CN116995254A - Composite structure catalyst for synthesizing supported Pt-MXene and preparation method and application thereof - Google Patents
Composite structure catalyst for synthesizing supported Pt-MXene and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 132
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 28
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- 238000010907 mechanical stirring Methods 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
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- 239000000446 fuel Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
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- 238000000231 atomic layer deposition Methods 0.000 description 5
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
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- 150000001336 alkenes Chemical class 0.000 description 1
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- 239000003426 co-catalyst Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
The application relates to a synthetic supported Pt-MXene composite structure catalyst and a preparation method and application thereof, belonging to the technical field of electrochemical catalyst preparation. The catalyst of the composite structure of the synthetic supported Pt-MXene takes MXene as a carrier and platinum as an active substance, the platinum is uniformly dispersed on the surface of the MXene, and the platinum comprises Pt taking 0-valence platinum metal particles as a main component 0 With Pt 2+ . The application solves the technical problems of complex preparation method of platinum catalyst, large size of platinum metal particles, poor stability and the like in the prior art. The platinum nano particles are uniformly dispersed by utilizing strong interaction of the MXene carrier and the interface of metal, the size of platinum particles loaded on the surface of the MXene can reach below 2nm, and the platinum catalytic activity is improved by the electron coupling effect of the bimetal; the platinum metal particles and the MXene have stronger metal-carrier interface interaction, which is beneficial to improving the stability and the dispersibility of the catalyst.
Description
Technical Field
The application belongs to the technical field of electrochemical catalyst preparation, and particularly relates to a catalyst with a synthetic supported Pt-MXene composite structure, and a preparation method and application thereof.
Background
Development of a high-efficiency stable supported platinum catalyst is a key material technology for promoting commercial application of proton exchange membrane fuel cells. The common platinum-carbon catalyst is limited by poor thermal stability of the carbon support material and insufficient specific activity of platinum atoms. The nonmetal alkene MXene with good conductivity and corrosion resistance is searched to be used as a novel two-dimensional material, has the characteristics of metal and ceramic, has a plurality of surface active sites, is favorable for forming a platinum dispersion structure with high dispersibility, and has wide application prospect as a substitute of a carbon carrier. The uniform distribution of platinum on the support is the limit to increase the activity per unit mass of the catalyst, while bringing the catalytic science to a smaller research scale.
Atomic Layer Deposition (ALD) or Chemical Vapor Deposition (CVD) is typically required to achieve nanoscale platinum catalytic structures. ALD (atomic layer deposition) method can effectively control the deposition morphology of metal on the surface of a substrate to realize a nano thin film structure (4-5 nanometers) of noble metal, but has high cost and low yield, and limits industrial application. The CVD method has the advantages that the deposition temperature required is high (generally 900-2000 ℃) and is easy to damage materials, the selection of a substrate and a deposition layer is limited, and a gas source participating in the deposition reaction and residual gas after the reaction have certain toxicity and potential safety hazard.
The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The preparation method and application of the composite structure catalyst for synthesizing the supported Pt-MXene are provided for solving the technical problems of complex preparation method, high reaction temperature, high energy consumption, potential safety hazard, large size of platinum metal particles, poor dispersibility and stability of the platinum catalyst in the prior art.
The first aspect of the present application provides a catalyst for synthesizing a supported Pt-MXene composite structure, the catalyst comprising MXene as a carrier and platinum as an active material, the platinum being uniformly dispersed on the surface of the MXene, the platinum comprising 0-valent platinum metal particles (Pt 0 ) With Pt 2+ 。
Platinum atoms (platinum 0-valent metal particles) formed on MXene surface and Pt 2+ Has stronger interface interaction, and is beneficial to improving the stability and the dispersibility of the catalyst.
In some embodiments, the particle size of the 0-valent platinum metal particles is 1-5 nm;
and/or, the 0-valence platinum metal particles on the surface of the MXene account for more than 70% of the total Pt content.
In some embodiments, the 0-valent platinum metal particles can reach a particle size of 2nm or less.
The second aspect of the application provides a preparation method of the synthetic supported Pt-MXene composite structure catalyst, wherein the preparation method adopts a glycol reduction impregnation method and comprises the following steps:
step S1: adding MXene into urea aqueous solution, uniformly mixing by ultrasonic, adding chloroplatinic acid, stirring, mixing, heating for reaction, and cooling to room temperature after reaction to obtain mixed solution;
step S2: and (2) adding ethylene glycol into the mixed solution obtained in the step (S1), mixing, stirring, heating, continuing stirring after heating, and performing aftertreatment to obtain the synthesized supported Pt-MXene composite structure catalyst.
