CN112133926A - Preparation method of platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst - Google Patents

Preparation method of platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst Download PDF

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CN112133926A
CN112133926A CN201910548100.0A CN201910548100A CN112133926A CN 112133926 A CN112133926 A CN 112133926A CN 201910548100 A CN201910548100 A CN 201910548100A CN 112133926 A CN112133926 A CN 112133926A
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titanium carbide
graphene
platinum
carbide nanosheet
nanosheet
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黄华杰
杨翠珍
李伟华
姜全国
何海燕
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Hohai University HHU
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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
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • 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
    • 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
    • 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 provides a preparation method of a platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst, which relates to the field of electrode catalysts and comprises the following steps: firstly, etching carbon aluminum titanium by using lithium fluoride and hydrochloric acid, carrying out ultrasonic treatment to obtain titanium carbide nanosheets, then carrying out ultrasonic dispersion on the titanium carbide nanosheets in an ethylene glycol solution, adding graphene oxide into the ethylene glycol solution, carrying out ultrasonic mixing treatment again, then adding a platinum salt solution, stirring to fully mix the solution, carrying out hydrothermal reaction to obtain a hydrogel-like product, carrying out dialysis water washing treatment, and carrying out freeze drying to obtain the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst. According to the invention, titanium carbide nanosheets and graphene are used as templates, and crystalline platinum nanoparticles are deposited on the surfaces of the titanium carbide nanosheets and the graphene, so that the prepared composite electrode catalyst has the advantages of three-dimensional porous structure, high catalytic activity and high toxicity resistance.

Description

Preparation method of platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst
Technical Field
The invention relates to a preparation method of an electrode catalyst, in particular to a preparation method of a platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst.
Background
With the increasingly prominent energy crisis and environmental pollution in the world, the development of an efficient and clean energy production system has important practical significance for the sustainable development of the modern society. The direct methanol fuel cell attracts wide attention due to its characteristics of high energy density, less pollution emission, simple structure, easy storage of fuel, etc. Platinum metal is the best catalyst material for catalyzing the oxidation reaction of methanol, but the high price and easy poisoning property of platinum greatly prevent the large-scale commercial application of the platinum. Therefore, the novel composite platinum-based catalyst which has excellent performances such as high catalytic activity, high toxicity resistance and the like and is relatively low in cost is synthesized, and the commercialization process of the direct methanol fuel cell can be effectively promoted.
Transition metal carbides or carbon/nitrides MXene, a new member of the two-dimensional family of materials, two-dimensional Ti3C2TxThe nanosheet is similar to graphene in structure, and has good hydrophilicity and unique electrochemical properties. The study shows that Ti3C2TxThe nanosheet can be used as a carrier material to improve the utilization efficiency of metal platinum, and is mainly based on: (1) ti3C2TxThe nano-sheet has large specific surface area, and the surface of the material has a large amount of-OH and-F functional groups, and the functional groups provide rich growth sites for the deposition of noble metal particles; (2) ti3C2TxThe good conductivity of the nano-sheets can reduce the charge transfer resistance of the catalyst, so that the electrocatalytic activity of the composite system is further improved; (3) ti3C2TxThe nano sheet can regulate and control the electronic structure of the metal platinum, improve the intrinsic electrocatalytic activity of the nano sheet, and enhance the anti-poisoning capability of the metal platinum on reaction byproducts (mainly CO). So far, there are researches to directly load platinum nanoparticles on graphene or titanium carbide nanoparticlesThe surface of the sheet is used to synthesize a platinum/graphene or platinum/titanium carbide nanosheet catalyst (Li Y, Gao W, et al, catalytic performance of Pt nanoparticles on reduced graphene oxide for methanol electro-oxidation, Carbon,2010,48, 1124-1130; Wang Y, Wang J, et al, Pt purified Ti)3C2MXene for enhanced methanol oxidation reaction, Ceramics International,2019, 45,2411-2417), and no study has been reported on the construction of a three-dimensional composite carrier by using graphene and titanium carbide nanosheets and the loading of platinum nanoparticles by using the carrier.
Chinese patent No. CN201710324833.7 discloses a preparation method of a two-dimensional titanium carbide/carbon nano tube loaded platinum particle composite material, and the method is to strip Ti by HF chemistry3AlC2Preparing two-dimensional titanium carbide by using the aluminum atomic layer, combining the two-dimensional titanium carbide and MWNTs by using a solvothermal method, and loading platinum nanoparticles to obtain Ti3C2MWNTs-Pt nanocomposite; however, like other two-dimensional sheet material structures, Ti3C2The strong attraction between different sheet layers of the nano sheet is easy to generate the phenomena of agglomeration and stacking, and the interlayer spacing is small, so that the problems greatly limit the transmission speed of electrolyte ions in the material, and can cause partial reaction active sites to be covered to reduce the catalytic efficiency, and seriously reduce Ti3C2The electrochemical activity of the/MWNTs-Pt nano composite material.
