Preparation method of date kernel-shaped porous copper oxide catalyst for degrading rhodamine B

Abstract

The present application relates to the technical field of photocatalytic degradation, and discloses a preparation method of date kernel-shaped porous copper oxide catalyst for degrading rhodamine B, comprising the following steps: S1, mixing initial materials to prepare: after measuring copper salt and non-ionic surfactant, adding organic amine to form mixture A; S2, preparing a surface active solution: dissolving anionic surfactant solid in deionized water to form a surface active solution; S3, mixing catalyst to prepare: mixing mixture A and the surface active solution, heating and stirring to form catalyst initial liquid; S4, washing and drying the catalyst: centrifugal precipitation is carried out on the prepared catalyst initial liquid, and the precipitate is collected, washed, dried and ground. The prepared copper oxide catalyst has simple process, low energy consumption, unique morphology characteristics, can effectively and quickly remove organic dyes in water, shows excellent treatment efficiency, and has high chemical stability and reusability.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of photocatalytic degradation, in particular to a preparation method of a jujube kernel-shaped porous copper oxide catalyst for degrading rhodamine B. BACKGROUND

[0002] The continuous development of the textile industry and other light industries brings huge benefits and contributions to the economy. However, a large amount of dyes is released into the environment without treatment, causing water pollution and bringing many negative effects to the aquatic ecosystem. Many different dyes used in the textile industry usually have functional groups such as azo, anthraquinone, methyl, nitro, arylmethane, carbonyl, etc. Even some toxic chemical dyes can cause serious damage to the ecosystem even at a concentration as low as 1 mg / L. Among them, rhodamine B is an artificially synthesized dye with bright pink color, which is widely used for dyeing of paints, plastics, textiles and other fabrics, and biological products. When directly released into the water supply, it has high persistence, toxicity and carcinogenicity to organisms and humans. According to the International Agency for Research on Cancer (IARC) of the World Health Organization, both ingestion and skin contact with rhodamine B dye can cause acute and chronic poisoning.

[0003] To avoid such harm, there are many studies trying to degrade rhodamine B from wastewater. Photocatalytic technology is an efficient means of degrading persistent organic pollutants. Traditional photocatalysts are mainly TiO2, but they can only utilize about 5% of the short-wavelength ultraviolet light of natural light, resulting in low light utilization. Copper oxide nanomaterials have stronger light capturing capacity and can broaden the light absorption range to visible light-near infrared light. However, traditional copper oxide powder catalysts have uneven morphology, low specific surface area and unsuitable band structure, which leads to easy recombination of photo-generated charges and is not conducive to the progress of the catalytic reaction. Therefore, it is urgent to seek a preparation method of efficient, simple and easy-to-obtain copper oxide photocatalyst to efficiently degrade persistent organic pollutants rhodamine B under visible light. SUMMARY

[0004] To solve the technical problem of low degradation efficiency of persistent organic pollutants, the application provides a preparation method of a jujube kernel-shaped porous copper oxide catalyst for degrading rhodamine B.

[0005] The application adopts the following technical scheme: a preparation method of a jujube kernel-shaped porous copper oxide catalyst for degrading rhodamine B, comprising the following steps:

[0006] S1 preparation of mixed raw materials:

[0007] After the copper salt and the non-ionic surfactant are measured, an organic amine is added to form a mixture A;

[0008] S2 preparation of a surface active solution:

[0009] The anionic surfactant is dissolved in deionized water to form a surfactant solution;

[0010] S3 catalyst mixing preparation:

[0011] Mixing mixture A with the surfactant solution, heating and stirring to form a catalyst stock solution;

[0012] S4 catalyst washing and drying:

[0013] The prepared catalyst stock solution is centrifuged and precipitated, and after collecting the precipitate, it is washed, dried and ground, thereby preparing a powder-shaped copper oxide catalyst.

[0014] As a further improvement of the above scheme, the copper salt is at least any one of copper acetate or copper sulfate, copper nitrate, copper chloride, cuprous chloride, copper acetylacetone, copper bromide, copper phosphonate.

[0015] As a further improvement of the above scheme, the washing uses water washing.

[0016] As a further improvement of the above scheme, the non-ionic surfactant is at least any one of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyacrylamide, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyvinylpyrrolidone, monoglyceride, lauroyl diethanolamine, allyl polyethylene glycol.