In some embodiments, the post-treatment comprises filtration, washing with deionized water, washing 3 times.
In some embodiments, the MXene is a group IIIB-VIB metal carbide.
In some embodiments, the MXene is Mo 2 CT x 、Ti 3 C 2 Tx、V 2 CTx、Nb 2 CTx and Cr 2 One of CTx, preferably, the MXene is Mo 2 CT x Or Ti (Ti) 3 C 2 Tx。
The etched A-site metal is Al or G.
In some embodiments, the method of producing MXene comprises: and carrying out ultrasonic treatment on the precursor MAX in etching solution, carrying out etching reaction, and washing and drying to obtain the MXene.
When MXene is Mo 2 CT x In the case of Mo, the precursor MAX is 2 Al 2 C or Mo 2 Ga 2 C；
When MXene is Ti 3 C 2 At Tx, its precursor MAX is Ti 3 AlC 2 Or Ti (Ti) 3 GaC 2 ；
When MXene is V 2 In CTx, its precursor MAX is V 2 AlC or V 2 GaC；
When MXene is Nb 2 In CTx, the precursor MAX is Nb 2 AlC or Nb 2 GaC；
When MXene is Cr 2 In CTx, its precursor MAX is Cr 2 AlC/Cr 2 GaC。
In some embodiments, the etching solution is a mixed solution of hydrochloric acid and ammonium fluoride, the concentration of the hydrochloric acid is 30-60wt%, and the mass ratio of the ammonium fluoride to the MAX is 1:1;
and/or the ultrasonic treatment time is 30-60 min;
and/or the temperature of the etching reaction is 140-160 ℃, and the time of the etching reaction is 12-24 h.
The ammonium fluoride and the hydrochloric acid indirectly form HF and are used for etching the substrate, compared with the method of directly using HF for etching, the method has the advantages of more stable reaction and higher safety.
In some embodiments, the mass-to-water volume ratio of urea in the urea aqueous solution in the step S1 is (300-400) mg/(200-300) ml;
and/or the concentration of the chloroplatinic acid in the step S1 is 0.05M;
and/or stirring in the step S1 is mechanical stirring, wherein the time of mechanical stirring is 3-4 hours, or stirring in the step S1 is ultrasonic stirring, and the time of ultrasonic stirring is 30-60 minutes;
and/or the heating temperature in the step S1 is 90-100 ℃, and the heating time is 1-2 hours;
and/or the volume ratio of the glycol to the mixed solution in the step S2 is 1:1-1:1.5;
and/or, the mixing and stirring in the step S2 is mechanical stirring, the time of the mechanical stirring is 3-4 hours, or the mixing and stirring in the step S2 is ultrasonic stirring, and the ultrasonic stirring time is 30-60 minutes;
and/or the heating temperature in the step S2 is 120-130 ℃ and the heating time is 1-2 h;
and/or, continuously stirring for 12-14 h after heating and ending in the step S2.
At above 90 ℃, urea is hydrolyzed in chloroplatinic acid solution to generate OH - Uniform distribution of OH in solution - Thereby avoiding the formation of precipitation of Pt hydroxide by abrupt pH rise; the temperature is controlled to be not higher than 100 ℃ in order to reduce resource waste, and meanwhile, the hydrolysis reaction can be slowly carried out.
Due to the presence of ethylene glycol, acetaldehyde is generated after the temperature rises above 100 ℃, so that the formed high-valence compounds of Pt can be reduced to form metal particles of Pt, and if the temperature does not reach 100 ℃, the reducing agent can not effectively act, and the reaction rate is too high, so that the Pt particles are aggregated.
The third aspect of the application provides an application of the synthetic supported Pt-MXene composite structure catalyst or the synthetic supported Pt-MXene composite structure catalyst prepared by the preparation method as a proton exchange membrane fuel cell oxygen reduction catalyst, a water electroanalysis oxygen catalyst or a carbon dioxide electroreduction catalyst.