Therefore, a new preparation method is developed to reduce Ti in the composite system3C2The stacking of the nano-sheets makes the unique advantages of the nano-sheets effectively exerted in the field of electrocatalysis become the key point and difficulty of work.
Disclosure of Invention
In order to solve the defects and shortcomings in the prior art, the invention provides a preparation method of a platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst, the method takes the titanium carbide nanosheet and the graphene as templates, and crystalline platinum nanoparticles are deposited on the surfaces of the titanium carbide nanosheet and the graphene, so that the prepared composite electrode catalyst has the advantages of three-dimensional porous structure, high catalytic activity and high toxicity resistance.
The preparation method of the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid;
s2, adding graphene oxide into the titanium carbide nanosheet dispersion liquid obtained in the step S1, and performing ultrasonic dispersion to obtain a titanium carbide nanosheet/graphene oxide binary composite solution, wherein the addition amount of the graphene oxide and the titanium carbide is 1-9: 1-9;
s3, adding a potassium chloroplatinite solution into the binary compound solution obtained in the step S2, and uniformly stirring to obtain a potassium chloroplatinite/titanium carbide nanosheet/graphene oxide ternary compound solution, wherein the addition amount of the platinum element in the potassium chloroplatinite solution and the titanium carbide nanosheet/graphene oxide binary compound is 1-20: 1-20;
s4, carrying out hydrothermal reaction on the ternary compound solution obtained in the step S3 to obtain a hydrogel-like product, dialyzing, washing with water, and carrying out freeze drying to obtain the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst.
According to the method, titanium carbide and graphene oxide are used as carriers, platinum is used as a catalyst, two-dimensional titanium carbide is generated by a chemical etching method, a single-layer or few-layer titanium carbide nanosheet is obtained by ultrasonically stripping a two-dimensional titanium carbide sheet layer, then a mixed solution of the titanium carbide nanosheet and the graphene oxide is prepared, then a potassium chloroplatinate solution is added, platinum ions are adsorbed on the surface of the titanium carbide through ion exchange with oxygen-containing functional groups on the surface of the titanium carbide, the titanium carbide nanosheet is combined with the graphene oxide by adopting a hydrothermal reaction, and simultaneously, with the increase of temperature, the platinum ions are reduced into platinum nanoparticles loaded in three-dimensional pores formed by the titanium carbide nanosheet and the graphene oxide.
The graphene and the titanium carbide nanosheets are self-assembled into a three-dimensional porous hybrid aerogel structure by a synthesis method from bottom to top, microporous channels in the three-dimensional porous network skeleton of the graphene-titanium carbide nanosheets form a mutually communicated microporous network, so that not only can the dispersion of metal platinum nanoparticles be facilitated, but also more electrochemical active sites can be formed due to the special pore structure of the graphene-titanium carbide nanosheets, external electrolyte can easily enter the material, the graphene-titanium carbide nanosheets have quick ion transfer capability and efficient electrochemical active surface, and better electrochemical properties can be obtained. In contrast, the two-dimensional layered titanium carbide directly stacked has a compact two-dimensional structure, so that the rapid transmission of electrolyte ions in the material is greatly limited, and the catalytic performance of the material is seriously reduced; therefore, the electrochemical performance of the three-dimensional porous network skeleton constructed by the two-dimensional layered material is better.
Further, in step S2, the addition amount of the graphene oxide and the titanium carbide is 1 to 4: 5 to 9.
Further, in step S3, the addition amount of the platinum element and the titanium carbide nanosheet/graphene oxide binary composite in the potassium chloroplatinite solution is 1: 4 to 9.
Further, in step S3, the stirring conditions are: stirring for 0.2-5 h at 0-50 ℃.
Further, in step S4, the hydrothermal reaction conditions are: and carrying out hydrothermal reaction for 8-14 h at the temperature of 80-120 ℃.
Further, in step S4, the dialysis water washing time is 3 to 10 days, and the drying pressure during freeze drying is 0 to 200 Pa.
