CN111945185A - Graphene aerogel working electrode material and preparation method thereof, graphene aerogel working electrode and preparation method and application thereof - Google Patents
Graphene aerogel working electrode material and preparation method thereof, graphene aerogel working electrode and preparation method and application thereof Download PDFInfo
- Publication number
- CN111945185A CN111945185A CN202010856473.7A CN202010856473A CN111945185A CN 111945185 A CN111945185 A CN 111945185A CN 202010856473 A CN202010856473 A CN 202010856473A CN 111945185 A CN111945185 A CN 111945185A
- Authority
- CN
- China
- Prior art keywords
- graphene aerogel
- working electrode
- graphene
- aerogel
- oxide powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- 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
- Y02P20/141—Feedstock
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a graphene aerogel working electrode material and a preparation method thereof, and a graphene aerogel working electrode and a preparation method and application thereof. The working electrode material comprises graphene aerogel and nanometer cuprous oxide powder loaded on the graphene aerogel, wherein the graphene aerogel is a three-dimensional porous CNT-doped graphene aerogel material prepared from graphene oxide and carbon nanotubes serving as raw materials. This graphite alkene aerogel working electrode, it includes electrode substrate and above-mentioned graphite alkene aerogel working electrode material, and graphite alkene aerogel working electrode material is attached to electrode substrate surface. The nanometer cuprous oxide powder can be uniformly distributed in the structure of the graphene aerogel, the tendency of condensation of the nanometer cuprous oxide powder is low, the stability of the catalyst is improved, the stability can be stabilized for more than 3 hours, and the preparation method of the graphene aerogel working electrode is simple in process, easy to operate and good in application prospect.
Description
Technical Field
The invention relates to the technical field of electrode preparation processes, in particular to a graphene aerogel working electrode material and a preparation method thereof, and a graphene aerogel working electrode and a preparation method and application thereof.
Background
Since the 21 st century, increasing importance has been placed on greenhouse effect, and CO has been carried out2The realization of carbon recycling economy has become a widespread consensus in international society. But CO2The properties are stable, the high temperature and high pressure are required for the current relatively mature reduction routes such as catalytic hydromethanation, methanol synthesis, dimethyl ether synthesis, low-carbon olefin synthesis and the like, and the reaction conditions are harsh, so that the CO reaction conditions are milder2Electrochemical reduction has become a focus of research in recent years.
Electrocatalytic carbon dioxide reduction is a process in which carbon dioxide molecules or carbon dioxide solvated ions in a solution obtain electrons from the surface of an electrode to perform a reduction reaction. In an aqueous solution, carbon dioxide has low solubility in water, so that carbon dioxide is difficult to diffuse to the surface of an electrode, and thus the reaction rate is low; although the organic solvent and the ionic liquid have the characteristics of good conductivity, small viscosity and strong capability of dissolving carbon dioxide, the use cost is high, and the organic solvent has volatility and toxic and side effects. Therefore, the electrocatalytic reduction of carbon dioxide in the prior art has the problems that the use amount of organic solvent is high, and the reduction reaction efficiency is still to be improved.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a graphene aerogel working electrode material and a preparation method thereof, and a graphene aerogel working electrode and a preparation method and application thereof.
The invention is realized by the following steps:
in a first aspect, an embodiment of the present invention provides a graphene aerogel working electrode material, which includes a graphene aerogel and a nano cuprous oxide powder loaded on the graphene aerogel, where the graphene aerogel is a three-dimensional porous CNT-doped graphene aerogel material prepared from graphene oxide and carbon nanotubes as raw materials.
In a second aspect, an embodiment of the present invention further provides a preparation method of the graphene aerogel working electrode material, where the preparation method includes: and loading the nano cuprous oxide powder on the graphene aerogel.
In a third aspect, an embodiment of the present invention further provides a graphene aerogel working electrode, which includes an electrode substrate and the graphene aerogel working electrode material, where the graphene aerogel working electrode material is attached to a surface of the electrode substrate.
Optionally, the electrode substrate is carbon paper or carbon nanotube sponge;
optionally, the specifications of the carbon paper and the carbon nanotube sponge are any one of 1cm × 1cm, 1cm × 1.5cm, 1.5cm × 2cm and 2cm × 2 cm;
optionally, the carbon nanotube sponge is a spongy carbon nanotube macroscopic body formed by self-assembly of multi-walled carbon nanotubes, and the thickness of the spongy carbon nanotube macroscopic body is 1 mm-4 mm.