Compared with the prior art, the application has the following technical effects:
(1) The application synthesizes the supported Pt-MXene structure monoatomic platinum catalyst by adopting a glycol reduction method (wet chemical method) and selecting Mo 2 CT x 、Ti 3 C 2 T x After the reaction, the MXene two-dimensional material is used as a two-dimensional carrier and a co-catalyst, and the surface of the MXene carrier is loaded with not only 0-valence platinum metal particles but also Pt 2+ Wherein the 0-valence platinum metal particles can reach more than 70%, on the one hand, the MXene carrier and the metal are utilizedThe interface is in strong interaction, so that uniformly dispersed platinum nano particles are obtained, the size of platinum particles loaded on the surface of MXene obtained by characterization of a synthetic material can reach below 2nm, and the catalytic activity of platinum is improved by virtue of the electron coupling effect of bimetal; on the other hand, pt 2+ Has stronger interface interaction with platinum 0 valence metal atoms, and is favorable for improving the stability and the dispersibility of the catalyst.
(2) Compared with the traditional atomic layer deposition and other processes, the process method has the advantages of simpler process, short synthesis period, lower reaction temperature compared with the CVD synthesis method, and improved experiment safety while avoiding resource waste.
(3) The urea and glycol reduction method adopted in the application is not mentioned in the MXene-TM synthesis method in the prior art, and utilizes the uniform nanoparticle distribution and good conductive synergistic effect of the synthetic Pt-MXene catalyst and Ti 3 C 2 T x 、Mo 2 CT x The two-dimensional high-surface unique chemical structure of the equal two-dimensional material can realize the uniform dispersion of Pt nano particles at the edge of the MXene two-dimensional material, and the synthetic Pt/MXene can be clearly seen from a TEM image to be approximately single-atomic-level dispersed on the surface morphology, can reach below 2nm, realize a stable platinum catalytic structure and is beneficial to improving the catalytic performance of the electrocatalyst.
(4) The wet chemical synthesis method adopted by the application has the advantages of simple process, low cost, low reaction temperature, safety and reliability, and is convenient for large-scale industrial production, and the preparation process for synthesizing MXene is simpler and safer than an HF etching method; the experimental method is simultaneously suitable for preparing the single-atom structure of the non-noble metal catalyst on the MXene substrate, and can be widely applied.
Drawings
FIG. 1 is a diagram showing Mo obtained by etching in example 1 of the present application 2 CT x A two-dimensional material SEM image;
FIG. 2 is Mo after etching in example 1 of the present application 2 CT x XRD characterization pattern of (d) and Pt/Mo 2 CT x Composite materialXRD pattern;
FIG. 3 is a Pt/Mo alloy in example 1 of the present application 2 CT x An XPS diagram of the composite material, wherein (a) is a full spectrum, and (b) is a peak spectrum of platinum;
FIG. 4 is a Pt/Mo alloy in example 1 of the present application 2 CT x TEM, EDS and particle size distribution diagrams of the composite material, wherein (a) and (c) are Pt/Mo 2 CT x (b) is Pt/Mo 2 CT x And (d) is Pt/Mo 2 CT x Particle size distribution map of (2);
FIG. 5 is a diagram of Pt/Mo in example 2 of the present application 2 CT x TEM and EDS images of the composite, where (a) is Pt/Mo 2 CT x (b) is Pt/Mo 2 CT x Is characterized by EDS;
FIG. 6 shows Pt/Ti as in example 3 of the present application 3 C 2 T x TEM, EDS and particle size distribution of the composite, wherein (a) is Pt/Ti 3 C 2 T x (b) is Pt/Ti 3 C 2 T x And (c) is Pt/Ti 3 C 2 T x Particle size distribution map of (2);
FIG. 7 shows Pt/Mo obtained in inventive example 1 and example 2 2 CT x Composite material, mo 2 CT X And LSV comparison graph in Pt/C electrochemical performance test;
FIG. 8 is an SEM and EDS characterization of the composite material of comparative example 1, wherein (a) is an SEM image and (b) is an EDS image;
FIG. 9 is an EDS characterization of the composite material of comparative example 2 of the present application, wherein (a) is the EDS of the composite material and (b) is the EDS of the Pt element of the composite material;
fig. 10 is a TEM image of the composite material produced in comparative example 3 of the present application.
