CN109433273B - Photocatalyst NiGa2O4/AQ/MoO3And preparation method and application thereof - Google Patents
Photocatalyst NiGa2O4/AQ/MoO3And preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 156
- 230000001699 photocatalysis Effects 0.000 claims abstract description 39
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 28
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 93
- 150000004056 anthraquinones Chemical class 0.000 claims description 93
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 229910052724 xenon Inorganic materials 0.000 claims description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- 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 3
- 238000009835 boiling Methods 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 24
- 238000000926 separation method Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 238000012546 transfer Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 230000027756 respiratory electron transport chain Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
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- 239000013078 crystal Substances 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002826 nitrites Chemical class 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
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- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
The invention relates to a photocatalyst NiGa2O4/AQ/MoO3And a preparation method and application thereof, belonging to the technical field of photocatalysts. The invention adopts a hydrothermal method to prepare NiGa2O4/AQ/MoO3Mixing nano NiGa2O4AQ and nano MoO3Adding into anhydrous ethanol, ultrasonically dispersing, heating and boiling the obtained suspension, keeping the temperature constant for 30min, filtering, drying the obtained filtrate for 8.0h, and grinding the powder to obtain NiGa2O4/AQ/MoO3. NiGa prepared by the invention2O4/AQ/MoO3The composite material shows high-efficiency and stable photocatalytic activity in the process of converting nitrite and sulfite, and has wide application prospect in the treatment of nitrite and sulfite wastewater.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to a photocatalyst NiGa2O4/AQ/MoO3And a preparation method and application thereof.
Background
Nitrites and sulfites are widely used as food additives in various fields of food processing. However, nitrite has certain toxicity, and the discharge of waste water containing excessive nitrite into water body can cause metabolic dysfunction and immunity reduction of aquatic organisms, so that the aquatic organisms suffer from pathological changes and even die. Discharge of waste water containing excess sulfite into a water body may cause serious damage to the nervous system and respiratory system of aquatic animals. Therefore, the removal of nitrites and sulfites from industrial wastewater is important to maintain a balanced and stable aquatic ecosystem. The photocatalysis technology taking the semiconductor material as the core provides a new ideal pollution treatment idea for people. The application of the photocatalysis technology to treat nitrite and sulfite is a green, clean and effective treatment mode. The core problem faced by the photocatalytic technology is to find a photocatalyst with excellent performance, so that the screening and preparation of the high-efficiency photocatalyst are the core subjects of photocatalytic research.
The key for improving the photocatalytic efficiency of the Z-type photocatalyst is to enhance the separation efficiency of the photo-generated electron-hole pairs. The traditional method is to add a conductive channel such as noble metal, graphene, carbon nanotube, etc. to enable a photo-generated electron on a conduction band of one semiconductor to be capable of being recombined with a photo-generated hole on a valence band of the other semiconductor through the conductive channel, thereby improving the separation efficiency of the photo-generated electron and the hole pair. In the process of transferring electrons by using the conductive channel, because the electrons have mass and resistance exists in the transferring process, the speed of electron transfer can be slowed down, and the photocatalytic efficiency is influenced. Therefore, it is an urgent problem to provide a photocatalyst that is free from the limitation of electron quality and transmission distance.
Disclosure of Invention
Aiming at the problems, the invention designs and synthesizes the composite photocatalyst NiGa which takes AQ (anthraquinone) as a conductive channel to effectively accelerate the electron transfer rate2O4/AQ/MoO3. The compound belongs to a Z-type semiconductor photocatalyst, is applied to simultaneously converting nitrite and sulfite and generating ammonium sulfate fertilizer, and has the advantages of simple operation, no pollution, good catalyst stability and easy operationAnd (5) separating.
