photo-generated electrons and the photo-generated holes is increased, the adsorption effect of nitrogen oxide and oxygen is weakened, the photo-generated electrons cannot be effectively transferred to the oxygen molecules, the removal amount of the nitrogen oxide is gradually reduced along with the reduction of the solid-liquid ratio, the percentage ratio of the generation amount of the nitrogen dioxide to the removal amount of the nitrogen oxide is higher than 28%, and the percentage ratio of the generation amount of the nitrogen dioxide to the removal amount of the nitrogen oxide is gradually improved along with the reduction of the solid-liquid ratio. When the solid-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution is 1: 1-3 mg/mL, the fumaric acid radical-doped patina and the acetylacetone radical-doped patina are fully loaded on the surfaces of the graphite carbon nitride particles, particle cracks and cavities in the preparation process of the catalyst, and Fe2+/Fe3+The ion pair effect is obvious, in the photocatalytic oxidation process, nitric oxide and oxygen are effectively adsorbed on the patina particles, and inorganic nitrogen salt and part of nitrogen dioxide migrate to the interior of the patina particles in time, so that the removal amount of the nitric oxide is higher than 33 mu mol, and the generation amount of the nitrogen dioxide is lower than 7.7 mu mol; when the solid-to-liquid ratio of the graphitic carbon nitride to the ethanol solution of ferrous fumarate is higher than 1: 3mg/mL (as shown in Table 2, the solid-to-liquid ratio of the graphitic carbon nitride to the ethanol solution of ferrous fumarate is 1: 3.2mg/mL, 1: 3.5mg/mL, 1: 4mg/mL and higher ratios not listed in Table 2), the catalyst is prepared by the process of preparing the catalystThe root-doped patina and the acetylacetonate root-doped patina were sufficiently loaded on the surface of the graphite carbon nitride particles, in the cracks and cavities of the particles, but the removal amount of nitric oxide and the generation amount of nitrogen dioxide did not significantly change with further increase in the solid-to-liquid ratio. Therefore, in summary, the benefit and the cost are combined, and when the solid-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution is equal to 1: 1-3 mg/mL, the improvement of the performance of the nitric oxide photocatalyst is facilitated.
Example 3 comparison of the performance of graphite carbon nitride, the photocatalyst prepared in the absence of iron acetylacetonate powder, and the photocatalyst prepared in the presence of nitric oxide
Preparation of nitric oxide photocatalyst: ferrous fumarate, ferric acetylacetonate powder and sodium hydroxide are respectively weighed according to the molar ratio of ferrous ions, ferric ions and hydroxide radicals of 3:1: 5. Mixing ferrous fumarate into absolute ethanol according to the solid-liquid ratio of 1: 10mmol/mL, and continuously stirring at the rotating speed of 60rpm under a sealed condition until the ferrous fumarate is completely dissolved in the ethanol to prepare a ferrous fumarate ethanol solution. Weighing the graphite carbon nitride according to the solid-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution of 1: 3mg/mL, mixing the graphite carbon nitride with the ferrous fumarate ethanol solution, and continuously and uniformly stirring at the rotating speed of 60rpm under a sealed condition to obtain the graphite carbon nitride loaded ferrous ethanol solution. And (3) mixing a corresponding amount of ferric acetylacetonate into anisole with the same volume, and continuously stirring at the rotating speed of 60rpm under a sealed condition until the ferric acetylacetonate is completely dissolved in the anisole to prepare the ferric acetylacetonate anisole solution. And (3) mixing a corresponding amount of sodium hydroxide into absolute ethyl alcohol, and continuously stirring at the rotating speed of 60rpm under a sealed condition until the sodium hydroxide is completely dissolved in the ethyl alcohol to prepare a sodium hydroxide ethyl alcohol solution. Mixing the carbon nitride graphite loaded ferrous ethanol solution, the ferric acetylacetonate anisole solution and the sodium hydroxide ethanol solution, fully stirring under a sealed condition, centrifuging at the rotating speed of 12000rmp, drying in vacuum, grinding and sieving by a 400-mesh sieve to obtain the photocatalyst for removing the nitric oxide.
