CN114182285B - Pt nano-particle with interphase distribution vacancy and preparation method thereof - Google Patents

Pt nano-particle with interphase distribution vacancy and preparation method thereof Download PDF

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CN114182285B
CN114182285B CN202111588578.XA CN202111588578A CN114182285B CN 114182285 B CN114182285 B CN 114182285B CN 202111588578 A CN202111588578 A CN 202111588578A CN 114182285 B CN114182285 B CN 114182285B
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carbon cloth
minutes
placing
ultrapure water
solution
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CN114182285A (en
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王宗鹏
张欢欢
林志萍
钟文武
申士杰
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Taizhou University
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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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
    • 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
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Abstract

The invention discloses a Pt nano particle with interphase distribution vacancy, which has a Pt atom Schottky defect, and the defect is distributed in an interval mode; the invention also discloses a method for preparing the Pt nano-particles with the interphase distribution vacancy.

Description

Pt nano-particle with interphase distribution vacancy and preparation method thereof
Technical Field
The invention relates to a nano material, in particular to Pt nano particles with interphase distribution vacancies and a preparation method thereof.
Technical Field
With the continuous exploitation of non-renewable energy sources such as coal, petroleum and the like, the remaining fossil energy sources cannot meet the increasingly prominent energy gap of the human society, and the search for new green and renewable energy sources has become a major scientific and technological problem facing all human beings. The combustion process of fossil fuel is accompanied by the emission of pollutants containing S, N and the like and various greenhouse gases, which causes serious environmental problems and accelerates the application of green energy.
The hydrogen has the advantages of high combustion heat value and no pollution of products, and is an ideal green and renewable energy source. At present, the main method for industrially preparing hydrogen is water gas decomposition, and a large amount of pollution byproducts exist, which is contrary to the aim of green synthesis. The electrocatalytic decomposition of water to produce hydrogen is an ideal method for obtaining hydrogen.
The electrocatalytic water decomposition process needs a certain overpotential to occur, and in order to save electric energy and improve the hydrogen yield, a hydrogen evolution catalyst needs to be applied. Some transition metal chalcogenide compounds show certain catalytic performance, but the catalytic activity is still low, and the requirement of preparing hydrogen in large quantity cannot be met. Pt is the best hydrogen evolution catalyst, however, pt element is less on earth and expensive. By designing the microstructure of the material, the catalytic capability of Pt is further improved, the requirement of Pt element is reduced, the cost for producing hydrogen is reduced, and the utilization of hydrogen energy is promoted.
Disclosure of Invention
The invention aims to disclose Pt nano particles with interphase distribution vacancies, which optimize the catalytic activity of Pt and reduce the demand of Pt element under the same condition.
The Pt nano particle with the interphase distribution vacancy is characterized in that the Pt nano particle is spherical and has the diameter of 5 nanometers; pt atom vacancies exist in the Pt nano particles, and the Pt atom vacancies are in a mutually spaced distribution state.
Another object of the present invention is to propose a method for preparing said Pt nanoparticles with interstitial distributed vacancies.
The invention provides a method for preparing Pt nano particles with interphase distribution vacancies, which is characterized by comprising the following steps: 2 mmol of H are taken 2 PtCl 6 20 ml of ultrapure water and 5 ml of alcohol are placed in a beaker, and the mixture is subjected to ultrasonic treatment for 20 mlThe method comprises the following steps of (1) taking minutes; cutting a piece of carbon cloth with the size of 1.5 multiplied by 1.5 square centimeters; placing the cut carbon cloth in concentrated nitric acid of 12 mol/L for ultrasonic cleaning for 15 minutes; placing the cut carbon cloth in ultrapure water for ultrasonic cleaning for 15 minutes; drying the cleaned carbon cloth in a vacuum drying oven for 30 minutes at the temperature of 40 ℃; placing the dried carbon cloth in a beaker filled with the solution, and soaking for 72 hours; quickly placing the soaked carbon cloth in a freeze drying box for drying for 24 hours at the temperature of minus 20 ℃; 30 ml of sulfuric acid with the concentration of 0.1 mol per liter, 15 ml of ethylene glycol and 1 mmol of potassium sulfate are taken and placed in a beaker to be subjected to ultrasonic treatment for 10 