A method for growing nanometal-oxide structure catalyst materials on a substrate using the joule heating method

Abstract

The application discloses a method for growing nano metal-oxide structure catalyst on a substrate (foamed nickel, nickel felt, foamed copper, foamed stainless steel, nickel mesh, stainless steel mesh, titanium fiber felt, stainless steel fiber felt, etc.) by using Joule heat method, and belongs to the field of material science and engineering technology and chemistry. The metal involved in growing the nano metal-oxide structure catalyst on the substrate includes Pt, Ir, Ru, Cu and Ag, and the oxide involved includes NiO, CoO, Fe2O3 and MnO. Firstly, a metal precursor dispersion solution A with a certain concentration is configured; after being uniformly dispersed, the A is uniformly sprayed on the surface of the substrate (or the substrate is soaked in the uniformly dispersed precursor solution A for a certain time), and the step is recorded as 1; the substrate B after spraying is connected with the positive and negative poles of a direct current power supply through pure copper wires with alligator clips at both ends, a certain power is output, and the process is continued for a certain time, and the step is recorded as 2; after repeating steps 1 and 2 for a certain number of times, the product is obtained through washing and drying. The method has the advantages of simple operation, high efficiency and reliability, wide application range, large-scale preparation, uniform and stable structure and the like.

Description

(1)TECHNICAL FIELD

[0001] The present application relates to a method for growing nanometer metal-oxide structure catalyst materials on a substrate by Joule heat method, belonging to the field of material science and engineering technology and chemistry. (2)BACKGROUND

[0002] With the global industrial restructuring and industrial upgrading, energy development and utilization technology is undergoing profound changes, and green low carbon is gradually becoming the global energy development trend. Hydrogen energy has the characteristics of wide source, high heat value, clean and carbon-free, flexible and efficient, and is considered to be the most ideal carrier to promote the clean and efficient utilization of traditional fossil energy and even support the large-scale development of renewable energy. Among them, water electrolysis is considered to be the most promising method for producing hydrogen due to its green and environmentally friendly production process and high product purity. However, the existing working electrode (including cathode and anode) as an important part of the water electrolysis device has defects such as insufficient catalytic activity and instability, which leads to high cost and low efficiency of water electrolysis, limiting its large-scale promotion. Therefore, it is necessary to improve the overall efficiency of water electrolysis and reduce the application cost from the aspects of scientific principles and technological progress, and to greatly optimize the cost-effectiveness and catalytic efficiency of the working electrode is the key to solving the above problems.

[0003] Traditional coated electrodes use a polymer binder to bond catalyst powder and conductive additives (carbon materials) to the current collector layer. However, in practical applications, the binder and coating process not only increases the overall cost of electrode development, but also increases the internal resistance of the system, hindering ion and electron transport and leading to high charge overpotential and low round-trip efficiency. More importantly, the catalyst is easily peeled off from the conductive substrate when running at high current density. An effective strategy to solve the above problems is to build an integrated electrode (self-supporting electrode). However, the method of synthesizing integrated electrodes by electrodeposition and solvothermal method has the characteristics of long preparation period, low raw material utilization rate and high energy consumption, and in most cases the construction of a specific coordination environment means complex preparation steps.

[0004] Therefore, the present application uses Joule heat method to directly grow nanometer metal-oxide structure catalyst on conductive substrate, realizing rapid and large-scale preparation of high-performance water electrolysis electrode. (3)SUMMARY

[0005] 1、Objectives of the present application

[0006] The application aims to provide a method for growing a nano metal-oxide structure catalyst on a substrate by using a Joule heat method. A conductive substrate soaked (or sprayed) with a metal precursor solution is connected to both ends of a direct current power supply, and the power supply is controlled to output a certain power on the conductive substrate, so that the nano metal-oxide structure catalyst is grown on the substrate. The method greatly simplifies the complicated preparation process of the working electrode in the water electrolysis device, and significantly reduces the process cost of the electrode. The prepared electrode material has excellent catalytic activity and stability in OER and HER.

[0007] 2, the application points of the present technology

[0008] The application points of the present application are as follows:

[0009] (1) A certain amount of metal precursor chemical reagent is dissolved in deionized water to prepare a solution A with a molar concentration of 0.005-0.5 mol / L, and the solution is transferred into a cuboid glass tank; the metal precursor chemical reagent is chloroplatinic acid, chloroiridic acid, ruthenium chloride, copper chloride, iron chloride, cobalt chloride, manganese chloride and nickel chloride, etc.