Photocatalyst preparation lacking iron acetylacetonate: ferrous fumarate and sodium hydroxide are weighed according to the molar ratio of ferrous ions to hydroxyl being 3: 5 respectively. Mixing ferrous fumarate into ethanol according to the solid-liquid ratio of 1: 5mmol/mL, and continuously stirring at the rotating speed of 60rpm under a sealed condition until the ferrous fumarate is completely dissolved in the ethanol to prepare a ferrous fumarate ethanol solution. Weighing the graphite carbon nitride according to the solid-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution of 1: 3mg/mL, mixing the graphite carbon nitride with the ferrous fumarate ethanol solution, and continuously and uniformly stirring at the rotating speed of 60rpm under a sealed condition to obtain the graphite carbon nitride loaded ferrous ethanol solution. And (3) mixing a corresponding amount of sodium hydroxide into ethanol, and continuously stirring at the rotating speed of 60rpm under a sealed condition until the sodium hydroxide is completely dissolved in the ethanol to prepare a sodium hydroxide ethanol solution. Mixing the carbon nitride graphite loaded ferrous ethanol solution and the sodium hydroxide ethanol solution, fully stirring under a sealed condition, centrifuging at a rotating speed of 12000rmp, drying in vacuum, grinding and sieving with a 400-mesh sieve to obtain the photocatalyst for removing nitric oxide.
And (3) testing the performance of the nitric oxide photocatalyst: graphite carbon nitride, the photocatalyst prepared without iron acetylacetonate powder, and the nitrogen monoxide photocatalyst performance test of the photocatalyst prepared are in accordance with the international standard BS ISO 22197-1: 2016, Fine ceramics (advanced ceramics, advanced technical ceramics) -Test method for air purification performance of chemical catalytic materials-Part 1: removal of nitric oxide was performed, and the amount of NO removed (μmol) and the amount of NO generated (μmol) and the percentage of NO generated and NO removed in the standard were selected as the monitoring and evaluation indexes, and the test results are shown in Table 3.
TABLE 3 comparison of the performance of graphitic carbon nitride, prepared photocatalyst lacking iron acetylacetonate powder, prepared photocatalyst for nitric oxide
As can be seen from Table 3, the amounts of nitrogen monoxide removed from the graphite carbon nitride, the photocatalyst prepared without the iron acetylacetonate powder, and the photocatalyst prepared were 16.43. mu. mol, 18.21. mu. mol, and 37.18. mu. mol, respectively, and the percentages of the amounts of nitrogen dioxide produced and nitrogen monoxide removed were 50.21%, 49.53%, and 16.62%, respectively. Compared with graphite carbon nitride and the prepared photocatalyst lacking ferric acetylacetonate powder, the photocatalyst prepared by improving the graphite carbon nitride can obviously improve the removal amount of nitric oxide, reduce the generation amount of nitrogen dioxide and the removal amount percentage of the nitric oxide and improve the safety of the nitric oxide in the photocatalytic oxidation process.