Further, the step S1 of preparing the titanium carbide nanosheet dispersion specifically includes the following steps:
p1, etching the carbon-aluminum-titanium by using lithium fluoride and hydrochloric acid, and then centrifugally washing to obtain a multilayer titanium carbide precipitate;
p2, adding a small amount of distilled water into the multilayer titanium carbide precipitate, ultrasonically stripping, and freeze-drying to obtain a single-layer or few-layer titanium carbide nanosheet;
and P3, dissolving the titanium carbide nanosheets in an ethylene glycol solution, and performing ultrasonic dispersion to obtain a titanium carbide nanosheet dispersion liquid.
Further, in step P1, the etching reaction conditions are: the etching reaction time is 24-60 h, the reaction temperature is 10-50 ℃, and the concentration of hydrochloric acid is 6-12 mol/L.
Further, in step P1, the centrifugal water washing conditions are as follows: the centrifugal rotating speed is 3500-8000 rpm, and the water washing is carried out until the pH value of the supernatant is close to neutral.
Further, in step P2, the ultrasonic peeling conditions are: and (3) carrying out ultrasonic stripping for 0.5-6 h, continuously introducing argon as a protective gas while carrying out ultrasonic treatment, carrying out centrifugal screening at a rotating speed of 5000-8000 rpm after the ultrasonic treatment is finished, and freeze-drying the centrifugal supernatant to obtain the single-layer or few-layer titanium carbide nanosheet.
Further, in the step P3, the concentration of the titanium carbide nanosheet dispersion is 0.1-10 g/L.
Further, in step P3 and step S1, the ultrasonic conditions are: the ultrasonic time is 0.5-6 h, and the ultrasonic temperature is 0-50 ℃.
The invention achieves the following beneficial technical effects:
1. according to the preparation method of the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst, the prepared electrode catalyst has the advantages of high catalytic activity, three-dimensional porous structure, good stability, high toxicity resistance, high utilization rate of precious metals and the like; the platinum/titanium carbide nanosheet/graphene ternary composite electrode catalyst prepared by the method has good application prospect and economic benefit in the fields of direct methanol fuel cells and the like.
2. The preparation method provided by the invention is simple and controllable, has good repeatability and low cost, and is beneficial to large-scale industrial production.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is an external view of a gel-like product of example 3 of the present invention;
fig. 3 shows an X-ray diffraction (XRD) spectrum (fig. a) and a raman spectrum (fig. B) of the platinum/titanium carbide nanosheet/graphene composite electrode catalyst prepared by the method of example 3 of the present invention;
fig. 4 is a field emission scanning electron microscope (FE-SEM) photograph of the platinum/titanium carbide nanosheet/graphene composite electrode catalyst prepared by the method of example 3 of the present invention;
fig. 5 is a Transmission Electron Microscope (TEM) photograph of the platinum/titanium carbide nanosheet/graphene composite electrode catalyst prepared by the method of example 3 of the present invention;
fig. 6 is a nitrogen adsorption and desorption graph of the platinum/titanium carbide nanosheet/graphene composite electrode catalyst prepared by the method of embodiment 3 of the present invention;
FIG. 7 shows a platinum/titanium carbide nanosheet/graphene composite electrode catalyst (Pt/G-Ti) prepared by the method of embodiment 3 of the present invention3C2Tx) With platinum/titanium carbide nanosheets (Pt/Ti)3C2Tx) Platinum/graphene (Pt/G), platinum/carbon nanotube (Pt/CNT) and platinum/carbon black (Pt/C) materials at 0.5mol/L H2SO4Cyclic voltammogram in solution (FIG. 7A) and at 0.5mol/L H2SO4And 0.5mol/L CH3Cyclic voltammogram in OH mixed solution (fig. 7B);
FIG. 8 shows a Pt/Ti carbide nanosheet/graphene composite electrode catalyst (Pt/G-Ti) prepared by the method of embodiment 3 of the present invention3C2Tx) With platinum/titanium carbide nanosheets (Pt/Ti)3C2Tx) Potentiostatic oxidation tests of platinum/graphene (Pt/G), platinum/carbon nanotube (Pt/CNT), and platinum/carbon black (Pt/C) materials (fig. 8A); chronopotentiometric test curves (fig. 8B).