In a fourth aspect, an embodiment of the present invention further provides a preparation method of the graphene aerogel working electrode, where the preparation method includes: and coating the nano cuprous oxide powder and the dispersion turbid liquid of the graphene aerogel on the surface of the electrode matrix.
Optionally, the electrode matrix coated with the dispersion suspension is dried, preferably by infrared lamp drying.
In a fifth aspect, an embodiment of the present invention further provides an application of the graphene aerogel working electrode material or the graphene aerogel working electrode in electrocatalytic reduction of carbon dioxide.
In a sixth aspect, embodiments of the present invention further provide a method for electrocatalytic reduction of carbon dioxide, including: the graphene aerogel working electrode is used as a cathode electrode to carry out electrocatalytic reduction on carbon dioxide;
alternatively, a double-chamber electrolytic cell is adopted, and external voltage is applied, and potassium bicarbonate water solution is used as electrolyte solution.
Alternatively, an H-type two-compartment cell is used, separated by a Nafion117 proton exchange membrane, allowing only H+The counter electrode is a platinum net, the reference electrode is Ag/AgCl, voltage is provided by an AUTOLAB electrochemical workstation, electrolyte solution is 0.1-0.5 mol/L potassium bicarbonate solution, and carbon dioxide gas is continuously introduced into the H-shaped double-chamber electrolytic cell in the electrocatalysis process. Optionally, carbon dioxide gas is introduced into the electrolyte for 30-60 min before the reaction is carried out.
Optionally, in the electrocatalytic reduction carbon dioxide system, the electrode clamp adopts a glassy carbon substrate electrode clamp.
One of the schemes of the above embodiments of the present invention has at least the following beneficial effects: the graphene aerogel used as a carrier of the electrochemical catalyst has the advantages of rich oxygen-containing groups on the surface of the graphene, high electron transmission speed, large specific surface area of the aerogel and high porosity, can provide a plurality of adsorption sites, is favorable for gas diffusion and flow, enables gas molecules to be easily contacted with the adsorption sites, promotes carbon dioxide in a solution to be diffused to the surface of an electrode for reaction, has high current density, and can improve the microstructure of the aerogel by utilizing the reinforcing effect of the carbon nano tube. Furthermore, as the nano copper metal powder can be uniformly distributed in the structure of the graphene aerogel, the nano cuprous oxide powder has small tendency of agglomeration, the stability of the catalyst is improved, and the efficiency of catalytic reaction is also improved, so that an organic solvent is not needed in the reaction process of electrocatalytic reduction of carbon dioxide, and the cost and toxic and side effects caused by the organic solvent are reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a plot of the linear voltammetry scans of different working electrodes of example 1 and comparative examples 1-2 of the present invention;
FIG. 2 is a comparison of current densities at different applied voltages for example 1 of the present invention and comparative example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The graphene aerogel working electrode material and the preparation method thereof, the graphene aerogel working electrode and the preparation method and the application thereof provided by the invention are specifically explained below.
Some embodiments of the present invention provide a graphene aerogel working electrode material, which includes a graphene aerogel and a nano cuprous oxide powder loaded on the graphene aerogel, wherein the graphene aerogel is a three-dimensional porous CNT-doped graphene aerogel material prepared from graphene oxide and carbon nanotubes as raw materials.
In electrocatalytic reduction of CO2In the study of (2), the nano-scale cuprous oxide powder has a larger contact area with the reactant, but is easily aggregated to cause a decrease in catalytic effect, and is poor in stability. The graphene aerogel takes graphene oxide and Carbon Nano Tubes (CNT) as raw materials, and is subjected to freeze dryingOr a three-dimensional porous CNT-doped graphene aerogel material self-assembled by a specific reduction method. The air is used as a medium, and the nano porous three-dimensional network structure is formed by mutual aggregation of colloidal particles or high polymer molecules. Through a large amount of researches and practices, the inventor finds that the nanometer cuprous oxide powder is combined with the graphene aerogel, so that the nanometer cuprous oxide powder can be uniformly distributed in the structure of the graphene aerogel, the agglomeration trend of the nanometer cuprous oxide powder is further reduced, and the nanometer cuprous oxide can be sufficiently electrocatalyzed. The graphene aerogel serving as a carrier of the electrochemical catalyst has the advantages of rich oxygen-containing groups on the surface of the graphene, high electron transmission speed, large specific surface area of aerogel and high porosity, can provide a plurality of adsorption sites, is favorable for gas diffusion and flow, enables gas molecules to be easily contacted with the adsorption sites, promotes carbon dioxide in a solution to be diffused to the surface of an electrode for reaction, has high current density, and can improve the microstructure of the aerogel by utilizing the reinforcing effect of the carbon nano tube, so that the carbon nano tube-doped graphene aerogel and the nano cuprous oxide jointly promote the catalytic reaction.
