CN108977827B - Comprising FeSe2-Co3O4Composite material and preparation method thereof, catalyst and application - Google Patents

Comprising FeSe2-Co3O4Composite material and preparation method thereof, catalyst and application Download PDF

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CN108977827B
CN108977827B CN201810861039.0A CN201810861039A CN108977827B CN 108977827 B CN108977827 B CN 108977827B CN 201810861039 A CN201810861039 A CN 201810861039A CN 108977827 B CN108977827 B CN 108977827B
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fese
composite material
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rgo
rgo composite
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CN108977827A (en
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程修文
张惠璇
郭若男
马秋羚
李波
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Lanzhou 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
    • 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
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    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • 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
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    • 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

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Abstract

The invention provides a FeSe-containing fertilizer2‑Co3O4Relates to the field of preparation and application of electrocatalyst materials, and relates to a preparation method and a catalyst of the composite material, and application of the catalyst. FeSe2‑Co3O4Composite material comprising FeSe2And Co3O4Said FeSe2Modified in Co3O4To obtain FeSe on the surface2‑Co3O4. The FeSe provided by the invention2‑Co3O4The composite material is prepared from cheap and easily available raw materials with low cost and FeSe2And Co3O4The active ingredients have double catalytic functions of electro-catalysis hydrogen production and oxygen production, improve the hydrogen production and oxygen production performance, and reduce the energy consumption of hydrogen production and oxygen production.

Description

Comprising FeSe2-Co3O4Composite material and preparation method thereof, catalyst and application
Technical Field
The invention relates to the field of preparation and application of an electrocatalyst material, in particular to a catalyst containing FeSe2-Co3O4The composite material, a preparation method, a catalyst and application thereof.
Background
Hydrogen is a renewable clean energy source, and has the outstanding advantages of abundant resources, easy storage and the like. With the exhaustion of fossil fuels and the growing environmental problems, hydrogen, a renewable clean energy source, is receiving more and more attention.
Electrocatalytic decomposition of water is considered an attractive, sustainable process. High purity hydrogen is obtained by electrochemically decomposing water into hydrogen and oxygen. In general, the water splitting reaction involves an oxygen evolution reaction at the cathode and a hydrogen evolution reaction at the anode. However, both of them require a large overpotential due to thermodynamics, and thus consume a large amount of electric energy, which makes the production cost high. Therefore, it is very urgent to develop an efficient electrocatalyst to reduce energy consumption. Currently, platinum-based materials and iridium-based materials are the most effective electrocatalysts for electrocatalytic hydrogen and oxygen evolution, respectively. However, scarcity and high cost have prevented their large-scale use. It is therefore highly desirable to develop cost-effective electrocatalysis of non-noble metals.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide FeSe2-Co3O4Composite material of FeSe2-Co3O4The composite material has the advantages of cheap and easily-obtained raw materials and low cost, has the double catalytic action of hydrogen production and oxygen production, and reduces the energy consumption of hydrogen production and oxygen production.
The FeSe provided by the invention2-Co3O4Composite material comprising FeSe2And Co3O4Said FeSe2Modified in Co3O4To obtain FeSe on the surface2-Co3O4A composite material;
preferably, the FeSe2-Co3O4FeSe in composite material2And Co3O4In a molar ratio of (5-7): (3-5), more preferably (5-6): (3-4).
The second purpose of the invention is to provide FeSe2-Co3O4The preparation method of the composite material has the advantages of simple operation, cheap and easily obtained materials, low manufacturing cost, low energy consumption and no pollution.
The invention providesFeSe2-Co3O4The preparation method of the composite material comprises the following steps: dispersing trivalent ferric salt, selenium powder, reducing agent and optional surfactant in water, and adding Co3O4Obtaining FeSe through hydrothermal reaction2-Co3O4A composite material.
The third purpose of the invention is to provide FeSe2-Co3O4-rGO composite, the FeSe2-Co3O4The raw materials of the rGO composite material are cheap and easy to obtain, the cost is low, the double catalytic effects of hydrogen production and oxygen production are achieved, and the energy consumption of hydrogen production and oxygen production is reduced.
The FeSe provided by the invention2-Co3O4-rGO composites including FeSe2、Co3O4And rGO, said FeSe2Modified in Co3O4To obtain FeSe on the surface2-Co3O4Said FeSe2-Co3O4The rGO is loaded to obtain FeSe2-Co3O4-rGO composite;
preferably, the FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4In a molar ratio of (5-7): (3-5), more preferably (5-6): (3-4).
The fourth purpose of the invention is to provide FeSe2-Co3O4The preparation method of the-rGO composite material has the advantages of simple operation, cheap and easily-obtained materials, low manufacturing cost, low energy consumption and no pollution.
The FeSe provided by the invention2-Co3O4-a process for the preparation of rGO composite material comprising the steps of: dispersing trivalent ferric salt, selenium powder, reducing agent and optional surfactant in water, and adding Co3O4And GO suspension is subjected to hydrothermal reaction to obtain FeSe2-Co3O4-rGO composite.
