Core-shell type bifunctional electrocatalyst with crystalline amorphous interface and preparation method and application of core-shell type bifunctional electrocatalyst

Abstract

The invention discloses a core-shell type bifunctional electrocatalyst with a crystalline amorphous interface and a preparation method and application thereof, the preparation method comprises the following steps: loading ZIF-Co powder on CuO nanorods, and then carrying out vitrification through a melting quenching method to obtain the core-shell type bifunctional electrocatalyst with the crystalline amorphous interface. According to the preparation method, amorphous ZIF-Co is uniformly molten and coated on the surface of CuO by utilizing a vitrification technology, so that the core-shell type electrocatalyst with a crystalline amorphous compact nano interface is obtained, and the generation of more active sites is remarkably promoted. The material is a bifunctional catalyst with excellent performance and long-term stability, and is applied to anode electrooxidation of 5-hydroxymethylfurfural and cathode electrocatalytic hydrogen production. And the preparation method is simple, the price is low, the glassy material can be directly fused and attached to the electrode material without a binder, and device assembly and industrial large-scale production are facilitated.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrocatalysis, and in particular relates to a core-shell bifunctional electrocatalyst with a crystalline amorphous interface, a preparation method and an application thereof. Background Art

[0002] 5-Hydroxymethylfurfural (HMF), a key biomass platform compound, has garnered widespread attention in recent years. It can be converted into a variety of high-value-added chemicals through oxidation reactions, including 2,5-furandicarboxylic acid (FDCA), dialdehyde furfural (DFF), and 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). FDCA, a key precursor for renewable polymers, holds significant application value in engineering plastics, textiles, and pharmaceuticals. Compared to traditional thermochemical oxidation, electrocatalytic oxidation is a "green" catalytic process with mild reaction conditions. HMF can be selectively oxidized to FDCA via anodic electrocatalytic oxidation at ambient temperature and pressure. This method utilizes electrode potential and current density as two additional controllable parameters, enabling tunable substrate reactivity and high selectivity for the target product. Furthermore, the HMF electrocatalytic oxidation reaction (HMFOR) can replace the kinetically sluggish oxygen evolution reaction (OER) in alkaline water electrolysis and couple with the hydrogen evolution reaction (HER), significantly reducing the energy consumption of hydrogen production while simultaneously producing high-value-added chemicals, demonstrating significant economic and environmental benefits.

[0003] Although significant progress has been made in the development of efficient HMFOR electrocatalysts (such as transition-metal-based oxides, alloys, and sulfides), existing catalysts typically exhibit only oxidation activity for HMFOR and require a combination with a reduction-active HER catalyst. Practical applications of such dual-catalyst systems face challenges such as complex electrode preparation and high electrolysis equipment costs, limiting their scalable development. Therefore, there is an urgent need to develop electrocatalysts with both HMFOR and HER activity to achieve efficient and stable co-production of FDCA and H₂, thereby simplifying electrolysis system design, reducing production costs, and promoting the high-value utilization of biomass resources. Recent studies have demonstrated that metal-organic frameworks (MOFs) possess significant potential for both electrocatalytic oxidation and reduction due to their diverse structures and morphologies, rapid kinetics, and excellent porosity. However, compared with some noble metal-based electrocatalysts, most MOFs still suffer from poor conductivity and insufficient intrinsic activity. Furthermore, many powdered MOF electrocatalysts require binders, which can block active sites and hinder assembly and processing of devices for large-scale industrial applications. Summary of the Invention

[0004] In order to solve the technical problem of low catalytic efficiency of catalysts in the prior art, the purpose of the present invention is to provide a core-shell bifunctional electrocatalyst with a crystalline amorphous interface, a preparation method and an application. The catalyst obtained by this method has more abundant active sites and stronger substrate adsorption capacity, and is an electrocatalyst with high activity of both HMFOR and HER. Moreover, due to its unique melting characteristics, the catalyst can be directly coated on the nanoarray electrode without the need for a binder, which facilitates the development and industrial application of large-scale devices.

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

[0006] A method for preparing a core-shell bifunctional electrocatalyst having a crystalline-amorphous interface comprises the following steps:

[0007] ZIF-Co powder was loaded on CuO nanorods and then vitrified by a melt-quenching method to obtain a core-shell bifunctional electrocatalyst with a crystalline-amorphous interface.

[0008] Furthermore, the CuO nanorods are prepared by the following process: soaking a foam copper substrate in a sodium hydroxide solution containing ammonium persulfate and then calcining the solution to obtain the CuO nanorods.

[0009] Furthermore, the concentration of sodium hydroxide in the sodium hydroxide solution is 2-3 mol / L, the molar ratio of ammonium persulfate to sodium hydroxide is 18:1-25:1, the soaking time is 15-45 minutes, the calcination temperature is 150-250° C., and the calcination time is 20-60 minutes.

[0010] Furthermore, the ZIF-Co powder is prepared by the following process: a solution containing a cobalt salt and an organic ligand is subjected to a hydrothermal reaction to obtain the ZIF-Co powder.

[0011] Furthermore, the cobalt salt is cobalt nitrate, the organic ligand is a mixture of imidazole and benzimidazole, and the solvent in the solution is N,N-dimethylformamide.

[0012] Furthermore, the molar ratio of imidazole to benzimidazole is 5:1-8:1; the molar ratio of organic ligand to cobalt salt is 2:1-4:1; the mass ratio of cobalt salt to solvent is 1:60-1:120, the hydrothermal reaction temperature is 120-150° C., and the time is 48-168 hours.

