CN111744519A - Preparation method of three-dimensional MXene-based carrier hydrogen evolution catalyst - Google Patents
Preparation method of three-dimensional MXene-based carrier hydrogen evolution catalyst Download PDFInfo
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- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 229910003178 Mo2C Inorganic materials 0.000 claims description 2
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- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
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- 238000001816 cooling Methods 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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Abstract
The invention discloses a preparation method of a three-dimensional MXene-based catalyst for hydrogen evolution reaction, which utilizes a three-dimensional MXene-based material as a catalyst carrier for the electrolysis water hydrogen evolution reaction under an alkaline condition and loads catalytic active particles so as to prepare the three-dimensional catalyst. Compared with the traditional noble metal catalyst such as (Pt/C) catalyst, the novel catalyst prepared by the invention has better electrocatalytic activity and stability.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a preparation method of a three-dimensional MXene-based carrier hydrogen evolution catalyst.
Background
The hydrogen production by water electrolysis is a clean and efficient hydrogen production technology, the preparation conditions are mild, the requirement on equipment is low, the purity of the prepared hydrogen can reach 99.99 percent, and the method has high economic and social benefits. Compared with other hydrogen production methods, the hydrogen production by electrolyzing water utilizes clean water as a raw material for reaction, and the preparation method is green and environment-friendly, so that the method is known as a method for continuously producing hydrogen. Therefore, the water electrolysis hydrogen production technology will become the core technology of the future hydrogen production industry.
Noble metal materials such as platinum, palladium and the like are the most suitable hydrogen evolution catalysts with the best catalytic performance at present, but the noble metal materials have low earth crust storage capacity and high price and cannot be applied to industrial hydrogen production on a large scale. Currently, researchers are working on finding catalysts for the hydrogen evolution reaction by electrolysis, which have a novel structure, higher catalytic activity and more stable electrochemical performance. Therefore, the research on the catalyst for the water electrolysis hydrogen evolution reaction which has a stable structure and can carry out high-efficiency catalytic reaction is an important development trend of hydrogen production by water electrolysis.
Disclosure of Invention
The invention aims to provide a preparation method of a three-dimensional MXene-based carrier hydrogen evolution catalyst, which synthesizes the hydrogen evolution catalyst by using novel three-dimensional MXene-based composite carrier loaded catalyst active particles. The carrier has a three-dimensional structure, has a large specific surface area and more catalyst active particle attachment sites, and has more advantages than the traditional carbon black as a catalyst carrier. The catalyst prepared by the carrier has higher catalytic activity and better electrochemical stability.
The preparation method of the three-dimensional MXene-based carrier hydrogen evolution catalyst comprises the steps of compounding MXene and a carbon material to serve as a catalyst carrier for an electrolytic water hydrogen evolution reaction under an alkaline condition, and then loading catalyst active particles to obtain a novel carrier hydrogen evolution catalyst so as to improve the catalytic activity and the stability of the catalyst. The method specifically comprises the following steps:
step 1: adding 0.1-20 parts of MXene into 1-20 parts of solvent, and uniformly dispersing by ultrasonic to obtain MXene dispersion liquid;
step 2: adding 0.1-20 parts of carbon material into 1-20 parts of solvent, and uniformly dispersing by ultrasonic to obtain a carbon material dispersion liquid;
and step 3: mixing the MXene dispersion liquid obtained in the step 1 and the carbon material dispersion liquid obtained in the step 2, uniformly dispersing by ultrasonic waves, transferring the mixture into a hydrothermal reaction kettle, introducing nitrogen for 0.5-5 hours, then carrying out hydrothermal reaction, cooling and washing for a plurality of times after the reaction is finished, and carrying out freeze drying for 12 hours to obtain an MXene-carbon material three-dimensional composite carrier;
and 4, step 4: dispersing 0.1-40 parts of the MXene-carbon material three-dimensional composite carrier obtained in the step (3) into 1-40 parts of a solvent, and performing ultrasonic dispersion for 0.1-20 hours;
and 5: calculating the amount of a precursor of the required catalyst active particles according to the proportion that the mass of the catalyst active particles is 1-60% of the total mass of the catalyst, and adding the precursor of the required catalyst active particles into the dispersion liquid obtained in the step (4) after the precursor of the catalyst active particles is uniformly dispersed in a solvent by ultrasonic;
step 6: and (3) dropwise adding a reducing agent solution into the mixed dispersion liquid obtained in the step (5), washing with deionized water after dropwise adding is finished, and then placing in a vacuum drying oven for vacuum drying for more than 0.5 hour to obtain the three-dimensional MXene-based carrier hydrogen evolution catalyst.
In the preparation process of the invention, the raw materials comprise the following components in parts by mass:
the MXene is Ti3C2、Ti2C、Nb3C2、Nb2C、TiNbC、Cr2TiC、Ti3CN、Ti4N3、Ta4C3、V2C、Mo2C or MoTiC2。
The carbon material is Graphene Oxide (GO), graphene, Carbon Nanotubes (CNT) or activated carbon.
The precursor of the active particles of the catalyst is H2PtCl6·6H2O、PdCl2、Na2PdCl4、K2PdCl6、NiCl2、CoCl2、CuCl2、ZnCl2Any one of the above.
The reducing agent is NaBH4Hydrazine hydrate, LiBH4And formaldehyde.
The solvent is any one of deionized water and ethylene glycol. The mass parts of the solvent refer to the total amount of the solvent used in the preparation process.
Further, the mass ratio of the MXene to the carbon material in the mixed solution is 0.1-10: 0.1 to 10.
Further, in the step 3, the reaction temperature of the hydrothermal reaction is 80-160 ℃, and the reaction time is 1-10 hours.
Further, the mass ratio of the reducing agent to the catalyst active particle precursor is 1-20: 1.
The invention has the beneficial effects that:
the invention prepares a new material with a three-dimensional structure by compounding MXene and a carbon material under high-temperature hydrothermal conditions, and the new material is used as a carrier of a catalyst for an electrolytic water hydrogen evolution reaction. The carrier has interconnected pores and is a porous three-dimensional structure. Compared with the traditional Pt/C catalyst, the hydrogen evolution catalyst prepared by utilizing the novel carrier has better electrocatalytic performance and electrochemical stability.
Drawings
FIG. 1 is Ti3C2Tx-a micro-topography of the GO three-dimensional composite support.
FIG. 2 is a graph in which Pt particles are supported on Ti3C2Tx-catalytic hydrogen evolution polarization curve of catalyst obtained on GO three-dimensional composite carrier in 1M KOH solution environment.
FIG. 3 is a graph in which Pt particles are supported on Ti3C2TxAnd (3) testing the 25000s constant current stability of the catalyst obtained on the GO three-dimensional composite carrier in a 1M KOH solution environment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and 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.
Example 1:
the three-dimensional MXene-based carrier hydrogen evolution catalyst in the embodiment comprises the following raw materials: MXene40mg, GO40mg, catalyst active particle precursor 80mg, reducing agent 240mg and solvent 120 mg.
Wherein MXene is Ti3C2TxThe carbon material is GO, and the precursor of the catalyst active particles is H2PtCl6·6H2O, the reducing agent is NaBH4And the solvent is deionized water.
The preparation method of the hydrogen evolution catalyst of the three-dimensional MXene-based carrier in the embodiment comprises the following operation steps:
(1) 40mg of Ti were weighed3C2TxUltrasonically dispersing in 20mg of deionized water for 30 minutes;
(2) weighing 40mg of GO and ultrasonically dispersing in 20mg of deionized water for 30 minutes;
(3) mixing Ti3C2TxMixing the dispersion liquid with the GO dispersion liquid, carrying out ultrasonic treatment on the obtained mixed dispersion liquid in an ultrasonic machine for 1 hour, transferring the mixed dispersion liquid into a hydrothermal reaction kettle, introducing nitrogen for 0.5 hour, and carrying out hydrothermal reaction in an oven at 100 ℃ for 3 hours;
(4) freezing and drying the reactant after the hydrothermal reaction for 12 hours at the temperature of minus 60 ℃ to obtain the three-dimensional Ti3C2TxA base support;
(5) weighing 80mg of three-dimensional Ti3C2TxDispersing the base carrier in 80ml deionized water, adding 80mgH after ultrasonic homogenizing2PtCl6·6H2O；
(6) Adding 240mgNaBH4After bubbles completely disappear, centrifugally washing for 6 times by using deionized water, carrying out suction filtration on a washed sample, drying a filter cake obtained after suction filtration in a vacuum drying oven at 60 ℃ for 12 hours to obtain the three-dimensional Ti3C2TxPt/Ti based support3C2Tx-GO hydrogen evolution catalyst.
Subsequently, 450. mu.L of deionized water, 500. mu.L of isopropyl alcohol, and 50. mu.L of a Nafion membrane mixed solution were added to a 3ml centrifuge tube, and 5.0mg of a catalyst powder was weighed, added to the centrifuge tube containing the above solution, and subjected to ultrasonic treatmentAnd carrying out in-machine ultrasound to obtain the uniformly dispersed electrocatalyst paste. Ti3C2TxAfter hydrothermal reaction with GO, a porous three-dimensional structure is formed, and the two components are overlapped or coalesced with each other to form physical crosslinking sites of the skeleton. Three-dimensional Pt/Ti3C2TxGO catalyst at 10mA cm-2The overpotential of 58mV is shown, which is much lower than that of commercial Pt/C (86 mV). And the three-dimensional catalyst is at 10mA cm-2After the reactor is operated for 25000s under the action of constant current, the overpotential drop is only 21mV, and good stability is shown.
Example 2:
the three-dimensional MXene-based carrier hydrogen evolution catalyst in the embodiment comprises the following raw materials: MXene40mg, GO40mg, catalyst active particle precursor 80mg, reducing agent 240mg and solvent 120 mg.
Wherein MXene is Ti3C2TxThe carbon material is GO, and the precursor of the catalyst active particles is H2PtCl6·6H2O, the reducing agent is NaBH4And the solvent is deionized water.
The preparation method of the hydrogen evolution catalyst of the three-dimensional MXene-based carrier in the embodiment comprises the following operation steps:
(1) 40mg of Ti were weighed3C2TxUltrasonically dispersing in 20mg of deionized water for 30 minutes;
(2) weighing 40mg of GO and ultrasonically dispersing in 20mg of deionized water for 30 minutes;
(3) mixing Ti3C2TxMixing the dispersion liquid with the GO dispersion liquid, carrying out ultrasonic treatment on the obtained mixed dispersion liquid in an ultrasonic machine for 1 hour, transferring the mixed dispersion liquid into a hydrothermal reaction kettle, introducing nitrogen for 0.5 hour, and carrying out hydrothermal reaction in an oven at 80 ℃ for 4 hours;
(4) freezing and drying the reactant after the hydrothermal reaction for 12 hours at the temperature of minus 60 ℃ to obtain the three-dimensional Ti3C2TxA base support;
(5) weighing 80mg of three-dimensional Ti3C2TxDispersing the base carrier in 80ml deionized water, adding 80mgH after ultrasonic homogenizing2PtCl6·6H2O；
(6) 240mg of NaBH was added4After bubbles completely disappear, centrifugally washing for 6 times by using deionized water, carrying out suction filtration on a washed sample, drying a filter cake obtained after suction filtration in a vacuum drying oven at 60 ℃ for 12 hours to obtain the three-dimensional Ti3C2TxPt/Ti based support3C2Tx-GO hydrogen evolution catalyst.
Subsequently, 450. mu.L of deionized water, 500. mu.L of isopropanol, and 50. mu.L of a Nafion membrane mixed solution were added to a 3ml centrifuge tube, 5.0mg of catalyst powder was weighed, added to the centrifuge tube containing the above solution, and subjected to ultrasonication in an ultrasonicator to obtain a uniformly dispersed electrocatalyst slurry. Ti3C2TxAfter hydrothermal reaction with GO, a porous three-dimensional structure is formed, and the two components are overlapped or coalesced with each other to form physical crosslinking sites of the skeleton. Three-dimensional Pt/Ti3C2TxGO catalyst at 10mA cm-2The overpotential of 89mV is shown, and good electrocatalytic performance is shown.
Example 3:
the three-dimensional MXene-based carrier hydrogen evolution catalyst in the embodiment comprises the following raw materials: MXene40mg, GO40mg, catalyst active particle precursor 80mg, reducing agent 240mg and solvent 120 mg.
Wherein MXene is Ti3C2TxThe carbon material is GO, and the precursor of the catalyst active particles is H2PtCl6·6H2O, the reducing agent is NaBH4And the solvent is deionized water.
The preparation method of the hydrogen evolution catalyst of the three-dimensional MXene-based carrier in the embodiment comprises the following operation steps:
(1) 40mg of Ti were weighed3C2TxUltrasonically dispersing in 20mg of deionized water for 30 minutes;
(2) weighing 40mg of GO and ultrasonically dispersing in 20mg of deionized water for 30 minutes;
(3) mixing Ti3C2TxMixing the dispersion with GO dispersion to obtainCarrying out ultrasonic treatment on the mixed dispersion liquid in an ultrasonic machine for 1 hour, then transferring the mixed dispersion liquid into a hydrothermal reaction kettle, introducing nitrogen for 0.5 hour, and then carrying out hydrothermal reaction in an oven at 100 ℃ for 4 hours;
(4) freezing and drying the reactant after the hydrothermal reaction for 12 hours at the temperature of minus 60 ℃ to obtain the three-dimensional Ti3C2TxA base support;
(5) weighing 80mg of three-dimensional Ti3C2TxDispersing the base carrier in 80ml deionized water, adding 80mgH after ultrasonic homogenizing2PtCl6·6H2O；
(6) 240mg of NaBH was added4After bubbles completely disappear, centrifugally washing for 6 times by using deionized water, carrying out suction filtration on a washed sample, drying a filter cake obtained after suction filtration in a vacuum drying oven at 60 ℃ for 12 hours to obtain the three-dimensional Ti3C2TxPt/Ti based support3C2Tx-GO hydrogen evolution catalyst.
Subsequently, 450. mu.L of deionized water, 500. mu.L of isopropanol, and 50. mu.L of a Nafion membrane mixed solution were added to a 3ml centrifuge tube, 5.0mg of catalyst powder was weighed, added to the centrifuge tube containing the above solution, and subjected to ultrasonication in an ultrasonicator to obtain a uniformly dispersed electrocatalyst slurry. Ti3C2TxAfter hydrothermal reaction with GO, a porous three-dimensional structure is formed, and the two components are overlapped or coalesced with each other to form physical crosslinking sites of the skeleton. Three-dimensional Pt/Ti3C2TxGO catalyst at 10mA cm-2The overpotential of 74mV is shown, and good electrocatalytic performance is shown.
Claims (10)
1. A preparation method of a three-dimensional MXene-based supported hydrogen evolution catalyst is characterized by comprising the following steps:
step 1: adding MXene into a solvent, and uniformly dispersing by ultrasonic to obtain MXene dispersion liquid;
step 2: adding a carbon material into a solvent, and uniformly dispersing by using ultrasonic waves to obtain a carbon material dispersion liquid;
and step 3: mixing the MXene dispersion liquid obtained in the step 1 and the carbon material dispersion liquid obtained in the step 2, uniformly dispersing by ultrasonic waves, transferring the mixture into a hydrothermal reaction kettle, introducing nitrogen for 0.5-5 hours, then carrying out hydrothermal reaction, cooling and washing for a plurality of times after the reaction is finished, and carrying out freeze drying for 12 hours to obtain an MXene-carbon material three-dimensional composite carrier;
and 4, step 4: dispersing the MXene-carbon material three-dimensional composite carrier obtained in the step (3) into a solvent, and performing ultrasonic dispersion for 0.1-20 hours;
and 5: calculating the amount of a precursor of the required catalyst active particles according to the proportion that the mass of the catalyst active particles is 1-60% of the total mass of the catalyst, and adding the precursor of the required catalyst active particles into the dispersion liquid obtained in the step (4) after the precursor of the catalyst active particles is uniformly dispersed in a solvent by ultrasonic;
step 6: and (3) dropwise adding a reducing agent solution into the mixed dispersion liquid obtained in the step (5), washing with deionized water after dropwise adding is finished, and then placing in a vacuum drying oven for vacuum drying for more than 0.5 hour to obtain the three-dimensional MXene-based carrier hydrogen evolution catalyst.
2. The preparation method of claim 1, wherein the raw materials comprise the following components in parts by mass:
3. the production method according to claim 1 or 2, characterized in that:
the MXene is Ti3C2、Ti2C、Nb3C2、Nb2C、TiNbC、Cr2TiC、Ti3CN、Ti4N3、Ta4C3、V2C、Mo2C or MoTiC2。
4. The production method according to claim 1 or 2, characterized in that:
the carbon material is graphene oxide, graphene, carbon nanotubes or activated carbon.
5. The production method according to claim 1 or 2, characterized in that:
the precursor of the active particles of the catalyst is H2PtCl6·6H2O、PdCl2、Na2PdCl4、K2PdCl6、NiCl2、CoCl2、CuCl2、ZnCl2Any one of the above.
6. The production method according to claim 1 or 2, characterized in that:
the reducing agent is NaBH4Hydrazine hydrate, LiBH4And formaldehyde.
7. The production method according to claim 1 or 2, characterized in that:
the solvent is any one of deionized water and ethylene glycol.
8. The production method according to claim 1 or 2, characterized in that:
the mass ratio of the MXene to the carbon material in the mixed solution is 0.1-10: 0.1 to 10.
9. The method of claim 1, wherein:
in the step 3, the reaction temperature of the hydrothermal reaction is 80-160 ℃, and the reaction time is 1-10 hours.
10. The production method according to claim 1 or 2, characterized in that:
the mass ratio of the reducing agent to the catalyst active particle precursor is 1-20: 1.
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| CN112310417A (en) * | 2020-11-05 | 2021-02-02 | 中国科学院合肥物质科学研究院 | Preparation method, product and application of three-dimensional platinum/Mxene-reduced graphene oxide catalyst |
| CN112619679A (en) * | 2020-12-15 | 2021-04-09 | 河南理工大学 | Thorn-ball-shaped Mo2C/CdS photocatalyst, preparation method thereof and photocatalytic method |
| CN112795937A (en) * | 2020-12-24 | 2021-05-14 | 郑州大学 | Composite material for photoelectrochemical water decomposition, preparation method and application thereof, and electrode |
| CN113422077A (en) * | 2021-06-22 | 2021-09-21 | 合肥工业大学 | CO-resistant MXene-based catalyst for proton exchange membrane fuel cell and preparation method thereof |
| CN113629265A (en) * | 2021-08-09 | 2021-11-09 | 合肥工业大学 | Preparation method of MXene-based anode antipole catalyst for proton exchange membrane fuel cell |
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| CN113881959A (en) * | 2021-07-23 | 2022-01-04 | 西京学院 | Electrocatalyst D-Mo2TiC2/Ni nanosheet and preparation method and application thereof |
| CN114457371A (en) * | 2021-11-05 | 2022-05-10 | 天津师范大学 | MXene loaded Ni nano-particle composite hydrogen evolution electrocatalyst and preparation method and application thereof |
| CN114899432A (en) * | 2022-05-11 | 2022-08-12 | 黑龙江哈船碳材料科技有限公司 | Composite electrode material for direct sodium borohydride fuel cell and preparation method thereof |
| CN116145173A (en) * | 2023-01-10 | 2023-05-23 | 华南理工大学 | Mxene supported Pd-Ag bimetallic composite nanoparticle hydrogen evolution electrocatalyst and preparation method and application thereof |
| CN117504750A (en) * | 2024-01-04 | 2024-02-06 | 中国科学院合肥物质科学研究院 | Low Pt-loaded MXene-carbon nanotube aerogel film, and preparation method and application thereof |
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Cited By (15)
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| CN112310417A (en) * | 2020-11-05 | 2021-02-02 | 中国科学院合肥物质科学研究院 | Preparation method, product and application of three-dimensional platinum/Mxene-reduced graphene oxide catalyst |
| CN112619679A (en) * | 2020-12-15 | 2021-04-09 | 河南理工大学 | Thorn-ball-shaped Mo2C/CdS photocatalyst, preparation method thereof and photocatalytic method |
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| CN113422077A (en) * | 2021-06-22 | 2021-09-21 | 合肥工业大学 | CO-resistant MXene-based catalyst for proton exchange membrane fuel cell and preparation method thereof |
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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 |
| CN114457371A (en) * | 2021-11-05 | 2022-05-10 | 天津师范大学 | MXene loaded Ni nano-particle composite hydrogen evolution electrocatalyst and preparation method and application thereof |
| CN114899432A (en) * | 2022-05-11 | 2022-08-12 | 黑龙江哈船碳材料科技有限公司 | Composite electrode material for direct sodium borohydride fuel cell and preparation method thereof |
| CN114899432B (en) * | 2022-05-11 | 2023-08-22 | 黑龙江哈船碳材料科技有限公司 | Composite electrode material for direct sodium borohydride fuel cell and preparation method thereof |
| CN116145173A (en) * | 2023-01-10 | 2023-05-23 | 华南理工大学 | Mxene supported Pd-Ag bimetallic composite nanoparticle hydrogen evolution electrocatalyst and preparation method and application thereof |
| WO2024148694A1 (en) * | 2023-01-10 | 2024-07-18 | 华南理工大学 | Mxene-loaded pd-ag bimetallic composite nanoparticle hydrogen evolution electrocatalyst, preparation method therefor, and use thereof |
| CN117504750A (en) * | 2024-01-04 | 2024-02-06 | 中国科学院合肥物质科学研究院 | Low Pt-loaded MXene-carbon nanotube aerogel film, and preparation method and application thereof |
| CN117504750B (en) * | 2024-01-04 | 2024-04-05 | 中国科学院合肥物质科学研究院 | Low Pt-loaded MXene-carbon nanotube aerogel film, and preparation method and application thereof |
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