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, a preparation method of a platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid;
s2, adding graphene oxide into the titanium carbide nanosheet dispersion liquid obtained in the step S1, wherein the addition amount of the graphene oxide and the titanium carbide is 1-9: 9-1, and ultrasonically dispersing for 0.5-6 h at the temperature of 0-50 ℃ to obtain a titanium carbide nanosheet/graphene oxide binary composite solution;
s3, adding a potassium chloroplatinite solution into the binary compound solution in the step S4, wherein the addition amount of the platinum element and the titanium carbide nanosheet/graphene oxide binary compound in the potassium chloroplatinite solution is 1-20: 1-20, stirring for 0.2-5 h at the temperature of 0-50 ℃ to obtain a potassium platinochloride/titanium carbide nanosheet/graphene oxide ternary complex solution;
s4, carrying out hydrothermal reaction on the ternary compound solution obtained in the step S3 at the temperature of 80-120 ℃ for 8-14 h to obtain a hydrogel-like product, then dialyzing and washing for 3-10 d, and carrying out freeze drying under the drying pressure of 0-200 Pa to obtain the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst.
The step S1 of preparing the titanium carbide nanosheet dispersion specifically comprises the following steps:
p1, etching the carbon-aluminum-titanium by using lithium fluoride and hydrochloric acid, wherein the etching reaction time is 24-60 h, the reaction temperature is 10-50 ℃, and the hydrochloric acid concentration is 6-12 mol/L; centrifuging at 3500-8000 rpm, washing with water until the pH of the supernatant is close to neutral to obtain multilayer titanium carbide precipitate;
p2, adding a small amount of distilled water into the multilayer titanium carbide precipitate, ultrasonically stripping for 0.5-6 h, continuously introducing protective gas argon while ultrasonically treating, centrifugally screening at a rotating speed of 5000-8000 rpm after ultrasonically treating, taking the centrifugal supernatant, and freeze-drying to obtain a single-layer or few-layer titanium carbide nanosheet;
p3, dissolving the titanium carbide nanosheets in an ethylene glycol solution, and ultrasonically dispersing for 0.5-6 h at the temperature of 0-50 ℃ to obtain 0.1-10 g/L titanium carbide nanosheet dispersion liquid;
example 1
A preparation method of a platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid;
s2, adding graphene oxide into the titanium carbide nanosheet dispersion liquid obtained in the step S1, wherein the addition amount of the graphene oxide and the titanium carbide is 9: 1, performing ultrasonic dispersion for 1h at the temperature of 10 ℃ to obtain a titanium carbide nanosheet/graphene oxide binary composite solution;
s3, adding a potassium chloroplatinite solution into the binary compound solution in the step S2, wherein the addition amount of the platinum element and the titanium carbide nanosheet/graphene oxide binary compound in the potassium chloroplatinite solution is 1: 9, stirring for 40min at the temperature of 20 ℃ to obtain a potassium platinochloride/titanium carbide nanosheet/graphene oxide ternary complex solution;
s4, placing the ternary composite solution obtained in the step S3 at 120 ℃ for a hydrothermal reaction for 11 hours to obtain a hydrogel-like product, then dialyzing and washing for 4 days, and freeze-drying under the drying pressure of 200Pa to obtain the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst.
The step S1 of preparing the titanium carbide nanosheet dispersion specifically comprises the following steps:
p1, etching the carbon-aluminum-titanium by using lithium fluoride and hydrochloric acid, wherein the etching reaction time is 24 hours, the reaction temperature is 25 ℃, and the hydrochloric acid concentration is 6 mol/L; then centrifuging at 5000rpm, washing with water until the pH of the supernatant is close to neutral, and obtaining multilayer titanium carbide precipitate;
p2, adding a small amount of distilled water into the multilayer titanium carbide precipitate, ultrasonically stripping for 1h, continuously introducing argon as a protective gas while ultrasonically treating, centrifugally screening at the rotating speed of 7000rpm after the ultrasonic treatment is finished, and freeze-drying the centrifugal supernatant to obtain single-layer or few-layer titanium carbide nanosheets;
and P3, dissolving the titanium carbide nanosheets in an ethylene glycol solution, and ultrasonically dispersing for 1h at the temperature of 10 ℃ to obtain 5g/L of titanium carbide nanosheet dispersion liquid.
Example 2
A preparation method of a platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid;
s2, adding graphene oxide into the titanium carbide nanosheet dispersion liquid obtained in the step S1, wherein the addition amount of the graphene oxide and the titanium carbide is 4: 5; ultrasonically dispersing for 3h at the temperature of 30 ℃ to obtain a titanium carbide nanosheet/graphene oxide binary composite solution;
s3, adding a potassium chloroplatinite solution into the binary compound solution in the step S2, wherein the addition amount of the platinum element and the titanium carbide nanosheet/graphene oxide binary compound in the potassium chloroplatinite solution is 1: 7, stirring for 30min at the temperature of 10 ℃ to obtain a potassium platinochloride/titanium carbide nanosheet/graphene oxide ternary complex solution;
s4, placing the ternary composite solution obtained in the step S3 at 100 ℃ for a hydrothermal reaction for 10 hours to obtain a hydrogel-like product, as shown in figure 2, then dialyzing and washing for 5 days, and freeze-drying under the drying pressure of 100Pa to obtain the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst.
The step S1 of preparing the titanium carbide nanosheet dispersion specifically comprises the following steps:
p1, etching the carbon-aluminum-titanium by using lithium fluoride and hydrochloric acid, wherein the etching reaction time is 36h, the reaction temperature is 35 ℃, and the hydrochloric acid concentration is 9 mol/L; then centrifuging at 6000rpm, washing with water until the pH of the supernatant is close to neutral, and obtaining multilayer titanium carbide precipitates;
p2, adding a small amount of distilled water into the multilayer titanium carbide precipitate, ultrasonically stripping for 1h, continuously introducing argon as a protective gas while ultrasonically treating, centrifugally screening at 8000rpm after the ultrasonic treatment is finished, and freeze-drying the centrifugal supernatant to obtain single-layer or few-layer titanium carbide nanosheets;
and P3, dissolving the titanium carbide nanosheets in an ethylene glycol solution, and ultrasonically dispersing for 3 hours at the temperature of 30 ℃ to obtain 5g/L of titanium carbide nanosheet dispersion liquid.
Example 3
A preparation method of a platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid;
s2, adding graphene oxide into the titanium carbide nanosheet dispersion liquid obtained in the step S1, wherein the addition amount of the graphene oxide and the titanium carbide is 3: 7, performing ultrasonic dispersion for 0.5h at the temperature of 0 ℃ to obtain a titanium carbide nanosheet/graphene oxide binary composite solution;
s3, adding a potassium chloroplatinite solution into the binary compound solution in the step S2, wherein the addition amount of the platinum element and the titanium carbide nanosheet/graphene oxide binary compound in the potassium chloroplatinite solution is 1: stirring for 30min at the temperature of 10 ℃ to obtain a potassium platinochloride/titanium carbide nanosheet/graphene oxide ternary complex solution;
s4, placing the ternary composite solution obtained in the step S3 at 100 ℃ for a hydrothermal reaction for 10 hours to obtain a hydrogel-like product, as shown in figure 2, then dialyzing and washing for 5 days, and freeze-drying under the drying pressure of 25Pa to obtain the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst.
The step S1 of preparing the titanium carbide nanosheet dispersion specifically comprises the following steps:
p1, etching the carbon-aluminum-titanium by using lithium fluoride and hydrochloric acid, wherein the etching reaction time is 36h, the reaction temperature is 35 ℃, and the hydrochloric acid concentration is 9 mol/L; then centrifuging at 6000rpm, washing with water until the pH of the supernatant is close to neutral, and obtaining multilayer titanium carbide precipitates;
p2, adding a small amount of distilled water into the multilayer titanium carbide precipitate, ultrasonically stripping for 1h, continuously introducing argon as a protective gas while ultrasonically treating, centrifugally screening at 8000rpm after the ultrasonic treatment is finished, and freeze-drying the centrifugal supernatant to obtain single-layer or few-layer titanium carbide nanosheets;
and P3, dissolving the titanium carbide nanosheets in an ethylene glycol solution, and ultrasonically dispersing for 0.5h at the temperature of 0 ℃ to obtain 5g/L of titanium carbide nanosheet dispersion liquid.
Example 4
The embodiment 4 is different from the embodiment 3 in that, in the step S2, the addition amount of the graphene oxide and the titanium carbide is 1: 5; ultrasonic dispersing at 0 deg.C for 2 hr.
Example 5
A preparation method of a platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid;
s2, adding graphene oxide into the titanium carbide nanosheet dispersion liquid obtained in the step S1, wherein the addition amount of the graphene oxide and the titanium carbide is 1: 9, performing ultrasonic dispersion for 4 hours at the temperature of 20 ℃ to obtain a titanium carbide nanosheet/graphene oxide binary composite solution;
s3, adding a potassium chloroplatinite solution into the binary compound solution in the step S2, wherein the addition amount of the platinum element and the titanium carbide nanosheet/graphene oxide binary compound in the potassium chloroplatinite solution is 9: 1, stirring for 60min at the temperature of 0 ℃ to obtain a potassium platinochloride/titanium carbide nanosheet/graphene oxide ternary complex solution;
s4, placing the ternary composite solution obtained in the step S3 at 80 ℃ for a hydrothermal reaction for 12 hours to obtain a hydrogel-like product, then dialyzing and washing for 5 days, and freeze-drying under the drying pressure of 25Pa to obtain the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst.
