Preparation method and application of a two-phase basic copper chloride heterojunction material

Abstract

The application relates to a preparation method and application of a two-phase basic copper chloride heterojunction material. A phosphate is dissolved in deionized water to obtain solution A; copper acetate is dispersed in deionized water to obtain solution B; a chloride is added into the solution B to obtain a mixed solution C; the solution A is placed in an open container, the solution C is sprayed into the solution A in a static state, and a flocculent insoluble precursor is generated; the precursor is transferred into a container for ripening, so that the floating flocculent material is changed into a precipitate; after the ripening is completed and the temperature is lowered to room temperature, the obtained product is separated, washed and dried, and the two-phase basic copper chloride heterojunction material is obtained. The two-phase basic copper chloride heterojunction material prepared by the application is composed of two homologous basic copper chlorides, and simultaneously, there are different metal element dopings or different metal compound compounding in the inside.

Description

Technical Field

[0001] This invention relates to the fields of nanomaterials and electrochemistry, specifically to a method for preparing and applying a biphase basic copper chloride heterojunction material. Background Technology

[0002] Copper-based catalysts possess abundant d-electron structures, exhibiting negative *CO adsorption energy and positive *H adsorption energy during catalysis. They exhibit different adsorption modes and intensities with CO2R and HER intermediates (*H, *OCHO, *COOH, and *CO), making them the only metal catalysts capable of catalyzing the formation of multiple products from carbon dioxide. However, single copper-based catalysts suffer from high overpotentials and poor selectivity for specific C2 products. Phase engineering to construct heterostructures allows for the regulation of intermediate adsorption properties, thereby controlling the catalytic reaction pathway and catalytic products. On the other hand, basic copper chloride exhibits a two-dimensional chain structure along the ac direction and a typical layered structure along the ab plane, with layers connected by hydrogen bonds. This layered structure provides a large specific surface area, thus generating sufficient catalytic active sites, making it a highly promising nanomaterial.

[0003] Currently, the methods for synthesizing basic copper chloride include cuprous chloride reduction oxidation [Chen K, Xue D. Room-temperature chemical transformation route to CuO nanowires toward high-performance electrode materials[J].The Journal of Physical Chemistry C,2013,117(44):22576-22583.], electrolysis [Ye Tao. A method for preparing basic copper chloride, CN201710577119.9], and hydrothermal method [Teng Fei et al. A method for preparing and using a sheet-like basic copper chloride catalyst, CN201610345454.1]. However, the products obtained from the aforementioned methods are all pure-phase materials, which cannot achieve the goal of controlling their structure and properties through phase engineering. Summary of the Invention

[0004] The purpose of this invention is to address the aforementioned technical problems by providing a method for preparing and applying a dual-phase basic copper chloride heterojunction material.

[0005] To achieve the above objectives, the preparation method of the present invention is as follows:

[0006] 1) Dissolve phosphate in deionized water to obtain solution A with a concentration of 5-100 mmol / L;

[0007] 2) Disperse copper acetate in deionized water to obtain solution B with a concentration of 1-50 mmol / L;

[0008] 3) Add chloride to solution B at a mass ratio of chloride to copper acetate of (0.01 to 1.5):1 to obtain mixed solution C;

[0009] 4) Take solution A and solution C in a volume ratio of 10:1. Place solution A in an open container and let it stand. Then spray solution C into solution A to generate a precursor of flocculent insoluble matter.

[0010] 5) Transfer the precursor obtained in 4) into a container and mature it at 30-150℃ to turn the floating flocculent matter into precipitate;

[0011] 6) After the curing process is completed and the temperature is lowered to room temperature, the resulting product is separated, washed, and dried to obtain the biphase basic copper chloride heterojunction material.

[0012] The phosphate in step 1) is one of diammonium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, or a mixture thereof in any proportion.

[0013] The concentration of solution A in step 1) is 5–10 mmol / L.

[0014] The concentration of solution B in step 2) is 1–5 mmol / L.

[0015] The chloride in step 3) is a metal chloride or its hydrate that can dissolve in deionized water to form an ionic metal.

[0016] The chloride is one of cobalt chloride hexahydrate, ferric chloride, nickel chloride hexahydrate, and ferrous chloride tetrahydrate, or a mixture thereof in any proportion.

[0017] Steps 1, 2 and 3) involve continuous stirring using magnetic stirring for 0.5 to 2 hours.

[0018] Step 4) spraying speed ≥ 1 mL / s.

[0019] The maturation in step 5) is carried out by direct heating, water bath heating or oil bath heating.

[0020] The biphase basic copper chloride heterojunction material prepared by the above method can be used as an electrocatalytic material, a secondary ion battery electrode material, a photocatalytic material, and a photoanode material.

[0021] The biphase basic copper chloride heterojunction material of the present invention comprises basic copper chloride of different phases and heterogeneous metal ions or compounds doped therein. Due to the different types of chlorides, the resulting basic copper chloride can be amorphous basic copper chloride and / or crystalline basic copper chloride, as well as mixtures thereof.

[0022] Compared with the prior art, the present invention has the following beneficial technical effects:

[0023] (1) The biphase basic copper chloride heterojunction material prepared by this invention is composed of two isomeric basic copper chlorides, and contains heterogeneous metal element doping or heterogeneous metal compound composites. (2) The crystallinity of the product can be controlled by adjusting the type of chloride used in the technical route disclosed in this invention. (3) By establishing a heterojunction structure to control the electronic structure of the material, the electrocatalytic reaction path can be optimized and the electrocatalytic performance of the material can be improved. (4) The preparation process of this invention requires very few controllable factors and has very simple requirements for equipment and instruments, while the obtained material has a rich pore structure and a large specific surface area. (5) The preparation process is simple, easy to control and operate, has good safety and stability, is green and environmentally friendly, and is easy to achieve industrial-scale production. Attached Figure Description

[0024] Figure 1 This is the XRD pattern of the two-phase basic copper chloride heterojunction material prepared in Example 4 of this invention;

[0025] Figure 2 This is the XRD pattern of the biphase basic copper chloride heterojunction material prepared in Example 5 of this invention;

[0026] Figure 3 This is a linear sweep voltammetric curve of the biphase basic copper chloride heterojunction material prepared in Example 5 of the present invention for electrocatalytic hydrogen evolution.

[0027] Figure 4 This is a linear sweep voltammetric curve of the biphase basic copper chloride heterojunction material prepared in Example 4 of the present invention for electrocatalytic oxygen evolution performance. Detailed Implementation

[0028] The present invention will be further described in detail below with reference to the accompanying drawings and embodiments:

[0029] Example 1:

[0030] 1) Disodium hydrogen phosphate was dissolved in deionized water under magnetic stirring and stirred continuously for 0.5 h to obtain solution A with a concentration of 5 mmol / L;

[0031] 2) Copper acetate was dispersed in deionized water under magnetic stirring and stirred continuously for 0.5 h to obtain solution B with a concentration of 1 mmol / L;

[0032] 3) Add the chloride to solution B at a mass ratio of cobalt chloride hexahydrate to copper acetate of 0.9:1, and stir magnetically for 2 hours to obtain mixed solution C;

[0033] 4) Take solution A and solution C in a volume ratio of 10:1. Place solution A in an open container and let it stand. Then, use an ultrasonic sprayer to spray solution C into solution A at a spray rate of 1 mL / s to generate a precursor of flocculent insoluble matter.

[0034] 5) Transfer the precursor obtained in 4) into a container and mature it at 60°C to turn the floating flocculent matter into precipitate;

[0035] 6) After the curing process is completed and the temperature is lowered to room temperature, the resulting product is separated, washed, and dried to obtain the biphase basic copper chloride heterojunction material.

[0036] Example 2

[0037] 1) Dissolve dipotassium hydrogen phosphate in deionized water under magnetic stirring and continue stirring for 0.5 h to obtain solution A with a concentration of 7 mmol / L;

[0038] 2) Copper acetate was dispersed in deionized water under magnetic stirring and stirred continuously for 0.5 h to obtain solution B with a concentration of 3 mmol / L;

[0039] 3) Add the chloride to solution B at a mass ratio of ferric chloride to copper acetate of 1:1, and stir magnetically for 2 hours to obtain mixed solution C;

[0040] 4) Take solution A and solution C in a volume ratio of 10:1. Place solution A in an open container and let it stand. Then, use an electric sprayer to spray solution C into solution A at a spray rate of 2 mL / s to generate a precursor of flocculent insoluble matter.

[0041] 5) Transfer the precursor obtained in 4) into a container and heat it in a water bath at 70°C to mature it, so that the floating flocculent matter turns into precipitate;

[0042] 6) After the curing process is completed and the temperature is lowered to room temperature, the resulting product is separated, washed, and dried to obtain the biphase basic copper chloride heterojunction material.

[0043] Example 3

[0044] 1) Dissolve diammonium hydrogen phosphate in deionized water under magnetic stirring and continue stirring for 0.5 h to obtain solution A with a concentration of 10 mmol / L;

[0045] 2) Copper acetate was dispersed in deionized water under magnetic stirring and stirred continuously for 0.5 h to obtain solution B with a concentration of 5 mmol / L;

[0046] 3) Add the chloride to solution B at a mass ratio of 1.2:1 of the mixture of cobalt chloride hexahydrate and anhydrous ferric chloride to copper acetate, and stir magnetically for 2 hours to obtain mixed solution C;

[0047] 4) Take solution A and solution C in a volume ratio of 10:1. Place solution A in an open container and let it stand. Then, spray solution C into solution A with a spray bottle at a spray rate of 1 mL / s to generate a precursor of flocculent insoluble matter.

[0048] 5) Transfer the precursor obtained in 4) into a container and heat it in an oil bath at 80°C to turn the floating flocculent matter into a precipitate;

[0049] 6) After the curing process is completed and the temperature is lowered to room temperature, the resulting product is separated, washed, and dried to obtain the biphase basic copper chloride heterojunction material.

[0050] Example 4

[0051] 1) Dissolve diammonium hydrogen phosphate in deionized water under magnetic stirring and continue stirring for 0.5 h to obtain solution A with a concentration of 8 mmol / L;

[0052] 2) Copper acetate was dispersed in deionized water under magnetic stirring and stirred continuously for 0.5 h to obtain solution B with a concentration of 1 mmol / L;

[0053] 3) Add the chloride to solution B at a mass ratio of nickel chloride hexahydrate to copper acetate of 0.9:1, and stir magnetically for 2 hours to obtain mixed solution C;

[0054] 4) Take solution A and solution C in a volume ratio of 10:1. Place solution A in an open container and let it stand. Then, spray solution C into solution A with a spray bottle at a spray rate of 1 mL / s to generate a precursor of flocculent insoluble matter.

[0055] 5) Transfer the precursor obtained in 4) into a container and heat it in a water bath at 90°C to turn the floating flocculent matter into a precipitate;

[0056] 6) After the curing process is completed and the temperature is lowered to room temperature, the resulting product is separated, washed, and dried to obtain the biphase basic copper chloride heterojunction material.

[0057] Example 5

[0058] 1) Dissolve diammonium hydrogen phosphate in deionized water under magnetic stirring and continue stirring for 0.5 h to obtain solution A with a concentration of 8 mmol / L;

[0059] 2) Copper acetate was dispersed in deionized water under magnetic stirring and stirred continuously for 0.5 h to obtain solution B with a concentration of 1 mmol / L;

[0060] 3) Add the chloride to solution B at a mass ratio of ferrous chloride tetrahydrate to copper acetate of 1.1:1, and stir magnetically for 2 hours to obtain mixed solution C;

[0061] 4) Take solution A and solution C in a volume ratio of 10:1. Place solution A in an open container and let it stand. Then, spray solution C into solution A with a spray bottle at a spray rate of 1 mL / s to generate a precursor of flocculent insoluble matter.

[0062] 5) Transfer the precursor obtained in 4) into a container and heat it in an oil bath at 90°C to turn the floating flocculent matter into a precipitate;

[0063] 6) After the curing process is completed and the temperature is lowered to room temperature, the resulting product is separated, washed, and dried to obtain the biphase basic copper chloride heterojunction material.

[0064] Example 6

[0065] 1) Dissolve a mixture of disodium hydrogen phosphate and dipotassium hydrogen phosphate in deionized water under magnetic stirring, and continue stirring for 1 hour to obtain a solution A with a concentration of 50 mmol / L.

[0066] 2) Copper acetate was dispersed in deionized water under magnetic stirring and stirred continuously for 2 hours to obtain solution B with a concentration of 30 mmol / L;

[0067] 3) Add the chloride to solution B at a mass ratio of cobalt chloride hexahydrate to copper acetate of 0.01:1, and stir magnetically for 0.5 h to obtain mixed solution C;

[0068] 4) Take solution A and solution C in a volume ratio of 10:1. Place solution A in an open container and let it stand. Then, use an ultrasonic sprayer to spray solution C into solution A at a spray rate of 1 mL / s to generate a precursor of flocculent insoluble matter.

[0069] 5) Transfer the precursor obtained in 4) into a container and mature it at 30°C to turn the floating flocculent matter into precipitate;

[0070] 6) After the curing process is completed and the temperature is lowered to room temperature, the resulting product is separated, washed, and dried to obtain the biphase basic copper chloride heterojunction material.

[0071] Example 7

[0072] 1) Disodium hydrogen phosphate was dissolved in deionized water under magnetic stirring and stirred continuously for 2 hours to obtain solution A with a concentration of 100 mmol / L;

[0073] 2) Copper acetate was dispersed in deionized water under magnetic stirring and stirred continuously for 1 hour to obtain solution B with a concentration of 50 mmol / L;

[0074] 3) Add the chloride to solution B at a mass ratio of ferric chloride to copper acetate of 1.5:1, and stir magnetically for 1 hour to obtain mixed solution C;

[0075] 4) Take solution A and solution C in a volume ratio of 10:1. Place solution A in an open container and let it stand. Then, use an electric sprayer to spray solution C into solution A at a spray rate of 2 mL / s to generate a precursor of flocculent insoluble matter.

[0076] 5) Transfer the precursor obtained in 4) into a container and mature it at 150°C to turn the floating flocculent matter into precipitate;

[0077] 6) After the curing process is completed and the temperature is lowered to room temperature, the resulting product is separated, washed, and dried to obtain the biphase basic copper chloride heterojunction material.

[0078] from Figure 1 As can be seen, when nickel chloride hexahydrate is used as a raw material, the diffraction peaks of the prepared material correspond well to standard cards 85-1731 and 71-2027, corresponding to the phases Botallackite Cu2Cl(OH)3 and Atacamite Cu2Cl(OH)3, respectively. The diffraction peaks are sharp and exhibit good crystallinity. Furthermore, a blue shift of varying degrees is observed in the diffraction peaks, indicating that the interplanar spacing is increased due to nickel ion doping. This demonstrates that the technical route described in this invention can yield doped two-phase basic copper chloride heterojunction materials.

[0079] from Figure 2 It can be seen that when ferrous chloride tetrahydrate is used as a raw material, the resulting product has very poor crystallinity and is an amorphous substance. Combined with... Figure 1 It can be observed that by changing the type of chloride, the crystallinity of the resulting product can be controlled using the technical route of this invention.

[0080] from Figure 3 and Figure 4 It can be seen that the prepared biphase basic copper chloride heterojunction material can be used for electrocatalytic water splitting. Under alkaline conditions, the current density of the hydrogen evolution and oxygen evolution reactions reaches 10 mA / cm². 2 When the overpotentials are 184 mV and 471 mV respectively, they exhibit good catalytic hydrogen evolution and oxygen evolution properties, indicating that the biphase basic copper chloride heterojunction prepared in this invention can be used as a bifunctional catalyst for water electrolysis and has great application potential.

Claims

1. A method for preparing a two-phase basic copper chloride heterojunction material, characterized in that... Includes the following steps: 1) Dissolve phosphate in deionized water to obtain solution A with a concentration of 5~100 mmol / L; 2) Disperse copper acetate in deionized water to obtain solution B with a concentration of 1~50 mmol / L; 3) Add chloride to solution B at a mass ratio of chloride to copper acetate of (0.01~1.5):1 to obtain mixed solution C; 4) Take solution A and solution C in a volume ratio of 10:

1. Place solution A in an open container and let it stand. Then spray solution C into solution A to generate a precursor of flocculent insoluble matter. 5) Transfer the precursor obtained in 4) into a container and mature it at 30~150℃ to turn the floating flocculent matter into precipitate; 6) After the curing process is completed and the temperature is lowered to room temperature, the resulting product is separated, washed, and dried to obtain the biphase basic copper chloride heterojunction material.

2. The method for preparing the dual-phase basic copper chloride heterojunction material according to claim 1, characterized in that: The phosphate in step 1) is one of diammonium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, or a mixture thereof in any proportion.

3. The method for preparing the dual-phase basic copper chloride heterojunction material according to claim 1, characterized in that: The concentration of solution A in step 1) is 5~10 mmol / L.

4. The method for preparing the dual-phase basic copper chloride heterojunction material according to claim 1, characterized in that: The concentration of solution B in step 2) is 1~5 mmol / L.

5. The method for preparing the dual-phase basic copper chloride heterojunction material according to claim 1, characterized in that: The chloride in step 3) is a metal chloride or its hydrate that can dissolve in deionized water to form an ionic metal.

6. The method for preparing the dual-phase basic copper chloride heterojunction material according to claim 5, characterized in that: The chloride is one of cobalt chloride hexahydrate, ferric chloride, nickel chloride hexahydrate, and ferrous chloride tetrahydrate, or a mixture thereof in any proportion.

7. The method for preparing the dual-phase basic copper chloride heterojunction material according to claim 1, characterized in that: Steps 1, 2 and 3) involve continuous stirring using magnetic stirring for 0.5 to 2 hours.

8. The method for preparing the dual-phase basic copper chloride heterojunction material according to claim 1, characterized in that: Step 4) The spraying speed is ≥1 mL / s.

9. The method for preparing the dual-phase basic copper chloride heterojunction material according to claim 1, characterized in that: The maturation in step 5) is carried out by direct heating, water bath heating or oil bath heating.

10. The application of the biphase basic copper chloride heterojunction material prepared by any one of the preparation methods in claims 1-7 as an electrocatalytic material.

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