CN114717592A - Electrocatalyst and preparation method thereof - Google Patents

Electrocatalyst and preparation method thereof Download PDF

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CN114717592A
CN114717592A CN202210405830.7A CN202210405830A CN114717592A CN 114717592 A CN114717592 A CN 114717592A CN 202210405830 A CN202210405830 A CN 202210405830A CN 114717592 A CN114717592 A CN 114717592A
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layer
substrate
alq
electrocatalyst
solution
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CN114717592B (en
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易丹
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Chengdu College of University of Electronic Science and Technology of China
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    • 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
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    • Y02E60/50—Fuel cells

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Abstract

The invention 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 substrate NF into a vacuum coating chamber, and carrying out Alq in a high vacuum environment3Deposition of (2) on a substrate NF to form Alq3A layer; will be formed with Alq3Placing the substrate NF of the layer into a first high-pressure reaction kettle; preparing solution A, pouring the solution A into a first high-pressure reaction kettle for carrying out first solvothermal reaction, and carrying out reaction on Alq3Formation of Bi on the layer2S3A layer; will be formed with Alq3Layer and Bi2S3Putting the substrate NF of the layer into a second high-pressure reaction kettle; preparing solution B, pouring the solution B into a second high-pressure reaction kettle for second solvothermal treatmentReaction of in Bi2S3Formation of MoS on the layer2And (3) a layer. The electrocatalyst introduces organic micromolecular functional material Alq3The method can effectively improve the active sites of the electrocatalyst, increase the selection range of the electrocatalyst, improve the catalytic efficiency and reduce the cost.

Description

Electrocatalyst and preparation method thereof
Technical Field
The invention relates to the technical field of catalysis, in particular to an electrocatalyst and a preparation method thereof.
Background
In the prior art, the electrocatalyst with good effect mainly comprises Pt-series noble metal and RuO2And IrO2And the like. However, these precious metals have a limited storage in the earth's crust, are expensive and have poor stability, which is not conducive to large-scale production for electrocatalysisIn the reaction of formation. Many research teams have performed excellent work on the design and preparation of non-noble metal electrocatalysts, and there are several major categories of sulfides, selenides, phosphides, carbides, heteroatom-doped carbon materials, and the like.
MoS of two-dimensional layered structure in sulfide2Widely used in HER studies. But MoS2Have poor conductivity and are prone to aggregation, limiting HER catalytic activity, and to improve activity, MoS has been studied in large numbers2The prepared nano-catalyst with different morphologies, such as nano-particles, nano-wires or films, can increase exposed active sites and improve the conductivity of the nano-catalyst. The whole body develops towards the direction of smaller grain diameter, better dispersity and more exposed active sites.
However, research materials showing better catalytic properties are mainly focused on inorganic matters, organic materials are not widely used due to the fact that the conductive performance of the organic materials is not as good as that of most of the inorganic matters, and the actual organic materials have good ductility and strong space stereo, so that a better development space still exists.
Disclosure of Invention
Therefore, the invention provides an electrocatalyst and a preparation method thereof, which aim to solve the problem that the application of organic materials in the electrocatalyst is limited.
In order to achieve the above purpose, the invention provides the following technical scheme:
according to a first aspect of the present invention, there is provided a method of preparing an electrocatalyst comprising the steps of:
step S1: pretreating a substrate NF, placing the substrate NF in a vacuum coating chamber, and carrying out Alq in a high vacuum environment3Forming Alq on the substrate NF by vapor deposition3A layer;
step S2: will be formed with Alq3Placing 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 for carrying out first solvothermal reaction, and reacting in the Alq3Forming Bi on the layer2S3A layer;
step S3: will be formed with Alq3Layer and Bi2S3Substrate of layerPlacing NF into a second high-pressure reaction kettle; preparing solution B, pouring the solution B into the second high-pressure reaction kettle for second solvothermal reaction, and reacting Bi in the solution B2S3Formation of MoS on the layer2Layer, obtaining the electrocatalyst.
Further, in step S1, the specific method for pre-treating the substrate NF is as follows:
the substrate NF is divided into two sections, acetone is used for pretreatment, then double distilled water and pure ethanol are used for cleaning for 10 minutes in an ultrasonicator in sequence, then dry nitrogen is used for drying, then the substrate NF is placed in a pretreatment chamber, oxygen plasma sputtering cleaning is carried out for 20 minutes, and the substrate NF is cooled to the room temperature.
