CN110787820B - Heteroatom nitrogen surface modification MoS2Preparation and application of nano material - Google Patents

Heteroatom nitrogen surface modification MoS2Preparation and application of nano material Download PDF

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CN110787820B
CN110787820B CN201910837039.1A CN201910837039A CN110787820B CN 110787820 B CN110787820 B CN 110787820B CN 201910837039 A CN201910837039 A CN 201910837039A CN 110787820 B CN110787820 B CN 110787820B
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water
reaction kettle
mos
carbon cloth
temperature
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CN110787820A (en
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吴则星
宋敏
刘希恩
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Qingdao University of Science and Technology
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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
    • B01J35/33
    • 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
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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
    • H01M4/8825Methods for deposition of the catalytic active composition
    • 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
    • Y02E60/50Fuel cells

Abstract

Heteroatom nitrogen surface modified MoS2The preparation and application of nanometer material, and belongs to the field of electrocatalytic material synthesizing technology. The prepared catalyst has excellent electrocatalytic oxygen evolution performance. The preparation process comprises the following steps: (1) carbon cloth (3 x 3cm) is respectively treated with ultrasonic treatment in acetone, ethanol and water for 10 minutes; (2) mixing ammonium molybdate and thiourea in water in proportion, reacting the mixture with clean carbon cloth in a reaction kettle at a high temperature, cooling to room temperature, washing the carbon cloth with ethanol and water in sequence, and drying; (3) MoS obtained in the step (2)2Placing the nanosheets and ammonia water in a reaction kettle to react for a certain time at a high temperature to obtain heteroatom nitrogen modified MoS2And (3) nano materials. The catalyst obtained by the invention has excellent electro-catalytic performance, and the preparation process is simple, low in cost and suitable for large-scale production.

