CN112295581A - Electrocatalyst material and application thereof - Google Patents

Electrocatalyst material and application thereof Download PDF

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Publication number
CN112295581A
CN112295581A CN201910669273.8A CN201910669273A CN112295581A CN 112295581 A CN112295581 A CN 112295581A CN 201910669273 A CN201910669273 A CN 201910669273A CN 112295581 A CN112295581 A CN 112295581A
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electrocatalyst material
material according
nitrogen
cubic phase
electrocatalyst
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CN112295581B (en
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杨明辉
元瑶
萨米拉阿迪米
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24Nitrogen compounds
    • B01J35/23
    • B01J35/33
    • B01J35/50
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00Hybrid cells; Manufacture thereof
    • H01M12/04Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8878Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882Heat treatment, e.g. drying, baking
    • H01M4/8885Sintering or firing
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9091Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides an electrocatalyst material whose catalytically active component is Ni2Mo3N、Ni2Mo3One or more of N composite material, the Ni2Mo3N is cubic phase Ni2Mo3N; ni of the invention2Mo3The N nano-particle catalyst achieves the aim of catalytic activity and stabilityThe higher level; the nitrogen source for preparing the nitride is derived from urea, and ammonia gas with strong corrosivity is not used as a nitriding atmosphere, so that the method is green and environment-friendly; the sol precursor is directly put at high temperature for nitridation reaction, so that the crystallization and solidification process is avoided, and the method is favorable for large-scale industrial production.