minutes; clamping the freeze-dried carbon cloth by using an electrode clamp, and immersing the carbon cloth into the solution; clamping the graphite rod by using the other electrode clamp, and immersing the graphite rod into the solution; heating the solution to 60 ℃ and keeping the temperature; the carbon cloth is used as a cathode, the graphite rod is used as an anode, square wave pulse current is applied between the cathode and the anode, the current density amplitude is 50 milliamperes per square centimeter, the pulse time is 20 milliseconds, the interval time is 200 milliseconds, and the pulse period is 2000; taking off the carbon cloth, and soaking in ultrapure water for 30 minutes; the carbon cloth was taken out of the ultrapure water and placed in a vacuum drying oven to dry for 30 minutes at a temperature of 40 ℃.
The Pt nano particle with the interphase distribution vacancy provided by the invention has a unique vacancy distribution form, is used for hydrogen evolution reaction under an alkaline condition, has an overpotential of 39 millivolts under an exchange current density of 10 milliamperes per square centimeter, and is obviously superior to commercial Pt/C powder.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings used in the examples will be briefly described below.
FIG. 1 is a transmission electron microscope photograph of a sample prepared by the method of example.
FIG. 2 is a scanning transmission electron microscope image of a sample prepared by the method of example.
FIG. 3 is an electrocatalytic hydrogen evolution overpotential diagram for a sample prepared by the method of the example.
Detailed Description
The following describes the implementation of the present invention in detail with reference to specific embodiments.
The specific steps of this example are as follows: 2 mmol of H are taken 2 PtCl 6 20 ml of ultrapure water and 5 ml of alcohol are placed in a beaker and subjected to ultrasonic treatment for 20 minutes; cutting a piece of carbon cloth with the size of 1.5 multiplied by 1.5 square centimeters; placing the sheared carbon cloth in concentrated nitric acid of 12 mol/L for ultrasonic cleaning for 15 minutes; placing the cut carbon cloth in ultrapure water for ultrasonic cleaning for 15 minutes; drying the cleaned carbon cloth in a vacuum drying oven for 30 minutes at 40 ℃; placing the dried carbon cloth in a beaker filled with the solution, and soaking for 72 hours; quickly placing the soaked carbon cloth in a freeze drying box for drying for 24 hours at the temperature of minus 20 ℃; 30 ml of sulfuric acid with the concentration of 0.1 mol per liter, 15 ml of ethylene glycol and 1 mmol of potassium sulfate are taken and placed in a beaker to be subjected to ultrasonic treatment for 10 minutes; clamping the freeze-dried carbon cloth by using an electrode clamp, and immersing the carbon cloth into the solution; clamping the graphite rod by using the other electrode clamp, and immersing the graphite rod into the solution; heating the solution to 60 ℃ and keeping the temperature; taking carbon cloth as a cathode and a graphite rod as an anode, applying square wave pulse current between the cathode and the anode, wherein the current density amplitude is 50 milliamperes per square centimeter, the pulse time is 20 milliseconds, the interval time is 200 milliseconds, and the pulse period is 2000; taking off the carbon cloth, and soaking in ultrapure water for 30 minutes; the carbon cloth was taken out of the ultrapure water and placed in a vacuum drying oven for drying at 40 degrees celsius for 30 minutes.
The invention is further illustrated by the following examples in conjunction with the accompanying drawings.
FIG. 1 is a transmission electron micrograph of a sample prepared according to the method of example, in which a pronounced spherical morphology with a diameter of 4 to 8 nm can be seen. The ICP test results show that the mass fraction of the Pt element is below 1%. Fig. 2 is a scanning transmission electron microscope photograph of a sample prepared in accordance with the method of example, and it can be seen that Pt atoms are conspicuous, the Pt atoms have a cubic lattice structure, and schottky defects, i.e., pt atom vacancies, exist in the lattice, and the Pt atom vacancies are present in a spaced-apart form. The special vacancy distribution changes the coordination structure of Pt atoms on the surface and optimizes the local electronic state, thereby optimizing the adsorption and desorption performance of active hydrogen and improving the catalytic activity. FIG. 3 is a plot of the overpotential for the electrocatalytic hydrogen evolution under alkaline conditions for samples prepared according to the example method, with an overpotential of 39 mV at an exchange current density of 10 mA/cm.
It should be noted that the above description is only a preferred embodiment of the present invention, and the present invention is not limited to the above examples. It is to be understood that other modifications and variations directly derivable or suggested to one skilled in the art without departing from the basic idea of the present invention are to be considered within the scope of protection of the present invention.