Claims (9)
1. A photocatalyst for removing nitric oxide, which is characterized by being mainly prepared from the following components: the preparation method comprises the following steps of:
1) weighing ferrous fumarate, ferric acetylacetonate powder and sodium hydroxide according to the molar ratio of ferrous ions, ferric ions and hydroxyl ions of 1-4: 1: 2-6 respectively;
2) mixing ferrous fumarate into absolute ethanol according to the solid-to-liquid ratio of 1: 5-10 mmol/mL, and continuously stirring under a sealed condition until the ferrous fumarate is completely dissolved in the absolute ethanol to prepare a ferrous fumarate ethanol solution;
3) weighing the graphite carbon nitride according to the solid-to-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution of 1: 0.5-4 mg/mL, mixing the graphite carbon nitride with the ferrous fumarate ethanol solution, and continuously and uniformly stirring under a sealed condition to obtain a graphite carbon nitride loaded ferrous ethanol solution;
4) mixing a corresponding amount of ferric acetylacetonate into anisole with the same volume, and continuously stirring under a sealed condition until the ferric acetylacetonate is completely dissolved in the anisole to prepare ferric acetylacetonate anisole solution;
5) mixing a corresponding amount of sodium hydroxide into absolute ethyl alcohol, continuously stirring under a sealed condition until the sodium hydroxide is completely dissolved in the ethyl alcohol, and preparing a sodium hydroxide ethanol solution;
6) mixing the carbon nitride graphite loaded ferrous ethanol solution, the ferric acetylacetonate anisole solution and the sodium hydroxide ethanol solution, fully stirring under a sealed condition, centrifuging, drying in vacuum, and grinding to obtain the photocatalyst for removing the nitric oxide.
2. The photocatalyst for removing nitric oxide according to claim 1, wherein the molar ratio of ferrous ions, ferric ions and hydroxyl groups is 2-3: 1: 3-5, and the solid-to-liquid ratio of the graphitic carbon nitride to the ferrous fumarate ethanol solution is 1: 1-3 mg/mL.
3. A method for preparing a photocatalyst for removing nitric oxide according to any one of claims 1 or 2, comprising the steps of:
1) weighing ferrous fumarate, ferric acetylacetonate powder and sodium hydroxide according to the molar ratio of ferrous ions, ferric ions and hydroxyl ions of 1-4: 1: 2-6 respectively;
2) mixing ferrous fumarate into absolute ethanol according to the solid-to-liquid ratio of 1: 5-10 mmol/mL, and continuously stirring under a sealed condition until the ferrous fumarate is completely dissolved in the absolute ethanol to prepare a ferrous fumarate ethanol solution;
3) weighing the graphite carbon nitride according to the solid-to-liquid ratio of the graphite carbon nitride to the ferrous fumarate ethanol solution of 1: 0.5-4 mg/mL, mixing the graphite carbon nitride with the ferrous fumarate ethanol solution, and continuously and uniformly stirring under a sealed condition to obtain a graphite carbon nitride loaded ferrous ethanol solution;
4) mixing a corresponding amount of ferric acetylacetonate into anisole with the same volume, and continuously stirring under a sealed condition until the ferric acetylacetonate is completely dissolved in the anisole to prepare ferric acetylacetonate anisole solution;
5) mixing a corresponding amount of sodium hydroxide into absolute ethyl alcohol, continuously stirring under a sealed condition until the sodium hydroxide is completely dissolved in the ethyl alcohol, and preparing a sodium hydroxide ethanol solution;
6) mixing the carbon nitride graphite loaded ferrous ethanol solution, the ferric acetylacetonate anisole solution and the sodium hydroxide ethanol solution, fully stirring under a sealed condition, centrifuging, drying in vacuum, and grinding to obtain the photocatalyst for removing the nitric oxide.
4. The method for preparing the photocatalyst for removing nitric oxide according to claim 3, wherein the stirring speed in the step 2) is 20 to 60 rpm.
5. The method for preparing the photocatalyst for removing nitric oxide according to claim 3, wherein the stirring speed in the step 3) is 20 to 60 rpm.
6. The method for preparing the photocatalyst for removing nitric oxide according to claim 3, wherein the stirring speed in the step 4) is 20 to 60 rpm.
7. The method for preparing the photocatalyst for removing nitric oxide according to claim 3, wherein the stirring speed in the step 5) is 20 to 60 rpm.
8. The method for preparing the photocatalyst for removing nitric oxide according to claim 3, wherein the centrifugation rate in step 6) is 6000 to 1200 rpm.
9. The method for preparing the photocatalyst for removing nitric oxide according to claim 3, wherein the step 6) is performed by sieving with a 200-400 mesh sieve after grinding.
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