Further, in order to improve the catalytic performance of the nano cuprous oxide powder, the load of the nano cuprous oxide powder needs to be required, the load of the nano cuprous oxide powder is too small, so that the catalytic effect of a better surface is difficult to achieve, the load of the nano cuprous oxide powder is too large, the influence of the nano cuprous oxide powder on the pore structure of the graphene aerogel is easily caused, and the catalytic performance is reduced. Therefore, in some embodiments, the loading amount of the nanometer cuprous oxide powder is 0.1-5 mg/cm2For example, the loading may be 0.1mg/cm2、0.2mg/cm2、0.3mg/cm2、0.4mg/cm2、0.5mg/cm2、0.6mg/cm2、0.7mg/cm2、0.8mg/cm2、0.9mg/cm2、1mg/cm2、1.1mg/cm2、1.2mg/cm2、1.3mg/cm2、1.4mg/cm2、1.5mg/cm2、1.6mg/cm2、1.7mg/cm2、1.8mg/cm2、1.9mg/cm2、2.0mg/cm2、2.1mg/cm2、2.2mg/cm2、2.3mg/cm2、2.4mg/cm2、2.5mg/cm2、2.6mg/cm2、2.7mg/cm2、2.8mg/cm2、2.9mg/cm2、3mg/cm2、3.2mg/cm2、3.4mg/cm2、3.5mg/cm2、3.7mg/cm2、3.9mg/cm2、4.1mg/cm2、4.3mg/cm2、4.5mg/cm2、4.6mg/cm2、4.7mg/cm2、4.9mg/cm2Or 5mg/cm2The loading amount is preferably 0.5-3 mg/cm2More preferably 1 to 2mg/cm2Most preferably 1mg/cm2。
Further, in order to achieve better performance of the formed graphene aerogel, in some embodiments, the mass ratio of the carbon nanotubes in the raw material is 9-11%, preferably 10%.
In some embodiments, the nano cuprous oxide powder has an average particle size of 20nm to 60 nm. The nanometer cuprous oxide powder with the particle size has better catalytic performance, and can be easily loaded in a three-dimensional pore structure of the graphene aerogel and cannot be easily condensed.
Some embodiments of the present invention also provide a preparation method of the graphene aerogel working electrode material, including: and loading the nano cuprous oxide powder on the graphene aerogel.
Specifically, the method for loading the nano cuprous oxide powder on the graphene aerogel specifically comprises the following steps:
s1, preparing graphene aerogel: and (3) freeze-drying the uniform mixture of the graphene oxide and the carbon nano tube to obtain the three-dimensional porous CNT-doped graphene aerogel material.
In some embodiments, graphene oxide and carbon nanotubes are uniformly mixed in water, and then freeze-dried to obtain the three-dimensional porous CNT-doped graphene aerogel material. Wherein the water is deionized water.
In some embodiments, after freeze-drying to obtain the three-dimensional porous CNT-doped graphene aerogel material, the three-dimensional porous CNT-doped graphene aerogel material is ground into powder. It should be noted that the freeze-drying parameters are conventional.
And S2, dispersing and mixing the nano cuprous oxide powder and the graphene aerogel in a solution system, and drying to obtain the nano cuprous oxide powder-graphene aerogel.
In some embodiments, the graphene aerogel is in a powder form, which is the powder developed in the above step. In some embodiments, the solvent of the solution system comprises alcohol, water and Nafion solution, preferably, the alcohol comprises ethanol and isopropanol, preferably, the volume ratio of alcohol to water is 1: 5-5: 1, the volume ratio of ethanol to isopropanol is 1: 5-5: 1, the volume ratio of Nafion solution to water is 1: 5-1: 20, the mass concentration of the Nafion solution is 5 wt%.
In some embodiments, in order to allow the reaction to be sufficiently performed, the step of dispersing and mixing the nano cuprous oxide powder and the graphene aerogel in the solution system comprises: mixing the powdery graphene aerogel with the nano cuprous oxide powder, and then adding ethanol, isopropanol, water and a Nafion solution to perform ultrasonic dispersion until the mixture is uniform, wherein preferably, the water is deionized water.
Further, in order to enable uniform loading of the desired loading amount of the nano cuprous oxide powder in the three-dimensional pore structure of the graphene aerogel, in some embodiments, the mass ratio of the graphene aerogel to the nano cuprous oxide powder is 1: 1-30, preferably 1: 5.
some embodiments of the present invention also provide a graphene aerogel working electrode, comprising: electrode substrate and above-mentioned graphite alkene aerogel working electrode material, graphite alkene aerogel working electrode material is attached to electrode substrate surface. The working electrode with the graphene aerogel working electrode material can fully play a role in electrocatalysis of carbon dioxide reduction, and the current density is stable.
In some embodiments, the electrode substrate is carbon paper or carbon nanotube sponge; further, the specification of the carbon paper and the carbon nanotube sponge may be any one of 1cm × 1cm, 1cm × 1.5cm, 1.5cm × 2cm, and 2cm × 2cm, according to actual needs.
In some embodiments, the carbon nanotube sponge is a spongy carbon nanotube macroscopic body formed by self-assembly of multi-walled carbon nanotubes, and the thickness of the spongy carbon nanotube macroscopic body is 1 mm-4 mm.
Some embodiments of the present invention also provide a preparation method of the graphene aerogel working electrode, including: and coating the nano cuprous oxide powder and the dispersion turbid liquid of the graphene aerogel on the surface of the electrode matrix.
Specifically, the preparation method of the graphene aerogel working electrode can comprise the following steps:
s1, preparing graphene aerogel: and (3) freeze-drying the uniform mixture of the graphene oxide and the carbon nano tube to obtain the three-dimensional porous CNT-doped graphene aerogel material.
For specific operations, reference is made to the preparation method of the graphene aerogel working electrode material, which is not described herein again.
S2, dispersing and mixing the nano cuprous oxide powder and the graphene aerogel in a solution system to obtain a dispersion suspension.
For specific operations, reference is made to the preparation method of the graphene aerogel working electrode material, which is not described herein again.
And S3, uniformly coating the ink suspension on carbon paper or carbon nanotube sponge, and drying by an infrared lamp to obtain the working electrode.
Some embodiments of the invention also provide application of the graphene aerogel working electrode material or the graphene aerogel working electrode in electrocatalytic reduction of carbon dioxide.
Some embodiments of the present invention also provide a method of electrocatalytic reduction of carbon dioxide, comprising: the graphene aerogel working electrode is used as a cathode electrode to carry out electrocatalytic reduction on carbon dioxide;
specifically, a double-chamber electrolytic cell may be used, to which an external voltage is applied, using an aqueous solution of potassium bicarbonate as an electrolyte solution.
Further, an H-type two-compartment cell can be used, separated by a Nafion117 proton exchange membrane, allowing only H+The counter electrode is a platinum net, the reference electrode is Ag/AgCl, the voltage is provided by an AUTOLAB electrochemical workstation, and the electrolyte solution is 0.1-0.5 mol/L of carbonAnd (3) continuously introducing carbon dioxide gas into the H-type double-chamber electrolytic cell in the electrocatalysis process of the potassium hydrogen chloride solution, and more preferably introducing the carbon dioxide gas into the electrolyte for 30-60 min before the reaction is carried out.
Further, in some embodiments, in the system for electrocatalytic reduction of carbon dioxide, the electrode clamp adopts a glassy carbon substrate electrode clamp, which can effectively prevent the interference of hydrogen evolution of the platinum substrate electrode clamp on the system.
Some embodiments of the present invention also provide a method of electrocatalytic reduction of carbon dioxide, comprising: the reaction adopts an H-shaped double-chamber electrolytic cell, the middle of the H-shaped double-chamber electrolytic cell is separated by a Nafion117 proton exchange membrane, and only H is allowed+The counter electrode is a platinum net, the reference electrode is Ag/AgCl, voltage is provided by an AUTOLAB electrochemical workstation, electrolyte solution is 0.1-0.5 mol/L potassium bicarbonate solution, and carbon dioxide gas is continuously introduced into the double-chamber electrolytic cell. The carbon paper or carbon nanotube sponge substrate adopts the specification of 1cm multiplied by 1.5 cm. Carbon dioxide gas is required to be introduced into the electrolyte for 30-60 min before the reaction, and the test process is carried out at normal temperature.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The preparation method comprises the steps of taking graphene oxide and carbon nanotubes as raw materials, controlling the mass ratio of the carbon nanotubes to be 10%, uniformly mixing in a deionized water solution, and freeze-drying to obtain the three-dimensional porous CNT-doped graphene aerogel material.
Respectively weighing 50mg of nano cuprous oxide powder and 10mg of graphene aerogel powder, adding 1200 mu L of absolute ethyl alcohol, 1200 mu L of isopropanol, 2400 mu L of deionized water and 200 mu L of Nafion solution, uniformly mixing, placing the mixture into an ultrasonic instrument, ultrasonically dispersing for 1h, taking 200 mu L of suspension liquid drops by using a liquid-transferring gun, coating the suspension liquid drops on carbon paper with the thickness of 1cm multiplied by 1.5cm, drying by using an infrared lamp to obtain the graphene aerogel working electrode, wherein the surface of the working electrode is made of a graphene aerogel working electrode material, and the loading amount of the catalyst is 1mg/cm through calculation2. An H-shaped double-chamber electrolytic cell is adopted, the middle is separated by a Nafion117 proton exchange membrane, a graphene aerogel working electrode is taken as a working electrode,Ag/AgCl is used as a reference electrode, a platinum net is used as a counter electrode, 0.1mol/L potassium bicarbonate solution is used as an electrolyte solution, and CO is added into a double-chamber electrolytic cell at the flow rate of 20mL/min2After aeration is carried out for 40min, electrification is carried out to carry out electrocatalytic reduction on carbon dioxide, linear volt-ampere scanning is carried out in the electrocatalytic reduction process, the scanning range is-3.0V-0V, and the scanning speed is 20 mV/s.
Comparative example 1
Carbon paper of 1cm multiplied by 1.5cm is taken as a working electrode, Ag/AgCl is taken as a reference electrode, a platinum net is taken as a counter electrode, 0.1mol/L potassium bicarbonate solution is taken as an electrolyte solution, and CO is contained in a double-chamber electrolytic cell at the flow rate of 20mL/min2And performing linear volt-ampere scanning after aerating for 40min, wherein the scanning range is-3.0V-0V, and the scanning rate is 20 mV/s.
Comparative example 2
Weighing 50mg of nanometer cuprous oxide powder, adding 1200 mu L of absolute ethyl alcohol, 1200 mu L of isopropanol, 2400 mu L of deionized water and 200 mu L of Nafion solution, uniformly mixing, placing the mixture into an ultrasonic instrument, ultrasonically dispersing for 1h, taking 200 mu L of suspension liquid drop by using a liquid transfer gun, coating the suspension liquid on carbon paper with the thickness of 1cm multiplied by 1.5cm, drying by using an infrared lamp to obtain a working electrode, and calculating that the loading capacity of the catalyst is 1mg/cm2. Ag/AgCl is used as a reference electrode, a platinum net is used as a counter electrode, 0.1mol/L potassium bicarbonate solution is used as an electrolyte solution, and CO is added into a double-chamber electrolytic cell at the flow rate of 20mL/min2And performing linear volt-ampere scanning after aerating for 40min, wherein the scanning range is-3.0V-0V, and the scanning rate is 20 mV/s. The linear voltammogram scans of the different working electrodes of example 1 and comparative examples 1-2 above are shown in figure 1. As can be seen from fig. 1, the peak potential of the working electrode having the graphene aerogel as a carrier is shifted forward. With the increase of the potential, the current density is gradually increased, and the current density of electrocatalytic reduction of carbon dioxide in the working electrode material with the graphene aerogel as the carrier is always higher than that of the working electrode material without the graphene aerogel as the carrier, which shows that the existence of the graphene aerogel increases the electrocatalytic activity of the nano cuprous oxide powder catalyst on carbon dioxide, and the current density is increased by more than 40%, as shown in fig. 2.
The sample was sampled 30min after the start of the reaction between example 1 and comparative example 2, the electrochemical reduction time was 2 hours or more, and the faradaic efficiency was calculated from FE% of nzF/Q × 100% by gas chromatography. Under the condition that the external potential is-2.2V vs. Ag/AgCl, the Faraday efficiency of the product ethylene is increased from 8.22% to 11.33%, and the Faraday efficiency is improved by 3 percentage points.
In summary, the embodiment of the invention adopts the graphene aerogel as the carrier of the electrochemical catalyst, has the advantages of rich oxygen-containing groups on the surface of the graphene, high electron transmission speed, large specific surface area of the aerogel and high porosity, can provide a plurality of adsorption sites, is favorable for gas diffusion and flow, enables gas molecules to be easily contacted with the adsorption sites, promotes carbon dioxide in the solution to be diffused to the surface of the electrode for reaction, and has high current density; the carbon nanotube-doped graphene aerogel can improve the microstructure of the aerogel by utilizing the reinforcing effect of the carbon nanotubes; because the nanometer cuprous oxide powder can be uniformly distributed in the structure of the graphene aerogel, the tendency of condensation of the nanometer cuprous oxide powder is low, the stability of the catalyst is improved, and the stability can be stabilized for more than 3 hours.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The graphene aerogel working electrode material is characterized by comprising graphene aerogel and nanometer cuprous oxide powder loaded on the graphene aerogel, wherein the graphene aerogel is a three-dimensional porous CNT-doped graphene aerogel material prepared from graphene oxide and carbon nanotubes serving as raw materials.
2. The graphene aerogel working electrode material as claimed in claim 1, wherein the loading amount of the nano cuprous oxide powder is 0.1-5 mg/cm2Preferably 0.5 to 3mg/cm2More preferably 1 to 2mg/cm2。
3. The graphene aerogel working electrode material as claimed in claim 1, wherein the mass ratio of the carbon nanotubes in the raw material is 9-11%, preferably 10%;
preferably, the average particle size of the nanometer cuprous oxide powder is 20 nm-60 nm.
4. The preparation method of the graphene aerogel working electrode material according to any one of claims 1 to 3, comprising the following steps: and loading the nano cuprous oxide powder on the graphene aerogel.
5. The preparation method according to claim 4, wherein the nano cuprous oxide powder and the graphene aerogel are obtained by dispersing and mixing in a solution system and then drying;
preferably, the graphene aerogel is in a powder form;
preferably, the solvent of the solution system comprises alcohol, water and a Nafion solution, preferably, the alcohol comprises ethanol and isopropanol, and preferably, the volume ratio of the alcohol to the water is 1: 5-5: 1, the volume ratio of the ethanol to the isopropanol is 1: 5-5: 1, the volume ratio of the Nafion solution to water is 1: 5-1: 20, wherein the mass concentration of the Nafion solution is 4-6 wt%;
preferably, the step of dispersing and mixing the nano cuprous oxide powder and the graphene aerogel in a solution system comprises the following steps: mixing the graphene aerogel in a powder form with nano cuprous oxide powder, and then adding ethanol, isopropanol, water and a Nafion solution to perform ultrasonic dispersion until the mixture is uniform, wherein preferably the water is deionized water;
preferably, the mass ratio of the graphene aerogel to the nano cuprous oxide powder is 1: 1 to 30.
6. The preparation method according to claim 4 or 5, characterized in that the preparation method of the graphene aerogel comprises the following steps: freeze-drying the uniform mixture of graphene oxide and carbon nanotubes to obtain the three-dimensional porous CNT-doped graphene aerogel material;
preferably, graphene oxide and carbon nanotubes are uniformly mixed in water, and then are freeze-dried to obtain the three-dimensional porous CNT-doped graphene aerogel material;
preferably, the three-dimensional porous CNT-doped graphene aerogel material is milled into a powder.
7. A graphene aerogel working electrode, comprising: the graphene aerogel working electrode material as claimed in any one of claims 1 to 3, and an electrode substrate, wherein the graphene aerogel working electrode material is attached to the surface of the electrode substrate;
preferably, the electrode substrate is carbon paper or carbon nanotube sponge;
preferably, the specifications of the carbon paper and the carbon nanotube sponge are any one of 1cm × 1cm, 1cm × 1.5cm, 1.5cm × 2cm and 2cm × 2 cm;
preferably, the carbon nanotube sponge is a spongy carbon nanotube macroscopic body formed by self-assembly of multi-wall carbon nanotubes, and the thickness of the spongy carbon nanotube macroscopic body is 1 mm-4 mm.
8. The method of preparing a graphene aerogel working electrode of claim 7, comprising: coating the nano cuprous oxide powder and the dispersed suspension of the graphene aerogel on the surface of the electrode matrix;
preferably, the electrode matrix coated with the dispersion suspension is dried, preferably by infrared lamp drying.
9. Use of the graphene aerogel working electrode material of any one of claims 1 to 3 or the graphene aerogel working electrode of claim 7 for electrocatalytic reduction of carbon dioxide.
