Nanoporous r-pptcu 1-x ni x (NiCu)2al3 intermetallic compound heterostructure electrode, method of making and use thereof

Abstract

The application discloses a kind of nano-porous r-PtCu 1‑x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode and its preparation method and application, comprising: a, cleaning metal and melting alloy ingot;B, preparation alloy sheet and chemical dealloying;C, replace Pt and heat treatment: after drying, nano-porous CuNi / (NiCu)2Al3 electrode is soaked into 0.1mM H2PtCl6 and 0.1g / L PVP mixed solution, under the magnetic stirring of room temperature, keep 30min;Ultra-pure water, ethanol is sequentially used to clean the alloy sheet soaked multiple times, and is placed into vacuum drying oven and dried;After soaking, the nano-porous electrode dried is placed into tube furnace, and is heat treated under the mixed atmosphere of Ar:H2 volume ratio 95:5, after 2h heat preservation at 500 DEG C, to room temperature, obtain nano-porous r-PtCu 1‑x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and more specifically, to a nanoporous r-PtCu 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode, its preparation method and application. Background Technology

[0002] Biodiesel, as a green, renewable fossil fuel alternative with good engine starting and combustion performance, produces a large amount of glycerol as a byproduct. With the expansion of the biodiesel industry, glycerol production has been increasing year by year, impacting global market absorption capacity and leading to a continuous decline in glycerol prices. The disposal of large quantities of surplus glycerol as waste also causes environmental pollution. Glycerol electro-oxidation technology can, under mild conditions, greenly and efficiently convert inexpensive glycerol into high-value chemicals, especially glyceric acid, which is widely used in food, chemical, and pharmaceutical fields, offering a value increase of over 6000 times compared to glycerol. However, the glycerol electro-oxidation reaction is complex. Branching pathway reactions involve multiple electrochemical and non-electrochemical processes such as dehydrogenation, isomerization, hydrolysis, and Cannizaro rearrangement. The design of highly active, stable, and selective catalysts requires the simultaneous regulation and optimization of the adsorption strength and configuration of multiple glycerol oxidation reaction intermediates. However, commercial Pt / C materials are difficult to meet the industrial requirements of high current density, high selectivity, and long-term stable operation due to poor co-adsorption performance of glycerol reaction intermediates and reactive oxygen species, accumulation of poisoned intermediates, and coexistence of multiple adsorption modes. The unique geometric and electronic effects of ordered intermetallic compounds endow them with the ability to simultaneously optimize the activity, stability, and selectivity of glycerol oxidation reactions. Summary of the Invention

[0003] This invention provides a nanoporous r-PtCu 1-x Ni x The invention relates to a heterostructure electrode of intermetallic compound (NiCu)2Al3, its preparation method, and its application, aiming to at least solve the technical problems in the prior art, such as insufficient activity, glyceric acid selectivity, and long-term stability of glycerol electrooxidation catalysts, as well as the difficulty in simultaneously controlling the adsorption strength and configuration of multiple glycerol oxidation reaction intermediates.

[0004] According to one aspect of the present invention, in order to achieve the objective, a nanoporous r-PtCu is provided. 1-x Ni x The preparation method of the (NiCu)2Al3 intermetallic compound heterostructure electrode includes the following steps:

[0005] a. Cleaning the metal and smelting the alloy ingot: Soak and clean the high-purity Cu and Ni metal sheets with dilute hydrochloric acid; soak in dilute potassium hydroxide to remove oxides from the surface of the Al metal wire; then wash the treated high-purity Cu, Ni, and Al metal sheets and the Al metal wire several times with ultrapure water; finally, place the ultrapure water-washed Cu, Ni, and Al metal sheets and the Al metal wire in a vacuum drying oven for drying; weigh the dried Cu, Ni, and Al according to an atomic ratio of 10:10:80, with a total mass of 10-15g for each metal; place the weighed metals in a vacuum arc melting furnace, use argon as a protective gas, and repeat the melting process 8-10 times to obtain a uniform alloy ingot; wait for the circulating cooling water system to cool the alloy ingot to room temperature, open the furnace door and take out the cooled alloy ingot.

