CN115011972B - Nonmetal electrocatalytic material and preparation method and application thereof - Google Patents
Nonmetal electrocatalytic material and preparation method and application thereof Download PDFInfo
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- CN115011972B CN115011972B CN202210823228.5A CN202210823228A CN115011972B CN 115011972 B CN115011972 B CN 115011972B CN 202210823228 A CN202210823228 A CN 202210823228A CN 115011972 B CN115011972 B CN 115011972B
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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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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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
- C25B11/065—Carbon
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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
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
The invention provides a nonmetallic electrocatalytic material, a preparation method and application thereof, and relates to the technical field of electrocatalytic materials. The preparation method of the nonmetal electrocatalytic material provided by the invention comprises the following steps: mixing graphene oxide, black phosphorus nano-sheets, water and an alcohol organic solvent, and carrying out reduction reaction to obtain the nonmetal electrocatalytic material. According to the invention, graphene oxide is used as a carrier and reacts with the black phosphorus nanosheets, wherein the black phosphorus nanosheets reduce the graphene oxide into reduced graphene oxide, reduce oxygen atoms of the graphene oxide, and enhance the conductivity of the composite material, so that the bifunctional nonmetallic electrocatalytic material is prepared. The nonmetal electrocatalytic material prepared by the invention shows good electrocatalytic activity through the regulation and control of the black phosphorus nanosheets, solves the problem of weak catalytic capacity of the nonmetal catalyst, and provides a new idea for obtaining the nonmetal electrocatalytic material with environmental protection, low cost and high performance.
Description
Technical Field
The invention relates to the technical field of electrocatalytic materials, in particular to a nonmetallic electrocatalytic material, and a preparation method and application thereof.
Background
In recent years, the development of green and sustainable energy is promoted due to the ever-increasing energy demand, rapid exhaustion of traditional fossil fuels and the increasing environmental problems. Hydrogen energy is considered a sustainable, renewable, environmental energy source. Currently, scientists in various countries are actively working on developing a technology for electrolyzing water to produce hydrogen so as to realize efficient and green large-scale preparation of hydrogen energy. In addition, the anodic oxygen evolution reaction of the semi-reaction for producing hydrogen by water electrolysis is one of the main factors for limiting the hydrogen production by water electrolysis due to the slow catalytic reaction kinetics. In order to effectively improve the hydrogen production efficiency of the electrolyzed water, finding a proper electrode material is one of the most effective breakthrough points for improving the catalytic efficiency of the electrolyzed water. However, the electrode materials at the present stage are often metal materials such as Ru and Ir, and cannot be prepared and applied on a large scale due to the influence of the disadvantages such as high cost, high pollution, scarcity and the like. Therefore, the prepared catalyst has great significance for green energy utilization in the carbon neutralization background.
Black phosphorus nanoplates (BPNanosheets) are the most stable allotrope of phosphorus as a two-dimensional layered nanomaterial, and have a unique pleated honeycomb structure, excellent charge carrying capacity and large specific surface area, and have great potential in electrocatalysis and energy storage. In addition, graphene Oxide (GO) has a large specific surface area, good chemical stability and flexibility, and is an ideal nanomaterial substrate. The two inorganic nonmetallic materials provide a new idea for preparing the environment-friendly, low-cost and high-performance nonmetallic catalyst. However, such non-metals as black phosphorus nanoplatelets and graphene oxide are inherently less conductive, preventing their use as electrode materials.
Disclosure of Invention
The invention aims to provide a nonmetal electrocatalytic material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a nonmetal electrocatalytic material, which comprises the following steps:
mixing graphene oxide, black phosphorus nano-sheets, water and an alcohol organic solvent, and carrying out reduction reaction to obtain the nonmetal electrocatalytic material.
Preferably, the temperature of the reduction reaction is 50-220 ℃; the time of the reduction reaction is 5-24 h.
Preferably, the reduction reaction is carried out in an argon atmosphere; the reduction reaction is carried out under a dark condition.
Preferably, the alcohol organic solvent comprises one or more of methanol, ethanol, glycerol, benzyl alcohol and isopropanol.
Preferably, after the reduction reaction, the method further comprises: and freeze-drying the obtained black precipitate under the dark condition to obtain the nonmetallic electrocatalytic material.
The invention provides a nonmetal electrocatalytic material prepared by the preparation method, which comprises a reduced graphene oxide nano sheet and a black phosphorus nano sheet loaded on the surface of the reduced graphene oxide nano sheet.
The invention provides an application of the nonmetal electrocatalytic material in preparing hydrogen by electrocatalytic water splitting.
Preferably, the mass ratio of the graphene oxide to the black phosphorus nano-sheet is 1:10 to 50 percent.
The invention provides an application of the nonmetal electrocatalytic material in preparing oxygen by electrocatalytic water splitting.
Preferably, the mass ratio of the graphene oxide to the black phosphorus nano-sheet is 1:0.1 to 10.
The invention provides a preparation method of a nonmetal electrocatalytic material, which is characterized in that graphene oxide, black phosphorus nano-sheets, water and an alcohol organic solvent are mixed, and the graphene oxide is reduced and loaded by utilizing the reducibility of black phosphorus to obtain a nonmetal electrocatalytic material (BP Nanosheets/rGO). According to the invention, graphene oxide is used as a carrier and reacts with the black phosphorus nanosheets, wherein the black phosphorus nanosheets reduce the graphene oxide into reduced graphene oxide, reduce oxygen atoms of the graphene oxide, and enhance the conductivity of the composite material, so that the bifunctional nonmetallic electrocatalytic material is prepared. The nonmetal electrocatalytic material prepared by the invention shows good electrocatalytic activity through the regulation and control of the black phosphorus nanosheets, solves the problem of weak catalytic capacity of the nonmetal catalyst, and provides a new idea for obtaining the nonmetal electrocatalytic material with environmental protection, low cost and high performance.
The invention adopts a one-pot method to prepare the nonmetallic electrocatalytic material, reduces the complicated steps of catalyst synthesis and improves the production efficiency. The nonmetal electrocatalytic material prepared by the invention shows different electrocatalytic water splitting performances under the adjustment of different mass ratios of the black phosphorus nano-sheets, and shows good electrocatalytic activity. In the invention, when the nonmetallic electrocatalytic material is used as a catalyst, the problem of weak catalytic capability of the nonmetallic material is solved, and a new idea is provided for the design of low-cost and high-performance electrocatalytic materials. In addition, the nonmetal electrocatalytic material is simple in preparation steps, does not need large equipment and training professional experimenters, has good electrocatalytic hydrolysis performance when being used as a catalyst, is low in cost, is favorable for later industrial preparation, and can be further popularized and used. The nonmetal electrocatalytic material prepared by the method can be used under acidic and alkaline conditions, and the application range of the nonmetal electrocatalytic material is greatly enlarged.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the nonmetallic electrocatalytic material prepared in example 1;
fig. 2 is an XPS diagram of the C element corresponding to the graphene oxide nanoplatelets in example 2;
fig. 3 is an XPS diagram of the C element corresponding to the reduced graphene oxide reduced with black phosphorus in example 3;
FIG. 4 is a graph showing the comparison of the electrocatalytic hydrogen production effect of the non-metallic electrocatalytic material prepared in example 5 with other materials; in fig. 4, BPNanosheets represent black phosphorus nanoplatelets, GO represents graphene oxide, rGO represents reduced graphene oxide, and BPNanosheets/rGO represents a non-metallic electrocatalytic material;
FIG. 5 is a graph showing the comparison of the electrocatalytic oxygen production effect of the non-metallic electrocatalytic material prepared in example 6 with other materials; in fig. 5 BPNanosheets represent black phosphorus nanoplatelets, GO represents graphene oxide, rGO represents reduced graphene oxide, and BPNanosheets/rGO represents a non-metallic electrocatalytic material.
Detailed Description
The invention provides a preparation method of a nonmetal electrocatalytic material, which comprises the following steps:
mixing graphene oxide, black phosphorus nano-sheets, water and an alcohol organic solvent, and carrying out reduction reaction to obtain the nonmetal electrocatalytic material.
In the present invention, the graphene oxide preferably has a size of 5 to 10 μm; the graphene oxide is preferably a graphene oxide nano sheet or a graphene oxide quantum dot. In the present invention, the size of the black phosphorus nanoplatelets is preferably 200nm to 2 μm. In the invention, the mass ratio of the graphene oxide to the black phosphorus nano-sheet is preferably 1:0.1 to 50. In the invention, when the mass ratio of the graphene oxide to the black phosphorus nano-sheet is 1:0.1 to 10 percent, the obtained nonmetallic electrocatalytic material is used for electrocatalytic oxygen evolution reaction; when the mass ratio of the graphene oxide to the black phosphorus nano sheet is 1: and 10-50, wherein the obtained nonmetal electrocatalytic material is used for electrocatalytic hydrogen evolution reaction.
In the present invention, the water is preferably oxygen-free water. In the present invention, the alcohol-based organic solvent preferably includes one or more of methanol, ethanol, glycerol, benzyl alcohol and isopropyl alcohol. In the present invention, the mass ratio of the water to the alcohol organic solvent is preferably 1 to 3:1, more preferably 1.5 to 2:1. In the present invention, the mass ratio of the graphene oxide to the alcohol organic solvent is preferably 1:0.1 to 500, more preferably 1:1 to 200.
In the present invention, the temperature of the reduction reaction is preferably 50 to 220 ℃, more preferably 80 to 200 ℃, still more preferably 100 to 150 ℃; the reduction reaction time is preferably 5 to 24 hours, more preferably 8 to 20 hours, and still more preferably 10 to 15 hours. In the present invention, the reduction reaction is preferably performed in an argon atmosphere; the reduction reaction is preferably carried out in the absence of light. In the reduction reaction process, the black phosphorus nano-sheet is compounded with the graphene oxide, and the graphene oxide is reduced into the reduced graphene oxide, so that the oxygen atom content on the surface of the graphene oxide is reduced, the carbon content is increased, and the electrocatalytic activity of the nonmetal electrocatalytic material is improved.
After the reduction reaction, the obtained system is preferably subjected to centrifugal washing to obtain black precipitate. In the present invention, the washing liquid used for the centrifugal washing is preferably ultrapure water. In the present invention, the number of times of the centrifugal washing is preferably 3 to 6, and the temperature of the centrifugal washing is preferably 4 to 15 ℃, more preferably 4 to 10 ℃; the rotational speed of the centrifugal washing is preferably 1000 to 8000rpm, more preferably 1000 to 5000rpm; the time of the single centrifugal washing is preferably 1 to 45 minutes, more preferably 5 to 30 minutes.
In the present invention, after the reduction reaction, it is preferable that: and freeze-drying the obtained black precipitate under the dark condition to obtain the nonmetallic electrocatalytic material. In the present invention, the freeze-drying is preferably vacuum freeze-drying; the temperature of the freeze drying is preferably-50 to-60 ℃ and the time is preferably 12 to 24 hours.
The invention provides a nonmetal electrocatalytic material prepared by the preparation method, which comprises a reduced graphene oxide nano sheet and a black phosphorus nano sheet loaded on the surface of the reduced graphene oxide nano sheet. In the present invention, the size of the nonmetallic electrocatalytic material is preferably 5 to 20 μm.
The invention provides an application of the nonmetal electrocatalytic material in preparing hydrogen by electrocatalytic water splitting. In the invention, the mass ratio of the graphene oxide to the black phosphorus nano sheet is 1:10 to 50, more preferably 1:20 to 25. In the present invention, the pH of the application is preferably 0.5 to 14. In the present invention, the application preferably includes: dispersing the nonmetallic electrocatalytic material in water to obtain catalytic ink; and coating the catalytic ink on a glassy carbon electrode, and performing electrocatalytic hydrogen evolution in an acidic solution or an alkaline solution. In the present invention, the concentration of the catalytic ink is preferably 1 to 15mg/mL, more preferably 2 to 10mg/mL. In the present invention, the acidic solution is preferably a sulfuric acid solution or a perchloric acid solution, the concentration of the sulfuric acid solution is preferably 0.5mol/L, and the concentration of the perchloric acid solution is preferably 0.1mol/L; the alkaline solution is preferably a potassium hydroxide solution, and the concentration of the potassium hydroxide solution is preferably 0.1 to 1mol/L.
The invention provides an application of the nonmetal electrocatalytic material in preparing oxygen by electrocatalytic water splitting. In the invention, the mass ratio of the graphene oxide to the black phosphorus nano sheet is 1:0.1 to 10, more preferably 1:0.2 to 5. In the present invention, the pH of the application is preferably 0.5 to 14. In the present invention, the application preferably includes: dispersing the nonmetallic electrocatalytic material in water to obtain catalytic ink; and coating the catalytic ink on a glassy carbon electrode, and performing electrocatalytic oxygen evolution in an acidic solution or an alkaline solution. In the present invention, the concentration of the catalytic ink is preferably 1 to 30mg/mL, more preferably 2 to 10mg/mL. In the present invention, the acidic solution is preferably a sulfuric acid solution or a perchloric acid solution, the concentration of the sulfuric acid solution is preferably 0.5mol/L, and the concentration of the perchloric acid solution is preferably 0.1mol/L; the alkaline solution is preferably a potassium hydroxide solution, and the concentration of the potassium hydroxide solution is preferably 0.1 to 1mol/L.
The nonmetal electrocatalytic material provided by the invention can be used as an electrocatalyst for preparing hydrogen and oxygen by electrocatalytic water decomposition.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) Respectively taking 12.5mg of black phosphorus nano-sheets and 0.5mg of graphene oxide nano-sheets, adding the black phosphorus nano-sheets and the graphene oxide nano-sheets into 30mL of oxygen-free water, then adding 20mL of ethanol, and fully and uniformly mixing;
(2) Heating the sample to 100 ℃ in an argon atmosphere, and reacting for 13 hours under the dark condition;
(3) And then cooling the sample to room temperature in an argon atmosphere, centrifugally washing with ultrapure water, wherein the rotational speed of centrifugal washing is 3000rpm, centrifuging for 15min in a centrifuge at 4 ℃, discarding the supernatant, repeatedly centrifugally washing for 3 times, and freeze-drying the finally precipitated sample under a dark condition to obtain the nonmetallic electrocatalytic material.
The transmission electron microscope picture of the nonmetallic electrocatalytic material prepared in this example is shown in fig. 1. As can be seen from fig. 1, the black phosphorus nanoplatelets are supported on the surface of the reduced graphene oxide nanoplatelets.
Application example 1
(1) 1mg of the nonmetallic electrocatalytic material prepared in example 1 was uniformly dispersed in 0.5mL of ultrapure water to obtain a catalytic ink;
(2) mu.L of the catalytic ink was applied to a 3mm diameter glass carbonThe electrocatalytic Hydrogen Evolution (HER) effect of the nonmetallic electrocatalytic material was tested on the electrode in 1mol/L KOH solution. The scanning rate is 10mV/S, the reference electrode is a saturated calomel electrode, and the current density is 10mA/cm 2 The prepared nonmetallic electrocatalytic material has an overpotential of 290mV.
Example 2
(1) Respectively taking 5.0mg of black phosphorus nano-sheets and 0.5mg of graphene oxide nano-sheets, adding into 40mL of oxygen-free water, then introducing into 20mL of methanol, and fully and uniformly mixing;
(2) Heating the sample to 130 ℃ in argon atmosphere, and reacting for 12 hours under dark condition;
(3) And then cooling the sample to room temperature in an argon atmosphere, centrifugally washing with ultrapure water, wherein the rotational speed of centrifugal washing is 2000rpm, centrifuging for 20min in a centrifuge at 10 ℃, discarding supernatant, repeatedly centrifugally washing for 4 times, and placing the finally precipitated sample in a vacuum freeze dryer, and freeze-drying under dark conditions to obtain the nonmetallic electrocatalytic material.
In this embodiment, an XPS diagram of a C element corresponding to the graphene oxide nanoplatelets is shown in fig. 2. As can be seen from fig. 2, the graphene oxide nanoplatelets are mainly composed of c—c bonds, c=o bonds, and c—o bonds.
Application example 2
(1) 2mg of the nonmetallic electrocatalytic material prepared in example 2 was uniformly dispersed in 0.2mL of ultrapure water to obtain a catalytic ink;
(2) 2. Mu.L of the catalytic ink was coated on a glassy carbon electrode of 3mm diameter and the electrocatalytic Oxygen Evolution (OER) effect of the nonmetallic electrocatalytic material was tested in 1mol/L KOH solution. The scanning rate is 5mV/S, the reference electrode is a mercury oxide electrode, when the current density is 10mA/cm 2 The prepared nonmetallic electrocatalytic material had an overpotential of 350mV.
Example 3
(1) Respectively taking 6.0mg of black phosphorus nano-sheets and 0.3mg of graphene oxide nano-sheets, adding the black phosphorus nano-sheets and the graphene oxide nano-sheets into 30mL of oxygen-free water, then adding 30mL of isopropanol, and fully and uniformly mixing;
(2) Heating the sample to 100 ℃ in argon atmosphere, and reacting for 15 hours under dark condition;
(3) And then cooling the sample to room temperature in an argon atmosphere, centrifugally washing with ultrapure water, wherein the rotational speed of centrifugal washing is 1000rpm, centrifuging for 30min in a centrifuge at 6 ℃, discarding supernatant, repeatedly centrifugally washing for 4 times, and placing the finally precipitated sample in a vacuum freeze dryer, and freeze-drying under dark conditions to obtain the nonmetallic electrocatalytic material.
In this embodiment, an XPS diagram of the C element corresponding to the reduced graphene oxide reduced by black phosphorus is shown in fig. 3. As can be seen from fig. 3, after the graphene oxide nano-sheets and the black phosphorus nano-sheets are loaded, the c—c bond content is increased, and the c=o bond content is significantly reduced. Indicating that the graphene oxide nanoplatelets were successfully reduced to reduced graphene oxide nanoplatelets.
Application example 3
(1) 1mg of the nonmetallic electrocatalytic material prepared in example 3 was uniformly dispersed in 0.1mL of ultrapure water to obtain a catalytic ink;
(2) 2. Mu.L of the catalytic ink was applied to a 3mm diameter glassy carbon electrode at 0.5mol/L H 2 SO 4 The electrocatalytic Hydrogen Evolution (HER) effect of the nonmetallic electrocatalytic material was tested in solution. The scanning rate is 10mV/S, the reference electrode is a saturated calomel electrode, and the current density is 10mA/cm 2 When the prepared nonmetallic electrocatalytic material has an overpotential of 360mV, the nonmetallic electrocatalytic material has better catalytic activity under an acidic condition.
Example 4
(1) Respectively taking 0.4mg of black phosphorus nano-sheets and 2.0mg of graphene oxide nano-sheets, adding into 15mL of oxygen-free water, then introducing into 15mL of ethanol, and fully and uniformly mixing;
(2) Heating the sample to 140 ℃ in argon atmosphere, and reacting for 10 hours under dark condition;
(3) And then cooling the sample to room temperature in an argon atmosphere, centrifugally washing with ultrapure water, wherein the rotational speed of centrifugal washing is 4000rpm, centrifuging for 10min in a centrifuge at 6 ℃, discarding supernatant, repeatedly centrifugally washing for 5 times, and placing the finally precipitated sample in a vacuum freeze dryer, and freeze-drying under dark conditions to obtain the nonmetallic electrocatalytic material.
