CN115779941A - Bismuth oxycarbonate-nickel-iron hydrotalcite composite photocatalyst and preparation method and application thereof - Google Patents
Bismuth oxycarbonate-nickel-iron hydrotalcite composite photocatalyst and preparation method and application thereof Download PDFInfo
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- CN115779941A CN115779941A CN202211487912.7A CN202211487912A CN115779941A CN 115779941 A CN115779941 A CN 115779941A CN 202211487912 A CN202211487912 A CN 202211487912A CN 115779941 A CN115779941 A CN 115779941A
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- nickel
- bismuth
- composite photocatalyst
- carbonate
- iron hydrotalcite
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 61
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 61
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 61
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 33
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910000863 Ferronickel Inorganic materials 0.000 claims abstract description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 4
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims description 43
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 claims description 32
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 150000001621 bismuth Chemical class 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229940036358 bismuth subcarbonate Drugs 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- QSBNOZODKXUXSP-UHFFFAOYSA-K bismuth;azane;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound N.[Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QSBNOZODKXUXSP-UHFFFAOYSA-K 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 2
- 239000001095 magnesium carbonate Substances 0.000 claims description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000005215 recombination Methods 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 14
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- MQYRLAZBVBHGDU-UHFFFAOYSA-J iron(2+) nickel(2+) dicarbonate Chemical compound C([O-])([O-])=O.[Ni+2].[Fe+2].C([O-])([O-])=O MQYRLAZBVBHGDU-UHFFFAOYSA-J 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a bismuth oxycarbonate-nickel-iron hydrotalcite composite photocatalyst and a preparation method and application thereof. The bismuth oxycarbonate-ferronickel hydrotalcite composite photocatalyst can inhibit photoproduction electron-hole recombination, improve the reaction activity of photocatalytic degradation of NO, and effectively inhibit the generation of intermediate toxic byproducts.
Description
Technical Field
The invention relates to the field of photocatalysts, in particular to a bismuth oxycarbonate-nickel-iron hydrotalcite composite photocatalyst and a preparation method thereof, and also relates to an application of the bismuth oxycarbonate-nickel-iron hydrotalcite composite photocatalyst.
Background
With the rapid development of modern industry and agriculture, the air pollution problem is increasingly serious. For example, a large amount of nitrogen oxides (NOx) discharged from the fields of industry, manufacturing industry, automobile exhaust and the like can cause serious photochemical smog, large-area ozone layer cavities, acid rain, haze and the like. On one hand, the air pollution can stimulate the mucosa of human beings and animals to generate a series of toxicological reactions, thereby causing great harm to human beings; on the other hand, an ozone cavity is formed, so that ultraviolet rays and X rays are directly emitted to the earth surface, the building corrosion is aggravated, the visibility is reduced, the air quality is greatly influenced, and the normal work and life of people are hindered.
Conventional industrial denitrification strategies (e.g., selective catalytic reduction and non-selective catalytic reduction) can effectively remove high concentrations of nitrogen oxides, but still leave a portion of low concentrations of NO (less than 1 ppm) remaining. When NO and O 2 When in contact, they are oxidized into nitrogen dioxide, which is a serious health hazard. Therefore, a new method for effectively removing NOx is urgently required.
It has been reported that bismuth oxycarbonate photocatalysis can be used for removing low concentration of NOx, but the following problems still exist: the wider band gap limits the effective utilization of sunlight; the photoproduction electron-hole recombination rate is high; toxic by-products are produced during the reaction. Therefore, how to improve the bismuth oxycarbonate photocatalyst leads to the technical problem which needs to be solved urgently.
Disclosure of Invention
In view of the above, the invention aims to provide a bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst, and a preparation method and an application thereof, which can inhibit photoproduction electron-hole recombination, improve the reaction activity of photocatalytic degradation of NO, and effectively inhibit the generation of intermediate toxic byproducts.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a bismuth oxycarbonate-nickel-iron hydrotalcite composite photocatalyst, which contains bismuth oxycarbonate and nickel-iron hydrotalcite, wherein the nickel-iron hydrotalcite grows on the bismuth oxycarbonate in situ.
As a preferred technical scheme, the bismuth oxycarbonate is in the shape of petal-shaped microspheres, and the nickel-iron hydrotalcite is in the shape of nanosheets.
As a preferable technical scheme, the mass ratio of the bismuth oxycarbonate to the nickel-iron hydrotalcite in the bismuth oxycarbonate-nickel-iron hydrotalcite composite photocatalyst is 1.0-0.1.
