Preparation method of Cu-Co bimetallic semi-crystalline material and application of the Cu-Co bimetallic semi-crystalline material to adsorption of dyes

Abstract

A preparation method of a Cu-Co bimetallic semi-crystalline material and its application in dye adsorption belong to the field of nanomaterial and environmental material preparation. The invention comprises the following steps: weighing a Cu salt and a Co salt of the same type in a mass ratio of 1:3 to 3:1, mixing them in an ethanol solution, and ultrasonically promoting dissolution and thorough mixing of the two, which is named solution A; adding an organic ligand into deionized water, and using an auxiliary reagent under ultrasonic conditions to adjust the concentration of the organic ligand to 0.2 mol / L, which is named solution B; mixing solutions A and B in a volume ratio of 1:2, stirring under uniform stirring until the mixture is in a flowable liquid state, which is named substance C; collecting substance C by centrifugation and drying it to obtain a dry Cu-Co bimetallic semi-crystalline material; the preparation method of the Cu-Co bimetallic semi-crystalline material of the invention is simple, rapid, and has low energy consumption; the synthesized Cu-Co bimetallic semi-crystalline material has a multi-element pore structure, a large specific surface area, and multi-element active sites, and has a strong adsorption capacity.

Description

Technical Field

[0001] The invention belongs to the field of nanomaterial and environmental material preparation, and particularly relates to a preparation method of a Cu-Co bimetallic semi-crystalline material and its application in dye adsorption. Background Art

[0002] With the rapid development of the industrial, textile, papermaking, clothing, and cosmetics industries, organic dyes including Congo red, methylene blue, methyl orange, and rhodamine B are widely used. The use of these substances produces highly polluting dye wastewater. Dye wastewater has poor biodegradability, high chroma, and large variations in water quality and quantity, making it difficult to effectively treat with conventional water treatment technologies. When dye-carrying wastewater enters natural water bodies, it will damage the ecosystem and pose a threat to the growth of plants and animals. Therefore, there is an urgent need for an effective treatment method for removing dyes from water bodies.

[0003] Semi-crystalline materials are a special type of material between metal-organic framework materials and metal-organic gel materials. They have a rich pore structure, multiple active sites and a large specific surface area, which can promote the mass transfer process of pollutants in water bodies within the material and help them be quickly adsorbed and removed in the water body. In particular, due to the different binding abilities of different metal ions with organic ligands during the preparation process, the pore structure of bimetallic semi-crystalline materials will be more complete, which can improve the capture and removal of pollutants in water bodies. However, most of the preparation processes of semi-crystalline materials require a large amount of energy and chemicals, and the preparation time is long, which is not conducive to energy conservation, environmental protection and practical application. Therefore, the simple method for preparing bimetallic semi-crystalline materials still faces challenges. Summary of the Invention

[0004] The present invention aims to address the problems encountered in the aforementioned background art by providing a method for preparing a Cu-Co bimetallic semicrystalline material and its application in dye adsorption. This method is simple to operate, has a high material yield, consumes little energy, and requires minimal preparation time. The resulting bimetallic semicrystalline material exhibits a rich pore structure, diverse active sites, and a large specific surface area, enabling rapid adsorption and removal of high-concentration dyes from water.

[0005] A method for preparing a Cu-Co bimetallic semi-crystalline material comprises the following steps:

[0006] Step 1: Weigh the same type of Cu salt and Co salt, where the salt type can be nitrate, sulfate, or chloride, with a mass ratio of Cu salt to Co salt of 1:3 to 3:1, mix them in an ethanol solution, and ultrasonically promote dissolution and thorough mixing of the two. The concentration of the mixed solution is 0.25 mol / L, and it is named Solution A.

[0007] Step two: a certain amount of organic ligand is weighed and added into deionized water, and the organic ligand is dissolved in water under ultrasonic condition by using an auxiliary agent to promote the dissolution, so that the concentration of the organic ligand is 0.2 mol / L, and the solution is named as B solution, and the volume ratio of the B solution and the auxiliary agent is 10:1 to 40:1;

[0008] Step three: the A solution and the B solution are mixed in a volume ratio of 1:2, and are stirred to a flowable liquid state under uniform stirring, and are named as C substance;

[0009] Step four: the C substance obtained in step three is centrifuged and washed with ethanol for several times to remove excess ion solution and organic ligand, and is dried in an oven at 45 degrees to obtain a dry Cu-Co bimetallic semi-crystalline material.

[0010] The organic ligand used in step two is terephthalic acid, or trimesic acid, or nitrobenzoic acid, or amino benzoic acid.

[0011] The auxiliary agent used in step two is trimethylamine or triethylamine.

[0012] The Cu-Co bimetallic semi-crystalline material prepared according to the above method is used for the adsorption of dyes in water, and the amount of the Cu-Co bimetallic semi-crystalline material is 0.5 g / L.

[0013] The beneficial effects of the present application are as follows:

[0014] The Cu-Co bimetallic semi-crystalline material preparation method provided by the present application is simple, fast and low in energy consumption, and the prepared Cu-Co bimetallic semi-crystalline material can be used as an adsorbent for dyes in water to achieve the purpose of rapid adsorption and removal of dyes.

[0015] The Cu-Co bimetallic semi-crystalline material preparation method provided by the present application is simple, fast and low in energy consumption, and the prepared Cu-Co bimetallic semi-crystalline material can be used as an adsorbent for dyes in water to achieve the purpose of rapid adsorption and removal of dyes. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is the BET graph of the Cu-Co bimetallic semi-crystalline material prepared by the present application;

[0017] Figure 2 is the pore size distribution graph of the Cu-Co bimetallic semi-crystalline material prepared by the present application;

[0018] Figure 3 is the infrared spectrum graph of the Cu-Co bimetallic semi-crystalline material prepared by the present application;

[0019] Figure 4is the adsorption effect diagram of the Cu-Co bimetallic semi-crystalline material prepared by the application on the dye in the water body. DETAILED DESCRIPTION Embodiment 1

[0020] A preparation method of a Cu-Co bimetallic semi-crystalline material, comprising the following steps:

[0021] Step one: take Cu(NO3)2 and Co(NO3)2 with a mass ratio of 1:3, mix them in an appropriate amount of ethanol solution, promote the dissolution and mixing of the two by ultrasonic, the concentration of the mixed solution is 0.25 mol / L, and the mixed solution is named as A solution;

[0022] Step two: take a certain amount of nitrobenzoic acid, add deionized water, promote the dissolution of the nitrobenzoic acid in water under ultrasonic condition by using trimethylamine as an auxiliary reagent, so that the concentration of the nitrobenzoic acid is 0.2 mol / L, the solution is named as B solution, and the volume ratio of the B solution to the trimethylamine is 10:1;

[0023] Step three: take A solution and B solution with a volume ratio of 1:2, mix them, and stir them under uniform stirring condition until they become a flowable liquid, and the mixed solution is named as C substance;

[0024] Step four: centrifugally collect the C substance obtained in step three, wash the C substance with ethanol for three times to remove the excess ion solution and the nitrobenzoic acid, and dry the C substance in an oven at 45 degrees to obtain dry Cu-Co bimetallic semi-crystalline material. Embodiment 2

[0025] A preparation method of a Cu-Co bimetallic semi-crystalline material, comprising the following steps:

[0026] Step one: take CuSO4 and CoSO4 with a mass ratio of 1:1, mix them in an appropriate amount of ethanol solution, promote the dissolution and mixing of the two by ultrasonic, the concentration of the mixed solution is 0.25 mol / L, and the mixed solution is named as A solution;

[0027] Step two: take a certain amount of terephthalic acid, add deionized water, promote the dissolution of the terephthalic acid in water under ultrasonic condition by using triethylamine as an auxiliary reagent, so that the concentration of the terephthalic acid is 0.2 mol / L, the solution is named as B solution, and the volume ratio of the B solution to the triethylamine is 20:1;

[0028] Step three: take A solution and B solution with a volume ratio of 1:2, mix them, and stir them under uniform stirring condition until they become a flowable liquid, and the mixed solution is named as C substance;

[0029] Step four: centrifugally collect the C substance obtained in step three, wash the C substance with ethanol for four times to remove the excess ion solution and the terephthalic acid, and dry the C substance in an oven at 45 degrees to obtain dry Cu-Co bimetallic semi-crystalline material. Example 3

[0030] A method for preparing a Cu-Co bimetallic semi-crystalline material comprises the following steps:

[0031] Step 1: Weigh CuCl2 and CoCl in a mass ratio of 3:1 2， Mix them in an appropriate amount of ethanol solution, and use ultrasound to promote their dissolution and thorough mixing. The concentration of the mixed solution is 0.25 mol / L and is named solution A.

[0032] Step 2: Weigh a certain amount of aminobenzoic acid and add it to deionized water. Under ultrasonic conditions, use trimethylamine as an auxiliary reagent to promote its dissolution in water to a concentration of 0.2 mol / L of aminobenzoic acid. This is named Solution B, and the volume ratio of Solution B to trimethylamine is 40:1.

[0033] Step 3: Mix solutions A and B in a volume ratio of 1:2 and stir at a constant speed until they become a flowable liquid. This is named substance C.

[0034] Step 4: Collect the C substance obtained in step 3 by centrifugation, wash it with ethanol 5 times to remove excess ion solution and aminobenzoic acid, and dry it in an oven at 45 degrees to obtain a dry Cu-Co bimetallic semi-crystalline material. Example 4

[0035] The Cu-Co bimetallic semi-crystalline material prepared in Example 1 is used as an adsorbent to adsorb and remove Congo red dye from water.

[0036] In practical applications, the adsorbent provided in this embodiment can be used to remove Congo red dye from water using the following scheme: Congo red solutions of 100 mg / L, 500 mg / L, 1000 mg / L, 1500 mg / L, 2000 mg / L, 3000 mg / L, and 4000 mg / L were prepared, 0.5 g / L of Cu / Co bimetallic semi-crystalline material was added, and samples were taken regularly at 25 degrees Celsius. The samples were filtered using a 0.22 μm membrane filter, and the concentration of residual Congo red in the water was measured at a wavelength of 497 nm. The amount of Congo red adsorbed by the material was calculated. According to the isotherm model fitting results, the Cu-Co bimetallic semi-crystalline material involved in Example 1 can adsorb 3980.11 mg / g of dye in water.

Claims

1. Preparation of a Cu-Co bimetallic semi-crystalline material for the adsorption of dyes in water, characterized by: The amount of the Cu-Co bimetallic semi-crystalline material is 0.5 g / L; The steps include: Step 1: Weigh the same type of Cu salt and Co salt, where the salt type is nitrate, sulfate, or chloride, with a mass ratio of Cu salt to Co salt of 1:3 to 3:1, mix them in an ethanol solution, and sonicate to promote dissolution and thorough mixing of the two. The concentration of the mixed solution is 0.25 mol / L, and is named Solution A. Step 2: Weigh a certain amount of organic ligand and add it to deionized water. Under ultrasonic conditions, use auxiliary reagents to promote its dissolution in water to make the concentration of organic ligand 0.2 mol / L. This is named solution B. The volume ratio of solution B to auxiliary reagent is 10:1 to 40:

1. Step 3: Mix solutions A and B in a volume ratio of 1:2 and stir at a constant speed until they become a flowable liquid. This is named substance C. Step 4: The C substance obtained in step 3 was collected by centrifugation and washed several times with ethanol to remove excess ion solution and organic ligands. The dried Cu-Co bimetallic semi-crystalline material was obtained after drying in an oven at 45 degrees.

2. The use according to claim 1, characterized in that: The organic ligand used in the step 2 is terephthalic acid, trimesic acid, nitrobenzoic acid or aminobenzoic acid.

3. The application according to claim 1, characterized in that: The auxiliary reagent used in the step 2 is trimethylamine or triethylamine.

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