Copper-based alloy nano composite material as well as preparation method and application thereof

Abstract

The invention relates to a copper-based alloy nano composite material, the copper-based alloy nano composite material comprises a nano carbon material and copper-based alloy nano particles loaded on the nano carbon material, the copper-based alloy nano particles comprise cuprous ions and at least one non-copper metal element, and the cuprous ions and the at least one non-copper metal element are not in contact with each other. The non-copper metal element is any one of VIII group elements or IB group elements. According to the copper-based alloy nano composite material provided by the invention, the copper-based alloy nano particles containing various metal elements are loaded on the nano carbon material, so that the copper-based alloy nano composite material is formed, and a new copper-based alloy nano material is developed.

Description

Technical Field

[0001] This application relates to the field of nanomaterials, and particularly to copper-based nanomaterials. Background Art

[0002] Cu + Due to its special electronic structure, it exhibits special advantages in catalyzing some reactions, such as electrolysis of water to produce hydrogen. Therefore, copper-based nanomaterials containing Cu + have great potential for catalytic applications. Cu + itself has poor stability. An effective way to enhance its stability is to make Cu + form an alloy with other metals. Alloy materials with nanostructures are a type of novel materials with potential for catalytic applications. Due to the intermetallic electron effects and synergistic effects among multiple metals and the quantum size effect of nanostructures, it is easy to design materials with high catalytic activity. However, due to the formation of alloy nanostructures being driven by thermodynamics and affected by reducing agents, different metal elements tend to form a phase separation structure with a lower entropy value rather than mixing to form an alloy solid solution structure. Therefore, copper-based alloy nanomaterials still need to be developed. Summary of the Invention

[0003] Embodiments of this application provide a copper-based alloy nanocomposite material, its preparation method and application to solve the technical problem that copper-based alloy nanomaterials still need to be developed.

[0004] In a first aspect, embodiments of this application provide a copper-based alloy nanocomposite material, which includes a nanocarbon material and copper-based alloy nanoparticles loaded on the nanocarbon material. The copper-based alloy nanoparticles include cuprous ions and at least one non-copper metal element, and the non-copper metal element is any one of Group VIII or Group IB elements.

[0005] In some embodiments of this application, the non-copper metal element is selected from any one of Pd, Pt, and Au.

[0006] In some embodiments of this application, the copper-based alloy nanoparticles include one non-copper metal element, and the non-copper metal element is Pd. The ratio of the number of Cu atoms to the number of Pd atoms in the copper-based alloy nanoparticles is 3:1.

[0007] In some embodiments of this application, the copper-based alloy nanoparticles include one non-copper metal element, and the non-copper metal element is Pt. The ratio of the number of Cu atoms to the number of Pt atoms in the copper-based alloy nanoparticles is 3:1.

[0008] In some embodiments of the present application, the copper-based alloy nanoparticles include three non-copper metal elements, namely Pt, Pd, and Au, and the atomic ratio of Cu atoms to Pt atoms, Pd atoms, and Au atoms in the copper-based alloy nanoparticles is 9:1:1:1.

[0009] In some embodiments of the present application, the diameter of the copper-based alloy nanoparticles is 3 to 7 nm.

[0010] In some embodiments of the present application, the nano-carbon material is any one of carbon nanoparticles, carbon nanotubes, graphene, or a mixed material of any at least two of them, or a composite material formed by any at least two of them combined.

[0011] In some embodiments of the present application, the nano-carbon material is carbon black.

[0012] In some embodiments of the present application, based on mass percentage, the loading amount of the alloy nanoparticles on the nano-carbon material is 18% to 22%.

[0013] In a second aspect, embodiments of the present application provide a method for preparing a copper-based alloy nanocomposite material, and the method includes the following steps:

[0014] Disperse the nano-carbon material, the precursor of Cu + and the precursor of at least one non-copper metal element in a liquid including a reducing agent to form a first solution;

[0015] Perform ultrasonic treatment on the first solution to obtain a second solution;

[0016] Centrifuge the second solution to obtain a precipitate;

[0017] Wash and dry the precipitate to obtain the copper-based alloy nanocomposite material,

[0018] wherein, the non-copper metal element is any one of Group VIII or Group IB elements, and the valence states of the metal elements in the precursor of Cu + and the precursor of the non-copper metal element are positive valence states.

[0019] In some embodiments of the present application, the precursor is any one of HAuCl4, H2PtCl6, and K2PdCl4.

