CN115961305A - (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and preparation method thereof - Google Patents

(FeCoNiCuZn) F high-entropy fluoride electrocatalyst and preparation method thereof Download PDF

Info

Publication number
CN115961305A
CN115961305A CN202310047413.4A CN202310047413A CN115961305A CN 115961305 A CN115961305 A CN 115961305A CN 202310047413 A CN202310047413 A CN 202310047413A CN 115961305 A CN115961305 A CN 115961305A
Authority
CN
China
Prior art keywords
feconicuzn
entropy
fluoride
electrocatalyst
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310047413.4A
Other languages
Chinese (zh)
Inventor
齐西伟
包阿特尔
王轩宇
张晓燕
谷耀行
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northeastern University Qinhuangdao Branch
Original Assignee
Northeastern University Qinhuangdao Branch
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northeastern University Qinhuangdao Branch filed Critical Northeastern University Qinhuangdao Branch
Priority to CN202310047413.4A priority Critical patent/CN115961305A/en
Publication of CN115961305A publication Critical patent/CN115961305A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

A (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and a preparation method thereof belong to the field of catalyst material preparation. The (FeCoNiCuZn) F high-entropy fluoride electrocatalyst adopts a precursor solution in which the molar ratio of metal ions is Fe 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ =1:1:1:1:1, according to 10cm 3 The molar weight of the FeCoNiCuZn high-entropy alloy added with the fluorine-containing compound is 0.054-0.067 mol. The preparation method comprises the following steps: preparing a precursor solution according to the molar ratio of metal ions, performing electrodeposition to form FeCoNiCuZn high-entropy alloy on the porous conductive foamed nickel substrate, and performing fluorination treatment on the FeCoNiCuZn high-entropy alloy to form the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst. The preparation method is simple and easy to operate, low in preparation cost and quick in preparation time, and the obtained electro-catalyst is stable in structure and has excellent hydrogen evolution and oxygen evolution double-function electro-catalysis performance.

