CN111974417B - Cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst, preparation method and application - Google Patents
Cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst, preparation method and application Download PDFInfo
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- QLTKZXWDJGMCAR-UHFFFAOYSA-N dioxido(dioxo)tungsten;nickel(2+) Chemical compound [Ni+2].[O-][W]([O-])(=O)=O QLTKZXWDJGMCAR-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 75
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 19
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 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 16
- 238000005406 washing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 11
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 229910006167 NiWO4 Inorganic materials 0.000 abstract description 5
- 230000006798 recombination Effects 0.000 abstract description 4
- 238000005215 recombination Methods 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 229940107698 malachite green Drugs 0.000 description 22
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- OQFRENMCLHGPRB-UHFFFAOYSA-N copper;dioxido(dioxo)tungsten Chemical compound [Cu+2].[O-][W]([O-])(=O)=O OQFRENMCLHGPRB-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PQDPFQKKQAYNSU-UHFFFAOYSA-N [S-2].[Cd+2].[Ni+2].[S-2] Chemical compound [S-2].[Cd+2].[Ni+2].[S-2] PQDPFQKKQAYNSU-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 229910019408 CoWO4 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LKDOLJJHAKAFGK-UHFFFAOYSA-N copper cadmium(2+) disulfide Chemical compound [S-2].[Cd+2].[Cu+2].[S-2] LKDOLJJHAKAFGK-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001046 green dye Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
A cadmium sulfide/nickel tungstate composite visible light catalyst, a preparation method and an application belong to the technical field of semiconductor photocatalytic nano materials. The invention provides a preparation method of a cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst. The method of the invention is realized by constructing NiWO4And the composite material and the CdS heterostructure reserve the oxidation-reduction capability of the material, inhibit the recombination of photon-generated carriers, effectively enhance the photocatalytic activity of the composite material and enable the composite material to show excellent photocatalytic activity under the irradiation of visible light.
Description
Technical Field
The invention belongs to the technical field of semiconductor photocatalytic nano materials, and particularly relates to preparation and application of a cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst.
Background
The photocatalysis technology relieves the problems of energy exhaustion, ecological environment damage and the like by producing renewable fuels and degrading and mineralizing toxic pollutants, and has great application prospect. On one hand, the semiconductor photocatalytic material can be used for converting low-density solar energy into high-density chemical energy (photocatalytic water splitting for hydrogen production) or electric energy (dye-sensitized solar cell); on the other hand, the semiconductor material is used for treating industrial wastewater and organic pollutants by utilizing the redox activity of photo-generated electrons and holes generated by excitation.
Cadmium sulfide (CdS) is a typical direct band gap narrow bandgap semiconductor material in II-VI families, and the band gap width of bulk CdS at room temperature is 2.42 eV. The high-purity cadmium sulfide is a semiconductor with good performance and has strong photoelectric response to visible light. However, CdS is susceptible to photo-corrosion during visible light photo-reaction, and the high recombination rate of photo-generated electrons and holes limits the wide application of CdS in photocatalysis.
In recent years, Bi has become a factor2WO6、CuWO4、CoWO4And NiWO4And many tungstates have been studied extensively because of their narrow band gap energy, excellent optical properties and photocatalytic activity. Nickel tungstate (NiWO), a member of the tungstate family4) Has narrow band gap energy (2.6eV), has certain capability of oxidizing and decomposing a plurality of organic matters, is considered to have a wide prospect, but still has low photocatalytic activity of pure nickel tungstate due to high electron-hole recombination rate.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: based on the problems in the background art, the invention provides a preparation method of a cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst. The method of the invention is realized by constructing NiWO4The composite material and the CdS heterostructure inhibit the recombination of photon-generated carriers, retain the oxidation reduction capability of the material, effectively enhance the photocatalytic activity of the composite material and enable the composite material to show excellent photocatalytic activity under the irradiation of visible light.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst comprises the following steps:
(1) preparing nickel tungstate: respectively adding nickel nitrate and sodium tungstate into deionized water, stirring for 2-3 hours, dropwise adding the obtained sodium tungstate solution into the nickel nitrate solution, continuously stirring for 2-3 hours, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 170-190 ℃ for 16-24 hours, cooling, carrying out suction filtration, washing, drying, placing into a muffle furnace, and calcining at 700 ℃ for 3-5 hours to obtain nickel tungstate;
(2) preparing a cadmium sulfide/nickel tungstate composite photocatalyst: adding nickel tungstate into ethylene glycol, stirring for 0.5-1 h, then adding cadmium acetate, performing ultrasonic treatment for 0.5-1 h, then adding thioacetamide and polyvinylpyrrolidone, continuing stirring for 0.5-1 h, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 24-36 h at 80-120 ℃, naturally cooling the hydrothermal reaction kettle to room temperature, performing suction filtration, washing and drying on the obtained solution, and thus obtaining the cadmium sulfide/nickel tungstate composite visible light catalyst.
