CN108855140B - CuS/Bi2WO6Heterojunction photocatalyst and preparation method and application thereof - Google Patents
CuS/Bi2WO6Heterojunction photocatalyst and 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 27
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 40
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 55
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 44
- 239000011259 mixed solution Substances 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 3
- 238000006731 degradation reaction Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
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- 238000013032 photocatalytic reaction Methods 0.000 abstract description 3
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- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
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- 239000002077 nanosphere Substances 0.000 abstract 1
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- 230000005501 phase interface Effects 0.000 abstract 1
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- 238000005303 weighing Methods 0.000 description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 231100000331 toxic Toxicity 0.000 description 2
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- 239000002351 wastewater Substances 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
- 238000002835 absorbance Methods 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 printing and dyeing Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明提供了一种CuS/Bi2WO6异质结光催化剂及其制备方法和应用。本发明将Bi2WO6加入到以硫脲和乙酸铜为原料的CuS前驱体溶液中，通过共沉淀‑水热法原位合成CuS/Bi2WO6，在不需要表面活性剂和复杂工艺条件便可制出纳米微球结构的CuS/Bi2WO6异质结光催化剂，其制备过程简单，成本低，无毒性，反应条件可控性强，制得的光催化剂的微观颗粒为CuS纳米片弥散分布在Bi2WO6纳米微球表面，两种相界面形成异质结结构，从而增强了可见光的吸收范围，较单一的CuS半导体具有更优异的光催化活性，较单一的Bi2WO6在光催化反应中具有更好的抗酸性，同时该催化剂具有较高的结晶性，无其他杂质产生。The invention provides a CuS/Bi 2 WO 6 heterojunction photocatalyst and a preparation method and application thereof. In the present invention, Bi 2 WO 6 is added to the CuS precursor solution using thiourea and copper acetate as raw materials, and CuS/Bi 2 WO 6 is synthesized in situ by a co-precipitation-hydrothermal method, without the need for surfactants and complex processes. The nano-microsphere-structured CuS/Bi 2 WO 6 heterojunction photocatalyst can be prepared under certain conditions. The preparation process is simple, the cost is low, it is non-toxic, and the reaction conditions are highly controllable. The microscopic particles of the prepared photocatalyst are CuS The nanosheets are dispersed on the surface of Bi 2 WO 6 nanospheres, and the two phase interfaces form a heterojunction structure, which enhances the absorption range of visible light, and has better photocatalytic activity than a single CuS semiconductor. WO 6 has better acid resistance in the photocatalytic reaction, and at the same time, the catalyst has high crystallinity, and no other impurities are produced.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to CuS/Bi2WO6A heterojunction photocatalyst, a preparation method and application thereof.
Background
The organic wastewater in the industries of medicine, printing and dyeing, paper making and the like has large discharge amount and contains a large amount of pollutants which are difficult to degrade and can generate adverse effects on human health, and the organic wastewater is a great pollution source which causes damage to the water ecological environment and seriously influences the utilization of water resources. The photocatalysis technology can convert 'green' solar energy into chemical energy or electric energy by utilizing a semiconductor photocatalysis material, effectively remove organic pollutants in water under mild reaction conditions, and is one of the most potential technologies for solving energy and environmental problems.
In recent years, in order to improve the photocatalytic activity and stability of semiconductor catalytic materials, researchers at home and abroad have developed a large number of novel photocatalytic materials, such as structural novel compounds, multi-element metal oxides, layered compounds, metal hydroxides, and the like. Bi2WO6Few photocatalysts capable of photolyzing water under visible light irradiation and degrading organic pollutants are hot spots researched in the field of photocatalysis in recent years. However, conventional Bi2WO6Can be decomposed into tungstic acid under the acidic condition, has low stability and is difficult to meet the requirements of practical application. Therefore, appropriate measures must be taken to increase Bi2WO6The acid resistance of (2) improves the stability thereof, thereby enabling the reaction to proceed smoothly. At the present stage, most of the preparation of the composite photocatalyst adopts a multi-step growth method, the contact area of two semiconductors in a heterojunction is limited, the preparation process is complicated, toxic other substances are easily generated, the environment is polluted, and the like. Therefore, the development of a green, simple and convenient preparation method of the heterojunction photocatalyst has important significance for photocatalytic degradation of organic pollutants in water.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a CuS/Bi2WO6The heterojunction photocatalyst, the preparation method and the application thereof have the advantages of simple preparation process, low cost, no introduction of toxic and harmful surfactant in the preparation process, and excellent photocatalytic activity of the prepared photocatalyst.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
CuS/Bi2WO6The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) mixing CuS and Bi2WO6Mixing according to a molar ratio of 1: 1-6;
(2) adjusting the pH value of the mixed solution obtained in the step (1) to 4-6, and continuously stirring for 20-40min to uniformly mix;
(3) reacting the product obtained in the step (2) at the temperature of 140-160 ℃ for 6-12h, naturally cooling to room temperature, washing and drying to obtain the product.
Further, CuS and Bi in the step (1)2WO6In a molar ratio of 1: 4.
Further, the CuS is prepared by the following method: dissolving copper acetate in ethylene glycol to prepare a solution A; dissolving thiourea in ethylene glycol to prepare a solution B, and uniformly mixing the solution A and the solution B to prepare the water-based ink.
Further, the molar ratio of copper acetate to thiourea was 1: 4.
Further, the pH value of the mixed solution is adjusted by acetic acid or nitric acid in the step (2).
Further, in the step (3), the product obtained in the step (2) is reacted for 12 hours at the temperature of 160 ℃.
Further, deionized water and absolute ethyl alcohol are alternately used for washing in the step (3).
CuS/Bi prepared by adopting method2WO6Application of a heterojunction photocatalyst in sewage degradation.
The CuS/Bi provided by the invention2WO6The heterojunction photocatalyst and the preparation method thereof have the following beneficial effects:
(1) CuS has a band gap of 1.76eV-2.48eV and also has certain photocatalytic performance, but the responsivity to light and the transfer efficiency of photogenerated carriers in a photocatalytic reaction are not very high, and Bi2WO6Forms a heterojunction with CuS, is favorable for expanding the photoresponse range of the CuS and promoting the effective separation of electron hole pairs, thereby improving the photocatalytic efficiency of single CuS, and the CuS/Bi2WO6The composite photocatalyst has high stability under acidic conditions, and shows excellent photocatalytic activity in the experimental process.
(2) In the invention, Bi2WO6Adding the solution into a CuS precursor solution which takes thiourea and copper acetate as raw materials, and synthesizing CuS/Bi in situ by a coprecipitation-hydrothermal method2WO6The heterojunction photocatalyst can prepare CuS/Bi with a nano microsphere structure without a surfactant and complex process conditions2WO6The heterojunction photocatalyst has the advantages of simple preparation process, low cost, no toxicity and strong controllability of reaction conditions.
(3) CuS/Bi prepared by the invention2WO6The micro particles of the heterojunction photocatalyst are CuS nanosheets dispersed in Bi2WO6On the surface of the nano microsphere, a heterojunction structure is formed at the interface of two phases. The heterojunction photocatalyst has higher crystallinity, does not generate other impurities, enhances the absorption range of visible light by forming a heterojunction structure, has more excellent photocatalytic activity than a single CuS semiconductor, and has single Bi2WO6Has better acid resistance in the photocatalysis reaction.
Drawings
FIG. 1 shows CuS/Bi obtained in example 12WO6XRD pattern of the heterojunction photocatalyst.
FIG. 2 shows CuS/Bi obtained in example 12WO6SEM image of heterojunction photocatalyst.
FIG. 3 shows CuS/Bi obtained in example 12WO6The heterojunction photocatalyst photocatalysts degrade rhodamine B solution (20mg/L) in an activity diagram under a xenon lamp.
Detailed Description
Example 1
CuS/Bi2WO6The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) weighing 0.25mmol of copper acetate solid at room temperature, and dissolving the copper acetate solid in 40mL of ethylene glycol to form a solution A;
(2) weighing 1mmol of thiourea and dissolving the thiourea in 40mL of glycol to form a solution B;
(3) uniformly mixing the solution A and the solution B, and adding 1mmol of Bi into the mixed solution2WO6Solid powder is evenly stirred;
(4) dropwise adding a 36% acetic acid solution into the mixed solution obtained in the step (3) under the stirring condition until the pH value of the mixed solution is 4, and continuously stirring for 30 min;
(5) and (4) transferring the mixed solution obtained in the step (4) into a 100mL hydrothermal kettle, reacting for 12h at 160 ℃, naturally cooling to room temperature, alternately washing with deionized water and absolute ethyl alcohol, and drying at 80 ℃ to obtain the catalyst.
Example 2
CuS/Bi2WO6The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) weighing 1mmol of copper acetate solid and dissolving the copper acetate solid in 40mL of glycol at room temperature to form a solution A;
(2) weighing 4mmol of thiourea and dissolving the thiourea in 40mL of glycol to form a solution B;
(3) uniformly mixing the solution A and the solution B, and adding 1mmol of Bi into the mixed solution2WO6Solid powder is evenly stirred;
(4) dropwise adding a 36% acetic acid solution into the mixed solution obtained in the step (3) under the stirring condition until the pH value of the mixed solution is 5, and continuously stirring for 30 min;
(5) and (4) transferring the mixed solution obtained in the step (4) into a 100mL hydrothermal kettle, reacting for 12h at 150 ℃, naturally cooling to room temperature, alternately washing with deionized water and absolute ethyl alcohol, and drying at 80 ℃ to obtain the catalyst.
Example 3
CuS/Bi2WO6The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) weighing 0.25mmol of copper acetate solid at room temperature, and dissolving the copper acetate solid in 40mL of ethylene glycol to form a solution A;
(2) weighing 4mmol of thiourea and dissolving the thiourea in 40mL of glycol to form a solution B;
(3) uniformly mixing the solution A and the solution B, and adding 1.5mmol of Bi into the mixed solution2WO6Solid powder is evenly stirred;
(4) dropwise adding a 36% acetic acid solution into the mixed solution obtained in the step (3) under the stirring condition until the pH value of the mixed solution is 6, and continuously stirring for 30 min;
(5) and (4) transferring the mixed solution obtained in the step (4) into a 100mL hydrothermal kettle, reacting for 12h at 140 ℃, naturally cooling to room temperature, alternately washing with deionized water and absolute ethyl alcohol, and drying at 80 ℃ to obtain the catalyst.
Example 4
CuS/Bi2WO6The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) weighing 0.25mmol of copper acetate solid at room temperature, and dissolving the copper acetate solid in 40mL of ethylene glycol to form a solution A;
(2) weighing 1mmol of thiourea and dissolving the thiourea in 40mL of glycol to form a solution B;
(3) uniformly mixing the solution A and the solution B, and adding 1mmol of Bi into the mixed solution2WO6Solid powder is evenly stirred;
(4) dropwise adding a 36% acetic acid solution into the mixed solution obtained in the step (3) under the stirring condition until the pH value of the mixed solution is 5, and continuously stirring for 30 min;
(5) and (3) transferring the mixed solution obtained in the step (4) into a 100mL hydrothermal kettle, reacting for 6h at 150 ℃, naturally cooling to room temperature, alternately washing with deionized water and absolute ethyl alcohol, and drying at 80 ℃ to obtain the catalyst.
Example 5
CuS/Bi2WO6The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) weighing 0.25mmol of copper acetate solid at room temperature, and dissolving the copper acetate solid in 40mL of ethylene glycol to form a solution A;
(2) weighing 1mmol of thiourea and dissolving the thiourea in 40mL of glycol to form a solution B;
(3) uniformly mixing the solution A and the solution B, and adding 1mmol of Bi into the mixed solution2WO6Solid powder is evenly stirred;
(4) dropwise adding a 36% acetic acid solution into the mixed solution obtained in the step (3) under the stirring condition until the pH value of the mixed solution is 6, and continuously stirring for 30 min;
(5) and (4) transferring the mixed solution obtained in the step (4) into a 100mL hydrothermal kettle, reacting for 6h at 140 ℃, naturally cooling to room temperature, alternately washing with deionized water and absolute ethyl alcohol, and drying at 80 ℃ to obtain the catalyst.
Example 6
CuS/Bi2WO6The preparation method of the heterojunction photocatalyst comprises the following steps:
(1) weighing 0.25mmol of copper acetate solid at room temperature, and dissolving the copper acetate solid in 40mL of ethylene glycol to form a solution A;
(2) weighing 1mmol of thiourea and dissolving the thiourea in 40mL of glycol to form a solution B;
(3) uniformly mixing the solution A and the solution B, and adding 1mmol of Bi into the mixed solution2WO6Solid powder is evenly stirred;
(4) dropwise adding a 36% acetic acid solution into the mixed solution obtained in the step (3) under the stirring condition until the pH value of the mixed solution is 4, and continuously stirring for 30 min;
(5) and (4) transferring the mixed solution obtained in the step (4) into a 100mL hydrothermal kettle, reacting for 6h at 160 ℃, naturally cooling to room temperature, alternately washing with deionized water and absolute ethyl alcohol, and drying at 80 ℃ to obtain the catalyst.
Comparative example 1
A photocatalyst, the preparation method of which comprises the following steps:
(1) weighing Bi (NO) at room temperature3)3·5H2Dissolving the O solid in deionized water to form a colorless transparent solution;
(2) weighing Na2WO6·2H2Dissolving O solid in deionized water, adding the O solid into the solution obtained in the step (1) after the O solid is completely dissolved to form a mixed solution, wherein Bi (NO)3)3·5H2O and Na2WO6·2H2The molar ratio of O is 2: 1;
(3) dropwise adding 2mol/L NaOH solution into the mixed solution obtained in the step (2) under the stirring condition until the pH value of the mixed solution is 3, and continuously stirring for 30 min;
(4) and (4) transferring the mixed solution obtained in the step (3) into a 100mL hydrothermal kettle, reacting for 14h at 160 ℃, naturally cooling to room temperature, alternately washing with deionized water and absolute ethyl alcohol, and drying at 80 ℃ to obtain the catalyst.
Comparative example 2
A photocatalyst, the preparation method of which comprises the following steps:
(1) weighing 12mol of thiourea solid at room temperature, dissolving the thiourea solid in 40mL of ethylene glycol, weighing 3mmol of copper acetate solid after complete dissolution, adding the copper acetate solid into the solution while stirring, weighing 0.4g of PVP, adding the PVP into the solution, and stirring for 30 min;
(2) and transferring the mixed solution into a 100mL hydrothermal kettle, reacting for 3h at 160 ℃, naturally cooling to room temperature, alternately washing with deionized water and absolute ethyl alcohol, and drying at 80 ℃ to obtain the catalyst.
Test examples
1. X-ray diffraction pattern detection
FIG. 1 shows CuS/Bi obtained in example 12WO6The X-ray diffraction pattern of the heterojunction photocatalyst is compared with a standard card to know that the diffraction peak in the pattern and Bi2WO6(PDF 00-026-1044) standard spectra were matched and CuS/Bi2WO6No other hetero-phases are present in the diffraction pattern of the heterojunction photocatalyst. The X-ray diffraction pattern does not detect the diffraction peak of CuS, which is caused by the small CuS particles and high dispersity.
2. Scanning electron microscope
FIG. 2 shows CuS/Bi obtained in example 12WO6FIG. 2 shows that the prepared heterojunction photocatalyst presents a nano microsphere structure, and various irregular CuS nanosheets are attached to the surface of the microsphere, which indicates that the hydrothermal synthesis method can be used for in-situ synthesis of CuS/Bi2WO6A heterojunction photocatalyst.
3. Photocatalytic degradation
The specific detection process is as follows: taking 20mg/L rhodamine B solution as a degradation object, adding 0.1g of each of samples prepared in a comparative example 1, a comparative example 2 and the invention example 1 into 100mL of the rhodamine B solution, adsorbing for 30min under dark conditions, transferring the mixed reaction solution into a water-cooling reaction tank for photocatalytic reaction, adopting a 300W xenon lamp as a reaction light source, filtering out an ultraviolet light part with the wavelength of less than 420nm by using an optical filter, collecting 4mL of the rhodamine B reaction solution every 10min, realizing solid-liquid separation by using filter paper, and measuring the absorbance of the rhodamine B solution before and after the reaction at 554 nm. The test results are shown in FIG. 3.
FIG. 3 shows Bi2WO6(comparative example 1), CuS (comparative example 2) and CuS/Bi obtained in example 12WO6And (3) carrying out photocatalytic degradation on the activity diagram of the rhodamine B (20mg/L) solution with the pH value of 3 under the full light condition by using the sample.
Through comparison, CuS/Bi2WO6The photocatalytic activity of the sample is obviously better than that of a single CuS sample and is more than that of single Bi2WO6The sample had better acid resistance (Bi)2WO6Decomposed under acidic conditions), and when the solution is irradiated for 70min, the rhodamine B solution is completely degraded. Overall, CuS/Bi2WO6Can greatly improve single CuS and Bi2WO6Adsorption performance and photocatalytic activity.
Claims (8)
1. CuS/Bi2WO6The preparation method of the heterojunction photocatalyst is characterized by comprising the following steps:
(1) mixing CuS and Bi2WO6Mixing according to a molar ratio of 1: 1-6;
the CuS is prepared by the following method: dissolving copper acetate in ethylene glycol to prepare a solution A; dissolving thiourea in ethylene glycol to prepare a solution B, and uniformly mixing the solution A and the solution B to prepare the solution B;
(2) adjusting the pH value of the mixed solution obtained in the step (1) to 4-6, and stirring and uniformly mixing;
(3) carrying out hydrothermal reaction on the substance obtained in the step (2) at the temperature of 140-160 ℃ for 6-12h, naturally cooling to room temperature, washing and drying to obtain the product.
2. The CuS/Bi of claim 12WO6The preparation method of the heterojunction photocatalyst is characterized in that CuS and Bi in the step (1)2WO6In a molar ratio of 1: 4.
3. The CuS/Bi of claim 12WO6A method for preparing a heterojunction photocatalyst, characterized in thatThe molar ratio of copper acetate to thiourea was 1: 4.
4. The CuS/Bi of claim 12WO6The preparation method of the heterojunction photocatalyst is characterized in that the pH value of the mixed solution is adjusted by using acetic acid or nitric acid in the step (2).
5. The CuS/Bi of claim 12WO6The preparation method of the heterojunction photocatalyst is characterized in that the substance obtained in the step (2) reacts for 12 hours at the temperature of 160 ℃ in the step (3).
6. The CuS/Bi of claim 12WO6The preparation method of the heterojunction photocatalyst is characterized in that deionized water and absolute ethyl alcohol are alternately washed in the step (3).
7. CuS/Bi produced by the method of any of claims 1 to 62WO6A heterojunction photocatalyst.
8. The CuS/Bi of claim 72WO6Application of a heterojunction photocatalyst in sewage degradation.
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