The step S1 of preparing the titanium carbide nanosheet dispersion specifically comprises the following steps:
p1, etching the carbon-aluminum-titanium by using lithium fluoride and hydrochloric acid, wherein the etching reaction time is 60 hours, the reaction temperature is 45 ℃, and the hydrochloric acid concentration is 10 mol/L; then centrifuging at 6000rpm, washing with water until the pH of the supernatant is close to neutral, and obtaining multilayer titanium carbide precipitates;
p2, adding a small amount of distilled water into the multilayer titanium carbide precipitate, ultrasonically stripping for 2 hours, continuously introducing argon as a protective gas while ultrasonically treating, centrifugally screening at a rotating speed of 5000rpm after the ultrasonic treatment is finished, and freeze-drying the centrifugal supernatant to obtain single-layer or few-layer titanium carbide nanosheets;
and P3, dissolving the titanium carbide nanosheets in an ethylene glycol solution, and performing ultrasonic dispersion for 4 hours at the temperature of 20 ℃ to obtain 8g/L of titanium carbide nanosheet dispersion liquid.
Comparative example 1
The comparative example 1 is different from the example 3 in that, in the step S2, the addition amount of the graphene oxide and the titanium carbide is 1: 12; stirring at 0 deg.C for 60 min.
Comparative example 2
The comparative example 2 is different from the example 3 in that, in the step S2, the addition amount of the graphene oxide and the titanium carbide is 12: 1; stirring at 0 deg.C for 60 min.
Comparative example 3
Comparative example 3 is different from example 3 in that carbon nanotubes are used instead of graphene oxide, the amount of the carbon nanotubes added is the same as that of graphene oxide, and the preparation method is the same as that of example 3.
Application case Performance characterization
The platinum/titanium carbide nanosheet/graphene composite electrode catalyst prepared by the method of example 3 is taken as an example for performance characterization.
1) Appearance of hydrogel-like product
Fig. 2 is an electron photograph of a hydrogel product of platinum/titanium carbide nanosheet/graphene prepared by the method of example 3, and it can be seen from fig. 2 that titanium carbide and graphene form a three-dimensional hydrogel structure through the action of a hydrothermal method.
2) Analysis of X-ray powder diffraction pattern and Raman spectrum
Fig. 3 is an X-ray powder diffraction pattern and a raman spectrum of the platinum/titanium carbide nanosheet/graphene composite electrode catalyst prepared by the method of example 3, and characteristic peaks of metal platinum and graphite oxide can be clearly seen from the XRD pattern of fig. 3A, which indicates that the composite product contains the two components, and the XRD pattern does not have an obvious characteristic peak of titanium carbide, mainly because the three-dimensional porous network structure can effectively prevent the titanium carbide nanosheets from agglomerating. Fig. 3B is a raman spectrum of the platinum/titanium carbide nanosheet/graphene composite electrode catalyst, from which characteristic peaks of titanium carbide and graphite oxide can be clearly seen, and the simultaneous existence of platinum, titanium carbide and graphene is confirmed in combination with fig. 3A.
3) Field emission scanning electron microscopy analysis
As can be seen from fig. 4A and 4B, the catalyst has a distinct three-dimensional porous network structure, while both graphene and titanium carbide components are present in the form of two-dimensional flakes, where fig. 4C and 4D are partially enlarged views of titanium carbide and graphene, respectively, and it can be seen that platinum particles are uniformly distributed on the sheets of both, forming a good dispersion.
4) Transmission Electron microscopy analysis
Fig. 5 is a transmission electron microscope image of a platinum/titanium carbide nanosheet/graphene composite electrode catalyst, and fig. 5A further demonstrates that the platinum particles are distributed more uniformly on the titanium carbide nanosheet and graphene hybrid framework without significant agglomeration; the lattice fringes of the platinum particles can be clearly seen in fig. 5B.
The results show that the platinum/titanium carbide nanosheet/graphene composite electrode catalyst has an anti-stacking three-dimensional porous network framework, is large in specific surface area, can enable metal platinum nanoparticles to be uniformly distributed on the three-dimensional framework, and has higher catalytic performance and electrochemical activity.
5) Nitrogen adsorption and desorption test
As can be seen from the adsorption and desorption test graph of FIG. 6, the specific surface area of the catalyst is 214.6m2g-1And has a significant pore structure.