Detailed Description
The technical scheme of the application is described below through specific embodiments with reference to the accompanying drawings. It is to be understood that the reference to one or more steps of the application does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the application, which relative changes or modifications may be regarded as the scope of the application which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
In some embodiments, a method for synthesizing a supported Pt-MXene composite structure catalyst comprises:
step 1: and dissolving 300-400 mg of urea in 200-300 mL of deionized water, adding MXene into the solution, and carrying out ultrasonic treatment for 30-40 min. Urea is used for slowly regulating pH value of solution to assist deposition, and at above 90 deg.C, urea is hydrolyzed in platinum acid solution to produce OH - Uniform distribution of OH in solution - Thus avoiding the formation of precipitation of Pt hydroxide by abrupt pH rise.
Step 2: and (3) adding the chloroplatinic acid solution into the mixed solution obtained in the step (1), stirring for 3-4 hours, heating the mixture at 90-100 ℃ for 1-2 hours, and cooling to room temperature to obtain the mixed solution.
Step 3: 200-230 ml of ethylene glycol is added into the mixed solution cooled to room temperature in the step 2, stirred for 3-4 h, heated for 1h at 120-130 ℃, and stirred for 10-12 h. Due to the presence of ethylene glycol, acetaldehyde is generated after the temperature rises above 100 degrees celsius, thereby being able to reduce the compound of Pt that has formed, forming metal particles of Pt. Pt can be clearly seen from XPS figures of the following figures 0 Metal particles and Pt 2+ And (5) generating. In this step, if the temperature does not reach 100 ℃, the reducing agent cannot function effectively, and the temperature is too high so that the reaction rate is too fast to cause aggregation of Pt particles.
Step 4: filtering, washing, and drying at 60-80 ℃ for 12-14 h to obtain the synthetic supported Pt-MXene composite platinum catalyst.
Example 1: pt/Mo 2 CT x
(1) Preparation of MXene:
ultrasonically mixing ammonium fluoride 2 g with 40 mL 6M hydrochloric acid solution (11.8 mol/L) for 30 min to obtain an etching solution; then 2 g MAX (Mo 2 Ga 2 C) Immersing in etching solution, adding the mixed solution into a stainless steel reaction kettle with a Teflon lining of 100 ml capacity, heating to 140 ℃, continuously heating for 24 h, and finally cooling to room temperature. Washing the mixed solution with deionized water, centrifuging until pH reaches 6, washing with ethanol for 3 times, and drying the obtained powder at 60deg.C for 12h to obtain Mo 2 CT x Two-dimensional material.
（2）Pt/Mo 2 CT x Is prepared from
300mg of urea was dissolved in 200mL of deionized water, 60mg of Mo 2 CT x Adding into the solution, and ultrasonic treating for 30 min.5mL of 0.05M H 2 PtCl 6 ·6H 2 O was added to the solution (chloroplatinic acid and Mo 2 CT x The molar ratio of (2) is 1:1), ultrasonic stirring for 10-20min, and then heating the mixture at 90 ℃ for 1h, and cooling to room temperature. 200ml of ethylene glycol was added to the solution, stirred for 3 hours, heated at 120℃for 1 hour, and then stirred for 12 hours. Filtering, washing, drying at 80 ℃ for 12 hours to obtain Pt/Mo 2 CT x The particle size distribution of the composite material and the platinum nano particles is 2-5nm.
Example 2: pt/Mo 2 CT x
In this example 0.05M H 2 PtCl 6 ·6H 2 The addition amount of O was 1ml (chloroplatinic acid and Mo) 2 CT x The molar ratio of (2) was 1:5), otherwise the same as in example 1. Obtaining Pt/Mo 2 CT x Composite material, pt metal particles in Mo 2 CTx surface is evenly dispersed in atomic level, and the grain diameter can reach below 2 nm.
Example 3: pt/Ti 3 C 2 T x Is prepared from
(1) Preparation of MXene:
ultrasonically mixing ammonium fluoride 2 g with 40 mL 6M hydrochloric acid solution (11.8 mol/L) for 30 min to obtain an etching solution;then 2 g MAX (Ti 3 AlC 2 ) Immersing in etching solution, adding the mixed solution into a stainless steel reaction kettle with a Teflon lining of 100 ml capacity, heating to 140 ℃, continuously heating for 24 h, and finally cooling to room temperature. Washing the mixed solution with deionized water, centrifuging until pH reaches 6, washing with ethanol for 3 times, and drying the obtained powder at 60deg.C for 12h to obtain Ti 3 C 2 T x Two-dimensional material.