Further, in step S1, the vapor deposition conditions are: pressure of 2X 10-3Pa-4×10-3Pa, evaporation rate of 0.05nm/s-0.15nm/s, temperature of 200-250 deg.C.
Further, in step S1, the Alq is3The thickness of the layer is 50nm-70 nm.
Further, in step S2, the specific method for preparing solution a is as follows: adding Bi (NO)3)3·5H2O and CH4N2And S is added into ethylene glycol according to the molar ratio of 1 to (1.5-2) and is uniformly stirred to obtain the solution A.
Further, in step S2, the specific method of the first solvothermal reaction is as follows: will be provided with Alq3Keeping a first high-pressure reaction kettle for the substrate NF and the solution A of the layer for 15 to 20 hours at the temperature of between 150 and 170 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for many times, and baking in a vacuum oven at 50-70 deg.C for 7-9 h.
Further, in step S3, the specific method for preparing solution B is as follows: mixing PPA with Na2MoO4·2H2And fully stirring the O according to the molar ratio of (4-6) to 1 until the O is transparent.
Further, in step S3, the specific method of the second solvothermal reaction is as follows: will be provided with Alq3Layer and Bi2S3Substrate NF of the layer and of said solution BThe second high-pressure reaction kettle is kept for 5 to 10 hours at the temperature of between 180 and 220 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for many times, and baking in a vacuum oven at 40-60 deg.C 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 NF3Layer, Bi2S3Layer and MoS2And (3) a layer.
Further, the electrocatalyst has a current density of 10mA cm-2When the voltage is over-potential is 140mV-160mV, the Tafel slope is 60mV dec-1-70mV·dec-1。
The invention has the following advantages:
the invention uses organic Alq3And sulfide Bi2S3And MoS2Preparing an electrocatalyst by a combined mode, and introducing an organic micromolecular functional material Alq into the electrocatalyst3The method can effectively improve the active sites of the electrocatalyst, thereby increasing the selection range of the electrocatalyst, improving the catalytic efficiency and reducing the cost. Electrocatalyst of the present application utilizing Bi2S3Asymmetric SP of lone pair electrons3Hybrid mode pair MoS2Produce electron induction effect to make MoS2The excellent electrocatalytic performance is shown.
Drawings
In order to more clearly illustrate the embodiments of the present invention 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 should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so that those skilled in the art can understand and read the present invention, and do not limit the conditions for implementing the present invention, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the functions and purposes of the present invention, should still fall within the scope of the present invention.
FIG. 1 is a process flow diagram of a method of making an electrocatalyst according to the present application;
fig. 2 is a schematic structural diagram of an electrocatalyst provided herein.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In a first aspect, an embodiment of the present application provides a method for preparing an electrocatalyst, a process flow diagram of which is shown in fig. 1, and specifically includes the following steps:
step S1: pretreating a substrate NF, placing the substrate NF in a vacuum coating chamber, and carrying out Alq in a high vacuum environment3Forming Alq on the substrate NF by vapor deposition3And (3) a layer.
Step S2: will be formed with Alq3Placing 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 for carrying out first solvothermal reaction, and reacting in the Alq3Forming Bi on the layer2S3And (3) a layer.
Step S3: will be formed with Alq3Layer and Bi2S3Putting the substrate NF of the layer into a second high-pressure reaction kettle; preparing solution B, pouring the solution B into the second high-pressure reaction kettle for second solvothermal reaction, and reacting Bi in the solution B2S3Formation of MoS on the layer2Layer, obtaining the electrocatalyst.
The substrate NF is nickel foam. Alq3The 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 an ultraviolet-visible spectrum), is stable in chemical property and has good electron transport capacity. Bi2S3With unique asymmetric SP3The electronic structure of the heterojunction can be modulated in a hybridization way, so that the electronic distribution in the electrocatalytic material can be influenced, and the electrocatalytic performance can be improved. MoS2Is a typical representative of transition metal disulfides, and has a two-dimensional layered structure similar to graphene, in which Mo-S and Mo-Mo are bonded by strong covalent bonds in the layers, and S-S are bonded by weak van der Waals force in the layers, and MoS2The medium sulfur element has high unsaturation, extremely high reaction activity and MoS2Has the characteristics of huge specific surface area, porosity, unsaturation and easy combination with other atoms, and is an excellent electrocatalyst material.
