CN114836714A - FeCoNiMn high-entropy alloy film, and preparation method and application thereof - Google Patents

FeCoNiMn high-entropy alloy film, and preparation method and application thereof Download PDF

Info

Publication number
CN114836714A
CN114836714A CN202210479105.4A CN202210479105A CN114836714A CN 114836714 A CN114836714 A CN 114836714A CN 202210479105 A CN202210479105 A CN 202210479105A CN 114836714 A CN114836714 A CN 114836714A
Authority
CN
China
Prior art keywords
entropy alloy
feconimn
alloy film
percent
sputtering
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.)
Granted
Application number
CN202210479105.4A
Other languages
Chinese (zh)
Other versions
CN114836714B (en
Inventor
方峰
丁富远
张泽灵
徐邦利
翁诗雅
周雪峰
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.)
Southeast University
Original Assignee
Southeast University
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 Southeast University filed Critical Southeast University
Priority to CN202210479105.4A priority Critical patent/CN114836714B/en
Publication of CN114836714A publication Critical patent/CN114836714A/en
Application granted granted Critical
Publication of CN114836714B publication Critical patent/CN114836714B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • 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
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a FeCoNiMn high-entropy alloy film, a preparation method and application thereof, wherein the high-entropy alloy film comprises the following components in percentage by mass: 23.1 to 36.8 percent of Fe, 16.9 to 48.9 percent of Co, 7.4 to 20.4 percent of Ni and 7.6 to 38.9 percent of Mn. The preparation method comprises the steps of splicing target raw materials into a sputtering target by adopting a radio frequency magnetron sputtering method, and sputtering and depositing a FeCoNiMn high-entropy alloy film on the surface of a substrate by taking at least one protective gas as a working gas. The amorphous FeCoNiMn high-entropy alloy film electrode material is prepared by a radio frequency magnetron sputtering process, the film is well combined with a substrate, the catalytic activity is higher, 97% of organic matters can be electrochemically catalytically degraded within 60min, and a foundation is laid for the application of the high-entropy alloy film in the aspect of electrically catalytically degrading organic matter wastewater.

Description

FeCoNiMn high-entropy alloy film, and preparation method and application thereof
Technical Field
The invention relates to a high-entropy alloy material, a preparation method and application thereof, in particular to a FeCoNiMn high-entropy alloy film, a preparation method and application thereof.
Background
With the continuous development of modern industry, the harmful components in industrial wastewater are gradually complicated, and azo dyes are one of the common components. At present, the catalyst for degrading azo dyes in commercial use can not mineralize organic pollutants, so that organic matters containing benzene rings are generated, and the organic matters are difficult to recycle. Common RuO with better catalytic performance 2 、IrO 2 Expensive material, PbO 2 、SnO 2 It pollutes the environment, which limits the application of the above materials. Therefore, the development of a catalytic material with good catalytic performance, low price and environmental friendliness is urgently needed.
When the high-entropy alloy is firstly proposed, the design concept that the traditional alloy is mainly composed of one or two elements is broken through, and five or more elements are used for forming the multi-principal-element alloy. The atomic percentage of each element in the high-entropy alloy is between 5 and 35 percent, and the mixed entropy value delta S is more than 1.61R. The high-entropy alloy has multiple forms of solid solution or amorphous, and has lower free energy and higher phase stability. The special component design and phase structure endow the high-entropy alloy with the properties of high strength, high wear resistance, high catalytic activity and the like.
As a novel alloy film material, the high-entropy alloy film has high catalytic activity, and particularly the catalytic performance of the FeCoNi-based non-noble metal high-entropy alloy film can be comparable with that of a noble metal electrocatalyst. The high-entropy alloy film material can be used as an anode material for electrocatalytic oxidation degradation of organic pollutants, thoroughly mineralizes the organic pollutants by an advanced oxidation technology, and has the effects of simple equipment, high energy efficiency, air floatation, flocculation, sterilization and the like.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a FeCoNiMn high-entropy alloy film with high catalytic activity;
the second purpose of the invention is to provide a preparation method of the FeCoNiMn high-entropy alloy film;
the third purpose of the invention is to provide the application of the FeCoNiMn high-entropy alloy film in electrode materials.
The technical scheme is as follows: the FeCoNiMn high-entropy alloy film comprises the following components in percentage by mass: 23.1 to 36.8 percent of Fe, 16.9 to 48.9 percent of Co, 7.4 to 20.4 percent of Ni and 7.6 to 38.9 percent of Mn.
According to the preparation method of the FeCoNiMn high-entropy alloy film, the target raw materials are spliced into the sputtering target by adopting a radio frequency magnetron sputtering method, and the FeCoNiMn high-entropy alloy film is sputtered and deposited on the surface of the matrix by taking at least one protective gas as a working gas. The method specifically comprises the following steps:
(1) matrix pretreatment:
polishing the matrix, performing alkali washing, and then performing acid washing and etching to increase the surface roughness of the matrix;
(2) preparing a sputtering target material:
splicing four transition metal element raw materials into a sputtering target material, and then putting the target material and a substrate into corresponding positions in a sputtering chamber;
(3) and (3) film deposition:
and vacuumizing the sputtering chamber, introducing working gas, performing pre-sputtering, and moving the substrate above the target material to perform sputtering deposition on the high-entropy alloy film.
Wherein, in the step (1), a titanium sheet is selected as a base material for magnetron sputtering; polishing the substrate by using sand paper with different meshes, and polishing the sharp part of the edge of the substrate by using 240-400-mesh sand paper to eliminate the point discharge of the edge; then, using 600-sand 800-mesh sand paper to polish the surface of the substrate to remove the oxide layer; finally, 180-sand 240-mesh sand paper is used for polishing the surface of the substrate, so that the surface roughness of the substrate is increased, and the film-substrate binding force is improved; performing ultrasonic alkaline washing by using NaOH solution to remove oil stains on the surface of the substrate, wherein the concentration of the NaOH solution is preferably 30-40 wt%; using H 2 C 2 O 4 The solution is subjected to ultrasonic acid cleaning and etching, and H 2 C 2 O 4 The concentration of the solution is 5-10 wt.%; the alkaline washing and acid washing time is 1.5-2 h; the ultrasonic temperature of the acid washing and the alkali washing is 70-80 ℃.
In the step (2), the splicing proportion of Fe plates in the sputtering target material is 90-120 degrees; the splicing proportion of the Co target is 60-90 degrees; the splicing proportion of the Ni sheets is 60-90 degrees; the splicing proportion of the Mn target is between 90 and 120 degrees.
Wherein in the step (3), the sputtering power is 40-80W; the sputtering time is 1-3 h. Wherein the sputtering chamber is evacuated to 5 × 10 -4 ～6×10 -4 Pa; the working gas is argon; the concentration of the argon is 99.00-99.99%, the flow of the argon is 20-30 sccm, and the working pressure is 0.5-1 Pa.
The invention provides an application of the FeCoNiMn high-entropy alloy film in an electrode material.
The FeCoNiMn high-entropy alloy film material is of an amorphous structure, and a large number of pits and bulges are formed on the surface of the film. The high-entropy alloy film can be made into 20mm multiplied by 30mm multiplied by 1mm anode, stainless steel sheet with the same size is used as cathode, 0.1M Na is used 2 SO 4 The solution was used as electrolyte, the distance between the electrodes was 20mm, and the current density was 2.5mA/cm 2 97 percent of 50mg/L methyl orange solution can be electro-catalytically degraded within 60 min.
Has the advantages that: compared with the prior art, the invention has the following remarkable effects: (1) the FeCoNiMn high-entropy alloy film has high catalytic activity; (2) through a magnetron sputtering method, the target material is composed of an Fe sheet, an Ni sheet, a Co target and an Mn target according to the Fe sheet angle of 90-120 degrees; co target 60-90 degree; ni sheet 60-90 degree; the Mn target is spliced at 90-120 degrees, so that the required high-entropy alloy film component and the uniformity of the film component obtained by subsequent sputtering are ensured; (3) according to the invention, the radio frequency magnetron sputtering power is controlled to be 40W-80W, the sputtering time is 1 h-3 h, the FeCoNiMn high-entropy alloy film is deposited on the surface of the matrix, and the film is well combined with the substrate, has a high specific surface area and simultaneously has high catalytic activity. (4) The invention is used as an electrode material, and after 60min of catalytic degradation, the removal efficiency of the organic methyl orange can reach 97%.
Drawings
FIG. 1 is a composition diagram of FeCoNiMn high entropy alloy film deposited under different sputtering conditions;
FIG. 2 is an XRD pattern of FeCoNiMn high entropy alloy thin film deposited under different sputtering conditions;
FIG. 3 is an SEM image of a FeCoNiMn high-entropy alloy thin film with sputtering power of 80W and sputtering time of 1 h;
FIG. 4 is a schematic view of an FeCoNiMn high-entropy alloy film as an anode material for electrocatalytic degradation of methyl orange;
FIG. 5 is a graph of the catalytic degradation efficiency of FeCoNiMn high-entropy alloy thin films deposited under different sputtering powers on methyl orange.
Detailed Description
The present invention is described in further detail below.
Example 1
A preparation method of a FeCoNiMn high-entropy alloy film with high catalytic activity comprises the following components in percentage by mass: 23.1 percent of Fe, 48.9 percent of Co, 20.4 percent of Ni and 7.6 percent of Mn. Preparing a high-entropy alloy film by adopting a radio frequency magnetron sputtering technology, and determining the raw material ratio of target elements by target splicing; then, pre-sputtering the target material, wherein argon is used as working gas during pre-sputtering; depositing a FeCoNiMn high-entropy alloy film on the surface of the cleaned titanium sheet substrate; before the titanium plate substrate is used, alkali washing is needed to remove oil, and acid washing and etching are needed to increase the specific surface area.
The specific process is as follows:
(1) polishing the titanium sheet substrate by using different abrasive papers to remove sharp edges and oxide layers, cleaning the titanium sheet substrate by using NaOH solution for 2H, and using H 2 C 2 O 4 After the titanium sheet substrate is etched by the solution for 2 hours, the residual solution is cleaned by deionized water, and the titanium sheet substrate is dried by nitrogen and placed into a sputtering chamber for later use.
(2) Four transition metal raw materials of an Fe sheet, an Ni sheet, a Co target and a Mn target are spliced into a sputtering target material according to equal proportion.
(3) And pre-sputtering the target to remove pollutants on the surface of the target. During pre-sputtering, the vacuum degree is kept at 6X 10 - 4 Pa, the working gas is argon, the purity is 99.99%, the working pressure is 0.5Pa, and the pre-sputtering time is 10 min.
(4) And depositing a FeCoNiMn high-entropy alloy film on the cleaned and dried titanium sheet substrate. The vacuum degree is kept at 6 multiplied by 10 during the radio frequency magnetron sputtering -4 Pa, the working gas is argon, the purity is 99.99%, the argon flow is 30sccm, the working pressure is 0.5Pa, the magnetron sputtering power is adjusted to be 40W, and the sputtering time is 1 h.
The thickness of the FeCoNiMn high-entropy alloy film is 677 nm.
Making the high-entropy alloy film into an anode with a diameter of 20mm multiplied by 30mm multiplied by 1mm, taking a stainless steel sheet with the same size as a cathode, and taking 0.1M Na 2 SO 4 The solution is used as electrolyte, and 50mg/L methyl orange solution is used as a target pollutant for catalytic degradation. The distance between the electrodes was 20mm, and the current density was 2.5mA/cm 2 . The degradation efficiency of the catalytic degradation organic matter after 1 hour is measured and calculated to be 97%.
Example 2
A preparation method of a FeCoNiMn high-entropy alloy film with high catalytic activity comprises the following components in percentage by mass: 35.9 percent of Fe, 27.4 percent of Co, 13.8 percent of Ni and 22.9 percent of Mn. Preparing a high-entropy alloy film by adopting a radio frequency magnetron sputtering technology, and determining the raw material ratio of target elements by target splicing; then, pre-sputtering the target material, wherein argon is used as working gas during pre-sputtering; depositing a FeCoNiMn high-entropy alloy film on the surface of the cleaned titanium sheet substrate; before the titanium plate substrate is used, alkali washing is needed to remove oil, and acid washing and etching are needed to increase the specific surface area.
The specific process is as follows:
(1) polishing the titanium sheet substrate by using different abrasive papers to remove sharp edges and oxide layers, cleaning the titanium sheet substrate by using NaOH solution for 2H, and using H 2 C 2 O 4 After the titanium plate substrate is etched by the solution for 2 hours, the residual solution is washed by deionized water, and the titanium plate substrate is dried by nitrogen and is placed into a sputtering chamber for standby.
(2) The sputtering target material is prepared by splicing four transition metal raw materials of Fe sheet, Ni sheet, Co target and Mn target according to the proportion of Fe120 degrees, Ni60 degrees, Co60 degrees and Mn120 degrees.
(3) And (4) pre-sputtering the target material to remove pollutants on the surface of the target material. During pre-sputtering, the vacuum degree is kept at 6X 10 - 4 Pa, the working gas is argon, the purity is 99.99%, the working pressure is 0.5Pa, and the pre-sputtering time is 10 min.
(4) Cleaning in clearAnd depositing a FeCoNiMn high-entropy alloy film on the titanium sheet substrate subjected to washing and drying. The vacuum degree is kept at 6 multiplied by 10 during the radio frequency magnetron sputtering -4 Pa, the working gas is argon, the purity is 99.99%, the argon flow is 30sccm, the working pressure is 0.5Pa, the magnetron sputtering power is adjusted to be 80W, and the sputtering time is 3 h.
The thickness of the FeCoNiMn high-entropy alloy film is 1909 nm.
Making the high-entropy alloy film into an anode with a diameter of 20mm multiplied by 30mm multiplied by 1mm, taking a stainless steel sheet with the same size as a cathode, and taking 0.1M Na 2 SO 4 The solution is used as electrolyte, and 50mg/L methyl orange solution is used as a target pollutant for catalytic degradation. The distance between the electrodes was 20mm, and the current density was 2.5mA/cm 2 . The degradation efficiency of the catalytic degradation organic matter after 1 hour is measured and calculated to be 90%.
Example 3
A preparation method of a FeCoNiMn high-entropy alloy film with high catalytic activity comprises the following components in percentage by mass: 36.8 percent of Fe, 16.9 percent of Co, 7.4 percent of Ni and 38.9 percent of Mn. Preparing a high-entropy alloy film by adopting a radio frequency magnetron sputtering technology, and determining the raw material ratio of target elements by target splicing; then, pre-sputtering the target material, wherein argon is used as working gas during pre-sputtering; depositing a FeCoNiMn high-entropy alloy film on the surface of the cleaned titanium sheet substrate; before the titanium plate substrate is used, alkali washing is needed to remove oil, and acid washing and etching are needed to increase the specific surface area.
The specific process is as follows:
(1) polishing the titanium sheet substrate by using different abrasive papers to remove sharp edges and oxide layers, cleaning the titanium sheet substrate by using NaOH solution for 2H, and using H 2 C 2 O 4 After the titanium sheet substrate is etched by the solution for 2 hours, the residual solution is cleaned by deionized water, and the titanium sheet substrate is dried by nitrogen and placed into a sputtering chamber for later use.
(2) Four transition metal raw materials of an Fe sheet, an Ni sheet, a Co target and a Mn target are spliced into a sputtering target material according to equal proportion.
(3) And pre-sputtering the target to remove pollutants on the surface of the target. During pre-sputtering, the vacuum degree is kept at 6X 10 - 4 Pa, argon as working gas, purity of 99.99%, and working pressure of 0.5Pand a, the pre-sputtering time is 10 min.
(4) And depositing a FeCoNiMn high-entropy alloy film on the cleaned and dried titanium sheet substrate. The vacuum degree is kept at 6 multiplied by 10 during the radio frequency magnetron sputtering -4 Pa, the working gas is argon gas, the purity is 99.99%, the argon gas flow is 30sccm, the working pressure is 0.5Pa, the magnetron sputtering power is adjusted to be 80W, and the pre-sputtering time is 1 h.
The thickness of the FeCoNiMn high-entropy alloy film is tested to be 756 nm.
Making the high-entropy alloy film into 20mm × 30mm × 1mm anode, using stainless steel sheet with the same size as cathode, and 0.1M Na 2 SO 4 The solution is used as electrolyte, and 50mg/L methyl orange solution is used as a target pollutant for catalytic degradation. The distance between the electrodes was 20mm, and the current density was 2.5mA/cm 2 . The degradation efficiency of the catalytic degradation organic matter after 1 hour is measured and calculated to be 81 percent.
Comparative example 1
The comparative example provides a preparation method of a FeCoNiMn high-entropy alloy film material, and the difference between the comparative example and the example 1 is that the obtained high-entropy alloy film comprises the following components in percentage by mass: 18.3 percent of Fe, 43.7 percent of Co, 30.5 percent of Ni and 7.6 percent of Mn. The sputtering power of the sputtering deposition of the comparative example is 100W, so that the composition of the obtained high-entropy alloy thin film is different from that of the embodiment 1, and the rest is the same as that of the embodiment 1. The high-entropy alloy film obtained by the comparative example is used for electrocatalytic degradation of methyl orange, and the degradation efficiency of the high-entropy alloy film after 1h of catalytic degradation of organic matters is 55 percent and is lower than that of the high-entropy alloy film obtained by the example 1.
Comparative example 2
The comparative example provides a preparation method of a FeCoNiMn high-entropy alloy film material, and the difference between the comparative example and the example 2 is that the obtained high-entropy alloy film comprises the following components in percentage by mass: 34.4 percent of Fe, 38.2 percent of Co, 6.7 percent of Ni and 20.7 percent of Mn. The sputtering time of the sputtering deposition of the comparative example is 5 hours, so that the components of the obtained high-entropy alloy thin film are different from those of the embodiment 2, and the rest is the same as the embodiment 2. The high-entropy alloy film obtained by the comparative example is used for electrocatalytic degradation of methyl orange, and the degradation efficiency of the high-entropy alloy film after 1h of catalytic degradation of organic matters is 58% which is lower than that of the high-entropy alloy film obtained by the example 2.
Comparative example 3
The comparative example provides a preparation method of a FeCoNiMn high-entropy alloy film material, and the difference between the comparative example and the example 3 is that the obtained high-entropy alloy film comprises the following components in percentage by mass: 33.4 percent of Fe, 25.8 percent of Co, 28.5 percent of Ni and 12.3 percent of Mn. In the sputtering deposition of the comparative example, the sputtering target is formed by blending the raw materials of the sputtering target according to the proportion of Fe120 degrees, Ni60 degrees, Co60 degrees and Mn120 degrees, so that the components of the obtained high-entropy alloy film are different from those of the high-entropy alloy film obtained in the example 3, and the rest is the same as that of the high-entropy alloy film obtained in the example 3. The high-entropy alloy film obtained by the comparative example is used for electrocatalytic degradation of methyl orange, and the degradation efficiency of the high-entropy alloy film after 1h of catalytic degradation of organic matters is 59 percent and is lower than that of the high-entropy alloy film obtained by the example 3.
Comparative example 4
The comparative example provides a preparation method of a FeCoNiMn high-entropy alloy film material, and the difference between the comparative example and the example 1 is that the obtained high-entropy alloy film comprises the following components in percentage by mass: 39.1 percent of Fe, 23.5 percent of Co, 27.2 percent of Ni and 10.2 percent of Mn. The sputtering power of the sputtering deposition of the comparative example is 30W, so that the composition of the obtained high-entropy alloy thin film is different from that of the embodiment 1, and the rest is the same as that of the embodiment 1. The high-entropy alloy film obtained by the comparative example is used for electrocatalytic degradation of methyl orange, and the degradation efficiency of the high-entropy alloy film after 1h of catalytic degradation of organic matters is 43 percent and is lower than that of the high-entropy alloy film obtained by the example 1.
Comparative example 5
The comparative example provides a preparation method of a FeCoNiMn high-entropy alloy film material, and the difference between the comparative example and the example 3 is that the obtained high-entropy alloy film comprises the following components in percentage by mass: 42.6 percent of Fe, 25.7 percent of Co, 15.8 percent of Ni and 15.9 percent of Mn. The sputtering time of the sputtering deposition of the comparative example is 0.5h, so that the composition of the obtained high-entropy alloy thin film is different from that of the example 3, and the rest is the same as that of the example 3. The high-entropy alloy film obtained by the comparative example is used for electrocatalytic degradation of methyl orange, and the degradation efficiency of the high-entropy alloy film after 1h of catalytic degradation of organic matters is 51 percent and is lower than that of the high-entropy alloy film obtained by the example 3.
The FeCoNiMn high-entropy alloy thin films obtained by deposition in the above examples 1-3 were subjected to composition measurement, and the specific data are shown in FIG. 1. Comprises the following components in percentage by mass: 23.1 to 36.8 percent of Fe, 16.9 to 48.9 percent of Co, 7.4 to 20.4 percent of Ni and 7.6 to 38.9 percent of Mn.
XRD spectrum measurement is carried out on the FeCoNiMn high-entropy alloy thin films obtained by deposition in the above examples 1-3, and the result is shown in figure 2, when the sputtering power is 80W and the sputtering time is 1h, a relatively obvious high-entropy alloy diffraction peak exists, and the diffraction peak is widened due to smaller crystal grains, which corresponds to example 3.
The surface topography of the FeCoNiMn high-entropy alloy thin film obtained by deposition in the above examples 1-3 was measured, and the result is shown in FIG. 3, where FIG. 3 is the surface topography of the high-entropy alloy thin film with a sputtering power of 80W and a sputtering time of 1h, corresponding to example 3. It can be seen that the surface of the film has a large number of recesses and projections, increasing the specific surface area.
The FeCoNiMn high entropy alloy thin film obtained by deposition in the above examples 1-3 is subjected to electrocatalytic oxidation organic matter methyl orange performance measurement, and the schematic diagram is shown in FIG. 4. FIG. 5 shows the result of electrocatalytic oxidation of methyl orange by FeCoNiMn high-entropy alloy thin film, and it can be seen from the figure that after 60min of catalytic degradation, the degradation rate of the high-entropy alloy thin film with sputtering power of 40W and sputtering time of 1h is 97%, the degradation rate of the high-entropy alloy thin film with sputtering power of 80W and sputtering time of 3h is 90%, and the degradation rate of the high-entropy alloy thin film with sputtering power of 80W and sputtering time of 1h is 81%.

Claims (9)

1. The FeCoNiMn high-entropy alloy film is characterized by comprising the following components in percentage by mass: 23.1 to 36.8 percent of Fe, 16.9 to 48.9 percent of Co, 7.4 to 20.4 percent of Ni and 7.6 to 38.9 percent of Mn.
2. A preparation method of the FeCoNiMn high-entropy alloy film in the claim 1, characterized in that the target material is spliced into a sputtering target material by a radio frequency magnetron sputtering method, and at least one protective gas is used as a working gas to sputter and deposit the FeCoNiMn high-entropy alloy film on the surface of a substrate.
3. The method for preparing the FeCoNiMn high-entropy alloy film according to claim 2, wherein the splicing proportion of Fe plates in the sputtering target material is 90-120 degrees; the splicing proportion of the Co target is 60-90 degrees; the splicing proportion of the Ni sheets is 60-90 degrees; the splicing proportion of the Mn target is between 90 and 120 degrees.
4. The method for preparing the FeCoNiMn high-entropy alloy thin film according to claim 2, wherein the sputtering power is 40W-80W.
5. The method for preparing the FeCoNiMn high-entropy alloy thin film according to claim 2, wherein the sputtering time is 1-3 h.
6. The method for preparing the FeCoNiMn high-entropy alloy thin film according to claim 2, wherein the substrate is a titanium sheet.
7. The method for preparing a FeCoNiMn high-entropy alloy thin film according to claim 2, wherein the working gas is argon.
8. The method for preparing the FeCoNiMn high-entropy alloy thin film according to claim 7, wherein the concentration of the argon gas is 99.00-99.99%, the flow rate of the argon gas is 20-30 sccm, and the working pressure is 0.5-1 Pa.
9. An application of the FeCoNiMn high-entropy alloy film of claim 1 in an electrode material.
CN202210479105.4A 2022-05-05 2022-05-05 FeCoNiMn high-entropy alloy film, and preparation method and application thereof Active CN114836714B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210479105.4A CN114836714B (en) 2022-05-05 2022-05-05 FeCoNiMn high-entropy alloy film, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210479105.4A CN114836714B (en) 2022-05-05 2022-05-05 FeCoNiMn high-entropy alloy film, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN114836714A true CN114836714A (en) 2022-08-02
CN114836714B CN114836714B (en) 2023-10-03

Family

ID=82568007

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210479105.4A Active CN114836714B (en) 2022-05-05 2022-05-05 FeCoNiMn high-entropy alloy film, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114836714B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116162842A (en) * 2023-02-21 2023-05-26 昆明理工大学 High Jiang Gaoshang alloy and preparation method thereof
CN116288219A (en) * 2023-05-19 2023-06-23 西南交通大学 FeCoNiCu high-entropy alloy doped amorphous carbon film, and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112662928A (en) * 2020-12-16 2021-04-16 西安交通大学 Amorphous-coated nanocrystalline dual-phase high-strength high-entropy alloy film and preparation method thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112662928A (en) * 2020-12-16 2021-04-16 西安交通大学 Amorphous-coated nanocrystalline dual-phase high-strength high-entropy alloy film and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
SHUNDA JIANG等: "Amorphous High-entropy Non-precious metal oxides with surface reconstruction toward highly efficient and durable catalyst for oxyg evolution reaction", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》, vol. 606 *
XIAOYAO SUN等: "Microstructure, mechanical and physical properties of FeCoNiAlMnW high- entropy films deposited by magnetron sputtering", 《APPLIED SURFACE SCIENCE 》, vol. 507 *
张泽灵等: "FeCoNiMoCr高熵合金薄膜电极的电催化析氧性能", 《材料研究学报》, vol. 35, no. 3 *
谈淑咏: "磁控溅射 CoCrFeNi 高熵合金薄膜的 硬度和电阻率研究", 《表面技术 》, vol. 48, no. 10 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116162842A (en) * 2023-02-21 2023-05-26 昆明理工大学 High Jiang Gaoshang alloy and preparation method thereof
CN116162842B (en) * 2023-02-21 2023-12-26 昆明理工大学 High Jiang Gaoshang alloy and preparation method thereof
CN116288219A (en) * 2023-05-19 2023-06-23 西南交通大学 FeCoNiCu high-entropy alloy doped amorphous carbon film, and preparation method and application thereof
CN116288219B (en) * 2023-05-19 2023-08-11 西南交通大学 FeCoNiCu high-entropy alloy doped amorphous carbon film, and preparation method and application thereof

Also Published As

Publication number Publication date
CN114836714B (en) 2023-10-03

Similar Documents

Publication Publication Date Title
CN114836714B (en) FeCoNiMn high-entropy alloy film, and preparation method and application thereof
Fu et al. Electrochemical study of a novel high-efficiency PbO2 anode based on a cerium-graphene oxide co-doping strategy: electrodeposition mechanism, parameter optimization, and degradation pathways
EP1975280B1 (en) Use of an electrode for the generation of hydrogen
CN110684946A (en) Metal bipolar plate high-conductivity corrosion-resistant protective coating and preparation method and application thereof
CN112803033B (en) Film for fuel cell metal bipolar plate and preparation method thereof
Hu et al. Improved SnO2–Sb2O4 based anode modified with Cr3C2 and CNT for phenol oxidation
Yu et al. Efficient Electrocatalytic Degradation of 4-Chlorophenol Using a Ti/RuO 2–SnO 2–TiO 2/PbO 2–CeO 2 Composite Electrode
EP0099866A1 (en) Electrolytic cell anode
WO2006013430A1 (en) Diamond electrodes
CN112458416A (en) Method for preparing quinary high-entropy alloy spinel coating by magnetron sputtering method
CN110655150B (en) Titanium-based tin oxide anode electrode and preparation method thereof
JP2004139951A (en) Separator for fuel cell and its manufacturing method
Awaludin et al. Preparation of reduced tantalum pentoxide by electrochemical technique for oxygen reduction reaction
CN111229271B (en) Catalyst material and method of forming the same
CN108598497A (en) A kind of nano metal layer and preparation method for fuel battery metal pole plate
Zhang et al. Fabrication of a boron-doped nanocrystalline diamond grown on an WC–Co electrode for degradation of phenol
JP2008063607A (en) Diamond-covered substrate, electrode and method for electrochemical treatment, and manufacturing method of diamond-covered substrate
CN115947614B (en) Titanium dioxide ceramic electrode, preparation method and application thereof, and electric equipment
CN113328111B (en) Stainless steel bipolar plate with chromium-based nitride composite coating and preparation method thereof
CN111254460A (en) Membrane electrode assembly and method for producing hydrogen by electrolysis
CN111250130B (en) Nitride catalyst and method of forming the same
Ye et al. Pulse electrodeposition of Ti/Sn-SbOX/β-PbO2 anodes with high oxygen evolution activity in zinc electrowinning
CN201329707Y (en) Novel coating gravure printing roller
CN112221892A (en) Novel metal bipolar plate surface modification method
Xie et al. Promote the catalytic performance and service life of Ti-based oxide coatings through sandblasting

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
GR01 Patent grant
GR01 Patent grant