（2）Pt/Ti 3 C 2 T x Is prepared from
600 mg urea was dissolved in 400 mL deionized water, 65 mg Ti 3 C 2 T x Adding into the solution, and ultrasonic treating for 30 min.5mL of 0.05M H 2 PtCl 6 ·6H 2 O was added to the solution and stirred 3h, then the mixture was heated to 90 ℃, 1h, and cooled to room temperature. 200ml of ethylene glycol was added to the solution, stirred for 3h, heated at 120℃for 1h, and then stirred for 12h. Filtering, washing, drying at 80 ℃ for 12h to obtain Pt/Ti 3 C 2 T x A composite material. The particle size distribution of the Pt nano particles is 2-5nm.
Product characterization and analysis
(1) Mo in example 1 2 CT x SEM analysis of two-dimensional materials
For Mo obtained in example 1 2 CT x SEM analysis of the two-dimensional material, as shown in FIG. 1, can see Mo after etching 2 CT x The catalyst is multilayer, so that the contact area of the catalyst can be increased, and the catalytic activity of the catalyst can be improved.
(2) Mo in example 1 2 CTx and Pt/Mo 2 CT x XRD analysis of composite materials
For Mo obtained in example 1 2 CT x Two-dimensional material and Pt/Mo 2 CT x XRD analysis was performed, and the results are shown in FIG. 2, which shows diffraction peaks of the respective components, indicating that Mo was obtained by successful etching in the MXene preparation step 2 CTx two-dimensional material, after being reduced by glycol, pt nano particles are effectively loaded on Mo 2 CT x A surface.
(3) Implementation of the embodimentsPt/Mo in example 1 2 CT x XPS, TEM, EDS and particle size distribution analysis of composite materials
As shown in FIG. 3, it is clearly seen in the XPS characterization chart that 0-valent metal particles of Pt account for 70% or more of the total Pt compound and have Pt 2+ The method comprises the steps of carrying out a first treatment on the surface of the As is apparent from FIG. 4, it is apparent that monoatomic Pt is found in Mo 2 CT x The surface is deposited and evenly distributed, and the size of the nano particles is about 2 nm.
(4) Pt/Mo in example 2 2 CT x TEM and EDS analysis of composite materials
As shown in FIG. 5, it is apparent from the figure that Pt is in Mo 2 CT x The surface is uniformly distributed with the Pt nano particles dispersed in atomic scale, and the size of the Pt nano particles is below 2 nm.
(5) Example 3 Pt/Ti 3 C 2 T x TEM, EDS and particle size distribution analysis of composite materials
As shown in FIG. 6, it is apparent from the graph that Pt particles around 2nm are present in Ti 3 C 2 Tx surface was uniformly distributed, demonstrating that the synthesis method provided by the application is applicable to a variety of MXene substrates.
(6) Pt/Mo in example 1, example 2 2 CT x Electrochemical performance testing of composite materials
The reference electrode is a mercury oxidized mercury electrode and the carbon rod is a counter electrode by using oxygen to saturate 0.1M KOH electrolyte. 2 mg Ke Ji Hei, 20 mg sample, 260 μl isopropanol, 200 μl ethanol and 40 μl 5% Nafion solution are mixed together, and subjected to ice bath ultrasonic treatment for 40 min, 10 μl catalyst ink is taken and spin coated on the glassy carbon electrode to obtain a catalyst film. Electrochemical performance testing was then performed using a rotating disk electrode. The LSV pattern obtained is shown in FIG. 7, pt/Mo obtained in example 1 2 CT x The initial potential and the half-wave potential of the composite material are respectively 1.04V and 0.87V, which are superior to those of commercial platinum carbon Pt electrodes, and the composite material has good ORR (electro-catalytic oxygen reduction reaction) catalytic effect.
Comparative example 1
Comparative example 1 differs from example 1 in that urea was not added, and the other is the same as example 1.
The composite material prepared in the comparative example is subjected to SEM characterization and EDS characterization, and as shown in FIG. 8, the deposition effect of noble metal is not ideal, pt particles are aggregated together, the deposition amount is small, and the surface content of Pt is low by only 3%.
Comparative example 2
Comparative example 2 was different from example 1 in that no ethylene glycol was added, and the other was the same as example 1.