Further, the reducing agent comprises at least one of hydrazine hydrate or sodium borohydride, preferably hydrazine hydrate;
and/or the surfactant is a cationic surfactant, preferably a quaternary ammonium salt cationic surfactant, and further preferably cetyl trimethyl ammonium bromide.
Further, the hydrothermal reaction temperature is 140-160 ℃, preferably 145-155 ℃, and further preferably 150 ℃;
and/or the hydrothermal reaction time is 10-15h, preferably 11-14h, and further preferably 12 h.
Further, the Co3O4The preparation method comprises the following steps: adding water into divalent cobalt salt, and calcining to obtain Co3O4；
Preferably, the calcination temperature is 300-500 ℃, more preferably 350-450 ℃, and even more preferably 400 ℃; and/or the calcination time is 1-5h, more preferably 2-4h, and still more preferably 4 h; and/or the heating rate of the calcination is 5-15 ℃/min, more preferably 8-12 ℃/min, and still more preferably 10 ℃/min.
Further, the GO suspension is prepared by adopting a modified Hummers method;
preferably, the preparation method of the GO suspension comprises the following steps: firstly, graphite and NaNO are mixed3And concentrated H2SO4Mixing with KMnO4And reacting with water, and aging to obtain GO suspension.
It is a fifth object of the present invention to provide a composition comprising FeSe2-Co3O4Composite materials or FeSe2-Co3O4The catalyst has excellent electro-catalysis hydrogen production and oxygen production performance under acidic and alkaline conditions, so that electro-catalysis full electrolysis of water can be realized, renewable clean energy can be produced by using low-cost and low-consumption electric energy, the catalyst has magnetism, can be separated by using external magnetic force for recycling, and has wide application prospect in the aspect of producing clean energy.
The catalyst provided by the invention comprises the FeSe2-Co3O4Composite materialThe material or FeSe prepared by the preparation method2-Co3O4Composite material or FeSe2-Co3O4-rGO composite material or FeSe prepared by the preparation method2-Co3O4-rGO composite.
The sixth purpose of the invention is to provide FeSe2-Co3O4Composite materials or comprising FeSe2-Co3O4Catalysts or FeSe of composite materials2-Co3O4-rGO composites or comprising FeSe2-Co3O4The application of the catalyst of the rGO composite material in electrocatalytic decomposition water realizes electrocatalytic total hydrolysis by utilizing the double catalytic action of hydrogen production and oxygen production in electrocatalysis, reduces the energy consumption of hydrogen production and oxygen production, produces renewable clean energy with low energy consumption, and has wide application prospect in the aspect of producing renewable clean energy by electrocatalysis.
The invention provides the FeSe2-Co3O4Composite material or FeSe prepared by the preparation method2-Co3O4Composite material or FeSe2-Co3O4-rGO composite material or FeSe prepared by the preparation method2-Co3O4-use of rGO composite or the above catalyst in electrocatalytic decomposition of water;
preferably, the electrocatalytic decomposition of water comprises the steps of: FeSe is reacted with2-Co3O4Composite material and FeSe2-Co3O4-any one of the rGO composite material or the catalyst is coated on an electrochemical glassy carbon electrode to serve as a working electrode, in an acidic solution, a graphite electrode is used as a counter electrode, an SCE electrode is used as a reference electrode, and under the assistance of an electric field, the voltage changes along with the current when water is decomposed by electrocatalysis in the solution to produce hydrogen; in an alkaline solution, Pt is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and the current changes with voltage when water is decomposed by electrocatalysis in the solution to generate oxygen under the assistance of an electric field.
Compared with the prior art, the invention has the following beneficial effects:
the FeSe provided by the invention2-Co3O4The composite material is prepared from cheap and easily available raw materials with low cost and FeSe2And Co3O4The active ingredients have double catalytic functions of electro-catalysis hydrogen production and oxygen production, improve the hydrogen production and oxygen production performance, and reduce the energy consumption of hydrogen production and oxygen production.
The FeSe provided by the invention2-Co3O4The rGO composite material takes rGO as a carrier, the overpotential is lower, the tafel slope is smaller, the hydrogen-producing and oxygen-producing catalytic performance is further improved, and the energy consumption for producing hydrogen and oxygen is reduced. In addition, due to the existence of iron and cobalt, the composite material has magnetism, is easy to recycle, can be repeatedly used as a catalyst, and is economic and environment-friendly.
The FeSe provided by the invention2-Co3O4The preparation method of the composite material is simple to operate, the material is cheap and easy to obtain, the manufacturing cost is low, the energy consumption is low, and no pollution is caused.
The FeSe provided by the invention2-Co3O4The preparation method of the-rGO composite material is simple to operate, the material is cheap and easy to obtain, the manufacturing cost is low, the energy consumption is low, and no pollution is caused.
The catalyst provided by the invention has excellent electro-catalytic hydrogen production and oxygen production performance under both acidic and alkaline conditions, so that electro-catalytic full electrolysis of water can be realized, renewable clean energy can be produced by using low-cost and low-consumption electric energy, the catalyst has magnetism, can be separated by using external magnetic force for recycling, and has wide application prospect in the aspect of producing clean energy.