[0020] In some embodiments of the present application, dispersing the nano-carbon material, the precursor of Cu + and the precursor of at least one non-copper metal element in a liquid including a reducing agent is specifically:

[0021] Disperse the nano-carbon material, Cu(Ac)2, and K2PdCl4 in a liquid including a reducing agent.

[0022] In some embodiments of the present application, a nano-carbon material, a precursor of Cu + , and a precursor of at least one non-copper metal element are dispersed in a liquid including a reducing agent. Specifically:

[0023] Disperse the nano-carbon material, Cu(Ac)2, and H2PtCl6 in a liquid including a reducing agent.

[0024] In some embodiments of the present application, a nano-carbon material, a precursor of Cu + , and a precursor of at least one non-copper metal element are dispersed in a liquid including a reducing agent. Specifically:

[0025] Disperse the nano-carbon material, Cu(Ac)2, HAuCl4, H2PtCl6, and K2PdCl4 in a liquid including a reducing agent.

[0026] In some embodiments of the present application, the nano-carbon material is any one of carbon nanoparticles, carbon nanotubes, and graphene, or a mixed material of any at least two of them, or a composite material formed by any at least two of them being combined.

[0027] In some embodiments of the present application, the nano-carbon material is carbon black.

[0028] In some embodiments of the present application, the total weight of the metal elements in the precursor of Cu + and the precursor of the non-copper metal element is 18% - 22% of the nano-carbon material.

[0029] In some embodiments of the present application, the reducing agent is ethylene glycol.

[0030] In some embodiments of the present application, the liquid is ethylene glycol.

[0031] In some embodiments of the present application, in the ultrasonic treatment, the treatment duration is 4 - 8 min, and the frequency of the ultrasonic wave is 18 - 22 kHz.

[0032] In some embodiments of the present application, when washing the precipitate, the washing liquid used for washing is ethanol.

[0033] In a third aspect, an electrolyzed water catalyst is provided in an embodiment of the present application. The electrolyzed water catalyst includes the copper-based alloy nano-composite material described in any embodiment of the first aspect, or the copper-based alloy nano-composite material prepared by the method described in any embodiment of the second aspect.

[0034] The above technical solutions provided in the embodiments of the present application have the following advantages compared with the prior art:

[0035] The copper-based alloy nanocomposite provided by the embodiments of the present application loads copper-based alloy nanoparticles containing multiple metal elements onto a nanocarbon material to form a copper-based alloy nanocomposite, and develops a new copper-based alloy nanomaterial. Description of the Drawings

[0036] The drawings herein are incorporated into the specification and form a part of this specification, showing embodiments in line with the present application, and are used together with the specification to explain the principles of the present application.

[0037] To more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative efforts.

[0038] Figure 1 XRD diagrams of the copper-based alloy nanocomposites provided in Embodiments 1-4 of the present application;

[0039] Figure 2 TEM diagrams of the copper-based alloy nanocomposites provided in Embodiments 1-4 of the present application. Detailed Embodiments

[0040] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present application with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some, but not all, of the embodiments of the present application. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present application without creative efforts fall within the scope of protection of the present application.

[0041] Unless otherwise specifically stated, the terms used herein should be understood as having the meanings commonly used in the art. Therefore, unless otherwise defined, all technical and scientific terms used herein have the same meaning as the general understanding of those skilled in the art to which the present application belongs. In case of conflict, this specification prevails.

[0042] Unless otherwise specifically stated, various raw materials, reagents, instruments, and equipment used in the present application can all be obtained through market purchases or can be prepared by existing methods.

[0043] Existing copper-based alloy nanomaterials still need to be developed.

[0044] The technical solutions provided by the embodiments of the present application to solve the above technical problems have the following general ideas:

[0045] In a first aspect, an embodiment of the present application provides a copper-based alloy nanocomposite, which includes a nanocarbon material and copper-based alloy nanoparticles loaded on the nanocarbon material. The copper-based alloy nanoparticles include cuprous ions and at least one non-copper metal element, and the non-copper metal element is any one of Group VIII or Group IB elements.

[0046] The electronic effect between multi-component metals can greatly enhance the stability of the copper-based alloy nanoparticles, so that Cu + can exist stably.

[0047] In the present application, copper-based alloy nanoparticles containing multiple metal elements are loaded onto a nanocarbon material to form a copper-based alloy nanocomposite, developing a new copper-based alloy nanomaterial.

[0048] In some embodiments of the present application, the non-copper metal element is selected from any one of Pd, Pt, and Au.

