Nitrogen-doped carbon-loaded palladium-copper particle electrocatalyst and preparation method thereof

Abstract

A preparation method of the nitrogen-doped carbon-loaded palladium-copper particle electrocatalyst comprises the following steps: soaking foamy copper in a hydrochloric acid solution to remove a surface oxide layer; soaking the copper hydroxide nano array in a mixed solution of ammonium persulfate and sodium hydroxide to prepare a copper hydroxide nano array; the prepared copper hydroxide nano array is soaked in a TCPP solution, and a copper-TCPP nano array is generated; the prepared copper-TCPP nano array is soaked in a sodium chloropalladate water solution, and a copper-palladium-TCPP nano array is generated; and heating the copper palladium-TCPP nano array in nitrogen at a set heating rate to a preset temperature, and carrying out heat preservation to obtain a final product, namely the nitrogen-doped carbon-loaded palladium-copper particle electrocatalyst. The invention further provides a preparation method of the nitrogen-doped carbon-loaded palladium-copper particle electrocatalyst. The preparation process is simple, the reaction time is short, and the material prepared at normal temperature and normal pressure has excellent electro-catalysis alkynol semi-hydrogenation performance.

Description

Technical Field

[0001] The invention relates to a nitrogen-doped carbon-supported palladium copper particle electrocatalyst and a preparation method thereof. Background Art

[0002] The semihydrogenation of alkynols is an important reaction in the production of chemical products. 2-Methyl-3-butene-2-ol (MBE) is a key intermediate for pharmaceutical and pesticide chemicals. 2 ) is used as the hydrogen source for the semi-hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to achieve industrial production. However, the related safety issues in hydrogen production, storage and transportation cannot be ignored. In contrast, the electrocatalytic semi-hydrogenation of alkynols using water as the hydrogen source has the advantages of low cost, low energy consumption and high safety. However, it also faces challenges such as low conversion rate of electrocatalytic semi-hydrogenation of alkynols, over-hydrogenation to produce 2-methyl-2-butanol (MBA) and competition with the hydrogen evolution reaction (HER).

[0003] Copper-based materials are ideal catalytic materials for electrocatalytic hydrogenation reactions because of their large hydrogen adsorption free energy, which can effectively inhibit the competitive hydrogen evolution reaction. However, due to the weak water dissociation ability of copper, a higher voltage is usually required to ensure a high conversion rate of alkynols. In contrast, palladium-based materials usually have excellent hydrogen adsorption and water dissociation abilities and show high activity in hydrogenation reactions. However, palladium has a strong adsorption effect on enols, which may lead to excessive hydrogenation of alkynols to alkanols. Therefore, combining the advantages of copper and palladium to develop electrocatalytic alkynol semi-hydrogenation catalysts with high activity and selectivity is a promising research direction.

[0004] In addition, the electrocatalytic activity can be further enhanced by precisely controlling the morphology and structure of the catalyst. Metal-support interaction can effectively regulate the adsorption and desorption process of intermediate molecules on the metal surface by regulating the electronic interaction between the metal and the support, thereby improving the electrocatalytic activity. Therefore, constructing a palladium-copper catalyst with metal-support interaction is considered to be a promising strategy for achieving efficient electrocatalytic semi-hydrogenation of alkynols. Summary of the invention

[0005] In order to overcome the shortcomings of the prior art, the present invention provides a nitrogen-doped carbon-supported palladium copper particle electrocatalyst and a preparation method thereof. The preparation process is simple and the reaction time is short. The prepared nitrogen-doped carbon-supported palladium copper particle catalyst has excellent electrocatalytic semi-hydrogenation performance of alkynols to prepare enols, and has good application prospects.

