CN114717592B - Electrocatalyst and preparation method thereof - Google Patents

Electrocatalyst and preparation method thereof Download PDF

Info

Publication number
CN114717592B
CN114717592B CN202210405830.7A CN202210405830A CN114717592B CN 114717592 B CN114717592 B CN 114717592B CN 202210405830 A CN202210405830 A CN 202210405830A CN 114717592 B CN114717592 B CN 114717592B
Authority
CN
China
Prior art keywords
layer
substrate
alq
electrocatalyst
solution
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.)
Active
Application number
CN202210405830.7A
Other languages
Chinese (zh)
Other versions
CN114717592A (en
Inventor
易丹
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.)
Chengdu College of University of Electronic Science and Technology of China
Original Assignee
Chengdu College of University of Electronic Science and Technology of China
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 Chengdu College of University of Electronic Science and Technology of China filed Critical Chengdu College of University of Electronic Science and Technology of China
Priority to CN202210405830.7A priority Critical patent/CN114717592B/en
Publication of CN114717592A publication Critical patent/CN114717592A/en
Application granted granted Critical
Publication of CN114717592B publication Critical patent/CN114717592B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/061—Metal or alloy
    • 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
    • C23C14/12—Organic material
    • 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
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Mechanical Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The application discloses an electrocatalyst and a preparation method thereof, which relate to the technical field of catalysis and comprise the following steps: pretreating a substrate NF, placing the pretreated substrate NF in a vacuum coating chamber, and carrying out Alq under a high vacuum environment 3 Vapor deposition of (C) to form Alq on substrate NF 3 A layer; will be formed with Alq 3 Placing the substrate NF of the layer into a first high-pressure reaction kettle; preparing a solution A, pouring the solution A into a first high-pressure reaction kettle to perform a first solvothermal reaction, and obtaining Alq 3 Bi is formed on the layer 2 S 3 A layer; will be formed with Alq 3 Layer and Bi 2 S 3 Placing the substrate NF of the layer into a second high-pressure reaction kettle; preparing a solution B, pouring the solution B into a second high-pressure reaction kettle to perform a second solvothermal reaction, and obtaining Bi 2 S 3 Formation of MoS on layer 2 A layer. The electrocatalyst of the application introduces the organic micromolecular functional material Alq 3 The active site of the electrocatalyst can be effectively improved, the selection range of the electrocatalyst is increased, the catalytic efficiency is improved, and the cost is reduced.