Description

Heteroatom nitrogen surface modification MoS2Preparation and application of nano material
Technical Field
The technical field of electrocatalytic material synthesis, in particular to heteroatom nitrogen surface modified MoS2Preparation and application of nanometer material.
Background
As an alternative to traditional fossil fuels, hydrogen energy has received much attention due to its high energy density, zero pollutant emissions, and abundant reserves. Electrolysis of water provides an ideal production method for renewable pure hydrogen without the formation of by-products. The electrolyzed water consists of two half-reactions, namely cathodic hydrogen evolution and anodic oxygen evolution. The anodic oxygen evolution reaction is a four-electron-proton coupling reaction, and higher energy (higher overpotential) is needed, so that the oxygen evolution overpotential is far higher than the theoretical decomposition voltage (1.23V) of water. In order to reduce overpotential and promote reaction kinetics during electrolysis of water, a highly efficient electrocatalyst is essential. Noble metal materials such as platinum, iridium, ruthenium, etc., which have been the most effective electrolytic water reaction catalysts so far, have high prices and limited reserves, which seriously affect their wide application. Therefore, high activity, inexpensive and abundant non-noble metal electrocatalysts are of paramount importance for the wide application of electrocatalytic water splitting. The present research shows that the transition metal sulfide has excellent electrocatalytic performance, wherein MoS of a layered structure2Is a high-efficiency nano material for hydrogen evolution reaction. However, for the other half-reaction oxygen evolution reaction of the water splitting reaction,MoS2There is no catalytic effect. Therefore, for MoS2The modification is carried out, and the reduction of the overpotential in the oxygen evolution process is important for the water decomposition reaction.
Disclosure of Invention
In order to solve the problems that a noble metal catalyst is expensive in price, small in reserve and difficult to widely apply, and a non-noble metal catalyst is high in overpotential and wastes energy, the invention provides heteroatom nitrogen surface modified MoS2The preparation and the application of the nano material solve the problem of the prior MoS2The catalyst preparation method is complex and has low oxygen evolution activity.
The method mainly comprises the following steps:
(1) mixing carbon cloth (3 x 3cm)2) Sequentially carrying out ultrasonic treatment on acetone, ethanol and water for 10 minutes for later use;
(2) mixing ammonium molybdate and thiourea in water according to a ratio, wherein the molar ratio of the ammonium molybdate to the thiourea is 1:5, and stirring until the ammonium molybdate and the thiourea are completely dissolved to obtain a uniform solution;
(3) transferring the uniformly stirred solution to a reaction kettle with a stainless steel substrate, putting the reaction kettle into carbon cloth subjected to ultrasonic treatment, and putting the reaction kettle in an air-blowing drying oven to keep the temperature of 180 ℃ for 12 hours; cooling to room temperature, taking out the carbon cloth, washing with ethanol and water in sequence, and drying to obtain MoS2A nano-platelet catalyst.
(4) The obtained MoS2Adding ammonia water with different volumes into a reaction kettle with a stainless steel substrate, and adding MoS2Above the ammonia, there is no contact with the ammonia. Putting the reaction kettle in a blast drying oven for high-temperature reaction, cooling to room temperature, taking out the carbon cloth, sequentially washing with ethanol and water, and drying to obtain the heteroatom nitrogen surface modified MoS2And (3) nano materials.
The molar ratio of the transition metal salt to the thiourea in the step (2) is 1: 5.
The volume of the ammonia water in the step (3) is 5mL, 10mL and 15 mL.
The high-temperature reaction temperature in the step (3) is 90 ℃, 150 ℃ and 180 ℃.
The high-temperature reaction time in the step (3) is 8 hours, 12 hours and 18 hours.
According to the method of the invention, a heteroatom nitrogen surface modified MoS is provided2The preparation method of the nano material applied to the electrocatalyst.
The electrocatalyst is used for catalyzing the oxygen evolution reaction of the fuel cell or the electrolytic cell.
In general, compared to the prior art, the heteroatom surface modified MoS prepared by the above technical solution of the inventive concept is prepared by a simple hydrothermal method2The nano material catalyst improves the oxygen evolution catalytic performance, has mild reaction conditions, easy control, simple reaction process and low raw material price, and is suitable for large-scale production.
Drawings
FIG. 1a is a Scanning Electron Microscope (SEM) schematic of example 1 of the invention, showing the MoS formed2Has a sheet-like structure.
FIG. 1b is a Scanning Electron Microscope (SEM) schematic diagram of example 2 of the invention, which shows that ammonia water treatment has a great influence on the morphology.
FIG. 2a is a schematic contact angle diagram of example 1 of the present invention, showing the MoS formed2The hydrophilicity is poor.
Fig. 2b is a schematic diagram of the contact angle of example 2 of the present invention, which shows that the material treated with ammonia has excellent hydrophilicity.
FIG. 3 is a graph showing the oxygen evolution performance of examples 1 and 2 of the present invention, and shows that the prepared material has excellent electrocatalytic oxygen evolution performance.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
The first step is as follows: mixing carbon cloth (3 x 3cm)2) Sequentially carrying out ultrasonic treatment on acetone, ethanol and water for 10 minutes for later use;
the second step is that: mixing ammonium molybdate and thiourea in water according to a ratio, wherein the molar ratio of the ammonium molybdate to the thiourea is 1:5, and stirring until the ammonium molybdate and the thiourea are completely dissolved to obtain a uniform solution, wherein the volume of the water is 35 mL;
the third step: stirring evenlyTransferring the solution to a reaction kettle with a stainless steel substrate, putting the reaction kettle into carbon cloth which is subjected to ultrasonic treatment, and putting the reaction kettle in a forced air drying oven to keep the temperature at 180 ℃ for 12 hours; cooling to room temperature, taking out the carbon cloth, washing with ethanol and water in sequence, and drying to obtain MoS2A nano-platelet catalyst.