[0006] The technical solution adopted by the present invention is:

[0007] A nitrogen-doped carbon-supported palladium copper particle electrocatalyst is prepared by the following method:

[0008] (1) 2 to 10 cm 2 The copper foam is immersed in hydrochloric acid to remove the surface oxide layer and oil stains; then, the treated copper foam is immersed in a mixed solution of 8-40 mL of ammonium persulfate and sodium hydroxide at room temperature, with the concentration of ammonium persulfate being 0.05-0.1 mol L -1 , sodium hydroxide concentration is 1~2 mol L -1 The copper hydroxide nanoarrays generated by the reaction were washed and dried in an oven for later use;

[0009] (2) The prepared copper hydroxide nanoarray was immersed in 8-40 mL TCPP (meso-tetrakis (4-carboxyphenyl) porphine) solution at room temperature for 8-12 hours, with a TCPP concentration of 0.5-1 mg mL -1 , generating a copper-TCPP nanoarray, and washing the obtained copper-TCPP nanoarray with deionized water and ethanol for 3 to 5 times respectively;

[0010] (3) placing the prepared copper-TCPP nanoarray in 5-25 mL of deionized water, then adding 30-150 μL of sodium chloropalladate aqueous solution to the deionized water, wherein the concentration of the added sodium chloropalladate aqueous solution is 0.5-16 mM, and keeping the solution in a water bath at 85-150° C. for 3-5 hours to generate a copper-palladium-TCPP nanoarray; washing the product with deionized water and ethanol for 3-5 times each, and then drying it in an oven at 50-60° C. for 1-3 hours;

[0011] (4) The copper palladium-TCPP nanoarray was placed in a tube furnace in a nitrogen atmosphere with a nitrogen flow rate of 150-200 mL min -1 , heating rate is 3~5℃min -1 The temperature is raised to 400-450° C. and kept at this temperature for 3-5 hours to obtain the final product, i.e., nitrogen-doped carbon-supported palladium copper particle electrocatalyst.

[0012] In the present invention, a typical nitrogen-doped carbon-supported palladium copper particle electrocatalyst is synthesized by a four-step method. In the first step, copper hydroxide nanoarrays are prepared by an immersion method. In the second step, copper hydroxide forms a coordination bond with the carboxyl group of TCPP to synthesize a copper-TCPP nanoarray. In the third step, palladium is introduced into the copper-TCPP nanoarray by an immersion method, and palladium forms a coordination bond with nitrogen atoms to synthesize a copper-palladium-TCPP nanoarray. In the fourth step, N 2 Upon calcination, the TCPP ligands are transformed into nitrogen-doped carbon supports, and the copper and palladium cations are reduced and combined into bimetallic palladium-copper nanoparticles embedded in the nitrogen-doped carbon supports.

[0013] A method for preparing a nitrogen-doped carbon-supported palladium copper particle electrocatalyst comprises the following steps:

[0014] (1) 2 to 10 cm 2 The copper foam is immersed in hydrochloric acid to remove the surface oxide layer and oil stains; then, the treated copper foam is immersed in a mixed solution of 8-40 mL of ammonium persulfate and sodium hydroxide at room temperature, with the concentration of ammonium persulfate being 0.05-0.1 mol L -1 , sodium hydroxide concentration is 1~2 mol L -1 The copper hydroxide nanoarrays generated by the reaction were washed and dried in an oven for later use;

[0015] (2) The prepared copper hydroxide nanoarray was immersed in 8-40 mL TCPP (meso-tetrakis (4-carboxyphenyl) porphine) solution at room temperature for 8-12 hours, with a TCPP concentration of 0.5-1 mg mL -1 , generating a copper-TCPP nanoarray, and washing the obtained copper-TCPP nanoarray with deionized water and ethanol for 3 to 5 times respectively;

[0016] (3) placing the prepared copper-TCPP nanoarray in 5-25 mL of deionized water, then adding 30-150 μL of sodium chloropalladate aqueous solution to the deionized water, wherein the concentration of the added sodium chloropalladate aqueous solution is 0.5-16 mM, and keeping the solution in a water bath at 85-150° C. for 3-5 hours to generate a copper-palladium-TCPP nanoarray; washing the product with deionized water and ethanol for 3-5 times each, and then drying it in an oven at 50-60° C. for 1-3 hours;

[0017] (4) The copper palladium-TCPP nanoarray was placed in a tube furnace in a nitrogen atmosphere with a nitrogen flow rate of 150-200 mL min -1 , heating rate is 3~5℃min -1 The temperature is raised to 400-450° C. and kept at this temperature for 3-5 hours to obtain the final product, i.e., nitrogen-doped carbon-supported palladium copper particle electrocatalyst.