The FeSe provided by the invention2-Co3O4Composite materials or comprising FeSe2-Co3O4Catalysts or FeSe of composite materials2-Co3O4-rGO composites or comprising FeSe2-Co3O4The catalyst of the rGO composite material has double catalytic effects of producing hydrogen and oxygen in electrocatalytic decomposition water, realizes electrocatalytic total hydrolysis, reduces energy consumption of producing hydrogen and oxygen, produces renewable clean energy with low energy consumption, and produces renewable clean energy in electrocatalytic decompositionHas wide application prospect in the aspect of clean energy.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 shows Co prepared in the first, third, fourth and ninth embodiments of the present invention3O4Nanomaterial, FeSe2Nanoparticles, FeSe2-Co3O4Composite material and FeSe2-Co3O4-XRD profile of rGO composite;
FIG. 2 shows FeSe prepared in four and nine embodiments of the present invention2-Co3O4Composite material and FeSe2-Co3O4-SEM image of rGO composite; wherein, FIG. 2(a) is FeSe2-Co3O4Composite material, FIG. 2(b) is FeSe2-Co3O4-rGO composite;
FIG. 3 shows FeSe prepared in four and nine embodiments of the present invention2-Co3O4Composite material and FeSe2-Co3O4-TEM images of rGO composite; wherein, FIG. 3(a) is FeSe2-Co3O4The composite material, FIG. 3(b) is FeSe2-Co3O4-rGO composite;
FIG. 4 shows FeSe prepared in example nine of the present invention2-Co3O4-a VSM image of rGO composite;
FIG. 5 is a comparison of lsv and tafel slopes for electrocatalytic hydrogen production in a fourteenth embodiment of the invention; wherein, FIG. 5(a) is an lsv diagram, and FIG. 5(b) is a tafel slope comparison diagram;
FIG. 6 is a lsv plot and a tafel slope comparison plot of electrocatalytic oxygen production for a fourteenth embodiment of the invention; fig. 6(a) is an lsv chart, and fig. 6(b) is a tafel slope comparison chart.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to a first aspect of the present invention, there is provided a FeSe2-Co3O4Composite material comprising FeSe2And Co3O4Said FeSe2Modified in Co3O4To obtain FeSe on the surface2-Co3O4A composite material.
Iron, one of the most abundant elements on earth, is one of the candidates for electrocatalysts for electrocatalytic oxygen evolution in alkaline electrolytes, but it is unstable in acidic electrolytes. Iron diselenide (FeSe) consisting of selenium and iron2) Has narrow band gap energy (Eg ═ 1.0eV) and good conductivity, and can be used as an effective catalyst for electrocatalytic hydrogen evolution.
Cobaltosic oxide (Co)3O4) Can be used as one of effective catalysts for electrocatalytic oxygen evolution due to the excellent performance. However, due to Co3O4Rapid corrosion in a strongly acidic environment, the widespread use of which is limited, in particular the simultaneous generation of oxygen at potentials higher than 1.47V (vs. rhe).
The FeSe provided by the invention2-Co3O4the-rGO composite material is prepared from cheap and easily-available raw materials with low cost and FeSe2And Co3O4Is effective component, has dual catalytic effects of electro-catalysis hydrogen production and oxygen production, improves hydrogen production and oxygen production performance, and reduces hydrogen production and oxygen production performanceAnd (4) consuming.
In a preferred embodiment, the FeSe is2-Co3O4FeSe in composite material2And Co3O4In a molar ratio of (5-7): (3-5), more preferably (5-6): (3-4).
Wherein, FeSe2-Co3O4FeSe in composite material2And Co3O4May be, but is not limited to, 5: 3. 5: 5. 6: 4. 7: 3 or 7: 5.
according to a second aspect of the present invention, there is provided a FeSe2-Co3O4The preparation method of the composite material comprises the following steps: dispersing trivalent ferric salt, selenium powder, reducing agent and optional surfactant in water, and adding Co3O4Obtaining FeSe through hydrothermal reaction2-Co3O4A composite material.
Ferric salts can be selected, but are not limited to, ferric sulfate (Fe)2(SO4)3) Iron nitrate (Fe (NO)3)3) Iron nitrate nonahydrate (9H)2O·Fe(NO3)3) Or ferric chloride (FeCl)3)。
The FeSe provided by the invention2-Co3O4The preparation method of the composite material is simple to operate, the material is cheap and easy to obtain, the manufacturing cost is low, the energy consumption is low, and no pollution is caused.
According to a third aspect of the present invention, there is provided a FeSe2-Co3O4-rGO composites including FeSe2、Co3O4And rGO, said FeSe2Modified in Co3O4To obtain FeSe on the surface2-Co3O4Said FeSe2-Co3O4The rGO is loaded to obtain FeSe2-Co3O4-rGO composite.
Reduced graphene oxide (rGO) is obtained by reducing Graphene Oxide (GO), and the rGO is used as a carrier, so that the transfer of electrons can be accelerated, the conductivity of the composite material is increased, and the hydrogen and oxygen production performance is improved; and the mechanical strength of the composite material can be increased, and the stability of the electrode is improved.