[0049] Pt, Au, and Pd themselves have good stability, which is beneficial to improving the chemical stability of copper-based alloy nanoparticles; Pt, Au, and Pd also have high catalytic activity, are easy to form alloys with Cu, and are easy to form alloys with each other, which is beneficial to improving the stability of Cu + valence state.

[0050] In some embodiments of the present application, the copper-based alloy nanoparticles include one non-copper metal element, which is Pd, and the ratio of the number of Cu atoms to Pd atoms in the copper-based alloy nanoparticles is 3:1.

[0051] Cu and Pd atoms in the above ratio can form a relatively stable Cu3Pd1 crystal form, which is beneficial to stabilizing the valence state of Cu + valence state.

[0052] In some embodiments of the present application, the copper-based alloy nanoparticles include one non-copper metal element, which is Pt, and the ratio of the number of Cu atoms to Pt atoms in the copper-based alloy nanoparticles is 3:1.

[0053] Cu and Pt atoms in the above ratio can form a relatively stable Cu3Pt1 crystal form, which is beneficial to stabilizing the valence state of Cu + valence state.

[0054] In some embodiments of the present application, the copper-based alloy nanoparticles include three non-copper metal elements, namely Pt, Pd, and Au, and the ratio of the number of Cu atoms to Pt atoms, Pd atoms, and Au atoms in the copper-based alloy nanoparticles is 9:1:1:1.

[0055] The Cu and Pt, Au, Pd atoms in the above ratio can form a relatively stable Cu 3( (PtAuPd)1 crystal form, which is beneficial to stabilizing Cu + valence state.

[0056] In some embodiments of the present application, the diameter of the copper-based alloy nanoparticles is 3 to 7 nm.

[0057] In some embodiments of the present application, the nano-carbon material is any one of carbon nanoparticles, carbon nanotubes, graphene, or a mixed material of any at least two, or a composite material formed by any at least two composites.

[0058] As an example, the nano-carbon material can be one of carbon black, graphene powder, carbon nanotube powder, graphene-carbon nanotube composite film, and graphene-carbon black composite aerogel.

[0059] In some embodiments of the present application, the nano-carbon material is carbon black.

[0060] The beneficial effect of selecting carbon black as the nano-carbon material is to improve the conductivity of the catalyst and the dispersion of metal particles.

[0061] In some embodiments of the present application, by mass percentage, the loading amount of the alloy nanoparticles on the nano-carbon material is 18% to 22%.

[0062] The beneficial effect of the loading amount of the copper-based alloy nanoparticles on the nano-carbon material being 18% to 22% is that, on the basis of ensuring a large loading amount and increasing the electrolytic water catalytic ability of the multi-component alloy nanocomposite material, the alloy nanoparticles are not too densely distributed on the nano-carbon material and are not easily agglomerated.

[0063] Second, embodiments of the present application provide a preparation method of a copper-based alloy nanocomposite material, and the method includes the following steps:

[0064] S1: Disperse the nano-carbon material, the precursor of Cu + and the precursor of at least one non-copper metal element simple substance into a liquid including a reducing agent to form a first solution;

[0065] S2: Perform ultrasonic treatment on the first solution to obtain a second solution;

[0066] S3: Centrifuge the second solution to obtain a precipitate;

[0067] S4: Wash and dry the precipitate to obtain the copper-based alloy nanocomposite material,

[0068] Among them, the non - copper metal element is any one of the elements in Group VIII or Group IB, and the valence state of the metal element in the precursor of + Cu and the precursor of the non - copper metal element in its elemental form is a positive valence state.

[0069] It is easy to understand that the method described in the second aspect of the present application can be used to prepare the copper - based alloy nanocomposite material described in any embodiment of the first aspect.

[0070] Ultrasonic treatment can produce a cavitation effect, creating an instantaneous high - pressure and high - temperature environment at the microscale, reducing the metal element in the positive valence state to the metal in its elemental form by a reducing agent, and the metal atoms aggregate to form alloy spheres of several nanometers.

[0071] The method for synthesizing a multi - component alloy is usually the "calcination and smelting method", which fuses various metal blocks under high temperature and high pressure. This method requires a large amount of energy consumption, and the obtained material is a bulk solid. It is very difficult to control the morphology and size of the synthesized material to reach the nanoscale and cannot meet the requirements such as high atomic utilization rate and exposure of active sites in the catalytic field. The "liquid - phase chemical reduction method" is a commonly used method for preparing alloy nanoparticles. Under oil - bath heating and the action of a reducing agent, metal ions are reduced and aggregated to form alloy particles. However, this method is not applicable to the preparation of alloy nanoparticles containing + Cu. On the one hand, + Cu itself has poor stability. The more components the alloy has, the more beneficial it is to the stability of the alloy nanoparticles. However, the operation of oil - bath heating limits the energy that this method can provide and is mostly used for synthesizing binary alloy nanoparticles. It is very difficult to meet the thermodynamic conditions for alloying of alloys with three or more metal components. Most of the currently reported ones are binary alloys. On the other hand, + Cu itself has oxidizing properties. When preparing alloy nanoparticles containing + Cu by the liquid - phase chemical reduction method, there are strict requirements for the reduction ability of the reducing agent, which in turn leads to an increase in the cost of the reducing agent and is not conducive to large - scale production.

[0072] In the present application, by ultrasonically treating the first solution containing a reducing agent and the precursor of + Cu and the precursor of at least one non - copper metal element in its elemental form, with the help of the cavitation effect generated by ultrasonic treatment, the high - valence Cu (generally divalent positive) in the precursor of + Cu is reduced to monovalent + Cu, and the metal element in the positive valence state in the precursor of the non - copper metal element in its elemental form is reduced to the metal in its elemental form by the reducing agent. Copper - based alloy nanoparticles can be rapidly formed on the surface of the nanocarbon material at room temperature to form a copper - based alloy nanocomposite material. The method has the advantages of simplicity and rapidity.

[0073] In some embodiments of the present application, the precursor is any one of HAuCl4, H2PtCl6, and K2PdCl4.

[0074] The above-mentioned precursors are reagents capable of stably preparing Pt, Au, and Pd, and the obtaining method is relatively simple, and they are easily reduced by a reducing agent under ultrasonic conditions.

[0075] In some embodiments of the present application, the nanocarbon material, the precursor of Cu + , and the precursor of at least one non-copper metal element simple substance are dispersed in a liquid including a reducing agent, specifically:

[0076] S11: Disperse the nanocarbon material, Cu(Ac)2, and K2PdCl4 in a liquid including a reducing agent.

[0077] The Cu(Ac)2 is copper acetate.

[0078] Based on the method of step S11, copper-based alloy nanoparticles with a Cu3Pd1 crystal form can be prepared.

[0079] In some embodiments of the present application, the nanocarbon material, the precursor of Cu + , and the precursor of at least one non-copper metal element simple substance are dispersed in a liquid including a reducing agent, specifically:

[0080] S12: Disperse the nanocarbon material, Cu(Ac)2, and H2PtCl6 in a liquid including a reducing agent.

[0081] Based on the method of step S12, copper-based alloy nanoparticles with a Cu3Pt1 crystal form can be prepared.

[0082] In some embodiments of the present application, the nanocarbon material, the precursor of Cu + , and the precursor of at least one non-copper metal element simple substance are dispersed in a liquid including a reducing agent, specifically:

[0083] S13: Disperse the nanocarbon material, Cu(Ac)2, HAuCl4, H2PtCl6, and K2PdCl4 in a liquid including a reducing agent.

[0084] Based on the method of step S13, copper-based alloy nanoparticles with a Cu 3( (PtAuPd)1 crystal form can be prepared.

[0085] It is easy to understand that the above steps S11 to S13 are in a parallel relationship. If an implementation scheme is selected from them, only one should be selected.

[0086] In some embodiments of the present application, the nanocarbon material is any one of carbon nanoparticles, carbon nanotubes, and graphene, or any mixture of at least two of them, or any composite material formed by the combination of at least two of them.

[0087] As an example, the nano-carbon material may be one of carbon black, graphene powder, carbon nanotube powder, graphene-carbon nanotube composite film, and graphene-carbon black composite aerogel.

[0088] In some embodiments of the present application, the nanocarbon material is carbon black.

[0089] In some embodiments of the present application, the Cu + The total weight of the metal elements in the precursor and the non-copper metal element precursor is 18% to 22% of the nano-carbon material.

[0090] The Cu + The total weight of the metal elements in the precursor and the precursor of the non-copper metal element is 18% to 22% of the nano-carbon material, so that the loading amount of the copper-based alloy nanoparticles on the nano-carbon material is 18% to 22%. The beneficial effect of the loading amount of the copper-based alloy nanoparticles on the nano-carbon material being 18% to 22% is that, on the basis of ensuring a large loading amount and increasing the electrolytic water catalytic ability of the multi-element alloy nano-composite material, the alloy nanoparticles are not distributed too densely on the nano-carbon material and are not easy to agglomerate.

[0091] In some embodiments of the present application, the reducing agent is ethylene glycol.

