CN110791776A - Preparation method of proton corrosion-assisted electrolytic water anode in ferrous environment - Google Patents
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Abstract
The invention relates to a preparation method of an electrolytic water anode assisted by proton corrosion in a ferrous environment, which comprises the following steps: firstly, ultrasonic degreasing and cleaning are carried out on a metallic nickel substrate in acetone, then ultrasonic surface oxide layer corrosion treatment is carried out in hydrochloric acid solution, and the metallic nickel substrate obtained by treatment is placed in acidic ferrous solution containing sodium citrate for heat treatment. The preparation process of the electrolytic water anode is simple, large-scale equipment is not needed, and the metal nickel substrate can be directly converted into the electrolytic water anode through chemical reaction for electrolytic catalysis reaction; the high-activity ferronickel combined oxidation state substance is introduced to the surface of the electrode, so that the intrinsic catalytic activity of the electrolyzed water is improved; the preparation process has the advantages of extremely low raw material consumption, low cost and little pollution, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of electrolytic water anode preparation, and particularly relates to a proton corrosion-assisted electrolytic water anode preparation method in a ferrous environment.
Background
In future energy formats, hydrogen energy will play an important role due to its high efficiency and cleanliness, and especially the energy usage pattern from "renewable energy to electrical energy, and then from electrical energy to hydrogen energy" this "physical to electrical, electrical to chemical" will be of great interest. And hydrogen as an energy carrier or raw material will provide the cleanest source for the downstream hydrogen field. The most common way to convert electrical energy to hydrogen energy is to electrolyze water to produce hydrogen. The performance restriction points of hydrogen production by electrolyzing water at present are mainly as follows: 1) the over potential of the cathode is too high; 2) the over-potential of the anode is too high; 3) the diaphragm voltage drops too high. The anode reaction kinetics are slow, and the intrinsic equilibrium potential is high, so that the anode reaction kinetics are often a limiting step for water electrolysis.
Most of the traditional anodes are made of pure metal nickel-based materials, so that the performance is poor, and the requirement of low energy consumption under the condition of high gas yield of equipment cannot be met. The good anode materials acknowledged by the scientific research at present mainly comprise noble metal series, including ruthenium dioxide and iridium dioxide; and transition metal families including nickel-iron composite oxides, hydroxides, nitrides, phosphides. However, these anode materials have not been industrially applied to actual water electrolysis apparatuses, mainly because: 1) noble metal series are expensive; 2) the catalyst is difficult to fix on the surface of the electrode substrate under the working conditions of high temperature and high pressure in the reaction process. Therefore, around the transition metal electrocatalyst with lower price, the development of the electrode preparation method with simple process, low cost and stable performance has important significance.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing an electrolyzed water anode assisted by proton corrosion in a ferrous environment, and the method has the advantages of low cost and low pollution.
The invention provides a preparation method of an electrolytic water anode assisted by proton corrosion in a ferrous environment, which comprises the following steps:
s1, cleaning: cleaning the metal nickel substrate to remove a surface grease layer and a surface oxidation layer of the metal nickel substrate to obtain a clean metal nickel substrate;
s2, proton corrosion treatment: and (2) placing the clean metal nickel substrate into an acidic ferrous mixed solution containing sodium citrate, carrying out heat treatment for 2-20 h at 50-150 ℃, cooling to room temperature, taking out, washing with distilled water, and drying to obtain the electrolytic water anode with the surface being a ferronickel combined oxidation state substance.
Preferably, the cleaning process in step S1 is specifically: placing a metal nickel substrate in an acetone solution, ultrasonically cleaning for 10-30 min, and repeatedly cleaning with ethanol to remove a surface grease layer of the metal nickel substrate; and then placing the metal nickel substrate with the surface grease layer removed in a hydrochloric acid solution with the concentration of 1-6 mol/L for ultrasonic cleaning for 5-25 min, standing for 10-30 min, repeatedly cleaning with distilled water to remove the surface oxide layer of the metal nickel substrate, and drying to obtain the clean metal nickel substrate.
Preferably, the metallic nickel substrate is selected from one of a nickel mesh, a nickel foam and a nickel sheet.
Preferably, the solvent of the acidic ferrous solution is one or more selected from hydrochloric acid, sulfuric acid, formic acid, acetic acid and oxalic acid.
Preferably, the solute of the acidic ferrous solution is one or more selected from ferrous chloride, ferrous sulfate, ferrous acetate and ferrous ammonium sulfate.
