CN113877614A - Modified graphene roll and preparation method and application thereof - Google Patents

Modified graphene roll and preparation method and application thereof Download PDF

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CN113877614A
CN113877614A CN202111253224.XA CN202111253224A CN113877614A CN 113877614 A CN113877614 A CN 113877614A CN 202111253224 A CN202111253224 A CN 202111253224A CN 113877614 A CN113877614 A CN 113877614A
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graphene
mxene
roll
modified
metal particles
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CN113877614B (en
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王珺
杜真真
王晶
于帆
李炯利
王刚
***
罗圭纳
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Beijing Graphene Technology Research Institute Co Ltd
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Beijing Graphene Technology Research Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J35/33—
    • 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
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • 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
    • C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
    • 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
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to a preparation method of a modified graphene roll, which comprises the following steps: mixing MXene material, graphene and water to obtain MXene-graphene mixed solution, wherein the ratio of the mass sum of the MXene material and the graphene to the volume of the water is (0.1-1 mg) to 1 mL; sequentially heating, cooling by liquid nitrogen and freeze-drying the MXene-graphene mixed solution to obtain an MXene-graphene roll; and loading metal particles on the surface of the MXene-graphene roll. The modified graphene roll prepared by the preparation method of the modified graphene roll has good conductivity, and has good catalytic performance and stability.

Description

Modified graphene roll and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, and particularly relates to a modified graphene roll and a preparation method and application thereof.
Background
The metal catalyst is a catalyst commonly used for oxidation-reduction reaction (ORR). In a conventional metal catalyst, a carrier carrying metal particles includes carbon black, Carbon Nanotubes (CNTs), graphene, and the like.
The carbon black can meet the requirement of a catalyst on the conductivity, but the ratio of micropores in the structure of the carbon black is high, and a conductive polymer cannot enter the micropores, so that metal particles attached to the micropores are difficult to participate in catalytic reaction, and the metal particles attached to the surface of the carbon black are easy to dissolve, agglomerate and fall off in the reaction process, so that the utilization rate of the metal particles is low; at the same time, carbon black has poor resistance to electrochemical corrosion. The CNT has better conductivity, stability and electrochemical corrosion resistance, but has smaller specific surface area and less active sites capable of being loaded by metal particles, so that the catalytic performance of the CNT is limited. When the graphene is used as a carrier of the metal particles, the surface of the graphene is chemically inert, the capability of loading the metal particles is weak, and the active area cannot be fully utilized; when graphene is used as a carrier, sheet stacking exists, the active area cannot be completely released, the carrying amount of metal particles is limited, and the catalytic performance of the metal particles is poor; in addition, the van der waals force between graphene layers is strong, and recombination agglomeration is easy to occur, so that the supported metal particles agglomerate, fall off, and even are inactivated, and the overall stability and durability of the metal catalyst are poor.
In the traditional method, other polymer systems are introduced to modify graphene, so that the loading capacity of active sites can be enhanced, but the graphene modified by the method is low in conductivity, and the electron transmission of the catalyst is influenced, so that the catalytic performance is low.
Disclosure of Invention
Based on the modified graphene roll, the preparation method and the application thereof, the modified graphene roll prepared by the preparation method is good in conductivity and good in stability and catalytic performance.
The technical scheme of the invention for solving the technical problems is as follows.
A preparation method of a modified graphene roll comprises the following steps:
mixing MXene materials, graphene and water to obtain MXene-graphene mixed solution, wherein the ratio of the mass sum of the MXene materials and the graphene to the volume of the water is (0.1-1 mg) 1 mL;
sequentially heating the MXene-graphene mixed solution, cooling by liquid nitrogen and freeze-drying to obtain an MXene-graphene roll;
and loading metal particles on the surface of the MXene-graphene roll.
In some embodiments, in the method for preparing the modified graphene roll, the metal particles are at least one selected from Pt, Pd, Ru, and Au.
In some embodiments, in the method for preparing the modified graphene roll, the MXene material is selected from Ti2C3Tx、Ti2CTxAnd Cr2CTxWherein, T isxis-OH or-F.