Application example 4
(1) 1mg of the nonmetallic electrocatalytic material prepared in example 4 was uniformly dispersed in 0.2mL of ultrapure water to obtain a catalytic ink;
(2) 4 mu L of the catalytic ink was coated on a glassy carbon electrode with a diameter of 3mm, and the electrocatalytic Oxygen Evolution (OER) effect of the nonmetallic electrocatalytic material was tested in 0.1mol/L KOH solution. The scanning rate is 10mV/S, the reference electrode is a mercury oxide electrode, when the current density is 10mA/cm 2 When the prepared nonmetallic electrocatalytic material has an overpotential of 330mV, the nonmetallic electrocatalytic material has better catalytic activity under alkaline conditions.
Example 5
(1) Respectively taking 10.0mg of black phosphorus nano-sheets and 0.2mg of graphene oxide nano-sheets, adding the black phosphorus nano-sheets and the graphene oxide nano-sheets into 60mL of oxygen-free water, then introducing the oxygen-free water into 40mL of benzyl alcohol, and fully and uniformly mixing the oxygen-free water and the benzyl alcohol;
(2) Heating the sample to 110 ℃ in argon atmosphere, and reacting for 14 hours under dark condition;
(3) And then cooling the sample to room temperature in an argon atmosphere, centrifugally washing with ultrapure water, wherein the rotational speed of centrifugal washing is 1500rpm, centrifuging for 20min in a centrifugal machine at 8 ℃, discarding supernatant, repeatedly centrifugally washing for 6 times, and placing the finally precipitated sample in a vacuum freeze dryer, and freeze-drying under a dark condition to obtain the nonmetallic electrocatalytic material.
Application example 5
(1) 1mg of the nonmetallic electrocatalytic material prepared in example 5 was uniformly dispersed in 0.5mL of ultrapure water to obtain a catalytic ink;
(2) mu.L of the catalytic ink was coated on a 3mm diameter glassy carbon electrode and the electrocatalytic Hydrogen Evolution (HER) effect of the nonmetallic electrocatalytic material was tested in 1mol/L KOH solution.
As shown in fig. 4, the HER catalytic performance of the black phosphorus nanoplatelets and the graphene oxide nanoplatelets is poor, but the catalytic performance of the nonmetal electrocatalytic material prepared by compositing the black phosphorus nanoplatelets and the graphene oxide nanoplatelets is obviously improved, and the nonmetal electrocatalytic material has good HER catalytic activity. At a scan rate of 10mV/S, the reference electrode is oxidizedA mercury electrode with a current density of 10mA/cm 2 The prepared nonmetallic electrocatalytic material had an overpotential of 253mV.
Example 6
(1) Respectively taking 1.0mg of black phosphorus nano-sheets and 10.0mg of graphene oxide nano-sheets, adding the black phosphorus nano-sheets and the graphene oxide nano-sheets into 30mL of oxygen-free water, then adding 20mL of ethanol, and fully and uniformly mixing;
(2) Heating the sample to 150 ℃ in argon atmosphere, and reacting for 10 hours under dark condition;
(3) And then cooling the sample to room temperature in an argon atmosphere, centrifugally washing with ultrapure water, wherein the rotational speed of centrifugal washing is 5000rpm, centrifuging for 5min in a centrifuge at 4 ℃, discarding supernatant, repeatedly centrifugally washing for 3 times, and placing the finally precipitated sample in a vacuum freeze dryer, and freeze-drying under dark conditions to obtain the nonmetallic electrocatalytic material.
Application example 6
(1) 1mg of the nonmetallic electrocatalytic material prepared in example 6 was uniformly dispersed in 0.5mL of ultrapure water to obtain a catalytic ink;
(2) mu.L of the catalytic ink was coated on a glassy carbon electrode with a diameter of 3mm, and the electrocatalytic Oxygen Evolution (OER) effect of the nonmetallic electrocatalytic material was tested in a 1mol/L KOH solution. The scanning rate is 10mV/S, the reference electrode is a saturated calomel electrode, when the current density is 10mA/cm 2 The prepared nonmetallic electrocatalytic material had an overpotential of 440mV.
As shown in FIG. 5, the OER catalytic performance of the black phosphorus nano-sheet and the graphene oxide nano-sheet is poor, but the catalytic performance of the nonmetal electrocatalytic material prepared by compounding the black phosphorus nano-sheet and the graphene oxide nano-sheet is obviously improved, and the OER electrocatalytic performance is good.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A preparation method of a nonmetal electrocatalytic material comprises the following steps:
mixing graphene oxide, black phosphorus nano-sheets, water and an alcohol organic solvent, and carrying out reduction reaction to obtain a nonmetal electrocatalytic material;
the nonmetallic electrocatalytic material comprises a reduced graphene oxide nano-sheet and a black phosphorus nano-sheet loaded on the surface of the reduced graphene oxide nano-sheet.
2. The method according to claim 1, wherein the temperature of the reduction reaction is 50 to 220 ℃; the time of the reduction reaction is 5-24 h.
3. The production method according to claim 1, wherein the reduction reaction is performed in an argon atmosphere; the reduction reaction is carried out under a dark condition.
4. The method according to claim 1, wherein the alcoholic organic solvent comprises one or more of methanol, ethanol, glycerol, benzyl alcohol and isopropyl alcohol.
5. The method according to claim 1, further comprising, after the reduction reaction: and freeze-drying the obtained black precipitate under the dark condition to obtain the nonmetallic electrocatalytic material.
6. The nonmetal electrocatalytic material prepared by the preparation method of any one of claims 1 to 5, comprising reduced graphene oxide nanoplatelets and black phosphorus nanoplatelets loaded on the surfaces of the reduced graphene oxide nanoplatelets.
7. The use of the nonmetallic electrocatalytic material of claim 6 for preparing hydrogen by electrocatalytic water splitting.
8. The use according to claim 7, wherein the mass ratio of graphene oxide to black phosphorus nanoplatelets is 1:10 to 50 percent.
9. The use of the non-metallic electrocatalytic material of claim 6 for preparing oxygen by electrocatalytic water splitting.
10. The use according to claim 9, wherein the mass ratio of graphene oxide to black phosphorus nanoplatelets is 1:0.1 to 10.
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| CN113019405A (en) * | 2021-01-08 | 2021-06-25 | 深圳万物创新集团有限公司 | Preparation method and application of metal composite black phosphorus-based electrocatalyst |
| CN114100660A (en) * | 2021-11-29 | 2022-03-01 | 西藏大学 | Titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst, and preparation method and application thereof |
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| WO2019237188A1 (en) * | 2018-06-15 | 2019-12-19 | Institut National De La Recherche Scientifique | Metal-free few-layer phosphorous nanomaterial: method for its preparation and use thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190042291A (en) * | 2017-10-16 | 2019-04-24 | 성균관대학교산학협력단 | Black phosphorus and graphene composite and method of manufacturing the composite |
| CN113019405A (en) * | 2021-01-08 | 2021-06-25 | 深圳万物创新集团有限公司 | Preparation method and application of metal composite black phosphorus-based electrocatalyst |
| CN114100660A (en) * | 2021-11-29 | 2022-03-01 | 西藏大学 | Titanium nitride and nitrogen-doped composite graphene-black phosphorus-based catalyst, and preparation method and application thereof |
Non-Patent Citations (1)
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| 二维材料的合成方法及在催化领域应用的研究进展;杨晨;高凤雨;唐晓龙;易红宏;苗磊磊;于庆君;赵顺征;;材料导报(13);9-20 * |
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