[0006] b. Preparation of alloy sheets and chemical dealloying: The precursor alloy ingot is cut with a diamond wire cutter to obtain alloy sheets of a preset size; the alloy sheets are placed in a 6M KOH solution saturated with N2 at 80℃ for etching until no more bubbles are generated, and the alloy sheets are washed with ultrapure water multiple times to obtain nanoporous CuNi / (NiCu)2Al3 electrodes, which are then placed in a vacuum drying oven for drying.

[0007] c. Pt Replacement and Heat Treatment: The dried nanoporous CuNi / (NiCu)2Al3 electrode was immersed in a mixed solution of 0.1 mL M H2PtCl6 and 0.1 g / L PVP and kept under magnetic stirring at room temperature for 30 min. The immersed alloy sheet was then washed several times with ultrapure water and ethanol, and dried in a vacuum drying oven. The dried nanoporous electrode was then placed in a tube furnace and heat-treated in a mixed atmosphere of Ar:H2 volume ratio of 95:5. After holding at 500℃ for 2 h, the temperature was lowered to room temperature to obtain nanoporous r-PtCu. 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode.

[0008] Furthermore, in step a, the alloy composition of the alloy ingot precursor is Cu at% 10 Ni 10 Al 80 .

[0009] Further, in step b, the alloy sheet cut by a diamond wire cutter has a thickness of 450-500 μm. The surface oxide layer is removed by sanding with sandpaper, and the thickness is reduced to 400 μm.

[0010] Further, in step b, the alloy sheet is placed in a 6M KOH solution saturated with N2 at 80°C for etching until no more bubbles are generated.

[0011] Further, in step c, the nanoporous CuNi / (NiCu)2Al3 electrode was immersed in a mixed solution of 0.1 mM H2PtCl6 and 0.1 g / L PVP and kept at room temperature with magnetic stirring for 30 min.

[0012] Further, in step c, the soaked and dried nanoporous electrode is placed in a tube furnace and heat-treated in a mixed atmosphere with an Ar:H2 volume ratio of 95:5. The electrode is heated to 500°C at a heating rate of 5°C / min and held for 2 hours, and then cooled to room temperature in the furnace.

[0013] According to one embodiment of the present invention, a method for preparing nanoporous r-PtCu is also provided. 1- x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode.

[0014] According to one embodiment of the present invention, a nanoporous r-PtCu is also provided. 1-x Ni x The application of the (NiCu)2Al3 intermetallic compound heterostructure electrode will bring together the aforementioned nanoporous r-PtCu 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode was used as the electrode for the glycerol oxidation reaction.

[0015] Furthermore, the electrode was directly used as the working electrode, with a carbon rod as the counter electrode, an Ag / AgCl electrode as the reference electrode, and a mixed solution of 1M KOH and 0.1M glycerol as the electrolyte, forming a standard three-electrode system for electrochemical testing. The electrochemical tests included: testing the polarization curve of the glycerol oxidation reaction at a scan rate of 5mV / s within the voltage range of 0.3–1.5V relative to the reversible hydrogen electrode; testing the electrochemical impedance spectroscopy at a potential of 0.65V relative to the reversible hydrogen electrode with an amplitude of 5mV and a frequency of 10mHz–100kHz; electrolyzing for 2h at a potential of 0.6–1.4V relative to the reversible hydrogen electrode and testing the distribution of glycerol electrooxidation products using a nuclear magnetic resonance spectrometer; and conducting stability tests for up to 400h at pulse potentials of 0.8V, 100s / 0.35V, and 10s, obtaining current density versus time curves.

[0016] Furthermore, using the electrodes as cathode and anode, and a mixed solution of 1M KOH and 0.1M glycerol as electrolyte, a two-electrode electrolytic cell system was assembled. The polarization curves of the two-electrode electrolytic cell were tested in the cell voltage range of 0V to 1.2V at a scan rate of 5mV / s. The stability of the electrodes was tested under pulse potentials of 0.9V cell voltage held for 100s and 0V cell voltage held for 10s, and the current density versus time curves were obtained.

[0017] In this invention, high electron transport and mass transport efficiency can increase the specific surface area of ​​the material and expose more active sites; the precursor intermetallic compound (NiCu)₂Al₃ and the topologically constructed novel phase r-PtCu 1-x Ni x The coherent interface improves the structural robustness of the catalyst; r-PtCu 1-x Ni x The unique geometric and electronic effects of intermetallic compounds simultaneously optimize the adsorption strength of glycerol and reactive oxygen intermediates, and regulate the adsorption configuration of glycerol from multiple adsorption modes to a monodentate end-group adsorption mode. This improves the kinetics of glycerol oxidation and the selectivity of glyceric acid, providing a material basis for large-scale, efficient, highly selective and long-term stable electro-oxidation of glycerol. This solves the technical problems of insufficient activity, glyceric acid selectivity and long-term stability of glycerol electro-oxidation catalysts in existing technologies, as well as the difficulty in simultaneously regulating the adsorption strength and configuration of multiple glycerol oxidation reaction intermediates. Attached Figure Description

[0018] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this application, illustrate exemplary embodiments of the invention and, together with their description, serve to explain the invention and do not constitute an undue limitation thereof. In the drawings:

[0019] Figure 1 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni x Transmission electron microscopy (STEM) image of a heterostructure electrode made of (NiCu)2Al3 intermetallic compound;

[0020] Figure 2 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni x Transmission electron microscopy (STEM) image of the (NiCu)2Al3 intermetallic compound heterostructure electrode and its elemental mapping (ED Selemental mapping);

[0021] Figure 3 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni x X-ray diffraction (XRD) pattern of a heterostructure electrode made of (NiCu)2Al3 intermetallic compound;

[0022] Figure 4 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni xHigh-resolution transmission electron microscopy (HRTEM) image of a heterostructure electrode made of (NiCu)2Al3 intermetallic compound;

[0023] Figure 5 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni x Polarization curves of the glycerol oxidation reaction of the (NiCu)2Al3 intermetallic compound heterostructure electrode in a mixed electrolyte of 1M KOH and 0.1M glycerol;

[0024] Figure 6 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni x Electrochemical impedance spectroscopy (EIS) of the (NiCu)2Al3 intermetallic compound heterostructure electrode and the circuit element diagram on which the fitting was based.

[0025] Figure 7 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni x Distribution of glycerol electro-oxidation products at different potentials using a (NiCu)2Al3 intermetallic compound heterostructure electrode;

[0026] Figure 8 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode yield of glycerol oxidation products at different potentials;

[0027] Figure 9 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni x Three-electrode pulse stability test of (NiCu)2Al3 intermetallic compound heterostructure electrode (current density-time curve);

[0028] Figure 10 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni x Polarization curves of a water-mediated glycerol oxidation electrolyzer assembled with an intermetallic compound heterostructure electrode of / (NiCu)2Al3, wherein the electrolyte is a mixed solution of 1M KOH and 0.1M glycerol;

[0029] Figure 11 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni xDistribution of glycerol electro-oxidation products in a water-mediated glycerol oxidation electrolyzer assembled with an intermetallic compound heterostructure electrode of / (NiCu)2Al3.

[0030] Figure 12 This is a nanoporous r-PtCu according to one embodiment of the present invention. 1-x Ni x Stability of a water-mediated glycerol oxidation electrolyzer assembled with an intermetallic compound heterostructure electrode of / (NiCu)2Al3. Detailed Implementation

[0031] To enable those skilled in the art to better understand the present invention, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0032] Example 1

[0033] One embodiment of the present invention provides a nanoporous r-PtCu 1-x Ni x The preparation method of the (NiCu)2Al3 intermetallic compound heterostructure electrode includes the following steps:

[0034] a. Cleaning the metal and smelting the alloy ingot: Soak and clean the high-purity Cu and Ni metal sheets with dilute hydrochloric acid; soak in dilute potassium hydroxide to remove oxides from the surface of the Al metal wire; then wash the treated high-purity Cu, Ni, and Al metal sheets and the Al metal wire several times with ultrapure water; finally, place the ultrapure water-washed Cu, Ni, and Al metal sheets and the Al metal wire in a vacuum drying oven for drying; weigh the dried Cu, Ni, and Al according to an atomic ratio of 10:10:80, with a total mass of 10-15g for each metal; place the weighed metals in a vacuum arc melting furnace, use argon as a protective gas, and repeat the melting process 8-10 times to obtain a uniform alloy ingot; wait for the circulating cooling water system to cool the alloy ingot to room temperature, open the furnace door and take out the cooled alloy ingot.