Understandably, the present invention uses organic Alq3And sulfide Bi2S3And MoS2Preparing an electrocatalyst by a combined mode, and introducing an organic micromolecular functional material Alq into the electrocatalyst3The method can effectively improve the active sites of the electrocatalyst, thereby increasing the selection range of the electrocatalyst, improving the catalytic efficiency and reducing the cost. Electrocatalyst of the present application utilizing Bi2S3Asymmetric SP of lone pair electrons3Hybrid mode pair MoS2Produce electron induction effect to make MoS2The excellent electrocatalytic performance is shown.
The present solution is described in detail below:
as an alternative technical solution of the present application, in step S1, the specific method for pretreating the substrate NF is as follows:
the substrate NF is divided into two sections, acetone is firstly used for pretreatment, then double distilled water and pure ethanol are used for cleaning for 10 minutes respectively in an ultrasonic crusher in sequence, then dry nitrogen is used for drying, then the substrate NF is placed into a pretreatment chamber for oxygen plasma sputtering cleaning for 20 minutes, and the substrate NF is cooled to the room temperature.
The method comprises the steps of pretreating a substrate NF by using acetone, cleaning the substrate NF by using double distilled water and pure ethanol respectively, drying the substrate NF by using dry nitrogen, putting the substrate NF into a pretreatment chamber, and carrying out oxygen plasma sputtering cleaning, so that the surface of the substrate NF is clean, free of impurities and smooth, and the method is favorable for carrying out subsequent evaporation and solvent thermal reaction.
As an optional technical solution of the present application, in step S1, the evaporation conditions are: pressure of 2X 10-3Pa-4×10-3Pa, evaporation rate of 0.05nm/s-0.15nm/s, temperature of 200-250 deg.C.
Alternatively, the pressure may be 2 × 10-3Pa、2.2×10-3Pa、2.3×10-3Pa、2.5×10-3Pa、2.8×10- 3Pa、3.0×10-3Pa、3.2×10-3Pa、3.5×10-3Pa、3.8×10-3Pa or 4X 10-3Pa, etc., may be any other value within the above range, and is 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., although other values within the above range are possible and are not limited thereto. The temperature may be 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, or 250 ℃, or may be other values within the above range, and is not limited herein. Understandably, by limiting the pressure, evaporation rate and temperature during evaporation, better formation of Alq on the substrate NF is possible3And (3) a layer.
As an optional technical solution of the present application, in step S1, the Alq is set3The thickness of the layer is 50nm-70 nm.
Alternatively, Alq3The thickness of the layer may be 50nm, 52nm, 55nm, 58nm, 60nm, 62nm, 65nm, 68nm, 70nm, or the like, or 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 solution a is as follows: adding Bi (NO)3)3·5H2O and CH4N2And S is added into ethylene glycol according to the molar ratio of 1 to (1.5-2) and is uniformly stirred to obtain the solution A.
Alternatively, Bi (NO)3)3·5H2O and CH4N2The molar ratio of S may be 1: 1.5, 1: 1.6, 1: 1.7, 1: 1.8, 1: 1.9, 1: 2, etc., or may be other values within the above range, and is not limited thereto.
As an alternative technical solution of the present application, in step S2, the specific method of the first solvothermal reaction is as follows: will be provided with Alq3Keeping a first high-pressure reaction kettle for the substrate NF and the solution A of the layer for 15 to 20 hours at the temperature of between 150 and 170 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for many times, and baking in a vacuum oven at 50-70 deg.C for 7-9 h.
Alternatively, the reaction temperature of the first autoclave may be 150 ℃, 155 ℃, 160 ℃, 165 ℃ or 170 ℃, or the like, or may be other values within the above range, and the reaction time may be 15h, 16h, 17h, 18h, 19h or 20h, or the like, or may be other values within the above range, and the reaction temperature is not limited thereto. The temperature of the vacuum oven may be 50 ℃, 52 ℃, 55 ℃, 58 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃ or 70 ℃, although other values within the above range are possible, and the baking time of the vacuum oven is not limited herein, and may be 7h, 7.2h, 7.5h, 7.8h, 8h, 8.2h, 8.5h, 8.8h or 9h, and other values within the above range are also possible, and the baking time is not limited herein.
