A Cu2S-rGO composite material, its preparation method and application

Abstract

This invention discloses a Cu2S-rGO composite material, its preparation method, and its application, using vitamin B1 hydrochloride as a sulfur source and surfactant. 2+ CuS is generated by the sulfur source provided by vitamin B1 hydrochloride, and the formaldehyde and ammonia decomposition products of hexamethylenetetramine simultaneously reduce CuS and GO in situ and directly composite them to obtain Cu2S-rGO composite material. When used as an adsorbent and added to antibiotic waste liquid, it can efficiently and rapidly adsorb antibiotics, and the adsorption capacity of tetracycline can reach 121.6 mg / g.

Description

Technical Field

[0001] This invention belongs to the field of materials preparation and environmental protection technology, specifically relating to a Cu2S-rGO composite material, its preparation method, and its application in adsorbing antibiotics. Background Technology

[0002] Antibiotics are widely used in livestock and aquaculture due to their broad spectrum and low cost. However, these antibiotics are not completely absorbed by the body, and most are excreted in their original form or as metabolites through feces, causing water and soil pollution. Besides causing chemical pollution, antibiotics in the environment may, more importantly, induce the production of resistant microorganisms and resistance genes, accelerating the spread of antibiotic resistance. These resistant microorganisms can enter the human body through direct or indirect contact, enhancing drug resistance and posing a threat to public health. Therefore, research on the removal mechanisms of antibiotics in the environment and their environmental behavior is essential. Adsorption methods for treating antibiotics in wastewater are an effective strategy for remediating contaminated antibiotic wastewater due to their high efficiency, environmental friendliness, and low cost.

[0003] Currently, many adsorbents have been developed for the remediation of environmental pollutants emitted from industrial processes, such as activated carbon, zeolite molecular sieves, diatomaceous earth, and clay. Developing more adsorbents for the adsorption and treatment of antibiotics in wastewater is of practical significance. Summary of the Invention

[0004] The purpose of this invention is to provide a Cu2S-rGO composite material, its preparation method, and its application, using vitamin B1 hydrochloride as a sulfur source and surfactant, Cu 2+ The sulfur source provided by vitamin B1 hydrochloride is used to generate CuS, and the generated CuS is reduced and compounded with GO in situ to obtain Cu2S-rGO composite material, which can efficiently adsorb antibiotics.

[0005] To achieve the above-mentioned technical objectives, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing Cu2S-rGO composite material involves dissolving vitamin B1 hydrochloride and soluble copper salt in water to obtain a mixture A; dissolving hexamethylenetetramine in water to obtain a solution B; ultrasonically pulverizing GO in ethanol and water to obtain a solution C; then adding mixture A to solution C under stirring and stirring thoroughly before adding solution B and stirring thoroughly to obtain a mixture D; and subjecting mixture D to hydrothermal treatment to obtain the Cu2S-rGO composite material.

[0007] This invention uses vitamin B1 hydrochloride as a sulfur source and surfactant, Cu 2+CuS is generated by the sulfur source provided by vitamin B1 hydrochloride, and the formaldehyde and ammonia, decomposition products of hexamethylenetetramine, simultaneously reduce CuS and GO in situ and directly composite them to obtain Cu2S-rGO composite material.

[0008] Furthermore, the soluble copper salt is selected from one or more of copper nitrate, copper sulfate, and copper acetate.

[0009] Furthermore, the molar ratio of the soluble copper salt and vitamin B1 hydrochloride is 1:1 to 5; the concentration of the soluble copper salt in mixture A is 0.02 to 0.2 mol / L.

[0010] Furthermore, the molar ratio of the soluble copper salt to hexamethylenetetramine is 1:1 to 4.

[0011] Furthermore, the mass ratio of the soluble copper salt to GO is 1 to 10:1.

[0012] Furthermore, the hydrothermal treatment is performed at a temperature of 100–180°C for a duration of 6–24 hours.

[0013] The present invention also provides a Cu2S-rGO composite material prepared by the above preparation method.

[0014] The present invention also provides the application of the above-mentioned Cu2S-rGO composite material, which is used as an adsorbent and added to antibiotic waste liquid for adsorbing antibiotics.

[0015] Furthermore, the mass-to-volume ratio of the Cu2S-rGO composite material to the antibiotic waste liquid is 1 mg: 0.5–4 mL.

[0016] Compared with the prior art, the advantages of the present invention are:

[0017] 1. This invention uses vitamin B1 hydrochloride as a sulfur source and surfactant, Cu 2+ CuS is generated by the sulfur source provided by vitamin B1 hydrochloride, and the formaldehyde and ammonia, decomposition products of hexamethylenetetramine, simultaneously reduce CuS and GO in situ and directly composite them to obtain Cu2S-rGO composite material.

[0018] 2. The Cu2S-rGO composite material of the present invention can efficiently adsorb antibiotics, especially tetracycline, with an adsorption capacity of up to 121.6 mg / g. Attached Figure Description

[0019] Figure 1 SEM image of the material obtained in Example 1;

[0020] Figure 2 The image shows the XRD pattern of the material prepared in Comparative Example 1. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0022] Example 1

[0023] 75 mg GO was dispersed in 30 mL of ethanol and 10 mL of deionized water. 20 mL of an aqueous solution containing 4 mmol VB1-Cl and 2 mmol copper nitrate was added dropwise while stirring. After stirring for 30 min, 20 mL of an aqueous solution containing 4 mmol hexamethylenetetramine was added dropwise. The mixture was transferred to a hydrothermal reactor, sealed, and hydrothermally treated at 160 °C for 12 h. After washing three times with water and three times with ethanol, the mixture was dried at 60 °C for 12 h to obtain Cu2S-rGO-1.

[0024] Example 2

[0025] 37.5 mg of GO was dispersed in 30 mL of ethanol and 10 mL of deionized water. 100 mL of an aqueous solution containing 2 mmol VB1-Cl and 2 mmol copper nitrate was added dropwise while stirring. After stirring for 30 min, 20 mL of an aqueous solution containing 2 mmol hexamethylenetetramine was added dropwise. The mixture was transferred to a hydrothermal reactor, sealed, and hydrothermally treated at 100 °C for 24 h. After washing three times with water and three times with ethanol, the mixture was dried at 60 °C for 12 h to obtain Cu2S-rGO-2.

[0026] Example 3

[0027] 375 mg of GO was dispersed in 100 mL of ethanol and 30 mL of deionized water. 10 mL of an aqueous solution containing 10 mmol VB1-Cl and 2 mmol copper nitrate was added dropwise while stirring. After stirring for 30 min, 20 mL of an aqueous solution containing 8 mmol hexamethylenetetramine was added dropwise. The mixture was transferred to a hydrothermal reactor, sealed, and hydrothermally treated at 180 °C for 6 h. After washing three times with water and three times with ethanol, the mixture was dried at 60 °C for 12 h to obtain Cu2S-rGO-3.

[0028] Example 4

[0029] 75 mg GO was dispersed in 100 mL of ethanol and 30 mL of deionized water. 10 mL of an aqueous solution containing 10 mmol VB1-Cl and 2 mmol copper acetate was added dropwise while stirring. After stirring for 30 min, 20 mL of an aqueous solution containing 8 mmol hexamethylenetetramine was added dropwise. The mixture was transferred to a hydrothermal reactor, sealed, and hydrothermally treated at 160 °C for 6 h. After washing three times with water and three times with ethanol, the mixture was dried at 60 °C for 12 h to obtain Cu2S-rGO-4.

[0030] Comparative Example 1

[0031] 40 mL of 2 mmol copper nitrate aqueous solution (0.05 mol / L) was slowly added dropwise to 30 mL of aqueous solution containing 4 mmol hexamethylenetetramine and 2.5 mmol vitamin B1 hydrochloride. After stirring for 1 h, the solution was sealed and hydrothermally treated at 160 °C for 24 h. After washing three times with water and three times with ethanol, the solution was dried at 60 °C for 12 h to obtain Cu2S.

[0032] like Figure 2 As shown, the copper compound obtained by the method of the present invention is Cu2S, not CuS.

[0033] Comparative Example 2

[0034] 40 mL of 2 mmol copper nitrate aqueous solution (0.05 mol / L) was slowly added dropwise to 30 mL of aqueous solution containing 4 mmol sodium hydroxide and 2.5 mmol vitamin B1 hydrochloride. After stirring for 1 h, the solution was sealed and hydrothermally treated at 160 °C for 24 h. The solution was then washed three times with water and three times with ethanol, and dried at 60 °C for 12 h to obtain CuS.

[0035] Comparative Example 3

[0036] 75 mg C3N4 was dispersed in 30 mL of ethanol and 10 mL of deionized water. 20 mL of an aqueous solution containing 4 mmol VB1-Cl and 2 mmol copper nitrate was added dropwise while stirring. After stirring for 30 min, 20 mL of an aqueous solution containing 4 mmol hexamethylenetetramine was added dropwise. The mixture was transferred to a hydrothermal reactor, sealed, and hydrothermally treated at 160 °C for 12 h. After washing three times with water and three times with ethanol, the mixture was dried at 60 °C for 12 h to obtain Cu2S-C3N4.

[0037] Comparative Example 4

[0038] 75 mg GO was dispersed in 30 mL of ethanol and 10 mL of deionized water. 20 mL of aqueous solution containing 2 mmol copper nitrate was added dropwise while stirring. After stirring for 30 min, 20 mL of aqueous solution containing 4 mmol Na2S and 4 mmol hexamethylenetetramine was added dropwise. The mixture was transferred to a hydrothermal reactor, sealed, and hydrothermally treated at 160 °C for 12 h. After washing three times with water and three times with ethanol, the mixture was dried at 60 °C for 12 h to obtain Cu2S-rGO-5.

[0039] Comparative Example 5

[0040] 75 mg of GO was dispersed in 30 mL of ethanol and 10 mL of deionized water. 20 mL of an aqueous solution containing 4 mmol VB1-Cl and 2 mmol copper nitrate was added dropwise while stirring. After stirring for 30 min, 20 mL of an aqueous solution containing 4 mmol sodium hydroxide was added dropwise. The mixture was transferred to a hydrothermal reactor, sealed, and hydrothermally treated at 160 °C for 12 h. After washing three times with water and three times with ethanol, the mixture was dried at 60 °C for 12 h to obtain CuS-GO.

[0041] Antibiotic adsorption:

[0042] At room temperature, the Cu2S-rGO-1 composite material prepared in Example 1 was added to aqueous solutions of tetracycline, oxytetracycline, and ofloxacin, respectively, and adsorbed in the dark for a period of time. After filtration to remove the catalyst, the concentration of each antibiotic was detected, and the adsorption rate and adsorption amount were calculated as shown in Table 1.

[0043] Table 1. Adsorption data of Cu2S-rGO-1 composite material in Example 1

[0044] antibiotic tetracycline Oxytetracycline ofloxacin Adsorption time (min) 12 60 120 Catalyst addition amount (mg) 25 50 50 Antibiotic volume (mL) 100 50 25 Initial concentration (mg / L) 10 100 12 Residual concentration (mg / L) 0.2 6.9 0.4 Adsorption rate (%) 99.6 80.6 72.6

[0045] At room temperature, 30 mg of the materials prepared in Examples 1-4 and Comparative Examples 1-5 were added to 100 mL of a 50 mg / L tetracycline aqueous solution for adsorption in the dark for 60 min. After filtration to remove the catalyst, the concentration of residual tetracycline was measured, and the adsorption rate and adsorption amount were calculated as shown in Table 2.

[0046] Table 2. Tetracycline Adsorption Rate Data

[0047]

Claims

1. A method for preparing Cu2S-rGO composite material, characterized in that, Vitamin B1 hydrochloride and soluble copper salt were dissolved in water to obtain mixture A; hexamethylenetetramine was dissolved in water to obtain solution B; GO was added to ethanol and water and ultrasonically pulverized to obtain solution C. Then, mixture A was added to solution C under stirring and stirred thoroughly before adding solution B and stirring thoroughly to obtain mixture D. Mixture D was subjected to hydrothermal treatment to obtain Cu2S-rGO composite material.

2. The preparation method according to claim 1, characterized in that, The soluble copper salt is selected from one or more of copper nitrate, copper sulfate, and copper acetate.

3. The preparation method according to claim 1, characterized in that, The molar ratio of the soluble copper salt to vitamin B1 hydrochloride is 1:1 to 5; the concentration of the soluble copper salt in mixture A is 0.02 to 0.2 mol / L.

4. The preparation method according to claim 1, characterized in that, The molar ratio of the soluble copper salt to hexamethylenetetramine is 1:1 to 4.

5. The preparation method according to claim 1, characterized in that, The mass ratio of the soluble copper salt to GO is 1 to 10:

1.

6. The preparation method according to claim 1, characterized in that, The hydrothermal treatment is performed at a temperature of 100–180°C for a duration of 6–24 hours.

7. The Cu2S-rGO composite material prepared by the preparation method according to any one of claims 1-6.

8. The application of the Cu2S-rGO composite material according to claim 7, characterized in that, It was added to antibiotic waste liquid as an adsorbent to adsorb antibiotics.

9. The application according to claim 8, characterized in that, The mass-to-volume ratio of the Cu2S-rGO composite material to the antibiotic waste liquid is 1 mg: 0.5–4 mL.

10. The application according to claim 8, characterized in that: The antibiotic is one or more of tetracycline, oxytetracycline, and ofloxacin.

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