[0013] Furthermore, ZIF-Co powder was loaded on the CuO nanorods, including: dispersing the ZIF-Co powder in an ethanol / isopropanol solution, and evenly dropping the powder onto the CuO nanorods after ultrasonic homogenization. The average ZIF loading was 2 mg / cm 2 .

[0014] Furthermore, vitrification is performed by a melt quenching method, comprising: heating the CuO nanorods loaded with ZIF-Co powder at 450-480° C. for 5-25 min under an argon or nitrogen inert gas atmosphere, and cooling;

[0015] The temperature is raised to 450-480°C at a heating rate of 8-15°C / min, and the cooling rate is 8-10°C / min.

[0016] A core-shell bifunctional electrocatalyst with a crystalline-amorphous interface.

[0017] Application of a core-shell bifunctional electrocatalyst with a crystalline-amorphous interface in the electrooxidation of 5-hydroxymethylfurfural and hydrogen evolution reaction.

[0018] Compared with the existing technology, the present invention has the following beneficial effects:

[0019] The present invention is the first to melt-load amorphous ZIF-Co onto the surface of CuO nanorods to construct a crystalline amorphous nano-interface catalyst with uniform and dense structure. The catalyst has a nano-morphology, and the charge redistribution between the interfaces can lead to the generation of more active sites, which is beneficial to the electrocatalytic reaction. The present invention promotes the electrochemical reconstruction process by using the interface effect formed by the vitrification process. Due to the charge redistribution between CuO and ZIF-Co, the catalyst undergoes deep reconstruction during the oxidation reaction and has abundant active sites at the interface. In addition, the formation of the interface promotes substrate adsorption and electron transfer capabilities, thereby having excellent HMF electro-oxidation and hydrogen evolution performance. The preparation method of a core-shell bifunctional electrocatalyst with a crystalline amorphous interface proposed by the present invention has simple equipment, mild reaction conditions, low cost, easy process control, and no need to add toxic and harmful reagents, which facilitates the industrialization and engineering application of the catalyst.

[0020] Furthermore, the vitrification process in the present invention is a key factor in determining catalyst performance. This process, achieved through a melt-quenching method, not only allows the amorphous ZIF to be uniformly coated on the CuO shell, but also induces an interfacial effect, which facilitates the formation of active sites at the interface, improving substrate adsorption and charge transfer capabilities. Therefore, precise control of the heating temperature and the rates of heating and cooling become essential factors in optimizing the vitrification effect and, in turn, improving catalyst performance.

[0021] The glassy electrocatalyst prepared by the present invention is melt-adhered to the surface of the CuO nanorods, achieving full contact without the need for additional adhesives, while achieving rapid charge transfer and solving the difficult problem of powdered MOFs catalysts being difficult to process.

[0022] The CuO@ZIF-Co(g) material with a crystalline-amorphous interface prepared by the present invention is an electrocatalyst with both HMFOR and HER dual functional activities. It can avoid the problems of complex electrode preparation and high cost of electrolysis equipment in practical applications of traditional dual-catalyst systems, simplify the design of electrolysis systems and reduce production costs, which is conducive to industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in this application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creativity and labor.

[0024] Figure 1 The preparation principle diagram of CuO@ZIF-Co(g) provided by the present invention and the microscopic morphology of the corresponding materials; wherein (a) is the principle diagram, (b) is CF, (c) is CuO, (d) is CuO@ZIF-Co, and (e) is CuO@ZIF-Co(g);

[0025] Figure 2 TEM image of CuO@ZIF-Co(g) obtained in Example 1 of the present invention;

[0026] Figure 3 This is a transmission electron microscope image of CuO@ZIF-Co obtained in Comparative Example 1 of the present invention;

[0027] Figure 4 The X-ray diffraction patterns of the catalysts obtained in Example 1, Comparative Example 1, and Comparative Example 2 of the present invention are shown; wherein (a) is an X-ray diffraction pattern, (b) is a partial enlarged view of the prescription box A in Figure (a), and (c) is a partial enlarged view of the prescription box B in Figure (a);

[0028] Figure 5 HMF oxidation cyclic voltammetry curves of the catalysts obtained in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention;

[0029] Figure 6 The catalysts obtained in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention are -2 Potential comparison diagram of HMF oxidation reaction under different current densities;

[0030] Figure 7 The cyclic voltammetry curves of the hydrogen evolution reaction of the catalysts obtained in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention are as follows;

[0031] Figure 8The catalysts obtained in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention were tested at 10 mA cm -2 Comparison of overpotentials of hydrogen evolution reaction at different current densities;

[0032] Figure 9 This is a current-time diagram of the HMF electrolysis process using the CuO@ZIF-Co(g) catalyst obtained in Example 1 of the present invention;

[0033] Figure 10 1 is a graph showing the conversion of HMF, the yield of FDCA, and the Faraday efficiency cycle stability of FDCA in the electrooxidation of HMF using the CuO@ZIF-Co(g) catalyst obtained in Example 1 of the present invention;

[0034] Figure 11 Figure 1 shows the it stability test graph of the CuO@ZIF-Co(g) catalyst obtained in Example 1 of the present invention for the hydrogen evolution reaction and the LSV comparison graph before and after 1000 CV cycles, where (a) is the it stability test graph and (b) is the LSV comparison graph;

[0035] Figure 12 The conversion rate (con.) of HMF, the yield (yield) of FDCA and the Faradaic efficiency (FE) of FDCA after the electrolysis of HMF using the catalysts obtained in Example 1, Comparative Example 1 and Comparative Example 2 of the present invention are shown.