[0010] (2) The cleaned substrate is soaked in solution A for a certain time, or solution A is uniformly sprayed on the cleaned substrate, and the treated substrate is marked as substrate B. The soaking time is generally 2-5 s, and the substrate surface is completely covered with solution A.

[0011] (3) The two ends of the substrate B are connected to the positive and negative electrodes of the direct current power supply through pure copper wires with alligator clips, and a certain power is outputted and lasts for a certain time. The output power is generally 50-250 W, and the duration is 4-10 s.

[0012] (4) Steps (2) and (3) are repeated for a certain number of times, and then the obtained material is washed with deionized water and dried; the treatment times are generally 15-35 times according to the type of the substrate.

[0013] The method for growing metal nanoparticle materials on a substrate by using a Joule heat method has the following advantages: this method is widely applicable, and can grow various nano metal-oxide structures, including Pt-NiO, Ir-NiO, Ru-NiO, Cu-NiO, Ag-NiO, Pt-CoO, Ir-CoO, Ru-CoO, Ir-Fe2O3, Ru-Fe2O3, Pt-MnO2, Ir-MnO2, etc. Meanwhile, this method is also suitable for various substrates, such as foamed nickel, foamed iron, foamed copper, foamed stainless steel, nickel mesh, stainless steel mesh, iron mesh, copper mesh, titanium fiber felt, stainless steel fiber felt, etc. The prepared materials have excellent mechanical and chemical stability, stable catalytic performance, simple and reliable preparation process, and are easy to mass-produce. (4)BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 Figure 2 is a scanning electron microscope image of a Pt@NiO material prepared by the method of the present application.

[0015] Figure 2 Figure 3 is a Raman spectrum of a Pt@NiO material prepared by the method of the present application. (5)EMBODIMENT OF THE PRESENT INVENTION

[0016] The following describes an embodiment of the method of the present application:

[0017] Embodiment 1

[0018] Preparation of a nano-Pt (metal) -NiO (oxide) catalyst material grown on a nickel foam

[0019] First, a metal precursor solution A: an aqueous solution of 0.005 mol / L chloroplatinic acid (H2PtCl6) is prepared and transferred into a cuboid glass tank. Cleaned nickel foam with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is referred to as step 1. The two ends of the soaked nickel foam are connected to the positive and negative poles of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and for a certain time to cause liquid boiling on the surface of the substrate. The output power is 100 W and the output time is 4 s. This step is referred to as step 2. Steps 1 and 2 are repeated for 20 times. After the above operation is completed, the nickel foam is rinsed with deionized water and placed in a vacuum drying oven for drying. Thus, a nickel foam electrode with a nano-Pt (metal) -NiO (oxide) catalyst is obtained.

[0020] Embodiment 2

[0021] Preparation of a nano-Ir (metal) -NiO (oxide) catalyst material grown on a nickel foam

[0022] First, a metal precursor solution A: an aqueous solution of 0.005 mol / L chloroiridic acid (H2IrCl6) is prepared and transferred into a cuboid glass tank. The two ends of the soaked nickel foam are connected to the positive and negative poles of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and for a certain time to cause liquid boiling on the surface of the substrate. The output power is 100 W and the output time is 4 s. This step is referred to as step 2. Steps 1 and 2 are repeated for 25 times. After the above operation is completed, the nickel foam is rinsed with deionized water and placed in a vacuum drying oven for drying. Thus, a nickel foam electrode with a nano-Ir (metal) -NiO (oxide) catalyst is obtained.

[0023] Embodiment 3

[0024] Preparation of a nano Ru (metal) -NiO (oxide) catalyst material grown on nickel foam

[0025] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L ruthenium chloride (RuCl3) and 0.1 mol / L nickel chloride (NiCl2) is prepared and transferred into a cuboid glass tank. A piece of nickel foam with a length of 5 cm and a width of 2 cm is cleaned and then placed in the solution A. After soaking for about 2 s, the nickel foam is taken out, and this step is recorded as Step 1. The two ends of the soaked nickel foam are connected to the positive and negative poles of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and for a certain time to cause liquid boiling on the surface of the substrate. The output power is 100 W, and the output time is 4 s. This step is recorded as Step 2. Steps 1 and 2 are repeated for 25 times. After the above operation is completed, the nickel foam is rinsed with deionized water and dried in a vacuum drying oven. Thus, a nickel foam electrode with a nano Ru (metal) -NiO (oxide) catalyst grown thereon is obtained.

[0026] Example 4

[0027] Preparation of a nano Cu (metal) -NiO (oxide) catalyst material grown on nickel foam

[0028] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L copper chloride (CuCl2) and 0.1 mol / L nickel chloride (NiCl2) is prepared and transferred into a cuboid glass tank. A piece of nickel foam with a length of 5 cm and a width of 2 cm is cleaned and then placed in the solution A. After soaking for about 2 s, the nickel foam is taken out, and this step is recorded as Step 1. The two ends of the soaked nickel foam are connected to the positive and negative poles of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and for a certain time to cause liquid boiling on the surface of the substrate. The output power is 100 W, and the output time is 4 s. This step is recorded as Step 2. Steps 1 and 2 are repeated for 25 times. After the above operation is completed, the nickel foam is rinsed with deionized water and dried in a vacuum drying oven. Thus, a nickel foam electrode with a nano Cu (metal) -NiO (oxide) catalyst grown thereon is obtained.

[0029] Example 5

[0030] Preparation of a nano Ag (metal) -NiO (oxide) catalyst material grown on nickel foam

[0031] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L silver nitrate (AgNO3) and 0.1 mol / L nickel chloride (NiCl2) is prepared and transferred into a cuboid glass tank. A cleaned foam nickel with a length and width of 5 cm*2 cm is placed in the solution A, soaked for about 2 s, and then taken out, which is recorded as step 1. The two ends of the soaked foam nickel are connected to the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and time to make the substrate surface appear liquid boiling phenomenon, the output power is 100 W, and the output time is 4 s, which is recorded as step 2. Steps 1 and 2 are repeated for 25 times. After the above operation, the foam nickel is rinsed with deionized water and dried in a vacuum drying oven. The foam nickel electrode with nano Ag (metal)-NiO (oxide) catalyst material is obtained.

[0032] Example 6

[0033] Preparation of nano Pt (metal)-CoO (oxide) catalyst material on foam nickel

[0034] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L silver nitrate (AgNO3) and 0.1 mol / L nickel chloride (NiCl2) is prepared and transferred into a cuboid glass tank. A cleaned foam nickel with a length and width of 5 cm*2 cm is placed in the solution A, soaked for about 2 s, and then taken out, which is recorded as step 1. The two ends of the soaked foam nickel are connected to the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and time to make the substrate surface appear liquid boiling phenomenon, the output power is 100 W, and the output time is 4 s, which is recorded as step 2. Steps 1 and 2 are repeated for 25 times. After the above operation, the foam nickel is rinsed with deionized water and dried in a vacuum drying oven. The foam nickel electrode with nano Ag (metal)-NiO (oxide) catalyst material is obtained.

[0035] Example 7

[0036] Preparation of nano Ir (metal)-CoO (oxide) catalyst material on foam nickel

[0037] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L of chloro iridic acid (H2IrCl6) and 0.1 mol / L of cobalt chloride (CoCl2) is prepared and transferred into a cuboid glass tank. A cleaned foam nickel with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is recorded as step 1. The two ends of the soaked foam nickel are connected to the positive and negative poles of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and time to make the surface of the substrate appear liquid boiling phenomenon. The output power is 100 W, and the output time is 4 s. This step is recorded as step 2. Steps 1 and 2 are repeated for 25 times. After the above operation, the foam nickel is rinsed with deionized water and dried in a vacuum drying oven. The foam nickel electrode with grown nano Ir (metal)-CoO (oxide) catalyst is obtained.

[0038] Example 8

[0039] Preparation of a nano Ru (metal)-CoO (oxide) catalyst material grown on foam nickel

[0040] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L of chloro iridic acid (H2IrCl6) and 0.1 mol / L of cobalt chloride (CoCl2) is prepared and transferred into a cuboid glass tank. A cleaned foam nickel with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is recorded as step 1. The two ends of the soaked foam nickel are connected to the positive and negative poles of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and time to make the surface of the substrate appear liquid boiling phenomenon. The output power is 100 W, and the output time is 4 s. This step is recorded as step 2. Steps 1 and 2 are repeated for 25 times. After the above operation, the foam nickel is rinsed with deionized water and dried in a vacuum drying oven. The foam nickel electrode with grown nano Ir (metal)-CoO (oxide) catalyst is obtained.