Preferably, in the acid ferrous iron mixed solution containing sodium citrate: the concentration of hydrogen ions is 0.01-2 mol/L, the concentration of ferrous ions is 0.02-1 mmol/L, and the concentration of sodium citrate is 0.001-0.05 mmol/L.
Preferably, the ferronickel combined oxidation state substance comprises one or two of nickel oxide and nickel hydroxide, and also comprises one or more of ferric oxide, ferrous oxide, ferric hydroxide, iron-doped nickel oxide and iron-doped nickel hydroxide.
Compared with the prior art, the method has the advantages that the metal nickel substrate is subjected to proton corrosion treatment in a ferrous environment, the metal nickel substrate is directly converted into an electrolytic water anode, and the high-activity nickel-iron combined oxidation state substance is introduced to the surface of the electrode and is tightly combined with the substrate, so that the intrinsic catalytic activity and catalytic durability of the electrolytic water are improved.
Drawings
FIG. 1 is a scanning electron microscope image of a nickel mesh provided in example 1 of the present invention without any treatment;
FIG. 2 is a scanning electron microscope picture of the surface of the anode of the electrolyzed water obtained in example 1 of the present invention and a corresponding X-ray energy spectrum;
FIG. 3 is a plot of a three-electrode electrolytic voltammetric sweep for all examples of the invention and comparative examples.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples, but it is to be understood that these examples are intended merely to illustrate further features and advantages of the invention, and are not intended to limit the scope of the claims. The present invention is not limited to the following examples.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
S1, cleaning: cleaning the metal nickel substrate to remove a surface grease layer and a surface oxidation layer of the metal nickel substrate to obtain a clean metal nickel substrate;
specifically, the metal nickel substrate is placed in an acetone solution for ultrasonic cleaning for 10-30 min, and then repeatedly cleaned by ethanol to remove a surface grease layer of the metal nickel substrate; and then, placing the metal nickel substrate with the surface grease layer removed in a hydrochloric acid solution with the concentration of 1-6 mol/L for ultrasonic cleaning for 5-25 min, and standing for 10-30 min, wherein the concentration of hydrochloric acid is more preferably 4 mol/L. And repeatedly cleaning with distilled water to remove the oxide layer on the surface of the metal nickel substrate, and drying to obtain the clean metal nickel substrate. The metallic nickel substrate in the present invention is preferably one selected from the group consisting of a nickel mesh, a nickel foam and a nickel sheet.
S2, proton corrosion treatment: and (2) placing the clean metal nickel substrate into an acidic ferrous mixed solution containing sodium citrate, carrying out heat treatment for 2-20 h at 50-150 ℃, cooling to room temperature, taking out, washing with distilled water, and drying to obtain the electrolytic water anode with the surface being a ferronickel combined oxidation state substance.
First, an acidic ferrous iron mixed solution containing sodium citrate is prepared. Specifically, sodium citrate is added into the acidic ferrous solution to obtain an acidic ferrous mixture containing sodium citrateAnd (3) solution. The solvent of the ferrous acid solution in the present invention is preferably selected from hydrochloric acid (HCl) and sulfuric acid (H)2SO4) Formic acid (HCOOH), acetic acid (CH)3COOH) and oxalic acid (HOOCCOOH), more preferably hydrochloric acid (HCl) or sulfuric acid (H)2SO4). The solute of the acidic ferrous solution is selected from ferrous chloride (FeCl)2) Ferrous sulfate (FeSO)4) Ferrous acetate (Fe (CH)3COO)2) Ammonium ferrous sulfate (NH)4Fe(SO4)2) More preferably ferrous chloride (FeCl)2) Or ferrous sulfate (FeSO)4). In the invention, the hydrogen ion concentration in the acid ferrous iron mixed solution containing sodium citrate is preferably 0.01-2 mol/L, more preferably 0.5mol/L, the ferrous ion concentration is preferably 0.02-1 mmol/L, more preferably 0.5mmol/L, and sodium citrate (Na)3C6H5O7) The concentration of (B) is preferably 0.001 to 0.05mmol/L, more preferably 0.01 mmol/L.
And then, placing the clean metallic nickel substrate obtained by the cleaning treatment in the step S1 in an acidic ferrous mixed solution containing sodium citrate, carrying out heat treatment for 2-20 h at 50-150 ℃, preferably at 100 ℃ for 10h, cooling to room temperature, washing with distilled water, and drying to obtain the electrolytic water anode with the surface being the ferronickel combined oxidation state substance. The nickel-iron composite oxidation state substance comprises nickel oxide (NiO), nickel hydroxide (Ni (OH)2) One or two of them, and also contains ferric oxide (Fe)2O3) Ferrous oxide (FeO), iron hydroxide (Fe (OH)3) Iron-doped nickel oxide (Fe)xNi1-xO), iron-doped nickel hydroxide (Fe)xNi1-x(OH)2) One or more of them.