The technical scheme adopted by the invention is as follows: photocatalyst NiGa2O4/AQ/MoO3The preparation method comprises the following steps: mixing nano NiGa2O4AQ and nano MoO3Adding the mixture into absolute ethyl alcohol, carrying out ultrasonic dispersion, heating the obtained suspension, keeping the temperature at 100 ℃ for 10-20 min, filtering, drying the obtained filtrate, and grinding to obtain NiGa2O4/AQ/MoO3。
Preferably, one of the above photocatalysts NiGa2O4/AQ/MoO3Said NiGa2O4The preparation method of the AQ comprises the following steps: mixing nano NiGa2O4Adding absolute ethyl alcohol into a beaker, performing ultrasonic dispersion for 20-40 min, uniformly mixing by magnetic stirring, heating to boiling, keeping the temperature at 100 ℃ for 10-30 min, adding nano AQ, cleaning with absolute ethyl alcohol and distilled water, centrifuging, drying, and grinding to obtain nano NiGa2O4/AQ。
Preferably, one of the above photocatalysts NiGa2O4/AQ/MoO3And the temperature of magnetic stirring is 40-60 ℃.
Preferably, one of the above photocatalysts NiGa2O4/AQ/MoO3The preparation method of (1), the nanometer NiGa2O4The preparation method comprises the following steps: ga is mixed with2O3Adding the solid into a nickel nitrate solution, adjusting the pH of the generated mixed solution to 12 by using a sodium hydroxide solution, stirring for 30-40 min while adjusting, transferring the obtained suspension solution into a reaction kettle for reaction, cooling a sample to room temperature, washing the obtained precipitate by using deionized water, drying at 80 ℃, roasting for 2-3 h at 500 ℃, and grinding to obtain the nano NiGa2O4。
Preferably, one of the above photocatalysts NiGa2O4/AQ/MoO3And reacting the suspension solution in a reaction kettle at 180 ℃ for 48 hours.
Preferably, one of the above photocatalysts NiGa2O4/AQ/MoO3The nano MoO3The preparation method comprises the following steps: will be (NH)4)6Mo7O24·4H2O dissolved in 65% HNO3Adding deionized water into the solution, completely dissolving, transferring the reaction solution into a stainless steel autoclave with a Teflon lining for reaction, cooling, centrifuging, washing the obtained solid with deionized water, and drying at 80 ℃ to obtain nano MoO3。
Preferably, one of the above photocatalysts NiGa2O4/AQ/MoO3The reaction solution was reacted in a Teflon-lined stainless steel autoclave at 180 ℃ for 24 hours.
Preferably, one of the above photocatalysts NiGa2O4/AQ/MoO3By volume ratio, (NH)4)6Mo7O24·4H2O and HNO3The mixed solution of (a): deionized water 1: 5.
The photocatalyst NiGa2O4/AQ/MoO3The application in the photocatalytic conversion of nitrite and/or sulfite. The method comprises the following steps: mixing nano NiGa2O4/AQ/MoO3Adding into wastewater containing nitrite and/or sulfite, and irradiating with 500W xenon lamp for 4.0 h.
The invention has the beneficial effects that:
1. the nanometer NiGa prepared by the invention2O4/AQ/MoO3The photocatalyst has stable property, high temperature resistance and simple NiGa2O4And MoO3Compared with the prior art, the efficiency of converting nitrite and sulfite under the irradiation of sunlight by the catalyst is greatly improved.
2. Photocatalyst NiGa prepared in the invention2O4/AQ/MoO3Not only has the advantages of the traditional photocatalyst, but also has the most attention to the NiGa2O4And MoO3The bandwidth characteristic has the position uniqueness of a conduction band and a valence band, the method solves the problem of the recombination of photoproduction electrons and holes, and the efficiency of converting nitrite and sulfite by photocatalysis is greatly improved.
3. The present invention provides a new conductive mode, charge transfer, which is not limited by electron mass and transmission distance, and by this mode, the electron transfer efficiency is greatly raised, so that the photocatalytic activity is enhanced.
4. Anthraquinone (AQ) is selected as a bridge for charge transfer, and the oxidation-reduction reaction of the AQ can quickly transfer charges, so that electrons do not need to move in a conductive channel. Electrons obtained by AQ are reduced and then oxidized by holes to AQ, forming a redox recombination center centered on AQ. Because the oxidation-reduction potential of AQ is located at MoO3Position of conduction band and NiGa2O4Between valence band positions, whereby AQ can be MoO3The negative charge at the position of the conduction band is reduced and then is oxidized by NiGa2O4And (3) oxidizing holes at the position of the valence band to realize charge transfer.