Description

(FeCoNiCuZn) F high-entropy fluoride electrocatalyst and preparation method thereof
Technical Field
The invention belongs to the field of catalyst material preparation, and particularly relates to a (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and a preparation method thereof.
Background
The electrolytic water system consists of two half reactions of cathodic hydrogen evolution reaction and anodic oxygen evolution reaction, and both need noble metal electro-catalysts (Pt and IrO) in view of slow reaction kinetics process 2 、RuO 2 ) The conversion efficiency between electric energy and chemical energy is improved, but the precious metal resource is scarce and expensive, and the large-scale application of the precious metal resource in an electrolytic water system is limited. Therefore, the development of the transition metal-based electrocatalyst with efficient and stable performance and low cost is the key for promoting the large-scale application of the electrolyzed water and is also the problem which needs to be overcome urgently at present.
The high entropy material catalyst comprising a plurality of metallic components has excellent electrocatalytic efficiency due to multi-element synergistic effect. High-entropy anionic compound electrocatalysts have attracted much attention in the field of electrocatalysis due to their high conductivity, stable structure and excellent performance. The high-entropy anionic compound electrocatalyst reported at present mainly comprises high-entropy oxides, high-entropy sulfides, high-entropy phosphides and the like, but the high-entropy anionic compound electrocatalyst is simple in preparation method and high in catalytic activity, less in process capable of being prepared in a practical large range, and especially important in development of new-component high-entropy anionic compound electrocatalysis and preparation process flow.
Disclosure of Invention
Aiming at the urgent need of the prior art, the invention provides a (FeCoNiCuZn) F high-entropy fluoride electrocatalyst, a preparation method and application thereof. The preparation method is simple and easy to operate, low in preparation cost and quick in preparation time. The prepared (FeCoNiCuZn) F high-entropy fluoride electrocatalyst has great scientific research significance, is beneficial to realizing large-scale mass actual production, and has certain economic value potential.
The preparation method of the invention takes the foamed nickel as a substrate, utilizes a constant potential electrodeposition method to uniformly reduce and deposit five metal ions on the substrate, and then obtains the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst through the fluorination treatment of a simple molten salt method.
The invention has the advantages of easy acquisition of equipment, simple operation process flow, stable structure of the prepared (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and excellent hydrogen and oxygen evolution double-function electrocatalysis performance.
The (FeCoNiCuZn) F high-entropy fluoride electrocatalyst adopts a precursor solution in which the molar ratio of metal ions is Fe 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ =1:1:1:1:1, the amount of fluorine-containing compound is determined according to the area of FeCoNiCuZn high-entropy alloy, preferably 10cm 3 The corresponding molar weight of the FeCoNiCuZn high-entropy alloy added with the fluorine-containing compound is 0.054-0.067 mol;
further, the fluorine-containing compound is preferably ammonium fluoride.
The (FeCoNiCuZn) F high-entropy fluoride electrocatalyst has a structure of a cubic crystal system and a Fm-3m space group. Under the alkaline condition of 1mol/LKOH, the hydrogen evolution reaction of the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst is measured under the current density of 10 mA-cm -2 The overpotential of time is 21mV, and the Tafel slope is 24.57mV dec -1 (ii) a The current density is measured at 100mA cm by oxygen evolution reaction -2 The overpotential is 274mV, the Tafel slope is 48.86mV dec -1 Has excellent electrocatalytic performance of hydrogen evolution reaction and oxygen evolution reaction.
The invention relates to a preparation method of a (FeCoNiCuZn) F high-entropy fluoride electrocatalyst, which is characterized in that Fe is in a metal ion molar ratio 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ =1:1:1:1:1 preparing a precursor solution, carrying out electrodeposition, forming FeCoNiCuZn high-entropy alloy on a porous conductive foamed nickel matrix, and carrying out fluorination treatment on the alloy to form the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst.
The method specifically comprises the following steps:
step 1, preparing a precursor solution:
weighing corresponding FeCl according to the molar ratio of metal ions 3 ·6H 2 O、CoCl 2 、NiCl 2 ·6H 2 O、CuCl 2 ·6H 2 O、ZnCl 2 Mixing, dissolving in deionized water, and stirring to obtain precursor solution;
step 2, preparing the high-entropy alloy:
(1) Taking the precursor solution as electrolyte of an electrolytic cell, controlling the pH value of the electrolyte to be 4-4.5, and heating to 40-45 ℃;
(2) Under a three-electrode system, foam nickel is used as a working electrode, a graphite rod is used as a counter electrode, constant potential electrodeposition is carried out, the deposition potential range is minus 0.2 +/-0.05V, and the deposition time is 800-900 s;
(3) After the deposition is finished, carrying out ultrasonic cleaning on the foamed nickel electrode deposited with the FeCoNiCuZn high-entropy alloy, and then standing and drying in the air to obtain the FeCoNiCuZn high-entropy alloy uniformly deposited on the foamed nickel;
step 3, fluorination treatment by a molten salt method:
(1) Weighing ammonium fluoride according to the molar weight of fluorine in the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst, and heating and melting to obtain molten ammonium fluoride;
(2) And (2) placing the FeCoNiCuZn high-entropy alloy into molten ammonium fluoride for fluorination treatment to obtain the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst.
The preparation method of the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst comprises the following steps:
in the step 1, the molar ratio of the metal ions is Fe 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ =1:1:1:1:1, the concentration range of the total metal ions in the precursor solution is 0.1-0.5 mol/L.
In the step 2 (1), the process of controlling the pH value of the electrolyte at 4-4.5 is as follows: under the stirring state, ammonia water or 0.1mol/L dilute hydrochloric acid is used as a pH regulator to regulate the pH value of the electrolyte to 4-4.5, and the stirring speed is 200-300 rpm.
In the step 2 (2), the size of the foamed nickel used is 20mm × 10mm × 1mm. And (3) ultrasonically pretreating the foamed nickel by using 0.5mol/L dilute HCl solution for less than or equal to 20min to remove oxides on the surface layer of the foamed nickel, repeatedly washing the foamed nickel by using deionized water and absolute ethyl alcohol for many times, and standing and drying the foamed nickel in the air for later use.
In the step 2 (2), the working electrode clamp and the reference electrode clamp are clamped on the working electrode simultaneously; the foam nickel substrate needs to be placed 1-1.5 cm below the liquid level of the precursor solution and soaked for 30-60 s, and the spacing distance between the foam nickel substrate and the graphite rod is kept 2-2.5 cm.
In the step 2 (3), after the deposition time is over, immediately taking out the sample, and ultrasonically cleaning the sample by using deionized water and absolute ethyl alcohol for multiple times in sequence to remove redundant deposits on the surface, wherein the ultrasonic cleaning time is preferably 5-10 min, standing and drying the sample in the air for standby application, and the natural drying time is more than or equal to 24h.
In the step 3 (1), the temperature of the constant-temperature heating table is kept at 240-250 ℃, the mass of ammonium fluoride is 2-2.5 g, and 5 FeCoNiCuZn high-entropy alloys with the size specification of 20mm multiplied by 10mm multiplied by 1mm can be fluoridized.
And in the step 3 (2), the fluorination treatment time is 60-70 s, the fluorination treatment is quickly taken out and placed in deionized water, the deionized water is used for washing for many times to remove surface impurities, and the fluorination treatment is carried out in the air and is dried.
The equimolar FeCl 3 ·6H 2 O、CoCl 2 、NiCl 2 ·6H 2 O、CuCl 2 ·6H 2 O、ZnCl 2 The mixed precursor solution is subjected to constant potential electrodeposition on a foam nickel substrate to obtain a FeCoNiCuZn high-entropy alloy electrocatalyst, and the FeCoNiCuZn F high-entropy fluoride electrocatalyst obtained after fluorination treatment, washing, standing and drying can be directly used as a working electrode.
Compared with the prior art, the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and the preparation method and the application thereof have the beneficial effects that:
the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst consists of low-cost transition group metal elements Fe, co, ni, cu and Zn, and is compared with the Pt and IrO commercially used in the existing electrocatalytic hydrogen evolution reaction and oxygen evolution reaction 2 、RuO 2 The noble metal catalyst not only has the advantage of cost, but also has excellent electrocatalytic activity with double functions of hydrogen evolution reaction and oxygen evolution reaction, and has certain excellent potential in the field of water electrolysis.