Example 2
The first step is as follows: mixing carbon cloth (3 x 3cm)2) Sequentially carrying out ultrasonic treatment on acetone, ethanol and water for 10 minutes for later use;
the second step is that: mixing ammonium molybdate and thiourea in water according to a ratio, wherein the molar ratio of the ammonium molybdate to the thiourea is 1:5, and stirring until the ammonium molybdate and the thiourea are completely dissolved to obtain a uniform solution, wherein the volume of the water is 35 mL;
the third step: transferring the uniformly stirred solution to a reaction kettle with a stainless steel substrate, putting the reaction kettle into carbon cloth subjected to ultrasonic treatment, and putting the reaction kettle in an air-blowing drying oven to keep the temperature of 180 ℃ for 12 hours; cooling to room temperature, taking out the carbon cloth, washing with ethanol and water in sequence, and drying to obtain MoS2A nanosheet catalyst.
Fourthly, 10mL of ammonia water is put into a reaction kettle, and MoS is put into the reaction kettle2Placing the nanosheet above ammonia water without contacting with the ammonia water, placing the reaction kettle in a forced air drying oven at 150 ℃ for 12 hours, taking out the carbon cloth after the reaction kettle is cooled to room temperature, sequentially washing the carbon cloth with ethanol and water, and drying to obtain the heteroatom nitrogen surface modified MoS2A nanomaterial catalyst.
Example 3
The first step is as follows: mixing carbon cloth (3 x 3cm)2) Sequentially carrying out ultrasonic treatment on acetone, ethanol and water for 10 minutes for later use;
the second step is that: mixing ammonium molybdate and thiourea in water according to a ratio, wherein the molar ratio of the ammonium molybdate to the thiourea is 1:5, and stirring until the ammonium molybdate and the thiourea are completely dissolved to obtain a uniform solution, wherein the volume of the water is 35 mL;
the third step: transferring the uniformly stirred solution to a reaction kettle with a stainless steel substrate, putting the reaction kettle into carbon cloth subjected to ultrasonic treatment, and putting the reaction kettle in an air-blowing drying oven to keep the temperature of 180 ℃ for 12 hours; cooling to room temperature, taking out the carbon cloth, washing with ethanol and water in sequence, and drying to obtain MoS2Nanosheet catalysisAnd (3) preparing.
Fourthly, 5mL of ammonia water is put into a reaction kettle, and MoS is put into the reaction kettle2Placing the nanosheet above ammonia water without contacting with the ammonia water, placing the reaction kettle in a forced air drying oven at 150 ℃ for 8 hours, taking out the carbon cloth after the reaction kettle is cooled to room temperature, sequentially washing the carbon cloth with ethanol and water, and drying to obtain the heteroatom nitrogen surface modified MoS2A nanomaterial catalyst.
Example 4
The first step is as follows: mixing carbon cloth (3 x 3cm)2) Sequentially carrying out ultrasonic treatment on acetone, ethanol and water for 10 minutes for later use;
the second step is that: mixing ammonium molybdate and thiourea in water according to a ratio, wherein the molar ratio of the ammonium molybdate to the thiourea is 1:5, and stirring until the ammonium molybdate and the thiourea are completely dissolved to obtain a uniform solution, wherein the volume of the water is 35 mL;
the third step: transferring the uniformly stirred solution to a reaction kettle with a stainless steel substrate, putting the reaction kettle into carbon cloth subjected to ultrasonic treatment, and putting the reaction kettle in an air-blowing drying oven to keep the temperature of 180 ℃ for 12 hours; cooling to room temperature, taking out the carbon cloth, washing with ethanol and water in sequence, and drying to obtain MoS2A nanosheet catalyst.
Fourthly, 10mL of ammonia water is put into a reaction kettle, and MoS is put into the reaction kettle2Placing the nanosheet above ammonia water without contacting with the ammonia water, placing the reaction kettle in a forced air drying oven, keeping the temperature at 180 ℃ for 18 hours, taking out the carbon cloth after the temperature is reduced to room temperature, sequentially washing the carbon cloth with ethanol and water, and drying to obtain the heteroatom nitrogen surface modified MoS2A nanomaterial catalyst.
Example 5
The first step is as follows: mixing carbon cloth (3 x 3cm)2) Sequentially carrying out ultrasonic treatment on acetone, ethanol and water for 10 minutes for later use;
the second step is that: mixing ammonium molybdate and thiourea in water according to a ratio, wherein the molar ratio of the ammonium molybdate to the thiourea is 1:5, and stirring until the ammonium molybdate and the thiourea are completely dissolved to obtain a uniform solution, wherein the volume of the water is 35 mL;
the third step: transferring the uniformly stirred solution to a reaction kettle with a stainless steel substrate, putting the reaction kettle into carbon cloth subjected to ultrasonic treatment, and putting the reaction kettle in an air-blowing drying oven to keep the temperature of 180 ℃ for 12 hours; cooling to room temperatureThen, the carbon cloth is taken out and washed clean by ethanol and water in sequence, and dried to obtain MoS2A nanosheet catalyst.
Fourthly, 15mL of ammonia water is put into a reaction kettle, and MoS is put into the reaction kettle2Placing the nanosheet above ammonia water without contacting with the ammonia water, placing the reaction kettle in a forced air drying oven, keeping the temperature at 90 ℃ for 12 hours, taking out the carbon cloth after the temperature is reduced to room temperature, sequentially washing the carbon cloth with ethanol and water, and drying to obtain the heteroatom nitrogen surface modified MoS2A nanomaterial catalyst.
Example 6
The product prepared in the example was tested for oxygen evolution performance, the prepared carbon cloth was fixed on an electrode holder as a working electrode, and then the oxygen evolution performance was tested on an electrochemical workstation using a three-electrode method (reversible hydrogen as a reference electrode, carbon rod as an auxiliary electrode).