6) Test for catalytic Activity
Electrochemical tests of the samples were all carried out on a CHI760E electrochemical workstation, and the test system was a conventional three-electrode system, in which a platinum wire was used as a counter electrode, a saturated calomel electrode was used as a reference electrode, and a glassy carbon electrode coated with an active material and having a diameter of 3mm was used as a working electrode. The preparation process of the working electrode comprises the following steps: 2mg of the catalyst powder was weighed and dispersed in a mixed solution of 0.5mL of deionized water, 0.5mL of ethanol and 0.05mL of Nafion, and subjected to ultrasonication for 30 min. 0.005mL of the dispersion of the catalyst sample was dropped on the surface of a glassy carbon electrode, and dried at room temperature for 0.5 hour, followed by conducting a test. The electrochemically active surface area (ECSA) of the catalyst and the catalytic activity of the methanol oxidation were measured by cyclic voltammetry with 0.5mol/L H of electrolyte, respectively2SO4Solution and 0.5mol/L H2SO4And 0.5mol/L CH3OH mixed solution, scanning speed of 20mV. s-1. The stability and methanol tolerance of the catalyst are evaluated by a constant potential oxidation method and a chronopotentiometric method. Investigating catalysts by electrochemical AC impedance testingConductive property, frequency range is 1050.02Hz and an amplitude of 10 mV.
By calculating the area of the curve in fig. 7A in the hydrogen adsorption region, it can be found that the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst has the highest electrochemical active surface area (90.1 m)2g-1) Applicants also conducted a methanol oxidation catalyst performance test on platinum/titanium carbide nanosheets/graphene catalysts, see fig. 7B, which had a forward current density of 1102.0mA mg-1. To further illustrate the catalytic activity of the catalyst, applicants also compared cyclic voltammetry tests of different materials for methanol oxidation, and it can be seen from fig. 7 that the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst, regardless of the active surface area or the forward peak current density, is significantly higher than the other four comparative samples, indicating that it has the highest catalytic activity.
The electrochemical stability test of the platinum/titanium carbide nanosheet/graphene three-dimensional coincidence catalyst adopts a constant potential oxidation method. As can be seen from fig. 8A: within the test time of 2000s, the platinum/titanium carbide nanosheet/graphene three-dimensional composite catalyst always maintains the lowest current attenuation rate and the highest oxidation current density, which indicates that the catalyst has good catalytic durability. It is clearly observed from fig. 8B that the catalyst can stay at a low potential for a longer time under galvanostatic test conditions. It can be seen from the figure that both the catalytic durability and the resistance to poisoning of the catalyst are superior to the other four comparative samples.
The results of the methanol oxidation reaction test on the catalysts prepared by the methods of examples 1 to 5 are shown in table 1.
TABLE 1 Performance index of catalysts prepared in examples 1-5 for methanol oxidation
Figure BDA0002104662310000121
As can be seen from Table 1, the catalysts prepared by the methods of examples 1-5 all have high catalytic activity and stable catalytic activity. With the increase of the addition amount of the titanium carbide in the titanium carbide nanosheet/graphene oxide binary composite solution, the active surface area, the mass activity and the apparent activity of the catalyst are increased, but with the further increase of the addition amount of the titanium carbide, the performance of the catalyst is reduced in comparison with that of examples 3 and 4 in example 5, and when the content of the titanium carbide is increased to the content of the comparative example 1, the performance of the catalyst is sharply reduced; the reason is that titanium carbide itself cannot form a three-dimensional network structure, and the addition of a large amount of titanium carbide causes the agglomeration of titanium carbide itself and the reduction of active sites, thereby reducing the catalytic activity, so the addition ratio of titanium carbide and graphene is very important, and the proper ratio of graphene and titanium carbide is favorable for forming a good three-dimensional porous structure. The good graphene/titanium carbide three-dimensional porous structure is beneficial to uniform dispersion of platinum nanoparticles and quick transmission of electrolyte in the reaction process, so that the catalytic performance is effectively improved. Compared with the embodiments 1-5, in the comparative example 2, the content of the titanium carbide nanosheet in the titanium carbide nanosheet/graphene oxide binary composite solution is too low, so that on one hand, sufficient growth sites cannot be provided for metal platinum particles, and on the other hand, the electronic structure of platinum cannot be effectively regulated and controlled, so that the poor CO poisoning resistance of the platinum is caused, and the catalytic performance is reduced. Compared with example 3, the carbon nanotube is adopted to replace graphene oxide, and the performance of the catalyst is remarkably reduced, because the surface of the carbon nanotube is hydrophobic and has low bonding force with a titanium carbide nanosheet, the agglomeration of the titanium carbide nanosheet is aggravated, and the dispersion of platinum nanoparticles is not facilitated, so that the performance of the catalyst is reduced.