In some embodiments, in the method for preparing a modified graphene roll, the graphene is selected from at least one of graphene, graphene oxide, reduced graphene oxide, doped graphene oxide, and doped reduced graphene oxide.
In some embodiments, in the preparation method of the modified graphene roll, the mass ratio of the MXene material to the graphene in the MXene-graphene mixed solution is (0.1-1): 50.
In some embodiments, in the method for preparing the modified graphene roll, the step of loading the metal particles on the surface of the MXene-graphene roll includes the following steps:
mixing a metal source precursor, a reducing agent, a solvent and the MXene-graphene coil, and carrying out reduction reaction.
In some embodiments, in the method for preparing the modified graphene roll, the reducing agent is at least one selected from sodium borohydride, sodium citrate, hydrazine hydrate, formaldehyde and formic acid.
In some embodiments, in the method for preparing the modified graphene roll, the metal source precursor is selected from at least one of chloroplatinic acid platinum chloride, palladium chloride, ruthenium chloride, gold chloride, and chloroauric acid.
In some embodiments, in the preparation method of the modified graphene roll, the heating is performed to a temperature of 60 ℃ to 100 ℃.
In some embodiments, in the method for preparing a modified graphene roll, the freeze-drying is: drying for 1-72 h at 0-50 ℃.
The invention provides a modified graphene roll prepared by the preparation method of the modified graphene roll.
The invention also provides application of the modified graphene roll in catalytic oxidation-reduction reaction.
Compared with the prior art, the modified graphene roll has the following beneficial effects:
according to the preparation method of the modified graphene roll, the MXene-graphene mixed solution obtained by mixing the raw materials is sequentially heated, cooled by liquid nitrogen and freeze-dried to obtain the MXene-graphene roll, metal particles are further loaded on the surface of the MXene-graphene roll, and the metal particles and the MXene-graphene roll have strong interaction, so that the adhesion of the metal particles on the surface of the MXene-graphene roll is effectively enhanced, and the phenomena of dissolution, agglomeration and falling off of the metal particles in the reaction process are avoided; meanwhile, the interaction between the metal particles and the MXene-graphene roll can change the electronic structure of the metal particles, and effectively enhance the oxidation resistance, corrosion resistance and durability of the metal particles. Moreover, contact points between the MXene-graphene rolls are small, the ratio of the exposed specific surface area is high, and the MXene-graphene is rolled into a roll shape, so that the problem that graphene sheet layers are easy to stack is solved, the active sites of the MXene-graphene rolls are increased, and the carrying capacity of metal particles is improved; thereby effectively improving the catalytic performance of the modified graphene roll.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an SEM image of a Pt/MXene-graphene roll catalyst prepared in example 1;
FIG. 2 is a TEM image of a Pt/MXene-graphene roll catalyst prepared in example 1;
FIG. 3 is a LSV curve of the catalysts prepared in examples 1-3 and comparative examples 1-2 and commercial Pt/C catalysts;
FIG. 4 is the LSV profile of examples 1, 4 and commercial Pt/C catalysts;
FIG. 5 is a LSV plot for examples 1, 5 and commercial Pt/C catalysts;
FIG. 6 is a LSV plot for examples 1, 6 and commercial Pt/C catalysts;
FIG. 7 is a LSV plot before and after 1000 cycles of Pt/MXene-graphene roll catalyst prepared in example 1;
FIG. 8 is a LSV plot before and after 1000 cycles of the Pt/graphene roll catalyst prepared in comparative example 1;
fig. 9 is a plot of LSV before and after 1000 cycles of Pt/MXene-graphene catalyst prepared in comparative example 2.
Detailed Description
The modified graphene roll of the present invention, and the preparation method and application thereof are further described in detail with reference to specific examples below. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, "at least one" means one, two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
Terms and definitions:
"graphene" is generally denoted by GF and refers to a material having a monolayer of two-dimensional cellular lattice structure closely packed with carbon atoms attached in an sp2 hybridization.
"graphene oxide" is generally indicated by GO and refers to an oxide of graphene, which has excellent dispersibility in water.
The term "reduced graphene oxide" is generally referred to as rGO, and means that a group having an oxidizing property is lost by reduction based on graphene oxide.
The "doped graphene" refers to graphene prepared by introducing doping atoms into a graphene lattice, and the doping atoms are usually N atoms, S atoms, F atoms, and the like.
"MXene materials" belong to two-dimensional inorganic compounds, generally consisting of a transition metal carbide, nitride or carbonitride of a few atomic layer thicknesses.
An embodiment of the invention provides a preparation method of a modified graphene roll, which comprises steps S10-S30.
Step S10: mixing MXene material, graphene and water to obtain MXene-graphene mixed solution, wherein the ratio of the mass sum of the MXene material and the graphene to the volume of the water is (0.1-1 mg) to 1 mL.
The MXene material and graphene are dispersed in water to generate electrostatic repulsion, so that the dispersibility of the graphene in water is improved on the basis of not introducing additives such as a modifier, a surfactant and a reducing agent and not needing complex reaction with organic polymers, the complete lamellar structure of the graphene is retained, and the conductivity is ensured.
It can be understood that the MXene material and the graphene can be respectively dissolved in water, and then the aqueous solution formed by the MXene material and the graphene can be mixed, or the MXene material and the graphene can be mixed with water, or the MXene material can be added into the aqueous solution of the graphene. Preferably, the MXene material and the graphene are mixed with water in a mixed powder.
In some examples, in step S10, MXene material and graphene are mixed by grinding or ball milling, and then mixed with water.
In some examples, in step S10, the rotation speed of the ball mill is 200rpm to 700rpm, and the time is 0.5h to 72 h.
In some examples, the MXene material is selected from Ti in step S102C3Tx、Ti2CTxAnd Cr2CTxWherein, T isxis-OH or-F.
In some specific examples, in step S10, the MXene material is Ti2C3Tx(Txis-OH or-F).
In some examples, in step S10, the graphene is selected from at least one of Graphene (GF), Graphene Oxide (GO), reduced graphene oxide (rGO), doped graphene oxide, and doped reduced graphene oxide.
In some specific examples, in step S10, the graphene is graphene GF.
In some examples, in step S10, the doping atoms in the doped graphene, the doped graphene oxide and the doped reduced graphene oxide may be doping atoms commonly used in the art, including but not limited to metal atoms, non-metal atoms, etc., the metal atoms may be Fe atoms, Cu atoms, Co atoms, Ni atoms, Zn atoms, etc., and the non-metal atoms may be N atoms, P atoms, S atoms, B atoms, F atoms, etc. Preferably, the doping atom is a non-metal atom, and more preferably, the doping atom is at least one of an N atom, an S atom, and an F atom.
In some examples, in step S10, the graphene GF may be at least one of single-layer graphene, double-layer graphene, few-layer graphene, and multi-layer graphene, wherein the number of layers of the few-layer graphene may be 3 to 10, and the number of layers of the multi-layer graphene may be 10 to 100. Preferably, the graphene is single-layer graphene, double-layer graphene or 3-10 layers of few-layer graphene.
In some examples, in the step S10, the mass ratio of MXene materials to graphene in the MXene-graphene mixed solution is (0.1-1): 50; optionally, the mass ratio of the MXene material to the graphene is (0.2-0.8): 50.
In some specific examples, in the step S10, the mass ratio of the MXene material to the graphene is (0.5-0.8): 50; preferably, the mass ratio of the MXene material to the graphene is 0.5: 50.
In some examples, in step S10, the ratio of the sum of the masses of the MXene material and the graphene to the volume of water is (0.1mg to 0.5mg):1 mL.
By controlling the concentration of the MXene-graphene mixed solution, the MXene-graphene can be coiled well, the specific surface area is large, and the graphene stacking behavior is avoided.
Step S20: and sequentially heating the MXene-graphene mixed solution, cooling by liquid nitrogen and freeze-drying to obtain the MXene-graphene roll.
