CN113215616B - IrCoFe @ MXene composite catalyst and preparation method and application thereof - Google Patents

IrCoFe @ MXene composite catalyst and preparation method and application thereof Download PDF

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CN113215616B
CN113215616B CN202110494344.2A CN202110494344A CN113215616B CN 113215616 B CN113215616 B CN 113215616B CN 202110494344 A CN202110494344 A CN 202110494344A CN 113215616 B CN113215616 B CN 113215616B
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mxene
ircofe
containing compound
composite catalyst
preparation
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CN113215616A (en
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田明
陈强
盛维武
李小婷
魏嘉
许健
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China Petroleum and Chemical Corp
Sinopec Engineering Group Co Ltd
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China Petroleum and Chemical Corp
Sinopec Engineering Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses an IrCoFe @ MXene composite catalyst and a preparation method and application thereof, and relates to the technical field of novel electrocatalytic materials. The preparation method comprises the following steps: maintaining the mixed solution dispersed with the iridium-containing compound, the cobalt-containing compound, the iron-containing compound, the coordination acid, the MXene carrier and the solvent at the temperature of 150-170 ℃ for more than 5 hours, cooling to obtain a suspension, washing the suspension, and freeze-drying to obtain the iridium-containing compound/cobalt-containing compound/iron-containing compound/coordination acid/MXene carrier suspension; wherein, the molar ratio of iridium ions, cobalt ions and iron ions in the mixed solution is 5. The preparation method has the advantages that the composition of elements is controlled by regulating the proportion of the metal precursor, the use of the noble metal Ir is reduced, the catalyst cost is reduced, the preparation method is simple and convenient, the prepared IrCoFe @ MXene composite catalyst has excellent catalytic performance, and the IrCoFe @ MXene composite catalyst can be widely applied to a PEM electrolytic cell to decompose water to prepare hydrogen and used as an anode catalyst layer.

Description

IrCoFe @ MXene composite catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of new electrocatalytic materials, in particular to an IrCoFe @ MXene composite catalyst and a preparation method and application thereof.
Background
Since fossil fuel is a non-renewable primary energy source, the problems of resource shortage, environmental pollution, climate change and the like brought by the fossil fuel bring great pressure on energy supply, and therefore carbon reduction and hydrogen increase are imperative to the development of clean energy. Due to the advantages of high efficiency, cleanness, renewability and the like, the hydrogen energy occupies an important position in the industrial fields of aerospace, electronic appliances and the like and human life, has an irreplaceable function in the aspect of fuel power, and is one of the most potential energy sources for solving the future energy crisis. Hydrogen is an ideal secondary energy source, and has a high hydrogen calorific value and an energy density more than twice that of solid fuel, compared with other energy sources. Hydrogen is an excellent energy storage medium for renewable and sustainable energy systems. The hydrogen as an energy carrier has the advantages that: the hydrogen and the electric energy can be efficiently converted into each other by the water electrolysis technology; the compressed hydrogen has a very high energy density; hydrogen has the potential to scale up to grid-scale applications.
Among the hydrogen production by water electrolysis based on renewable energy, PEM hydrogen production by water electrolysis is a potential industrial process that can produce large amounts of high-purity hydrogen without releasing conventional byproducts associated with fossil fuels, and avoids the disadvantages of alkaline liquid electrolyzers using strongly alkaline liquid electrolytes. Has the advantages of high efficiency, high gas purity, environmental protection, low energy consumption, no alkali liquor, small volume, safety, reliability, capability of realizing higher gas production pressure and the like.