As an optional technical solution of the present application, in step S3, the specific method for preparing the solution B is as follows: mixing PPA with Na2MoO4·2H2And fully stirring the O according to the molar ratio of (4-6) to 1 until the O is transparent.
Alternatively, PPA and Na2MoO4·2H2The molar ratio of O may be 4: 1, 4.5: 1, 4.8: 1, 5: 1, 5.5: 1, 5.8: 1 or 6: 1, etc., and may be other values within the above range, which is not limited herein.
As an optional technical solution of the present application, in step S3, the specific method of the second solvothermal reaction is as follows: will be provided with Alq3Layer and Bi2S3Keeping the substrate NF of the layer and the second high-pressure reaction kettle of the solution B for 5 to 10 hours at the temperature of between 180 and 220 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for many times, and baking in a vacuum oven at 40-60 deg.C for 7-9 h.
Alternatively, the reaction temperature of the second autoclave may be 180 ℃, 190 ℃, 200 ℃, 210 ℃ or 220 ℃, although other values within the above range are also possible, and the reaction time is 5h, 6h, 7h, 8h, 9h or 10h, and the reaction time is also other values within the above range, and the reaction time is not limited. The temperature of the vacuum oven may be 40 ℃, 42 ℃, 45 ℃, 48 ℃, 50 ℃, 52 ℃, 55 ℃, 58 ℃ or 60 ℃, although other values within the above range are possible and not limited thereto, 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, and other values within the above range are also possible and not limited thereto.
In a second aspect, the embodiment of the present application further provides an electrocatalyst prepared by the preparation method described above; as shown in FIG. 2, the catalyst comprises a substrate NF 1 and Alq sequentially formed on the substrate NF 13Layer 2, Bi2S3Layer 3 and MoS2And (4) a layer.
The current density of the electrocatalyst is 10 mA-cm-2When the voltage is over-potential is 140mV-160mV, the Tafel slope is 60mV dec-1-70mV·dec-1。
The following examples are given for the purpose of illustration only. The present embodiments are not limited to the following specific examples. The present invention can be modified as appropriate within the scope of protection.
Example 1
A method of preparing an electrocatalyst, comprising the steps of:
step S1: dividing a substrate NF into two sections (2cm x 4cm), pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonication instrument for 10 minutes, blow-drying with dry nitrogen, and placing into an OLED-V type multifunctional deviceCarrying out oxygen plasma sputtering cleaning for about 20min in a pretreatment chamber of the organic film forming equipment, and transferring into a vacuum coating chamber after cooling to room temperature; at 3X 10-3Alq is carried out in a high vacuum environment of Pa3Forming Alq on the substrate NF by vapor deposition3And (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 thickness of the film is monitored to be 60nm by a Proteck9100 film thickness instrument in situ.
Step S2: adding Bi (NO)3)3·5H2O (1.0mmol) and CH4N2S (1.75mmol) is added into 60ml of ethylene glycol and stirred evenly to obtain the solution A. Subsequently, the solution a was poured into a polytetrafluoroethylene-substrate stainless steel first autoclave charged with NF that completed step S1, and kept at 160 ℃ for 16 hours. Cooling to room temperature, repeatedly cleaning the treated NF with distilled water and ethanol for several times, baking in a vacuum oven at 60 deg.C for 8 hr, and adding Alq3Forming Bi on the layer2S3A layer.
Step S3: PPA (6.25mmol), Na2MoO4·2H2Fully stirring O (1.25mmol) to be transparent, pouring into a second high-pressure reaction kettle which is provided with a polytetrafluoroethylene substrate stainless steel and is provided with NF after the step S2, baking for 8 hours at 200 ℃, cooling to room temperature, repeatedly cleaning for many times by using distilled water and ethanol, baking for 8 hours in a vacuum oven at 50 ℃, and putting Bi in the Bi2S3Formation of MoS on the layer2Layer, obtaining the electrocatalyst.