Description

Electrocatalyst material and application thereof
Technical Field
The invention relates to an electrocatalyst material and applications thereof.
Background
Energy is an important material basis for economic growth and social development. Every epoch-like transition of energy technology is accompanied with the leap of productivity, and the great development and progress of the whole human society are promoted. With the increase of population and the rapid development of economy, the global demand for energy is increasing. Energy crisis and environmental issues have become the focus of important and scientific research in politics, economy, military, diplomatic and other areas of today's international society. The green renewable energy technology is explored and developed, and the dependence on fossil fuel can be fundamentally removed. Therefore, more and more scientific researchers are beginning to search for and develop sustainable energy devices, such as fuel cells, solar cells, metal-air batteries, lithium ion batteries, super capacitors, and the like, without losing their power. The hydrogen energy is used as green energy, has the advantages of wide source, high specific energy, recycling and the like, is a creditable clean energy star, and the hydrogen production by water electrolysis becomes the main hydrogen energy mode in the future. When the water is electrolyzed to produce hydrogen, the anode can generate oxygen evolution reaction along with hydrogen evolution of the cathode, and the over-high anode overpotential is the primary factor and the core problem of the energy consumption of the water electrolysis for producing the hydrogen. However, Ir, Ru and their oxide anode catalysts with high catalytic activity are expensive, scarce in resources and poor in stability. This has led to the active search for the development of a noble metal-substituted catalyst which is excellent in performance and low in cost. The non-noble transition metal nitride often has unsaturated d electron orbitals, excellent corrosion resistance and high electrical conductivity, and is expected to replace noble metals in the application and development of electrochemical catalysis through reasonable design regulation and control of the structure/composition and the like.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: an electrocatalyst material and its uses are provided. The applicant of the present invention has found that cubic phase Ni is a problem in the prior art2Mo3The N material has excellent oxygen evolution electrocatalytic performance and can replace a noble metal catalyst (IrO) in electrolytic water2/CB) as anodeThe catalyst has the characteristics of low cost, high activity and high stability.
The technical solution of the invention is as follows: an electrocatalyst material with Ni as its catalytically active component2Mo3N、Ni2Mo3One or more of N composite materials.
Preferably, the Ni is2Mo3N is cubic phase Ni2Mo3N。
The cubic phase Ni2Mo3The preparation method of N comprises the following steps:
1) dissolving nickel chloride and molybdenum chloride in an ethanol solution to obtain a clear solution;
2) adding a nitrogen source into the clear solution obtained in the step 1), and standing to obtain a colloidal precursor;
3) calcining the precursor obtained in the step 2) in inert gas at the temperature of more than 500 ℃ to obtain cubic phase Ni2Mo3And N nano-particles.
Preferably, the ethanol solution is absolute ethanol, and the nitrogen source is a nitrogen-containing organic substance.
The nitrogen-containing organic matter is urea, and the inert gas is nitrogen or argon.
The application of the electrocatalyst material comprises all electrocatalytic applications including water electrolysis and metal-air batteries containing oxygen evolution.
The invention discloses a ternary transition metal nitride Ni2Mo3A preparation method of N nano-particles and application of electrocatalytic oxygen evolution. The method uses two metal chlorides as metal sources and urea as a nitrogen source, and the pure-phase Ni can be obtained by heating in an inert atmosphere2Mo3An N-nitride catalyst. The precursor used for high-temperature nitridation is sol-like and can be obtained by dissolving metal chloride and urea in absolute ethyl alcohol and standing for a certain time. Ni obtained after nitriding2Mo3The N particles have uniform nano-morphology, can be used as an electrocatalyst for catalyzing the oxygen evolution reaction, and have higher catalytic activity and stability. The synthesis method has controllable synthesis components and is nanoElectrically oxygen evolving catalytic materials which are structurally controllable and have a high specific surface area and good durability offer great possibilities. The method is simple and easy to implement, low in cost, green and environment-friendly, is suitable for large-scale production, and shows superior commercial IrO in electrochemical oxygen evolution reaction2The excellent activity and stability of the/CB catalyst have good industrial application prospect.
The invention has the beneficial effects that: compared with the prior art, the method of the invention has obvious differences:
1) ni obtained by the method of the invention2Mo3The N nano-particle catalyst reaches a higher level in both catalytic activity and stability;
2) the nitrogen source for preparing the nitride is derived from urea, and ammonia gas with strong corrosivity is not used as a nitriding atmosphere, so that the method is green and environment-friendly;
3) the invention directly puts the sol precursor at high temperature for nitridation reaction, thereby avoiding the crystallization and solidification process and being beneficial to large-scale industrial production;
4) nitride oxide precursor NiMoO by traditional method4The preparation process can directly adjust the initial charge ratio of the nickel element and the molybdenum element, so that the charge ratio is equal to the crystal structure element ratio, and the additional purification process is avoided;
5) preparation of Ni2Mo3When N nano-particle catalyst is used, a small amount of other metal salts, such as other metal chlorides, are directly mixed into the precursor to obtain doped Ni2Mo3An N nanoparticle catalyst;
6) the raw materials used in the method are all common industrial products which are easy to obtain.
Drawings
FIG. 1 shows Ni prepared in examples of the present invention2Mo3X-ray diffraction pattern of N nanoparticle catalyst.
FIG. 2 shows Ni prepared in an example of the present invention2Mo3An X-ray photoelectron spectrum of the N nanoparticle catalyst Ni 2 p.
FIG. 3 shows Ni prepared in an example of the present invention2Mo3An X-ray photoelectron spectrum of the N nanoparticle catalyst Mo 3 d.
FIG. 4 shows Ni prepared in examples of the present invention2Mo3Scanning electron microscopy of N nanoparticle catalyst.
FIG. 5 shows Ni prepared in an example of the present invention2Mo3N nanoparticle catalyst and commercial IrO2Rotating disk electrode polarization plot (disk rotation speed 1600 rpm) versus Tafel plot for the/CB catalyst. In the figure, a and Ni2Mo3N;b、IrO2/CB。
FIG. 6 shows Ni prepared in examples of the present invention2Mo3Stability test results of N nanoparticle catalysts. In the figure, a and Ni2Mo3N;b、IrO2/CB。
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Examples
Preparing an electrocatalyst:
a. dissolving 3 mmol of anhydrous molybdenum chloride and 2 mmol of nickel chloride hexahydrate in 2 mL of ethanol solution to obtain clear and transparent solution;
b. adding 1 g of urea into the solution obtained in the step a, and standing for more than 12 hours at room temperature to obtain a sol precursor;
c. and c, placing the precursor obtained in the step b in a sealed tube furnace, calcining for 3 hours at the temperature of more than 800 ℃ in the argon atmosphere, and raising the temperature at the speed of 2 ℃/min. Naturally cooling to room temperature to obtain Ni2Mo3N nanoparticle catalysts. The X-ray diffraction result of the obtained product is shown in figure 1, the X-ray photoelectron spectroscopy is shown in figures 2 and 3, and the scanning electron microscopy is shown in figure 4;
electrochemical performance test
Weighing 5 mg of catalyst powder obtained by the method, dispersing the catalyst powder in 1 mL of isopropanol aqueous solution containing 0.05% of naphthol solution (the volume ratio of water to isopropanol is 1: 4), uniformly performing ultrasonic treatment, dripping 10 uL of catalyst powder on a pyrolytic graphite electrode (phi =5 mm) of a rotary disc device, completely volatilizing the dispersion liquid at room temperature, testing the performance of electrocatalytic oxygen evolution reaction by using the rotary disc electrode device, using a silver/silver chloride electrode as a reference electrode, using a platinum wire as a counter electrode, and using 0.1 mol/L of potassium hydroxide aqueous solution as electrolyte. Specifically, the polarization curve of the rotating disk electrode and the tafel plot are shown in fig. 5, and the stability test is shown in fig. 6.
Prepared Ni2Mo3The N nano-particle catalyst has higher catalytic activity, and the catalyst is 10 mA cm-2The overpotential under the current density is 290 mV, and the Tafel slope is 68 mV dec-1And has excellent stability.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.