Electrocatalytic decomposition of water, including Oxygen Evolution Reactions (OERs) and Hydrogen Evolution Reactions (HERs), where OER is the rate-determining step in electrocatalytic decomposition of water, has been accomplished with a number of anode catalysts effective in increasing OER history, e.g., the noble metal RuO 2 Transition non-noble metal cobalt, nickel oxide, and the like. However, there has been little development of electrocatalysts that are effective in promoting OER in acidic electrolytes. Iridium (Ir) is generally considered to be the best catalyst for OER under acidic conditions, its reserves are scarce and its abundance is even 10 times lower than that of platinum. In order to reduce the consumption of noble metal Ir, the commonly used means at present is to improve the activity of Ir-based catalyst by changing the atomic arrangement or to form a core-shell structure or alloy nanoparticles by adding non-noble metal ions and Ir, thereby changing the electronic performance of Ir, improving the water electrolysis efficiency and simultaneously reducing the consumption of Ir metal. For example, by adding Ni metal ions to Ir oxide, the resulting NiIr alloy oxide can improve the OER performance to some extent. In order to reduce the cost of PEM electrolytic cells, a simpler preparation method is designed, the dosage of noble metal Ir is reduced, and the stability and durability of the catalyst are imperatively maintained.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of an IrCoFe @ MXene composite catalyst, which is simple, controls the composition of elements by regulating the proportion of metal precursors, reduces the use of a noble metal Ir, and reduces the cost of the catalyst.
The invention aims to provide an IrCoFe @ MXene composite catalyst which is excellent in catalytic performance.
The invention aims to provide application of an IrCoFe @ MXene composite catalyst as an anode catalyst layer in a hydrogen production process by decomposing water in a PEM electrolytic cell.
The invention is realized by the following steps:
in a first aspect, the invention provides a preparation method of an IrCoFe @ MXene composite catalyst, which comprises the following steps: maintaining the mixed solution dispersed with iridium-containing compound, cobalt-containing compound, iron-containing compound, coordination acid, MXene carrier and solvent at 150-170 ℃ for more than 5h, cooling to obtain suspension, washing the suspension, and freeze-drying to obtain the IrCoFe @ MXene composite catalyst;
wherein the molar ratio of iridium ions, cobalt ions and iron ions in the mixed solution is 5.
In an alternative embodiment, the MXene carrier comprises at least one of MXene nanoplatelets and MXene nanofibers.
In an alternative embodiment, the method for preparing MXene nanoplatelets comprises: mixing and etching lithium fluoride, concentrated hydrochloric acid and MAX powder, washing and centrifuging to obtain the MXene nanosheet;
preferably, the etching comprises heating and stirring for 24-48h at 30-40 ℃;
preferably, the mass to volume ratio of the lithium fluoride to the concentrated hydrochloric acid is (1-2) g: (30-50) mL;
preferably, the mass ratio of the MAX powder to the lithium fluoride is 1:1-2.
Preferably, the concentration of the concentrated hydrochloric acid solution is 8-10mol/L;
preferably, the MAX powder is Ti 3 AlC 2 。
In an alternative embodiment, the method for preparing the MXene nanofibers comprises: fully hydrolyzing the MXene nanosheets in an aqueous solution of NaOH and N-methylpyrrolidone to obtain MXene nanofibers;
preferably, the mass to volume ratio of the MXene nanoplatelets, the NaOH and the N-methylpyrrolidone is 200mg:8-12mL:1-2mL;
preferably, the concentration of NaOH in the aqueous solution is 5-7mol/L;
preferably, the hydrolysis is carried out for 4-6h under the condition of 80-100 ℃ under the protection of nitrogen;
preferably, after the hydrolysis, the method further comprises repeatedly washing until the pH value is 7-8, and freeze-drying to obtain the MXene nanofibers.
In an alternative embodiment, the forming of the mixed solution comprises:
dissolving the iridium-containing compound, the cobalt-containing compound, the iron-containing compound and the coordination acid in a part of the solvent to form a first solution;
dispersing the MXene carrier in the rest of the solvent to form a second solution;
ultrasonically mixing the first solution and the second solution for 8-12min to obtain a mixed solution;
preferably, the mixed solution is kept for more than 5 hours at the temperature of 150-170 ℃ under the protection of nitrogen.