Claims (4)

1. Heteroatom nitrogen surface modification MoS2The preparation method of the nano material comprises the following steps:
(1) the area is 3 x 3cm2The carbon cloth is sequentially subjected to ultrasonic treatment in acetone, ethanol and water for 10 minutes for later use;
(2) mixing ammonium molybdate and thiourea in water according to a ratio, wherein the molar ratio of the ammonium molybdate to the thiourea is 1:5, and stirring until the ammonium molybdate and the thiourea are completely dissolved to obtain a uniform solution;
(3) transferring the uniformly stirred solution to a reaction kettle with a stainless steel substrate, putting the reaction kettle into carbon cloth subjected to ultrasonic treatment, and putting the reaction kettle in an air-blowing drying oven to keep the temperature of 180 ℃ for 12 hours; cooling to room temperature, taking out the carbon cloth, washing with ethanol and water in sequence, and drying to obtain MoS2Nanosheets;
(4) the obtained MoS2Adding nanosheets and ammonia water with different volumes into a reaction kettle with a stainless steel substrate, and adding MoS2The nanosheet is arranged above ammonia water and is not contacted with the ammonia water, the reaction kettle is placed in a forced air drying oven for high-temperature reaction, the temperature is reduced to room temperature, the carbon cloth is taken out and washed clean by ethanol and water in sequence, and drying is carried out, so that the heteroatom nitrogen surface modified MoS is obtained2And (3) nano materials.
2. The method according to claim 1, wherein the volume of the aqueous ammonia in the step (4) is 5mL, 10mL or 15 mL.
3. The method according to claim 1, wherein the high temperature reaction temperature in the step (4) is 90 ℃ or 150 ℃ or 180 ℃.
4. The method according to claim 1, wherein the high-temperature reaction time in the step (4) is 8 hours, 12 hours or 18 hours.
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CN111185201B (en) * 2020-02-25 2022-07-19 辽宁大学 Rhenium-doped molybdenum sulfide nanosheet/carbon cloth composite material, preparation method thereof and application thereof in hydrogen production by electrocatalysis of water
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