The obtained electro-catalyst is used as a working electrode, and Hg/HgO and a platinum sheet are respectively used as a reference electrode and a counter electrode to assemble an electro-catalytic three-electrode system for electro-catalytic test. At a current density of 10mA cm-2When the overpotential is 157mV, the Tafel slope is 65mV dec-1。
Example 2
Step S1: dividing a substrate NF into two sections (2cm x 4cm), pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonicator for 10 minutes, blow-drying with dry nitrogen, and placing into an OLED-V type multifunctional organic filmCarrying out oxygen plasma sputtering cleaning for about 20min in a pretreatment chamber of the equipment, and transferring the equipment into a vacuum coating chamber after cooling to room temperature; at 2X 10-3Carrying out Alq in a high vacuum environment of Pa3Forming Alq on the substrate NF by vapor deposition3And (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 thickness of the film is monitored to be 50nm by a Proteck9100 film thickness instrument in situ.
Step S2: adding Bi (NO)3)3·5H2O (1.0mmol) and CH4N2S (1.5mmol) is added into 60ml of glycol and stirred evenly to obtain the solution A. Subsequently, the solution a was poured into a polytetrafluoroethylene-substrate stainless steel first autoclave charged with NF that completed step S1, and was maintained in an environment of 150 ℃ for 18 hours. Cooling to room temperature, repeatedly cleaning the treated NF with distilled water and ethanol for several times, baking in a vacuum oven at 50 deg.C for 9 hr, and adding Alq3Forming Bi on the layer2S3And (3) a layer.
Step S3: PPA (5mmol), Na2MoO4·2H2Fully stirring O (1.25mmol) to be transparent, pouring into a second high-pressure reaction kettle which is provided with a polytetrafluoroethylene substrate stainless steel and is provided with NF after the step S2, baking for 10 hours in an environment of 180 ℃, cooling to room temperature, repeatedly cleaning for many times by using distilled water and ethanol, baking for 9 hours in a vacuum oven at the temperature of 40 ℃, and putting Bi in the mixture2S3Formation of MoS on layer2Layer, obtaining the electrocatalyst.
The obtained electro-catalyst is used as a working electrode, and Hg/HgO and a platinum sheet are respectively used as a reference electrode and a counter electrode to assemble an electro-catalytic three-electrode system for electro-catalytic test. At a current density of 10 mA-cm-2When the overpotential is 145mV, the Tafel slope is 60mV dec-1。
Example 3
Step S1: dividing a substrate NF into two sections (2cm x 4cm), pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonication instrument for 10 minutes, blow-drying with dry nitrogen, and pre-treating with OLED-V type multifunctional organic film forming equipmentTreating the chamber, carrying out oxygen plasma sputtering cleaning for about 20min, cooling to room temperature, and transferring into a vacuum coating chamber; at 4X 10-3Alq is carried out in a high vacuum environment of Pa3Forming Alq on the substrate NF by vapor deposition3And (3) a layer. Wherein, 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 thickness of the film is monitored to be 70nm by a Proteck9100 film thickness instrument in situ.
Step S2: adding Bi (NO)3)3·5H2O (1.0mmol) and CH4N2S (2mmol) is added into 60ml of ethylene glycol and stirred evenly to obtain the solution A. Subsequently, the solution a was poured into a polytetrafluoroethylene-substrate stainless steel first autoclave containing NF that completed step S1, and kept at 170 ℃ for 15 hours. Cooling to room temperature, repeatedly cleaning the treated NF with distilled water and ethanol for several times, baking in a vacuum oven at 70 deg.C for 7 hr, and adding Alq3Forming Bi on the layer2S3And (3) a layer.
Step S3: PPA (7.5mmol), Na2MoO4·2H2Fully stirring O (1.25mmol) to be transparent, pouring into a second high-pressure reaction kettle which is provided with a polytetrafluoroethylene substrate stainless steel and is provided with NF after the step S2, baking for 5 hours in an environment of 220 ℃, cooling to room temperature, repeatedly cleaning for many times by using distilled water and ethanol, baking for 7 hours in a vacuum oven at the temperature of 60 ℃, and putting Bi in the mixture2S3Formation of MoS on the layer2Layer, obtaining the electrocatalyst.