[0036] Figure 13 2 are the current density-scan rate curves of the catalysts obtained in Example 1, Comparative Example 1 and Comparative Example 2. DETAILED DESCRIPTION

[0037] To facilitate understanding of the present invention, the present invention will be described more fully below with reference to the accompanying drawings. The accompanying drawings illustrate preferred embodiments of the present invention. However, the present invention may be implemented in a variety of different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and comprehensive understanding of the disclosure of the present invention.

[0038] Metal-organic frameworks (MOFs) have shown broad application prospects in the field of electrocatalytic redox reactions due to their high porosity, large specific surface area, and tunable chemical structure. In recent years, a new type of glassy MOFs has shown great potential in the field of photo / electrocatalysis due to its unique disordered long-range structure, excellent processing properties, and outstanding ionic conductivity. Studies have shown that glassy zeolite imidazolate frameworks (ZIFs) prepared by a melt-quenching process can firmly adhere to the substrate surface, avoiding the dependence of traditional powdered MOFs on binders, thereby effectively solving the problem of catalytic performance degradation caused by binders blocking active sites or hindering electron transport. In addition, the structural disorder and inherent defect characteristics of glassy MOFs enable them to exhibit more efficient charge transfer capabilities compared to crystalline MOFs, thus endowing them with superior electrocatalytic activity. This characteristic gives them a unique advantage in the development of efficient bifunctional electrocatalysts and is expected to provide innovative solutions for the coordinated production of biomass-derived high-value-added chemicals and clean energy.

[0039] The present invention provides a method for preparing a core-shell bifunctional electrocatalyst with a crystalline-amorphous interface and its application in HMF electrooxidation and hydrogen evolution. The catalyst obtained by this method has more abundant active sites, stronger substrate adsorption capacity, and excellent catalytic activity, solving the problems of low catalytic efficiency, insufficient active sites, and low electron transfer efficiency of existing catalysts. In addition, due to its unique melting characteristics, the catalyst can be directly coated on a nanoarray electrode without the need for a binder, showing potential for industrial application.

[0040] The present invention provides a method for preparing a core-shell bifunctional electrocatalyst having a crystalline-amorphous interface, comprising the following steps:

[0041] (1) Cut the foam copper base into 1*1cm 2 size, ultrasonically cleaned in dilute hydrochloric acid (mass concentration of 3 mol / L), ethanol, and deionized water for 5-10 minutes, and dried in a vacuum drying oven at 50-70°C for 12 hours; a certain amount of ammonium persulfate was added to 30 ml of 2-3 mol / L NaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 18:1-25:1, and the cleaned foamed copper was placed in the solution, stirred at 600 rpm for 3 minutes, and then allowed to soak for 15-45 minutes. After washing with deionized water, the foamed copper was placed in a vacuum oven at 50-70°C for 12 hours; and finally calcined in a muffle furnace at 150-250°C for 20-60 minutes to obtain CuO nanorods;

[0042] (2) adding a metal salt (cobalt nitrate) and an organic ligand (a mixture of imidazole and benzimidazole) to an N,N-dimethylformamide solvent and stirring for 60-90 minutes to obtain a mixture, wherein the molar ratio of imidazole to benzimidazole is 5:1-8:1, the molar ratio of the organic ligand to the metal salt is 2:1-4:1, and the mass ratio of the metal salt to N,N-dimethylformamide is 1:60-1:120; transferring the mixture to a high-pressure reactor, heating at 120-140°C for 48-168 hours, washing the product with N,N-dimethylformamide and methanol 2-4 times each, centrifuging and drying to obtain ZIF-Co powder;

[0043] (3) ZIF-Co powder was dispersed in ethanol / isopropanol solution and evenly drop-coated onto CuO nanorods after ultrasonic homogenization. The average ZIF loading was 2 mg / cm 2 , obtaining an electrode material loaded with ZIF; placing the electrode material loaded with ZIF in a tube furnace under an argon or nitrogen inert gas atmosphere, rapidly heating it to 450-480°C at a heating rate of 8-15°C / min to melt it, holding it for 5-25 minutes, and then rapidly cooling it at a cooling rate of 8-10°C / min to vitrify it, thereby obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline-amorphous interface;

[0044] A core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline-amorphous interface is prepared according to the method described above. The catalyst structure has a crystalline CuO nanorod as the core and is uniformly coated with a layer of amorphous glassy ZIF-Co material. A crystalline CuO nanoarray is obtained by in-situ etching and calcination using a foamed copper substrate. The present invention utilizes vitrification technology to uniformly melt-coat the amorphous ZIF-Co(g) on ​​the CuO surface, resulting in a core-shell electrocatalyst with a dense crystalline-amorphous nanointerface. The built-in electric field between the Cu and Co atoms significantly promotes the generation of more active sites, resulting in a higher electrochemically active surface area for the CuO@ZIF-Co(g) and enhanced electrocatalytic activity.

[0045] Application of the core-shell bifunctional catalyst with a crystalline-amorphous interface as described above in the electrooxidation and hydrogen evolution of 5-hydroxymethylfurfural (HMF).

[0046] Figure 1 This is a schematic diagram of the preparation principle of the CuO@ZIF-Co(g) electrocatalyst provided by the present invention. Figure 1In Figures (a)-(e), a copper foam (CF) substrate was used as the substrate. CuO nanorod arrays were in situ grown on its surface by etching and calcining. Hydrothermally synthesized ZIF-Co was then loaded onto the surface via a drop-coating method. The drop-coated catalyst was further treated by a two-step melt-quenching process, resulting in a core-shell structure of CuO nanorods uniformly coated with glassy ZIF-Co, namely the CuO@ZIF-Co (g) electrocatalyst.