The composite material prepared in the comparative example is subjected to SEM characterization and EDS characterization, and as shown in FIG. 9, it can be seen that the particle size distribution of Pt metal particles deposited on the surface of MXene is less uniform, and a part of nanoparticles are larger.
Comparative example 3
Comparative example 3 differs from example 1 in that no ethylene glycol was added and NaBH was added 4 The reducing agent was the same as in example 1.
The test shows that the composite material prepared by the comparative example has larger particles and uneven distribution. A TEM image of the composite produced in this comparative example is shown in fig. 10.
The foregoing descriptions of specific exemplary embodiments of the present application are presented for purposes of illustration and description. It is not intended to limit the application to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the application and its practical application to thereby enable one skilled in the art to make and utilize the application in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the application be defined by the claims and their equivalents.
Claims (10)
1. A catalyst with a composite structure of synthesizing supported Pt-MXene is characterized in that the catalyst takes MXene as a carrier and platinum as an active substance, the platinum is uniformly dispersed on the surface of the MXene, and the platinum comprises 0-valence platinum metal particles and Pt 2+ 。
2. The synthetic supported Pt-MXene composite structural catalyst of claim 1, characterized in that the 0-valent platinum metal particles have a particle size of 1-5 nm;
and/or, 0-valence platinum metal particles on the surface of the MXene account for more than 70% of the total Pt content.
3. The synthetic supported Pt-MXene composite structural catalyst of claim 1 in which the 0-valent platinum metal particles have a particle size of up to 2nm or less.
4. The method for preparing the synthetic supported Pt-MXene composite structure catalyst according to claim 1, characterized in that the preparation method adopts a glycol reduction impregnation method comprising:
step S1: adding MXene into urea aqueous solution, uniformly mixing by ultrasonic, adding chloroplatinic acid, stirring, mixing, heating for reaction, and cooling to room temperature after reaction to obtain mixed solution;
step S2: and (2) adding ethylene glycol into the mixed solution obtained in the step (S1), mixing, stirring, heating, continuing stirring after heating, and performing aftertreatment to obtain the synthesized supported Pt-MXene composite structure catalyst.
5. The method of claim 4, wherein the MXene is a group IIIB-VIB metal carbide.
6. The method according to claim 4, wherein the MXene is Mo 2 CT x 、Ti 3 C 2 Tx、V 2 CTx、Nb 2 CTx and Cr 2 One of CTx.
7. The method of claim 4, wherein the method of producing MXene comprises: and carrying out ultrasonic treatment on the precursor MAX in etching solution, carrying out etching reaction, and washing and drying to obtain the MXene.
8. The method according to claim 7, wherein the etching solution is a mixed solution of hydrochloric acid and ammonium fluoride, the concentration of the hydrochloric acid is 30-60wt%, and the mass ratio of the ammonium fluoride to the MAX is 1:1;
and/or the ultrasonic treatment time is 30-60 min;
and/or the temperature of the etching reaction is 140-160 ℃, and the time of the etching reaction is 12-24 h.
9. The method according to claim 4, wherein the ratio of the mass of urea in the aqueous urea solution to the volume of water in step S1 is (300-400) mg/(200-300) ml;
and/or the concentration of the chloroplatinic acid in the step S1 is 0.05M;
and/or stirring in the step S1 is mechanical stirring, wherein the time of mechanical stirring is 3-4 hours, or stirring in the step S1 is ultrasonic stirring, and the time of ultrasonic stirring is 30-60 minutes;
and/or the heating temperature in the step S1 is 90-100 ℃, and the heating time is 1-2 hours;
and/or the volume ratio of the glycol to the mixed solution in the step S2 is 1:1-1:1.5;
and/or, the mixing and stirring in the step S2 is mechanical stirring, the time of the mechanical stirring is 3-4 hours, or the mixing and stirring in the step S2 is ultrasonic stirring, and the ultrasonic stirring time is 30-60 minutes;
and/or the heating temperature in the step S2 is 120-130 ℃ and the heating time is 1-2 h;
and/or, continuously stirring for 12-14 h after heating and ending in the step S2.
10. Use of a synthetic supported Pt-MXene composite-structure catalyst according to any one of claims 1-3 or a synthetic supported Pt-MXene composite-structure catalyst prepared according to the method of any one of claims 4-9 as a proton exchange membrane fuel cell oxygen reduction catalyst, a hydro-electric oxygen desorption catalyst or a carbon dioxide electro-reduction catalyst.
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