The obtained electro-catalyst is used as a working electrode, and Hg/HgO and a platinum sheet are respectively used as a reference electrode and a counter electrode to assemble an electro-catalytic three-electrode system for electro-catalytic test. At a current density of 10mA cm-2When the overpotential is 160mV, the Tafel slope is 70mV dec-1。
Example 4
Step S1: dividing a substrate NF into two sections (2cm x 4cm), pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonic crusher for 10 minutes, blow-drying with dry nitrogen, and placing into a pretreatment chamber of OLED-V type multifunctional organic film forming equipment for carrying outCarrying out sputtering cleaning on the oxygen plasma for about 20min, cooling to room temperature, and transferring into a vacuum coating chamber; at 2.5X 10-3Alq is carried out in a high vacuum environment of Pa3Forming Alq on the substrate NF by vapor deposition3And (3) a layer. Wherein, 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 thickness of the film is in-situ monitored to be 55nm by a Proteck9100 film thickness instrument.
Step S2: adding Bi (NO)3)3·5H2O (1.0mmol) and CH4N2S (1.6mmol) is added into 60ml of glycol and stirred evenly to obtain the solution A. Subsequently, the solution a was poured into a polytetrafluoroethylene-substrate stainless steel first autoclave containing NF that completed step S1, and kept at 155 ℃ for 18 hours. Cooling to room temperature, repeatedly cleaning the treated NF with distilled water and ethanol for several times, baking in a vacuum oven at 60 deg.C for 8 hr, and adding Alq3Forming Bi on the layer2S3And (3) a layer.
Step S3: PPA (5.75mmol), Na2MoO4·2H2O (1.25mmol) is fully stirred to be transparent, then poured into a stainless steel second high-pressure reaction kettle with a polytetrafluoroethylene substrate and the NF after the step S2 is finished, baked for 9 hours at 190 ℃, cooled to room temperature, repeatedly cleaned for many times by distilled water and ethanol, finally baked for 8.5 hours in a vacuum oven at 55 ℃, and Bi is added2S3Formation of MoS on the layer2Layer, the electrocatalyst was obtained.
The obtained electro-catalyst is used as a working electrode, and Hg/HgO and a platinum sheet are respectively used as a reference electrode and a counter electrode to assemble an electro-catalytic three-electrode system for electro-catalytic test. At a current density of 10mA cm-2When the overpotential is 155mV, the Tafel slope is 63mV dec-1。
Example 5
Step S1: dividing a substrate NF into two sections (2cm x 4cm), pretreating with acetone, sequentially cleaning with double distilled water and pure ethanol in an ultrasonicator for 10 minutes, blow-drying with dry nitrogen, placing into a pretreatment chamber of OLED-V type multifunctional organic film forming equipment, and performing oxygen oxidationCarrying out sputtering cleaning on the plasma for about 20min, cooling to room temperature, and then transferring into a vacuum coating chamber; at 3.5X 10-3Alq is carried out in a high vacuum environment of Pa3Forming Alq on the substrate NF by vapor deposition3And (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 thickness of the film is monitored to be 65nm by a Proteck9100 film thickness instrument in situ.
Step S2: adding Bi (NO)3)3·5H2O (1.0mmol) and CH4N2S (1.9mmol) is added into 60ml of ethylene glycol and stirred evenly to obtain the solution A. Subsequently, the solution a was poured into a polytetrafluoroethylene-substrate stainless steel first autoclave containing NF that completed step S1, and kept at 165 ℃ for 18 hours. Cooling to room temperature, repeatedly cleaning the treated NF with distilled water and ethanol for several times, baking in a vacuum oven at 65 deg.C for 7.5 hr, and adding Alq3Forming Bi on the layer2S3And (3) a layer.
Step S3: PPA (6.75mmol), Na2MoO4·2H2Stirring O (1.25mmol) thoroughly to transparent state, pouring into a stainless steel second high-pressure reaction kettle with polytetrafluoroethylene substrate containing NF obtained after step S2, baking at 215 deg.C for 6 hr, cooling to room temperature, repeatedly cleaning with distilled water and ethanol for multiple times, baking at 55 deg.C for 7.5 hr, and adding Bi2S3Formation of MoS on the layer2Layer, obtaining the electrocatalyst.