[0018] The electrocatalytic alkynol semi-hydrogenation to enol performance test was carried out at room temperature and pressure. The specific operation process is as follows:

[0019] (1) Weigh 5-10 mg of sample and disperse it in 0.5-1.5 mL of ultrapure water. Ultrasonicate to obtain a uniform dispersion. Take 100-500 μL of sample and drop it on the surface of carbon paper. After drying, drop 10-100 μL of Nafion solution on the catalyst surface to make a working electrode. The reference electrode is an Ag / AgCl electrode and the counter electrode is a carbon rod.

[0020] (2) The electrocatalytic alkynol semi-hydrogenation test to enol was carried out in 0.5-1M sodium carbonate + 0.1-1M 2-methyl-3-butyn-2-ol solution, and the linear sweep voltammetry (LSV) and constant potential (IT) test procedures were selected for the test. The current was observed at different scan rates. Finally, the alkynol conversion rate and enol selectivity were calculated based on the measured data and the corresponding formula.

[0021] The beneficial effects of the present invention are mainly reflected in:

[0022] (1) Nitrogen-doped carbon-supported palladium-copper particle electrocatalyst was successfully prepared and its application in the electrocatalytic semi-hydrogenation of acetylenes to enols was demonstrated.

[0023] (2) The nitrogen-doped carbon-supported palladium-copper particle catalyst exhibited excellent electrocatalytic performance in the semi-hydrogenation of acetylenic alcohols to enols in the above system, and had outstanding electrocatalytic activity and durability. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 These are SEM images and TEM images of the nitrogen-doped carbon-supported palladium copper particle electrocatalyst at different scales in specific example 1 of the present invention.

[0025] Figure 2 This is the XRD diagram of the nitrogen-doped carbon-supported palladium copper particle electrocatalyst according to specific example 1 of the present invention.

[0026] Figure 3 This is the atomic mass percentage of the nitrogen-doped carbon-supported palladium-copper particle electrocatalyst according to the specific embodiment 1 of the present invention.

[0027] Figure 4 Specific Example 1 of the present invention is the linear sweep voltammetry curve of the half-hydrogenation of alkynols under alkaline conditions over nitrogen-doped carbon-supported palladium-copper particle electrocatalyst, and the change in conversion selectivity over time.

[0028] Figure 5 This is the conversion rate of alkynol and the selectivity of ene alcohol of nitrogen-doped carbon-supported palladium copper particle electrocatalyst at different potentials in specific embodiment 1 of the present invention.

[0029] Figure 6 This is the stability test result of the nitrogen-doped carbon-supported palladium-copper particle electrocatalyst of the specific embodiment 1 of the present invention.

[0030] Figure 7 These are SEM and TEM images of the nitrogen-doped carbon-supported palladium copper particle electrocatalyst according to specific example 2 of the present invention.

[0031] Figure 8 This is the atomic distribution percentage of the nitrogen-doped carbon-supported palladium copper particle electrocatalyst according to specific embodiment 2 of the present invention.

[0032] Fig. 9 This is the conversion rate of alkynol and the selectivity of ene alcohol at different potentials for the nitrogen-doped carbon-supported palladium copper particle electrocatalyst in specific embodiment 2 of the present invention.

[0033] Fig.10 These are SEM and TEM images of the nitrogen-doped carbon-supported palladium copper particle electrocatalyst according to specific example 3 of the present invention.

[0034] Fig.11 This is the atomic distribution percentage of the nitrogen-doped carbon-supported palladium copper particle electrocatalyst according to specific embodiment 3 of the present invention.

[0035] Fig.12 This is the conversion rate of alkynol and the selectivity of ene alcohol at different potentials for the nitrogen-doped carbon-supported palladium copper particle electrocatalyst in specific example 3 of the present invention. DETAILED DESCRIPTION

[0036] The present invention is further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto:

[0037] Reference Figure 1 to Figure 6 , a nitrogen-doped carbon-supported palladium copper particle electrocatalyst, prepared by the following method:

[0038] (1) 2 to 10 cm 2 The copper foam is immersed in hydrochloric acid to remove the surface oxide layer and oil stains; then, the treated copper foam is immersed in a mixed solution of 8-40 mL of ammonium persulfate and sodium hydroxide at room temperature, with the concentration of ammonium persulfate being 0.05-0.1 mol L -1 , sodium hydroxide concentration is 1~2 mol L -1 The copper hydroxide nanoarrays generated by the reaction were washed and dried in an oven for later use;