[0092] Ethylene glycol has a suitable reducing ability, which can not only enable the precursor to be reduced quickly, but also prevent the size of the alloy nanoparticles from being too large due to an overly violent reduction reaction.

[0093] In some embodiments of the present application, the liquid is ethylene glycol.

[0094] Ethylene glycol itself can be used as a solvent for dispersing the precursor and the carbon nanomaterial. By dispersing the precursor and the carbon nanomaterial in ethylene glycol for reaction, alloy nanoparticles with a diameter of 3 to 7 nm can be obtained.

[0095] In some embodiments of the present application, in the ultrasonic treatment, the treatment time is 4 to 8 minutes, and the frequency of the ultrasonic wave is 18 to 22 kHz.

[0096] In some embodiments of the present application, the precipitate is washed, and the washing liquid used for washing is ethanol.

[0097] In a third aspect, an embodiment of the present application provides a water electrolysis catalyst, which includes the copper-based alloy nanocomposite material described in any embodiment of the first aspect, or the copper-based alloy nanocomposite material prepared by the method described in any embodiment of the second aspect.

[0098] The electrolytic water catalyst is realized based on the copper-based alloy nanocomposite material described in the first aspect or the copper-based alloy nanocomposite material prepared by the method described in the second aspect. For the specific implementation manners of the electrolytic water catalyst, reference can be made to the examples in the first aspect or the second aspect. Since the electrolytic water catalyst adopts some or all of the technical solutions of the above examples, it has at least all the beneficial effects brought by the technical solutions of the above examples, which will not be elaborated one by one here.

[0099] The following further elaborates the present application in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and not to limit the scope of the present application. For the experimental methods without specific conditions indicated in the following examples, they are usually determined according to national standards. If there is no corresponding national standard, they are carried out according to general international standards, conventional conditions, or the conditions recommended by the manufacturer.

[0100] Example 1

[0101] This example provides a preparation method of a copper-based alloy nanocomposite material, and the method includes the following steps:

[0102] (1) Weigh 0.005 mmol of HAuCl4, 0.005 mmol of H2PtCl6, 0.005 mmol of Na2PdCl4, and 0.045 mmol of Cu(Ac)2, add them to 10 mL of ethylene glycol, and stir for 30 minutes to completely dissolve to obtain a mixed solution A.

[0103] (2) Weigh 0.022 grams of XC-72 carbon black, add it to 10 mL of ethylene glycol, and stir for 30 minutes to completely dissolve to obtain a mixed solution B.

[0104] (3) Mix the mixed solutions A and B in a beaker to obtain a mixed solution C. Place the ultrasonic probe 1 cm below the liquid surface of the mixture in the beaker. The ultrasonic probe selects a cylindrical probe with a diameter of 1.5 cm, and continuously ultrasonicate for 6 minutes at a low frequency of 20 kHz and a high power of 1200 watts. After the ultrasonic treatment is completed, a colloidal solution is obtained.

[0105] (4) Centrifuge the obtained colloidal solution at 8000 revolutions per minute to obtain a precipitate. Add 50 mL of ethanol to the precipitate and shake it to wash the organic matter in the precipitate, and then centrifuge at 8000 revolutions per minute to obtain a precipitate. The ethanol washing step is repeated 3 times. Place the obtained precipitate in a vacuum oven at 60 °C and dry it overnight to obtain a copper-based alloy nanocomposite material Cu3(AuPtPd)1 / C, where Cu3(AuPtPd)1 is copper-based alloy nanoparticles and C is a carbon black carrier.

[0106] Example 2

[0107] The difference between this example and Example 1 lies only in the different raw materials used in step (1), which are specifically as follows:

[0108] This example provides a method for preparing a copper-based alloy nanocomposite, and the method comprises the following steps:

[0109] (1) Weigh 0.015 mmol of Na2PdCl4 and 0.045 mmol of Cu(Ac)2, add them to 10 mL of ethylene glycol, and stir for 30 minutes until completely dissolved to obtain a mixed solution A.

[0110] (2) Weigh 0.022 grams of XC-72 carbon black, add it to 10 mL of ethylene glycol, and stir for 30 minutes until completely dissolved to obtain a mixed solution B.

[0111] (3) Mix the mixed solutions A and B in a beaker to obtain a mixed solution C. Place the ultrasonic probe 1 cm below the liquid level of the mixture in the beaker. The ultrasonic probe is a cylindrical probe with a diameter of 1.5 cm. Continuously ultrasonic for 6 minutes at a low frequency of 20 kHz and a high power of 1200 watts. After the ultrasonic treatment is completed, a colloidal solution is obtained.