In some examples, in step S20, heating to a temperature of 60 ℃ to 100 ℃; optionally, heating to a temperature of 60-80 ℃; preferably, heating is carried out to a temperature of 60 ℃.
In some examples, in step S20, the freeze-drying is performed at 0 ℃ to-50 ℃ for 1h to 72 h. .
In some of these examples, step S20, freeze-drying is performed in a lyophilization chamber.
In some examples, in step S20, the heated MXene-graphene mixed solution is frozen at-30 ℃ to-80 ℃ before the freeze-drying step. Thus, water-free can be ensured.
In some specific examples, in step S20, first freezing at-30 ℃ for 6 h; and then freeze-drying at-50 deg.C for 24 h.
Step S30: and loading metal particles on the surface of the MXene-graphene roll.
In some examples, in step S30, the metal particles are selected from at least one of Pt, Pd, Ru, and Au; preferably, the metal particles are Pt.
The MXene-graphene roll is obtained by sequentially heating, cooling by liquid nitrogen and freeze-drying an MXene-graphene mixed solution obtained by mixing raw materials, metal particles are further loaded on the surface of the MXene-graphene roll, and the metal particles and the MXene-graphene roll have stronger interaction, so that the adhesion of the metal particles on the surface of the MXene-graphene roll is effectively enhanced, and the phenomena of dissolution, agglomeration and falling off of the metal particles in the reaction process are avoided; meanwhile, the interaction between the metal particles and the MXene-graphene roll can change the electronic structure of the metal particles, and effectively enhance the oxidation resistance, corrosion resistance and durability of the metal particles. Moreover, contact points between the MXene-graphene rolls are small, the ratio of the exposed specific surface area is high, and the MXene-graphene is rolled into a roll shape, so that the problem that graphene sheet layers are easy to stack is solved, the active sites of the MXene-graphene rolls are increased, and the carrying capacity of metal particles is improved; thereby effectively improving the catalytic performance of the modified graphene roll.
In some preferred examples thereof, Ti is used in step S102C3Tx(Txis-OH or-F) is loaded with Pt particles on the surface of an MXene-graphene roll prepared from MXene materials. As can be understood, MXene and Pt particles have stronger interaction, and the electronic structure of Pt can be changed, so that the oxidation resistance and the corrosion resistance of Pt are enhanced, and the durability is stronger.
It is understood that in step S30, the MXene-graphene roll may be loaded with metal particles on its surface by using a dip reduction method, an organosol method, or a chemical vapor deposition method.
In some of these examples, the dip-reduction process includes step S31.
Step S31: mixing a metal source precursor, a reducing agent, a solvent and MXene-graphene coil, and carrying out reduction reaction.
In some examples, in step S31, the metal source precursor is selected from at least one of chloroplatinic acid, platinum chloride, palladium chloride, ruthenium chloride, gold chloride, and chloroauric acid. It can be understood that when the metal source precursor is chloroplatinic acid, the metal particles loaded on the surface of the MXene-graphene coil are Pt particles.
In some examples, in step S31, the reducing agent is selected from at least one of sodium borohydride, sodium citrate, hydrazine hydrate, formaldehyde, and formic acid. Preferably, the reducing agent is sodium borohydride.
In some examples, in step S31, the solvent is selected from at least one of water and ethylene glycol; preferably, the solvent is water.
In some examples, in step S31, in the reaction solution after mixing the metal source precursor, the reducing agent, the solvent and the MXene-graphene coil, the ratio of the mass of the MXene-graphene coil to the volume of the solvent is (0.1 mg-5 mg):1mL, the concentration of the metal source precursor is 1 mmol/L-50 mmol/L, and the concentration of the reducing agent is 0.1 mol/L-1 mol/L; optionally, the ratio of the mass of the MXene-graphene coil to the volume of the solvent is (1 mg-3 mg):1mL, the concentration of the metal source precursor is 30 mmol/L-50 mmol/L, and the concentration of the reducing agent is 0.1 mol/L-0.5 mol/L.
In some examples, in step S31, the metal source precursor, the MXene-graphene roll, and the solvent are mixed, and after stirring uniformly, the reducing agent is added.
In some examples, in step S31, the stirring time is 30min to 72 h; optionally, the stirring time is 12-36 h; preferably, the stirring time is 24 h.
It will be appreciated that the reducing agent may be added in the form of a drop. It can also be understood that after the reducing agent is dripped, the reducing agent enables the MXene-graphene roll to react with the metal source precursor, and after the reaction, the precipitate is filtered and freeze-dried to obtain the MXene-graphene roll loaded with metal particles, namely the modified graphene roll. In other words, the modified graphene coil in the present invention is an MXene-graphene coil loaded with metal particles.
It is understood that in some specific examples thereof, the modified graphene coil is a Pt/MXene-graphene coil.
In some examples, in step S31, the reaction time is 24h to 72 h; optionally, the reaction time is 24 h-48; preferably, the reaction time is 24 h.
In some examples, in step S31, the filtration may be performed by suction filtration or centrifugation. It is understood that the precipitate is washed after filtration, and the solvent for washing is the solvent used in the reaction.
In some examples, in step S31, the lyophilization is to dry at 0 ℃ to-50 ℃ for 1h to 72 h.
In some of these examples, step S31, the lyophilization is performed in a lyophilization chamber.
In some examples, in step S31, the precipitate is frozen at-30 ℃ to-80 ℃ before the lyophilization step is performed.
In some of these examples, the organosol process includes step S32.
Step S32: mixing a metal source precursor, a complexing agent, a solvent and MXene-graphene roll, adjusting the pH value to be more than 10 by using alkali, and reacting for 3-72 h at 60-200 ℃.
It is understood that the selection range of the metal source precursor and the solvent in step S32 is the same as that in step S31.
In some examples, in step S32, the complexing agent is selected from at least one of polyvinylpyrrolidone (PVP) and sodium citrate; preferably, the complexing agent is polyvinylpyrrolidone.
In some examples, the base is selected from NaOH or KOH in step S32.
It is understood that in some examples, in step S32, MXene-graphene roll is dispersed in a solvent, a complexing agent is added, and after stirring uniformly, a metal source precursor is added. It can also be understood that after the reaction in step S32, the precipitate is filtered and lyophilized to obtain an MXene-graphene roll loaded with metal particles, that is, a modified graphene roll. It is further understood that the parameters in step S32 and the filtration and lyophilization steps in step S31 may be the same.
An embodiment of the invention provides a modified graphene roll prepared by the preparation method of the modified graphene roll.
An embodiment of the invention provides an application of the modified graphene in a catalytic oxidation-reduction reaction.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The modified graphene roll and the preparation method and application thereof according to the present invention are illustrated below, and it is understood that the modified graphene roll and the preparation method and application thereof are not limited to the following examples.
Example 1
Preparation of graphene nanocoils
1) Mixing Ti2C3Tx(Txis-OH and/or-F) and graphene according to the mass ratio of 0.5:50, and after ball milling is carried out for 4 hours at 400rpm, the MXene-graphene mixed solution is dispersed in water according to the mass ratio of the sum of the MXene material and the graphene to the volume of the water of 0.5mg:1 mL;
2) stirring and heating the MXene-graphene mixed solution to 60 ℃, then quickly pouring liquid nitrogen, precooling for 6h at-30 ℃, and freeze-drying for 24h at-50 ℃ to obtain an MXene-graphene roll;
3) dispersing MXene-graphene roll in water, wherein the mass ratio of the MXene-graphene roll to the volume of the water is 1.5mg:1mL, adding chloroplatinic acid aqueous solution to ensure that the concentration of the chloroplatinic acid in the reaction solution is 38.6mmol/L, stirring uniformly, adding NaBH4Aqueous solution of NaBH4The concentration of the reaction solution is 0.3mol/L, the reaction is fully stirred for 24 hours, water and ethanol are used for filtering and washing for 3 times, precooling is carried out for 6 hours at minus 30 ℃, and then freeze drying is carried out for 24 hours at minus 50 ℃ to obtain the Pt/MXene-graphene roll. SEM images of the Pt/MXene-graphene rolls are shown in FIG. 1, and TEM images of the Pt/MXene-graphene rolls are shown in FIG. 2.