The invention adopts a simple constant potential electrodeposition method combined with a molten salt method to prepare the (FeCoNiCuZn) F high-entropy fluoride electrocatalystThe preparation method is simple and easy to operate, and the hydrogen evolution reaction of the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst is measured under the alkaline condition of 1mol/L KOH, and the current density is 10 mA-cm -2 The overpotential is 21mV, and the Tafel slope is 24.57mV dec -1 (ii) a In order to avoid the oxidation peak of the nickel foam to interfere with the performance test during the oxygen evolution reaction, the current density measured by the oxygen evolution reaction is 100 mA-cm -2 The overpotential is 274mV, the Tafel slope is 48.86mV dec -1 Has excellent electrocatalytic performance of hydrogen evolution reaction and oxygen evolution reaction.
Within the scope of understanding, the present invention is implemented by the method provided by the present invention and is not limited to the examples described above, and the invention can be implemented by the interval range of various preparation technical parameters (high entropy system component, electrolyte concentration, pH value, deposition potential, deposition time, ammonium fluoride usage amount), and the modifications and changes can be made by those skilled in the art according to the above description, and all such modifications and changes should fall within the protection scope of the appended claims.
Drawings
FIG. 1 XRD patterns of FeCoNiCuZn high entropy alloy and (FeCoNiCuZn) F high entropy fluoride electrocatalyst prepared by the embodiment of the present invention.
FIG. 2 is a comparison graph of X-ray photoelectron spectroscopy high resolution spectra of FeCoNiCuZn high entropy alloy and (FeCoNiCuZn) F high entropy fluoride electrocatalyst prepared by the embodiment of the present invention.
FIG. 3 is a graph showing the performance test of FeCoNiCuZn high-entropy alloy and (FeCoNiCuZn) F high-entropy fluoride electrocatalyst prepared according to the embodiment of the present invention; (a) a hydrogen evolution reaction polarization curve; (b) oxygen evolution reaction polarization curve; (c) electrochemical impedance diagram at a potential of-1.1V; (d) electrochemical impedance plot at potential of 0.48V; (e) a gradient diagram of the hydrogen evolution reaction tower; (f) Tafel slope diagram of the oxygen evolution reaction.
FIG. 4 is a comparison graph of performance tests of FeCoNiCuZn high-entropy alloy and (FeCoNiCuZn) F high-entropy fluoride electrocatalysts prepared by the embodiment of the present invention; (a) Hydrogen evolution reaction 10mA cm -2 And a corresponding current density at-0.075V; (b) Oxygen evolution reaction 100mA cm -2 And a corresponding current density at 1.53V.
FIG. 5 is a graph comparing the electrocatalytic performance tests of (FeCoNiCuZn) F high-entropy fluoride electrocatalyst prepared by the present invention example with that of (FeCoNiCuZn) S, (FeCoNiCuZn) N, (FeCoNiCuZn) P prepared by the comparative example; (a) a hydrogen evolution reaction polarization curve; (b) oxygen evolution reaction polarization curve.
Detailed Description
It should be noted that the following detailed description of the embodiments is provided to better explain the contents of the present invention, but the contents of the present invention are not limited to the following embodiments. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
Examples
The invention provides a (FeCoNiCuZn) F high-entropy fluoride electrocatalyst.
A preparation method of a (FeCoNiCuZn) F high-entropy fluoride electrocatalyst comprises the following specific steps:
step 1, preparing precursor electrolyte:
(1) According to the molar ratio of metal ions Fe 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ =1:1:1:1:1 weighing corresponding FeCl 3 ·6H 2 O(2.7029g)、CoCl 2 (1.298g)、NiCl 2 ·6H 2 O(2.3769g)、CuCl 2 ·6H 2 O(1.7048g)、ZnCl 2 (1.363 g) and dissolving in 100mL of deionized water, covering a sealing film on a beaker filled with electrolyte, and stirring for 3-4 h on a magnetic stirrer until uniformly mixed precursor solution is obtained;
step 2, preparing the high-entropy alloy:
(1) Measuring a certain volume of the mixed precursor solution obtained in the step 1, placing the mixed precursor solution in an electrolytic cell, stably clamping the mixed precursor solution on a constant-temperature water bath kettle, adopting ammonia water or 0.1mol/L dilute hydrochloric acid as a pH regulator under the stirring state, uniformly regulating the pH value of the electrolyte to be 4 at the stirring speed of 200rpm, and heating the electrolyte to 40 ℃ in a water bath;