[0112] (4) Centrifuge the obtained colloidal solution at 8000 revolutions per minute to obtain a precipitate. Add 50 mL of ethanol to the precipitate and shake it to wash the organic matter in the precipitate. Then centrifuge at 8000 revolutions per minute to obtain a precipitate. The ethanol washing step is repeated 3 times. Place the obtained precipitate in a vacuum oven at 60 °C and dry it overnight to obtain the copper-based alloy nanocomposite Cu3Pd1 / C, where Cu3Pd1 is copper-based alloy nanoparticles and C is a carbon black carrier.

[0113] Example 3

[0114] The difference between this example and Example 1 lies only in the different raw materials used in step (1), which are specifically as follows:

[0115] This example provides a method for preparing a copper-based alloy nanocomposite, and the method comprises the following steps:

[0116] (1) Weigh 0.015 mmol of H2PtCl6 and 0.045 mmol of Cu(Ac)2, add them to 10 mL of ethylene glycol, and stir for 30 minutes until completely dissolved to obtain a mixed solution A.

[0117] (2) Weigh 0.022 grams of XC-72 carbon black, add it to 10 mL of ethylene glycol, and stir for 30 minutes until completely dissolved to obtain a mixed solution B.

[0118] (3) Mix the mixed solutions A and B in a beaker to obtain a mixed solution C. Place the ultrasonic probe 1 cm below the liquid level of the mixture in the beaker. The ultrasonic probe is a cylindrical probe with a diameter of 1.5 cm. Continuously ultrasonic for 6 minutes at a low frequency of 20 kHz and a high power of 1200 watts. After the ultrasonic treatment, a colloidal solution is obtained.

[0119] (4) Centrifuge the obtained colloidal solution at 8000 revolutions per minute to obtain a precipitate. Add 50 mL of ethanol to the precipitate and shake it to wash the organic matter in the precipitate. Then centrifuge at 8000 revolutions per minute to obtain a precipitate. The ethanol washing step is repeated 3 times. Place the obtained precipitate in a vacuum oven at 60 °C and dry it overnight to obtain a copper-based alloy nanocomposite Cu3Pt1 / C, where Cu3Pt1 is copper-based alloy nanoparticles and C is a carbon black carrier.

[0120] Example 4

[0121] The difference between this example and Example 1 is only the raw materials used in step (1), which are as follows:

[0122] This example provides a method for preparing a copper-based alloy nanocomposite, and the method includes the following steps:

[0123] (1) Weigh 0.015 mmol of HAuCl4 and 0.045 mmol of Cu(Ac)2 and add them to 10 mL of ethylene glycol. Stir for 30 minutes until completely dissolved to obtain a mixed solution A.

[0124] (2) Weigh 0.022 grams of XC-72 carbon black and add it to 10 mL of ethylene glycol. Stir for 30 minutes until completely dissolved to obtain a mixed solution B.

[0125] (3) Mix the mixed solutions A and B in a beaker to obtain a mixed solution C. Place the ultrasonic probe 1 cm below the liquid level of the mixture in the beaker. The ultrasonic probe is a cylindrical probe with a diameter of 1.5 cm. Continuously ultrasonic for 6 minutes at a low frequency of 20 kHz and a high power of 1200 watts. After the ultrasonic treatment, a colloidal solution is obtained.

[0126] (4) Centrifuge the obtained colloidal solution at 8000 revolutions per minute to obtain a precipitate. Add 50 mL of ethanol to the precipitate and shake it to wash the organic matter in the precipitate. Then centrifuge at 8000 revolutions per minute to obtain a precipitate. The ethanol washing step is repeated 3 times. Place the obtained precipitate in a vacuum oven at 60 °C and dry it overnight to obtain a copper-based alloy nanocomposite Cu3Au1 / C, where Cu3Au1 is copper-based alloy nanoparticles and C is a carbon black carrier.

[0127] Related experiments and effect data:

[0128] The copper-based alloy nanocomposites obtained in Examples 1 to 4 were subjected to XRD testing, and the test results are as Figure 1 shown.

[0129] The XRD characterization results show that the XRD diffraction peaks of Cu3(AuPtPd)1 / C, Cu3Pd1 / C, and Cu3Pt1 / C in Examples 1 to 3 exhibit a set of crystal forms without peak splitting, proving that the synthesized materials are homogeneous materials rather than heterogeneous structures.

[0130] Cu3Au1 / C in Example 4 is different from Examples 1 to 3 in the range of 2θ from 35° to 50°. The diffraction peaks are close to those of intermetallic compound crystals rather than alloys, indicating that this material is an intermetallic compound material with an ordered distribution of two metals.