[0035] Among them, the alloy composition of the alloy ingot precursor is Cu at% 10 Ni 10 Al 80 .

[0036] b. Preparation of alloy sheets and chemical dealloying: The precursor alloy ingot is cut with a diamond wire cutter to obtain alloy sheets of a preset size; the alloy sheets are placed in a 6MKOH solution saturated with N2 at 80℃ for etching until no more bubbles are generated, and the alloy sheets are washed with ultrapure water multiple times to obtain nanoporous CuNi / (NiCu)2Al3 electrodes, which are then placed in a vacuum drying oven for drying.

[0037] The alloy sheet, cut using a diamond wire cutter, has a thickness of 450–500 μm. The surface oxide layer is removed by sanding, and the sheet is then polished to a thickness of 400 μm. The alloy sheet is then etched in a 6M KOH solution saturated with N2 at 80°C until no more bubbles are produced.

[0038] c. Pt Replacement and Heat Treatment: The dried nanoporous CuNi / (NiCu)2Al3 electrode was immersed in a mixed solution of 0.1 mL M H2PtCl6 and 0.1 g / L PVP and kept under magnetic stirring at room temperature for 30 min. The immersed alloy sheet was then washed several times with ultrapure water and ethanol, and dried in a vacuum drying oven. The dried nanoporous electrode was then placed in a tube furnace and heat-treated in a mixed atmosphere of Ar:H2 volume ratio of 95:5. After holding at 500℃ for 2 h, the temperature was lowered to room temperature to obtain nanoporous r-PtCu. 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode.

[0039] The nanoporous CuNi / (NiCu)2Al3 electrode was immersed in a mixed solution of 0.1 mM H2PtCl6 and 0.1 g / L PVP and kept at room temperature with magnetic stirring for 30 min. The dried nanoporous electrode was then placed in a tube furnace and heat-treated in a mixed atmosphere of Ar:H2 with a volume ratio of 95:5. The electrode was heated to 500 °C at a heating rate of 5 °C / min and held at that temperature for 2 h, and then cooled to room temperature in the furnace.

[0040] In this embodiment of the invention, high electron transport and mass transport efficiency are achieved, which can increase the specific surface area of ​​the material and expose more active sites; the precursor intermetallic compound (NiCu)2Al3 and the topologically constructed new phase r-PtCu 1-x Ni x The coherent interface improves the structural robustness of the catalyst; r-PtCu 1-x Ni xThe unique geometric and electronic effects of intermetallic compounds simultaneously optimize the adsorption strength of glycerol and reactive oxygen intermediates, and regulate the adsorption configuration of glycerol from multiple adsorption modes to a monodentate end-group adsorption mode. This improves the kinetics of glycerol oxidation and the selectivity of glyceric acid, providing a material basis for large-scale, efficient, highly selective and long-term stable electro-oxidation of glycerol. This solves the technical problems of insufficient activity, glyceric acid selectivity and long-term stability of glycerol electro-oxidation catalysts in existing technologies, as well as the difficulty in simultaneously regulating the adsorption strength and configuration of multiple glycerol oxidation reaction intermediates.

[0041] Example 2

[0042] According to one embodiment of the present invention, a method for preparing nanoporous r-PtCu is also provided. 1- x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode.

[0043] The nanoporous r-PtCu prepared in this embodiment 1-x Ni x The / (NiCu)2Al3 intermetallic compound heterostructure electrode possesses a nanoporous structure and r-PtCu 1-x Ni x The coherent heterostructure of / (NiCu)2Al3 combines high electron / mass transport efficiency, abundant active sites, and structural robustness. It can also optimize the adsorption of glycerol and reactive oxygen intermediates through the geometric and electronic effects of intermetallic compounds and regulate the adsorption configuration of glycerol to monodentate end-group adsorption, thereby significantly improving the kinetics of glycerol oxidation and the selectivity of glyceric acid.

[0044] Example 3

[0045] A nanoporous r-PtCu 1-x Ni x The application of / (NiCu)2Al3 intermetallic compound heterostructure electrodes will bring together the aforementioned nanoporous r-PtCu 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode was used as the electrode for the glycerol oxidation reaction.