(2) Using a CHI760E electrochemical workstation, under a three-electrode system, taking foamed nickel as a working electrode, taking a graphite rod as a counter electrode, simultaneously clamping a working electrode clamp and a reference electrode clamp onto the working electrode, and putting the working electrode clamp and the reference electrode clamp into a precursor solution; and the foam nickel substrate needs to be placed 1-1.5 cm below the liquid level of the precursor solution and soaked for 30-60 s, and keeps a spacing distance of 2-2.5 cm with the graphite rod, a constant potential electrodeposition method is used, the deposition potential is-0.2V, and the deposition time is 900s;
wherein the dimensions of the nickel foam used are 20mm × 10mm × 1mm. And (3) ultrasonically pretreating the foamed nickel by using 0.5mol/L dilute HCl solution for less than or equal to 20min to remove oxides on the surface layer of the foamed nickel, repeatedly washing the foamed nickel by using deionized water and absolute ethyl alcohol for many times, and standing and drying the foamed nickel in the air for later use.
(3) After deposition is finished, deionized water and absolute ethyl alcohol are sequentially used for carrying out ultrasonic washing on the foamed nickel matrix loaded with the high-entropy alloy for multiple times, the ultrasonic washing time is 5-10 min, the foamed nickel matrix is kept stand and dried in the air for more than or equal to 24h, the FeCoNiCuZn high-entropy alloy uniformly deposited on the matrix is obtained, an XRD (X-ray diffraction) diagram is shown in figure 1, and an X-ray photoelectron spectrum high-resolution spectrum is shown in figure 2.
Step 3, fluorination treatment:
(1) Adjusting the temperature of a constant-temperature heating table to 250 ℃, weighing 2g of ammonium fluoride, placing the ammonium fluoride in a beaker, and placing the beaker on the constant-temperature heating table;
(2) And (3) after the ammonium fluoride is completely melted, placing the FeCoNiCuZn high-entropy alloy obtained in the step (2) into the melted ammonium fluoride for 60s, then quickly taking out and placing into deionized water, washing with the deionized water for multiple times to remove surface impurities, standing and drying in the air to obtain the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst, wherein an XRD (X-ray diffraction) diagram is shown in figure 1, and an X-ray photoelectron spectrum high-resolution spectrum is shown in figure 2.
The invention provides an application of a (FeCoNiCuZn) F high-entropy fluoride electrocatalyst in electrocatalysis hydrogen evolution reaction and oxygen evolution reaction under the alkaline condition of 1mol/L KOH:
cutting the prepared (FeCoNiCuZn) F high-entropy fluoride electrocatalyst into a working electrode with the thickness of 10mm multiplied by 10mm, wherein the loading amount of the (FeCoNiCuZn) F high-entropy fluoride on a foam nickel matrix is 4.8-5.2 mg-cm -2 The Ag/AgCl electrode is used as a reference electrode, and the graphite rod is used as a counter electrode. Using ShanghaiChen Hua electrochemical workstation CHI760E was used for electrocatalysis performance testing. The number of cycles of Cyclic Voltammetry (CV) was 20, and the scanning rate was 50 mV.s -1 . Sex scanning voltammetry (LSV) scan rate of 5 mV.s -1 The ohmic compensation is 90%. The test environment was 50 ℃.
From the XRD results in FIG. 1, the XRD results of the FeCoNiCuZn high-entropy alloy and the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst are consistent with that of the standard PDF card (85-1326), are cubic, have a space group of Fm-3m (225), and indicate that the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst is a stable face-centered cubic single-phase structure. The high resolution spectrogram of X-ray photoelectron of fig. 2 shows that each metal element exists uniformly, and the valence state of Fe has a certain deviation to the low binding energy position after F doping. In fig. 3, the performance of hydrogen evolution reaction and oxygen evolution reaction of the FeCoNiCuZn high-entropy alloy electrocatalyst and the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst are tested. The hydrogen evolution reaction of the high-entropy fluoride electrocatalyst (FeCoNiCuZn) F in the embodiment under the alkaline condition of 1mol/L KOH is measured at the current density of 10 mA-cm -2 The overpotential is 21mV, and the Tafel slope is 24.57mV dec -1 (ii) a Oxygen evolution reaction at current density of 