[0047] The electrooxidation performance of HMF in Example 1 and Comparative Examples 1-2 was tested in a typical H-type electrolytic cell three-electrode system. The prepared catalyst (1×1 cm 2 ) is directly used as the working electrode, the carbon rod is used as the counter electrode, Hg / HgO is used as the reference electrode, and the electrolyte solution is 1.0 mol / L KOH containing 10 mmol / L HMF. The potential in the test can be converted into the reversible hydrogen electrode potential E(RHE) by the Stirling equation. The following HMF electrolysis product analysis tests of Example 1 and Comparative Examples 1-2 were carried out under a voltage of 1.45 V vs. RHE for a long time. The electrolyte was 10 mL of a 1.0 mol / L KOH solution containing 10 m mol / L HMF, and the sample liquid was taken at the anode end at regular intervals for analysis using high performance liquid chromatography. The electrocatalytic hydrogen evolution reaction was also tested in the above H-type electrolytic cell three-electrode system. The prepared catalyst (1×1 cm 2 ) was directly used as the working electrode, the carbon rod was used as the counter electrode, Hg / HgO was used as the reference electrode, and the electrolyte solution was 1.0 mol / L KOH.

[0048] The present invention is further illustrated by the following examples, which provide a better understanding of the present invention. However, it will be readily understood by those skilled in the art that the specific material ratios, process conditions, and results described in the examples are intended only to illustrate the present invention and should not, and do not, limit the present invention as described in detail in the claims.

[0049] Example 1

[0050] Step 1) Cut the foam copper base into 1*1cm 2 The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 10 minutes, respectively, and dried in a vacuum drying oven at 60°C for 12 hours; 0.89g of ammonium persulfate was added to 30ml of 2.67mol / LNaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 20:1, and the cleaned foam copper was placed in the solution, stirred at 600rpm for 3 minutes, and then allowed to stand and soak for 30 minutes. After washing with deionized water, it was placed in a vacuum oven at 60°C for 12 hours; finally, it was calcined in a muffle furnace at 180°C for 30 minutes to obtain CuO nanorods;

[0051] Step 2), 4 mmol of cobalt nitrate, 11.6 mmol of imidazole and 1.6 mmol of benzimidazole were added to 90 mL of N, N-dimethylformamide solvent and stirred for 60 min to obtain a mixture, which was transferred to an autoclave and heated at 130 ° C for 168 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 60 ° C for 10 h to obtain ZIF-Co powder;

[0052] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2 , obtaining an electrode material loaded with ZIF; placing the electrode material loaded with ZIF in a tube furnace under an argon atmosphere, rapidly heating it to 470°C at a heating rate of 10°C / min to melt it, holding it for 20 minutes, and then rapidly cooling it at a cooling rate of 10°C / min to vitrify it, obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline-amorphous interface;

[0053] Figure 2 The middle is a transmission electron microscope image of CuO@ZIF-Co(g) of Example 1, from which it can be clearly seen that the amorphous ZIF-Co(g) is evenly coated on the surface of the CuO nanorods.

[0054] from Figure 5 The linear sweep voltammetry (LSV) curves of HMF oxidation and Figure 6 10mAcm -2 The HMF oxidation reaction potential comparison diagram shows that CuO@ZIF-Co(g) exhibits good HMF electrooxidation performance at 10 mA cm -2 The potential of the electrocatalyst is only 1.30 V vs. RHE at a current density of 1.5 V. Compared with Comparative Examples 1 and 2, the potential of the electrocatalyst is reduced, which indicates that the glassy state-induced crystalline-amorphous interface can effectively promote the HMF electrooxidation reaction.

[0055] from Figure 7 The LSV curve of hydrogen evolution reaction and Figure 8 10mAcm -2 The comparison of hydrogen evolution reaction overpotentials also shows that CuO@ZIF-Co(g) exhibits good HER performance at 10 mA cm -2 The overpotential of the electrocatalyst is significantly reduced compared with Comparative Examples 1 and 2, indicating that the glassy state-induced crystalline-amorphous interface effectively promotes the HER reaction.

[0056] Figure 9: This is a current-time diagram of the HMF electrolysis process. It can be seen that the HMF electrooxidation process of CuO@ZIF-Co(g) prepared in Example 1 of the present invention takes only 30 minutes, which shows excellent reaction performance.

[0057] Figure 10 After 15 cycles of HMF electrooxidation catalysis, the HMF conversion, FDCA yield, and FDCA Faradaic efficiency of the CuO@ZIF-Co(g) prepared in Example 1 of the present invention did not show significant attenuation, demonstrating excellent catalytic cycle stability.

[0058] See also Figure 11 In (a) and (b), the hydrogen evolution current density decay of CuO@ZIF-Co(g) prepared in Example 1 of the present invention during the 48h constant voltage test is negligible, and the polarization curve does not change significantly after 1000 cycles ( Figure 11 (b)), demonstrating its excellent hydrogen evolution stability.

[0059] Comparative Example 1

[0060] Step 1) Cut the foam copper base into 1*1cm 2 The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 10 minutes, respectively, and dried in a vacuum drying oven at 60°C for 12 hours; 0.89g of ammonium persulfate was added to 30ml of 2.67mol / LNaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 20:1, and the cleaned foam copper was placed in the solution, stirred at 600rpm for 3 minutes, and then allowed to stand and soak for 30 minutes. After washing with deionized water, it was placed in a vacuum oven at 60°C for 12 hours; finally, it was calcined in a muffle furnace at 180°C for 30 minutes to obtain CuO nanorods;

[0061] Step 2), 4 mmol of cobalt nitrate, 11.6 mmol of imidazole and 1.6 mmol of benzimidazole were added to 90 mL of N, N-dimethylformamide solvent and stirred for 60 min to obtain a mixture, which was transferred to an autoclave and heated at 130 ° C for 168 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 60 ° C for 10 h to obtain ZIF-Co powder;

[0062] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2 , the electrode material loaded with ZIF was obtained, namely the catalyst CuO@ZIF-Co;

[0063] Figure 3The transmission electron micrograph (TEM) of the CuO@ZIF-Co catalyst in Comparative Example 1 shows that the ZIF-Co and CuO nanorods exhibit isolated structures. This is because the ZIF-Co catalyst, without vitrification, cannot form an interfacial effect. Under these conditions, the ZIF-Co catalyst remains crystalline and fails to form an effective interfacial contact with the CuO nanorods. This structural feature indicates that the ZIF-Co catalyst, without vitrification, lacks the necessary interaction with the CuO nanorods, resulting in the composite material failing to form an ideal interfacial structure.

[0064] Figure 4 (a), (b) and (c) are the X-ray diffraction (XRD) patterns of the catalyst of this comparative example and their partial enlarged views. The ZIF-Co crystalline Bragg peak observed at 2θ = 10 ~ 30° of CuO@ZIF-Co indicates that the ZIF is still in a crystalline state at this time; in addition, a broad scattering centered at 2θ = 16° was detected in the CuO@ZIF-Co(g) catalyst obtained in Example 1. This obvious change confirms that the crystalline ZIF-Co in the CuO@ZIF-Co has undergone a vitrification process, revealing the amorphous ZIF structure in the CuO@ZIF-Co(g) obtained by melt quenching.

[0065] from Figure 5 、 Figure 6 、 Figure 7 、 Figure 8 The LSV curve and overpotential comparison diagram show that CuO@ZIF-Co without interface formation has a high overpotential at 10 mA cm -2 At a current density of 1.5 Å, the HMF oxidation potential required was 1.34 V vs. RHE, and the HER overpotential was 194 mV. Compared with the CuO@ZIF-Co(g) with a crystalline-amorphous interface, both the HMF oxidation and HER performances were significantly reduced, indicating that the crystalline-amorphous interface can enhance the reaction activity.

[0066] Comparative Example 2

[0067] Step 1) Cut the foam copper base into 1*1cm 2 The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 10 min, respectively, and dried in a vacuum drying oven at 60 °C for 12 h;

[0068] Step 2), 4 mmol of cobalt nitrate, 11.6 mmol of imidazole and 1.6 mmol of benzimidazole were added to 90 mL of N, N-dimethylformamide solvent and stirred for 60 min to obtain a mixture, which was transferred to an autoclave and heated at 130 ° C for 168 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 60 ° C for 10 h to obtain ZIF-Co powder;

[0069] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and drop-coat 400 μL onto the foam copper electrode material. The average ZIF loading is 2 mg / cm 2 , obtaining an electrode material loaded with ZIF; placing the electrode material loaded with ZIF in a tubular furnace with an argon atmosphere, rapidly heating it to 470°C at a heating rate of 10°C / min, maintaining it for 20 minutes, and then rapidly cooling it at a cooling rate of 10°C / min to vitrify it, obtaining the catalyst ZIF-Co(g).

[0070] Figure 4 This is the X-ray diffraction (XRD) pattern of the catalyst of this comparative example. ZIF-Co(g) is amorphous and has a long-range disordered glassy structure.

[0071] from Figure 5 、 Figure 6 、 Figure 7 、 Figure 8 The LSV curve and overpotential comparison diagram show that ZIF-Co(g) has a high conductivity at 10 mA cm -2 At a current density of 1.5 Å, the HMF oxidation potential required was 1.37 V vs. RHE, and the HER overpotential was 263 mV. Compared to CuO@ZIF-Co(g), which incorporates CuO to form an interface, both HMF oxidation and HER performance are significantly reduced, indicating that the glass-induced interface is a key factor in catalytic activity, significantly enhancing the reaction activity.

[0072] Figure 12 Figure 2 shows the HMF conversion, FDCA yield, and FDCA Faradaic efficiency during the HMF electrolysis process. A comparison reveals that the CuO@ZIF-Co(g) prepared in Example 1 significantly outperforms the CuO@ZIF-Co and ZIF-Co(g) prepared in Comparative Examples 1 and 2, achieving a final HMF conversion of 100%, an FDCA yield of 99.5%, and an FDCA Faradaic efficiency of 99.1%. This demonstrates that the glass-induced crystalline-amorphous interface promotes the catalytic reaction, resulting in excellent performance.

[0073] Figure 13 The current density-scan rate curves of Example 1, Comparative Example 1 and Comparative Example 2 are obtained by applying CV with different scan rates in the non-Faraday region of the catalyst to obtain the corresponding current potential curves. The scan rate is used as the independent variable, the positive and negative current difference is used as the dependent variable, and the slope of the straight line after the linear fitting of the obtained data is C dl , because C dl There is a positive linear relationship between the electrochemical active surface area and the C dlThe electrochemically active surface area of ​​the catalyst can be determined by the size of the numerical value. By comparison, the CuO@ZIF-Co(g) prepared in Example 1 of the present invention has the highest Cdl value, indicating that the vitrification-induced crystalline-amorphous interface promotes the formation of more active sites, effectively enhancing the HMF electrooxidation and hydrogen evolution reaction activity.

[0074] Example 2

[0075] Step 1) Cut the foam copper base into 1*1cm 2 The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 10 minutes, respectively, and dried in a vacuum drying oven at 60°C for 12 hours; 0.8g of ammonium persulfate was added to 30ml of 2.67mol / L NaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 18:1, and the cleaned foam copper was placed in the solution, stirred at 600rpm for 3 minutes, and then allowed to soak for 45 minutes. After washing with deionized water, it was placed in a vacuum oven at 60°C for 12 hours; finally, it was calcined in a muffle furnace at 200°C for 40 minutes to obtain CuO nanorods;

[0076] Step 2), 4 mmol of cobalt nitrate, 11.6 mmol of imidazole and 1.6 mmol of benzimidazole were added to 90 mL of N, N-dimethylformamide solvent and stirred for 60 min to obtain a mixture, which was transferred to an autoclave and heated at 150 ° C for 48 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 60 ° C for 10 h to obtain ZIF-Co powder;

[0077] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2 , obtaining an electrode material loaded with ZIF; the electrode material loaded with ZIF was placed in a tube furnace with an argon atmosphere, and the temperature was rapidly increased to 465°C at a heating rate of 8°C / min to melt it. After holding for 25 minutes, it was rapidly cooled at a cooling rate of 8°C / min to vitrify it, obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline amorphous interface.

[0078] Example 3

[0079] Step 1) Cut the foam copper base into 1*1cm 2The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 10 minutes, respectively, and dried in a vacuum drying oven at 60°C for 12 hours; 0.97g of ammonium persulfate was added to 30ml of 2.67mol / LNaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 22:1, and the cleaned foam copper was placed in the solution, stirred at 600rpm for 3 minutes, and then allowed to stand and soak for 25 minutes. After washing with deionized water, it was placed in a vacuum oven at 60°C for 12 hours; finally, it was calcined in a muffle furnace at 150°C for 60 minutes to obtain CuO nanorods;

[0080] Step 2), 4 mmol of cobalt nitrate, 11.6 mmol of imidazole and 1.6 mmol of benzimidazole were added to 90 mL of N, N-dimethylformamide solvent and stirred for 60 min to obtain a mixture, which was transferred to an autoclave and heated at 120 ° C for 168 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 60 ° C for 10 h to obtain ZIF-Co powder;

[0081] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2 , obtaining an electrode material loaded with ZIF; the electrode material loaded with ZIF was placed in a tube furnace with an argon atmosphere, and the temperature was rapidly increased to 475°C at a heating rate of 12°C / min to melt it. After holding it for 20 minutes, it was rapidly cooled at a cooling rate of 10°C / min to vitrify it, obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline amorphous interface.

[0082] Example 4

[0083] Step 1) Cut the foam copper base into 1*1cm 2 The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 10 minutes, respectively, and dried in a vacuum drying oven at 60°C for 12 hours; 1.07g of ammonium persulfate was added to 30ml of 2.67mol / LNaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 24:1, and the cleaned foam copper was placed in the solution, stirred at 600rpm for 3 minutes, and then allowed to stand and soak for 15 minutes. After washing with deionized water, it was placed in a vacuum oven at 60°C for 12 hours; finally, it was calcined in a muffle furnace at 220°C for 30 minutes to obtain CuO nanorods;

[0084] Step 2), 4 mmol of cobalt nitrate, 11.6 mmol of imidazole and 1.6 mmol of benzimidazole were added to 90 mL of N, N-dimethylformamide solvent and stirred for 60 min to obtain a mixture, which was transferred to an autoclave and heated at 135 ° C for 96 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 60 ° C for 10 h to obtain ZIF-Co powder;

[0085] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2 , obtaining an electrode material loaded with ZIF; the electrode material loaded with ZIF was placed in a tube furnace with an argon atmosphere, and the temperature was rapidly increased to 455°C at a heating rate of 15°C / min to melt it. After holding it for 25 minutes, it was rapidly cooled at a cooling rate of 8°C / min to vitrify it, obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline amorphous interface.

[0086] Example 5

[0087] Step 1) Cut the foam copper base into 1*1cm 2 The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 10 minutes, respectively, and dried in a vacuum drying oven at 60°C for 12 hours; 1.11g of ammonium persulfate was added to 30ml of 2.67mol / LNaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 25:1, and the cleaned foam copper was placed in the solution, stirred at 600rpm for 3 minutes, and then allowed to stand and soak for 20 minutes. After washing with deionized water, it was placed in a vacuum oven at 60°C and dried for 12 hours; finally, it was calcined in a muffle furnace at 250°C for 35 minutes to obtain CuO nanorods;

[0088] Step 2), 4 mmol of cobalt nitrate, 11.6 mmol of imidazole and 1.6 mmol of benzimidazole were added to 90 mL of N, N-dimethylformamide solvent and stirred for 60 min to obtain a mixture, which was transferred to an autoclave and heated at 140 ° C for 72 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 70 ° C for 8 h to obtain ZIF-Co powder;

[0089] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2, obtaining an electrode material loaded with ZIF; the electrode material loaded with ZIF was placed in a tube furnace with an argon atmosphere, and the temperature was rapidly increased to 480°C at a heating rate of 13°C / min to melt it. After holding it for 8 minutes, it was rapidly cooled at a cooling rate of 10°C / min to vitrify it, obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline amorphous interface.