In an alternative embodiment, the suspension is washed with a mixed wash solution of ethanol and acetone.
In alternative embodiments, the iridium-containing compound is iridium chloride;
preferably, the cobalt-containing compound is cobalt acetylacetonate;
preferably, the iron-containing compound is iron acetylacetonate.
In an alternative embodiment, the coordinating acid is citric acid.
In a second aspect, the invention provides an ircofe @ mxene composite catalyst, which is prepared by the preparation method of the ircofe @ mxene composite catalyst according to any one of the foregoing embodiments.
In a third aspect, the invention provides an application of the ircofe @ mxene composite catalyst in a PEM electrolytic cell hydrogen production process by water decomposition as an anode catalyst layer.
The invention has the following beneficial effects:
the preparation method of the IrCoFe @ MXene composite catalyst provided by the application controls the composition of elements by regulating the proportion of the metal precursor, reduces the use of the noble metal Ir, reduces the cost of the catalyst, is simple and convenient to prepare, has excellent catalytic performance, and can be widely applied to a PEM electrolytic cell to be used as an anode catalyst layer in the hydrogen production process by decomposing water.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a schematic diagram of a preparation process of the IrCoFe @ MXene composite catalyst provided by the present application;
fig. 2 is a process for preparing MXene provided herein;
fig. 3 is a scanning electron microscope image of MXene nanoplatelets provided in example 1 of the present application;
fig. 4 is a scanning electron microscope image of MXene nanofibers provided in example 2 of the present application;
FIG. 5 is a comparative graph of electrochemical properties of IrFeCo @ MXene provided in the first experimental example of the present application;
FIG. 6 is a comparative graph of electrochemical properties of IrFeCo @ MXene in different metal ratios provided in the second experimental example of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a preparation method of IrCoFe @ MXene composite catalyst, please refer to FIG. 1, which comprises the following steps: maintaining the mixed solution dispersed with the iridium-containing compound, the cobalt-containing compound, the iron-containing compound, the coordination acid, the MXene carrier and the solvent at the temperature of 150-170 ℃ for more than 5 hours, cooling to obtain suspension, washing the suspension, and freeze-drying to obtain the IrCoFe @ MXene composite catalyst.
Specifically, the method comprises the following steps:
s1: and preparing MXene carrier.
The MXene carrier in the application comprises at least one of MXene nanosheet and MXene nanofiber.
The preparation method of the MXene nanosheet comprises the following steps: mixing lithium fluoride, concentrated hydrochloric acid and MAX powder, heating and stirring for 24-48h at 30-40 ℃ for etching, washing with water, and centrifuging to obtain MXene nanosheets.
Specifically, referring to fig. 2, lithium fluoride is placed in a 100mL polytetrafluoroethylene beaker, concentrated hydrochloric acid is poured into the beaker, and the mixture is uniformly stirred; mixing MAX (Ti) 3 AlC 2 ) Slowly adding into the solution in the beaker, mixing with concentrated hydrochloric acid, and selectively corroding Ti by hydrofluoric acid generated in the solution 3 AlC 2 All of the Al elements in (1), and-OH and-F in the solution as terminal groups substituted for Al.
Wherein the mass volume ratio of the lithium fluoride to the concentrated hydrochloric acid is (1-2) g: (30-50) ml; the mass ratio of MAX powder to lithium fluoride is 1:1-2. The concentration of the concentrated hydrochloric acid solution is 8-10mol/L; MAX powder is Ti 3 AlC 2 。
Specifically, in the application, the step of obtaining the MXene nanosheet by water washing and centrifugation comprises: and repeatedly washing the etched product with deionized water, and performing centrifugal separation (3500rpm, 10min) until the pH value of the solution after adding the deionized water and performing uniform ultrasound reaches 7. After the supernatant liquid is poured out, adding a proper amount of ethanol into a centrifuge tube, adding ice blocks into an ultrasonic machine, and keeping the ultrasonic for 1 hour at a low temperature. After re-centrifugation (10000 rpm, 10min), the bottom black slime was collected. Then dispersing the mucus in deionized water, and centrifuging to obtain MXene slices and multiple layers of MXene from the upper liquid and the lower liquid of the centrifugal tube respectively. By repeated centrifugation, the supernatant was taken and more MXene flakes were obtained by suction filtration. Drying for 4h by using a freeze drier to remove a large amount of moisture of MXene, and obtaining clay-like MXene solid as MXene nanosheets.