100 mA-cm -2 The overpotential is 274mV, and the Tafel slope is 48.86mV dec -1 . The performance comparison in FIG. 4 shows that in the hydrogen evolution reaction, the current density of the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst is nearly 4 times higher than that of the FeCoNiCuZn high-entropy alloy electrocatalyst at-0.075V, and at 10 mA. Cm. Simultaneously -2 The overpotential of the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst is much lower than that of the FeCoNiCuZn high-entropy alloy electrocatalyst at the current density of (FeCoNiCuZn), which shows that the hydrogen evolution reaction performance is greatly improved after fluorination treatment. For the oxygen evolution reaction, the current density of the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst is improved to a certain extent compared with that of a FeCoNiCuZn high-entropy alloy electrocatalyst at the potential of 1.53V, and meanwhile, the current density is increased to 100 mA-cm -2 The overpotential of the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst is reduced to a certain extent compared with that of a FeCoNiCuZn high-entropy alloy electrocatalyst under the current density of (FeCoNiCuZn). Further shows that the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst has excellent hydrogen evolution reaction and oxygen evolution reaction dual-function electrocatalysis performance.
Example 2
The difference from the example 1 is that in the process of preparing the high-entropy alloy, the pH value of the electrolyte is controlled to be 4.5, and the electrolyte is heated to 42 ℃; the deposition potential range was-0.25V and the deposition time was 850s.
Example 3
The same as example 1, except that the deposition potential was in the range of-0.25V and the deposition time was 800s.
Example 4
The same as example 1, except that the pH of the electrolyte was controlled at 4.2, and the electrolyte was heated to 45 ℃; the deposition potential range was-0.21V and the deposition time was 820s.
Example 5
The difference from the embodiment 1 is that the pH value of the electrolyte is controlled to be 4-4.5, and the electrolyte is heated to 40-45 ℃; the deposition potential range was-0.15V and the deposition time was 860s.
Comparative example 1
Ammonium fluoride is replaced by nitride (melamine), and the difference is that the nitriding process is carried out in a tube furnace filled with argon atmosphere, and the obtained nitride is (FeCoNiCuZn) N high-entropy nitride. In fig. 5, the hydrogen evolution reaction and oxygen evolution reaction performance of the (FeCoNiCuZn) N high entropy nitride is relatively poor compared to the (FeCoNiCuZn) F high entropy fluoride.
Comparative example 2
Ammonium fluoride was replaced by phosphide (sodium hypophosphite), except that the phosphating process was carried out in a tube furnace with argon atmosphere to obtain (FeCoNiCuZn) P high-entropy phosphide, which has relatively poor performance in hydrogen evolution and oxygen evolution compared to (FeCoNiCuZn) F high-entropy fluoride in fig. 5.
Comparative example 3
The difference between the substitution of ammonium fluoride with sulphide (thiourea) and the fact that the sulphiding process was carried out in a tube furnace with argon atmosphere, resulting in a (FeCoNiCuZn) P high entropy sulphide, is that in fig. 5 the hydrogen evolution and oxygen evolution reaction performance of the (FeCoNiCuZn) N high entropy nitride is relatively poor compared to the (FeCoNiCuZn) F high entropy fluoride.
In conjunction with all of the above comparative examples, (FeCoNiCuZn) F > (FeCoNiCuZn) S > (FeCoNiCuZn) P > (FeCoNiCuZn) N for hydrogen evolution reaction performance; for oxygen evolution reaction performance, (FeCoNiCuZn) F > (FeCoNiCuZn) P > (FeCoNiCuZn) N ≈ FeCoNiCuZn) S. Results show that compared with other chemical modification treatments, the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst prepared by fluoridation of FeCoNiCuZn high-entropy alloy has more excellent hydrogen evolution reaction and oxygen evolution reaction dual-function electrocatalytic activity.
The above description is only a preferred embodiment of the present invention, and there is no limitation to the present invention, and various modifications and changes may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The (FeCoNiCuZn) F high-entropy fluoride electrocatalyst is characterized in that the molar ratio of metal ions in the adopted precursor solution is Fe 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ =1:1:1:1:1, wherein, 10cm 3 The molar weight of the FeCoNiCuZn high-entropy alloy added with the fluorine-containing compound is 0.054-0.067 mol.
2. A (FeCoNiCuZn) F high entropy fluoride electrocatalyst according to claim 1, characterized in that the fluorine containing compound is ammonium fluoride.
3. A (FeCoNiCuZn) F high entropy fluoride electrocatalyst according to claim 1, characterized in that the structure of the (FeCoNiCuZn) F high entropy fluoride electrocatalyst is cubic, fm-3m space group.
4. The (FeCoNiCuZn) F high-entropy fluoride electrocatalyst according to claim 1, characterized in that the hydrogen evolution reaction of the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst is measured at a current density of 10 mA-cm under 1mol/LKOH alkaline conditions -2 The overpotential of time is 21mV, and the Tafel slope is 24.57mV dec -1 (ii) a The current density is 100 mA-cm measured by oxygen evolution reaction -2 The overpotential is 274mV, the Tafel slope is 48.86mV dec -1 。
5. A preparation method of a (FeCoNiCuZn) F high-entropy fluoride electrocatalyst is characterized in that Fe is adopted according to the molar ratio of metal ions 3+ ：Co 2+ ：Ni 2+ ：Cu 2+ ：Zn 2+ =1:1:1:1:1 preparing a precursor solution, carrying out electrodeposition, forming FeCoNiCuZn high-entropy alloy on a porous conductive foamed nickel matrix, and carrying out fluorination treatment on the alloy to form the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst.
6. Method for the preparation of a (FeCoNiCuZn) F high entropy fluoride electrocatalyst according to claim 5, characterized in that it comprises the steps of:
step 1, preparing a precursor solution:
weighing corresponding FeCl according to the molar ratio of metal ions 3 ·6H 2 O、CoCl 2 、NiCl 2 ·6H 2 O、CuCl 2 ·6H 2 O、ZnCl 2 Mixing, dissolving in deionized water, and stirring to obtain precursor solution;
step 2, preparing the high-entropy alloy:
(1) Taking the precursor solution as electrolyte of an electrolytic cell, controlling the pH value of the electrolyte to be 4-4.5, and heating to 40-45 ℃;
(2) Under a three-electrode system, foam nickel is used as a working electrode, a graphite rod is used as a counter electrode, constant potential electrodeposition is carried out, the deposition potential range is minus 0.2 +/-0.05V, and the deposition time is 800-900 s;
(3) After the deposition is finished, carrying out ultrasonic cleaning on the foamed nickel electrode deposited with the FeCoNiCuZn high-entropy alloy, and then standing and drying in the air to obtain the FeCoNiCuZn high-entropy alloy uniformly deposited on the foamed nickel;
step 3, fluorination treatment by a molten salt method:
(1) Weighing ammonium fluoride according to the molar weight of fluorine in the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst, and heating and melting to obtain molten ammonium fluoride;
(2) And (2) placing the FeCoNiCuZn high-entropy alloy into molten ammonium fluoride for fluorination treatment to obtain the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst.
7. The preparation method of the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst according to claim 5, characterized in that, in the step 1, the total metal ion concentration in the precursor solution is in the range of 0.1-0.5 mol/L.
8. The preparation method of the (FeCoNiCuZn) F high-entropy fluoride electrocatalyst according to claim 5, wherein in the step 2 (1), the process of controlling the pH value of the electrolyte at 4-4.5 is as follows: under the stirring state, ammonia water or 0.1mol/L dilute hydrochloric acid is used as a pH regulator to regulate the pH value of the electrolyte to 4-4.5, and the stirring speed is 200-300 rpm.
9. The method for preparing a (FeCoNiCuZn) F high-entropy fluoride electrocatalyst according to claim 5, wherein in the step 2 (2), the working electrode holder and the reference electrode holder are simultaneously clamped to the working electrode; the foam nickel substrate needs to be placed 1-1.5 cm below the liquid level of the precursor solution and soaked for 30-60 s, and the spacing distance between the foam nickel substrate and the graphite rod is kept 2-2.5 cm.
10. The method for preparing a (FeCoNiCuZn) F high-entropy fluoride electrocatalyst according to claim 5, characterized in that, in step 3 (1), the heating melting temperature is maintained at 240-250 ℃, and 2-2.5 g of ammonium fluoride mass can be fluorinated to 5 FeCoNiCuZn high-entropy alloys with dimensions of 20mm x 10mm x 1mm.
CN202310047413.4A 2023-01-31 2023-01-31 (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and preparation method thereof Pending CN115961305A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310047413.4A CN115961305A (en) 2023-01-31 2023-01-31 (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310047413.4A CN115961305A (en) 2023-01-31 2023-01-31 (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and preparation method thereof