The method adopts a two-step method to load granular cadmium sulfide on nickel tungstate.
Further, the molar ratio of the nickel nitrate to the sodium tungstate in the mixed solution in the step (1) is 1: 1.
Further, the molar ratio of the cadmium acetate, thioacetamide, polyvinylpyrrolidone and nickel tungstate in the step (2) is 1:1:3: 1-5.
Further, the solid-liquid volume ratio of the cadmium acetate, thioacetamide, polyvinylpyrrolidone and glycol liquid in the step (2) is 1: 50-70.
The cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst prepared by the method is used for photocatalytic degradation of dye wastewater, and the specific application method is as follows:
(1) weighing a certain amount of malachite green powder, and preparing a 20mg/L malachite green solution;
(2) weighing 30mg of nickel tungstate/cadmium sulfide composite photocatalyst, and adding the nickel tungstate/cadmium sulfide composite photocatalyst into a colorimetric tube filled with 50ml of malachite green solution of 20 mg/L;
(3) and putting the colorimetric tube into a photocatalytic reactor, and stirring for 30min under a dark condition to ensure that the material is fully contacted with the solution so as to achieve adsorption-desorption balance. Then, illuminating by using a xenon lamp with a light source of 1000w, absorbing 2ml of suspension every 20min, putting the suspension into a centrifuge with the rotating speed of 10000rmp, centrifuging for 2 min, and filtering by using a hydrophilic PTFE needle filter with the diameter of 0.22 mu m to obtain clear liquid;
(4) the absorbance of the clear solution was measured using a UV1800PC UV-visible spectrophotometer, and the formula D ═ 1-Ct/C0) X 100% to calculate the degradation rate of the sample for contaminants, where C0And CtRespectively, the absorbance of the malachite green solution at the maximum absorption wavelength before and after the photocatalytic reaction.
The invention has the beneficial effects that: the composite photocatalyst prepared by the method shows better photocatalytic degradation activity on malachite green dye than a single compound, has excellent photocatalytic activity and higher stability, is mainly benefited by a heterojunction structure formed by the composite material, enables photoproduction electrons and holes generated after the composite material is excited by light to be effectively separated, and CdS and NiWO4Synergistic effect between themShowing a stronger light absorption range. The material is simple in preparation method, low in cost, good in stability and has a certain potential application value.
Drawings
FIG. 1 is an X-ray diffraction pattern of a photocatalyst prepared in example 2 of the present invention and in comparative examples 1 to 2;
FIG. 2 is a transmission electron microscope image of the cadmium sulfide/nickel tungstate composite visible-light-induced photocatalyst prepared in example 2 of the present invention;
FIG. 3 is a graph showing the degradation effect of the photocatalysts prepared in examples 1 to 3 of the present invention and comparative examples 1 to 2.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
Example 1
(1) Preparing nickel tungstate: 0.33g of nickel nitrate and 0.291g of sodium tungstate were added to 30ml of deionized water, respectively, and magnetically stirred for 2 hours to obtain uniform solutions. Then dropwise adding the sodium tungstate solution into the nickel nitrate solution, continuously stirring for 2h, then transferring the obtained mixed solution into a 100ml reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 16 h. And centrifuging the obtained product, washing the product for 3 times by using deionized water and ethanol, drying the product at 100 ℃ for 2 hours, and finally calcining the obtained dried powder in a muffle furnace at 700 ℃ for 4 hours to obtain a light yellow powdery nickel tungstate sample.
(2) Weighing 0.1g of nickel tungstate, adding the nickel tungstate into 70ml of ethylene glycol, magnetically stirring for 1h, adding 0.018432g of cadmium acetate, continuing to perform ultrasonic treatment for 1h, adding 0.0052g of thioacetamide and 0.00688g of polyvinylpyrrolidone, performing ultrasonic treatment for 1h, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 24h at 100 ℃, naturally cooling the reaction kettle to room temperature, performing suction filtration, washing and drying on the obtained solution to obtain a sample. In the prepared cadmium sulfide nickel tungstate composite sample, the mass ratio of cadmium sulfide to nickel tungstate is 0.1: 1.
Example 2
(1) Preparing nickel tungstate: 0.33g of nickel nitrate and 0.291g of sodium tungstate were added to 30ml of deionized water, respectively, and magnetically stirred for 2 hours to obtain uniform solutions. Then dropwise adding the sodium tungstate solution into the nickel nitrate solution, continuously stirring for 2h, then transferring the obtained mixed solution into a 100ml reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 16 h. And centrifuging the obtained product, washing the product for 3 times by using deionized water and ethanol, drying the product at 100 ℃ for 2 hours, and finally calcining the obtained dried powder in a muffle furnace at 700 ℃ for 4 hours to obtain a light yellow powdery nickel tungstate sample.
(2) Weighing 0.1g of nickel tungstate, adding the nickel tungstate into 70ml of ethylene glycol, magnetically stirring for 1h, adding 0.036864g of cadmium acetate, continuing to perform ultrasonic treatment for 1h, adding 0.0104g of thioacetamide and 0.01376g of polyvinylpyrrolidone, performing ultrasonic treatment for 1h, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 24h at 100 ℃, naturally cooling the reaction kettle to room temperature, performing suction filtration, washing and drying on the obtained solution to obtain a sample. In the prepared cadmium sulfide nickel tungstate composite sample, the mass ratio of cadmium sulfide to nickel tungstate is 0.2: 1.
Example 3
(1) Preparing nickel tungstate: 0.33g of nickel nitrate and 0.291g of sodium tungstate were added to 30ml of deionized water, respectively, and magnetically stirred for 2 hours to obtain uniform solutions. Then dropwise adding the sodium tungstate solution into the nickel nitrate solution, continuously stirring for 2h, then transferring the obtained mixed solution into a 100ml reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 16 h. And centrifuging the obtained product, washing the product for 3 times by using deionized water and ethanol, drying the product at 100 ℃ for 2 hours, and finally calcining the obtained dried powder in a muffle furnace at 700 ℃ for 4 hours to obtain a light yellow powdery nickel tungstate sample.
(2) Weighing 0.1g of nickel tungstate, adding the nickel tungstate into 70ml of ethylene glycol, magnetically stirring for 1h, adding 0.055296g of cadmium acetate, continuing to perform ultrasonic treatment for 1h, adding 0.0156g of thioacetamide and 0.02064g of polyvinylpyrrolidone, performing ultrasonic treatment for 1h, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 24h at 100 ℃, naturally cooling the reaction kettle to room temperature, performing suction filtration, washing and drying on the obtained solution to obtain a sample. In the prepared cadmium sulfide nickel tungstate composite sample, the mass ratio of cadmium sulfide to nickel tungstate is 0.3: 1.
And (3) performance determination of the cadmium sulfide/nickel tungstate composite photocatalyst:
the crystal phase structure of the cadmium sulfide/nickel tungstate composite visible light catalyst prepared in example 2 is analyzed by a japanese D/max2500PC autorotation X-ray diffractometer, wherein the X-ray is a Cu target K α voltage of 40kV, the current is 100mA, the step size is 0.02 °, and the scanning range is 10 ° to 80 °. An X-ray diffraction pattern is shown in FIG. 1, the diffraction peak of cadmium sulfide is basically consistent with that of standard card (PDF #75-0581), and four characteristic diffraction peaks with 2 theta angles of 26.7 degrees, 44.1 degrees, 52.2 degrees and 70.7 degrees respectively correspond to (111), (220), (311) and (331) crystal faces of cubic sphalerite structure CdS; NiWO4The characteristic diffraction peaks of the compound are monoclinic crystalline phases and are matched with a standard card (PDF # 72-0480); the well-matched strong diffraction peaks of the composite demonstrate that the sample is a two-phase structure free of other impurities and has high crystallinity.