For further understanding of the present invention, the following examples and comparative examples are provided to illustrate the preparation method of the proton corrosion assisted electrolyzed water anode in ferrous environment, and the scope of the present invention is not limited by the following examples and comparative examples.
Example 1
Cleaning a nickel screen: placing the nickel screen in an acetone solution, ultrasonically cleaning for 20min, and repeatedly cleaning with ethanol to remove a surface grease layer; then placing the nickel screen without the surface grease layer in a hydrochloric acid solution with the concentration of 4mol/L for ultrasonic treatment for 10min, standing for 15min, and repeatedly cleaning with distilled water to remove a metal surface oxidation layer to obtain a clean nickel screen;
(II) proton corrosion treatment: carrying out hydrochloric acid corrosion treatment on a clean nickel screen in a ferrous chloride environment: and (3) putting the cleaned metal nickel screen into a mixed solution of 0.5mmol/L ferrous chloride, 0.5mol/L hydrochloric acid and 0.01mmol/L sodium citrate, carrying out heat treatment for 10h at 100 ℃, cooling to room temperature, washing with distilled water, and drying to obtain the electrolyzed water anode.
(III) analyzing the surface structure of the anode of the electrolyzed water:
fig. 1 shows the scanning electron microscope pictures of the nickel mesh surface without any treatment, which shows the clean and smooth characteristics. Fig. 2 shows a scanning electron microscope picture of the surface of the anode of the electrolyzed water and a corresponding X-ray energy spectrum obtained in this example, in which iron is uniformly distributed on the surface of the nickel mesh. In fig. 2, a, b, and c are scanning electron microscope images of the surface of the anode of the electrolyzed water with different magnifications obtained in example 1. Fig. 2d is a scanning electron microscope image of the anode sample of the electrolyzed water and the corresponding X-ray energy spectrum of the surface oxygen (O), iron (Fe), and nickel (Ni) elements thereof obtained based on the etching process in example 1.
(IV) analyzing the anode catalytic performance of the electrolyzed water:
the oxygen evolution performance of the electrolyzed water anode obtained in the embodiment was tested by a linear voltammetry scan test method. The test uses a three-electrode system, the anode of the electrolyzed water obtained in this example is a working electrode, silver/silver chloride is a reference electrode, a platinum mesh is an auxiliary electrode, the electrolyte adopts a potassium hydroxide solution with the mass of 1mol/L, the scanning speed is 5mv/s, and the scanning range is 0v to 1 v. The oxygen evolution performance was tested on an electrochemical workstation (CHI660E, shanghai chen instruments ltd) and the test results corresponded to fig. 3 and table 1.
Example 2
Cleaning foamed nickel:
placing the foamed nickel in an acetone solution, ultrasonically cleaning for 20min, and repeatedly cleaning with ethanol to remove the grease layer on the metal surface; and then placing the foamed nickel in a hydrochloric acid solution with the concentration of 4mol/L for ultrasonic treatment for 10min, standing for 15min, and repeatedly cleaning with distilled water to remove an oxide layer on the surface of the foamed nickel, thereby obtaining clean foamed nickel.
(II) proton corrosion treatment:
and (3) putting the clean foamed nickel into a mixed solution of 0.5mmol/L ferrous sulfate, 0.25mol/L sulfuric acid and 0.01mmol/L sodium citrate, carrying out heat treatment at 100 ℃ for 10h, cooling to room temperature, washing with distilled water, and drying to obtain the electrolyzed water anode of the embodiment.
(III) analysis of anode catalytic performance of the electrolyzed water:
the oxygen evolution performance of the electrolyzed water anode obtained in the embodiment was tested by a linear voltammetry scan test method. The test uses a three-electrode system, the anode of the electrolyzed water obtained in this example is a working electrode, silver/silver chloride is a reference electrode, a platinum mesh is an auxiliary electrode, the electrolyte adopts a potassium hydroxide solution with the mass of 1mol/L, the scanning speed is 5mv/s, and the scanning range is 0v to 1 v. The oxygen evolution performance was tested on an electrochemical workstation (CHI660E, shanghai chen instruments ltd) and the test results corresponded to fig. 3 and table 1.
Comparative example 1
The comparative example directly used a metallic nickel mesh as the anode for the electrolysis of water.
Cleaning a metallic nickel screen:
placing the metal nickel net in an acetone solution, ultrasonically cleaning for 20min, and repeatedly cleaning with ethanol to remove the grease layer on the metal surface; then, the metallic nickel sheet is placed in a hydrochloric acid solution with the concentration of 4mol/L for 10min by ultrasonic treatment, is kept stand for 15min, and is repeatedly washed by distilled water to remove an oxide layer on the surface of the metal.
(II) analysis of anode catalytic performance of the electrolyzed water:
and testing the oxygen evolution performance of the electrolyzed water anode obtained by the comparative example by adopting a linear voltammetry scanning test method. The test uses a three-electrode system, the anode of the electrolyzed water obtained in this example is a working electrode, silver/silver chloride is a reference electrode, a platinum sheet is an auxiliary electrode, the electrolyte adopts potassium hydroxide solution with the mass of 1mol/L, the scanning speed is 5mv/s, and the scanning range is 0v to 1 v. The oxygen evolution performance was tested on an electrochemical workstation (CHI660E, shanghai chen instruments ltd) and the test results corresponded to fig. 3 and table 1.
Comparative example 2
This comparative example directly used nickel foam as the anode for the electrolysis of water.
Cleaning foamed nickel:
placing the foamed nickel in an acetone solution, ultrasonically cleaning for 20min, and repeatedly cleaning with ethanol to remove the grease layer on the metal surface; and then placing the foamed nickel in a hydrochloric acid solution with the concentration of 4mol/L for ultrasonic treatment for 10min, standing for 15min, and repeatedly cleaning with distilled water to remove an oxide layer on the surface of the metal.
(II) analysis of anode catalytic performance of the electrolyzed water:
and testing the oxygen evolution performance of the electrolyzed water anode obtained by the comparative example by adopting a linear voltammetry scanning test method. The test uses a three-electrode system, the anode of the electrolyzed water obtained in this example is a working electrode, silver/silver chloride is a reference electrode, a platinum mesh is an auxiliary electrode, the electrolyte adopts a potassium hydroxide solution with the mass of 1mol/L, the scanning speed is 5mv/s, and the scanning range is 0v to 1 v. The oxygen evolution performance was tested on an electrochemical workstation (CHI660E, shanghai chen instruments ltd) and the test results corresponded to fig. 3 and table 1.
Comparative example 3
The comparative example provides a method for preparing an anode for electrolyzed water based on nickel screen and ferrous iron treatment.
Cleaning a metallic nickel screen:
placing the metal nickel net in an acetone solution, ultrasonically cleaning for 20min, and repeatedly cleaning with ethanol to remove the grease layer on the metal surface; then, the metal substrate is placed in a hydrochloric acid solution with the concentration of 4mol/L for 10min by ultrasonic treatment, stands for 15min, and is repeatedly washed by distilled water to remove an oxide layer on the surface of the metal.
(II) cleaning the treated nickel net, and treating in a ferrous chloride environment:
and (3) putting the cleaned metal nickel screen into a mixed solution of 0.25mmol/L ferrous acetate, 0.25mmol/L ferrous ammonium sulfate and 0.01mmol/L sodium citrate, carrying out heat treatment for 10h at 100 ℃, cooling to room temperature, washing with distilled water, and drying to obtain the electrolytic water anode of the embodiment.
(III) analysis of anode catalytic performance of the electrolyzed water:
and testing the oxygen evolution performance of the electrolyzed water anode obtained by the comparative example by adopting a linear voltammetry scanning test method. The test uses a three-electrode system, the anode of the electrolyzed water obtained in this example is a working electrode, silver/silver chloride is a reference electrode, a platinum mesh is an auxiliary electrode, the electrolyte adopts a potassium hydroxide solution with the mass of 1mol/L, the scanning speed is 5mv/s, and the scanning range is 0v to 1 v. The oxygen evolution performance was tested on an electrochemical workstation (CHI660E, shanghai chen instruments ltd) and the test results corresponded to fig. 3 and table 1.
Comparative example 4
The comparative example provides a method for preparing an anode for electrolyzed water based on a nickel mesh, proton corrosion treatment.
Cleaning a metallic nickel screen:
placing the metal nickel net in an acetone solution, ultrasonically cleaning for 20min, and repeatedly cleaning with ethanol to remove the grease layer on the metal surface; then, the metal substrate is placed in a hydrochloric acid solution with the concentration of 4mol/L for 10min by ultrasonic treatment, stands for 15min, and is repeatedly washed by distilled water to remove an oxide layer on the surface of the metal.
And (II) cleaning the treated nickel net, and treating in a proton environment:
and (3) putting the cleaned metal nickel screen into a mixed solution of 0.5mol/L hydrochloric acid and 0.01mmol/L sodium citrate, carrying out heat treatment for 10 hours at the temperature of 100 ℃, cooling to room temperature, washing with distilled water, and drying to obtain the electrolyzed water anode of the embodiment.
(III) analysis of anode catalytic performance of the electrolyzed water:
and testing the oxygen evolution performance of the electrolyzed water anode obtained by the comparative example by adopting a linear voltammetry scanning test method. The test uses a three-electrode system, the anode of the electrolyzed water obtained in this example is a working electrode, silver/silver chloride is a reference electrode, a platinum mesh is an auxiliary electrode, the electrolyte adopts a potassium hydroxide solution with the mass of 1mol/L, the scanning speed is 5mv/s, and the scanning range is 0v to 1 v. The oxygen evolution performance was tested on an electrochemical workstation (CHI660E, shanghai chen instruments ltd) and the test results corresponded to fig. 3 and table 1.
Table 1: potential of different test electrodes at different current densities
From the analysis of the data result of the three-electrode test, compared with the traditional industrial pure nickel mesh anode, the electrolyzed water anode prepared by the proton corrosion assistance in the ferrous environment has obviously improved electrocatalytic performance, especially at high current density (200 mAcm)-2) At least 0.2v of the potential decreases. On the basis of the traditional industrial pure nickel anode, the invention forms ferronickel combined oxidation state substances on the surface of the pure nickel anode by a one-step method through ferrous reaction and proton corrosion treatment processes.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A preparation method of an electrolytic water anode assisted by proton corrosion in a ferrous environment is characterized by comprising the following steps:
s1, cleaning: cleaning the metal nickel substrate to remove a surface grease layer and a surface oxidation layer of the metal nickel substrate to obtain a clean metal nickel substrate;
s2, proton corrosion treatment: and (2) placing the clean metal nickel substrate into an acidic ferrous mixed solution containing sodium citrate, carrying out heat treatment for 2-20 h at 50-150 ℃, cooling to room temperature, taking out, washing with distilled water, and drying to obtain the electrolytic water anode with the surface being a ferronickel combined oxidation state substance.
2. The method for producing an anode for electrolyzed water according to claim 1, wherein the cleaning treatment in step S1 is specifically: placing a metal nickel substrate in an acetone solution, ultrasonically cleaning for 10-30 min, and repeatedly cleaning with ethanol to remove a surface grease layer of the metal nickel substrate; and then placing the metal nickel substrate with the surface grease layer removed in a hydrochloric acid solution with the concentration of 1-6 mol/L for ultrasonic cleaning for 5-25 min, standing for 10-30 min, repeatedly cleaning with distilled water, removing the surface oxide layer of the metal nickel substrate, and drying to obtain the clean metal nickel substrate.
3. The electrolytic water anode production method according to claim 1 or 2, wherein the metallic nickel substrate is selected from one of a nickel mesh, a nickel foam and a nickel sheet.
4. The method for preparing an anode for electrolyzing water according to claim 1, wherein the solvent of the ferrous acid solution is selected from one or more of hydrochloric acid, sulfuric acid, formic acid, acetic acid and oxalic acid.
5. The method for preparing the anode of electrolyzed water according to claim 1, wherein the solute of the acidic ferrous solution is selected from one or more of ferrous chloride, ferrous sulfate, ferrous acetate and ferrous ammonium sulfate.
6. The method for preparing an anode for electrolyzing water according to claim 1, wherein in the mixed solution of ferrous acid containing sodium citrate: the concentration of hydrogen ions is 0.01-2 mol/L, the concentration of ferrous ions is 0.02-1 mmol/L, and the concentration of sodium citrate is 0.001-0.05 mmol/L.
7. The electrolytic water anode production method of claim 1, wherein the ferronickel combined oxidation state substance comprises one or both of nickel oxide and nickel hydroxide, and further comprises one or more of ferric oxide, ferrous oxide, ferric hydroxide, iron-doped nickel oxide and iron-doped nickel hydroxide.
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| CN110656349A (en) * | 2019-09-29 | 2020-01-07 | 安徽师范大学 | Fe-doped nickel oxalate nanorod growing in situ on foamed nickel, preparation method and application thereof |
| CN110952111A (en) * | 2019-10-31 | 2020-04-03 | 南通安思卓新能源有限公司 | Two-step oxidation synthesized electrolytic water anode and preparation method thereof |
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