The invention also provides a preparation method of the bismuthyl carbonate-ferronickel hydrotalcite composite photocatalyst, which comprises the following steps:
(1) Mixing bismuth salt and carbonate, dissolving in water, performing hydrothermal reaction, separating precipitate after full reaction, washing with water, and drying to obtain bismuthyl carbonate;
(2) Dispersing the bismuthyl carbonate obtained in the step (1) in an aqueous solution containing a crystal transfer agent, then adding an iron salt and a nickel salt, adding an alkaline solution into the obtained mixed solution, then carrying out a coprecipitation reaction, separating a precipitate after the full reaction, washing with water, and drying to obtain the bismuthyl carbonate-ferronickel hydrotalcite composite photocatalyst.
As a preferred technical scheme, in the step (1), the bismuth salt is one or a mixture of bismuth citrate, ammonium bismuth citrate, bismuth nitrate and bismuth chloride; the carbonate is one or more of sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate and magnesium carbonate.
As a preferred technical scheme, in the step (2), the ferric salt is one or a mixture of ferric nitrate, ferric chloride and ferric sulfate; the nickel salt is one or a mixture of nickel nitrate, nickel sulfate, nickel chloride and nickel sulfamate; the crystal transformation agent is one or a mixture of amino acid and formamide; the alkaline solution is sodium hydroxide or potassium hydroxide solution.
In the step (1), the molar ratio of the bismuth salt to the carbonate is 1.00 to 1.05; in the step (2), the molar ratio of the ferric salt to the nickel salt is 1:1-4.
In a preferable technical scheme, in the step (1), the hydrothermal reaction temperature is 150-170 ℃; in the step (2), the coprecipitation reaction temperature is 70-80 ℃.
In the step (2), the pH value of the solution is dynamically maintained at 9.5-10.5 by dropwise adding an alkaline solution during the reaction.
The invention also provides application of the bismuthyl carbonate-ferronickel hydrotalcite composite photocatalyst in photocatalytic degradation of NO.
The invention has the beneficial effects that: the photocatalyst is formed by growing the nickel-iron hydrotalcite on the bismuth subcarbonate in situ, has large interface combination area and higher interface quality, greatly inhibits the recombination of photoproduction electrons and holes, and optimizes the charge transfer performance; moreover, the surface of the nickel-iron hydrotalcite is rich in active hydroxyl, and the active hydroxyl can be converted into hydroxyl free radicals with high oxidation capacity under the excitation of visible light. When the bismuth oxycarbonate-ferronickel hydrotalcite composite photocatalyst is applied to removing NO in the air, the composite photocatalyst shows higher reaction activity, can effectively inhibit the generation of intermediate toxic byproducts, and has higher application value.
Drawings
In order to make the purpose, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is an SEM image of bismuth oxycarbonate prepared in comparative example 1;
FIG. 2 is an SEM image of bismuth oxycarbonate-nickel iron hydrotalcite prepared in example 1;
FIG. 3 is an XRD pattern of bismuth oxycarbonate prepared in comparative example 1 and bismuth oxycarbonate-nickel iron hydrotalcite prepared in example 1;
FIG. 4 is a PL diagram of bismuth oxycarbonate prepared in comparative example 1 and bismuth oxycarbonate-nickel iron hydrotalcite prepared in example 1;
FIG. 5 is a graph comparing the effect of bismuth oxycarbonate prepared in comparative example 1 and bismuth oxycarbonate-nickel iron hydrotalcite prepared in example 1 when applied to NO removal in the atmosphere;
FIG. 6 shows the application of bismuthyl carbonate prepared in comparative example 1 and bismuthyl carbonate-ferronickel hydrotalcite prepared in example 1 in the removal of NO in airGeneration of NO 2 A comparative graph of (a).
Detailed Description
The present invention is further described below in conjunction with the drawings and the embodiments so that those skilled in the art can better understand the present invention and can implement the present invention, but the embodiments are not to be construed as limiting the present invention.
Example 1: preparation of bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst (recorded as BOC/NiFe-LDH)
The method for preparing the bismuthyl carbonate-nickel-iron hydrotalcite composite photocatalyst comprises the following specific steps:
(1) Dissolving 5mmol of bismuth citrate and 5.5mmol of sodium carbonate in 65ml of deionized water, magnetically stirring for 30min, and transferring into a 100ml polytetrafluoroethylene liner;
(2) Moving the polytetrafluoroethylene inner container to a hydrothermal kettle, and carrying out sealed reaction for 24 hours at 160 ℃;
(3) Washing the obtained product with deionized water for 3 times, and drying in a drying oven at 60 ℃ overnight to obtain Bismuth Oxycarbonate (BOC);
(4) Weighing 5g of BOC, dissolving in 32ml of deionized water, adding 8ml of formamide, and performing ultrasonic treatment for 20min;
(5) Dropwise adding 40ml of mixed solution containing 4.0mmol of nickel nitrate hexahydrate and 2.0mmol of ferric nitrate nonahydrate into the BOC-containing formamide solution at the temperature of 80 ℃, dropwise adding 3M sodium hydroxide at the same time to keep the pH value of the mixed solution at about 10, and carrying out coprecipitation reaction at 70 ℃ for 15min;
(6) And after the reaction is finished, carrying out suction filtration and separation on the solid precipitate, washing with water for 3 times, and drying in an oven at 60 ℃ overnight to obtain the bismuthyl carbonate-ferronickel hydrotalcite composite photocatalyst.
Comparative example 1: preparation of bismuth oxycarbonate (denoted BOC)
(1) Dissolving 5.0mmol of bismuth citrate and 5.5mmol of sodium carbonate in 65ml of deionized water, magnetically stirring for 30min, and transferring into a 100ml polytetrafluoroethylene liner;
(2) Moving the polytetrafluoroethylene inner container to a hydrothermal kettle, and carrying out sealed reaction for 24 hours at 160 ℃;
(3) The obtained product is washed by deionized water for 3 times and then dried in a drying box at 60 ℃ overnight to obtain the BOC.
Fig. 1 is an SEM image of bismuth oxycarbonate prepared in comparative example 1, and it can be seen that bismuth oxycarbonate is a petal-shaped microsphere self-assembled from smooth nanosheets, and the diameter thereof is about 1 μm.
Fig. 2 is an SEM image of bismuth subcarbonate-nickel iron hydrotalcite prepared in example 1, and unlike the original petal-shaped bismuth subcarbonate microspheres, the surface of the compounded material petals is no longer smooth, and many attachments of nickel iron hydrotalcite nanosheets appear.
Fig. 3 is XRD patterns of bismuth oxycarbonate prepared in comparative example 1 and bismuth oxycarbonate-nickel iron hydrotalcite prepared in example 1, and the results show that the three main diffraction peaks of bismuth oxycarbonate prepared in comparative example 1 are 24.02, 30.07, 32.89, which is consistent with the standard card correspondence of bismuth oxycarbonate, and no miscellaneous peaks of other substances appear; the bismuth oxycarbonate-nickel iron hydrotalcite prepared in example 1 has no diffraction peak of hydrotalcite after being compounded, which is mainly because the nickel iron hydrotalcite has less compounding amount, low crystallinity and more coincident characteristic peak positions with bismuth oxycarbonate, so that the bismuth oxycarbonate can easily cover the diffraction peak.
Fig. 4 is a PL diagram of bismuth subcarbonate prepared in comparative example 1 and bismuth subcarbonate-nickel-iron hydrotalcite prepared in example 1, and the results show that the signal intensity of bismuth subcarbonate is much higher than that of bismuth subcarbonate-nickel-iron hydrotalcite, so that the bismuth subcarbonate-nickel-iron hydrotalcite composite photocatalysis can significantly inhibit the recombination of photogenerated electrons and holes.
Example 2: application of bismuthyl carbonate-ferronickel hydrotalcite composite photocatalyst
The bismuthyl carbonate prepared in the comparative example 1 and the bismuthyl carbonate-nickel iron hydrotalcite prepared in the example 1 are used as photocatalysts and applied to the removal of NO pollutants in the air under visible light, and the specific method is as follows:
(1) Putting a certain amount of bismuthyl carbonate or bismuthyl carbonate-nickel iron hydrotalcite into two 50 x 50 glass dishes, adding a proper amount of ethanol, ultrasonically dissolving, rotationally spreading, and finally drying in an oven at 60 ℃.
(2) Two glass dishes were taken out and put into a sealed transparent rectangular reactor (4.5L, 30cm. Times.15 cm. Times.10 cm), and then a mixed gas of NO (22.4 mL/min) and an air stream (2.4 mL/min) was introduced, and the concentration of NO after dilution was maintained at 500ppb, the detection limit was 0 to 20000ppb, and the accuracy was 0.001ppb.
(3) After the gas flow was stabilized, a 150W commercial tungsten halogen lamp was turned on and the NO removal efficiency in the system was monitored by real-time NO concentration measurement.
(4) The removal activity of the photocatalyst for NO is obtained by the following formula:
wherein: eta is the removal rate of NO in the system when the photocatalytic reaction is carried out to the time t, C 0 Is the initial concentration of NO; c t All concentration units are ppb for NO at time t.
For example, as shown in fig. 5, the using effect of the bismuthyl carbonate prepared in comparative example 1 and the bismuthyl carbonate-ferronickel hydrotalcite prepared in example 1 when applied to removal of NO in air is that the ferronickel hydrotalcite has almost NO removal activity, the NO removal efficiency of the bismuthyl carbonate is 24%, and the NO removal efficiency of the bismuthyl carbonate-ferronickel hydrotalcite is increased to 52%.
When the bismuthyl carbonate prepared in comparative example 1 and the bismuthyl carbonate-nickel-iron hydrotalcite prepared in example 1 are applied to the removal of NO in the air, an intermediate toxic byproduct NO is generated 2 The comparison of (A) and (B) is shown in fig. 6, and the result shows that the bismuth oxycarbonate-nickel iron hydrotalcite not only improves the removal activity of NO, but also inhibits the poisoning by-product NO in the reaction process 2 Is generated.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst is characterized in that: the bismuth oxycarbonate-nickel-iron hydrotalcite composite photocatalyst contains bismuth oxycarbonate and nickel-iron hydrotalcite, and the nickel-iron hydrotalcite grows on the bismuth oxycarbonate in situ.
2. The bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst according to claim 1, characterized in that: the shape of the bismuthyl carbonate is petal-shaped microspheres, and the shape of the nickel-iron hydrotalcite is nanosheet.
3. The bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst according to claim 1 or 2, which is characterized in that: the mass ratio of the bismuth subcarbonate to the nickel-iron hydrotalcite in the bismuth subcarbonate-nickel-iron hydrotalcite composite photocatalyst is 1.0-0.1.
4. The preparation method of the bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst of any one of claims 1 to 3, which is characterized by comprising the following steps: the method comprises the following steps:
(1) Mixing bismuth salt and carbonate, dissolving in water, performing hydrothermal reaction, separating precipitate after full reaction, washing with water, and drying to obtain bismuthyl carbonate;
(2) Dispersing the bismuthyl carbonate obtained in the step (1) in an aqueous solution containing a crystal transfer agent, then adding an iron salt and a nickel salt, adding an alkaline solution into the obtained mixed solution, then carrying out a coprecipitation reaction, separating a precipitate after the full reaction, washing with water, and drying to obtain the bismuthyl carbonate-ferronickel hydrotalcite composite photocatalyst.
5. The preparation method of the bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst according to claim 4, which is characterized in that: in the step (1), the bismuth salt is one or a mixture of bismuth citrate, ammonium bismuth citrate, bismuth nitrate and bismuth chloride; the carbonate is one or more of sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate and magnesium carbonate.
6. The preparation method of the bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst according to claim 4, which is characterized in that: in the step (2), the ferric salt is one or a mixture of ferric nitrate, ferric chloride and ferric sulfate; the nickel salt is one or a mixture of nickel nitrate, nickel sulfate, nickel chloride and nickel sulfamate; the crystal transformation agent is one or a mixture of amino acid and formamide; the alkaline solution is sodium hydroxide or potassium hydroxide solution.
7. The preparation method of the bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst according to claim 4, which is characterized in that: in the step (1), the molar ratio of the bismuth salt to the carbonate is 1.00; in the step (2), the molar ratio of the ferric salt to the nickel salt is 1:1-4.
8. The preparation method of the bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst according to claim 4, which is characterized in that: in the step (1), the hydrothermal reaction temperature is 150-170 ℃; in the step (2), the coprecipitation reaction temperature is 70-80 ℃.
9. The preparation method of the bismuth oxycarbonate-nickel iron hydrotalcite composite photocatalyst according to claim 4, which is characterized in that: in the step (2), the pH value of the solution is dynamically maintained at 9.5-10.5 by dropwise adding an alkaline solution in the reaction process.
10. Use of the bismuthyl carbonate-ferronickel hydrotalcite composite photocatalyst according to any one of claims 1 to 3 in photocatalytic degradation of NO.
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