As can be seen from FIG. 2, the small granular cadmium sulfide is attached to the nickel tungstate polyhedron, and the cadmium sulfide and the nickel tungstate are tightly loaded together.
Comparative example 1
Adding 0.4608g of cadmium acetate into 70ml of ethylene glycol, magnetically stirring for 1h, then respectively adding 0.1299g of thioacetamide and 0.172g of polyvinylpyrrolidone, magnetically stirring for 1h, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 24h at 100 ℃, naturally cooling the reaction kettle to room temperature, carrying out suction filtration, washing and drying on the obtained solution to obtain cadmium sulfide;
comparative example 2
0.33g of nickel nitrate and 0.291g of sodium tungstate were added to 30ml of deionized water, respectively, and magnetically stirred for 2 hours to obtain uniform solutions. And then dropwise adding the sodium tungstate solution into the nickel nitrate solution, continuously stirring for 2h, transferring the obtained mixed solution into a 100ml reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 16 h. And centrifuging the obtained product, washing the product for 3 times by using deionized water and ethanol, drying the product at 100 ℃ for 2 hours, and finally calcining the obtained dried powder in a muffle furnace at 700 ℃ for 4 hours to obtain a light yellow powdery nickel tungstate sample.
Comparative example 3
(1) Preparing cadmium sulfide: adding 0.4608g of cadmium acetate into 70ml of ethylene glycol, magnetically stirring for 1h, then respectively adding 0.1299g of thioacetamide and 0.172g of polyvinylpyrrolidone, magnetically stirring for 1h, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 24h at 100 ℃, naturally cooling the reaction kettle to room temperature, carrying out suction filtration, washing and drying on the obtained solution to obtain cadmium sulfide;
(2) preparing nickel tungstate: 0.33g of nickel nitrate and 0.291g of sodium tungstate were added to 30ml of deionized water, respectively, and magnetically stirred for 2 hours to obtain uniform solutions. Then dropwise adding the sodium tungstate solution into the nickel nitrate solution, continuously stirring for 2h, then transferring the obtained mixed solution into a 100ml reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 16 h. And centrifuging the obtained product, washing the product for 3 times by using deionized water and ethanol, drying the product at 100 ℃ for 2 hours, and finally calcining the obtained dried powder in a muffle furnace at 700 ℃ for 4 hours to obtain a light yellow powdery nickel tungstate sample.
(3) Preparing a cadmium sulfide/nickel tungstate composite photocatalyst: respectively weighing 0.02g of cadmium sulfide and 0.1g of nickel tungstate, dissolving in 30ml of ethanol, ultrasonically dispersing for 1 hour, dripping cadmium sulfide suspension into the nickel tungstate solution, continuously ultrasonically treating for 1 hour, adding 15ml of acetone, stirring for 24 hours, centrifuging, collecting precipitate, and drying to obtain a sample. In the prepared cadmium sulfide nickel tungstate composite sample, the mass ratio of cadmium sulfide to nickel tungstate is 0.2: 1.
Comparative example 4
(1) Preparing cadmium sulfide: adding 0.4608g of cadmium acetate into 70ml of ethylene glycol, magnetically stirring for 1h, then respectively adding 0.1299g of thioacetamide and 0.172g of polyvinylpyrrolidone, magnetically stirring for 1h, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 24h at 100 ℃, naturally cooling the reaction kettle to room temperature, carrying out suction filtration, washing and drying on the obtained solution to obtain cadmium sulfide;
(2) preparing copper tungstate: 1.596g of copper sulfate and 3.298g of sodium tungstate were added to 40ml of deionized water, respectively, and magnetic stirring was performed for 1 hour to obtain a uniform solution. Then, the sodium tungstate solution was dropwise added to the copper sulfate solution while adjusting the pH to 8 with 0.1M sodium hydroxide solution, and after stirring for 5 hours, the obtained precipitate was washed several times with distilled water, dried at 100 ℃ for 2 hours, and then placed in a muffle furnace, and calcined at 500 ℃ for 4 hours, to obtain a powdery copper tungstate sample.
(3) Preparing a cadmium sulfide/copper tungstate composite photocatalyst: respectively weighing 0.02g of cadmium sulfide and 0.1g of copper tungstate, dissolving in 30ml of ethanol, ultrasonically dispersing for 1 hour, dropwise adding the cadmium sulfide suspension into the copper tungstate suspension, continuously ultrasonically dispersing for 1 hour, then adding 15ml of acetone, stirring for 24 hours, centrifugally collecting precipitate, and drying to obtain a sample. In the prepared cadmium sulfide copper tungstate composite sample, the mass ratio of cadmium sulfide to copper tungstate is 0.2: 1.
Application example 1
The method comprises the following steps: preparing 20mg/L malachite green solution;
step two: weighing 30mg of the cadmium sulfide/nickel tungstate composite photocatalyst prepared in the example 1, and adding the cadmium sulfide/nickel tungstate composite photocatalyst into a colorimetric tube filled with 50ml of 20mg/L malachite green solution;
step three: placing the colorimetric tube into a photocatalytic reactor, performing dark reaction for 30min to make it reach adsorption and desorption balance, illuminating with a xenon lamp with a light source of 1000w, absorbing 2ml of suspension every 20min, placing into a centrifuge with the rotation speed of 10000rmp, centrifuging for 2 min, and filtering with a hydrophilic PTFE needle filter with the diameter of 0.22 μm to obtain a clear solution;
step four: the absorbance of the clear solution was measured using a UV1800PC UV-visible spectrophotometer, and the formula D ═ 1-Ct/C0) X 100% to calculate the degradation rate of the sample for contaminants. Wherein C is0And CtRespectively, the absorbance of the malachite green solution at the maximum absorption wavelength before and after the photocatalytic reaction.
The degradation effect of the cadmium sulfide/nickel tungstate composite photocatalyst prepared in example 1 is shown in fig. 3, after reacting for 80min, the degradation rate of the cadmium sulfide/nickel tungstate composite photocatalyst prepared in example 1 on malachite green is 89.8%, and the composite photocatalyst has high photocatalytic activity.
Application example 2
Step two: weighing 30mg of the cadmium sulfide/nickel tungstate composite photocatalyst prepared in the example 2, and adding the cadmium sulfide/nickel tungstate composite photocatalyst into a colorimetric tube filled with 50ml of 20mg/L malachite green solution;
the other steps are the same as in example 1.
The degradation effect of the cadmium sulfide/nickel tungstate composite photocatalyst prepared in example 2 is shown in fig. 3, wherein after the reaction is carried out for 80min, the degradation rate of the cadmium sulfide/nickel tungstate composite photocatalyst prepared in example 2 on malachite green is 93.4%, and the composite photocatalyst has high photocatalytic activity.
Application example 3
Step two: weighing 30mg of the cadmium sulfide/nickel tungstate composite photocatalyst prepared in the embodiment 3, and adding the cadmium sulfide/nickel tungstate composite photocatalyst into a colorimetric tube filled with 50ml of 20mg/L malachite green solution;
the other steps are the same as in example 1.
The degradation effect of the cadmium sulfide/nickel tungstate composite photocatalyst prepared in example 3 is shown in fig. 3, after the reaction lasts for 80min, the degradation rate of the cadmium sulfide/nickel tungstate composite photocatalyst prepared in example 3 on malachite green is 85.1%, and the composite photocatalyst has high photocatalytic activity.
Comparative application example 1
Step two: weighing 30mg of cadmium sulfide prepared in comparative example 1, and adding the weighed cadmium sulfide into a colorimetric tube filled with 50ml of 20mg/L malachite green solution;
the other steps are the same as in example 1.
The degradation effect of cadmium sulfide prepared in comparative example 1 is shown in fig. 3, and the degradation rate of cadmium sulfide to malachite green is 77% after reaction for 80 min.
Comparative application example 2
Step two: weighing 30mg of nickel tungstate prepared in comparative example 2, and adding the nickel tungstate into a colorimetric tube filled with 50ml of 20mg/L malachite green solution;
the other steps are the same as in example 1.
The degradation effect of nickel tungstate prepared in comparative example 2 is shown in fig. 3, and after reacting for 80min, the degradation rate of nickel tungstate on malachite green is 5%.
Comparative application example 3
Step two: weighing 30mg of the cadmium sulfide/nickel tungstate composite prepared in comparative example 3, and adding the cadmium sulfide/nickel tungstate composite into a colorimetric tube filled with 50ml of 20mg/L malachite green solution;
the other steps are the same as in example 1.
The degradation rate of the cadmium sulfide/nickel tungstate composite catalyst prepared in comparative example 3 on malachite green is 80%. The degradation rate of the cadmium sulfide/nickel tungstate composite photocatalyst prepared in the same mass ratio in example 2 to the malachite green is lower than 93.4%, and the superiority of the preparation method is further highlighted.
Comparative application example 4
Step two: weighing 30mg of the cadmium sulfide/copper tungstate composite prepared in comparative example 4, and adding the weighed composite into a colorimetric tube filled with 50ml of 20mg/L malachite green solution;
the other steps are the same as in example 1.
The degradation rate of the cadmium sulfide/copper tungstate composite catalyst prepared in comparative example 4 on malachite green is 60%.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (5)
1. A preparation method of a cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst is characterized by comprising the following steps:
(1) preparing nickel tungstate: respectively adding nickel nitrate and sodium tungstate into deionized water, stirring for 2-3 hours, dropwise adding the obtained sodium tungstate solution into the nickel nitrate solution, continuously stirring for 2-3 hours, transferring the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 170-190 ℃ for 16-24 hours, cooling, carrying out suction filtration, washing, drying, placing into a muffle furnace, and calcining at 700 ℃ for 3-5 hours to obtain nickel tungstate;
(2) preparing a cadmium sulfide/nickel tungstate composite photocatalyst: adding nickel tungstate into ethylene glycol, stirring for 0.5-1 h, then adding cadmium acetate, performing ultrasonic treatment for 0.5-1 h, then adding thioacetamide and polyvinylpyrrolidone, continuing stirring for 0.5-1 h, transferring the mixed solution into a hydrothermal reaction kettle, reacting for 24-36 h at 80-120 ℃, naturally cooling the hydrothermal reaction kettle to room temperature, performing suction filtration, washing and drying on the obtained solution, and thus obtaining the cadmium sulfide/nickel tungstate composite visible light catalyst.
2. The preparation method of the cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst according to claim 1, wherein the molar ratio of nickel nitrate to sodium tungstate in the mixed solution in the step (1) is 1: 1.
3. The preparation method of the cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst according to claim 1 or 2, wherein the molar ratio of cadmium acetate, thioacetamide, polyvinylpyrrolidone and nickel tungstate in the step (2) is 1:1:3: 1-5.
4. A cadmium sulfide/nickel tungstate composite visible-light-induced photocatalyst, which is characterized in that the cadmium sulfide/nickel tungstate composite visible-light-induced photocatalyst is prepared by the preparation method of any one of claims 1 to 3.
5. The application of the catalyst prepared by the preparation method of any one of claims 1 to 3, wherein the prepared cadmium sulfide/nickel tungstate composite visible-light-driven photocatalyst is used for photocatalytic degradation of dye wastewater.
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| CN110420647A (en) * | 2019-08-20 | 2019-11-08 | 常州大学 | A kind of preparation method and application of lead tungstate/cadmium sulfide composite visible light catalyst |
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| CN110420647A (en) * | 2019-08-20 | 2019-11-08 | 常州大学 | A kind of preparation method and application of lead tungstate/cadmium sulfide composite visible light catalyst |
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