[0039] (2) The prepared copper hydroxide nanoarray was immersed in 8-40 mL TCPP (meso-tetrakis (4-carboxyphenyl) porphine) solution at room temperature for 8-12 hours, with a TCPP concentration of 0.5-1 mg mL -1 , generating a copper-TCPP nanoarray, and washing the obtained copper-TCPP nanoarray with deionized water and ethanol for 3 to 5 times respectively;

[0040] (3) placing the prepared copper-TCPP nanoarray in 5-25 mL of deionized water, then adding 30-150 μL of sodium chloropalladate aqueous solution to the deionized water, wherein the concentration of the added sodium chloropalladate aqueous solution is 0.5-16 mM, and keeping the solution in a water bath at 85-150° C. for 3-5 hours to generate a copper-palladium-TCPP nanoarray; washing the product with deionized water and ethanol for 3-5 times each, and then drying it in an oven at 50-60° C. for 1-3 hours;

[0041] (4) The copper palladium-TCPP nanoarray was placed in a tube furnace in a nitrogen atmosphere with a nitrogen flow rate of 150-200 mL min -1 , heating rate is 3~5℃min -1 The temperature is raised to 400-450° C. and kept at this temperature for 3-5 hours to obtain the final product, i.e., nitrogen-doped carbon-supported palladium copper particle electrocatalyst.

[0042] The electrocatalytic alkynol semi-hydrogenation to enol performance test was carried out at room temperature and pressure. The specific operation process is as follows:

[0043] 1) Electrochemical tests were carried out using a working electrode (prepared electrocatalyst), a reference electrode (Ag / AgCl electrode) and a counter electrode (carbon rod) in a 0.5-1 M sodium carbonate + 0.1-1 M 2-methyl-3-butyn-2-ol solution.

[0044] 2) The electrocatalytic alkynol semi-hydrogenation test to enol was carried out in 0.5-1M sodium carbonate + 0.1-1M 2-methyl-3-butyn-2-ol solution, and the linear sweep voltammetry (LSV) and constant potential (IT) test procedures were selected for the test. The current was observed at different scan rates. Finally, the alkynol conversion rate and enol selectivity were calculated based on the measured data and the corresponding formula.

[0045] Embodiment 1:

[0046] A method for preparing a nitrogen-doped carbon-supported palladium copper particle electrocatalyst, the method comprising the following steps:

[0047] (1) 5cm 2 The copper foam was immersed in hydrochloric acid to remove the surface oxide layer and oil stains; then, the treated copper foam was immersed in a mixed solution of 20 mL of ammonium persulfate and sodium hydroxide at room temperature, with an ammonium persulfate concentration of 0.08 mol / L -1 , the concentration of sodium hydroxide is 1.5

[0048] mol L -1 The copper hydroxide nanoarrays generated by the reaction were washed and dried in an oven for later use;

[0049] (2) The prepared copper hydroxide nanoarrays were immersed in 20 mL TCPP solution at room temperature for 10 h. The TCPP concentration was 0.75 mg mL -1 , generating copper-TCPP nanoarrays, and the obtained copper-TCPP nanoarrays were washed 4 times with deionized water and ethanol respectively;

[0050] (3) The prepared copper-TCPP nanoarray was placed in 15 mL of deionized water, and then 100 μL of sodium chloropalladate aqueous solution was added to the deionized water, the concentration of the added sodium chloropalladate aqueous solution was 8 mM, and the mixture was kept in a 100° C. water bath for 4 hours to generate a copper-palladium-TCPP nanoarray; the product was washed with deionized water and ethanol 4 times each, and then dried in an oven at 55° C. for 2 hours;

[0051] (4) The copper palladium-TCPP nanoarray was placed in a tube furnace in a nitrogen atmosphere with a nitrogen flow rate of 175 mL min -1 , the heating rate is 4℃min -1 Heat to 425℃, keep warm for 4 hours,

[0052] The final product, nitrogen-doped carbon-supported palladium-copper particle electrocatalyst, was obtained.

[0053] The nitrogen-doped carbon-supported palladium copper particle electrocatalyst of this embodiment is prepared by the above-mentioned preparation method.