10. A method of electrocatalytic reduction of carbon dioxide, comprising: electrocatalytic reduction of carbon dioxide using the graphene aerogel working electrode of claim 7 as a cathode electrode;
preferably, a double-chamber electrolytic cell is adopted, external voltage is applied, and a potassium bicarbonate water solution is taken as an electrolyte solution;
preferably, an H-type two-compartment electrolytic cell is used, separated by a Nafion117 proton exchange membrane, allowing only H+The counter electrode is a platinum net, the reference electrode is Ag/AgCl, voltage is provided by an AUTOLAB electrochemical workstation, an electrolyte solution is 0.1-0.5 mol/L potassium bicarbonate solution, carbon dioxide gas is continuously introduced into the H-type double-chamber electrolytic cell in the electrocatalysis process, and more preferably, the carbon dioxide gas is introduced into the electrolyte for 30-60 min before the reaction is carried out;
preferably, in the electrocatalytic reduction carbon dioxide system, the electrode clamp adopts a glassy carbon substrate electrode clamp.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010856473.7A CN111945185B (en) | 2020-08-24 | 2020-08-24 | Graphene aerogel working electrode material and preparation method thereof, graphene aerogel working electrode and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010856473.7A CN111945185B (en) | 2020-08-24 | 2020-08-24 | Graphene aerogel working electrode material and preparation method thereof, graphene aerogel working electrode and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111945185A true CN111945185A (en) | 2020-11-17 |
| CN111945185B CN111945185B (en) | 2021-08-31 |
Family
ID=73360157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010856473.7A Active CN111945185B (en) | 2020-08-24 | 2020-08-24 | Graphene aerogel working electrode material and preparation method thereof, graphene aerogel working electrode and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111945185B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114931382A (en) * | 2022-05-23 | 2022-08-23 | 江苏集萃脑机融合智能技术研究所有限公司 | Composite electroencephalogram electrode, preparation method thereof, electroencephalogram cap and equipment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566934A (en) * | 2013-10-30 | 2014-02-12 | 东华大学 | Carbon dioxide electrochemical-reduction catalyst, and preparation and application thereof |
| CN109536991A (en) * | 2018-12-14 | 2019-03-29 | 天津大学 | A kind of application of the preparation method and cuprous oxide of loose porous cuprous oxide material in electro-catalysis reduction carbon dioxide |
| US10329677B2 (en) * | 2016-11-01 | 2019-06-25 | King Fahd University Of Petroleum And Minerals | Method for electrochemical reduction of carbon dioxide |
| CN110172711A (en) * | 2019-07-03 | 2019-08-27 | 辽宁大学 | Copper-based three-dimensional self-supporting electrocatalysis material and its preparation method and application |
| US20200248324A1 (en) * | 2019-01-31 | 2020-08-06 | Dimartech Fabrication Inc. | Metal-carbon nanostructures and method of manufacturing thereof |
-
2020
- 2020-08-24 CN CN202010856473.7A patent/CN111945185B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566934A (en) * | 2013-10-30 | 2014-02-12 | 东华大学 | Carbon dioxide electrochemical-reduction catalyst, and preparation and application thereof |
| US10329677B2 (en) * | 2016-11-01 | 2019-06-25 | King Fahd University Of Petroleum And Minerals | Method for electrochemical reduction of carbon dioxide |
| CN109536991A (en) * | 2018-12-14 | 2019-03-29 | 天津大学 | A kind of application of the preparation method and cuprous oxide of loose porous cuprous oxide material in electro-catalysis reduction carbon dioxide |
| US20200248324A1 (en) * | 2019-01-31 | 2020-08-06 | Dimartech Fabrication Inc. | Metal-carbon nanostructures and method of manufacturing thereof |
| CN110172711A (en) * | 2019-07-03 | 2019-08-27 | 辽宁大学 | Copper-based three-dimensional self-supporting electrocatalysis material and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| DIEGO C. B. ALVES ET AL.: "Copper nanoparticles stabilized by reduced graphene oxide for CO2 reduction reaction", 《MATER RENEW SUSTAIN ENERGY》 * |
| GUIZHI ZHU ET AL.: "Enhanced CO2 electroreduction on armchair graphene nanoribbons edge-decorated with copper", 《NANO RESEARCH》 * |
| R.A. GEIOUSHY ET AL.: "High efficiency graphene/Cu2O electrode for the electrochemical reduction of carbon dioxide to ethanol", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| 刁煜 等: "石墨烯／碳纳米管气凝胶的制备及其弹性性能", 《机械工程材料》 * |
| 杨梦茹 等: "二氧化碳电催化还原产乙烯: 催化剂、反应条件和反应机理", 《化学进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114931382A (en) * | 2022-05-23 | 2022-08-23 | 江苏集萃脑机融合智能技术研究所有限公司 | Composite electroencephalogram electrode, preparation method thereof, electroencephalogram cap and equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111945185B (en) | 2021-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zou et al. | A mediatorless microbial fuel cell using polypyrrole coated carbon nanotubes composite as anode material | |
| Liu et al. | A review of anode catalysis in the direct methanol fuel cell | |
| Maiyalagan | Synthesis and electro-catalytic activity of methanol oxidation on nitrogen containing carbon nanotubes supported Pt electrodes | |
| He et al. | Alcohol electro-oxidation on platinum–ceria/graphene nanosheet in alkaline solutions | |
| WO2018132937A1 (en) | Use of metal phthalocyanine/nanocarbon hybrid catalysts for efficient electrochemical reduction of co2 | |
| Zhou et al. | Electrochemical fabrication of novel platinum-poly (5-nitroindole) composite catalyst and its application for methanol oxidation in alkaline medium | |
| Li et al. | Metal-organic interface engineering for coupling palladium nanocrystals over functionalized graphene as an advanced electrocatalyst of methanol and ethanol oxidation | |
| An et al. | Synthesis of PtRu/carbon nanotube composites in supercritical fluid and their application as an electrocatalyst for direct methanol fuel cells | |
| CN110767914B (en) | Co-N doped porous carbon-coated carbon nanotube core-shell structure catalyst and preparation method and application thereof | |
| Li et al. | Graphitized carbon nanocages/palladium nanoparticles: Sustainable preparation and electrocatalytic performances towards ethanol oxidation reaction | |
| CN114232012B (en) | Ionic liquid modified nano carbon material catalyst and preparation method and application thereof | |
| CN113118451B (en) | Preparation method of magnesium monoatomic catalyst applied to efficient carbon dioxide reduction reaction for generating carbon monoxide | |
| Zhang et al. | High-efficiency palladium nanoparticles supported on hydroxypropyl-β-cyclodextrin modified fullerene [60] for ethanol oxidation | |
| Ariyanto et al. | Carbide-derived carbon with hollow core structure and its performance as catalyst support for methanol electro-oxidation | |
| Kang et al. | Al-Based porous coordination polymer derived nanoporous carbon for immobilization of glucose oxidase and its application in glucose/O 2 biofuel cell and biosensor | |
| Wang et al. | Self-assembled flower-like MnO2 grown on Fe-containing urea-formaldehyde resins based carbon as catalyst for oxygen reduction reaction in alkaline direct methanol fuel cells | |
| Elessawy et al. | Development and evaluation of cost-effective and green Bi-functional nickel oxide decorated graphene electrocatalysts for alkaline fuel cells | |
| Chandran et al. | 1D-2D integrated hybrid carbon nanostructure supported bimetallic alloy catalyst for ethanol oxidation and oxygen reduction reactions | |
| Li et al. | Pd deposited on MWCNTs modified carbon fiber paper as high-efficient electrocatalyst for ethanol electrooxidation | |
| Sano et al. | Direct synthesis of carbon nanotubes on stainless steel electrode for enhanced catalyst efficiency in a glucose fuel cell | |
| Wang et al. | Oxygen self-doping formicary-like electrocatalyst with ultrahigh specific surface area derived from waste pitaya peels for high-yield H2O2 electrosynthesis and efficient electro-Fenton degradation | |
| Li et al. | Thermal reduced graphene oxide enhanced in-situ H2O2 generation and electrochemical advanced oxidation performance of air-breathing cathode | |
| CN111945185B (en) | Graphene aerogel working electrode material and preparation method thereof, graphene aerogel working electrode and preparation method and application thereof | |
| Sheelam et al. | Flexible and free-standing polyvinyl alcohol-reduced graphene oxide-Cu 2 O/CuO thin films for electrochemical reduction of carbon dioxide | |
| Zhang et al. | Fabrications of metal organic frameworks derived hierarchical porous carbon on carbon nanotubes as efficient bioanode catalysts of NAD+-dependent alcohol dehydrogenase |
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 |