Description

Electrocatalyst and preparation method thereof
Technical Field
The application relates to the technical field of catalysis, in particular to an electrocatalyst and a preparation method thereof.
Background
In the prior art, the electrocatalyst has better effect and mainly comprises Pt noble metal and RuO 2 And IrO 2 Etc. However, these noble metals have limited reserves in the crust, are expensive and have poor stability, and are unfavorable for mass production for electrocatalytic reactions. There are many groups of research that have performed much outstanding work in the design and preparation of non-noble metal electrocatalysts, mainly sulfide, selenide, phosphide, carbide, and heteroatom-doped carbon materials.
MoS of two-dimensional lamellar structure in sulfide 2 Is widely used in HER research. But MoS 2 Has poor conductivity and is easily aggregated, so that its HER catalytic activity is limited, and in order to improve the activity, a lot of research has been conducted on MoS 2 The nano catalyst with different shapes, such as nano particles, nano wires or films, can not only increase exposed active sites, but also improve the conductivity of the nano catalyst. The whole is developed towards the directions of smaller particle size, better dispersibility and more exposed active sites.
However, research materials showing better catalytic properties are concentrated on inorganic matters, organic materials are not widely used because of the poor conductive performance compared with most inorganic matters, and the actual organic materials have good ductility, strong spatial three-dimensional and still have better development space.
Disclosure of Invention
Therefore, the application provides an electrocatalyst and a preparation method thereof, which are used for solving the problem that the application of organic materials in the electrocatalyst is limited.
In order to achieve the above object, the present application provides the following technical solutions:
according to a first aspect of the present application, there is provided a method of preparing an electrocatalyst comprising the steps of:
step S1: pretreating a substrate NF, placing the pretreated substrate NF in a vacuum coating chamber, and carrying out Alq under a high vacuum environment 3 Is deposited on the substrate NF to form Alq 3 A layer;
step S2: will be formed with Alq 3 Placing the substrate NF of the layer into a first high-pressure reaction kettle; preparing a solution A, pouring the solution A into the first high-pressure reaction kettle to perform a first solvothermal reaction, and obtaining Alq 3 Bi is formed on the layer 2 S 3 A layer;
step S3: will be formed with Alq 3 Layer and Bi 2 S 3 Placing the substrate NF of the layer into a second high-pressure reaction kettle; preparing a solution B, pouring the solution B into the second high-pressure reaction kettle to perform a second solvothermal reaction, and obtaining Bi 2 S 3 Formation of MoS on layer 2 Layers, giving electrocatalyst.
Further, in step S1, the specific method for pretreating the substrate NF is as follows:
dividing a substrate NF into two sections, pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonic crusher for 10 minutes respectively, drying with dry nitrogen, putting into a pretreatment chamber, performing oxygen plasma sputtering cleaning for 20 minutes, and cooling to room temperature.
Further, in step S1, the evaporation conditions are as follows: the pressure is 2X 10 -3 Pa-4×10 -3 Pa, the evaporation rate is 0.05nm/s-0.15nm/s, and the temperature is 200-250 ℃.
Further, in step S1, the Alq 3 The thickness of the layer is 50nm-70nm.
Further, in step S2, the specific method for preparing the solution a is as follows: bi (NO) 3 ) 3 ·5H 2 O and CH 4 N 2 S is added into glycol according to the mol ratio of 1:1.5-2, and the solution A is obtained after uniform stirring.
Further, in step S2, the specific method of the first solvothermal reaction is as follows: will be provided with Alq formed 3 The substrate NF of the layer and the first high-pressure reaction kettle of the solution A are kept for 15 to 20 hours in an environment of 150 to 170 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for a plurality of times, and then baking for 7-9 h in a vacuum oven with the temperature of 50-70 ℃.
Further, in step S3, the specific method for preparing the solution B is as follows: PPA and Na 2 MoO 4 ·2H 2 And (3) fully stirring the mixture according to the mol ratio of (4-6) to 1 until the mixture is transparent.
Further, in step S3, the specific method of the second solvothermal reaction is as follows: will be provided with Alq formed 3 Layer and Bi 2 S 3 The substrate NF of the layer and the second high-pressure reaction kettle of the solution B are kept for 5 to 10 hours in the environment of 180 to 220 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for multiple times, and then baking in a vacuum oven at 40-60 ℃ for 7-9 h.
According to a second aspect of the present application, there is provided an electrocatalyst prepared by the above-described method of preparation; the catalyst comprises a substrate NF and Alq sequentially formed on the substrate NF 3 Layer, bi 2 S 3 Layer and MoS 2 A layer.
Further, the electrocatalyst has a current density of 10 mA.cm -2 When the overpotential is 140mV-160mV, the Tafil slope is 60 mV.dec -1 -70mV·dec -1 。
The application has the following advantages:
the application uses organic matter Alq 3 And sulfide Bi 2 S 3 And MoS 2 An electrocatalyst is prepared by a combined mode, and an organic micromolecular functional material Alq is introduced into the electrocatalyst 3 The active site of the electrocatalyst can be effectively improved, the selection range of the electrocatalyst is further increased, the catalytic efficiency is improved, and the cost is reduced. The electrocatalyst of the application utilizes Bi 2 S 3 Asymmetric SP of lone pair electrons 3 Hybridization pattern pair MoS 2 Generating electron induction effect to make MoS 2 Exhibits excellent electrocatalytic properties.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It will be apparent to those of ordinary skill in the art that the drawings in the following description are exemplary only and that other implementations can be obtained from the extensions of the drawings provided without inventive effort.
The structures, proportions, sizes, etc. shown in the present specification are shown only for the purposes of illustration and description, and are not intended to limit the scope of the application, which is defined by the claims, so that any structural modifications, changes in proportions, or adjustments of sizes, which do not affect the efficacy or the achievement of the present application, should fall within the scope of the application.
FIG. 1 is a process flow diagram of a method for preparing an electrocatalyst according to the application;
fig. 2 is a schematic structural diagram of an electrocatalyst according to the application.
Detailed Description
Other advantages and advantages of the present application will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In a first aspect, an embodiment of the present application provides a method for preparing an electrocatalyst, where a process flow chart is shown in fig. 1, and specifically includes the following steps:
step S1: pretreating a substrate NF, placing the pretreated substrate NF in a vacuum coating chamber, and carrying out Alq under a high vacuum environment 3 Is deposited on the substrate NF to form Alq 3 A layer.
Step S2: will be formed with Alq 3 Placing the substrate NF of the layer into a first high-pressure reaction kettle; preparing a solution A, pouring the solution A into the first high-pressure reaction kettle to perform a first solvothermal reaction, and obtaining Alq 3 Bi is formed on the layer 2 S 3 A layer.
Step S3: will be formed with Alq 3 Layer and Bi 2 S 3 Placing the substrate NF of the layer into a second high-pressure reaction kettle; preparing a solution B, pouring the solution B into the second high-pressure reaction kettle to perform a second solvothermal reaction, and obtaining Bi 2 S 3 Formation of MoS on layer 2 Layers, giving electrocatalyst.
The substrate NF is nickel foam. Alq 3 Is tris (8-hydroxyquinoline) aluminum, is a very stable organic semiconductor fluorescent solid material, has an aromatic ring structure and an energy band gap of 2.5eV (calculated by ultraviolet visible spectrum), has stable chemical property and good electron transmission capability. Bi (Bi) 2 S 3 Having a unique asymmetric SP 3 The heterojunction electronic structure is modulated in a hybridization mode, the electronic distribution in the electrocatalytic material can be influenced, and therefore electrocatalytic performance can be improved. MoS (MoS) 2 Is a typical representation of transition metal disulfides, having a two-dimensional layered structure resembling graphene, with Mo-S and Mo-Mo in the layers being bound by strong covalent bonds, and S-S between the layers being connected by weak van der Waals forces, moS 2 The sulfur element in the catalyst has high unsaturation, extremely high reaction activity and MoS 2 Has huge specific surface area, is porous and unsaturated, and is easy to be matched with other sourcesThe characteristic of sub-phase combination is an excellent electrocatalyst material.
It will be appreciated that the present application uses the organic matter Alq 3 And sulfide Bi 2 S 3 And MoS 2 An electrocatalyst is prepared by a combined mode, and an organic micromolecular functional material Alq is introduced into the electrocatalyst 3 The active site of the electrocatalyst can be effectively improved, the selection range of the electrocatalyst is further increased, the catalytic efficiency is improved, and the cost is reduced. The electrocatalyst of the application utilizes Bi 2 S 3 Asymmetric SP of lone pair electrons 3 Hybridization pattern pair MoS 2 Generating electron induction effect to make MoS 2 Exhibits excellent electrocatalytic properties.
The following describes the present scheme in detail:
as an optional technical scheme of the present application, in step S1, the specific method for pretreating the substrate NF is as follows:
dividing a substrate NF into two sections, pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonic crusher for 10 minutes respectively, drying with dry nitrogen, putting into a pretreatment chamber, performing oxygen plasma sputtering cleaning for 20 minutes, and cooling to room temperature.
The substrate NF is pretreated by acetone, then is respectively cleaned by double distilled water and pure ethanol, and is dried by dry nitrogen and then is put into a pretreatment chamber for oxygen plasma sputtering cleaning, so that the surface of the substrate NF is clean, free of impurities and smooth, and the subsequent evaporation and solvothermal reaction are facilitated.
As an optional technical solution of the present application, in step S1, the evaporation conditions are as follows: the pressure is 2X 10 -3 Pa-4×10 -3 Pa, the evaporation rate is 0.05nm/s-0.15nm/s, and the temperature is 200-250 ℃.
Alternatively, the pressure may be 2×10 -3 Pa、2.2×10 -3 Pa、2.3×10 -3 Pa、2.5×10 -3 Pa、2.8×10 - 3 Pa、3.0×10 -3 Pa、3.2×10 -3 Pa、3.5×10 -3 Pa、3.8×10 -3 Pa or 4X 10 -3 Pa, etc., of course may be within the above rangeOther values are not limited herein. The evaporation rate may be 0.05nm/s, 0.06nm/s, 0.07nm/s, 0.08nm/s, 0.09nm/s, 0.10nm/s, 0.11nm/s, 0.12nm/s, 0.13nm/s, 0.14nm/s, or 0.15nm/s, etc., but may be other values within the above range, and is not limited thereto. The temperature may be 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃ or the like, and of course, other values within the above range may be used, without limitation. It will be appreciated that Alq formation on the substrate NF is better achieved by limiting the pressure, evaporation rate and temperature during evaporation 3 A layer.
As an optional solution of the present application, in step S1, the Alq 3 The thickness of the layer is 50nm-70nm.
Alternatively Alq 3 The thickness of the layer may be 50nm, 52nm, 55nm, 58nm, 60nm, 62nm, 65nm, 68nm, 70nm or the like, but may be other values within the above range, and is not limited thereto.
As an optional technical solution of the present application, in step S2, the specific method for preparing the solution a is as follows: bi (NO) 3 ) 3 ·5H 2 O and CH 4 N 2 S is added into glycol according to the mol ratio of 1:1.5-2, and the solution A is obtained after uniform stirring.
Alternatively, bi (NO 3 ) 3 ·5H 2 O and CH 4 N 2 The molar ratio of S may be 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, or 1:2, etc., but may be other values within the above range, and is not limited thereto.
As an optional technical solution of the present application, in step S2, the specific method of the first solvothermal reaction is as follows: will be provided with Alq formed 3 The substrate NF of the layer and the first high-pressure reaction kettle of the solution A are kept for 15 to 20 hours in an environment of 150 to 170 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for a plurality of times, and then baking for 7-9 h in a vacuum oven with the temperature of 50-70 ℃.
Alternatively, the reaction temperature of the first autoclave may be 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃ or the like, but may be any other value within the above range, and the reaction time may be 15h, 16h, 17h, 18h, 19h, 20h or the like, but may be any other value within the above range, and the reaction time is not limited thereto. The temperature of the vacuum oven may be 50 ℃, 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃, or 70 ℃, or the like, but of course, other values within the above range are also possible, and the baking time of the vacuum oven may be 7h, 7.2h, 7.5h, 7.8h, 8h, 8.2h, 8.5h, 8.8h, or 9h, or the like, or other values within the above range are also possible, and the present application is not limited thereto.
As an optional technical solution of the present application, in step S3, the specific method for preparing the solution B is as follows: PPA and Na 2 MoO 4 ·2H 2 And (3) fully stirring the mixture according to the mol ratio of (4-6) to 1 until the mixture is transparent.
Alternatively, PPA and Na 2 MoO 4 ·2H 2 The molar ratio of O may be 4:1, 4.5:1, 4.8:1, 5:1, 5.5:1, 5.8:1, 6:1, etc., although other values within the above range are also possible and are not limited thereto.
As an optional technical scheme of the present application, in step S3, the specific method of the second solvothermal reaction is as follows: will be provided with Alq formed 3 Layer and Bi 2 S 3 The substrate NF of the layer and the second high-pressure reaction kettle of the solution B are kept for 5 to 10 hours in the environment of 180 to 220 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for multiple times, and then baking in a vacuum oven at 40-60 ℃ for 7-9 h.
Alternatively, the reaction temperature of the second autoclave may be 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, or the like, but may be other values within the above range, and the reaction time may be 5h, 6h, 7h, 8h, 9h, 10h, or the like, or may be other values within the above range, and the reaction time is not limited thereto. The temperature of the vacuum oven may be 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃, 58 ℃, 60 ℃ or the like, and of course, other values within the above range may be used, and the baking time of the vacuum oven may be 7h, 7.2h, 7.5h, 7.8h, 8h, 8.2h, 8.5h, 8.8h, 9h or the like, and of course, other values within the above range may be used, and the present application is not limited thereto.
In a second aspect, the embodiment of the application also provides an electrocatalyst prepared by the preparation method described above; as shown in FIG. 2, the catalyst comprises a substrate NF 1 and Alq formed on the substrate NF 1 in sequence 3 Layer 2, bi 2 S 3 Layer 3 and MoS 2 Layer 4.
The electrocatalyst has a current density of 10mA cm -2 When the overpotential is 140mV-160mV, the Tafil slope is 60 mV.dec -1 -70mV·dec -1 。
The following describes embodiments of the present application in more detail. The embodiments of the present application are not limited to the following specific embodiments. The modification can be appropriately performed within the scope of protection.
Example 1
A method for preparing an electrocatalyst comprising the steps of:
step S1: dividing a substrate NF into two sections (2 cm 4 cm), pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonic crusher for 10 minutes respectively, drying with dry nitrogen, placing into a pretreatment chamber of OLED-V type multifunctional organic film forming equipment, performing oxygen plasma sputtering cleaning for about 20 minutes, cooling to room temperature, and transferring into a vacuum film coating chamber; at 3X 10 -3 Alq under high vacuum atmosphere of Pa 3 Is deposited on the substrate NF to form Alq 3 A layer. Wherein, in the evaporation process, the evaporation rate is controlled to be about 0.1nm/s, the temperature is controlled to be 220 ℃ by a thermocouple, and the film thickness is monitored to be 60nm in situ by a Proteck9100 film thickness meter.
Step S2: bi (NO) 3 ) 3 ·5H 2 O (1.0 mmol) and CH 4 N 2 S (1.75 mmol) was added to 60ml of ethylene glycol and stirred well to give the solution A. Subsequently, the solution A was poured into a first autoclave made of polytetrafluoroethylene-based stainless steel, which was placed with NF to complete the step S1, and kept at 160℃for 16 hours. Cooling to room temperature, repeatedly washing the treated NF with distilled water and ethanol for several times, and heating to 6 deg.CBaking in a vacuum oven at 0deg.C for 8 hr, and collecting the powder of Alq 3 Bi is formed on the layer 2 S 3 A layer.
Step S3: PPA (6.25 mmol), na 2 MoO 4 ·2H 2 Fully stirring O (1.25 mmol) to be transparent, pouring into a polytetrafluoroethylene substrate stainless steel second high-pressure reaction kettle with NF after finishing the step S2, baking for 8 hours at 200 ℃, cooling to room temperature, repeatedly cleaning with distilled water and ethanol for a plurality of times, baking for 8 hours in a vacuum oven with the temperature of 50 ℃, and obtaining Bi 2 S 3 Formation of MoS on layer 2 Layers, giving electrocatalyst.
And the obtained electrocatalyst is used as a working electrode, hg/HgO and a platinum sheet are respectively used as a reference electrode and a counter electrode, and an electrocatalytic three-electrode system is assembled for electrocatalytic testing. At a current density of 10 mA.cm -2 At an overpotential of 157mV, the Tafil slope was 65 mV.dec -1 。
Example 2
Step S1: dividing a substrate NF into two sections (2 cm 4 cm), pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonic crusher for 10 minutes respectively, drying with dry nitrogen, placing into a pretreatment chamber of OLED-V type multifunctional organic film forming equipment, performing oxygen plasma sputtering cleaning for about 20 minutes, cooling to room temperature, and transferring into a vacuum film coating chamber; at 2X 10 -3 Alq under high vacuum atmosphere of Pa 3 Is deposited on the substrate NF to form Alq 3 A layer. Wherein, in the evaporation process, the evaporation rate is controlled to be about 0.05nm/s, the temperature is controlled to be 200 ℃ by a thermocouple, and the film thickness is monitored to be 50nm in situ by a Proteck9100 film thickness meter.
Step S2: bi (NO) 3 ) 3 ·5H 2 O (1.0 mmol) and CH 4 N 2 S (1.5 mmol) was added to 60ml of ethylene glycol and stirred well to give the solution A. Subsequently, the solution A was poured into a first autoclave made of polytetrafluoroethylene-based stainless steel, which was placed with NF to complete the step S1, and maintained at 150℃for 18 hours. Cooling to room temperature, repeatedly washing the treated NF with distilled water and ethanol for several times, and vacuum-treating at 50deg.CBaking in oven for 9h, and baking in Alq 3 Bi is formed on the layer 2 S 3 A layer.
Step S3: PPA (5 mmol), na 2 MoO 4 ·2H 2 Fully stirring O (1.25 mmol) to be transparent, pouring into a polytetrafluoroethylene substrate stainless steel second high-pressure reaction kettle with NF after finishing the step S2, baking for 10 hours at 180 ℃, cooling to room temperature, repeatedly cleaning with distilled water and ethanol for a plurality of times, baking for 9 hours in a vacuum oven with the temperature of 40 ℃, and obtaining Bi 2 S 3 Formation of MoS on layer 2 Layers, giving electrocatalyst.
And the obtained electrocatalyst is used as a working electrode, hg/HgO and a platinum sheet are respectively used as a reference electrode and a counter electrode, and an electrocatalytic three-electrode system is assembled for electrocatalytic testing. At a current density of 10 mA.cm -2 At an overpotential of 145mV, a Tafil slope of 60 mV.dec -1 。
Example 3
Step S1: dividing a substrate NF into two sections (2 cm 4 cm), pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonic crusher for 10 minutes respectively, drying with dry nitrogen, placing into a pretreatment chamber of OLED-V type multifunctional organic film forming equipment, performing oxygen plasma sputtering cleaning for about 20 minutes, cooling to room temperature, and transferring into a vacuum film coating chamber; at 4X 10 -3 Alq under high vacuum atmosphere of Pa 3 Is deposited on the substrate NF to form Alq 3 A layer. In the evaporation process, the evaporation rate is controlled to be about 0.15nm/s, the temperature is controlled to be 250 ℃ by a thermocouple, and the film thickness is monitored to be 70nm in situ by a Proteck9100 film thickness meter.
Step S2: bi (NO) 3 ) 3 ·5H 2 O (1.0 mmol) and CH 4 N 2 S (2 mmol) was added to 60ml of ethylene glycol and stirred well to give the solution A. Subsequently, the solution A was poured into a first autoclave made of polytetrafluoroethylene-based stainless steel, which was placed with NF to complete the step S1, and maintained at 170℃for 15 hours. Cooling to room temperature, repeatedly cleaning the treated NF with distilled water and ethanol for several times, and baking in vacuum oven at 70deg.C7h, at Alq 3 Bi is formed on the layer 2 S 3 A layer.
Step S3: PPA (7.5 mmol), na 2 MoO 4 ·2H 2 Fully stirring O (1.25 mmol) to be transparent, pouring into a polytetrafluoroethylene substrate stainless steel second high-pressure reaction kettle with NF after finishing the step S2, baking for 5 hours at 220 ℃, cooling to room temperature, repeatedly cleaning with distilled water and ethanol for a plurality of times, baking for 7 hours in a vacuum oven with the temperature of 60 ℃, and obtaining Bi 2 S 3 Formation of MoS on layer 2 Layers, giving electrocatalyst.
And the obtained electrocatalyst is used as a working electrode, hg/HgO and a platinum sheet are respectively used as a reference electrode and a counter electrode, and an electrocatalytic three-electrode system is assembled for electrocatalytic testing. At a current density of 10 mA.cm -2 At an overpotential of 160mV, the Tafil slope was 70 mV.dec -1 。
Example 4
Step S1: dividing a substrate NF into two sections (2 cm 4 cm), pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonic crusher for 10 minutes respectively, drying with dry nitrogen, placing into a pretreatment chamber of OLED-V type multifunctional organic film forming equipment, performing oxygen plasma sputtering cleaning for about 20 minutes, cooling to room temperature, and transferring into a vacuum film coating chamber; at 2.5X10 -3 Alq under high vacuum atmosphere of Pa 3 Is deposited on the substrate NF to form Alq 3 A layer. In the evaporation process, the evaporation rate is controlled to be about 0.08nm/s, the temperature is controlled to be 210 ℃ by a thermocouple, and the film thickness is monitored to be 55nm in situ by a Proteck9100 film thickness meter.
Step S2: bi (NO) 3 ) 3 ·5H 2 O (1.0 mmol) and CH 4 N 2 S (1.6 mmol) was added to 60ml of ethylene glycol and stirred well to give the solution A. Subsequently, the solution A was poured into a first autoclave made of polytetrafluoroethylene-based stainless steel, which was placed with NF to complete the step S1, and maintained at 155℃for 18 hours. Cooling to room temperature, repeatedly cleaning the treated NF with distilled water and ethanol for several times, baking in vacuum oven at 60deg.C for 8 hr, and collecting the final productThe Alq 3 Bi is formed on the layer 2 S 3 A layer.
Step S3: PPA (5.75 mmol), na 2 MoO 4 ·2H 2 Fully stirring O (1.25 mmol) to be transparent, pouring into a polytetrafluoroethylene substrate stainless steel second high-pressure reaction kettle with NF after finishing the step S2, baking for 9 hours at 190 ℃, cooling to room temperature, repeatedly cleaning with distilled water and ethanol for a plurality of times, baking for 8.5 hours in a vacuum oven with the temperature of 55 ℃, and obtaining Bi 2 S 3 Formation of MoS on layer 2 Layers, giving electrocatalyst.
And the obtained electrocatalyst is used as a working electrode, hg/HgO and a platinum sheet are respectively used as a reference electrode and a counter electrode, and an electrocatalytic three-electrode system is assembled for electrocatalytic testing. At a current density of 10 mA.cm -2 At an overpotential of 155mV, the Tafil slope was 63 mV.dec -1 。
Example 5
Step S1: dividing a substrate NF into two sections (2 cm 4 cm), pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonic crusher for 10 minutes respectively, drying with dry nitrogen, placing into a pretreatment chamber of OLED-V type multifunctional organic film forming equipment, performing oxygen plasma sputtering cleaning for about 20 minutes, cooling to room temperature, and transferring into a vacuum film coating chamber; at 3.5X10 -3 Alq under high vacuum atmosphere of Pa 3 Is deposited on the substrate NF to form Alq 3 A layer. Wherein, in the evaporation process, the evaporation rate is controlled to be about 0.12nm/s, the temperature is controlled to be 240 ℃ by a thermocouple, and the film thickness is monitored to be 65nm in situ by a Proteck9100 film thickness meter.
Step S2: bi (NO) 3 ) 3 ·5H 2 O (1.0 mmol) and CH 4 N 2 S (1.9 mmol) was added to 60ml of ethylene glycol and stirred well to give the solution A. Subsequently, the solution A was poured into a first autoclave made of polytetrafluoroethylene-based stainless steel, which was placed with NF to complete the step S1, and kept at 165℃for 18 hours. Cooling to room temperature, repeatedly washing treated NF with distilled water and ethanol for several times, baking in vacuum oven at 65deg.C for 7.5 hr, and collecting the treated NF as Alq 3 Bi is formed on the layer 2 S 3 A layer.
Step S3: PPA (6.75 mmol), na 2 MoO 4 ·2H 2 Fully stirring O (1.25 mmol) to be transparent, pouring into a polytetrafluoroethylene substrate stainless steel second high-pressure reaction kettle with NF after finishing the step S2, baking for 6 hours at 215 ℃, cooling to room temperature, repeatedly cleaning with distilled water and ethanol for a plurality of times, baking for 7.5 hours in a vacuum oven with the temperature of 55 ℃, and obtaining Bi 2 S 3 Formation of MoS on layer 2 Layers, giving electrocatalyst.
And the obtained electrocatalyst is used as a working electrode, hg/HgO and a platinum sheet are respectively used as a reference electrode and a counter electrode, and an electrocatalytic three-electrode system is assembled for electrocatalytic testing. At a current density of 10 mA.cm -2 At an overpotential of 150mV, the Tafil slope was 62 mV.dec -1 。
While the application has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the application and are intended to be within the scope of the application as claimed.

Claims (7)

1. A method for preparing an electrocatalyst, comprising the steps of:
step S1: pretreating a substrate NF, placing the pretreated substrate NF in a vacuum coating chamber, and carrying out Alq under a high vacuum environment 3 Is deposited on the substrate NF to form Alq 3 A layer;
step S2: will be formed with Alq 3 Placing the substrate NF of the layer into a first high-pressure reaction kettle; preparing a solution A, pouring the solution A into the first high-pressure reaction kettle to perform a first solvothermal reaction, and obtaining Alq 3 Bi is formed on the layer 2 S 3 A layer;
step S3: will be formed with Alq 3 Layer and Bi 2 S 3 Placing the substrate NF of the layer into a second high-pressure reaction kettle; preparing a solutionB, pouring the solution B into the second high-pressure reaction kettle to perform a second solvothermal reaction, and obtaining Bi 2 S 3 Formation of MoS on layer 2 A layer to obtain an electrocatalyst;
in step S1, the Alq 3 The thickness of the layer is 50nm-70nm;
in step S2, the specific method for preparing the solution a is as follows: will beAnd CH (CH) 4 N 2 S is as follows: adding the molar ratio of (1.5-2) into ethylene glycol, and uniformly stirring to obtain a solution A;
in step S3, the specific method for preparing the solution B is as follows: PPA and PPA are combined withStirring thoroughly to transparent according to the molar ratio of (4-6): 1.
2. The method for preparing an electrocatalyst according to claim 1, wherein in step S1, the specific method for pretreating the substrate NF is as follows:
dividing a substrate NF into two sections, pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonic crusher for 10 minutes respectively, drying with dry nitrogen, putting into a pretreatment chamber, performing oxygen plasma sputtering cleaning for 20 minutes, and cooling to room temperature.
3. The method for preparing an electrocatalyst according to claim 1, wherein in step S1, the evaporation conditions are: the pressure is 2X 10 -3 Pa -4×10 -3 Pa, the evaporation rate is 0.05nm/s-0.15nm/s, and the temperature is 200-250 ℃.
4. The method for preparing an electrocatalyst according to claim 1, wherein in step S2, the specific method for the first solvothermal reaction is as follows: will be provided with Alq formed 3 First high pressure reaction of substrate NF of layer and said solution AThe kettle is kept for 15 to 20 hours in the environment of 150 to 170 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for a plurality of times, and then baking for 7-9 h in a vacuum oven with the temperature of 50-70 ℃.
5. The method for preparing an electrocatalyst according to claim 1, wherein in step S3, the specific method for the second solvothermal reaction is as follows: will be provided with Alq formed 3 Layer and Bi 2 S 3 The substrate NF of the layer and the second high-pressure reaction kettle of the solution B are kept for 5 to 10 hours in the environment of 180 to 220 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for multiple times, and then baking in a vacuum oven at 40-60 ℃ for 7-9 h.
6. An electrocatalyst prepared by the method of any one of claims 1 to 5; the catalyst comprises a substrate NF and Alq sequentially formed on the substrate NF 3 Layer, bi 2 S 3 Layer and MoS 2 A layer.
7. The electrocatalyst according to claim 6 wherein the electrocatalyst has a current density of 10mA cm −2 When the overpotential is 140mV-160mV, the Tafil slope is 60 mV.dec −1 -70mV·dec −1 。
CN202210405830.7A 2022-04-18 2022-04-18 Electrocatalyst and preparation method thereof Active CN114717592B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210405830.7A CN114717592B (en) 2022-04-18 2022-04-18 Electrocatalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210405830.7A CN114717592B (en) 2022-04-18 2022-04-18 Electrocatalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114717592A CN114717592A (en) 2022-07-08
CN114717592B true CN114717592B (en) 2023-08-29

Family

ID=82244151

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210405830.7A Active CN114717592B (en) 2022-04-18 2022-04-18 Electrocatalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114717592B (en)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111167480A (en) * 2020-02-14 2020-05-19 电子科技大学 Novel oxygen evolution electrocatalyst and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111167480A (en) * 2020-02-14 2020-05-19 电子科技大学 Novel oxygen evolution electrocatalyst and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
8-羟基喹啉-铝修饰碳糊电极的电催化作用;宝阿敏;朱永春;高鹰;肖楠;辛士刚;张宏波;;沈阳师范大学学报(自然科学版)(03);30-33 *

Also Published As

Publication number Publication date
CN114717592A (en) 2022-07-08

Similar Documents

Publication Publication Date Title
Khan et al. Current progress in 2D metal–organic frameworks for electrocatalysis
Ito et al. Cooperation between holey graphene and NiMo alloy for hydrogen evolution in an acidic electrolyte
Zhang et al. A Cost‐Efficient Bifunctional Ultrathin Nanosheets Array for Electrochemical Overall Water Splitting
Owens‐Baird et al. Structure–Activity Relationships for Pt‐Free Metal Phosphide Hydrogen Evolution Electrocatalysts
Guo et al. Hierarchically structured bimetallic electrocatalyst synthesized via template-directed fabrication MOF arrays for high-efficiency oxygen evolution reaction
Wu et al. Arrays of ZnSe/MoSe2 nanotubes with electronic modulation as efficient electrocatalysts for hydrogen evolution reaction
CN113718281B (en) Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof
He et al. Super‐Hydrophilic Microporous Ni (OH) x/Ni3S2 Heterostructure Electrocatalyst for Large‐Current‐Density Hydrogen Evolution
CN112108149A (en) Preparation method of electrocatalytic material, corresponding material and use method
CN107308959A (en) Cu2‑xSe nanometer sheet array foams carbon/carbon-copper composite material, preparation method and application
Fadil et al. Synthesis and electrocatalytic performance of atomically ordered nickel carbide (Ni 3 C) nanoparticles
Jiao et al. Co0. 5Ni0. 5P nanoparticles embedded in carbon layers for efficient electrochemical water splitting
Yang et al. A CoO x/FeO x heterojunction on carbon nanotubes prepared by plasma-enhanced atomic layer deposition for the highly efficient electrocatalysis of oxygen evolution reactions
KR20120129780A (en) Fabrication method of carbon-alloy composite by using intense pulsed light
CN110467162B (en) Novel graphite-phase carbon nitride polymer material and preparation method and application thereof
Jin et al. Ultrathin carbon coated CoO nanosheet arrays as efficient electrocatalysts for the hydrogen evolution reaction
CN111495399B (en) S-doped WP 2 Nanosheet array electrocatalyst and preparation method thereof
CN112058293A (en) Preparation method of nitrogen-phosphorus-codoped foam carbon nanosheet loaded NiCo nanoparticle composite material, product and application thereof
CN106540711A (en) A kind of method that green prepares Ag-ZnO grapheme foam nickel material
CN114351185B (en) Dual-function electrocatalyst with heterostructure nickel cobalt nitride nanosheet array and preparation and application thereof
CN114717592B (en) Electrocatalyst and preparation method thereof
Shi et al. Ni-Activated and Ni–P-Activated Porous Titanium Carbide Ceramic Electrodes as Efficient Electrocatalysts for Overall Water Splitting
Zhu et al. Metal/antiperovskite metal nitride composites Ag/AgNNi3 as novel efficient electrocatalysts for hydrogen evolution reaction in alkaline media
CN114100660A (en) Titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst, and preparation method and application thereof
JP2018528141A (en) Electrode material for electrolytic hydrogen generation

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