[0131] The copper-based alloy nanocomposites obtained in 1 to 4 were subjected to TEM testing, and the test results are as Figure 2 shown.

[0132] Figure 2 In the lower right figure in Figure 2 the upper right figure in Figure 2 the lower left figure in Figure 2 and the upper left figure in, the morphologies and element distributions of Cu3(AuPdPt)1 / C, Cu3Pd1 / C, Cu3Pt1 / C, and Cu3Au1 / C corresponding to Examples 1 to 4 can be seen respectively. Among them, the average diameters of Cu3(AuPdPt)1, Cu3Pd1, Cu3Pt1, and Cu3Au1 nanoparticles are about 3.2 nm, 5.4 nm, 6.3 nm, and 4.4 nm respectively. Several elements such as Cu, Au, Pd, or Pt are evenly distributed in the particles. The lattice spacings of Cu3Au1, Cu3Pd1, and Cu3Pt1 are and which are consistent with the lattice spacings of the corresponding intermetallic compound crystals.

[0133] Through the above X-ray diffraction, transmission electron microscopy, and EDS element scanning analysis, the analysis results prove that the materials prepared by the present invention are multi-component alloy nanoparticles supported by carbon black carriers, proving the feasibility and universality of the present synthesis method. The present ultrasonic-assisted liquid-phase chemical reduction method can rapidly synthesize binary and quaternary alloy nanoparticles with carbon black as the carrier, different metal compositions, and a diameter of about 5 nanometers under normal temperature and pressure, solving the problem of high energy consumption of the traditional calcination method, solving the problem that the size of the alloy materials synthesized by the calcination method cannot reach the nanoscale, and solving the problem that the types of components of the alloy nanoparticles synthesized by the traditional liquid-phase chemical reduction method are only two.

[0134] Various embodiments of the present application may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity and should not be construed as a rigid limitation on the scope of the present application; therefore, it should be considered that the described range description has specifically disclosed all possible sub-ranges and individual values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and individual numbers within the range, such as 1, 2, 3, 4, 5, and 6, and this applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0135] In the present application, unless otherwise stated, the orientation terms such as "upper" and "lower" specifically refer to the drawing direction in the drawings. Additionally, in the description of the present application specification, the terms "include", "comprise", etc. mean "including but not limited to". Moreover, the term "include", "comprise" or any other variant thereof is intended to cover non-exclusive inclusion, such that a process, method, article or device including a series of elements not only includes those elements but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. Without further limitation, the elements defined by the statement "including..." do not exclude the existence of additional identical elements in the process, method, article or device including the said elements. In this document, relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. In this document, "and / or" describes the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B may represent: A exists alone, A and B exist simultaneously, or B exists alone. For the association relationship of more than three associated objects described by "and / or", it means that these three associated objects can exist alone in any one item, or any at least two of them exist simultaneously. For example, for A, and / or B, and / or C, it may represent that any one of A, B, and C exists alone, or any two of them exist simultaneously, or all three of them exist simultaneously. In this document, "at least one" means one or more, and "a plurality" means two or more. "At least one kind", "at least one of the following items (pieces)" or similar expressions refer to any combination of these items, including any combination of single items (pieces) or plural items (pieces). For example, "at least one of a, b, or c", or, "at least one of a, b, and c" can both represent: a, b, c, a - b (i.e., a and b), a - c, b - c, or a - b - c, where a, b, and c can be single or multiple respectively.

[0136] The above are only specific embodiments of the present application, enabling those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be obvious to those skilled in the art. The general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but rather will be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A copper-based alloy nanocomposite material, characterized in that, The copper-based alloy nanocomposite material comprises a nanocarbon material and copper-based alloy nanoparticles loaded on the nanocarbon material. The copper-based alloy nanoparticles comprise cuprous ions and at least one non-copper metal element, and the non-copper metal element is any one of Group VIII or Group IB elements.

2. The copper-based alloy nanocomposite material according to claim 1, characterized in that, The non-copper metal element is selected from any one of Pd, Pt, and Au.

3. The copper-based alloy nanocomposite material according to claim 1, wherein, The copper-based alloy nanoparticles comprise one non-copper metal element, and the non-copper metal element is Pd. The ratio of the number of Cu atoms to Pd atoms in the copper-based alloy nanoparticles is 3:

1.

4. The copper-based alloy nanocomposite material according to claim 1, wherein The copper-based alloy nanoparticles comprise one non-copper metal element, and the non-copper metal element is Pt. The ratio of the number of Cu atoms to Pt atoms in the copper-based alloy nanoparticles is 3:

1.