As can be seen from the SEM image in fig. 1, the number of rolls of MXene-graphene loaded with Pt particles is large, and the effect is good; as can be seen from the TEM image of fig. 2, the Pt particles were uniformly supported on the MXene-graphene coil.
Example 2
MXene-graphene rolls prepared in the steps 1) and 2) of example 1 are dispersed in ethylene glycol, the mass ratio of the MXene-graphene rolls to the volume ratio of the ethylene glycol is 1.5mg:1mL, chloroplatinic acid-ethylene glycol solution is added to ensure that the concentration of the chloroplatinic acid in the reaction solution is 38.6mmol/L, the mixture is uniformly stirred, the pH value of the reaction solution is regulated to be more than 10 by KOH-ethylene glycol solution, the reaction solution is reacted in a water bath at 120 ℃ for 6h, water and ethanol are used for filtering and washing for 3 times, the pre-cooling is carried out at-30 ℃ for 6h, and the freeze drying is carried out at-50 ℃ for 24h to obtain the Pt/MXene-graphene roll catalyst.
Example 3
The method is basically the same as example 1, except that in step 3), Pd particles are supported on the surface of the MXene-graphene roll, that is, an aqueous chloroplatinic acid solution is replaced with an aqueous palladium chloride solution.
Example 4
Basically the same as example 1, except that MXene material was Cr2CTx(Txis-OH and/or-F).
Example 5
The method is basically the same as the embodiment 1, and is different from the step 1), specifically as follows:
1) mixing Ti2C3Tx(Txis-OH and/or-F) and graphene according to the mass ratio of 0.5:50, and after ball milling for 4 hours at 400rpm, the MXene-graphene mixed solution is dispersed in water according to the mass ratio of the sum of the MXene material and the graphene to the volume of the water of 0.1mg:1 mL.
Example 6
Substantially the same as in example 1, except that Ti2C3Tx(Txis-F and/or-OH) to graphene in a mass ratio of 0.8: 50.
Comparative example 1
Substantially the same as in example 1, except that graphene rolls not modified with MXene were dispersed in water and loaded with Pt particles. The method comprises the following specific steps:
1) dispersing graphene in water, heating to 60 ℃, then quickly pouring liquid nitrogen, precooling for 6h at-30 ℃, and freeze-drying for 24h at-50 ℃ to obtain a graphene roll;
2) dispersing graphene roll in water with the concentration of 1.5mg/ml, adding chloroplatinic acid aqueous solution to ensure that the concentration of chloroplatinic acid in the reaction solution is 38.6mmol/L, stirring uniformly, and adding NaBH4Aqueous solution of NaBH4And (3) fully stirring and reacting for 24h when the concentration in the reaction solution is 0.3mol/L, carrying out suction filtration and washing for 3 times by using water and ethanol, precooling for 6h at-30 ℃, and then carrying out freeze drying for 24h at-50 ℃ to obtain the Pt/graphene roll.
Comparative example 2
MXene modified graphene is directly used as a carrier to load Pt without coiling. The method comprises the following specific steps:
1) mixing Ti2C3Tx(Txis-OH and/or-F) and graphene according to the mass ratio of 0.5:50, and obtaining MXene modified graphene after ball milling for 4 hours at 400 rpm;
2) dispersing MXene modified graphene in water at a concentration of 1.5mg/ml, adding chloroplatinic acid aqueous solution to ensure that the concentration of chloroplatinic acid in reaction liquid is 38.6mmol/L, stirring uniformly, adding NaBH4Aqueous solution of NaBH4The concentration of the reaction solution is 0.3mol/L, the reaction is fully stirred for 24 hours, water and ethanol are used for filtering and washing for 3 times, precooling is carried out for 6 hours at minus 30 ℃, and then freeze drying is carried out for 24 hours at minus 50 ℃ to obtain Pt/MXene-graphene.
The ORR test was performed on the graphene materials prepared in examples 1 to 6 and comparative examples 1 to 2 as catalysts, and on a commercial Pt/C catalyst (purchased from JM, england) by the following specific steps:
at O2Saturated 0.5mol/L H2SO4In the medium, the catalyst loading is 80ug/cm2LSV voltage scan range: 0.2V-1.0V vs. Ag/AgCl, sweep speed of 5mV/s, rotation speed of 1600rpm, and the test results are shown in FIGS. 3-6; wherein a is the LSV curve of the Pt/MXene-graphene roll prepared in example 1, and b is the Pt/MXene-graphene roll prepared in example 2The LSV curve of the rolls, C is the LSV curve of the Pd/MXene-graphene roll prepared in example 3, d is the LSV curve of the Pt/MXene-graphene roll prepared in example 4, e is the LSV curve of the Pt/MXene-graphene roll prepared in example 5, f is the LSV curve of the Pt/MXene-graphene roll prepared in example 6, g is the LSV curve of commercial Pt/C, m is the LSV curve of the Pt/graphene roll prepared in comparative example 1, and n is the LSV curve of the Pt/MXene-graphene prepared in comparative example 2.
According to the modified graphene roll prepared in the embodiments 1-6, no additional conductive agent is needed to be added, the modified graphene roll is directly prepared into a dispersion liquid, and an ORR test can be performed; namely, the modified graphene roll prepared by the invention has good conductivity.
The LSV test results of the graphene materials prepared in example 1 and comparative examples 1 to 2 before and after 1000 cycles are shown in fig. 7 to 9; wherein, fig. 7 is an LSV curve before and after 1000 cycles of Pt/MXene-graphene coils prepared in example 1, a in fig. 7 is an LSV curve of 1 cycle, and a is an LSV curve of 1000 cycles; fig. 8 is a graph of LSV before and after 1000 cycles of Pt/graphene coils prepared in comparative example 1, where m in fig. 8 is an LSV curve of 1 cycle and m × is an LSV curve of 1000 cycles; fig. 9 is a LSV curve before and after 1000 cycles of Pt/MXene-graphene prepared in comparative example 2, where n in fig. 9 is an LSV curve of 1 cycle and n x is an LSV curve of 1000 cycles.
As can be seen from FIGS. 3 to 6, the ORR performance of the Pt/MXene-graphene rolls prepared in examples 1 to 2 and examples 4 to 6 is superior to that of the commercial Pt/C catalyst; the ORR performance of the Pt/graphene coil prepared in comparative example 1 and the Pt/MXene-graphene prepared in comparative example 2 were far inferior to the commercial Pt/C catalyst. The ORR performance of the Pd/MXene-graphene roll prepared in example 3 is slightly inferior to that of the commercial Pt/C catalyst, which is caused by the difference of metals of Pd and Pt, but the catalytic performance is still excellent compared with comparative examples 1-2. Namely, the modified graphene has better catalytic performance.
From fig. 7, after the Pt/MXene-graphene roll prepared in example 1 circulates 1000 cycles, the LSV of the Pt/MXene-graphene roll does not significantly attenuate, while from fig. 8 to 9, after the Pt/graphene roll prepared in comparative example 1 and the Pt/MXene-graphene roll prepared in comparative example 2 circulate 1000 cycles, the LSV of the catalyst significantly attenuates, which proves that the ORR stability and durability of the Pt/MXene-graphene roll prepared in the example are better.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. It should be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the appended claims. Therefore, the protection scope of the present invention should be subject to the content of the appended claims, and the description and the drawings can be used for explaining the content of the claims.

Claims (12)

1. A preparation method of a modified graphene roll is characterized by comprising the following steps:
mixing MXene materials, graphene and water to obtain MXene-graphene mixed solution, wherein the ratio of the mass sum of the MXene materials and the graphene to the volume of the water is (0.1-1 mg):1 mL;
sequentially heating the MXene-graphene mixed solution, cooling by liquid nitrogen and freeze-drying to obtain an MXene-graphene roll;
and loading metal particles on the surface of the MXene-graphene roll.