[0017] As a further improvement of the above scheme, the organic amine is at least any one of trioctylamine or oleylamine, acetamide, melamine, hexamethylenetetramine, acrylamide, hydroxylamine hydrochloride, N,N-dimethylformamide hexadecylamine, octadecylamine, ethylenediamine, tetrabutylammonium hydroxide, n-butylamine, tetramethylammonium bromide, ethylenediaminetetraacetic acid, ammonium acetate.

[0018] As a further improvement of the above scheme, the anionic surfactant is at least any one of alkylbenzenesulfonate, alpha-olefin sulfonate, alkyl sulfonate, alpha-sulfo monocarboxylic acid ester, fatty acid sulfonalkyl ester, succinate sulfonate, alkyl naphthalene sulfonate, petroleum sulfonate, lignin sulfonate, alkyl glyceryl ether sulfonate, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium hexadecylbenzenesulfonate, ammonium hexadecyltrimethyl p-toluenesulfonate, alpha-olefin sulfonate, alpha-sulfo fatty acid methyl ester, sodium oleoyloxyethanesulfonate, sodium diisooctyl succinate sulfonate.

[0019] As a further improvement of the above scheme, the mass ratio of the copper salt to the non-ionic surfactant, the organic amine and the anionic surfactant is 20-120:60-200:3700-38000:20-100.

[0020] A method for using a jujube core-shaped porous copper oxide catalyst for degrading rhodamine B, characterized in that it comprises the following steps:

[0021] The copper oxide catalyst is added to a water solution containing rhodamine B to be treated, and catalysis is carried out under light conditions.

[0022] As a further improvement of the above scheme, the initial concentration of rhodamine B is 15-25 mg / L, and the catalyst addition amount is 0.17-0.5 g / L.

[0023] As a further improvement of the above scheme, the light source uses a xenon lamp loaded with a CUT 420 nm filter.

[0024] Compared with the prior art, the present application has the following beneficial effects:

[0025] 1. The copper oxide catalyst prepared by the present application has a simple process and low energy consumption, and the prepared composite catalyst has unique morphological characteristics; by different preparation methods, two different surfactants are added to the surface of the copper source to make the reactants in the reaction system in the form of ultra-fine droplets, thereby facilitating the formation of jujube core-shaped porous morphology, which greatly increases the specific surface area of the product and is beneficial to the contact between the catalyst and the degradation material in the catalytic reaction process, thereby improving the degradation efficiency.

[0026] 2. The present application can effectively and quickly remove organic dyes in water and exhibits excellent treatment efficiency, and the catalyst has high chemical stability and reusability. DETAILED DESCRIPTION

[0027] Figure 1 X-ray diffraction pattern of the commercial CuO catalyst and the jujube core-shaped CuO catalyst in Example 2.

[0028] Figure 2 Raman spectrum of the jujube core-shaped CuO catalyst in Example 2.

[0029] Figure 3 X-ray electron spectrogram of the jujube core-shaped CuO catalyst in Example 2.

[0030] Figure 4 Transmission electron microscope image of the jujube core-shaped CuO catalyst in Example 2.

[0031] Figure 5 Photocatalytic degradation effect of the jujube core-shaped CuO catalyst on rhodamine B solution in Example 3.

[0032] Figure 6 Kinetics comparison chart of different mass of commercial CuO catalyst and jujube core-shaped CuO catalyst degrading rhodamine B in Example 3 and Example 4. DETAILED DESCRIPTION

[0033] The application will be further described below in conjunction with the drawings and specific embodiments. It should be noted that the following described embodiments or technical features can be combined in any manner to form new embodiments without conflict.

[0034] Embodiment 1

[0035] The method for preparing the jujube seed-shaped porous copper oxide catalyst for degrading rhodamine B comprises the following steps:

[0036] S1: preparation of a mixture of raw materials

[0037] After the copper salt and the non-ionic surfactant are measured, an organic amine is added to form a mixture A;

[0038] S2: preparation of a surface-active solution

[0039] The solid anionic surfactant is dissolved in deionized water to form a surface-active solution;

[0040] S3: preparation of a catalyst mixture

[0041] The mixture A is mixed with the surface-active solution, and heated and stirred to form a catalyst initial solution;

[0042] S4: washing and drying of the catalyst

[0043] The prepared catalyst initial solution is centrifuged and precipitated, and the precipitate is collected, washed, dried, and ground to prepare a powder-shaped copper oxide catalyst. The washing is performed by water washing.

[0044] The copper salt is at least any one of copper acetate, copper sulfate, copper nitrate, copper chloride, cuprous chloride, copper acetylacetonate, copper bromide, and copper phosphonate.

[0045] The non-ionic surfactant is at least any one of a fatty alcohol polyoxyethylene ether, an alkylphenol polyoxyethylene ether, a fatty acid polyoxyethylene ester, polyacrylamide, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyvinylpyrrolidone, monoglyceride, lauroyl diethanolamine, allyl polyethylene glycol.

[0046] The organic amine is at least any one of trioctylamine, oleylamine, acetamide, melamine, hexamethylenetetramine, acrylamide, hydroxylamine hydrochloride, N,N-dimethylformamide hexadecylamine, octadecylamine, ethylenediamine, tetrabutylammonium hydroxide, n-butylamine, tetramethylammonium bromide, ethylenediaminetetraacetic acid, and ammonium acetate.

[0047] The anionic surfactant is at least any one of alkyl benzene sulfonate, alpha-olefin sulfonate, alkyl sulfonate, alpha-sulfo monocarboxylic acid ester, fatty acid sulfobutyl ester, succinate sulfonate, alkyl naphthalene sulfonate, petroleum sulfonate, lignin sulfonate, alkyl glyceryl ether sulfonate, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium hexadecyl benzene sulfonate, ammonium hexadecyl trimethyl p-toluene sulfonate, alpha-olefin sulfonate, alpha-sulfo fatty acid methyl ester, sodium oleyloxyethanesulfonate, sodium diisooctyl succinate sulfonate.

[0048] The mass ratio of the copper salt, nonionic surfactant, organic amine and anionic surfactant is: 20-120: 60-200: 3700-38000: 20-100.

[0049] Example 2

[0050] As shown in Figures 1-4 A method for preparing a date kernel-shaped porous copper oxide catalyst for degrading rhodamine B, comprising the following steps:

[0051] S1 In a 100 mL three-necked flask, 20-120 mg of copper acetate or copper sulfate, copper nitrate, copper chloride, cuprous chloride, copper acetylacetonate, copper bromide, copper phosphonate, 60-200 mg of fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyacrylamide, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyvinylpyrrolidone, monoglyceride, lauroyl diethanolamine, allyl polyethylene glycol, 3.7-38 g of trioctylamine or oleylamine, acetamide, melamine, hexamethylenetetramine, acrylamide, hydroxylamine hydrochloride, N,N-dimethylformamide hexadecylamine, octadecylamine, ethylenediamine, tetrabutylammonium hydroxide, n-butylamine, tetramethylammonium bromide, ethylenediaminetetraacetic acid, ammonium acetate and 20-100 mg of alkyl benzene sulfonate, alpha-olefin sulfonate, alkyl sulfonate, alpha-sulfo monocarboxylic acid ester, fatty acid sulfobutyl ester, succinate sulfonate, alkyl naphthalene sulfonate, petroleum sulfonate, lignin sulfonate, alkyl glyceryl ether sulfonate, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium hexadecyl benzene sulfonate, ammonium hexadecyl trimethyl p-toluene sulfonate, alpha-olefin sulfonate, alpha-sulfo fatty acid methyl ester, sodium oleyloxyethanesulfonate, sodium diisooctyl succinate sulfonate are dissolved in 1-25 mL of deionized water to obtain a solution, a magnetic stirrer is added, heated to 60-180℃ in an oil bath, refluxed, and the color of the solution changes from green to black;

[0052] S2 The solution obtained in step S1 is centrifuged to collect the precipitate, washed with water several times, dried at 80℃, and ground to obtain a black powder-shaped copper oxide catalyst.

[0053] Example 3

[0054] As shown in Figures 5-6As shown in the method for using the date kernel-shaped porous copper oxide catalyst for degrading rhodamine B, the method comprises the following steps:

[0055] The copper oxide catalyst product is used for treating rhodamine B in a water body, and the specific steps are as follows: a rhodamine solution of 20 mg / L is configured in a beaker, a small amount of H2O2 (30 wt%) and the catalyst are added, stirring is performed under irradiation of a xenon lamp (equipped with a CUT 420 nm filter), sampling is performed at a fixed time, and the rhodamine B concentration in the water body is detected by using an ultraviolet-visible spectrophotometer. The addition amount of the catalyst is 0.17 g / L.