The catalytic reaction is only a surface reaction, only atoms on the surface can play a catalytic role, and atoms inside the surface do not participate in the reaction, so that the addition amount of platinum can play a good catalytic activity only under a proper condition, the platinum loading is too high, the uniform dispersibility of platinum nanoparticles is reduced, part of platinum atoms are stacked together to form an ineffective catalyst, the utilization rate is reduced, and the catalytic activity is also reduced due to too low content. The proportion of each component is determined through a large number of experiments, and the catalyst with good catalytic performance for the methanol direct fuel cell can be obtained only by the components with the proportion content.

Claims (10)

1. The preparation method of the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst is characterized by comprising the following steps of:
s1, preparing titanium carbide nanosheet dispersion liquid;
s2, adding graphene oxide into the titanium carbide nanosheet dispersion liquid obtained in the step S1, and performing ultrasonic dispersion to obtain a titanium carbide nanosheet/graphene oxide binary composite solution, wherein the addition amount of the graphene oxide and the titanium carbide is 1-9: 1-9;
s3, adding a potassium chloroplatinite solution into the binary compound solution obtained in the step S2, and uniformly stirring to obtain a potassium chloroplatinite/titanium carbide nanosheet/graphene oxide ternary compound solution, wherein the addition amount of the platinum element in the potassium chloroplatinite solution and the titanium carbide nanosheet/graphene oxide binary compound is 1-20: 1-20;
s4, carrying out hydrothermal reaction on the ternary compound solution obtained in the step S3 to obtain a hydrogel-like product, then dialyzing, washing with water, and freeze-drying to obtain the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst.
2. The preparation method of the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst according to claim 1, wherein in step S2, the addition amount of the graphene oxide and the titanium carbide is 1-4: 5 to 9.
3. The method for preparing the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst according to claim 1, wherein in step S3, the addition amount of the platinum element and the titanium carbide nanosheet/graphene oxide binary composite in the potassium chloroplatinite solution is 1: 4 to 9.
4. The method for preparing the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst according to claim 1, wherein in step S3, the stirring conditions are: stirring for 0.2-5 h at 0-50 ℃.
5. The preparation method of the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst according to claim 1, wherein in step S4, the hydrothermal reaction conditions are as follows: and carrying out hydrothermal reaction for 8-14 h at the temperature of 80-120 ℃.
6. The method for preparing the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst according to claim 1, wherein in step S4, the dialysis water washing time is 3-10 d, and the drying pressure during freeze drying is 0-200 Pa.
7. The preparation method of the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst as claimed in any one of claims 1 to 6, wherein the preparation of the titanium carbide nanosheet dispersion liquid in step S1 specifically comprises the following steps:
p1, etching the carbon-aluminum-titanium by using lithium fluoride and hydrochloric acid, and then centrifugally washing to obtain a multilayer titanium carbide precipitate;
p2, adding a small amount of distilled water into the multilayer titanium carbide precipitate, ultrasonically stripping, and freeze-drying to obtain a single-layer or few-layer titanium carbide nanosheet;
and P3, dissolving the titanium carbide nanosheets in an ethylene glycol solution, and performing ultrasonic dispersion to obtain a titanium carbide nanosheet dispersion liquid.
8. The preparation method of the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst according to claim 7, wherein in step P1, the etching reaction conditions are as follows: the etching reaction time is 24-60 h, the reaction temperature is 10-50 ℃, and the concentration of hydrochloric acid is 6-12 mol/L.
9. The preparation method of the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst according to claim 7, wherein in step P1, the centrifugal water washing conditions are as follows: and (4) centrifuging at 3500-8000 rpm, and washing with water until the pH value of the supernatant is close to neutral.
10. The preparation method of the platinum/titanium carbide nanosheet/graphene three-dimensional composite electrode catalyst according to claim 7, wherein in step P2, the ultrasonic peeling conditions are as follows: and (3) ultrasonic stripping time is 0.5-6 h, protective gas argon is continuously introduced while ultrasonic treatment is carried out, centrifugal screening is carried out at the rotating speed of 5000-8000 rpm after ultrasonic treatment is finished, and centrifugal supernatant is taken and freeze-dried to obtain the single-layer or few-layer titanium carbide nanosheet.
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CN113718281A (en) * 2021-09-26 2021-11-30 河海大学 Graphene quantum dot/MXene nanosheet two-dimensional composite material and preparation method and application thereof

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