The FeSe provided by the invention2-Co3O4The rGO composite material takes rGO as a carrier, the overpotential is lower, the tafel slope is smaller, the hydrogen-producing and oxygen-producing catalytic performance is further improved, and the energy consumption for producing hydrogen and oxygen is reduced. In addition, due to the existence of iron and cobalt, the composite material has magnetism, is easy to recycle, can be repeatedly used as a catalyst, and is economic and environment-friendly.
In a preferred embodiment, the FeSe is2-Co3O4FeSe in-rGO composite material2And Co3O4In a molar ratio of (5-7): (3-5), more preferably (5-6): (3-4).
Wherein, FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4May be, but is not limited to, 5: 3. 5: 5. 6: 4. 7: 3 or 7: 5.
according to a fourth aspect of the present invention, there is provided a FeSe2-Co3O4-a process for the preparation of rGO composite material comprising the steps of: dispersing trivalent ferric salt, selenium powder, reducing agent and optional surfactant in water, and adding Co3O4And GO suspension is subjected to hydrothermal reaction to obtain FeSe2-Co3O4-rGO composite.
Ferric salts can be selected, but are not limited to, ferric sulfate (Fe)2(SO4)3) Iron nitrate (Fe (NO)3)3) Iron nitrate nonahydrate (9H)2O·Fe(NO3)3) Or ferric chloride (FeCl)3)。
The FeSe provided by the invention2-Co3O4The preparation method of the-rGO composite material is simple to operate, the material is cheap and easy to obtain, the manufacturing cost is low, the energy consumption is low, and no pollution is caused.
In a preferred embodiment, the reducing agent comprises at least one of hydrazine hydrate or sodium borohydride, preferably hydrazine hydrate (N)2H4·H2O)。
In a preferred embodiment, the surfactant is a cationic surfactant, preferably a quaternary ammonium salt cationic surfactant, more preferably cetyltrimethylammonium bromide (CTAB).
In a preferred embodiment, the hydrothermal reaction temperature is 140-.
The appropriate hydrothermal reaction temperature can ensure that the reaction is carried out at a safe temperature and the FeSe is ensured2And Co3O4Fully supported on rGO support.
The hydrothermal reaction temperature may be, for example, but not limited to, 140 ℃, 142 ℃, 144 ℃, 146 ℃, 148 ℃, 150 ℃, 152 ℃, 158 ℃ or 160 ℃.
In a preferred embodiment, the hydrothermal reaction time is 10 to 15 hours, preferably 11 to 14 hours, and more preferably 12 hours.
The hydrothermal reaction time may be, for example, but not limited to, 10h, 11h, 12h, 13h, 14h, or 15 h.
In a preferred embodiment, the Co3O4The preparation method comprises the following steps: adding water into divalent cobalt salt, and calcining to obtain Co3O4。
The divalent cobalt salt can be selected from, but is not limited to, cobalt nitrate (Co (NO)3)2Cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), cobalt chloride (CoCl)2) Or cobalt chloride hexahydrate (CoCl)2·6H2O) in (A). The water is deionized water.
In a preferred embodiment of the present embodiment, the calcination temperature is 300-.
The calcination temperature may be, for example, but not limited to, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃ or 500 ℃.
In a preferred embodiment of the present embodiment, the calcination time is 1 to 5 hours, more preferably 2 to 4 hours, and still more preferably 4 hours.
The calcination time may be, but is not limited to, 1h, 2h, 3h, 4h, or 5 h.
In a preferred embodiment of the present embodiment, the heating rate for calcination is 5 to 15 ℃/min, more preferably 8 to 12 ℃/min, and still more preferably 10 ℃/min.
The heating rate of calcination can be, but is not limited to, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min, 10 deg.C/min, 11 deg.C/min, 12 deg.C/min, 13 deg.C/min, 14 deg.C/min, or 15 deg.C/min.
In a preferred embodiment, the GO suspension is prepared using a modified Hummers method.
In a preferred embodiment of this embodiment, the process for the preparation of said GO suspension comprises the steps of: firstly, graphite and NaNO are mixed3And concentrated H2SO4Mixing with KMnO4And reacting with water, and aging to obtain GO suspension.
According to a fifth aspect of the present invention, there is provided a catalyst comprising the above FeSe2-Co3O4Composite material or FeSe prepared by the preparation method2-Co3O4Composite material or FeSe2-Co3O4-rGO composite material or FeSe prepared by the preparation method2-Co3O4-rGO composite.
The catalyst provided by the invention has excellent electro-catalytic hydrogen production and oxygen production performance under both acidic and alkaline conditions, so that electro-catalytic full electrolysis of water can be realized, renewable clean energy can be produced by using low-cost and low-consumption electric energy, the catalyst has magnetism, can be separated by using external magnetic force for recycling, and has wide application prospect in the aspect of producing clean energy.
According to a sixth aspect of the present invention, there is provided a FeSe2-Co3O4Composite materials or comprising FeSe2-Co3O4Catalysts or FeSe of composite materials2-Co3O4-rGO composites or comprising FeSe2-Co3O4-use of a catalyst of rGO composite for electrocatalytic decomposition of water.
The FeSe provided by the invention2-Co3O4Composite materials or comprising FeSe2-Co3O4Catalysts or FeSe of composite materials2-Co3O4-rGO composites or comprising FeSe2-Co3O4The catalyst of the rGO composite material has double catalytic effects of producing hydrogen and oxygen in electrocatalytic decomposition water, realizes electrocatalytic total hydrolysis, reduces energy consumption for producing hydrogen and oxygen, produces renewable clean energy with low energy consumption, and has wide application prospect in the aspect of producing renewable clean energy by electrocatalytic decomposition.
In a preferred embodiment, the electrocatalytic decomposition of water comprises the steps of: FeSe is reacted with2-Co3O4Composite material and FeSe2-Co3O4-any one of the rGO composite material or the catalyst is coated on an electrochemical glassy carbon electrode to serve as a working electrode, in an acidic solution, a graphite electrode is used as a counter electrode, an SCE electrode is used as a reference electrode, and under the assistance of an electric field, the voltage changes along with the current when water is decomposed by electrocatalysis in the solution to produce hydrogen; in an alkaline solution, Pt is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and the current changes with voltage when water is decomposed by electrocatalysis in the solution to generate oxygen under the assistance of an electric field.
In order to facilitate a clearer understanding of the present invention, the technical solution of the present invention will be further described below with reference to examples and comparative examples.
Example one Co3O4Preparation of nanomaterials
The present embodiment provides a Co3O4The preparation method of the nano material comprises the following steps: mixing 5g Co (NO)3)2·6H2Placing O in a crucible, adding a plurality of drops of deionized water, calcining at 400 ℃ for 4h in a muffle furnace at the heating rate of 10 ℃/min, and naturally cooling to obtain Co3O4And (3) nano materials.
The material prepared in this example was scanned by an X-ray diffractometer as shown in figure 1.
EXAMPLE preparation of a GO suspension
This example provides a GO suspension preparation method, namely the modified Hummers method, comprising the steps of: under ice-water bath conditions, 1.5g of graphite powder and 0.75g of NaNO were mixed3The powder was added to 35mL of concentrated H2SO4(98%) then 4.5g KMnO was added slowly4The powder was stirred for 2H, then the mixture was removed from the ice bath and stirred in a 35 ℃ water bath for 2H, then 69mL of deionized water was slowly added to the mixture while maintaining the temperature of the mixture below 50 ℃, then the temperature of the mixture was raised to 98 ℃ for 15min, after which 50mL of deionized water and 7.5mL of H were added2O2(30 wt%) to obtain an earthy yellow solution and aged at room temperature for 24h, finally the final product was filtered and washed several times with a mixed solution of HCl and water (1:10 v/v) and water to obtain GO, formulated as a 2mg/L GO suspension.
Example three FeSe2Preparation of nanoparticles
The embodiment provides FeSe2The preparation method of the nano-particles, namely the modified Hummers method, comprises the following steps: 0.2703g (0.001mol) FeCl3·6H2O and 0.07289g (0.0002mol) CTAB were dispersed in 30mL of water, then 0.15792g (0.002mol) selenium powder was added under magnetic stirring, followed by slow addition of 20mL of N2H4·H2O and stirring for 0.5h, then transferring the mixture into an autoclave and treating at 150 ℃ for 12h, after the reaction kettle is cooled, centrifugally separating the obtained mixture and washing the mixture with water and ethanol for a plurality of times, and drying the black precipitate at 80 ℃ for 2h to obtain FeSe2And (3) nanoparticles.
The material prepared in this example was scanned by an X-ray diffractometer as shown in figure 1.
Example four FeSe2-Co3O4Composite material and preparation method thereof
The embodiment provides FeSe2-Co3O4Composite material comprising FeSe2And Co3O4Said FeSe2Modified in Co3O4To obtain FeSe on the surface2-Co3O4，FeSe2-Co3O4FeSe in composite material2And Co3O4In a molar ratio of 5: 3.
FeSe provided in the example2-Co3O4The preparation method of the composite material comprises the following steps: (1) preparation of Co according to the method of example one3O4A nanomaterial;
(2) 0.2703g (0.001mol) FeCl3·6H2O and 0.07289g (0.0002mol) CTAB were dispersed in 30mL of water, then 0.15792g (0.002mol) Se powder was added under magnetic stirring, followed by slow addition of 20mL of N2H4·H2O and stirred for 0.5h, then 0.1426g (0.0006mol) of Co3O4Adding the powder to the mixture and stirring for 0.5h, transferring the mixture to an autoclave and treating at 150 ℃ for 12h, after the autoclave is cooled, centrifuging the obtained mixture and washing with water and ethanol for several times, and drying the black precipitate at 80 ℃ for 2h to obtain FeSe2-Co3O4A composite material.
The composite material prepared in this example was scanned by an X-ray diffractometer as shown in fig. 1.
As can be seen from FIG. 1, FeSe was found2And Co3O4The characterization shows that the prepared material is FeSe2-Co3O4A composite material.
The composite material prepared in this example was characterized by a scanning electron microscope (as shown in fig. 2 (a)) and a transmission electron microscope (as shown in fig. 3 (a)).
As can be seen from FIGS. 2(a) and 3(a), the presence of spherical particles proves that FeSe2-Co3O4The composite material is successfully prepared.
Example five FeSe2-Co3O4Composite material and preparation method thereof
The embodiment provides FeSe2-Co3O4Composite material, different from example four, FeSe2-Co3O4FeSe in composite material2And Co3O4In a molar ratio of 5: 5.
FeSe provided in the example2-Co3O4The preparation method of the composite material is different from the fourth embodiment in that the hydrothermal reaction temperature is 145 ℃, and the hydrothermal reaction time is 14 h.
Example six FeSe2-Co3O4Composite material and preparation method thereof
The embodiment provides FeSe2-Co3O4Composite material, different from example four, FeSe2-Co3O4FeSe in composite material2And Co3O4In a molar ratio of 7: 5.
FeSe provided in the example2-Co3O4The preparation method of the composite material is different from the fourth embodiment in that the hydrothermal reaction temperature is 155 ℃ and the hydrothermal reaction time is 11 h.
Example seven FeSe2-Co3O4Composite material and preparation method thereof
The embodiment provides FeSe2-Co3O4Composite material, different from example four, FeSe2-Co3O4FeSe in composite material2And Co3O4In a molar ratio of 7: 3.
FeSe provided in the example2-Co3O4The preparation method of the composite material is different from the fourth embodiment in that the hydrothermal reaction temperature is 140 ℃ and the hydrothermal reaction time is 15 h.
Example eight FeSe2-Co3O4Composite material and preparation method thereof
The embodiment provides FeSe2-Co3O4Composite material, different from example four, FeSe2-Co3O4FeSe in composite material2And Co3O4In a molar ratio of 6: 4.
FeSe provided in the example2-Co3O4The preparation method of the composite material is different from the fourth embodiment in that the hydrothermal reaction temperature is 160 ℃ and the hydrothermal reaction time is 10 hours.
Example nine FeSe2-Co3O4-rGO composite material and preparation method thereof
The embodiment provides FeSe2-Co3O4-rGO composites including FeSe2、 Co3O4And rGO, said FeSe2And Co3O4The rGO is loaded to obtain FeSe2-Co3O4-rGO，FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4In a molar ratio of 5: 3.
FeSe provided in the example2-Co3O4-a process for the preparation of rGO composite material comprising the steps of: (1) preparation of Co according to the method of example one3O4A nanomaterial;
(2) GO suspension was prepared according to the method of example two;
(3) 0.2703g (0.001mol) FeCl3·6H2O and 0.07289g (0.0002mol) CTAB were dispersed in 30mL of water, then 0.15792g (0.002mol) Se powder was added under magnetic stirring, followed by slow addition of 20mL of N2H4·H2O and stirred for 0.5h, then 0.1426g (0.0006mol) of Co3O4The powder was added to the mixture and stirred for 0.5h, after which 26.74mL GO suspension was injected into the mixture and stirred for 0.5h, after which the mixture was transferred to an autoclave and treated at 150 ℃ for 12h, after the autoclave had cooled, the resulting mixture was centrifuged and washed several times with water and ethanol, after which the black precipitate was dried at 80 ℃ for 2h to give FeSe2-Co3O4-rGO composite.
The composite material prepared in this example was scanned by an X-ray diffractometer as shown in fig. 1.
As can be seen from FIG. 1Discovery of FeSe2And Co3O4But no characteristic diffraction peak of the rGO is observed due to the lower content of the rGO and the lower diffraction intensity, and the characterization shows that the prepared material is FeSe2-Co3O4A composite material.
The composite material prepared in this example was characterized by a scanning electron microscope (as shown in fig. 2 (b)) and a transmission electron microscope (as shown in fig. 3 (b)).
As can be seen from FIGS. 2(b) and 3(b), the presence of spherical particles with rGO lamellae indicates FeSe2-Co3O4Successfully attached to the rGO lamella, and proves that the nano FeSe2-Co3O4-successful preparation of rGO composite.
The composite material prepared in this example was tested for magnetic properties by VSM and applied magnetic field, as shown in fig. 4.
As can be seen from FIG. 4, FeSe2-Co3O4The magnetic property of the-rGO composite material is strong, and the saturation magnetic property is about 19.84emu/g, so that the nano material can be separated from a liquid phase through an external magnetic field, and the catalyst can be conveniently recycled in the aspect of application.
Example Ten FeSe2-Co3O4-rGO composite material and preparation method thereof
The embodiment provides FeSe2-Co3O4-rGO composite, unlike example nine, FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4In a molar ratio of 5: 5.
FeSe provided in the example2-Co3O4The preparation method of the composite material is different from the ninth embodiment in that the hydrothermal reaction temperature is 145 ℃, and the hydrothermal reaction time is 14 h.
EXAMPLE eleven FeSe2-Co3O4-rGO composite material and preparation method thereof
The embodiment provides FeSe2-Co3O4-rGO composite, unlike example nine,FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4In a molar ratio of 7: 5.
FeSe provided in the example2-Co3O4The difference of the preparation method of the-rGO composite material from the fourth embodiment is that the hydrothermal reaction temperature is 155 ℃, and the hydrothermal reaction time is 11 h.
Example twelve FeSe2-Co3O4-rGO composite material and preparation method thereof
The embodiment provides FeSe2-Co3O4-rGO composite, unlike example nine, FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4In a molar ratio of 7: 3.
FeSe provided in the example2-Co3O4The preparation method of the-rGO composite material is different from the fourth embodiment in that the hydrothermal reaction temperature is 140 ℃ and the hydrothermal reaction time is 15 h.
Example thirteen FeSe2-Co3O4-rGO composite material and preparation method thereof
The embodiment provides FeSe2-Co3O4-rGO composite, unlike example nine, FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4In a molar ratio of 6: 4.
FeSe provided in the example2-Co3O4The preparation method of the-rGO composite material is different from the fourth embodiment in that the hydrothermal reaction temperature is 160 ℃ and the hydrothermal reaction time is 10 hours.
Example fourteen FeSe2-Co3O4Application of-rGO composite material in hydrogen production by electrocatalytic decomposition of water
(1) Glassy carbon electrodes (GCE, 3mm) were polished using 0.3 μm and 0.05 μm alumina powders, followed by continuous ultrasonic cleaning with water and ethanol.
(2) Catalyst was deposited on glassy carbon electrodes using a drop casting method: 5mg of the examplesNine FeSe prepared2-Co3O4-the rGO composite is dispersed in 485 μ L water and 485 μ L isopropanol, continuously sonicated for 20 min; then, 30. mu.L of 5 wt% Nafion solution was added to the mixture and sonicated for 30min to disperse uniformly; finally, 5 μ L of the slurry was coated onto a glassy carbon electrode and dried at room temperature for 1 h.
(3) In the hydrogen evolution reaction, a graphite electrode (GC) and a Saturated Calomel Electrode (SCE) are respectively used as a counter electrode and a reference electrode, and a working electrode is loaded with FeSe2-Co3O4Glassy carbon electrode of-rGO composite, all HER tests at 0.5MH2SO4The reaction is carried out in solution at room temperature. The lsv curve (as shown in fig. 5 (a)) and the tafel slope plot (as shown in fig. 5 (b)) were plotted.
(4) In the oxygen evolution reaction, a platinum sheet and an Hg/HgO (1M) electrode are used as a counter electrode and a reference electrode, respectively, and a working electrode is FeSe-supported2-Co3O4Glassy carbon electrodes of rGO composite, while using a 1M KOH solution as electrolyte for OER tests, at room temperature. The lsv curve (as shown in fig. 6 (a)) and the tafel slope plot (as shown in fig. 6 (b)) were plotted.
All polarization curves have no iR compensation.
Co prepared in the first example was mixed according to the above method3O4Nano material, FeSe prepared in example III2Nanoparticles and FeSe prepared in example IV2-Co3O4The composite was tested.
The results show that FeSe2-Co3O4Composite material and FeSe2-Co3O4the-rGO composite materials have electrocatalytic hydrogen production and oxygen production performance, have smaller over potential and smaller tafel slope compared with other materials, and are FeSe2-Co3O4-rGO composite material vs FeSe2-Co3O4The overpotential and tafel slope of the composite material are lower, and the electrocatalytic hydrogen production and oxygen production performance is more excellent, so that FeSe2-Co3O4-rGO heterostructure as efficient overall decompositionA catalyst for water.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (27)

1. FeSe2-Co3O4Composite material, characterized in that it comprises FeSe2And Co3O4Said FeSe2Modified in Co3O4On the surface, ferric salt, selenium powder, reducing agent and optional surfactant are dispersed in water, and then Co is added3O4Obtaining FeSe through hydrothermal reaction2-Co3O4A composite material.
2. FeSe according to claim 12-Co3O4Composite material, characterized in that the FeSe is2-Co3O4FeSe in composite material2And Co3O4In a molar ratio of (5-7): (3-5).
3. FeSe according to claim 12-Co3O4Composite material, characterized in that the FeSe is2-Co3O4FeSe in composite material2And Co3O4In a molar ratio of (5-6): (3-4).
4. Preparation of FeSe according to any of claims 1 to 32-Co3O4A method of compounding a material, comprising the steps of: dispersing trivalent ferric salt, selenium powder, reducing agent and optional surfactant in waterPost-addition of Co3O4Obtaining FeSe through hydrothermal reaction2-Co3O4A composite material;
wherein the hydrothermal reaction temperature is 140-160 ℃, and the hydrothermal reaction time is 10-15 h.
5. FeSe2-Co3O4-rGO composite material, characterized in that it comprises FeSe2、Co3O4And rGO, said FeSe2Modified in Co3O4To obtain FeSe on the surface2-Co3O4Said FeSe2-Co3O4Loaded on the rGO, dispersing trivalent ferric salt, selenium powder, a reducing agent and an optional surfactant in water, and then adding Co3O4And GO suspension is subjected to hydrothermal reaction to obtain FeSe2-Co3O4-rGO composite.
6. FeSe according to claim 52-Co3O4-rGO composite material, characterized in that said FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4In a molar ratio of (5-7): (3-5).
7. FeSe according to claim 52-Co3O4-rGO composite material, characterized in that said FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4In a molar ratio of (5-6): (3-4).
8. Preparation of FeSe as claimed in any one of claims 5 to 72-Co3O4-a method of rGO composite characterized in that it comprises the following steps: dispersing trivalent ferric salt, selenium powder, reducing agent and optional surfactant in water, and adding Co3O4And GO suspension is subjected to hydrothermal reaction to obtain FeSe2-Co3O4-rGO composite;
wherein the hydrothermal reaction temperature is 140-160 ℃, and the hydrothermal reaction time is 10-15 h.
9. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-a process for the preparation of rGO composite material, characterized in that said reducing agent comprises at least one of hydrazine hydrate or sodium borohydride;
and/or the surfactant is a cationic surfactant.
10. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-a process for the preparation of rGO composite material, characterized in that the reducing agent is hydrazine hydrate.
11. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-a method for preparing a rGO composite, characterized in that said surfactant is a quaternary ammonium salt cationic surfactant.
12. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-a process for the preparation of rGO composite material, characterized in that the surfactant is cetyltrimethylammonium bromide.
13. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4The preparation method of the-rGO composite material is characterized in that the hydrothermal reaction temperature is 145-155 ℃;
and/or the hydrothermal reaction time is 11-14 h.
14. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-a method for the preparation of rGO composite material, characterized in that the hydrothermal reaction temperature is 150 ℃.
15. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-a method for the preparation of rGO composite material, characterized in that the hydrothermal reaction time is 12 h.
16. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-rGO composite material, characterized in that said Co is a component of a composite material3O4The preparation method comprises the following steps: adding water into divalent cobalt salt, and calcining to obtain Co3O4；
The calcination temperature is 300-500 ℃; the calcination time is 1-5 h; the heating rate of the calcination is 5-15 ℃/min.
17. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-rGO composite material, characterized in that said Co is a component of a composite material3O4The preparation method comprises the following steps: adding water into divalent cobalt salt, and calcining to obtain Co3O4；
The calcination temperature is 350-450 ℃.
18. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-rGO composite material, characterized in that said Co is a component of a composite material3O4The preparation method comprises the following steps: adding water into divalent cobalt salt, and calcining to obtain Co3O4；
The calcination temperature was 400 ℃.
19. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-rGO composite material, characterized in that said Co is a component of a composite material3O4The preparation method comprises the following steps: adding water into divalent cobalt salt, and calcining to obtain Co3O4；
The calcination time is 2-4 h.
20. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-rGO composite material, characterized in that said Co is a component of a composite material3O4The preparation method comprises the following steps: adding water into divalent cobalt salt, and calcining to obtain Co3O4；
The calcination time was 4 h.
21. FeSe according to claim 42-Co3O4Method for preparing composite material or FeSe according to claim 82-Co3O4-rGO composite material, characterized in that said Co is a component of a composite material3O4The preparation method comprises the following steps: adding water into divalent cobalt salt, and calcining to obtain Co3O4；
The heating rate of the calcination is 8-12 ℃/min.
22. FeSe according to claim 42-Co3O4Method or claim for the production of a composite materialFeSe according to claim 82-Co3O4-rGO composite material, characterized in that said Co is a component of a composite material3O4The preparation method comprises the following steps: adding water into divalent cobalt salt, and calcining to obtain Co3O4；
The heating rate of the calcination is 10 ℃/min.
23. FeSe according to claim 82-Co3O4-a process for the preparation of rGO composite material, characterized in that said GO suspension is prepared by a modified Hummers method.
24. The FeSe of claim 232-Co3O4-a process for the preparation of rGO composite material, characterized in that said process for the preparation of GO suspension comprises the following steps: firstly, graphite and NaNO are mixed3And concentrated H2SO4Mixing with KMnO4And reacting with water, and aging to obtain GO suspension.
25. A catalyst comprising FeSe according to any one of claims 1 to 32-Co3O4FeSe prepared from composite material or the preparation method of any one of claims 4 and 9 to 222-Co3O4A composite material or FeSe according to any of claims 5 to 72-Co3O4-rGO composite material or FeSe prepared by the preparation method of any one of claims 8 to 242-Co3O4-rGO composite.
26. FeSe as defined in any one of claims 1 to 32-Co3O4FeSe prepared from composite material or the preparation method of any one of claims 4 and 9 to 222-Co3O4A composite material or FeSe according to any of claims 5 to 72-Co3O4-rGO composite material or FeSe prepared by the preparation method of any one of claims 8 to 242-Co3O4-use of rGO composite or catalyst of claim 25 for electrocatalytic decomposition of water.
27. The use according to claim 26, the electrocatalytic decomposition of water comprising the steps of: FeSe is reacted with2-Co3O4Composite material and FeSe2-Co3O4-any one of the rGO composite material or the catalyst is coated on an electrochemical glassy carbon electrode to serve as a working electrode, in an acidic solution, a graphite electrode is used as a counter electrode, an SCE electrode is used as a reference electrode, and under the assistance of an electric field, the voltage changes along with the current when water is decomposed by electrocatalysis in the solution to produce hydrogen; in an alkaline solution, Pt is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and the current changes with voltage when water is decomposed by electrocatalysis in the solution to generate oxygen under the assistance of an electric field.
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