[0046] This embodiment uses nanoporous r-PtCu 1-x Ni x The (NiCu)2Al3 intermetallic compound heterostructure electrode, used as an electrode for glycerol oxidation reaction, can optimize the adsorption of glycerol and reactive oxygen intermediates and regulate glycerol adsorption to monodentate end groups by utilizing its nanoporous structure, coherent heterostructure, and geometric and electronic effects of intermetallic compounds, thereby improving the kinetics of glycerol oxidation reaction, the selectivity of glyceric acid, and long-term stability.

[0047] Example 4

[0048] Nanoporous r-PtCu 1-x Ni x The preparation method of the (NiCu)2Al3 intermetallic compound heterostructure electrode is as follows:

[0049] 1) Cleaning the metal: Soak and clean the high-purity Cu and Ni metal sheets with dilute hydrochloric acid, soak and clean the oxides on the surface of Al metal wire with dilute KOH solution, and then rinse the metal surface with ultrapure water multiple times to remove the residual dilute hydrochloric acid and dilute KOH solution. Place the cleaned metal in a vacuum drying oven.

[0050] 2) Melting metal ingots: Weigh the cleaned and dried Cu, Ni, and Al metals according to an atomic ratio of 10:10:80, with a total mass of 10-15g. Place the weighed metal in a vacuum arc melting furnace and melt the alloy 8-10 times using argon as a protective gas. Repeat the melting process to obtain a homogeneous alloy ingot. After cooling in the furnace, remove the alloy ingot, which has the composition Cu. 10 Ni 10 Al 80 (at%)

[0051] 3) Preparation of alloy thin sheets: Using a diamond wire cutter, Cu... 10 Ni 10 Al 80 The alloy ingot is cut into metal sheets with a thickness of 450-500 μm, and the surface oxide layer is removed by grinding to obtain alloy sheets with a thickness of ~400 μm.

[0052] 4) Chemical dealloying: The alloy sheet is placed in a 6M KOH solution saturated with N2 at 80℃ and etched until no more bubbles are generated. The alloy sheet is then washed multiple times with ultrapure water to obtain a nanoporous CuNi / (NiCu)2Al3 electrode, which is then placed in a vacuum drying oven to dry.

[0053] 5) Pt replacement: The dried nanoporous CuNi / (NiCu)2Al3 electrode was immersed in a mixed solution of 0.1 mM H2PtCl6 and 0.1 g / L PVP and kept at room temperature with magnetic stirring for 30 min; the immersed alloy sheet was washed several times with ultrapure water and ethanol, and then placed in a vacuum drying oven for drying.

[0054] 6) Heat treatment: The soaked and dried nanoporous electrode was placed in a tube furnace and heat-treated in a mixed atmosphere of Ar:H2 volume ratio of 95:5. After holding at 500℃ for 2 hours, it was cooled to room temperature to obtain nanoporous r-PtCu. 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode.

[0055] The morphology and structural characterization results of the intermetallic compound electrode are as follows:

[0056] Figure 1 Nanoporous r-PtCu 1-x Ni x Transmission electron microscopy (STEM) image of a (NiCu)2Al3 intermetallic compound heterostructure electrode, which has a nanoporous structure with a pore size of approximately 30–40 nm. Figure 2 They are nanoporous r-PtCu 1- x Ni x Transmission electron microscopy images of the (NiCu)2Al3 intermetallic compound heterostructure electrode and their elemental distribution show that Pt, Cu, Ni, and Al elements are uniformly distributed on the nanoporous framework. Figure 3 Nanoporous r-PtCu 1-x Ni x X-ray diffraction pattern of the (NiCu)2Al3 intermetallic compound heterostructure electrode, r-PtCu 1-x Ni x The XRD characteristic peaks of the / (NiCu)2Al3 electrode consist of characteristic peaks at 20.6°, 41.8°, and 70.6° corresponding to the (111), (110), and (309) crystal planes of the intermetallic compound PtCu, respectively, and characteristic peaks at 25.1°, 31.1°, 44.3°, 44.9°, 48.2°, 64.9°, and 77.7° corresponding to the (100), (101), (110), (102), (111), (202), and (004) crystal planes of the intermetallic compound Ni2Al3, respectively. The remaining diffraction peaks correspond to the crystal planes of Cu. Figure 4 Nanoporous r-PtCu 1-x Ni x High-resolution transmission electron microscopy (TEM) image of the / (NiCu)2Al3 intermetallic compound electrode, showing r-PtCu 1-x Ni x The (001) and (110) crystal planes (with interplanar spacings of 0.230 nm and 0.220 nm, respectively) and the (110) and (102) crystal planes of (NiCu)2Al3 (with interplanar spacings of 0.203 nm and 0.201 nm, respectively) are coherent at the interface of the two phases.

[0057] Example 5

[0058] The nanoporous r-PtCu prepared in Example 1 1-x Ni xThe (NiCu)₂Al₃ intermetallic compound heterostructure electrode was used directly as the working electrode, a carbon rod as the counter electrode, and an Ag / AgCl electrode as the reference electrode. A standard three-electrode system was formed using a 1M KOH and 0.1M glycerol mixed solution as the electrolyte for electrochemical testing. The specific testing procedure is as follows:

[0059] 1) Apply 5 mVs within a voltage range of 0.3–1.5 V (relative to the reversible hydrogen electrode). -1 The scanning rate was used to test the polarization curve of the glycerol oxidation reaction;

[0060] 2) At a potential of 0.65V (relative to the reversible hydrogen electrode), with an amplitude of 5mV and a frequency of 10mHz to 100kHz, the electrochemical impedance spectroscopy was tested.

[0061] 3) Electrolyze at a potential of 0.6–1.4 V (relative to the reversible hydrogen electrode) for 2 h, and use nuclear magnetic resonance to test the distribution of glycerol electro-oxidation products;

[0062] 4) Using the nanoporous r-PtCu prepared in Example 1 1-x Ni x The (NiCu)2Al3 intermetallic compound heterostructure electrode was used as the working electrode, and a stability test was conducted for ~400h at a pulse potential of 0.8V (100s) / 0.35V (10s) to obtain the current density-time curve.

[0063] Nanoporous r-PtCu 1-x Ni x The characterization results of the glycerol oxidation reaction performance of the (NiCu)2Al3 intermetallic compound heterostructure electrode are as follows:

[0064] Figure 5 Nanoporous r-PtCu was demonstrated 1-x Ni x A comparison of polarization curves of the glycerol oxidation reaction between the / (NiCu)2Al3 intermetallic compound heterostructure electrode and nanoporous Pt-Cu / Cu, Pt-Ni / Ni electrodes and a commercial Pt / C electrode. Nanoporous r-PtCu 1-x Ni x The (NiCu)2Al3 intermetallic compound heterostructure electrode achieves 301 mA / cm² at 0.75 V. -2 Its current density and activity are far higher than those of nanoporous Pt-Cu / Cu, Pt-Ni / Ni electrodes and commercial Pt / C electrodes. Figure 6 Nanoporous r-PtCu was demonstrated 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrodes have the smallest charge transfer resistance. Figure 7 This indicates that the nanoporous r-PtCu 1-x Ni x The (NiCu)2Al3 intermetallic compound heterostructure electrode exhibits extremely high glyceric acid selectivity, achieving 86% glyceric acid selectivity at 0.6V and maintaining 74% glyceric acid selectivity at 0.8V. Figure 8 Nanoporous r-PtCu 1-x Ni x The (NiCu)₂Al₃ intermetallic compound heterostructure electrode exhibits high glyceric acid yield, achieving 1.6 mmol / cm² at 0.8 V. -2 h -1 The yield of glyceric acid. Figure 9 Nanoporous r-PtCu 1-x Ni x The pulse stability of the (NiCu)2Al3 intermetallic compound electrode was tested. The electrode was able to operate stably for ~400h, demonstrating excellent electrochemical stability.

[0065] Example 6

[0066] The nanoporous r-PtCu prepared in Example 1 1-x Ni x Using a heterostructure electrode of (NiCu)2Al3 intermetallic compound as both cathode and anode, and a mixed solution of 1 M KOH and 0.1 M glycerol as electrolyte, a two-electrode electrolytic cell system was assembled, and its electrolytic performance was tested. The specific test procedure is as follows:

[0067] 1) At 0V cell ~1.2V cell The polarization curves of the two-electrode electrolytic cell were tested within the specified voltage range at a scan rate of 5 mV / s. -1 ;

[0068] 2) At 0.9V cell (100s) / 0V cell Testing of nanoporous r-PtCu under a pulse potential of (10s) 1-x Ni x The stability of the (NiCu)2Al3 intermetallic compound heterostructure electrode was tested over a period of approximately 1600 hours.

[0069] Figure 10 Nanoporous r-PtCu 1-x Ni x Two-electrode electrolytic cell polarization curves of / (NiCu)2Al3 intermetallic compound heterostructure electrode and commercial Pt / C electrode, nanoporous r-PtCu 1-x Ni xThe / (NiCu)2Al3 intermetallic compound heterostructure electrode exhibited excellent glycerol electro-oxidation activity nearly 10 times that of commercial Pt / C. Figure 11 Nanoporous r-PtCu 1- x Ni x Product distribution in a water-mediated glycerol oxidation electrolyzer assembled with an intermetallic compound heterostructure electrode of / (NiCu)2Al3 indicates that it still maintains a high glyceric acid selectivity of ~74% in a two-electrode system. Figure 12 Nanoporous r-PtCu 1- x Ni x The pulse stability curve of the (NiCu)2Al3 intermetallic compound electrode electrolytic cell after 1600 h of stable operation indicates that the electrode has excellent electrochemical stability.

[0070] In summary, this disclosure provides nanoporous r-PtCu 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode serves as a highly active, selective, and stable catalytic material for the glycerol oxidation reaction. r-PtCu 1-x Ni x The unique geometric effects and synergistic electronic effects of intermetallic compounds simultaneously optimize the adsorption strength of glycerol and reactive oxygen species intermediates, regulating the glycerol adsorption configuration from multiple coexisting adsorption modes to a monodentate end-group adsorption mode, thereby improving the kinetics and selectivity of glycerol oxidation. The precursor intermetallic compound (NiCu)₂Al₃ and the induced new phase r-PtCu... 1-x Ni x The coherent structure enhances the structural robustness of the catalyst, demonstrating excellent electrochemical performance with stable operation for over 1600 hours at high glyceric acid selectivity and high current density.

[0071] The above are merely preferred embodiments of the present invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A nanoporous r-PtCu 1-x Ni x The method for preparing a heterostructure electrode of intermetallic compound (NiCu)₂Al₃ is characterized by, Includes the following steps: a. Cleaning the metal and smelting the alloy ingot: Soak and clean the high-purity Cu and Ni metal sheets with dilute hydrochloric acid; soak in dilute potassium hydroxide to remove oxides from the surface of the Al metal wire; then wash the treated high-purity Cu, Ni, and Al metal sheets several times with ultrapure water; finally, place the ultrapure water-washed Cu, Ni, and Al metal sheets in a vacuum drying oven for drying; weigh the dried Cu, Ni, and Al according to an atomic ratio of 10:10:80, with a total mass of 10-15g for each metal; place the weighed metals in a vacuum arc melting furnace, using argon as a protective gas, and repeat the melting process 8-10 times to obtain a uniform alloy ingot; wait for the circulating cooling water system to cool the alloy ingot to room temperature, then open the furnace door and remove the cooled alloy ingot. b. Preparation of alloy sheets and chemical dealloying: The precursor alloy ingot is cut with a diamond wire cutter to obtain alloy sheets of a preset size; the alloy sheets are placed in a 6M KOH solution saturated with N2 at 80℃ for etching until no more bubbles are generated, and the alloy sheets are washed with ultrapure water multiple times to obtain nanoporous CuNi / (NiCu)2Al3 electrodes, which are then placed in a vacuum drying oven for drying. c. Pt Replacement and Heat Treatment: The dried nanoporous CuNi / (NiCu)2Al3 electrode was immersed in a mixed solution of 0.1 mM H2PtCl6 and 0.1 g / L PVP and kept at room temperature with magnetic stirring for 30 min. The immersed alloy sheet was then washed several times with ultrapure water and ethanol, and dried in a vacuum drying oven. The dried nanoporous electrode was then placed in a tube furnace and heat-treated in a mixed atmosphere of Ar:H2 volume ratio of 95:

5. After holding at 500℃ for 2 h, the temperature was lowered to room temperature to obtain nanoporous r-PtCu. 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode.

2. The nanoporous r-PtCu according to claim 1 1-x Ni x The method for preparing a heterostructure electrode of intermetallic compound (NiCu)₂Al₃ is characterized by, The alloy composition of the alloy ingot precursor in step a is Cu at% 10 Ni 10 Al 80 .

3. The nanoporous r-PtCu according to claim 1 1-x Ni x The method for preparing a heterostructure electrode of intermetallic compound (NiCu)₂Al₃ is characterized by, Step b involves cutting the alloy sheet with a diamond wire cutter to a thickness of 450–500 μm, then removing the surface oxide layer with sandpaper and polishing it to a thickness of 400 μm.

4. The nanoporous r-PtCu according to claim 1 1-x Ni x The method for preparing a heterostructure electrode of intermetallic compound (NiCu)₂Al₃ is characterized by, In step b, the alloy sheet is placed in a 6M KOH solution saturated with N2 at 80°C for corrosion until no more bubbles are generated.

5. The nanoporous r-PtCu according to claim 1 1-x Ni x The method for preparing a heterostructure electrode of intermetallic compound (NiCu)₂Al₃ is characterized by, In step c, the nanoporous CuNi / (NiCu)2Al3 electrode is immersed in a mixed solution of 0.1 mL M H2PtCl6 and 0.1 g / L PVP and kept at room temperature with magnetic stirring for 30 min.

6. The nanoporous r-PtCu according to claim 1 1-x Ni x The method for preparing a heterostructure electrode of intermetallic compound (NiCu)₂Al₃ is characterized by, In step c, the soaked and dried nanoporous electrode is placed in a tube furnace and heat-treated in a mixed atmosphere with an Ar:H2 volume ratio of 95:

5. The electrode is heated to 500°C at a heating rate of 5°C / min and held for 2 hours, and then cooled to room temperature in the furnace.

7. A preparation method according to any one of claims 1-6 to obtain nanoporous r-PtCu 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode.

8. A nanoporous r-PtCu 1-x Ni x The application of (NiCu)2Al3 intermetallic compound heterostructure electrodes is characterized by... The nanoporous r-PtCu as described in claim 7 1-x Ni x / (NiCu)2Al3 intermetallic compound heterostructure electrode was used as the electrode for the glycerol oxidation reaction.

9. The nanoporous r-PtCu according to claim 8 1-x Ni x The application of (NiCu)2Al3 intermetallic compound heterostructure electrodes is characterized by... The electrode was directly used as the working electrode, with a carbon rod as the counter electrode, an Ag / AgCl electrode as the reference electrode, and a mixed solution of 1M KOH and 0.1M glycerol as the electrolyte, forming a standard three-electrode system for electrochemical testing. The electrochemical tests included: testing the polarization curve of the glycerol oxidation reaction at a scan rate of 5mV / s within the voltage range of 0.3–1.5V relative to the reversible hydrogen electrode; testing the electrochemical impedance spectroscopy at a potential of 0.65V relative to the reversible hydrogen electrode with an amplitude of 5mV and a frequency of 10mHz–100kHz; electrolyzing for 2 hours at a potential of 0.6–1.4V relative to the reversible hydrogen electrode and testing the distribution of glycerol electrooxidation products using a nuclear magnetic resonance spectrometer; and conducting stability tests for up to 400 hours at pulse potentials of 0.8V, 100s / 0.35V, and 10s, obtaining current density versus time curves.

10. The nanoporous r-PtCu according to claim 8 1-x Ni x The application of (NiCu)2Al3 intermetallic compound heterostructure electrodes is characterized by... Using the electrodes as cathode and anode, and a mixed solution of 1M KOH and 0.1M glycerol as electrolyte, a two-electrode electrolytic cell system was assembled. The polarization curves of the two-electrode electrolytic cell were tested in the cell voltage range of 0V to 1.2V at a scan rate of 5mV / s. The stability of the electrodes was tested under pulse potentials of 0.9V cell voltage held for 100s and 0V cell voltage held for 10s, and the current density versus time curves were obtained.

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