[0054] The SEM and TEM images of the nitrogen-doped carbon-supported palladium copper particle electrocatalyst obtained in Example 1 are shown in Figure 1 The XRD pattern of the nitrogen-doped carbon-supported palladium-copper particle electrocatalyst obtained in Example 1 is shown in FIG. Figure 2 The mass ratio of copper to palladium in the obtained nitrogen-doped carbon-supported palladium-copper particle electrocatalyst of Example 1 is as follows: Figure 3 The linear sweep voltammetric curve of the nitrogen-doped carbon-supported palladium copper particle electrocatalyst in 0.5M sodium carbonate + 0.1M 2-methyl-3-butyn-2-ol solution and the contents of 2-methyl-3-butyn-2-ol, 2-methyl-3-butene-2-ol and 2-methyl-3-butane-2-ol at different reaction times were obtained in Example 1. Figure 4 The conversion rate of 2-methyl-3-butyn-2-ol and the selectivity of 2-methyl-3-butene-2-ol at different potentials of the nitrogen-doped carbon-supported palladium copper particle electrocatalyst obtained in Example 1 are shown in Table 1. Figure 5 The conversion rate of 2-methyl-3-butyn-2-ol and the selectivity of 2-methyl-3-butene-2-ol of the nitrogen-doped carbon-supported palladium copper particle catalyst obtained in Example 1 under the typical potential for ten consecutive cycles are shown in Table 1. Figure 6 .

[0055] First, the morphology and structure of the prepared nitrogen-doped carbon-supported palladium-copper particle electrocatalyst were characterized by scanning and transmission electron microscopy. The scanning electron microscope image proved that the sample was a composite material composed of nanosheet arrays supporting high-density nanoparticles. From the transmission electron microscope image, the nitrogen-doped carbon nanosheets and the high-density irregular crystalline nanoparticles supported by them were more clearly observed. The high-resolution transmission electron microscope image showed that the nitrogen-doped carbon-supported palladium-copper particles were highly crystalline. Further, through the XRD spectrum, obvious copper peaks were observed, and there were no diffraction peaks related to palladium, indicating that there were no palladium particles or clusters. The XPS spectrum further confirmed the presence of palladium, copper, carbon and nitrogen elements. Next, the electrochemical alkynol semi-hydrogenation synthesis of enols of nitrogen-doped carbon-supported palladium-copper particle catalyst was investigated. In an electrolyte containing 0.5M sodium carbonate + 0.1M 2-methyl-3-butyne-2-ol, the nitrogen-doped carbon-supported palladium-copper particles had an MBE yield of 18mmol h at a low voltage (-1.3V vs.Ag / AgCl). -1 cm -2 , the conversion rate of 2-methyl-3-butyne-2-ol reached 96.0%, and the selectivity of 2-methyl-3-butene-2-ol was 95.9%. Compared with other catalysts, the typical sample has better activity and selectivity for the electrosynthesis of 2-methyl-3-butene-2-ol. The typical nitrogen-doped carbon-supported palladium copper particles were tested for cyclic stability. After 10 consecutive cycles, the conversion rate of 2-methyl-3-butyne-2-ol and the selectivity of 2-methyl-3-butene-2-ol remained almost unchanged, indicating that it has excellent electrochemical alkynol semi-hydrogenation stability.

[0056] Embodiment 2:

[0057] A method for preparing a nitrogen-doped carbon-supported palladium copper particle electrocatalyst, the method comprising the following steps:

[0058] (1) 2cm 2 The copper foam was immersed in hydrochloric acid to remove the surface oxide layer and oil stains; then, the treated copper foam was immersed in a mixed solution of 8 mL of ammonium persulfate and sodium hydroxide at room temperature, with an ammonium persulfate concentration of 0.05 mol / L -1 , the concentration of sodium hydroxide is 1

[0059] mol L -1 The copper hydroxide nanoarrays generated by the reaction were washed and dried in an oven for later use;

[0060] (2) The prepared copper hydroxide nanoarrays were immersed in 8 mL TCPP solution at room temperature for 8 h. The TCPP concentration was 0.5 mg mL -1, generating copper-TCPP nanoarrays, and the obtained copper-TCPP nanoarrays were washed with deionized water and ethanol three times respectively;

[0061] (3) The prepared copper-TCPP nanoarray was placed in 5 mL of deionized water, and then 30 μL of sodium chloropalladate aqueous solution was added to the deionized water, the concentration of the added sodium chloropalladate aqueous solution was 0.5 mM, and the mixture was kept in a water bath at 85° C. for 3 hours to generate a copper-palladium-TCPP nanoarray; the product was washed with deionized water and ethanol for 3 times each, and then dried in an oven at 50° C. for 1 hour;

[0062] (4) The copper palladium-TCPP nanoarray was placed in a tube furnace in a nitrogen atmosphere with a nitrogen flow rate of 150 mL min -1 , heating rate is 3℃min -1 Heat to 400℃, keep warm for 3 hours,

[0063] The final product, nitrogen-doped carbon-supported palladium-copper particle electrocatalyst, was obtained.

[0064] The nitrogen-doped carbon-supported palladium copper particle electrocatalyst of this embodiment is prepared by the above-mentioned preparation method.

[0065] First, the morphology and structure of the prepared nitrogen-doped carbon-supported palladium copper particles were characterized by scanning electron microscopy, and it was found that the sample was a nanosheet array loaded with a large number of nanoparticle structures. Next, the performance of the nitrogen-doped carbon-supported palladium copper particles in the electrosynthesis of 2-methyl-3-butene-2-ol was investigated, and the performance of the nitrogen-doped carbon-supported palladium copper particles in the electrosynthesis of 2-methyl-3-butene-2-ol was tested in 0.5M sodium carbonate + 0.1M 2-methyl-3-butyne-2-ol solution. At -1.5V, it has excellent conversion rate of 2-methyl-3-butyne-2-ol and selectivity of 2-methyl-3-butene-2-ol.

[0066] Embodiment 3:

[0067] A method for preparing a nitrogen-doped carbon-supported palladium copper particle electrocatalyst, the method comprising the following steps:

[0068] (1) 10cm 2 The copper foam was immersed in hydrochloric acid to remove the surface oxide layer and oil stains; then, the treated copper foam was immersed in a mixed solution of 40 mL of ammonium persulfate and sodium hydroxide at room temperature, with an ammonium persulfate concentration of 0.1 mol / L -1 , the concentration of sodium hydroxide is 2

[0069] mol L -1 The copper hydroxide nanoarrays generated by the reaction were washed and dried in an oven for later use;

[0070] (2) The prepared copper hydroxide nanoarrays were immersed in 40 mL TCPP solution at room temperature for 12 h. The TCPP concentration was 1 mg mL -1 , generating copper-TCPP nanoarrays, and the obtained copper-TCPP nanoarrays were washed 5 times with deionized water and ethanol respectively;

[0071] (3) The prepared copper-TCPP nanoarray was placed in 25 mL of deionized water, and then 150 μL of sodium chloropalladate aqueous solution was added to the deionized water, the concentration of the added sodium chloropalladate aqueous solution was 16 mM, and the solution was kept in a 150° C. water bath for 5 hours to generate a copper-palladium-TCPP nanoarray; the product was washed with deionized water and ethanol for 5 times each, and then dried in an oven at 60° C. for 3 hours;

[0072] (4) The copper palladium-TCPP nanoarray was placed in a tube furnace in a nitrogen atmosphere with a nitrogen flow rate of 200 mL min -1 , heating rate is 5℃min -1 Heat up to 450℃ and keep warm for 5 hours.

[0073] The final product, nitrogen-doped carbon-supported palladium-copper particle electrocatalyst, was obtained.

[0074] The nitrogen-doped carbon-supported palladium copper particle electrocatalyst of this embodiment is prepared by the above-mentioned preparation method.

[0075] First, the morphology and structure of the prepared nitrogen-doped carbon-supported palladium copper particles were characterized by scanning electron microscopy, and it was found that the sample was a nanosheet array loaded with a large number of nanoparticle structures. Next, the performance of the nitrogen-doped carbon-supported palladium copper particles in the electrosynthesis of 2-methyl-3-butene-2-ol was investigated, and the performance of the nitrogen-doped carbon-supported palladium copper particles in the electrosynthesis of 2-methyl-3-butene-2-ol was tested in 0.5M sodium carbonate + 0.1M 2-methyl-3-butyne-2-ol solution. It has excellent conversion rate of 2-methyl-3-butyne-2-ol and selectivity of 2-methyl-3-butene-2-ol at -1.1V.