5. The copper-based alloy nanocomposite according to claim 1, wherein The copper-based alloy nanoparticles comprise three non-copper metal elements, namely Pt, Pd, and Au. The ratio of the number of Cu atoms to Pt atoms, Pd atoms, and Au atoms in the copper-based alloy nanoparticles is 9:1:1:

1.

6. The copper-based alloy nanocomposite material according to claim 1, characterized in that, The diameter of the copper-based alloy nanoparticles is 3-7 nm.

7. The copper-based alloy nanocomposite according to claim 1, characterized in that, The nanocarbon material is any one of carbon nanoparticles, carbon nanotubes, graphene, or a mixed material of any at least two of them, or a composite material formed by any at least two of them in combination.

8. The copper-based alloy nanocomposite according to claim 1, wherein The nanocarbon material is carbon black.

9. The copper-based alloy nanocomposite material according to claim 8, characterized in that, By mass percentage, the loading amount of the alloy nanoparticles on the nanocarbon material is 18%-22%.

10. A method for preparing a copper-based alloy nanocomposite material, characterized in that, The method comprises the following steps: Disperse a nanocarbon material, a precursor of Cu + and a precursor of at least one non-copper metal element in a liquid including a reducing agent to form a first solution; Performing ultrasonic treatment on the first solution to obtain a second solution; Centrifuging the second solution to obtain a precipitate; Washing and drying the precipitate to obtain the copper-based alloy nanocomposite material. Among them, the non-copper metal element is any one of the elements in Group VIII or Group IB, and the + valence state of the metal element in the precursor of Cu and the precursor of the non-copper metal element in its elemental form is a positive valence state.

11. The method for preparing the copper-based alloy nanocomposite material according to claim 10, wherein The precursor is any one of HAuCl4, H2PtCl6, and K2PdCl4.

12. The preparation method of the copper-based alloy nanocomposite material according to claim 10, characterized in that, Disperse a nanocarbon material, a precursor of Cu + and a precursor of at least one non-copper metal element in a liquid including a reducing agent. Specifically: Dispersing the nanocarbon material, Cu(Ac)2, and K2PdCl4 into a liquid comprising a reducing agent.

13. The preparation method of the copper-based alloy nanocomposite according to claim 10, characterized in that, Disperse a nanocarbon material, a precursor of Cu + and a precursor of at least one non-copper metal element simple substance into a liquid including a reducing agent. Specifically: Dispersing the nanocarbon material, Cu(Ac)2, and K2PtCl4 into a liquid comprising a reducing agent.

14. The preparation method of the copper-based alloy nanocomposite material according to claim 10, wherein, Disperse a nanocarbon material, a precursor of Cu + and a precursor of at least one non-copper metal element simple substance into a liquid including a reducing agent. Specifically: Dispersing the nanocarbon material, Cu(Ac)2, HAuCl4, H2PtCl6, and K2PdCl4 into a liquid comprising a reducing agent.

15. The preparation method of the copper-based alloy nanocomposite material according to claim 10, wherein, The nanocarbon material is any one of carbon nanoparticles, carbon nanotubes, graphene, or a mixed material of any at least two of them, or a composite material formed by any at least two of them in combination.

16. The preparation method of the copper-based alloy nanocomposite material according to claim 10, characterized in that, The nanocarbon material is carbon black.

17. The preparation method of the copper-based alloy nanocomposite material according to claim 16, characterized in that, The precursor of the Cu + and the total weight of the metal elements in the precursor of the non-copper metal element simple substance is 18% to 22% of the nano-carbon material.

18. The preparation method of the copper-based alloy nanocomposite material according to claim 10, characterized in that, The reducing agent is ethylene glycol.

19. The preparation method of the copper-based alloy nanocomposite according to claim 10, wherein The liquid is ethylene glycol.

20. The preparation method of the copper-based alloy nanocomposite material according to claim 10, characterized in that, In the ultrasonic treatment, the treatment duration is 4-8 min, and the frequency of the ultrasonic wave is 18-22 kHz.

21. The preparation method of the copper-based alloy nanocomposite material according to claim 10, characterized in that, When washing the precipitate, the washing liquid used for washing is ethanol.

22. An electrolyzed water catalyst, characterized in that, The electrolyzed water catalyst comprises the copper-based alloy nanocomposite material according to any one of claims 1-9, or the copper-based alloy nanocomposite material prepared by the method according to any one of claims 10-21.

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