2. The method of claim 1, wherein the metal particles are at least one selected from the group consisting of Pt, Pd, Ru, and Au.
3. The method of claim 1, wherein the MXene material is selected from Ti2C3Tx、Ti2CTxAnd Cr2CTxWherein, T isxis-OH or-F.
4. The method of claim 1, wherein the graphene is selected from at least one of graphene, graphene oxide, reduced graphene oxide, doped graphene oxide, and doped reduced graphene oxide.
5. The method for preparing the modified graphene coil according to any one of claims 1 to 4, wherein the mass ratio of the MXene material to the graphene in the MXene-graphene mixed solution is (0.1-1): 50.
6. The method for preparing the modified graphene roll according to any one of claims 1 to 4, wherein the step of loading the metal particles on the surface of the MXene-graphene roll comprises the following steps:
mixing a metal source precursor, a reducing agent, a solvent and the MXene-graphene coil, and carrying out reduction reaction.
7. The method according to claim 6, wherein the reducing agent is at least one selected from sodium borohydride, sodium citrate, hydrazine hydrate, formaldehyde, and formic acid.
8. The method of claim 6, wherein the metal source precursor is at least one selected from the group consisting of chloroplatinic acid, platinum chloride, palladium chloride, ruthenium chloride, gold chloride, and chloroauric acid.
9. The method for preparing the modified graphene roll according to any one of claims 1 to 4, wherein the heating is performed at a temperature of 60 ℃ to 100 ℃.
10. The method for preparing the modified graphene coil according to any one of claims 1 to 4, wherein the freeze-drying is: drying for 1-72 h at 0-50 ℃.
11. The modified graphene roll prepared by the preparation method of any one of claims 1 to 10.
12. Use of the modified graphene coil of claim 11 in a catalytic redox reaction.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114887591A (en) * 2022-04-14 2022-08-12 同济大学 Method for simply recovering gold from MXene/GO/NbFeB hydrogel by one-step method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105126829A (en) * 2015-09-09 2015-12-09 广西师范大学 Modified graphene platinized catalyst, preparation method of modified graphene platinized catalyst and application of modified graphene platinized catalyst
CN108336310A (en) * 2017-01-20 2018-07-27 中国科学院物理研究所 A kind of composite material and preparation method based on self-supporting redox graphene volume
CN111468121A (en) * 2020-06-11 2020-07-31 北京林业大学 Preparation and application of MXene modified biomass carbon nano metal catalyst
CN112103485A (en) * 2020-08-29 2020-12-18 温州玖源锂电池科技发展有限公司 Preparation method of 0D/2D quantum dot/graphene nanocolloid heterostructure electrode material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105126829A (en) * 2015-09-09 2015-12-09 广西师范大学 Modified graphene platinized catalyst, preparation method of modified graphene platinized catalyst and application of modified graphene platinized catalyst
CN108336310A (en) * 2017-01-20 2018-07-27 中国科学院物理研究所 A kind of composite material and preparation method based on self-supporting redox graphene volume
CN111468121A (en) * 2020-06-11 2020-07-31 北京林业大学 Preparation and application of MXene modified biomass carbon nano metal catalyst
CN112103485A (en) * 2020-08-29 2020-12-18 温州玖源锂电池科技发展有限公司 Preparation method of 0D/2D quantum dot/graphene nanocolloid heterostructure electrode material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CUIZHEN YANG，等: "Ultrafine Pt Nanoparticle-Decorated 3D Hybrid Architectures Built from Reduced Graphene Oxide and MXene Nanosheets for Methanol Oxidation" *
钟轶良;莫再勇;杨莉君;廖世军;: "改性石墨烯用作燃料电池阴极催化剂" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114887591A (en) * 2022-04-14 2022-08-12 同济大学 Method for simply recovering gold from MXene/GO/NbFeB hydrogel by one-step method and application
CN114887591B (en) * 2022-04-14 2024-01-12 同济大学 Method for simply recovering gold through MXene/GO/NbFeB hydrogel by one-step method and application

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