[0076] The contents described in the embodiments of this specification are merely enumerations of implementation forms of the inventive concept and are for illustrative purposes only. The protection scope of the present invention should not be considered to be limited to the specific forms described in this embodiment, and the protection scope of the present invention also extends to equivalent technical means that can be thought of by ordinary technicians in this field based on the inventive concept.

Claims

1. A nitrogen-doped carbon-supported palladium copper particle electrocatalyst, characterized in that: Prepared by the following method: (1) 2 to 10 cm 2 The copper foam is immersed in hydrochloric acid to remove the surface oxide layer and oil stains; then, the treated copper foam is immersed in a mixed solution of 8-40 mL of ammonium persulfate and sodium hydroxide at room temperature, with the concentration of ammonium persulfate being 0.05-0.1 mol L -1 , sodium hydroxide concentration is 1~2 mol L -1 The copper hydroxide nanoarrays generated by the reaction were washed and dried in an oven for later use; (2) The prepared copper hydroxide nanoarrays were immersed in 8-40 mL TCPP solution at room temperature for 8-12 hours, with a TCPP concentration of 0.5-1 mg mL -1 , generating a copper-TCPP nanoarray, and washing the obtained copper-TCPP nanoarray with deionized water and ethanol for 3 to 5 times respectively; (3) placing the prepared copper-TCPP nanoarray in 5-25 mL of deionized water, then adding 30-150 μL of sodium chloropalladate aqueous solution to the deionized water, wherein the concentration of the added sodium chloropalladate aqueous solution is 0.5-16 mM, and keeping the solution in a water bath at 85-150° C. for 3-5 hours to generate a copper-palladium-TCPP nanoarray; washing the product with deionized water and ethanol for 3-5 times each, and then drying it in an oven at 50-60° C. for 1-3 hours; (4) The copper palladium-TCPP nanoarray was placed in a tube furnace in a nitrogen atmosphere with a nitrogen flow rate of 150-200 mL min -1 , heating rate is 3~5℃min -1 The temperature is raised to 400-450° C. and kept at this temperature for 3-5 hours to obtain the final product, i.e., nitrogen-doped carbon-supported palladium copper particle electrocatalyst.

2. A method for preparing the nitrogen-doped carbon-supported palladium copper particle electrocatalyst as claimed in claim 1, characterized in that: The method comprises the following steps: (1) 2 to 10 cm 2 The copper foam is immersed in hydrochloric acid to remove the surface oxide layer and oil stains; then, the treated copper foam is immersed in a mixed solution of 8-40 mL of ammonium persulfate and sodium hydroxide at room temperature, with the concentration of ammonium persulfate being 0.05-0.1 mol L -1 , sodium hydroxide concentration is 1~2 mol L -1 The copper hydroxide nanoarrays generated by the reaction were washed and dried in an oven for later use; (2) The prepared copper hydroxide nanoarrays were immersed in 8-40 mL TCPP solution at room temperature for 8-12 hours, with a TCPP concentration of 0.5-1 mg mL -1 , generating a copper-TCPP nanoarray, and washing the obtained copper-TCPP nanoarray with deionized water and ethanol for 3 to 5 times respectively; (3) placing the prepared copper-TCPP nanoarray in 5-25 mL of deionized water, then adding 30-150 μL of sodium chloropalladate aqueous solution to the deionized water, wherein the concentration of the added sodium chloropalladate aqueous solution is 0.5-16 mM, and keeping the solution in a water bath at 85-150° C. for 3-5 hours to generate a copper-palladium-TCPP nanoarray; washing the product with deionized water and ethanol for 3-5 times each, and then drying it in an oven at 50-60° C. for 1-3 hours; (4) The copper palladium-TCPP nanoarray was placed in a tube furnace in a nitrogen atmosphere with a nitrogen flow rate of 150-200 mL min -1 , heating rate is 3~5℃min -1 The temperature is raised to 400-450° C. and kept at this temperature for 3-5 hours to obtain the final product, i.e., nitrogen-doped carbon-supported palladium copper particle electrocatalyst.

3. The method according to claim 2, characterized in that The morphology and structure of the nitrogen-doped carbon-supported palladium-copper particle electrocatalyst were controlled by controlling the concentrations of ammonium persulfate, sodium hydroxide, TCPP and sodium chloropalladate as well as the temperature.

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