Publications (1)

Publication Number Publication Date
CN115961305A true CN115961305A (en) 2023-04-14

Family

ID=87363788

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310047413.4A Pending CN115961305A (en) 2023-01-31 2023-01-31 (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115961305A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116510756A (en) * 2023-04-28 2023-08-01 广东工业大学 High-entropy fluoride quantum dot nano-enzyme, preparation method and biochemical detection application thereof
CN116715281A (en) * 2023-06-01 2023-09-08 南京工业大学 High-entropy fluoride composite asphalt-based carbon material and preparation method and application thereof
CN117026257A (en) * 2023-10-10 2023-11-10 河南师范大学 Preparation method of zinc-nitrate radical battery based on high-entropy oxide

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116510756A (en) * 2023-04-28 2023-08-01 广东工业大学 High-entropy fluoride quantum dot nano-enzyme, preparation method and biochemical detection application thereof
CN116510756B (en) * 2023-04-28 2023-10-03 广东工业大学 High-entropy fluoride quantum dot nano-enzyme, preparation method and biochemical detection application thereof
CN116715281A (en) * 2023-06-01 2023-09-08 南京工业大学 High-entropy fluoride composite asphalt-based carbon material and preparation method and application thereof
CN116715281B (en) * 2023-06-01 2024-04-12 南京工业大学 High-entropy fluoride composite asphalt-based carbon material and preparation method and application thereof
CN117026257A (en) * 2023-10-10 2023-11-10 河南师范大学 Preparation method of zinc-nitrate radical battery based on high-entropy oxide
CN117026257B (en) * 2023-10-10 2024-01-09 河南师范大学 Preparation method of zinc-nitrate radical battery based on high-entropy oxide

Similar Documents

Publication Publication Date Title
Gao et al. Electrochemical fabrication of porous Ni-Cu alloy nanosheets with high catalytic activity for hydrogen evolution
Hoang et al. High activity oxygen evolution reaction catalysts from additive-controlled electrodeposited Ni and NiFe films
CN115961305A (en) (FeCoNiCuZn) F high-entropy fluoride electrocatalyst and preparation method thereof
CN110205636B (en) Preparation method of self-supporting three-dimensional porous structure bifunctional catalytic electrode
Subramanya et al. Novel Co–Ni–graphene composite electrodes for hydrogen production
Jović et al. Kinetics of the oxygen evolution reaction on NiSn electrodes in alkaline solutions
CN110484934B (en) Preparation method of nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material
EP2377971A1 (en) Amorphous transition metal sulphide films or solids as efficient electrocatalysts for hydrogen production from water or aqueous solutions
Elias et al. Synthesis and characterization of Ni-P-Ag composite coating as efficient electrocatalyst for alkaline hydrogen evolution reaction
CN111545227A (en) 3D nanosheet network structure bimetallic phosphorus oxide electrocatalyst and preparation method and application thereof
Lucas et al. Electrodeposited Tin‐Antimony Alloys as Novel Electrocatalysts for Selective and Stable Carbon Dioxide Reduction to Formate
Ghahremani et al. Simultaneous hydrogen evolution and lignin depolymerization using NiSn electrocatalysts in a biomass-depolarized electrolyzer
CN111334820A (en) Low-cost and high-efficiency Ni-P series hydrogen evolution electrode and preparation method thereof
Oh et al. Activity and stability of Ir-based gas diffusion electrode for proton exchange membrane water electrolyzer
CN112981449B (en) Ordered PEM water electrolysis membrane electrode anode catalyst layer and preparation method and application thereof
CN110644016B (en) Preparation method of nickel phosphide-carbon cloth self-supporting electrode for hydrogen evolution by water and electricity dissociation
KR20150103864A (en) method of preparing electrocatalyst for hydrogen production in alkaline water electrolysis, method for controlling a electrocatalyst composition by changing electrolysis condition and electrocatalyst for hydrogen production in alkaline water electrolysis thereby
Peng et al. Niobium‐Incorporated CoSe2 Nanothorns with Electronic Structural Alterations for Efficient Alkaline Oxygen Evolution Reaction at High Current Density
Liu et al. Electrodeposition of Iridium-Nickel Thin Films on Copper Foam: Effects of Loading and Solution Temperature on Hydrogen Evolution Reaction Performance of Electrocatalyst in Alkaline Water: Improved performance and stability of catalyst for hydrogen energy applications
CN112023926B (en) Electro-catalytic hydrogen evolution material and preparation method and application thereof
CN115466979B (en) Preparation method of nickel-cobalt-phosphorus electrocatalyst for high-efficiency electrolysis of water to hydrogen
CN116288477A (en) Double-function high-entropy nano alloy electrocatalyst and preparation method thereof
Li et al. Electrodeposition of Ni‐P alloy from deep eutectic solvent and its electrocatalytic activity toward hydrogen evolution reaction
US7879750B2 (en) Anodes for alkaline electrolysis
JP2006118022A (en) Electrode for generating hydrogen, precursor of electrode for generating hydrogen, manufacturing method therefor, and electrolysis method using it

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination