CN111266125B - Preparation method and application of composite material of high-dispersion metal nitrogen carbon and layered sulfide - Google Patents

Preparation method and application of composite material of high-dispersion metal nitrogen carbon and layered sulfide Download PDF

Info

Publication number
CN111266125B
CN111266125B CN202010099300.5A CN202010099300A CN111266125B CN 111266125 B CN111266125 B CN 111266125B CN 202010099300 A CN202010099300 A CN 202010099300A CN 111266125 B CN111266125 B CN 111266125B
Authority
CN
China
Prior art keywords
metal
composite material
reaction
carbon
dispersion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010099300.5A
Other languages
Chinese (zh)
Other versions
CN111266125A (en
Inventor
张国新
陈建雯
邢旭
孙晓明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University of Science and Technology
Original Assignee
Shandong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong University of Science and Technology filed Critical Shandong University of Science and Technology
Priority to CN202010099300.5A priority Critical patent/CN111266125B/en
Publication of CN111266125A publication Critical patent/CN111266125A/en
Application granted granted Critical
Publication of CN111266125B publication Critical patent/CN111266125B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The application discloses a preparation method of a composite material of high-dispersion metal nitrogen carbon and layered sulfide, which comprises the following steps: in an inert atmosphere, the high-dispersion multi-element metal nitrogen-carbon precursor and a gasified sulfur source are subjected to a roasting reaction, and the composite material of the high-dispersion metal nitrogen-carbon and the layered sulfide is prepared by utilizing the difference of the affinities of different metals and sulfur elements. The invention also provides the application of the composite material of the high-dispersion metal nitrogen carbon and the layered sulfide as an electrochemical catalyst. The preparation method of the high-dispersion metal carbonitride and layered sulfide composite material provided by the invention is simple and convenient to operate, high in safety, free of post-treatment steps and beneficial to industrial scale-up production.

Description

Preparation method and application of composite material of high-dispersion metal nitrogen carbon and layered sulfide
Technical Field
The invention belongs to the field of controlled synthesis and electrochemical application of composite catalytic materials, and particularly relates to a preparation method and application of a composite material of high-dispersion metal nitrogen carbon and layered sulfide.
Background
Due to the increased environmental pollution caused by the burning of fossil fuels and the increasing global demand for energy, the pace of developing clean alternative energy sources has been accelerated. In the development of clean energy, electrochemical catalysis and energy storage technology hold an important position. The hydrogen energy is used as a renewable energy source, has the highest heat value, and the combustion product is pollution-free, so that the hydrogen energy is an ideal fossil fuel substitute, and the hydrogen production by water electrolysis is an important way for obtaining high-purity hydrogen and realizing sustainable distributed storage. In addition, important electrochemical reactions such as oxygen reduction and precipitation, electrochemical energy storage and the like also have important application value. The key to using electrocatalysis and energy storage technology is to prepare a catalyst with high efficiency and low price so as to reduce the consumption of electric energy. Currently, commercial platinum-carbon catalysts have excellent hydrogen evolution activity, but the scarcity, high cost and low stability of noble metals greatly limit their large-scale application. In recent years, transition metal sulfides have proven to be a potential substitute for noble metal catalysts, and have a unique layered structure, exhibiting high electrocatalytic activity. Researchers have made a lot of researches to improve the performance of metal sulfide catalysts, and among them, the synthesis of carbon-based compound and metal sulfide composite catalytic materials is one of the most effective methods.
On one hand, the metal sulfide and the carbon material are combined, the conductivity of the material is improved, meanwhile, the number of active sites is increased, meanwhile, the nitrogen-doped carbon material can remarkably improve the conductivity of the electrode, and can serve as a buffer layer to prevent the stacking of the layered nanosheets. On the other hand, when the dispersion degree of the active metal component reaches the monoatomic size, many new characteristics can be caused, such as sharply increased surface free energy, quantum size effect, unsaturated coordination environment, metal-carrier interaction and the like, and particularly for metals with higher price, the usage amount of the catalyst can be greatly reduced, the catalyst cost can be reduced, and the potential of the catalyst in large-scale application in industrial production can be improved. However, the single atom or cluster level catalyst also has obvious disadvantages, when the metal particles are reduced to the atom level, the specific surface area is sharply increased, the free energy of the metal surface is sharply increased, and agglomeration coupling is easily generated during preparation and reaction to form larger particles, so that the activity of the catalyst is greatly reduced, and therefore, the preparation of the metal high-dispersion catalyst with stable physicochemical properties faces huge challenges.
Therefore, how to combine the highly dispersed metal nitrocarbon with the layered metal sulfide to construct a novel composite structure, and further improve the electrocatalytic hydrogen evolution activity of the composite material is an urgent technical problem to be solved.
Disclosure of Invention
Aiming at the technical problems, the invention provides a preparation method of a composite material of high-dispersion metal nitrogen carbon and layered sulfide. The preparation strategy is as follows: firstly, formamide is polymerized and carbonized under the catalysis and coordination of mixed metal ions (at least one metal in a first metal and a second metal is used at the same time) to form a carbon material with higher nitrogen content, metal components are chelated in an atomic form by utilizing strong coordination to realize high dispersion of the metal components in the nitrogen-containing carbon material, rich high-dispersion transition metal nitrogen-carbon materials can be formed, and then the precursor material is subjected to gas phase vulcanization under the protection of inert atmosphere to obtain the composite material of the high-dispersion metal nitrogen-carbon and the layered sulfide. The preparation method is simple and easy to operate, and is suitable for laboratory research and industrial scale-up production.
The invention provides a preparation method of a metal nitrogen carbon and layered metal sulfide composite material, which is characterized by comprising the following steps:
and in an inert atmosphere, carrying out roasting reaction on the multi-element metal carbon nitrogen precursor prepared by the preparation method and a gasified sulfur source to obtain the composite material of the highly dispersed metal carbon nitrogen and the layered sulfide. The inert atmosphere is formed by nitrogen, helium, neon, argon, krypton, xenon or the like.
In one embodiment according to the present invention, the reaction conditions of the calcination reaction are: heating to 500-900 deg.c for 1-99 hr. Preferably, the calcination reaction is carried out by heating in a tube furnace or the like.
In one embodiment according to the present invention, the sulphur source is selected from one or more of sulphur powder, sodium sulphide, hydrogen sulphide, thioacetamide or thiourea.
The preparation method of the metal nitrogen-carbon precursor in one embodiment of the invention comprises the following steps:
mixing a first metal salt and a second metal salt in any proportion, and dissolving the mixture in a proper amount of formamide to obtain a mixed solution; placing the mixed solution in a container, and heating to the reaction temperature to carry out liquid phase reaction; after liquid phase reaction, separating and drying a solid product to obtain the catalyst;
wherein the first metal is selected from any one of Co, ni, fe, cu, mn, zn, ru, rh, ir and Pt; the second metal is at least one selected from Mo, W, V, sn and Bi; the first metal salt is selected from any one of hydrochloride, sulfate, nitrate, acetylacetonate and carbonyl salt of the first metal; the second metal salt is selected from at least one of hydrochloride, sulfate, nitrate, acetylacetonate and carbonyl salt of the second metal. Wherein the first metal is used as a main active component of the catalyst, and the second metal is used as a cocatalyst or an energy storage material. The formamide performs polymerization, carbonization and coordination reactions under the catalytic promotion of metal components, so as to realize the preparation of the precursor material of the catalyst composite.
In one embodiment according to the present invention, the total metal concentration in the mixed solution is 0.02 to 0.15mol/L.
In one embodiment according to the present invention, the concentration of the first metal salt in the mixed solution is: 0.01-0.05 mol/L.
In one embodiment according to the present invention, the concentration of the second metal salt in the mixed solution is: 0.01-0.1 mol/L.
In one embodiment according to the present invention, the mixed solution is mixed uniformly by an effective mixing method selected from one or more of manual shaking, mechanical shaking, ultrasound, and stirring. The container is preferably a safe container having good heat resistance, such as a flask, a polytetrafluoroethylene reaction vessel, or the like.
In one embodiment according to the present invention, the temperature of the liquid phase reaction is 100 to 300 ℃ and the duration of the liquid phase reaction is 1 to 99 hours. The means for effectively separating the solid product from the liquid after the liquid phase reaction comprises centrifugation, filtration, standing sedimentation and the like.
The invention further provides the layered metal sulfide composite material prepared by the preparation method.
The invention further provides application of the composite material of the high-dispersion metal nitrogen carbon and the layered sulfide in electrochemical catalytic reaction.
The invention also provides a catalyst for electrochemical catalytic reaction, which comprises the composite material of the high-dispersion metal nitrogen carbon and the layered sulfide.
The invention has the following beneficial effects:
the preparation method is simple and convenient to operate, high in safety, free of post-treatment steps and beneficial to industrial scale-up production. Meanwhile, the method has wide application range, and is beneficial to scientific research and production expansion aiming at different catalytic systems.
Drawings
FIG. 1 shows CoNC/MoS prepared in example 1 of the present invention 2 Transmission electron micrograph (c).
FIG. 2 shows CoNC/MoS prepared in example 2 of the present invention 2 Transmission electron microscope (c).
FIG. 3 shows CoNC/MoS prepared in example 3 of the present invention 2 Transmission electron micrograph (c).
FIG. 4 shows CoNC/MoS prepared in example 4 of the present invention 2 Transmission electron micrograph (c).
FIG. 5 shows NiNC/MoS prepared in example 5 of the present invention 2 Transmission electron micrograph (c).
FIG. 6 shows FeNC/MoS prepared in example 6 of the present invention 2 Transmission electron micrograph (c).
FIG. 7 is a CuNC/MoS prepared in example 7 of the present invention 2 Transmission electron micrograph (c).
FIG. 8 shows MnNC/MoS prepared in example 8 of the present invention 2 Transmission electron micrograph (c).
FIG. 9 shows CoNC/MoS prepared in example 3 of the present invention 2 X-ray diffraction pattern of (a).
FIG. 10 shows NiNC/MoS prepared in example 5 of the present invention 2 X-ray diffraction pattern of (a).
FIG. 11 shows NiMNC/MoS prepared according to examples 10 and 11 of the present invention 2 X-ray diffraction pattern of (a).
FIG. 12 shows CoNC/MoS prepared in example 3 of the present invention 2 XPS Co2p peak separation curve of (1).
FIG. 13 shows NiNC/MoS prepared in example 5 of the present invention 2 XPS Ni2p peak separation curve of (a).
FIG. 14 shows FeNC/MoS prepared in example 6 of the present invention 2 XPS Fe2p peak separationA wire.
FIG. 15 is a CuNC/MoS sample prepared in example 7 of the present invention 2 XPS Cu2p peak separation curve of (1).
FIG. 16 shows MnNC/MoS prepared in example 8 of the present invention 2 XPS Mn2p peak separation curve of (A).
FIG. 17 shows CoNC/MoS prepared in examples 1-4 of the present invention 2 And (3) evaluating the performance of the catalyst in the electrocatalytic hydrogen evolution reaction.
FIG. 18 shows MNC/MoS prepared in examples 5-8 of the present invention 2 And (3) evaluating the performance of the catalyst in the electrocatalytic hydrogen evolution reaction.
FIG. 19 shows NiMNC/MoS prepared according to examples 10 and 11 of the present invention 2 And (3) evaluating the performance of the catalyst in the electrocatalytic hydrogen evolution reaction.
FIG. 20 shows NiMNC/MoS prepared according to examples 10 and 11 of the present invention 2 Evaluation of the performance in the electrocatalytic oxygen evolution reaction.
Detailed Description
The following examples are intended to illustrate the present application but are not intended to limit the scope of the present application.
Specific embodiments of the present application will be described in more detail below. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
Example 1
30.0mL of anhydrous CoCl was dissolved in 0.01mol/L 2 (transition Metal salt) and 0.04mol/L Anhydrous MoCl 5 The formamide solution of (2) was put into a polytetrafluoroethylene reaction kettle having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. Naturally cooling after the reaction time is over, taking out the solid-liquid mixture, performing solid-liquid separation by using a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting and dryingAnd (3) placing a porcelain boat filled with 1.5g of sublimed sulfur on the upper part of the air flow by using a tube furnace under the protection of nitrogen, placing the porcelain boat filled with 0.1g of solid powder on the lower part of the air flow, and roasting at 600 ℃ for 1 hour to obtain the target product.
Example 2
30.0mL of anhydrous CoCl dissolved in 0.015mol/L 2 (transition Metal salt) and 0.035mol/L Anhydrous MoCl 5 The formamide solution was placed in a Teflon reaction vessel having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. And after the reaction time is over, naturally cooling, taking out a solid-liquid mixture, carrying out solid-liquid separation by using a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting dry powder, placing a ceramic boat filled with 1.5g of sublimed sulfur on the upper part of an air flow by using a tube furnace under the protection of nitrogen, placing the ceramic boat filled with 0.1g of solid powder on the lower part of the air flow, and roasting at the temperature of 600 ℃ for 1 hour to obtain the target product.
Example 3
30.0mL of anhydrous CoCl dissolved in 0.02mol/L 2 (transition Metal salt) and 0.03mol/L of anhydrous MoCl 5 The formamide solution was placed in a Teflon reaction vessel having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. And after the reaction time is over, naturally cooling, taking out a solid-liquid mixture, performing solid-liquid separation by using a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting dried powder, placing a porcelain boat filled with 1.5g of sublimed sulfur on the upper part of an air flow by using a tube furnace under the protection of nitrogen, placing a porcelain boat filled with 0.1g of solid powder on the lower part of the air flow, and roasting for 1 hour at the temperature of 600 ℃ to obtain a target product.
Prepared CoNC/MoS 2 The results of the evaluation of the electrocatalytic hydrogen evolution catalytic performance of the composite catalyst are shown in the attached figure 19.
Example 4
30.0mL of anhydrous CoCl dissolved in 0.025mol/L 2 (transition Metal salt) and 0.025mol/L Anhydrous MoCl 5 The formamide solution of (2) was put into a polytetrafluoroethylene reaction kettle having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. Naturally cooling after the reaction time is over, taking out the solid-liquid mixture, separating the solid from the liquid in a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting dry powder,placing the porcelain boat containing 1.5g of sublimed sulfur on the upper part of the air flow, placing the porcelain boat containing 0.1g of solid powder on the lower part of the air flow, and roasting at 600 ℃ for 1 hour under the protection of nitrogen by using a tube furnace to obtain the target product.
Example 5
30.0mL of anhydrous NiCl dissolved in 0.01mol/L 2 (transition Metal salt) and 0.04mol/L Anhydrous MoCl 5 The formamide solution of (2) was put into a polytetrafluoroethylene reaction kettle having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. And after the reaction time is over, naturally cooling, taking out a solid-liquid mixture, carrying out solid-liquid separation by using a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting dry powder, placing a ceramic boat filled with 1.5g of sublimed sulfur on the upper part of an air flow by using a tube furnace under the protection of nitrogen, placing the ceramic boat filled with 0.1g of solid powder on the lower part of the air flow, and roasting at the temperature of 600 ℃ for 1 hour to obtain the target product.
Example 6
30.0mL of anhydrous FeCl dissolved with 0.01mol/L 3 (transition Metal salt) and 0.04mol/L Anhydrous MoCl 5 The formamide solution was placed in a Teflon reaction vessel having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. And after the reaction time is over, naturally cooling, taking out a solid-liquid mixture, carrying out solid-liquid separation by using a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting dry powder, placing a ceramic boat filled with 1.5g of sublimed sulfur on the upper part of an air flow by using a tube furnace under the protection of nitrogen, placing the ceramic boat filled with 0.1g of solid powder on the lower part of the air flow, and roasting at the temperature of 600 ℃ for 1 hour to obtain the target product.
Example 7
30.0mL of anhydrous CuCl dissolved in 0.01mol/L 2 (transition Metal salt) and 0.04mol/L Anhydrous MoCl 5 The formamide solution was placed in a Teflon reaction vessel having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. Naturally cooling after the reaction time is over, taking out a solid-liquid mixture, performing solid-liquid separation by using a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting dried powder, placing a ceramic boat containing 1.5g of sublimed sulfur on the upper part of an air flow by using a tube furnace under the protection of nitrogen, placing the ceramic boat containing 0.1g of solid powder on the lower part of the air flow, and cooling at the temperature of 600 DEG CRoasting for 1 hour to obtain the target product.
Example 8
30.0mL of anhydrous MnCl was dissolved in 0.01mol/L 2 (transition Metal salt) and 0.04mol/L Anhydrous MoCl 5 The formamide solution of (2) was put into a polytetrafluoroethylene reaction kettle having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. And after the reaction time is over, naturally cooling, taking out a solid-liquid mixture, carrying out solid-liquid separation by using a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting dry powder, placing a ceramic boat filled with 1.5g of sublimed sulfur on the upper part of an air flow by using a tube furnace under the protection of nitrogen, placing the ceramic boat filled with 0.1g of solid powder on the lower part of the air flow, and roasting at the temperature of 600 ℃ for 1 hour to obtain the target product.
Example 9
30.0mL of anhydrous CoCl dissolved in 0.01mol/L 2 And 0.04mol/L of anhydrous WCl 6 The formamide solution was placed in a Teflon reaction vessel having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. And after the reaction time is over, naturally cooling, taking out a solid-liquid mixture, carrying out solid-liquid separation by using a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting dry powder, placing a ceramic boat filled with 1.5g of sublimed sulfur on the upper part of an air flow by using a tube furnace under the protection of nitrogen, placing the ceramic boat filled with 0.1g of solid powder on the lower part of the air flow, and roasting at the temperature of 600 ℃ for 1 hour to obtain the target product.
Example 10
30.0mL of anhydrous CoCl dissolved in 0.004mol/L 2 0.004mol/L of anhydrous NiCl 2 And 0.04mol/L of anhydrous MoCl 5 The formamide solution was placed in a Teflon reaction vessel having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. And after the reaction time is over, naturally cooling, taking out a solid-liquid mixture, carrying out solid-liquid separation by using a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting dry powder, placing a ceramic boat filled with 1.5g of sublimed sulfur on the upper part of an air flow by using a tube furnace under the protection of nitrogen, placing the ceramic boat filled with 0.1g of solid powder on the lower part of the air flow, and roasting at the temperature of 600 ℃ for 1 hour to obtain the target product.
Example 11
30.0mL of the solution was dissolved with 0.004mol/L of ethanolAqueous FeCl 2 0.004mol/L of anhydrous NiCl 2 And 0.04mol/L of anhydrous MoCl 5 The formamide solution was placed in a Teflon reaction vessel having a volume of 50.0mL and reacted at 180 ℃ for 12 hours. And after the reaction time is over, naturally cooling, taking out a solid-liquid mixture, carrying out solid-liquid separation by using a centrifugal mode, drying the solid in an oven at the temperature of 80 ℃, collecting dry powder, placing a ceramic boat filled with 1.5g of sublimed sulfur on the upper part of an air flow by using a tube furnace under the protection of nitrogen, placing the ceramic boat filled with 0.1g of solid powder on the lower part of the air flow, and roasting at the temperature of 600 ℃ for 1 hour to obtain the target product.
The product obtained according to the invention is characterized: transmission electron micrographs (FIGS. 1-8) show: using formamide, moCl 5 And a different first type transition metal (M) A ) The metal nitrogen carbon/molybdenum disulfide composite material synthesized by the salt is granular, and the transition metal M is not seen under the common high-resolution transmission A And (4) forming particles. The transmission electron microscope photo shows that: using formamide, moCl 5 And various concentrations of CoCl 2 Synthetic CoNC/MoS 2 The composite catalyst is granular, and under ordinary high-resolution transmission, co metal granules forming granules are not seen. The X-ray powder diffraction pattern (fig. 9-17) shows: in all the examples 1 to 8 included in the present invention, only the diffraction peak of the molybdenum disulfide material was detected, and the active metal M was not observed A Diffraction peaks of the fractions, confirmation of the activity M A The metal component exists at the atomic level or in the form of clusters.
The highly dispersed metal nitrogen carbon/molybdenum disulfide composite catalyst prepared by the invention regulates and controls the electronic structure of molybdenum disulfide by changing the metal doping amount and the metal type in the composite material, improves the conductivity of the material, reduces the charge transfer resistance of the material, improves the reaction speed of electrocatalytic hydrogen production, and realizes high-efficiency electrocatalytic hydrogen production.
Although the present application has been described in detail with respect to the general description and the specific embodiments, it will be apparent to those skilled in the art that some modifications or improvements may be made based on the present application. Accordingly, such modifications and improvements are intended to be within the scope of this invention as claimed.

Claims (8)

1. A preparation method of a composite material of high-dispersion metal nitrogen carbon and layered sulfide is characterized by comprising the following steps:
in an inert atmosphere, carrying out a roasting reaction on a high-dispersion multi-element metal carbon nitrogen precursor and a gasified sulfur source to obtain a high-dispersion metal carbon nitrogen and layered sulfide composite material;
the sulfur source is sulfur powder;
the preparation method of the high-dispersion multi-metal nitrogen-carbon precursor comprises the following steps:
mixing a first metal salt and a second metal salt in any proportion, and dissolving the mixture in a proper amount of formamide to obtain a mixed solution; placing the mixed solution in a container, and heating to the reaction temperature to carry out liquid phase reaction; after liquid phase reaction, separating and drying a solid product to obtain the catalyst; the temperature of the liquid phase reaction is 100-180 ℃, the reaction time is 1-12 hours, and the reaction vessel is a polytetrafluoroethylene reaction kettle;
wherein the first metal is selected from any one of Co, ni, fe, cu, mn and Zn; the second metal is Mo; the first metal salt is selected from any one of hydrochloride, sulfate, nitrate, acetylacetonate and carbonyl salt of the first metal; the second metal salt is selected from at least one of hydrochloride, sulfate, nitrate, acetylacetonate and carbonyl salt of the second metal.
2. The method of claim 1, wherein the calcination reaction is carried out under the following reaction conditions: heating to 500-900 deg.c for 1-99 hr.
3. The method according to claim 1, wherein the total metal concentration in the mixed solution is 0.02 to 0.15mol/L.
4. The method according to claim 3, wherein the concentration of the first metal salt in the mixed solution is: 0.01-0.05 mol/L.
5. The production method according to any one of claims 1 to 4, wherein the concentration of the second metal salt in the mixed solution is: 0.01-0.1 mol/L.
6. A composite material of highly dispersed metallic nitrocarbon and a layered sulfide, which is produced by the production method described in any one of claims 1 to 5.
7. Use of the composite material of claim 6 in electrochemical catalytic reactions.
8. A catalyst for electrochemical catalytic reactions, comprising the composite material of claim 6.
CN202010099300.5A 2020-02-18 2020-02-18 Preparation method and application of composite material of high-dispersion metal nitrogen carbon and layered sulfide Active CN111266125B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010099300.5A CN111266125B (en) 2020-02-18 2020-02-18 Preparation method and application of composite material of high-dispersion metal nitrogen carbon and layered sulfide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010099300.5A CN111266125B (en) 2020-02-18 2020-02-18 Preparation method and application of composite material of high-dispersion metal nitrogen carbon and layered sulfide

Publications (2)

Publication Number Publication Date
CN111266125A CN111266125A (en) 2020-06-12
CN111266125B true CN111266125B (en) 2022-10-28

Family

ID=70991247

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010099300.5A Active CN111266125B (en) 2020-02-18 2020-02-18 Preparation method and application of composite material of high-dispersion metal nitrogen carbon and layered sulfide

Country Status (1)

Country Link
CN (1) CN111266125B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106334582A (en) * 2016-09-22 2017-01-18 北京化工大学 Preparation method for graphene-based transition metal-nitrogen carbon composite materials
CN107930672A (en) * 2017-12-04 2018-04-20 北京化工大学 A kind of metal is in metal nitrogen carbon material, the preparation method and use that atom level is disperseed
CN109499600A (en) * 2018-12-14 2019-03-22 江苏科技大学 A kind of bimetallic nitrogen-doped carbon/molybdenum disulfide composite electro catalytic agent material, preparation method and applications
CN110252308A (en) * 2019-06-21 2019-09-20 山东科技大学 A kind of active metal is in the loaded catalyst and its preparation method and application of atom level dispersion in the carrier
CN110668415A (en) * 2019-09-19 2020-01-10 山东科技大学 Method for preparing atomic-scale dispersed metal nitrogen carbon material based on fumed silica

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106334582A (en) * 2016-09-22 2017-01-18 北京化工大学 Preparation method for graphene-based transition metal-nitrogen carbon composite materials
CN107930672A (en) * 2017-12-04 2018-04-20 北京化工大学 A kind of metal is in metal nitrogen carbon material, the preparation method and use that atom level is disperseed
CN109499600A (en) * 2018-12-14 2019-03-22 江苏科技大学 A kind of bimetallic nitrogen-doped carbon/molybdenum disulfide composite electro catalytic agent material, preparation method and applications
CN110252308A (en) * 2019-06-21 2019-09-20 山东科技大学 A kind of active metal is in the loaded catalyst and its preparation method and application of atom level dispersion in the carrier
CN110668415A (en) * 2019-09-19 2020-01-10 山东科技大学 Method for preparing atomic-scale dispersed metal nitrogen carbon material based on fumed silica

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"A general route via formamide condensation to prepare atomically dispersed metal-nitrogen-carbon electrocatalysts for energy technologies";Guoxin Zhang et al.;《Energy & Environmental Science》;20190325;第12卷;第1317-1325页 *
"Ultrafast Li-storage of MoS2 nanosheets grown on metal-organic framework-derived microporous nitrogen-doped carbon dodecahedrons";Jie Shao et al.;《Journal of Power Sources》;20160519;第324卷;第1-7页 *

Also Published As

Publication number Publication date
CN111266125A (en) 2020-06-12

Similar Documents

Publication Publication Date Title
Peng et al. Applications of metal–organic framework-derived N, P, S doped materials in electrochemical energy conversion and storage
CN109847778B (en) Cobalt disulfide/carbon nitrogen composite material for oxygen evolution by electrolyzing water and synthetic method thereof
Miao et al. Synthesis and application of single-atom catalysts in sulfur cathode for high-performance lithium–sulfur batteries
CN110694665B (en) Preparation method and application of manganese and nitrogen doped octa-sulfur-nonacobalt electrocatalyst
CN111659401A (en) Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof
Ma et al. Fabrication of P-doped Co9S8/g-C3N4 heterojunction for excellent photocatalytic hydrogen evolution
Park et al. Hybrid metal–Cu 2 S nanostructures as efficient co-catalysts for photocatalytic hydrogen generation
CN114517306B (en) N, P co-doped carbon-supported transition metal monoatomic material, preparation method and application thereof
Shin et al. Cobalt vanadate nanoparticles as bifunctional oxygen electrocatalysts for rechargeable seawater batteries
CN116139867B (en) MOFs derived ZnO@CDs@Co 3 O 4 Composite photocatalyst, preparation method and application thereof
Wang et al. Homogeneous pseudoamorphous metal phosphide clusters for ultra stable hydrogen generation by water electrolysis at industrial current density
CN111155146A (en) Preparation method of vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material
Chen et al. Monodispersed Eu2O3-Modified Fe3O4@ NCG Composites as Highly Efficient and Ultra-stable Catalysts for Rechargeable Zn–Air Batteries
Xie et al. Ultrasmall Co-NiP embedded into lantern shaped composite achieved by coordination confinement phosphorization for overall water splitting
CN114054066B (en) Doped g-C3N4Nanotube photocatalyst, preparation method and application
Wang et al. Preparation of Mn0. 8Cd0. 2S/NiCo2S4 Z-scheme heterojunction composite for enhanced photocatalytic hydrogen production
CN115044935A (en) Preparation method and application of nano high-entropy oxide
Wang et al. Enhanced oxygen reduction reaction performance of Co@ N–C derived from metal-organic frameworks ZIF-67 via a continuous microchannel reactor
Khan et al. Recent advancements in the synthetic mechanism and surface engineering of transition metal selenides for energy storage and conversion applications
Sharma et al. Recent advances in synthesis, structural properties, and regulation of nickel sulfide-based heterostructures for environmental water remediation: an insight review
Peng et al. Novel heterostructure Cu 2 S/Ni 3 S 2 coral-like nanoarrays on Ni foam to enhance hydrogen evolution reaction in alkaline media
CN111606320B (en) Preparation method and application of reduced graphene oxide coated sulfide/bimetallic oxide composite material
CN111266125B (en) Preparation method and application of composite material of high-dispersion metal nitrogen carbon and layered sulfide
CN110681370B (en) Molybdenum disulfide/gold/nitrogen-doped carbon nanotube complex and preparation method and application thereof
CN109482200B (en) Porous carbon supported defected molybdenum sulfide electrocatalyst and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant