Ligand-protected Pt6 sub-nanocluster and preparation method thereof, and catalyst and preparation method and application thereof

A sub-nano, catalyst technology, applied in the field of electrochemistry, can solve problems such as reducing catalyst activity and affecting catalyst stability

Active Publication Date: 2021-04-02
CHINA UNIV OF PETROLEUM (EAST CHINA) +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Theoretically, as the particle size of Pt decreases, the electrochemical surface area can be increased to increase the H 2 Active sites for adsorption and dissociation can improve catalytic activity, but in the actual production and application process, too small particle size (such as single-atom Pt) is prone to agglomeration, which will affect the stability of the catalyst and reduce the activity of the catalyst

Method used

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  • Ligand-protected Pt6 sub-nanocluster and preparation method thereof, and catalyst and preparation method and application thereof
  • Ligand-protected Pt6 sub-nanocluster and preparation method thereof, and catalyst and preparation method and application thereof
  • Ligand-protected Pt6 sub-nanocluster and preparation method thereof, and catalyst and preparation method and application thereof

Examples

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preparation example Construction

[0030] The invention provides a ligand-protected Pt 6The preparation method of the sub-nanometer cluster comprises the following steps: a ligand solution, chloroplatinic acid, a reducing agent and an alcohol are mixed for a reduction reaction to obtain a reduction product solution, and the reduction product is a ligand-protected Pt 6 sub-nanometer clusters; the ligand is a phosphine compound, the solvent of the ligand solution is a weak polar solvent, the polarity value of the weak polar solvent is 1-5, and the reducing agent is an amine complex things.

[0031] In the present invention, the phosphine compound is preferably one or more of triphenylphosphine, tributylphosphine, diphenylphosphine and dimethylphenylphosphine, more preferably triphenylphosphine; The amine complexes are preferably one or more of borane tert-butylamine complexes, boron trifluoride-monoethylamine complexes, borane-trimethylamine complexes and triethylborane amine complexes several, more preferably ...

Embodiment 1

[0051] (1) Thoroughly mix 200 μL of 20 mmol / L triphenylphosphine in toluene, 200 μL of 20 mmol / L chloroplatinic acid aqueous solution and 5 mL of ethanol.

[0052] (2) Vigorously stir the mixed solution obtained in step (1) and add 30 μL of 50 mmol / L ethanol solution of borane tert-butylamine complex, and react for 30 minutes until dark brown ligand-protected Pt 6 Subnano cluster solution.

[0053] figure 1 Protection of Pt for the resulting ligand 6 UV absorption spectrum (a) and ESI-MS spectrum (b) of subnano clusters; in figure 1 In the UV absorption spectrum in , Pt appeared at 385 and 355nm 6 The characteristic absorption peak of the sub-nanometer cluster, the peak at m / z=2400Da in the ESI-MS spectrum, the combined UV absorption spectrum and ESI-MS spectrum, and the calculation based on the molecular weight of the intermediate product, this example successfully synthesized a stable Existing Pt 6 subnanometer clusters.

Embodiment 2

[0055] (1) Get the ligand protection Pt prepared in 5mL embodiment 1 6 The subnano-cluster solution was mixed with 10, 20, and 40 mg of carbon black, respectively, and then 45 mL of ethanol was added, and mixed and stirred for 6 hours to obtain carbon-supported Pt with a loading of 8%, 4%, and 2%, respectively. 6 Subnano cluster solution.

[0056] (2) The solution obtained in step (1) is separated by suction filtration, and then vacuum-dried overnight at room temperature to obtain carbon-supported Pt 6 Subnanometer Cluster Catalysts.

[0057] figure 2 Pt on carbon with a loading of 2% 6 Electron microscope images of sub-nano cluster catalysts, where (a) is spherical aberration electron microscope images, (b) is TEM images, (c) and (d) are HAADF-STEM images of different parts; according to figure 2 It can be seen that Pt 6 Subnanometer clusters are evenly dispersed on the surface of carbon black.

[0058] Hydrogen electrocatalytic oxidation performance test: Take 2.5 mg...

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Abstract

The invention relates to the technical field of electrochemistry and provides a ligand-protected Pt6 sub-nanocluster and a preparation method thereof, and a catalyst and a preparation method and application thereof. According to the method, a phosphine compound is used as a ligand, a weakly polar solvent with the polarity value of 1-5 is used as a solvent of the ligand, an amine complex is used asa reducing agent, the number of Pt atoms in the cluster is accurately controlled under the cooperation of the phosphine compound, the weakly polar solvent and the amine complex, and synthesis of thePt6 sub-nanocluster is achieved. The carbon-loaded Pt6 sub-nanocluster catalyst provided by the invention comprises a carbon carrier and a ligand-protected Pt6 sub-nanocluster loaded on the carbon carrier, and under the protection of the ligand, the Pt6 sub-nanocluster can stably exist and is not easy to agglomerate in the catalytic process; the carbon-supported Pt6 sub-nanocluster catalyst provided by the invention has ultrahigh quality activity and good stability for hydrogen oxidation reaction, the quality activity and durability of the catalyst are higher than those of a commercial Pt/C catalyst, and the catalyst has a wide application prospect.

Description

technical field [0001] The invention relates to the field of electrochemical technology, in particular to a ligand-protected Pt 6 Subnanometer cluster and its preparation method, a catalyst, its preparation method and application. Background technique [0002] Hydrogen energy is regarded as the clean energy with the most development potential in the 21st century, and the efficient utilization of hydrogen energy has become the trend of the development of a new clean society in the future. Among them, the hydrogen fuel cell is an efficient power generation device that relies on hydrogen to obtain green electricity. [0003] Commercial proton exchange membrane fuel cells (PEMFCs) have been able to operate at low loads of noble metal Pt (≤0.05mg Pt cm -2 ) to achieve higher catalytic activity for the hydrogen oxidation reaction (HOR), but the oxygen reduction reaction (ORR) that occurs on the cathode side requires a higher Pt loading (0.2–0.4 mg Pt cm -2 ), which limits t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/88H01M4/92H01M8/22
CPCH01M4/8878H01M4/926H01M8/22Y02E60/50
Inventor 邢伟袁勋王小宁刘勇吴明铂
Owner CHINA UNIV OF PETROLEUM (EAST CHINA)
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