[0090] Example 6

[0091] Step 1) Cut the foam copper base into 1*1cm 2 The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 10 minutes, respectively, and dried in a vacuum drying oven at 60°C for 12 hours; 0.84g of ammonium persulfate was added to 30ml of 2.67mol / LNaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 19:1, and the cleaned foam copper was placed in the solution, stirred at 600rpm for 3 minutes, and then allowed to stand and soak for 45 minutes. After washing with deionized water, it was placed in a vacuum oven at 60°C for 12 hours; finally, it was calcined in a muffle furnace at 235°C for 35 minutes to obtain CuO nanorods;

[0092] Step 2), 4 mmol of cobalt nitrate, 11.6 mmol of imidazole and 1.6 mmol of benzimidazole were added to 90 mL of N, N-dimethylformamide solvent and stirred for 60 min to obtain a mixture, which was transferred to an autoclave and heated at 128 ° C for 120 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 65 ° C for 12 h to obtain ZIF-Co powder;

[0093] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2 , obtaining an electrode material loaded with ZIF; the electrode material loaded with ZIF was placed in a tube furnace with an argon atmosphere, and the temperature was rapidly increased to 460°C at a heating rate of 15°C / min to melt it. After holding for 15 minutes, it was rapidly cooled at a cooling rate of 9°C / min to vitrify it, obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline amorphous interface.

[0094] Example 7

[0095] Step 1) Cut the foam copper base into 1*1cm 2The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 10 minutes, respectively, and dried in a vacuum drying oven at 60°C for 12 hours; 0.93g of ammonium persulfate was added to 30ml of 2.67mol / LNaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 21:1, and the cleaned foam copper was placed in the solution, stirred at 600rpm for 3 minutes, and then allowed to stand and soak for 45 minutes. After washing with deionized water, it was placed in a vacuum oven at 60°C and dried for 12 hours; finally, it was calcined in a muffle furnace at 180°C for 30 minutes to obtain CuO nanorods;

[0096] Step 2), 4 mmol of cobalt nitrate, 11.6 mmol of imidazole and 1.6 mmol of benzimidazole were added to 90 mL of N, N-dimethylformamide solvent and stirred for 60 min to obtain a mixture, which was transferred to an autoclave and heated at 135 ° C for 144 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 60 ° C for 10 h to obtain ZIF-Co powder;

[0097] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2 , obtaining an electrode material loaded with ZIF; the electrode material loaded with ZIF was placed in a tube furnace with an argon atmosphere, and the temperature was rapidly increased to 450°C at a heating rate of 13°C / min to melt it. After holding for 25 minutes, it was rapidly cooled at a cooling rate of 8°C / min to vitrify it, obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline amorphous interface.

[0098] Example 8

[0099] Step 1) Cut the foam copper base into 1*1cm 2 The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 10 minutes, respectively, and dried in a vacuum drying oven at 60°C for 12 hours; 1.02g of ammonium persulfate was added to 30ml of 2.67mol / LNaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 23:1, and the cleaned foam copper was placed in the solution, stirred at 600rpm for 3 minutes, and then allowed to stand and soak for 15 minutes. After washing with deionized water, it was placed in a vacuum oven at 60°C and dried for 12 hours; finally, it was calcined in a muffle furnace at 240°C for 20 minutes to obtain CuO nanorods;

[0100] Step 2), 4 mmol of cobalt nitrate, 11.6 mmol of imidazole and 1.6 mmol of benzimidazole were added to 90 mL of N, N-dimethylformamide solvent and stirred for 60 min to obtain a mixture, which was transferred to an autoclave and heated at 132 ° C for 132 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 60 ° C for 10 h to obtain ZIF-Co powder;

[0101] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2 , obtaining an electrode material loaded with ZIF; the electrode material loaded with ZIF was placed in a tube furnace with an argon atmosphere, and the temperature was rapidly increased to 467°C at a heating rate of 8°C / min to melt it. After holding for 15 minutes, it was rapidly cooled at a cooling rate of 9°C / min to vitrify it, obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline amorphous interface.

[0102] Example 9

[0103] Step 1) Cut the foam copper base into 1*1cm 2 The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 5 minutes, respectively, and dried in a vacuum drying oven at 50°C for 12 hours; ammonium persulfate was added to 30ml of 2mol / L NaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 20:1, and the cleaned foam copper was placed in the solution, stirred at 600rpm for 3 minutes, and then allowed to stand and soak for 40 minutes. After washing with deionized water, it was placed in a vacuum oven at 50°C for 12 hours; finally, it was calcined in a muffle furnace at 150°C for 50 minutes to obtain CuO nanorods;

[0104] Step 2), 4 mmol of cobalt nitrate, 6.6 mmol of imidazole and 1.3 mmol of benzimidazole were added to 47 mL of N, N-dimethylformamide solvent and stirred for 70 min to obtain a mixture, which was transferred to an autoclave and heated at 125 ° C for 150 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 60 ° C for 10 h to obtain ZIF-Co powder;

[0105] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2, obtaining an electrode material loaded with ZIF; the electrode material loaded with ZIF was placed in a tube furnace with an argon atmosphere, and the temperature was rapidly increased to 460°C at a heating rate of 10°C / min to melt it. After holding for 5 minutes, it was rapidly cooled at a cooling rate of 8°C / min to vitrify it, obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline amorphous interface.

[0106] Example 10

[0107] Step 1) Cut the foam copper base into 1*1cm 2 The size was ultrasonically cleaned in dilute hydrochloric acid, ethanol, and deionized water for 7 minutes, respectively, and dried in a vacuum drying oven at 70°C for 12 hours. Ammonium persulfate was added to 30 ml of 3 mol / L NaOH solution, wherein the molar ratio of sodium hydroxide to ammonium persulfate was 25:1. The cleaned foam copper was placed in the solution, stirred at 600 rpm for 3 minutes, and then allowed to stand and soak for 30 minutes. After washing with deionized water, it was placed in a vacuum oven at 70°C for 12 hours. Finally, it was calcined in a muffle furnace at 210°C for 40 minutes to obtain CuO nanorods.

[0108] Step 2), 4 mmol of cobalt nitrate, 14.2 mmol of imidazole and 1.7 mmol of benzimidazole were added to 94 mL of N, N-dimethylformamide solvent and stirred for 90 min to obtain a mixture, which was transferred to an autoclave and heated at 130 ° C for 60 h. The product was washed twice with N, N-dimethylformamide and methanol, centrifuged, and vacuum dried at 60 ° C for 10 h to obtain ZIF-Co powder;

[0109] Step 3) Disperse 10 mg ZIF-Co powder in 2 ml ethanol solution, ultrasonically homogenize, and then drop-coat 400 μL onto the CuO nanorods. The average ZIF loading is 2 mg / cm 2 , obtaining an electrode material loaded with ZIF; the electrode material loaded with ZIF was placed in a tube furnace with an argon atmosphere, and the temperature was rapidly increased to 470°C at a heating rate of 15°C / min to melt it. After holding it for 22 minutes, it was rapidly cooled at a cooling rate of 10°C / min to vitrify it, obtaining a core-shell bifunctional catalyst CuO@ZIF-Co(g) with a crystalline amorphous interface.

[0110] The vitrification process in this invention is a crucial factor in determining catalyst performance. This process, achieved through melt-quenching technology, induces the formation of a dense, crystalline-amorphous nanostructured interface between the ZIF and CuO nanorods, redistributing the charge field between the Co and Cu atoms and facilitating the generation of more active sites at the highly reactive interface. Therefore, precise control of the heating temperature and the ramp rates are essential for optimizing the vitrification effect and, consequently, enhancing catalyst performance.

[0111] This invention utilizes vitrification to induce a core-shell structure with an interfacial effect, resulting in a bifunctional catalyst for HMF electrooxidation and hydrogen evolution with abundant active sites. This solves the practical problems of traditional dual-catalyst systems, such as complex electrode preparation and high electrolysis equipment costs. It simplifies electrolysis system design and reduces production costs, facilitating industrialization. Furthermore, the glassy MOFs electrocatalyst can be melt-bonded to the surface of CuO nanorods, ensuring sufficient contact without the need for additional adhesives, while achieving rapid charge transfer and overcoming the processing challenges of powdered MOFs catalysts.

[0112] The above description is merely a description of the preferred embodiment of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiment, and variations in the specific structure are permitted. Any variations made within the scope of the independent claims of the present invention are also within the scope of protection of the present invention.

[0113] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used herein in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

Claims

1. A method for preparing a core-shell bifunctional electrocatalyst having a crystalline-amorphous interface, characterized in that: The following steps are involved: ZIF-Co powder was loaded on CuO nanorods and then vitrified by a melt-quenching method to obtain a core-shell bifunctional electrocatalyst with a crystalline-amorphous interface.

2. The method for preparing a core-shell bifunctional electrocatalyst having a crystalline-amorphous interface according to claim 1, characterized in that: The CuO nanorods are prepared by the following process: a foam copper substrate is immersed in a sodium hydroxide solution containing ammonium persulfate and then calcined to obtain the CuO nanorods.

3. The method for preparing a core-shell bifunctional electrocatalyst having a crystalline amorphous interface according to claim 2, characterized in that: The concentration of sodium hydroxide in the sodium hydroxide solution is 2-3 mol / L, the molar ratio of ammonium persulfate to sodium hydroxide is 18:1-25:1, the soaking time is 15-45 minutes, the calcination temperature is 150-250° C., and the calcination time is 20-60 minutes.

4. The method for preparing a core-shell bifunctional electrocatalyst having a crystalline-amorphous interface according to claim 1, characterized in that: The ZIF-Co powder is prepared by the following process: a solution containing a cobalt salt and an organic ligand is subjected to a hydrothermal reaction to obtain the ZIF-Co powder.

5. The method for preparing a core-shell bifunctional electrocatalyst having a crystalline-amorphous interface according to claim 4, characterized in that: The cobalt salt is cobalt nitrate, the organic ligand is a mixture of imidazole and benzimidazole, and the solvent in the solution is N,N-dimethylformamide.

6. The method for preparing a core-shell bifunctional electrocatalyst having a crystalline-amorphous interface according to claim 5, characterized in that: The molar ratio of imidazole to benzimidazole is 5:1-8:1; The molar ratio of the organic ligand to the cobalt salt is 2:1-4:1; the mass ratio of the cobalt salt to the solvent is 1:60-1:120; the temperature of the hydrothermal reaction is 120-150° C.; and the time is 48-168 hours.

7. The method for preparing a core-shell bifunctional electrocatalyst having a crystalline-amorphous interface according to claim 1, characterized in that: The ZIF-Co powder is loaded on the CuO nanorods, comprising: dispersing the ZIF-Co powder in an ethanol / isopropanol solution, uniformly drop-coating the powder onto the CuO nanorods after ultrasonic homogenization, and the average ZIF loading is 2 mg / cm 2 .

8. The method for preparing a core-shell bifunctional electrocatalyst having a crystalline-amorphous interface according to claim 1, characterized in that: Vitrification is performed by a melt quenching method, comprising: heating the CuO nanorods loaded with ZIF-Co powder at 450-480° C. for 5-25 minutes under an argon or nitrogen inert gas atmosphere, and cooling; The temperature is raised to 450-480°C at a heating rate of 8-15°C / min, and the cooling rate is 8-10°C / min.

9. A core-shell bifunctional electrocatalyst having a crystalline-amorphous interface prepared by the method according to any one of claims 1 to 8.

10. Use of a core-shell bifunctional electrocatalyst having a crystalline-amorphous interface prepared by the method according to any one of claims 1 to 8 in electro-oxidation of 5-hydroxymethylfurfural and hydrogen evolution reaction.

Images