Drawings
FIG. 1 is a schematic view of NiGa2O4，AQ，MoO3And NiGa2O4/AQ/MoO3Scanning Electron Microscope (SEM) images of (a).
FIG. 2 is MoO3,NiGa2O4,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Photoluminescence spectrum (PL) diagram of (a).
FIG. 3 is a view of NiGa2O4/AQ/MoO3Transmission Electron Microscope (TEM) images of (a).
FIG. 4 is a view showing NiGa2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Photocurrent density (IT) graph of (a).
FIG. 5a-1 shows the use of NiGa2O4/MoO3Effect of light time on nitrite and sulfite conversion in the case of catalysts.
FIG. 5a-2 shows the use of NiGa2O4/AQ/MoO3Effect of light time on nitrite and sulfite conversion in the case of catalysts.
FIG. 5b-1 shows the use of NiGa2O4/MoO3Effect of light exposure time on nitrate and sulfate production rate in the case of catalyst.
FIG. 5b-2 shows the use of NiGa2O4/AQ/MoO3Effect of light exposure time on nitrate and sulfate production rate in the case of catalyst.
FIG. 6 is a view showing NiGa2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Graph of the effect on the photocatalytic conversion of nitrite and sulfite.
FIG. 7 is a view of NiGa2O4/AQ/MoO3Graph of the effect of the number of uses on the photocatalytic conversion of nitrite and sulfite.
FIG. 8 shows a photocatalyst NiGa2O4/AQ/MoO3Mechanism diagram of photocatalytic conversion of nitrite and sulfite.
Detailed Description
EXAMPLE 1 photocatalyst NiGa2O4/AQ/MoO3
The preparation method comprises
1. Preparation of Nano NiGa2O4
0.37g of nano Ga2O3Adding into 50mL solution containing 0.45g nickel nitrate, adjusting pH of the resultant mixture to 12 with 1mol/L sodium hydroxide, stirring for 30min while adjusting, transferring the obtained suspension solution into a reaction kettle, reacting at 180 ℃ for 48h, cooling the sample to room temperature to obtain light blue precipitate, and washing with deionized water for several times. Drying the obtained precipitate at 80 ℃ for 8h to obtain NiGa2O4And (3) powder. Grinding the powder, roasting for 2h in a muffle furnace at 500 ℃, taking out and grinding to obtain the nano NiGa2O4。
2. Preparation of Nano MoO3
1g (NH)4)6Mo7O24·4H2O dissolved in 36mL of 65% HNO3In volume ratio of (NH)4)6Mo7O24·4H2O and HNO3The mixed solution of (a): deionized water 1:5, adding deionized water, completely dissolving, and transferring the mixed solution to a stainless steel height liner made of TeflonAutoclave (50mL capacity) and reaction at 180 ℃ for 24 hours. Cooling to obtain white product, centrifuging, washing with deionized water, and oven drying the precipitate at 80 deg.C for 8 hr to obtain nanometer MoO3。
3. Preparation of Nano NiGa2O4/AQ
0.5g of nano NiGa2O4Adding 50mL of absolute ethyl alcohol into a beaker, performing ultrasonic dispersion for 30min, then performing magnetic stirring and mixing at 40-60 ℃, heating to boiling, keeping the temperature at 100 ℃ for 30min, adding 0.05g of nano AQ, then washing for several times by using absolute ethyl alcohol and distilled water, centrifuging, drying, and grinding to obtain the nano NiGa2O4/AQ。
4. Preparation of Nano NiGa2O4/AQ/MoO3
1.0g of NiGa2O4AQ and 1.0g of nano MoO3Adding into 100mL anhydrous ethanol, ultrasonically dispersing for 1 min, heating and boiling the suspension, keeping the temperature at 100 deg.C for 30min, filtering, drying the filtrate in oven at 60 deg.C for 8.0h, and grinding the powder to obtain nanometer NiGa2O4/AQ/MoO3。
(II) detection
1.NiGa2O4,AQ,MoO3And NiGa2O4/AQ/MoO3Scanning Electron Microscope (SEM) picture analysis of (c).
Observation of NiGa by Scanning Electron Microscope (SEM)2O4,AQ,MoO3And NiGa2O4/AQ/MoO3The results are shown in FIG. 1. In FIG. 1 (NiGa)2O4) In the presence of a number of bulk particles in the size range 100-200nm, which belong to NiGa2O4And (3) granules. Fig. 1 (AQ) is a SEM picture of purchased neat AQ particles, from which it can be seen that the neat AQ are irregular aggregates. From FIG. 1 (MoO)3) The uniform and smooth nano-rods can be seen and are MoO3And (3) granules. In FIG. 1 (NiGa)2O4/AQ/MoO3) In (A), it can be seen that the small particles of AQ are uniformly dispersed in the nanorods (MoO)3) And bulk particles (NiGa)2O4) This proves that NiGa has been successfully prepared2O4/AQ/MoO3And (3) sampling.
2.NiGa2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Photo luminescence spectroscopy (PL) picture analysis.
The rate of separation of electrons and holes from the semiconductor photocatalyst can be seen by PL analysis. In general, low fluorescence intensity shows good separation effect of electron-hole pairs, which indicates excellent photocatalytic performance. High fluorescence intensity shows poor separation effect of electron-hole pairs, which indicates low photocatalytic performance. In FIG. 2, NiGa is shown under excitation of light having wavelengths of 260nm, 325nm, 325nm and 325nm, respectively2O4，MoO3，NiGa2O4/MoO3And NiGa2O4/AQ/MoO3The PL spectrum of (1). It was found that pure NiGa2O4And MoO3Exhibit relatively high PL intensity reflecting their high rate of electron and hole recombination. When NiGa2O4And MoO3When combined, the formed Z-type NiGa2O4/MoO3With pure NiGa2O4And MoO3The samples showed significantly reduced PL intensity compared to that of the sample, indicating that type Z NiGa2O4/MoO3Is advantageous for the separation of electrons and holes. In particular, when AQ is added and Z-form NiGa is formed2O4/AQ/MoO3When PL intensity is minimal, it shows the optimal separation rate of electrons and holes.
3.NiGa2O4/AQ/MoO3Transmission Electron Microscope (TEM) picture analysis of (a).
Observation of NiGa by TEM2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Microstructure and morphology. In (a) of FIG. 3, it can be seen that the small particles having a relatively large size (200-300nm) are NiGa2O4The uniform and smooth nanorods are MoO3. According to the preparationMethod, it can be seen that NiGa2O4And MoO3With much smaller particles in between, these small particles were initially determined to be AQ. Their composition and structure can be further verified in fig. 3. In (b) in FIG. 3, it can be found that there exist crystal planes having an interplanar spacing of 0.280nm, which were determined to be NiGa2O4D of220A crystal plane. Furthermore, the facets have a interplanar spacing of 0.209nm, which is attributed to MoO3D of the particles040A crystal plane. In NiGa2O4And MoO3There are facets with a facet spacing of 0.253nm, according to the bragg formula: 2dsin θ ═ n λ (d: interplanar spacing, θ: half angle of diffraction, n: series of diffraction and λ: wavelength of target), 2 θ (half angle of diffraction) was calculated, which was about 34.5 °, corresponding to d of AQ312A crystal plane. These results indicate that NiGa has been prepared2O4/AQ/MoO3And (3) sampling.
4.NiGa2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Photo current density (IT) picture analysis.
To further estimate the effect of the separation rate of electrons and holes on the photocatalytic activity, the photocurrent density of the prepared sample was measured, and the results are shown in fig. 4. Generally, high photocurrent densities show high separation efficiency of electron and hole pairs. As can be seen, the prepared sample NiGa2O4,MoO3,NiGa2O4/MoO3And NiGa2O4/AQ/MoO3All have fast and stable sunlight irradiation transient photocurrent. Z-type NiGa2O4/MoO3The intensity of the photocurrent is higher than that of NiGa2O4And MoO3The result shows that the Z-type photocatalytic system can obviously improve the separation rate of electron and hole pairs. Further, NiGa of Z type2O4/AQ/MoO3The highest photocurrent intensity was shown in all samples, which means AQ acts as an electron transfer channel to rapidly transfer electrons and suppress the recombination of photo-generated electrons and holes. Z-type NiGa2O4/AQ/MoO3The photocatalyst will show the highest photocatalytic activity。
EXAMPLE 2 photocatalyst NiGa2O4/AQ/MoO3Application in photocatalytic conversion of nitrite and sulfite
0.05g of nano NiGa2O4/AQ/MoO3The mixture was added to 50mL of wastewater containing nitrite and sulfite, wherein the concentration of nitrite was 10ppm and the concentration of sulfite was 18.2 ppm. Irradiating with 500W xenon lamp for 4.0 h. The conversion rates of nitrite and sulfite are respectively measured in 0.00h, 1.00h, 2.00h, 3.00h and 4.00h of illumination.
Comparative example
0.05g of NiGa2O4，0.05g MoO3And 0.05g of NiGa2O4/MoO3Respectively adding the mixture into 50mL of wastewater containing nitrite and sulfite, wherein the concentration of the nitrite is 10ppm, and the concentration of the sulfite is 18.2 ppm. Irradiating with 500W xenon lamp for 4.0 h. The conversion rates of nitrite and sulfite are respectively measured in 0.00h, 1.00h, 2.00h, 3.00h and 4.00h of illumination.
Simulating the influence of the time of solar irradiation and the corresponding reaction kinetics on the photocatalytic conversion of nitrite and sulfite
In the Z-type NiGa2O4/MoO3And NiGa2O4/AQ/MoO3The influence of the illumination time on the conversion of nitrite and sulfite is respectively studied in a photocatalytic system. The equilibrium of adsorption and desorption is reached after half an hour in the dark, and NO can be found2 -And SO3 2-The conversion of (a) is slightly decreased. This indicates that the Z-form NiGa2O4/MoO3And NiGa2O4/AQ/MoO3Can only absorb small amount of NO2 -And SO3 2-. In FIGS. 5a-1 and 5a-2, NO increases with the daylight illumination time2 -And SO3 2-The conversion of (a) gradually increases. NO in the first hour with increasing light exposure time2 -And SO3 2-Photocatalytic conversion rate and NH of4 +，NO3 -，N2And SO4 2-The production rate of (a) increases rapidly, followed by a slow increase. This is probably due to the NO in solution with increasing reaction time2 -And SO3 2-The concentration of (a) decreases and then the photocatalytic conversion rate relatively decreases. Wherein NH4 +Is generated at a much higher rate than NO3 -And N2This indicates NO under weakly acidic conditions2 -The conversion product of (A) is mainly NH4 +. Furthermore, in FIG. 5a-2, NO was present under 4 hours of irradiation2 -And SO3 2-The conversion rates of the catalyst can respectively reach 89.81 percent and 94.47 percent, and NH4 +，NO3 -，N2And SO4 2-The production rates of (A) can reach 73.38%, 15.19%, 1.24% and 93.25%, respectively. Apparently, in NiGa2O4/AQ/MoO3Under the action of (2), NO2 -And SO3 2-Conversion of (3), and NH4 +， NO3 -，N2And SO4 2-The generation rate of the catalyst is higher than that of NiGa2O4/MoO3. This indicates that AQ as an electron transfer channel is in the Z-type NiGa2O4/AQ/MoO3In-conversion of NO2 -And SO3 2-Plays an important role.
Reaction kinetics allows for visual comparison of NO2 -And SO3 2-Conversion of (2), and calculated data-ln (C)t/C0) This is shown in fig. 5b-1 and 5 b-2. Wherein, CtAnd C0Representing the instantaneous and initial concentrations, respectively. -ln (C)t/C0) There is an approximately linear relationship between the calculated value of (c) and the solar light irradiation time (t). Thus, NO2 -And SO3 2-In the two Z-type photocatalytic systems NiGa2O4/MoO3And NiGa2O4/AQ/MoO3The first order reaction law is followed. In NiGa2O4/MoO3PhotocatalysisNO in the system2 -And SO3 2-Are respectively-ln (C)t/C0)＝0.2475t+ 0.4539(R20.9583) and-ln (C)t/C0)＝0.3347t+0.5232(R20.9780). The rate constants were 0.2475min-1 and 0.3347min-1, respectively. In the Z-type NiGa2O4/AQ/MoO3NO in photocatalytic systems2 -And SO3 2-Are respectively-ln (C)t/C0)＝0.4266t+0.5845(R20.9878) and-ln (C)t/C0)＝0.5535t +0.6523(R20.9938). The rate constants were 0.4266min-1 and 0.5535 min-1. In contrast, in NiGa2O4/MoO3NO in photocatalytic systems2 -And SO3 2-Rate constant lower than Z-type NiGa2O4/AQ/MoO3In photocatalytic systems. Therefore, it can be concluded that NiGa2O4/MoO3In contrast, NiGa of Z type2O4/AQ/MoO3Show relatively high NO2 -And SO3 2-The photocatalytic conversion rate of (a).
(II) comparing the effects of photocatalytic activity and the number of uses of the prepared samples on the photocatalytic conversion rates of nitrite and sulfite
Four prepared photocatalysts are studied for NO under simulated sunlight irradiation2 -And SO3 2-The results of the transformation are shown in FIG. 6. NO without any catalyst2 -And SO3 2-The conversion of (a) is very low. For the four prepared photocatalysts, NO2 -And SO3 2-With varying degrees of conversion, indicating the use of a photocatalyst for NO2 -And SO3 2-Is very important. It is clear that NiGa is present due to the Z-type photocatalytic system2O4/MoO3Formation of (e)-And h+Can be effectively inhibited from recombining with NiGa2O4And MoO3In contrast, in NO2 -And SO3 2-The photocatalytic activity in the conversion is further enhanced. In addition, in the Z-type NiGa2O4/AQ/MoO3The highest conversion and generation rates were found, and the enhanced photocatalytic activity was attributed to the rapid electron transfer and suppression of photogeneration by AQ as an electron transfer channel-And h+The recombination of (1).
The stability of the photocatalyst is an important factor in evaluating the performance in practical use. Thus, conversion of NO by photocatalysis2 -And SO3 2-The repeated use time is studied on the prepared Z-type NiGa2O4/AQ/MoO3Influence of the photocatalytic activity of the photocatalyst. As can be seen from FIG. 7, NO2 -And SO3 2-The photocatalytic conversion rate of (2) is slightly reduced along with the increase of the using times, and still reaches 85.51 percent and 89.24 percent respectively at the 5 th cycle. This indicates that the Z-form NiGa2O4/AQ/MoO3Has high stability. Briefly, NiGa in Z form2O4/AQ/MoO3Can be repeatedly used for many times and still keeps high photocatalytic performance.
(III) photocatalyst NiGa2O4/AQ/MoO3Mechanism for converting nitrite and sulfite by photocatalysis
To effectively suppress electrons (e) on a Conduction Band (CB)-) And a hole (h) in the Valence Band (VB)+) Of NiGa2O4And MoO3It is necessary to combine to form a photocatalytic system of the Z type. Since NiGa2O4Valence band and MoO3Conduction band potentials close to each other, MoO3Conduction band electrons are easily transferred to NiGa2O4Above the cavity. But to further increase their transfer rate. Anthraquinone (AQ) is selected as a bridge for charge transfer in the research, and the oxidation-reduction reaction of the AQ can be utilized to rapidly transfer charges, so that electrons do not need to move in a conductive channel. Electrons obtained by AQ are reduced and then oxidized by holes to AQ, forming a redox recombination center centered on AQ. As shown in FIG. 8, oxidation-reduction potential due to AQIn MoO3Position of conduction band and NiGa2O4Between valence band positions, whereby AQ can be MoO3The negative charge at the position of the conduction band is reduced and then is oxidized by NiGa2O4Hole oxidation at the valence band site effects charge transfer in a much faster manner than electron transfer in a conductive channel. The method has important significance for improving the photocatalytic activity and provides a new method for the subsequent research of the photocatalyst. NiGa2O4The electrons in the valence band have strong reducing power, and can make NO with certain oxidizability2 -Reduction to respectively generate NH4 +And N2. The specific product depends on the pH, and acidic conditions at pH less than 7 readily form NH4 +Ion, alkaline conditions with pH greater than 7 readily produce N2. At the same time in MoO3In the valence band of (3)3 2-Is oxidized to SO by a hole in the valence band4 2-Capable of reacting with the NH formed4 +Combined to form ammonium sulfate ((NH)4)2SO4). Substantially in NO2 -And SO3 2-During the treatment, ammonium sulfate ((NH) is finally generated4)2SO4) The aqueous solution of (a) can be used directly as a fertilizer after appropriate treatment.
Claims (9)
1. Photocatalyst NiGa2O4/AQ/MoO3The preparation method is characterized by comprising the following steps: mixing nano NiGa2O4AQ and nano MoO3Adding the mixture into absolute ethyl alcohol, carrying out ultrasonic dispersion, heating the obtained suspension, keeping the temperature at 100 ℃ for 10-30 min, filtering, drying the obtained filtrate, and grinding to obtain NiGa2O4/AQ/MoO3；
The nano NiGa2O4The preparation method of the/AQ comprises the following steps: mixing nano NiGa2O4Adding absolute ethyl alcohol into a beaker, ultrasonically dispersing for 20-40 min, magnetically stirring, uniformly mixing, heating to boil, keeping the temperature at 100 ℃ for 10-30 min, adding nano anthraquinone AQ, and adding absolute ethyl alcohol and distilled waterCleaning, centrifuging, drying and grinding to obtain the nano NiGa2O4/AQ。
2. The photocatalyst NiGa as claimed in claim 12O4/AQ/MoO3The method is characterized in that: the temperature of magnetic stirring is 40-60 ℃.
3. The photocatalyst NiGa as claimed in claim 12O4/AQ/MoO3Characterized in that the nano NiGa2O4The preparation method comprises the following steps: ga is mixed with2O3Adding the solid into a nickel nitrate solution, adjusting the pH of the generated mixed solution to 12 by using a sodium hydroxide solution, stirring for 30-40 min while adjusting, transferring the obtained suspension solution into a reaction kettle for reaction, cooling a sample to room temperature, washing the obtained precipitate by using deionized water, drying at 80 ℃, roasting for 2-3 h at 500 ℃, and grinding to obtain the nano NiGa2O4。
4. The photocatalyst NiGa as claimed in claim 32O4/AQ/MoO3The method is characterized in that: the suspension solution is reacted in a reaction kettle at 180 ℃ for 48 hours.
5. The photocatalyst NiGa as claimed in claim 12O4/AQ/MoO3The method is characterized in that: the nano MoO3The preparation method comprises the following steps: will be (NH)4）6Mo7O24•4H2O dissolved in 65% HNO3Adding deionized water into the solution, completely dissolving, transferring the reaction solution into a stainless steel autoclave with a Teflon lining for reaction, cooling, centrifuging, washing the obtained solid with deionized water, and drying at 80 ℃ to obtain nano MoO3。
6. The photocatalyst NiGa as claimed in claim 52O4/AQ/MoO3The method is characterized in that: reaction solution in Teflon lined stainless steelThe reaction was carried out in an autoclave at 180 ℃ for 24 hours.
7. The photocatalyst NiGa as claimed in claim 52O4/AQ/MoO3The method is characterized in that: by volume ratio, (NH)4）6Mo7O24•4H2O and HNO3The mixed solution of (a): deionized water =1: 5.
8. A photocatalyst NiGa as claimed in claim 12O4/AQ/MoO3The application in the photocatalytic conversion of nitrite and/or sulfite.
9. Use according to claim 8, characterized in that the method is as follows: mixing nano NiGa2O4/AQ/MoO3Adding into wastewater containing nitrite and/or sulfite, and irradiating with 500W xenon lamp for 4.0 h.
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