Claims (2)

1. A method for preparing Pt nanoparticles with interstitial distributed vacancies, comprising the steps of: 2 mmol of H are taken 2 PtCl 6 20 ml of ultrapure water and 5 ml of alcohol are placed in a beaker and subjected to ultrasonic treatment for 20 minutes; cutting a piece of carbon cloth with the size of 1.5 multiplied by 1.5 square centimeters; placing the cut carbon cloth in concentrated nitric acid of 12 mol/L for ultrasonic cleaning for 15 minutes; placing the cut carbon cloth in ultrapure water for ultrasonic cleaning for 15 minutes; drying the cleaned carbon cloth in a vacuum drying oven for 30 minutes at 40 ℃; placing the dried carbon cloth in a beaker filled with the solution, and soaking for 72 hours; quickly placing the soaked carbon cloth in a freeze drying box for drying for 24 hours at the temperature of minus 20 ℃; 30 ml of sulfuric acid with the concentration of 0.1 mol per liter, 15 ml of ethylene glycol and 1 mmol of potassium sulfate are taken and placed in a beaker to be subjected to ultrasonic treatment for 10 minutes; clamping the freeze-dried carbon cloth by using an electrode clamp, and immersing the carbon cloth into the solution; clamping the graphite rod by using the other electrode clamp, and immersing the graphite rod into the solution; heating the solution to 60 ℃ and keeping the temperature; the carbon cloth is used as a cathode, the graphite rod is used as an anode, square wave pulse current is applied between the cathode and the anode, the current density amplitude is 50 milliamperes per square centimeter, the pulse time is 20 milliseconds, the interval time is 200 milliseconds, and the pulse period is 2000; taking off the carbon cloth, and soaking in ultrapure water for 30 minutes; the carbon cloth was taken out of the ultrapure water and placed in a vacuum drying oven for drying at 40 degrees celsius for 30 minutes.
2. The Pt nano particle with the interphase distribution vacancy is characterized in that the Pt nano particle is spherical and has the diameter of 5 nanometers; pt atom vacancies exist in the Pt nano particles, and the Pt atom vacancies are in a mutually spaced distribution state; the Pt nanoparticles prepared by the method of claim 1.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200833877A (en) * 2007-02-09 2008-08-16 Nat Univ Tsing Hua Electrodeposition electrolyte with chloroplatic acid, ethylene glycol, and metal chloride
CN107552044A (en) * 2017-09-28 2018-01-09 中国科学院青岛生物能源与过程研究所 A kind of effectively elementization noble metal simultaneously lifts the preparation method of its electrocatalysis characteristic
CN109331820A (en) * 2018-10-29 2019-02-15 大连理工大学 A kind of method that pulse electrodeposition prepares Pt base catalyst under ultrasound condition
CN111326754A (en) * 2020-03-10 2020-06-23 中南林业科技大学 Preparation method of fusiform platinum nanoparticles
CN114959792A (en) * 2022-05-30 2022-08-30 北京化工大学 Preparation method of monatomic Pt catalyst and hydrogen evolution application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW200833877A (en) * 2007-02-09 2008-08-16 Nat Univ Tsing Hua Electrodeposition electrolyte with chloroplatic acid, ethylene glycol, and metal chloride
CN107552044A (en) * 2017-09-28 2018-01-09 中国科学院青岛生物能源与过程研究所 A kind of effectively elementization noble metal simultaneously lifts the preparation method of its electrocatalysis characteristic
CN109331820A (en) * 2018-10-29 2019-02-15 大连理工大学 A kind of method that pulse electrodeposition prepares Pt base catalyst under ultrasound condition
CN111326754A (en) * 2020-03-10 2020-06-23 中南林业科技大学 Preparation method of fusiform platinum nanoparticles
CN114959792A (en) * 2022-05-30 2022-08-30 北京化工大学 Preparation method of monatomic Pt catalyst and hydrogen evolution application thereof

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Title
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Effect of ethylene glycol on electrochemical and morphological features of platinum electrodeposits from chloroplatinic acid;Weldegebriel Yohannes等;《J Appl Electrochem》;20150321;第1-11页 *
Electrochemical Preparation of Platinum Nanocrystallites with Size Selectivity on Basal Plane Oriented Graphite Surfaces;J. V. Zoval等;《The Journal of Physical Chemistry. B》;19980212;第1166-1175页 *
Pt Schottky contacts to n-GaN formed by electrodeposition and physical vapor deposition;J. M. DeLucca等;《J. Appl. Phys》;20000930;第88卷(第5期);第2593-2600页 *
PtSe2/Pt Heterointerface with Reduced Coordination for Boosted Hydrogen Evolution Reaction;Wang, Zongpeng等;《Angewandte Chemie》;20210809;第133卷(第43期);第23576-23581页 *
Sub-Nanometer Pt Clusters on Defective NiFe LDH Nanosheets as Trifunctional Electrocatalysts for Water Splitting and Rechargeable Hybrid Sodium-Air Batteries;Xueqing Yu 等;《ACS applied materials & interfaces》;20210607;第13卷(第23期);第26891-26903页 *
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