The preparation method of the MXene nano fiber comprises the following steps: and (2) stirring MXene nanosheets in an aqueous solution of NaOH and N-methylpyrrolidone for 2-4h under the protection of nitrogen at 80-100 ℃ for sufficient hydrolysis, repeatedly washing until the pH value is 7-8, and freeze-drying to obtain the MXene nanofiber.
Wherein the mass-volume ratio of MXene nanosheets to NaOH to N-methylpyrrolidone is 200mg:8-12mL:1-2mL; the concentration of NaOH in the aqueous solution is 5-7mol/L.
S2: and (4) preparing a mixed solution.
The iridium-containing compound, the cobalt-containing compound, the iron-containing compound, the coordination acid, the MXene carrier and the solvent are mixed to form a mixed solution. Various ways of forming the mixed solution are available, and in the application, preferably, the iridium-containing compound, the cobalt-containing compound, the iron-containing compound and the coordination acid are dissolved in part of the solvent to form a first solution; then, dispersing the MXene carrier in the residual solvent to form a second solution; and ultrasonically mixing the first solution and the second solution for 8-12min to obtain a mixed solution.
Through forming first solution and second solution earlier in this application, mix first solution and second solution again, can improve the mixing uniformity of each component in the mixed solution. In the present application, the iridium-containing compound is iridium chloride; the cobalt-containing compound is cobalt acetylacetonate; the iron-containing compound is ferric acetylacetonate. The coordination acid is citric acid, and the solvent is benzyl alcohol.
The research of the inventor finds that the citric acid has a rich hydroxyl structure and a strong coordination effect, and the citric acid is used as the coordination acid to be beneficial to forming uniform nano-particles on the surface of the MXene carrier by metal ions. Meanwhile, the benzyl alcohol is selected to effectively dissolve the metal compound and the MXene carrier, so that the metal compound and the MXene carrier are uniformly dispersed in the benzyl alcohol, and subsequent loading is facilitated.
Wherein the molar ratio of iridium ions, cobalt ions and iron ions in the mixed solution is 5.
S3: and (4) loading.
And transferring the mixed solution into a high-pressure reaction glass tube, discharging air by nitrogen replacement, placing the mixed solution into an oil bath pan, and keeping the mixed solution at the temperature of between 150 and 170 ℃ for more than 5 hours for loading to obtain a suspension. The reaction temperature may be, for example, any one of 150 ℃, 152 ℃, 154 ℃, 156 ℃, 158 ℃, 160 ℃, 162 ℃, 164 ℃, 166 ℃, 168 ℃ and 170 ℃ or a range between any two of them.
S4: washed and freeze-dried.
And washing the obtained suspension with a mixed washing solution of ethanol and acetone, and freeze-drying to obtain the IrCoFe @ MXene composite catalyst. The mixed washing solution of ethanol and acetone selected in the application is a solution for routine experiments, for example, the volume ratio of ethanol to acetone is 1:1-2.
The preparation method of the IrCoFe @ MXene composite catalyst provided by the application controls the composition of elements by regulating the proportion of the metal precursor, reduces the use of the noble metal Ir, reduces the cost of the catalyst, is simple and convenient to prepare, has excellent catalytic performance, and can be widely applied to a PEM electrolytic cell to be used as an anode catalyst layer in the hydrogen production process by decomposing water.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides an IrCoFe @ MXene composite catalyst, and the preparation method comprises the following steps:
2g of lithium fluoride was weighed into a 100mL polytetrafluoroethylene beaker, 9M 40mL of hydrochloric acid was poured into the beaker, and the mixture was stirred uniformly for 30min (400 rpm); 2g of MAX (Ti) 3 AlC 2 ) Slowly added to the solution in the above beaker and stirred in an oil bath pan at constant temperature of 35 ℃ for 24h. Repeatedly washing the obtained mixed solution with deionized water, and separatingThe mixture was separated by centrifugation (3500rpm, 10min) until the pH of the solution reached 7 after the addition of deionized water and uniform sonication. After the supernatant liquid is poured out, adding a proper amount of ethanol into a centrifuge tube, adding ice blocks into an ultrasonic machine, and keeping the ultrasonic operation at a low temperature for 1 hour. After re-centrifugation (10000 rpm, 10min), the bottom black slime was collected. Then dispersing the mucus in deionized water, and centrifuging to obtain MXene slices and multiple layers of MXene from the upper liquid and the lower liquid of the centrifugal tube respectively. And repeatedly centrifuging, taking supernatant liquid, and obtaining more MXene slices by suction filtration. Drying for 4h by using a freeze dryer to remove a large amount of moisture of MXene to obtain clay-like MXene solid, and taking the solid after dispersion as shown in figure 3.
0.149g of iridium chloride (IrCl) was weighed out 3 ) 0.103g of cobalt acetylacetonate (Co (acac) 2 ) 0.0353g iron acetylacetonate (Fe (acac) 3 ) 0.063g of citric acid (monohydrate) was placed in 3ml of benzyl alcohol and dissolved by ultrasonic wave. 10mg of MXene nanosheets were placed in 1ml of benzyl alcohol and dispersed ultrasonically. The mass ratio of metal ion substances is Ir: co: fe = 5. Mixing the above two mixed solutions, and performing fusion ultrasonic treatment for 10min. It was then transferred to a high-pressure reaction glass tube, purged of air by nitrogen displacement, placed in an oil bath pan at 160 ℃ for 6h, and then cooled to room temperature. The obtained suspension was purified by a distillation method using a volume ratio of 1:1, washing with mixed washing liquor of ethanol and acetone, and freeze-drying to obtain the IrCoFe @ MXene composite catalyst.
Example 2
The embodiment provides an IrCoFe @ MXene composite catalyst, and the preparation method comprises the following steps:
200mg of MXene solid prepared in example 1 was weighed, placed in a high pressure reaction glass tube containing 10mL of 6M NaOH solution, 1mL of N-methylpyrrolidone was added dropwise, and stirred for 3 hours while keeping the temperature of 90 ℃ in an oil bath under nitrogen protection. And repeatedly washing until the pH value reaches 7, and freeze-drying to obtain MXene nanofiber powder as shown in figure 4.
0.149g of iridium chloride (IrCl) was weighed out 3 ) 0.103g of cobalt acetylacetonate (Co (acac) 2 ) 0.0353g iron acetylacetonate (Fe (acac) 3 ) 0.063g of citric acid (monohydrate) was placed in 3ml of benzyl alcohol and dissolved by ultrasonic wave. 10mg of nanofibers were placed in 1In ml of benzyl alcohol, ultrasonic dispersion is carried out. The mass ratio of metal ion substances is Ir: co: fe = 5. Mixing the above two mixed solutions, and performing fusion ultrasonic treatment for 10min. It was then transferred to a high-pressure reaction glass tube to remove air by nitrogen substitution, placed in an oil bath at 160 ℃ for 6 hours, and then cooled to room temperature. The obtained suspension was purified by a distillation method using a volume ratio of 1:1, washing by using mixed washing liquor of ethanol and acetone, and freeze-drying to obtain the IrCoFe @ MXene composite catalyst.
Examples 3 to 4
Examples 3-4 provide ircofe @ mxene composite catalyst which differs from example 2 in that: the amount ratio of the metal ion species is different.
In example 3, the ratio of the amount of the metal ion species is Ir: co: fe = 5.
In example 4, the ratio of the amount of the metal ion species is Ir: co: fe = 5.
Example 5
The embodiment provides an IrCoFe @ MXene composite catalyst, and the preparation method comprises the following steps:
2g of lithium fluoride was weighed into a 100mL polytetrafluoroethylene beaker, and 8M 30mL hydrochloric acid was poured into the beaker and stirred uniformly for 30min (400 rpm); 1g of MAX (Ti) 3 AlC 2 ) Slowly added to the solution in the above beaker and stirred in an oil bath pan at constant temperature of 35 ℃ for 24h. Repeatedly washing the obtained mixed solution with deionized water, and centrifuging (3500rpm, 10min) until the pH value of the solution after adding deionized water and uniformly performing ultrasonic treatment reaches 7. After the supernatant liquid is poured out, adding a proper amount of ethanol into a centrifuge tube, adding ice blocks into an ultrasonic machine, and keeping the ultrasonic for 1 hour at a low temperature. After re-centrifugation (10000 rpm, 10min), the bottom black slime was collected. Then dispersing the mucus in deionized water, and centrifuging to obtain MXene slices and multiple layers of MXene from the upper liquid and the lower liquid of the centrifugal tube respectively. By repeated centrifugation, the supernatant was taken and more MXene flakes were obtained by suction filtration. Drying for 4h by using a freeze drier to remove a large amount of moisture of MXene to obtain clay-like MXene solid for dispersing and taking. MXene solid (200 mg) was weighed, placed in a high pressure reaction glass tube containing 12mL of 7M NaOH solution, and 2ml of N-methylpyrrole was added dropwiseAnd (3) under the protection of nitrogen, keeping the temperature of 100 ℃ in an oil bath kettle, and stirring for 4 hours. Repeatedly washing until the pH value reaches 7, and freeze-drying to obtain MXene nanofiber powder.
0.149g of iridium chloride (IrCl) was weighed 3 ) 0.103g of cobalt acetylacetonate (Co (acac) 2 ) 0.0353g iron acetylacetonate (Fe (acac) 3 ) 0.063g of citric acid (monohydrate) was placed in 3ml of benzyl alcohol and dissolved by ultrasonic wave. 10mg of nanofibers were placed in 1ml of benzyl alcohol and dispersed ultrasonically. The mass ratio of metal ion substances is Ir: co: fe = 5. Mixing the above two mixed solutions, and performing fusion ultrasonic treatment for 10min. It was then transferred to a high-pressure reaction glass tube, purged of air by nitrogen displacement, placed in an oil bath pan at 160 ℃ for 6h, and then cooled to room temperature. The obtained suspension was purified by a distillation method using a volume ratio of 1:1, washing with mixed washing liquor of ethanol and acetone, and freeze-drying to obtain the IrCoFe @ MXene composite catalyst.
Experimental example 1
MXene nanosheets, MXene nanofibers, irFeCo @ MXene nanosheets prepared in example 1 and IrFeCo @ MXene nanofibers prepared in example 2 were respectively used as anode catalysts in 0.5M H 2 SO 4 In a three-electrode system as electrolyte, the modification was tested on a glassy carbon electrode (GC, d =3 mm) for water splitting performance, with an average mass of about 0.357mg cm -2 。
As can be seen from the linear sweep voltammetry curve of FIG. 5, irFeCo @ MXene nanofibers have the best electrocatalytic activity. The contact area between the MXene fiber skeleton structure and the loaded metal is larger, so that the electron transfer rate is effectively improved. In a PEM electrolytic cell, the MXene fiber skeleton structure is more favorable for the passing of gas and ions, and the transmission rate of the ions between a proton membrane and a diffusion layer is improved.
Experimental example two
The feeding amount of the metal ions is controlled by regulating and controlling the metal ions with different concentrations, and the feeding amount is controlled by H at 0.5M 2 SO 4 In a three-electrode system as an electrolyte, the feeding amount of an optimal transition metal precursor is determined by the electrocatalytic water decomposition performance of the three-electrode system, and the molar ratio of IrElectrocatalytic activity of the composite catalyst at different ratios.
As can be seen from fig. 6, when the molar ratio of Ir to Co to Fe is 5.
The preparation method of the IrCoFe @ MXene composite catalyst provided by the application controls the composition of elements by regulating and controlling the proportion of the metal precursor, reduces the use of noble metal Ir, reduces the cost of the catalyst, is simple and convenient to prepare, has excellent catalytic performance of the prepared IrCoFe @ MXene composite catalyst, and can be widely applied to a PEM electrolytic cell for decomposing water to produce hydrogen as an anode catalyst layer.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of IrCoFe @ MXene composite catalyst is characterized by comprising the following steps: maintaining the mixed solution dispersed with iridium-containing compound, cobalt-containing compound, iron-containing compound, coordination acid, MXene carrier and solvent at 150-170 ℃ for more than 5h under the protection of nitrogen, cooling to obtain suspension, washing the suspension, and freeze-drying to obtain the IrCoFe @ MXene composite catalyst;
wherein the molar ratio of iridium ions, cobalt ions and iron ions in the mixed solution is 5; the iridium-containing compound is iridium chloride, the cobalt-containing compound is cobalt acetylacetonate, the iron-containing compound is ferric acetylacetonate, and the coordination acid is citric acid;
the MXene carrier is MXene nano-fibers, and the preparation method of the MXene nano-fibers comprises the following steps: mixing and etching lithium fluoride, concentrated hydrochloric acid and MAX powder, washing and centrifuging to obtain MXene nanosheets; stirring the MXene nanosheets in an aqueous solution of NaOH and N-methylpyrrolidone under the protection of nitrogen for 4-6h for full hydrolysis at 80-100 ℃, repeatedly washing until the pH value is 7-8, and freeze-drying to obtain MXene nanofibers;
the mass-volume ratio of the MXene nanosheets to the NaOH to the N-methylpyrrolidone is 200mg:8-12mL:1-2mL;
the concentration of NaOH in the aqueous solution is 5-7mol/L.
2. The preparation method of IrCoFe @ MXene composite catalyst according to claim 1, wherein the etching comprises heating and stirring at 30-40 ℃ for 24-48h.
3. The preparation method of IrCoFe @ MXene composite catalyst according to claim 1, wherein the mass volume ratio of the lithium fluoride to the concentrated hydrochloric acid is (1-2) g: (30-50) mL.
4. The preparation method of IrCoFe @ MXene composite catalyst according to claim 1, wherein the mass ratio of the MAX powder to the lithium fluoride is 1-2.
5. The preparation method of IrCoFe @ MXene composite catalyst according to claim 1, wherein the concentration of the concentrated hydrochloric acid is 8-10mol/L.
6. The preparation method of IrCoFe @ MXene composite catalyst according to claim 1, wherein the MAX powder is Ti 3 AlC 2 。
7. The method for preparing IrCoFe @ MXene composite catalyst according to claim 1, wherein the forming of the mixed solution comprises:
dissolving the iridium-containing compound, the cobalt-containing compound, the iron-containing compound and the coordination acid in a part of the solvent to form a first solution;
then dispersing the MXene carrier in the rest of the solvent to form a second solution;
and ultrasonically mixing the first solution and the second solution for 8-12min to obtain the mixed solution.
8. The preparation method of IrCoFe @ MXene composite catalyst according to claim 1, wherein the suspension is washed with a mixed washing solution of ethanol and acetone.
9. An IrCoFe @ MXene composite catalyst, which is characterized by being prepared by the preparation method of the IrCoFe @ MXene composite catalyst according to any one of claims 1-8.
10. The use of ircofe @ mxene composite catalyst as claimed in claim 9 as an anode catalyst layer in the hydrogen production process by water splitting in PEM electrolysers.
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