A molybdenum-doped inverse perovskite nitride three-dimensional self-supporting material, a preparation method and applications thereof

Abstract

The application provides a molybdenum-doped reverse perovskite nitride three-dimensional self-supporting material and a preparation method and application thereof, and belongs to the technical field of electrocatalytic materials.The molybdenum-doped reverse perovskite nitride three-dimensional self-supporting material provided by the application is composed of copper, nitrogen, cobalt and molybdenum elements, and has a chemical formula of CuNCo 3‑x Mo x In the formula, x is the mole percentage content of the doping element Mo relative to the substrate element Co, and 0 < x <= 0.1.The molybdenum-doped reverse perovskite nitride three-dimensional self-supporting material provided by the application has high conductivity, good stability and high mechanical strength, and has the advantages of stable discharge voltage and good cycle stability when used as a catalytic electrode of a zinc-air battery.

Description

Technical Field

[0001] This invention relates to the field of electrocatalytic materials technology, and in particular to a molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material, its preparation method, and its application. Background Technology

[0002] With the increasing global energy demand, the excessive use of traditional fossil fuels (such as coal, oil, and natural gas) will not only cause irreversible damage to the global environment and climate, but also cause a serious energy crisis due to the overuse of these primary energy sources. Faced with increasingly depleted energy resources, we need to conserve energy and develop new energy sources, while also improving energy efficiency.

[0003] Rechargeable zinc-air batteries, as a novel energy conversion device, possess advantages such as environmental friendliness and high energy conversion efficiency. They have been experimentally applied in many fields and are attracting increasing attention. Furthermore, rechargeable zinc-air batteries are small in size, have a large charge capacity, are lightweight, can operate normally over a wide temperature range, are corrosion-free, and are safe and reliable. Therefore, rechargeable zinc-air batteries have excellent application prospects. The key factor restricting the development of rechargeable zinc-air batteries is the electrode catalyst material. The catalyst is the core component of rechargeable zinc-air batteries and a crucial material determining battery cost and performance.

[0004] Hydrogen energy has received widespread attention in recent years as a high-energy and pollution-free green renewable energy source. Electrochemical hydrogen evolution reaction (HER) is a green, energy-saving, and efficient method for producing hydrogen. Developing high-performance HER electrocatalysts is crucial for accelerating the large-scale development of the hydrogen production industry.

[0005] Currently, whether for zinc-air batteries or electrocatalysts for electrochemical hydrogen evolution, common catalysts can be categorized into noble metal catalysts and non-noble metal catalysts. However, noble metals such as platinum, iridium, and ruthenium-based catalysts suffer from limited reserves, high prices, and poor durability, limiting their widespread use in practical applications. Non-noble metal catalysts, such as transition metal carbides and sulfides, mostly exhibit high catalytic activity only in single catalytic reactions and are prone to dissolution and aggregation during long-term cycling.

[0006] Perovskite compounds are inexpensive and have varied structures, while transition metal nitrides have good electrical conductivity. Therefore, developing novel multifunctional nitride catalysts with anti-perovskite structures is an effective strategy for achieving low-cost, high-efficiency, and long-life non-precious metal catalysts. Summary of the Invention

[0007] In view of this, the purpose of this invention is to provide a molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material, its preparation method, and its application. The molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material provided by this invention has high conductivity, good stability, and high mechanical strength. As a catalytic electrode for zinc-air batteries, it has advantages such as stable discharge voltage and good cycle stability.

[0008] To achieve the above objectives, the present invention provides the following technical solution: a molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material, composed of copper, nitrogen, cobalt and molybdenum, with the chemical formula CuNCo. 3-x Mo x In the formula, x is the molar percentage of the dopant element Mo relative to the matrix element Co, and 0 < x ≤ 0.1.

[0009] This invention also provides a method for preparing the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material described in the above technical solution. The method involves using copper-containing compounds, molybdenum-containing compounds, cobalt-containing compounds, and nitrogen-containing compounds as raw materials, and deionized water as a solvent. After thoroughly mixing to obtain a mixed solution, a conductive substrate is added to the mixed solution. An electrode material loaded with copper-cobalt-molybdenum precursors is obtained via a hydrothermal method. Then, the electrode material loaded with copper-cobalt-molybdenum precursors is annealed under an ammonia atmosphere to obtain the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material.

[0010] Preferably, the molar ratio of copper to cobalt in the copper-containing compound and the cobalt-containing compound is 1:(2.9 to 2.99); the molar ratio of molybdenum to cobalt in the molybdenum-containing compound and the cobalt-containing compound is (0.023 to 0.24):1; and the molar ratio of nitrogen to copper in the nitrogen-containing compound and the copper-containing compound is (30 to 35):1.

[0011] Preferably, the copper-containing compound is a copper acetate, copper hydroxide, copper nitrate, or copper chloride; the molybdenum-containing compound is a molybdenum acetate, molybdenum hydroxide, molybdenum nitrate, or molybdenum chloride; the cobalt-containing compound is a cobalt acetate, cobalt hydroxide, cobalt nitrate, or cobalt chloride; and the nitrogen-containing compound is urea, hexamethylenetetramine, ammonium fluoride, pyrimidine, or ammonium cyanide.

[0012] Preferably, the conductive substrate is at least one of carbon cloth, nickel foam, and glassy carbon electrode.

[0013] Preferably, the hydrothermal reaction temperature in the hydrothermal method is 80–180°C; the hydrothermal reaction time is 6–72 h.

[0014] Preferably, the annealing temperature is 400–480°C and the annealing time is 3–6 hours.

[0015] The present invention also provides the application of the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material described above in electrocatalytic materials. The anti-perovskite nitride three-dimensional self-supporting material is used as a working electrode in the fields of zinc-air batteries and water electrolysis for hydrogen production.

[0016] Compared with the prior art, the present invention has the following beneficial technical effects:

[0017] 1. This invention utilizes the principle of inexpensive and abundant copper, cobalt, molybdenum, and nitrogen element compounds to prepare a three-dimensional self-supporting material of molybdenum-doped anti-perovskite nitrides. This material has high conductivity, good stability, fast ion conduction rate, and trifunctional catalytic performance, thereby reducing the preparation cost of catalysts.

[0018] 2. The molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material prepared by this invention has the advantages of stable discharge voltage and good cycle stability as a catalytic electrode for zinc-air batteries, and the introduction of molybdenum can effectively improve the HER performance of the catalyst.

[0019] 3. This invention provides a simple two-step method for synthesizing molybdenum-doped anti-perovskite nitride three-dimensional self-supporting materials, which has high preparation efficiency, low cost, and can be used for large-scale production.

[0020] 4. The raw materials for the materials prepared by this invention are readily available, the preparation process is simple, and it is suitable for industrial production. It has broad application prospects in energy storage and conversion fields such as zinc-air batteries and water electrolysis for hydrogen production. Attached Figure Description

[0021] Figure 1 CuNCo prepared in Example 1 2.95 Mo 0.05 X-ray diffraction pattern of three-dimensional self-supporting anti-perovskite nitride material;

[0022] Figure 2 CuNCo prepared in Example 1 2.95 Mo 0.05 Scanning electron microscope image of a three-dimensional self-supporting anti-perovskite nitride material;

[0023] Figure 3 CuNCo prepared in Example 1 2.95 Mo 0.05 A comparison of constant current cyclic charge-discharge of liquid zinc-air batteries prepared by anti-perovskite nitride three-dimensional self-supporting materials and liquid zinc-air batteries prepared by Pt / C+RuO2.

[0024] Figure 4 CuNCo prepared in Example 1 2.95 Mo 0.05Linear scanning voltammetry test curves of the anti-perovskite nitride three-dimensional self-supporting material and the CuNCo3 anti-perovskite phase nitride three-dimensional self-supporting material prepared in Comparative Example 1;

[0025] Figure 5 CuNCo prepared in Example 1 2.95 Mo 0.05 Hydrogen evolution reaction stability curve of anti-perovskite nitride three-dimensional self-supporting material; Detailed Implementation

[0026] This invention provides a molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material, composed of copper, nitrogen, cobalt, and molybdenum, with the chemical formula CuNCo. 3-x Mo x In the formula, x is the molar percentage of the dopant element Mo relative to the matrix element Co, and 0 < x ≤ 0.1.

[0027] This invention also provides a method for preparing the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material described in the above technical solution. The method involves using copper-containing compounds, molybdenum-containing compounds, cobalt-containing compounds, and nitrogen-containing compounds as raw materials, and deionized water as a solvent. After thoroughly mixing to obtain a mixed solution, a conductive substrate is added to the mixed solution. An electrode material loaded with copper-cobalt-molybdenum precursors is obtained via a hydrothermal method. Then, the electrode material loaded with copper-cobalt-molybdenum precursors is annealed under an ammonia atmosphere to obtain the molybdenum-doped anti-perovskite phase nitride three-dimensional self-supporting electrode material.

[0028] In some embodiments, the preparation method specifically includes the following steps:

[0029] (1) Prepare raw materials by mixing copper-containing compounds, molybdenum-containing compounds, cobalt-containing compounds and nitrogen-containing compounds with a molar ratio of copper to cobalt of 1:(2.9 to 2.99), a molar ratio of molybdenum to cobalt of (0.023 to 0.24):1, and a molar ratio of nitrogen to copper of (30 to 35):1. Weigh the raw materials accurately and dissolve them in deionized water to obtain a mixed solution.

[0030] In this invention, the copper-containing compound is preferably a copper acetate, copper hydroxide, copper nitrate, or copper chloride, more preferably a copper acetate, and most preferably copper acetate; the molybdenum-containing compound is preferably a molybdenum acetate, molybdenum hydroxide, molybdenum nitrate, or molybdenum chloride, more preferably a molybdenum acetate, and most preferably ammonium heptamolybdate ((NH4)6Mo7O). 24The cobalt-containing compound is cobalt acetate, cobalt hydroxide, cobalt nitrate, or cobalt chloride, more preferably cobalt acetate, and most preferably cobalt acetate tetrahydrate (C4H6CoO4·4H2O); the nitrogen-containing compound is preferably urea, hexamethylenetetramine, ammonium fluoride, pyrimidine, or ammonium cyanide, more preferably hexamethylenetetramine.

[0031] (2) The mixed solution from step (1) and the conductive substrate are added to a hydrothermal reactor for hydrothermal reaction. After the reaction is completed, the solid in the hydrothermal reactor is cooled and cleaned. After drying, the electrode material loaded with copper-cobalt-molybdenum precursor can be obtained.

[0032] In this invention, the conductive substrate is preferably at least one of carbon cloth, nickel foam, and glassy carbon electrode; the hydrothermal reaction temperature is preferably 80-180°C, more preferably 120-160°C; the reaction time is preferably 6-72 h, more preferably 10-30 h; the cooling is to cool to room temperature at a rate of 10-30°C / h; the cleaning is to rinse 3-9 times with ethanol and deionized water respectively; and the drying is to keep at 50-120°C for 1-24 h until completely dry.

[0033] (3) The electrode material loaded with copper-cobalt-molybdenum precursor obtained in step (2) is placed in a tube furnace and annealed in an ammonia atmosphere to obtain the molybdenum-doped anti-perovskite phase nitride three-dimensional self-supporting electrode material.

[0034] In this invention, the purity of the ammonia gas is ≥98%, the flow rate of the ammonia gas is 150-250 ml / min, the annealing temperature is preferably 400-480℃, more preferably 410-430℃, and the annealing time is preferably 3-6 h, more preferably 4-5 h.

[0035] The present invention also provides the application of the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material described above in electrocatalytic materials. The anti-perovskite nitride three-dimensional self-supporting material is used as a working electrode in the fields of zinc-air batteries and water electrolysis for hydrogen production.

[0036] To better understand this invention, the following embodiments further illustrate its content, but the scope of this invention is not limited to the embodiments described below. In this invention, unless otherwise specified, all reagents are commercially available products.

[0037] Example 1

[0038] Preparation of 5% molybdenum-doped anti-perovskite nitride three-dimensional self-supporting materials

[0039] (1) Weigh out 0.5 mmol of copper acetate (C4H6CuO4·H2O), 1.475 mmol of cobalt acetate tetrahydrate (C4H6CoO4·4H2O), and 0.025 mmol of ammonium heptamolybdate ((NH4)6Mo7O) respectively. 24 ·4H2O) and 4 mmol hexamethylenetetramine (C6H 12 N4), the purity of the above raw materials is all above 99.9%. The weighed raw materials are thoroughly mixed and dissolved in 25 mL of deionized water to obtain a mixed solution;

[0040] (2) The mixed solution obtained in step (1) and the 3×3cm nickel foam substrate were added to the hydrothermal reactor, and then added to a 50ml reaction vessel. The reaction was carried out at 120℃ for 12h. Then the mixture was cooled to room temperature at 10℃ / h. The solid in the hydrothermal reactor was rinsed three times with ethanol and deionized water respectively. The mixture was then placed at 60℃ for 12h until it was completely dry to obtain the electrode material loaded with copper cobalt molybdenum precursor.

[0041] (3) The electrode material loaded with copper-cobalt-molybdenum precursor obtained in step (2) is placed in a tube furnace and annealed in an atmosphere of ammonia purity ≥98% and flow rate 200 ml / min. The annealing temperature is 420℃ and the annealing time is 4h. After natural cooling, the CuNCo is obtained. 2.95 Mo 0.05 Three-dimensional self-supporting materials of anti-perovskite phase nitrides.

[0042] The obtained electrode material was characterized by X-ray diffraction patterns. Figure 1 It can be seen that the XRD pattern of the sample obtained in Example 1 is consistent with the standard card PDF#053-0435, indicating that the molybdenum-doped anti-perovskite nitride material was successfully synthesized.

[0043] The obtained electrode material was characterized by scanning electron microscopy. Figure 2 It can be seen that the obtained material presents a network of lines and grows uniformly on the nickel foam.

[0044] The obtained electrode material was subjected to hydrogen evolution reaction stability testing. Figure 5 It can be seen that the prepared material can withstand a constant current density of 10 mA·cm⁻¹ -2 Under these conditions, the electrocatalytic hydrogen evolution potential of the sample hardly changed after 24 hours, demonstrating good electrocatalytic hydrogen evolution stability.

[0045] Example 2

[0046] Preparation of 3% molybdenum-doped anti-perovskite nitride three-dimensional self-supporting materials

[0047] (1) Weigh out 0.5 mmol of copper acetate (C4H6CuO4·H2O), 1.485 mmol of cobalt acetate tetrahydrate (C4H6CoO4·4H2O), and 0.015 mmol of ammonium heptamolybdate ((NH4)6Mo7O) respectively. 24 ·4H2O) and 4 mmol hexamethylenetetramine (C6H 12 N4), the purity of the above raw materials is all above 99.9%. The weighed raw materials are thoroughly mixed and dissolved in 25 mL of deionized water to obtain a mixed solution;

[0048] (2) The mixed solution obtained in step (1) and the 3×3cm nickel foam substrate were added to the hydrothermal reactor, and then added to a 50ml reaction vessel. The reaction was carried out at 120℃ for 12h. Then the mixture was cooled to room temperature at 10℃ / h. The solid in the hydrothermal reactor was rinsed three times with ethanol and deionized water respectively. The mixture was then placed at 60℃ for 12h until it was completely dry to obtain the electrode material loaded with copper cobalt molybdenum precursor.

[0049] (3) The electrode material loaded with copper-cobalt-molybdenum precursor obtained in step (2) is placed in a tube furnace and annealed in an atmosphere of ammonia purity ≥98% and flow rate 200 ml / min. The annealing temperature is 420℃ and the annealing time is 4h. After natural cooling, the CuNCo is obtained. 2.97 Mo 0.03 Three-dimensional self-supporting material of anti-perovskite phase nitride.

[0050] The obtained material was characterized by X-ray diffraction, scanning electron microscopy, and hydrogen evolution reaction stability testing. The experimental results were similar to those in Example 1. This invention successfully synthesized molybdenum-doped anti-perovskite nitride material, which exhibits a network-like structure and grows uniformly on nickel foam. The material was successfully synthesized under a constant current density of 10 mA·cm⁻¹. -2 Under these conditions, the electrocatalytic hydrogen evolution potential of the sample hardly changed after 24 hours, demonstrating good electrocatalytic hydrogen evolution stability.

[0051] Example 3

[0052] Preparation of 1% molybdenum-doped anti-perovskite nitride three-dimensional self-supporting materials

[0053] (1) Weigh out 0.5 mmol of copper acetate (C4H6CuO4·H2O), 1.495 mmol of cobalt acetate tetrahydrate (C4H6CoO4·4H2O), and 0.005 mmol of ammonium heptamolybdate ((NH4)6Mo7O) respectively. 24 ·4H2O) and 4 mmol hexamethylenetetramine (C6H 12N4), the purity of the above raw materials is all above 99.9%. The weighed raw materials are thoroughly mixed and dissolved in 25 mL of deionized water to obtain a mixed solution;

[0054] (2) The mixed solution obtained in step (1) and the 3×3cm nickel foam substrate were added to the hydrothermal reactor, and then added to a 50ml reaction vessel. The reaction was carried out at 120℃ for 12h. Then the mixture was cooled to room temperature at 10℃ / h. The solid in the hydrothermal reactor was rinsed three times with ethanol and deionized water respectively. The mixture was then placed at 60℃ for 12h until it was completely dry to obtain the electrode material loaded with copper cobalt molybdenum precursor.

[0055] (3) The electrode material loaded with copper-cobalt-molybdenum precursor obtained in step (2) is placed in a tube furnace and annealed in an atmosphere of ammonia purity ≥98% and flow rate 200 ml / min. The annealing temperature is 420℃ and the annealing time is 4h. After natural cooling, the CuNCo is obtained. 2.99 Mo 0.01 Three-dimensional self-supporting material of anti-perovskite phase nitride.

[0056] The obtained material was characterized by X-ray diffraction, scanning electron microscopy, and hydrogen evolution reaction stability testing. The experimental results were similar to those in Example 1. This invention successfully synthesized molybdenum-doped anti-perovskite nitride material, which exhibits a network-like structure and grows uniformly on nickel foam. The material was successfully synthesized under a constant current density of 10 mA·cm⁻¹. -2 Under these conditions, the electrocatalytic hydrogen evolution potential of the sample hardly changed after 24 hours, demonstrating good electrocatalytic hydrogen evolution stability.

[0057] Example 4

[0058] Preparation of 7% molybdenum-doped anti-perovskite nitride three-dimensional self-supporting materials

[0059] (1) Weigh out 0.5 mmol of copper acetate (C4H6CuO4·H2O), 1.465 mmol of cobalt acetate tetrahydrate (C4H6CoO4·4H2O), and 0.035 mmol of ammonium heptamolybdate ((NH4)6Mo7O) respectively. 24 ·4H2O) and 4 mmol hexamethylenetetramine (C6H 12 N4), the purity of the above raw materials is all above 99.9%. The weighed raw materials are thoroughly mixed and dissolved in 25 mL of deionized water to obtain a mixed solution;

[0060] (2) The mixed solution obtained in step (1) and the 3×3cm nickel foam substrate were added to the hydrothermal reactor, and then added to a 50ml reaction vessel. The reaction was carried out at 120℃ for 12h. Then the mixture was cooled to room temperature at 10℃ / h. The solid in the hydrothermal reactor was rinsed three times with ethanol and deionized water respectively. The mixture was then placed at 60℃ for 12h until it was completely dry to obtain the electrode material loaded with copper cobalt molybdenum precursor.

[0061] (3) The electrode material loaded with copper-cobalt-molybdenum precursor obtained in step (2) is placed in a tube furnace and annealed in an atmosphere of ammonia purity ≥98% and flow rate 200 ml / min. The annealing temperature is 420℃ and the annealing time is 4h. After natural cooling, the CuNCo is obtained. 2.93 Mo 0.07 Three-dimensional self-supporting material of anti-perovskite phase nitride.

[0062] The obtained material was characterized by X-ray diffraction, scanning electron microscopy, and hydrogen evolution reaction stability testing. The experimental results were similar to those in Example 1. This invention successfully synthesized molybdenum-doped anti-perovskite nitride material, which exhibits a network-like structure and grows uniformly on nickel foam. The material was successfully synthesized under a constant current density of 10 mA·cm⁻¹. -2 Under these conditions, the electrocatalytic hydrogen evolution potential of the sample hardly changed after 24 hours, demonstrating good electrocatalytic hydrogen evolution stability.

[0063] Example 5

[0064] Preparation of 10% molybdenum-doped anti-perovskite nitride three-dimensional self-supporting materials

[0065] (1) Weigh out 0.5 mmol of copper acetate (C4H6CuO4·H2O), 1.45 mmol of cobalt acetate tetrahydrate (C4H6CoO4·4H2O), and 0.05 mmol of ammonium heptamolybdate ((NH4)6Mo7O) respectively. 24 ·4H2O) and 4 mmol hexamethylenetetramine (C6H 12 N4), the purity of the above raw materials is all above 99.9%. The weighed raw materials are thoroughly mixed and dissolved in 25 mL of deionized water to obtain a mixed solution;

[0066] (2) The mixed solution obtained in step (1) and the 3×3cm nickel foam substrate were added to the hydrothermal reactor, and then added to a 50ml reaction vessel. The reaction was carried out at 120℃ for 12h. Then the mixture was cooled to room temperature at 10℃ / h. The solid in the hydrothermal reactor was rinsed three times with ethanol and deionized water respectively. The mixture was then placed at 60℃ for 12h until it was completely dry to obtain the electrode material loaded with copper cobalt molybdenum precursor.

[0067] (3) The electrode material loaded with copper-cobalt-molybdenum precursor obtained in step (2) is placed in a tube furnace and annealed in an atmosphere of ammonia purity ≥98% and flow rate 200 ml / min. The annealing temperature is 420℃ and the annealing time is 4h. After natural cooling, the CuNCo is obtained. 2.9 Mo 0.1 Three-dimensional self-supporting material of anti-perovskite phase nitride.

[0068] The obtained material was characterized by X-ray diffraction, scanning electron microscopy, and hydrogen evolution reaction stability testing. The experimental results were similar to those in Example 1. This invention successfully synthesized molybdenum-doped anti-perovskite nitride material, which exhibits a network-like structure and grows uniformly on nickel foam. The material was successfully synthesized under a constant current density of 10 mA·cm⁻¹. -2 Under these conditions, the electrocatalytic hydrogen evolution potential of the sample hardly changed after 24 hours, demonstrating good electrocatalytic hydrogen evolution stability.

[0069] Comparative Example 1

[0070] Preparation of undoped molybdenum antiperovskite nitride three-dimensional self-supporting materials

[0071] (1) Weigh out 0.5 mmol of copper acetate (C4H6CuO4·H2O), 1.5 mmol of cobalt acetate tetrahydrate (C4H6CoO4·4H2O), and 4 mmol of hexamethylenetetramine (C6H6CoO4·4H2O), respectively. 12 N4), the purity of the above raw materials is all above 99.9%. The weighed raw materials are thoroughly mixed and dissolved in 25 mL of deionized water to obtain a mixed solution;

[0072] (2) The mixed solution obtained in step (1) and the 3×3cm nickel foam substrate were added to the hydrothermal reactor, and then added to a 50ml reaction vessel. The reaction was carried out at 120℃ for 12h. Then the mixture was cooled to room temperature at 10℃ / h. The solid in the hydrothermal reactor was rinsed three times with ethanol and deionized water respectively. The mixture was then placed at 60℃ for 12h until it was completely dry to obtain the electrode material loaded with copper cobalt molybdenum precursor.

[0073] (3) The electrode material loaded with copper cobalt molybdenum precursor obtained in step (2) is placed in a tube furnace and annealed in an atmosphere with ammonia purity ≥98% and a flow rate of 200 ml / min. The annealing temperature is 420℃ and the annealing time is 4h. After natural cooling, the CuNCo3 anti-perovskite phase nitride three-dimensional self-supporting material is obtained.

[0074] The materials obtained in Example 1 and Comparative Example 1 were subjected to linear sweep voltammetry testing. Figure 4It can be seen that, compared with the undoped anti-perovskite nitride three-dimensional self-supporting material, the electrochemical hydrogen evolution performance of the 5% molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material is significantly improved at a current density of 10 mA·cm⁻¹. -2 The overpotential at this point is only 85mV, indicating that the material has good hydrogen evolution catalytic activity.

[0075] Test case

[0076] The CuNCo obtained in Example 1 2.95 Mo 0.05 A performance comparison was made between a zinc-air battery fabricated from an anti-perovskite phase nitride three-dimensional self-supporting material and a commercially available Pt / C+RuO2-based zinc-air battery.

[0077] The liquid zinc-air battery prepared by Pt / C+RuO2 includes the following steps: RuO2 (OER catalyst, 99.9%, Aladdin) and Pt / C (ORR catalyst, 20%, Hesen) in a 1:1 mass ratio are weighed and thoroughly mixed with Nafion binder and ethanol to prepare a catalyst slurry. The catalyst slurry is then drop-coated onto a hydrophobic carbon cloth (0.25 cm²). 2 An air positive electrode was fabricated on one side, and a 1.5 × 1.5 cm thick electrode with a thickness of 0.3 mm was placed on the other side. 2 A polished zinc plate is used as the negative electrode, and a mixed solution of 0.2M ZnCl2 + 6M KOH is injected as the electrolyte. Finally, they are encapsulated together to form a liquid zinc-air battery.

[0078] CuNCo 2.95 Mo 0.05 The preparation method of liquid zinc-air batteries using anti-perovskite phase nitride three-dimensional self-supporting materials as cathode materials is the same as that of Pt / C+RuO2. The difference is that the three-dimensional self-supporting material is directly pressed onto hydrophobic carbon cloth.

[0079] For CuNCo 2.95 Mo 0.05 A comparison of constant current cyclic charge-discharge tests was conducted between a liquid zinc-air battery prepared from an anti-perovskite phase nitride three-dimensional self-supporting material and a liquid zinc-air battery prepared from Pt / C+RuO2. Figure 3 It can be seen that the charge-discharge cycle stability of the zinc-air battery based on the material prepared in Example 1 as the positive electrode material is better than that of the commercial Pt / C+RuO2-based zinc-air battery.

[0080] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made 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. The application of a molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material in electrocatalytic materials, characterized in that, The anti-perovskite nitride three-dimensional self-supporting material is used as a working electrode in zinc-air batteries and water electrolysis for hydrogen production. The molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material consists of a conductive substrate and a molybdenum-doped anti-perovskite nitride. The molybdenum-doped anti-perovskite nitride is composed of copper, nitrogen, cobalt, and molybdenum, with the chemical formula CuNCo. 3-x Mo x In the formula, x is the molar percentage of the dopant element Mo relative to the matrix element Co, and 0 < x ≤ 0.

1.

2. The application of the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material according to claim 1 in electrocatalytic materials, characterized in that, The preparation method of the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material is as follows: using copper-containing compounds, molybdenum-containing compounds, cobalt-containing compounds, and nitrogen-containing compounds as raw materials, and deionized water as solvent, the materials are thoroughly mixed to obtain a mixed solution. A conductive substrate is added to the mixed solution, and an electrode material loaded with copper-cobalt-molybdenum precursors is obtained by hydrothermal method. Then, the electrode material loaded with copper-cobalt-molybdenum precursors is annealed in an ammonia atmosphere to obtain the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material.

3. The application of the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material according to claim 2 in electrocatalytic materials, characterized in that, The molar ratio of copper to cobalt in the copper-containing compound and the cobalt-containing compound is 1:(2.9 to 2.99); the molar ratio of molybdenum to cobalt in the molybdenum-containing compound and the cobalt-containing compound is (0.023 to 0.24):1; and the molar ratio of nitrogen to copper in the nitrogen-containing compound and the copper-containing compound is (30 to 35):

1.

4. The application of the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material according to claim 2 in electrocatalytic materials, characterized in that, The copper-containing compound is a copper acetate, copper hydroxide, copper nitrate, or copper chloride; the molybdenum-containing compound is a molybdenum acetate, molybdenum hydroxide, molybdenum nitrate, or molybdenum chloride; the cobalt-containing compound is a cobalt acetate, cobalt hydroxide, cobalt nitrate, or cobalt chloride; and the nitrogen-containing compound is urea, hexamethylenetetramine, ammonium fluoride, pyrimidine, or ammonium cyanide.

5. The application of the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material according to claim 2 in electrocatalytic materials, characterized in that, The conductive substrate is at least one of carbon cloth, nickel foam, and glassy carbon electrode.

6. The application of the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material according to claim 2 in electrocatalytic materials, characterized in that, The hydrothermal reaction temperature in the hydrothermal method is 80–180℃; the hydrothermal reaction time is 6–72 h.

7. The application of the molybdenum-doped anti-perovskite nitride three-dimensional self-supporting material according to claim 2 in electrocatalytic materials, characterized in that, The annealing temperature is 400–480℃, and the annealing time is 3–6 hours.

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