[0041] Example 9

[0042] Preparation of a nano Ru (metal)-CoO (oxide) catalyst material grown on foam nickel

[0043] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L chloroiridic acid (H2IrCl6) and 0.1 mol / L ferric chloride (FeCl3) is prepared and transferred into a cuboid glass tank. A cleaned foam nickel with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is recorded as step 1. The two ends of the soaked foam nickel are connected to the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and time to make the surface of the substrate appear liquid boiling phenomenon. The output power is 100 W, and the output time is 4 s. This step is recorded as step 2. Steps 1 and 2 are repeated for 25 times. After the above operation, the foam nickel is rinsed with deionized water and dried in a vacuum drying oven. A foam nickel electrode with nano Ir (metal)-Fe2O3 (oxide) catalyst grown thereon is obtained.

[0044] Example 10

[0045] Preparation of a nano Pt (metal)-MnO2 (oxide) catalyst material grown on a foam nickel

[0046] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L chloroiridic acid (H2IrCl6) and 0.1 mol / L ferric chloride (FeCl3) is prepared and transferred into a cuboid glass tank. A cleaned foam nickel with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is recorded as step 1. The two ends of the soaked foam nickel are connected to the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and time to make the surface of the substrate appear liquid boiling phenomenon. The output power is 100 W, and the output time is 4 s. This step is recorded as step 2. Steps 1 and 2 are repeated for 25 times. After the above operation, the foam nickel is rinsed with deionized water and dried in a vacuum drying oven. A foam nickel electrode with nano Ir (metal)-Fe2O3 (oxide) catalyst grown thereon is obtained.

[0047] Example 11

[0048] Preparation of a nano Pt (metal)-MnO2 (oxide) catalyst material grown on a foam nickel

[0049] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L chloroplatinic acid (H2PtCl6) and 0.1 mol / L nickel chloride (NiCl2) is prepared and transferred into a cuboid glass tank. A cleaned nickel mesh with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is recorded as step 1. The two ends of the soaked nickel mesh are connected to the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and for a certain time to make the substrate surface appear liquid boiling phenomenon. The output power is 100 W, and the output time is 4 s. This step is recorded as step 2. Steps 1 and 2 are repeated for 25 times. After the above operation, the nickel mesh is rinsed with deionized water and dried in a vacuum drying oven. Thus, a nickel mesh electrode with a nano Pt (metal)-NiO (oxide) catalyst grown thereon is obtained.

[0050] Example 12

[0051] Preparation of a nano Pt (metal)-NiO (oxide) catalyst material grown on a stainless steel mesh

[0052] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L chloroplatinic acid (H2PtCl6) and 0.1 mol / L nickel chloride (NiCl2) is prepared and transferred into a cuboid glass tank. A cleaned nickel mesh with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is recorded as step 1. The two ends of the soaked nickel mesh are connected to the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and for a certain time to make the substrate surface appear liquid boiling phenomenon. The output power is 100 W, and the output time is 4 s. This step is recorded as step 2. Steps 1 and 2 are repeated for 25 times. After the above operation, the nickel mesh is rinsed with deionized water and dried in a vacuum drying oven. Thus, a nickel mesh electrode with a nano Pt (metal)-NiO (oxide) catalyst grown thereon is obtained.

[0053] Example 13

[0054] Preparation of a nano Pt (metal)-NiO (oxide) catalyst material grown on a stainless steel mesh

[0055] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L chloroplatinic acid (H2PtCl6) and 0.1 mol / L nickel chloride (NiCl2) is prepared and transferred into a cuboid glass tank. A clean stainless steel mesh with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is recorded as step 1. The two ends of the soaked stainless steel mesh are connected to the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and time to make the substrate surface appear liquid boiling phenomenon. The output power is 120 W, and the output time is 4 s. This step is recorded as step 2. Steps 1 and 2 are repeated for 30 times. After the above operation, the stainless steel mesh is rinsed with deionized water and dried in a vacuum drying oven. A stainless steel mesh electrode with grown nano Pt (metal)-NiO (oxide) catalyst is obtained.

[0056] Example 14

[0057] Preparation of a nano Pt (metal)-NiO (oxide) catalyst material grown on a nickel mesh

[0058] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L chloroplatinic acid (H2PtCl6) and 0.1 mol / L nickel chloride (NiCl2) is prepared and transferred into a cuboid glass tank. A clean stainless steel mesh with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is recorded as step 1. The two ends of the soaked stainless steel mesh are connected to the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and time to make the substrate surface appear liquid boiling phenomenon. The output power is 120 W, and the output time is 4 s. This step is recorded as step 2. Steps 1 and 2 are repeated for 30 times. After the above operation, the stainless steel mesh is rinsed with deionized water and dried in a vacuum drying oven. A stainless steel mesh electrode with grown nano Pt (metal)-NiO (oxide) catalyst is obtained.

[0059] Example 15

[0060] Preparation of a nano Pt (metal)-NiO (oxide) catalyst material grown on a titanium fiber felt

[0061] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L chloroplatinic acid (H2PtCl6) and 0.1 mol / L nickel chloride (NiCl2) is prepared and transferred into a cuboid glass tank. A cleaned titanium fiber felt with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is recorded as step 1. The two ends of the soaked titanium fiber felt are connected to the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and for a certain time to cause liquid boiling on the surface of the substrate. The output power is 140 W, and the output time is 4 s. This step is recorded as step 2. Steps 1 and 2 are repeated for 30 times. After the above operation, the titanium fiber felt is rinsed with deionized water and dried in a vacuum drying oven. A titanium fiber felt electrode with a nano Pt (metal)-NiO (oxide) catalyst is obtained.

[0062] Example 16

[0063] Preparation of a nano Pt (metal)-NiO (oxide) catalyst material grown on a foam stainless steel

[0064] First, a metal precursor solution A: a mixed aqueous solution of 0.005 mol / L chloroplatinic acid (H2PtCl6) and 0.1 mol / L nickel chloride (NiCl2) is prepared and transferred into a cuboid glass tank. A cleaned titanium fiber felt with a length of 5 cm and a width of 2 cm is placed in the solution A, soaked for about 2 s, and then taken out. This step is recorded as step 1. The two ends of the soaked titanium fiber felt are connected to the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips. The power supply is controlled to output a certain power and for a certain time to cause liquid boiling on the surface of the substrate. The output power is 140 W, and the output time is 4 s. This step is recorded as step 2. Steps 1 and 2 are repeated for 30 times. After the above operation, the titanium fiber felt is rinsed with deionized water and dried in a vacuum drying oven. A titanium fiber felt electrode with a nano Pt (metal)-NiO (oxide) catalyst is obtained.

Claims

1. A method for growing nanometal-oxide structure catalyst materials on a substrate using a Joule heating method, characterized by The method comprises the following steps: (1) using acetone, alcohol, dilute hydrochloric acid, and deionized water to clean the substrate respectively to remove grease and oxides on the surface of the substrate; the substrate is foamed nickel, foamed copper, nickel mesh, foamed stainless steel, stainless steel mesh, nickel felt, titanium fiber felt or stainless steel fiber felt used for metal current collector or catalyst metal carrier of electrolytic water device; (2) a certain amount of metal precursor chemical reagent is dissolved in deionized water to configure a solution A with a molar concentration of 0.005-0.5 mol / L, and the solution is transferred into a cuboid glass tank; the metal precursor chemical reagent is chloroplatinic acid, chloroiridic acid, ruthenium chloride, copper chloride, iron chloride, cobalt chloride, manganese chloride or nickel chloride; (3) the substrate in (1) is soaked in solution A for a certain time, or solution A is uniformly sprayed on the substrate in (1), and the treated substrate is denoted as substrate B; the soaking time is 2-5 s, and the surface of the substrate is completely covered with solution A; (4) the two ends of substrate B are connected with the positive and negative electrodes of a direct current power supply through pure copper wires with alligator clips, and a certain power is outputted and lasts for a certain time; the output power is 50-250 W; and the lasting time is 4-6 s; (5) steps (3) and (4) are repeated for a certain number of times, and then the substrate is rinsed with deionized water and dried to obtain the required material; the treatment times are 15-35 times according to the type of the substrate.

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