[0056] Example 4:

[0057] As shown in the method for using the date kernel-shaped porous copper oxide catalyst for degrading rhodamine B, the method comprises the following steps: Figures 5-6

[0058] The copper oxide catalyst product is used for treating rhodamine B in a water body, and the specific steps are as follows: a rhodamine solution of 20 mg / L is configured in a beaker, a small amount of H2O2 (30 wt%) and the catalyst are added, stirring is performed under irradiation of a xenon lamp (equipped with a CUT 420 nm filter), sampling is performed at a fixed time, and the rhodamine B concentration in the water body is detected by using an ultraviolet-visible spectrophotometer. The addition amount of the catalyst is 0.25 g / L.

[0059] Rhodamine B in Example 3 and Example 4 is detected, and the degradation rate of rhodamine B is shown in Table 1.

[0060] Table 1: Treatment rate of rhodamine B-containing water body with different catalyst addition amounts

[0061]

[0062] In summary, the copper oxide catalyst prepared by the method has the advantages of simple process, low energy consumption, unique morphology of the prepared composite catalyst, and the like. By using different preparation methods and adding two different surfactants on the surface of the copper source, the reactants can be in the state of ultra-fine droplets in the reaction system, so that the date kernel-shaped porous morphology is formed, the specific surface area of the product is greatly increased, the catalyst can be in contact with the degradation material in the catalytic reaction process, and the degradation efficiency is improved. The catalyst can effectively and quickly remove organic dyes in water and has excellent treatment efficiency. The catalyst has high chemical stability and reusability.

[0063] The above embodiments are only preferred embodiments of the present application, and cannot be used to limit the protection scope of the present application. Any non-essential changes and replacements made by those skilled in the art on the basis of the present application shall fall within the protection scope of the present application.​

Claims

1. A method for preparing a date-shaped porous copper oxide catalyst for degrading Rhodamine B, characterized in that, Includes the following steps: Preparation of S1 mixed raw materials: After metering copper salt and nonionic surfactant, organic amine is added to form mixture A; The copper salt is at least one of copper acetate or copper sulfate, copper nitrate, copper chloride, cuprous chloride, copper acetylacetonate, copper bromide, and copper phosphate. The nonionic surfactant is at least one of the following: fatty alcohol polyoxyethylene ether or alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester, polyvinylpyrrolidone, monoglyceride, lauroyl diethanolamine, and allyl polyethylene glycol. Preparation of S2 surface-active solution: Anionic surfactant solids are dissolved in deionized water to form a surfactant solution; The mass ratio of the copper salt to the nonionic surfactant, organic amine and anionic surfactant is 20-120: 60-200: 3700-38000: 20-100; S3 catalyst mixing preparation: Mixture A with surfactant solution, heat to 60-180°C in an oil bath, and stir to form initial catalyst solution; S4 catalyst washing and drying: The prepared catalyst solution was centrifuged and precipitated. The precipitate was collected, washed, dried, and ground to obtain a powdered copper oxide catalyst.

2. The method for preparing a date-shaped porous copper oxide catalyst for degrading Rhodamine B as described in claim 1, characterized in that, The washing process involves water washing.

3. The method for preparing a date-shaped porous copper oxide catalyst for degrading Rhodamine B as described in claim 1, characterized in that, The organic amine is at least one of trioctylamine, oleylamine, octadecylamine, ethylenediamine, and n-butylamine.

4. The method for preparing a date-shaped porous copper oxide catalyst for degrading Rhodamine B as described in claim 1, characterized in that, The anionic surfactant is at least one of the following: alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfonate, α-sulfonyl monocarboxylic acid ester, fatty acid sulfonyl ester, succinate sulfonate, alkylnaphthalene sulfonate, petroleum sulfonate, lignin sulfonate, alkyl glycerol ether sulfonate, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium hexadecylbenzene sulfonate, α-olefin sulfonate, α-sulfonyl fatty acid methyl ester, sodium oleoyloxyethanesulfonate, and sodium diisooctyl succinate sulfonate.

5. The method of using the date-shaped porous copper oxide catalyst for degrading Rhodamine B prepared by the method described in claim 1, characterized in that, Includes the following steps: The copper oxide catalyst was added to the aqueous solution containing Rhodamine B and catalytic activity was carried out under light irradiation.

6. The method of using the date-shaped porous copper oxide catalyst for degrading Rhodamine B as described in claim 5, characterized in that, The initial concentration of Rhodamine B is 15-25 mg / L, and the catalyst dosage is 0.17-0.5 g / L.

7. The method of using the date-shaped porous copper oxide catalyst for degrading Rhodamine B as described in claim 5, characterized in that, The light source is a xenon lamp, and it is equipped with a filter with a cut of 420 nm.

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