Claims (6)

1. An electrocatalyst material, characterized by: the catalytic active component is Ni2Mo3N、Ni2Mo3One or more of N composite materials.
2. An electrocatalyst material according to claim 1, wherein: the Ni2Mo3N is cubic phase Ni2Mo3N。
3. An electrocatalyst material according to claim 2, wherein: the cubic phase Ni2Mo3The preparation method of N comprises the following steps:
1) dissolving nickel chloride and molybdenum chloride in an ethanol solution to obtain a clear solution;
2) adding a nitrogen source into the clear solution obtained in the step 1), and standing to obtain a colloidal precursor;
3) calcining the precursor obtained in the step 2) in inert gas at the temperature of more than 500 ℃ to obtain cubic phase Ni2Mo3And N nano-particles.
4. An electrocatalyst material according to claim 3, wherein: the ethanol solution is absolute ethanol, and the nitrogen source is a nitrogen-containing organic matter.
5. An electrocatalyst material according to claim 4, wherein: the nitrogen-containing organic matter is urea, and the inert gas is nitrogen or argon.
6. Use of an electrocatalyst material according to any one of claims 1 to 5 wherein: all electrocatalytic applications involving oxygen evolution, including electrolysis of water, metal-air batteries.
CN201910669273.8A 2019-07-24 2019-07-24 Electrocatalyst material and application thereof Active CN112295581B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115000425A (en) * 2022-06-20 2022-09-02 巢湖学院 Molybdenum nitride quantum dot/nitrogen-doped carbon composite material and preparation method thereof
CN115000425B (en) * 2022-06-20 2024-05-14 巢湖学院 Molybdenum nitride quantum dot/nitrogen-doped carbon composite material and preparation method thereof

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CN101091917A (en) * 2006-06-23 2007-12-26 中国石油天然气股份有限公司 Catalyst of deep additional treatment of hydrogenising base oil for lubricant, preparation method and application
CN101099933A (en) * 2006-07-04 2008-01-09 中国石油天然气股份有限公司 Diesel oil aromatic saturated hydrogenation catalyst and its application
CN101099934A (en) * 2006-07-04 2008-01-09 中国石油天然气股份有限公司 Aromatic saturated hydrogenation catalyst and its preparing process
CN101837294A (en) * 2010-03-03 2010-09-22 巴州东辰工贸有限公司 Preparation method for solid acid catalyst r-AI203
RU2535990C1 (en) * 2013-07-05 2014-12-20 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" METHOD OF OBTAINING CATALYST OF CARBONIC ACID METHANATION BASED ON BI-METAL NITRIDE Ni2Mo3N
CN107522174A (en) * 2017-08-09 2017-12-29 江苏理工学院 A kind of new method for preparing ternary molybdenum system nitride nano-material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101091917A (en) * 2006-06-23 2007-12-26 中国石油天然气股份有限公司 Catalyst of deep additional treatment of hydrogenising base oil for lubricant, preparation method and application
CN101099933A (en) * 2006-07-04 2008-01-09 中国石油天然气股份有限公司 Diesel oil aromatic saturated hydrogenation catalyst and its application
CN101099934A (en) * 2006-07-04 2008-01-09 中国石油天然气股份有限公司 Aromatic saturated hydrogenation catalyst and its preparing process
CN101837294A (en) * 2010-03-03 2010-09-22 巴州东辰工贸有限公司 Preparation method for solid acid catalyst r-AI203
RU2535990C1 (en) * 2013-07-05 2014-12-20 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" METHOD OF OBTAINING CATALYST OF CARBONIC ACID METHANATION BASED ON BI-METAL NITRIDE Ni2Mo3N
CN107522174A (en) * 2017-08-09 2017-12-29 江苏理工学院 A kind of new method for preparing ternary molybdenum system nitride nano-material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115000425A (en) * 2022-06-20 2022-09-02 巢湖学院 Molybdenum nitride quantum dot/nitrogen-doped carbon composite material and preparation method thereof
CN115000425B (en) * 2022-06-20 2024-05-14 巢湖学院 Molybdenum nitride quantum dot/nitrogen-doped carbon composite material and preparation method thereof

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