The obtained electro-catalyst is used as a working electrode, and Hg/HgO and a platinum sheet are respectively used as a reference electrode and a counter electrode to assemble an electro-catalytic three-electrode system for electro-catalytic test. At a current density of 10mA cm-2When the overpotential is 150mV, the Tafel slope is 62mV dec-1。
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. A preparation method of an electrocatalyst is characterized by comprising the following steps:
step S1: pretreating a substrate NF, placing the substrate NF in a vacuum coating chamber, and carrying out Alq in a high vacuum environment3Forming Alq on the substrate NF by vapor deposition3A layer;
step S2: will be formed with Alq3Placing 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 for carrying out first solvothermal reaction, and reacting in the Alq3Forming Bi on the layer2S3A layer;
step S3: will be formed with Alq3Layer and Bi2S3Putting the substrate NF of the layer into a second high-pressure reaction kettle; preparing solution B, pouring the solution B into the second high-pressure reaction kettle for second solvothermal reaction, and reacting Bi in the solution B2S3Formation of MoS on layer2Layer, obtaining the electrocatalyst.
2. The method for preparing the electrocatalyst according to claim 1, wherein the specific method for pretreating the substrate NF in step S1 is as follows:
the substrate NF is divided into two sections, acetone is used for pretreatment, then double distilled water and pure ethanol are used for cleaning for 10 minutes in an ultrasonicator in sequence, then dry nitrogen is used for drying, then the substrate NF is placed in a pretreatment chamber, oxygen plasma sputtering cleaning is carried out for 20 minutes, and the substrate NF is cooled to the room temperature.
3. The method for preparing an electrocatalyst according to claim 1, wherein in step S1, the evaporation conditions are: pressure of 2X 10-3Pa-4×10-3Pa, evaporation rate of 0.05nm/s-0.15nm/s, temperature of 200-250 deg.C.
4. The method of preparing an electrocatalyst according to claim 1 wherein in step S1 the Alq is3The thickness of the layer is 50nm-70 nm.
5. The method for preparing the electrocatalyst according to claim 1, wherein in step S2, the specific method for preparing the solution a is as follows: adding Bi (NO)3)3·5H2O and CH4N2And S is added into ethylene glycol according to the molar ratio of 1 to (1.5-2) and is uniformly stirred to obtain the solution A.
6. The method for preparing an electrocatalyst according to claim 1, wherein in step S2, the first solvothermal reaction is performed by: will be provided with Alq3Maintaining the substrate NF of the layer and the first high-pressure reaction kettle of the solution A for 15 to 20 hours at the temperature of between 150 and 170 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for many times, and baking in a vacuum oven at 50-70 deg.C for 7-9 h.
7. The method for preparing the electrocatalyst according to claim 1, wherein in step S3, the specific method for preparing the solution B is as follows: mixing PPA with Na2MoO4·2H2And fully stirring the O according to the molar ratio of (4-6) to 1 until the O is transparent.
8. The method for preparing the electrocatalyst according to claim 1, wherein in step S3, the second solvothermal reaction is performed by: will be provided with Alq3Layer and Bi2S3Keeping the substrate NF of the layer and the second high-pressure reaction kettle of the solution B for 5 to 10 hours at the temperature of between 180 and 220 ℃; cooling to room temperature, repeatedly cleaning the treated substrate NF with distilled water and ethanol for many times, and baking in a vacuum oven at 40-60 deg.C for 7-9 h.
9. An electrocatalyst prepared by the process of any one of claims 1 to 8; the catalyst comprises a substrate NF and a catalyst layer sequentially formed on the substrate NFAlq3Layer, Bi2S3Layer and MoS2And (3) a layer.
10. The electrocatalyst according to claim 9 wherein the electrocatalyst is operated at a current density of 10 mA-cm-2When the voltage is over-potential is 140mV-160mV, the Tafel slope is 60mV dec-1-70mV·dec-1。
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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

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* 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

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Title
宝阿敏;朱永春;高鹰;肖楠;辛士刚;张宏波;: "8-羟基喹啉-铝修饰碳糊电极的电催化作用", 沈阳师范大学学报(自然科学版), no. 03, pages 30 - 33 *

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