CN108977827A - Include FeSe2-Co3O4Composite material and preparation method and catalyst and application - Google Patents
Include FeSe2-Co3O4Composite material and preparation method and catalyst and application Download PDFInfo
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- CN108977827A CN108977827A CN201810861039.0A CN201810861039A CN108977827A CN 108977827 A CN108977827 A CN 108977827A CN 201810861039 A CN201810861039 A CN 201810861039A CN 108977827 A CN108977827 A CN 108977827A
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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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—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
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- 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
Abstract
It include FeSe the present invention provides one kind2‑Co3O4Composite material and preparation method and catalyst and application, be related to electrocatalyst materials preparation and application field.FeSe2‑Co3O4Composite material, including FeSe2And Co3O4, the FeSe2Modification is in Co3O4FeSe is obtained on surface2‑Co3O4.FeSe provided by the invention2‑Co3O4Composite material is made by raw material cheap and easy to get, at low cost, with FeSe2And Co3O4For effective component, the dual catalytic effect that hydrogen produces oxygen is produced with electro-catalysis, production hydrogen is improved and produces oxygen performance, reduce and produce the energy consumption that hydrogen produces oxygen.
Description
Technical field
The present invention relates to electrocatalyst materials preparation and application fields, include FeSe more particularly, to one kind2-Co3O4Answer
Condensation material and preparation method and catalyst and application.
Background technique
Hydrogen is a kind of reproducible clean energy resource, has resourceful, many outstanding advantages such as easily stored.With change
The exhaustion of stone fuel and increasingly serious environmental problem, this reproducible clean energy resource of hydrogen receive more and more attention.
Electrocatalytic decomposition water is considered as a kind of attractive, sustainable method.It is split water by electrochemistry
Hydrogen and oxygen obtain the hydrogen of high-purity.In general, water decomposition reaction is related to the analysis of the oxygen evolution reaction and anode of cathode
Hydrogen reaction.But the two needs biggish overpotential due to thermodynamics, to need to consume a large amount of electric energy, so that being produced into
This is higher.Therefore efficient elctro-catalyst is developed to reduce energy consumption be very urgent.Currently, platinum-base material and iridium sill point
It is not for electrocatalytic hydrogen evolution and the electro-catalysis analysis most effective elctro-catalyst of oxygen.However, scarcity and high cost hinder them
Large-scale use.Therefore it is very urgent that exploitation, which has cost-benefit non-noble metal electro-catalysis,.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of FeSe2-Co3O4Composite material, the FeSe2-Co3O4Composite material
Raw material is cheap and easy to get, at low cost, has the dual catalytic effect that hydrogen produces oxygen that produces, and reduces and produces the energy consumption that hydrogen produces oxygen.
FeSe provided by the invention2-Co3O4Composite material, including FeSe2And Co3O4, the FeSe2Modification is in Co3O4Table
FeSe is obtained on face2-Co3O4Composite material；
Preferably, the FeSe2-Co3O4FeSe in composite material2And Co3O4Molar ratio be (5-7): (3-5), into one
Step is preferably (5-6): (3-4).
The second object of the present invention is to provide a kind of FeSe2-Co3O4The preparation method of composite material, preparation method behaviour
Make simply, material is cheap and easy to get, low manufacture cost, and energy consumption is small and pollution-free.
FeSe provided by the invention2-Co3O4The preparation method of composite material includes the following steps: trivalent iron salt, selenium
In water, Co is then added in powder, reducing agent and optional surfactant-dispersed3O4, FeSe is obtained through hydro-thermal reaction2-Co3O4It is multiple
Condensation material.
The third object of the present invention is to provide a kind of FeSe2-Co3O4- rGO composite material, the FeSe2-Co3O4- rGO is multiple
The raw material of condensation material is cheap and easy to get, at low cost, has the dual catalytic effect that hydrogen produces oxygen that produces, and reduces and produces the energy consumption that hydrogen produces oxygen.
FeSe provided by the invention2-Co3O4- rGO composite material, including FeSe2、Co3O4And rGO, the FeSe2Modification
In Co3O4FeSe is obtained on surface2-Co3O4, the FeSe2-Co3O4It is supported on the rGO and obtains FeSe2-Co3O4- rGO is multiple
Condensation material；
Preferably, the FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4Molar ratio be (5-7): (3-5),
Further preferably (5-6): (3-4).
The fourth object of the present invention is to provide a kind of FeSe2-Co3O4The preparation method of-rGO composite material, the preparation side
Method is easy to operate, and material is cheap and easy to get, low manufacture cost, and energy consumption is small and pollution-free.
FeSe provided by the invention2-Co3O4The preparation method of-rGO composite material includes the following steps: ferric iron
In water, Co is then added in salt, selenium powder, reducing agent and optional surfactant-dispersed3O4With GO suspension, through hydro-thermal reaction
Obtain FeSe2-Co3O4- rGO composite material.
Further, the reducing agent includes at least one of hydrazine hydrate or sodium borohydride, preferably hydrazine hydrate；
And/or the surfactant is cationic surfactant, preferably quaternary cationics,
Further preferably cetyl trimethylammonium bromide.
Further, the hydrothermal temperature is 140-160 DEG C, preferably 145-155 DEG C, further preferably 150
℃；
And/or the hydro-thermal reaction time is 10-15h, preferably 11-14h, further preferably 12h.
Further, the Co3O4Preparation method include the following steps: that water is added into divalent cobalt, through calcining obtain
Co3O4；
Preferably, the calcination temperature be 300-500 DEG C, further preferably 350-450 DEG C, still more preferably for
400℃；And/or the calcination time is 1-5h, further preferably 2-4h, is still more preferably 4h；And/or it described forges
Burning heating rate is 5-15 DEG C/min, and further preferably 8-12 DEG C/min, be still more preferably 10 DEG C/min.
Further, the GO suspension is using modified Hummers method preparation；
Preferably, the preparation method of the GO suspension includes the following steps: graphite, NaNO first3With dense H2SO4Mixing,
Again successively with KMnO4It is reacted with water, obtains GO suspension through aging.
The fifth object of the present invention is that providing a kind of includes FeSe2-Co3O4Composite material or FeSe2-Co3O4- rGO is multiple
The catalyst of condensation material, the catalyst all have outstanding electro-catalysis under acid and alkaline condition and produce hydrogen production oxygen performance, thus
It can be realized the full electrolysis water of electro-catalysis, using the reproducible clean energy resource of the lower electrical energy production of lower cost consumption, and
The catalysis has magnetism, can use additional magnetic force and carries out separation to it for recycling and reusing, in terms of producing clean energy resource
It has broad application prospects.
Catalyst provided by the invention includes above-mentioned FeSe2-Co3O4What composite material or above-mentioned preparation method were prepared
FeSe2-Co3O4Composite material or above-mentioned FeSe2-Co3O4The FeSe that-rGO composite material or above-mentioned preparation method are prepared2-
Co3O4- rGO composite material.
The sixth object of the present invention is to provide a kind of FeSe2-Co3O4Composite material or including FeSe2-Co3O4Composite wood
The catalyst or FeSe of material2-Co3O4- rGO composite material or including FeSe2-Co3O4The catalyst of-rGO composite material is urged in electricity
Change the application decomposed in water, is acted in electro-catalysis using the dual catalytic for producing hydrogen production oxygen, realize electro-catalysis all-hydrolytic, reduce and produce
Hydrogen produces oxygen energy consumption, produces reproducible clean energy resource with low energy consumption, has in terms of electro-catalysis produces reproducible clean energy resource
Wide application prospect.
Above-mentioned FeSe provided by the invention2-Co3O4The FeSe that composite material or above-mentioned preparation method are prepared2-Co3O4
Composite material or above-mentioned FeSe2-Co3O4The FeSe that-rGO composite material or above-mentioned preparation method are prepared2-Co3O4- rGO is multiple
The application of condensation material or above-mentioned catalyst in electrocatalytic decomposition water；
Preferably, the electrocatalytic decomposition water includes the following steps: FeSe2-Co3O4Composite material, FeSe2-Co3O4-
Any one in rGO composite material or catalyst is coated in as working electrode on electrochemistry glass-carbon electrode, in acid solution
In, it is to electrode with graphite electrode, SCE electrode is reference electrode, under electric field-assisted, tests electrocatalytic decomposition aquatic products in solution
When hydrogen voltage with electric current variation；It is to electrode with Pt, Hg/HgO electrode is reference electrode, auxiliary in electric field in alkaline solution
Help down, test solution in electrocatalytic decomposition aquatic products oxygen when electric current with voltage variation.
Compared with prior art, the invention has the following advantages:
FeSe provided by the invention2-Co3O4Composite material is made by raw material cheap and easy to get, at low cost, with FeSe2With
Co3O4For effective component, the dual catalytic effect that hydrogen produces oxygen is produced with electro-catalysis, raising produces hydrogen and produces oxygen performance, reduces and produces hydrogen production oxygen
Energy consumption.
FeSe provided by the invention2-Co3O4For-rGO composite material using rGO as carrier, overpotential is lower, Tafel slope
It is smaller, it further increases and produces hydrogen production oxygen catalytic performance, reduce and produce the energy consumption that hydrogen produces oxygen.In addition, this is multiple due to the presence of iron and cobalt
Condensation material has magnetism, is easily recycled, reusable as catalyst, economic and environment-friendly.
FeSe provided by the invention2-Co3O4The preparation method of composite material is easy to operate, and material is cheap and easy to get, is fabricated to
This is low, and energy consumption is small and pollution-free.
FeSe provided by the invention2-Co3O4The preparation method of-rGO composite material is easy to operate, and material is cheap and easy to get, system
Make at low cost, energy consumption is small and pollution-free.
Catalyst provided by the invention all has outstanding electro-catalysis under acid and alkaline condition and produces hydrogen production oxygen performance, from
And can be realized the full electrolysis water of electro-catalysis, using the reproducible clean energy resource of the lower electrical energy production of lower cost consumption, and
And the catalysis has magnetism, can use additional magnetic force and carries out separation to it for recycling and reusing, in production clean energy resource side
Mask has broad application prospects.
FeSe provided by the invention2-Co3O4Composite material or including FeSe2-Co3O4The catalyst of composite material or
FeSe2-Co3O4- rGO composite material or including FeSe2-Co3O4The catalyst of-rGO composite material has in electrocatalytic decomposition water
There is the dual catalytic effect that hydrogen produces oxygen that produces, realize electro-catalysis all-hydrolytic, reduction produces hydrogen and produces oxygen energy consumption, is produced with low energy consumption renewable
Clean energy resource, have broad application prospects in terms of electro-catalysis produces reproducible clean energy resource.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the Co that the embodiment of the present invention one, three, four and nine is prepared respectively3O4Nano material, FeSe2Nanometer
Grain, FeSe2-Co3O4Composite material and FeSe2-Co3O4The XRD curve of-rGO composite material；
Fig. 2 is the FeSe that the embodiment of the present invention four and nine is prepared respectively2-Co3O4Composite material and FeSe2-Co3O4-
The SEM image of rGO composite material；Wherein, Fig. 2 (a) is FeSe2-Co3O4Composite material, Fig. 2 (b) are FeSe2-Co3O4- rGO is multiple
Condensation material；
Fig. 3 is the FeSe that the embodiment of the present invention four and nine is prepared respectively2-Co3O4Composite material and FeSe2-Co3O4-
The TEM image of rGO composite material；Wherein, Fig. 3 (a) is FeSe2-Co3O4Composite material, Fig. 3 (b) are FeSe2-Co3O4- rGO is multiple
Condensation material；
Fig. 4 is the FeSe that the embodiment of the present invention nine is prepared2-Co3O4The VSM image of-rGO composite material；
Fig. 5 is that the electro-catalysis of the embodiment of the present invention 14 produces the lsv figure and tafel slope comparison diagram of hydrogen；Wherein, Fig. 5 (a)
For lsv figure, Fig. 5 (b) is tafel slope comparison diagram；
Fig. 6 is that the electro-catalysis of the embodiment of the present invention 14 produces the lsv figure and tafel slope comparison diagram of oxygen；Wherein, Fig. 6 (a)
It is tafel slope comparison diagram for lsv figure, 6 (b).
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument are not
Production firm person is indicated, is the conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, the present invention provides a kind of FeSe2-Co3O4Composite material, including FeSe2With
Co3O4, the FeSe2Modification is in Co3O4FeSe is obtained on surface2-Co3O4Composite material.
Iron is the candidate elctro-catalyst of electro-catalysis analysis oxygen in alkaline electrolyte as one of element the most abundant on the earth
One of, but it is unstable in acidic electrolyte bath.Two ferrous selenide (FeSe being made of selenium and iron2) there is narrow band-gap energy
(Eg=1.0eV) and good electric conductivity, it can be used as the effective catalyst of electrocatalytic hydrogen evolution.
Cobaltosic oxide (Co3O4) due to its outstanding performance can be used as electro-catalysis analysis oxygen one of effective catalyst.So
And due to Co3O4Fast erosion in strong acidic environment, is widely used and is restricted, and is especially being higher than 1.47V
(vs.RHE) oxygen is generated under potential simultaneously.
FeSe provided by the invention2-Co3O4- rGO composite material is made by raw material cheap and easy to get, at low cost, with FeSe2
And Co3O4For effective component, the dual catalytic effect that hydrogen produces oxygen is produced with electro-catalysis, raising produces hydrogen and produces oxygen performance, reduces and produces hydrogen production
The energy consumption of oxygen.
In one preferred embodiment, the FeSe2-Co3O4FeSe in composite material2And Co3O4Molar ratio be
(5-7): (3-5), further preferably (5-6): (3-4).
Wherein, FeSe2-Co3O4FeSe in composite material2And Co3O4Molar ratio such as can be, but be not limited to 5:3,
5:5,6:4,7:3 or 7:5.
According to the second aspect of the invention, the present invention provides a kind of FeSe2-Co3O4The preparation method of composite material,
Include the following steps: trivalent iron salt, selenium powder, reducing agent and optional surfactant-dispersed in water, Co to be then added3O4,
FeSe is obtained through hydro-thermal reaction2-Co3O4Composite material.
Trivalent iron salt can be selected, but be not limited to ferric sulfate (Fe2(SO4)3), ferric nitrate (Fe (NO3)3), nine nitric hydrates
Iron (9H2O·Fe(NO3)3) or iron chloride (FeCl3)。
FeSe provided by the invention2-Co3O4The preparation method of composite material is easy to operate, and material is cheap and easy to get, is fabricated to
This is low, and energy consumption is small and pollution-free.
According to the third aspect of the present invention, the present invention provides a kind of FeSe2-Co3O4- rGO composite material, including
FeSe2、Co3O4And rGO, the FeSe2Modification is in Co3O4FeSe is obtained on surface2-Co3O4, the FeSe2-Co3O4It is supported on
FeSe is obtained on the rGO2-Co3O4- rGO composite material.
Redox graphene (rGO) is obtained through graphene oxide (GO) reduction, using rGO as carrier, can speed up electricity
The transmitting of son increases the electric conductivity of composite material, and then improves and produce hydrogen production oxygen performance；The machinery that composite material can also be increased is strong
Degree, improves the stability of electrode.
FeSe provided by the invention2-Co3O4For-rGO composite material using rGO as carrier, overpotential is lower, Tafel slope
It is smaller, it further increases and produces hydrogen production oxygen catalytic performance, reduce and produce the energy consumption that hydrogen produces oxygen.In addition, this is multiple due to the presence of iron and cobalt
Condensation material has magnetism, is easily recycled, reusable as catalyst, economic and environment-friendly.
In one preferred embodiment, the FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4Mole
Than for (5-7): (3-5), further preferably (5-6): (3-4).
Wherein, FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4Molar ratio such as can be but to be not limited to
5:3,5:5,6:4,7:3 or 7:5.
According to the fourth aspect of the present invention, the present invention provides a kind of FeSe2-Co3O4The preparation side of-rGO composite material
Method includes the following steps: trivalent iron salt, selenium powder, reducing agent and optional surfactant-dispersed in water, to be then added
Co3O4With GO suspension, FeSe is obtained through hydro-thermal reaction2-Co3O4- rGO composite material.
Trivalent iron salt can be selected, but be not limited to ferric sulfate (Fe2(SO4)3), ferric nitrate (Fe (NO3)3), nine nitric hydrates
Iron (9H2O·Fe(NO3)3) or iron chloride (FeCl3)。
FeSe provided by the invention2-Co3O4The preparation method of-rGO composite material is easy to operate, and material is cheap and easy to get, system
Make at low cost, energy consumption is small and pollution-free.
In one preferred embodiment, the reducing agent includes at least one of hydrazine hydrate or sodium borohydride, excellent
It is selected as hydrazine hydrate (N2H4·H2O)。
In one preferred embodiment, the surfactant is cationic surfactant, preferably quaternary ammonium salt
Cationic surfactant, further preferably cetyl trimethylammonium bromide (CTAB).
In one preferred embodiment, the hydrothermal temperature be 140-160 DEG C, preferably 145-155 DEG C, into
One step is preferably 150 DEG C.
Suitable hydrothermal temperature should can ensure to react safety at a temperature of carry out, enough guarantee FeSe again2
And Co3O4It is sufficiently supported on rGO carrier.
Wherein, hydrothermal temperature for example can be, but be not limited to 140 DEG C, 142 DEG C, 144 DEG C, 146 DEG C, 148 DEG C, 150
DEG C, 152 DEG C, 158 DEG C or 160 DEG C.
In one preferred embodiment, the hydro-thermal reaction time be 10-15h, preferably 11-14h, further it is excellent
It is selected as 12h.
Wherein, the hydro-thermal reaction time for example can be, but be not limited to 10h, 11h, 12h, 13h, 14h or 15h.
In one preferred embodiment, the Co3O4Preparation method include the following steps: into divalent cobalt plus
Enter water, obtains Co through calcining3O4。
Divalent cobalt can be selected, but be not limited to cobalt nitrate (Co (NO3)2, cabaltous nitrate hexahydrate (Co (NO3)2·6H2O)、
Cobalt chloride (CoCl2) or cobalt chloride hexahydrate (CoCl2·6H2O in).Water is deionized water.
In a preferred embodiment of present embodiment, the calcination temperature is 300-500 DEG C, further preferably
350-450 DEG C, be still more preferably 400 DEG C.
Wherein, calcination temperature for example can be, but be not limited to 300 DEG C, 320 DEG C, 340 DEG C, 360 DEG C, 380 DEG C, 400 DEG C,
420 DEG C, 440 DEG C, 460 DEG C, 480 DEG C or 500 DEG C.
In a preferred embodiment of present embodiment, the calcination time be 1-5h, further preferably 2-4h,
It is still more preferably 4h.
Wherein, calcination time for example can be, but be not limited to 1h, 2h, 3h, 4h or 5h.
In a preferred embodiment of present embodiment, the calcining heating rate is 5-15 DEG C/min, further
Preferably 8-12 DEG C/min, be still more preferably 10 DEG C/min.
Wherein, calcining heating rate for example can be, but be 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 one preferred embodiment, the GO suspension is using modified Hummers method preparation.
In a preferred embodiment of present embodiment, the preparation method of the GO suspension includes the following steps:
First by graphite, NaNO3With dense H2SO4Mixing, then successively with KMnO4It is reacted with water, obtains GO suspension through aging.
According to the fifth aspect of the present invention, the present invention provides a kind of catalyst, including above-mentioned FeSe2-Co3O4It is compound
The FeSe that material or above-mentioned preparation method are prepared2-Co3O4Composite material or above-mentioned FeSe2-Co3O4- rGO composite material or
The FeSe that above-mentioned preparation method is prepared2-Co3O4- rGO composite material.
Catalyst provided by the invention all has outstanding electro-catalysis under acid and alkaline condition and produces hydrogen production oxygen performance, from
And can be realized the full electrolysis water of electro-catalysis, using the reproducible clean energy resource of the lower electrical energy production of lower cost consumption, and
And the catalysis has magnetism, can use additional magnetic force and carries out separation to it for recycling and reusing, in production clean energy resource side
Mask has broad application prospects.
According to the sixth aspect of the invention, the present invention provides a kind of FeSe2-Co3O4Composite material or including FeSe2-
Co3O4The catalyst or FeSe of composite material2-Co3O4- rGO composite material or including FeSe2-Co3O4- rGO composite material is urged
Application of the agent in electrocatalytic decomposition water.
FeSe provided by the invention2-Co3O4Composite material or including FeSe2-Co3O4The catalyst of composite material or
FeSe2-Co3O4- rGO composite material or including FeSe2-Co3O4The catalyst of-rGO composite material has in electrocatalytic decomposition water
There is the dual catalytic effect that hydrogen produces oxygen that produces, realize electro-catalysis all-hydrolytic, reduction produces hydrogen and produces oxygen energy consumption, is produced with low energy consumption renewable
Clean energy resource, have broad application prospects in terms of electro-catalysis produces reproducible clean energy resource.
In one preferred embodiment, the electrocatalytic decomposition water includes the following steps: FeSe2-Co3O4It is compound
Material, FeSe2-Co3O4Any one in-rGO composite material or catalyst is coated on electrochemistry glass-carbon electrode as work
Electrode is in an acidic solution to electrode with graphite electrode, and SCE electrode is reference electrode, under electric field-assisted, tests solution
When middle electrocatalytic decomposition aquatic products hydrogen voltage with electric current variation；It is to electrode with Pt, Hg/HgO electrode is ginseng in alkaline solution
Than electrode, under electric field-assisted, test solution in electrocatalytic decomposition aquatic products oxygen when electric current with voltage variation.
In order to facilitate the clearer understanding present invention, below in conjunction with embodiment and comparative example to technical side of the invention
Case is described further.
One Co of embodiment3O4The preparation of nano material
Present embodiments provide a kind of Co3O4The preparation method of nano material includes the following steps: 5g Co (NO3)2·
6H2O is placed in crucible, and few drops of deionized waters are added, and is then calcined with the heating rate of 10 DEG C/min at 400 DEG C in Muffle furnace
4h after natural cooling, obtains Co3O4Nano material.
The material that the present embodiment is prepared is scanned through x-ray diffractometer, as shown in Figure 1.
The preparation of two GO suspension of embodiment
A kind of preparation method of GO suspension is present embodiments provided, i.e., improved Hummers method includes the following steps:
Under the conditions of ice-water bath, by 1.5g powdered graphite and 0.75g NaNO3Powder is added to the dense H of 35mL2SO4(98%) in, then delay
It is slow that 4.5g KMnO is added4Powder stirs 2h, then takes out mixture from ice bath, and in 35 DEG C of stirred in water bath 2h, so
69mL deionized water is slowly added into mixture afterwards, while keeping the temperature of mixture lower than 50 DEG C, then by mixture
Temperature rise to 98 DEG C of holding 15min, 50mL deionized water and 7.5mL H are added later2O2(30wt%) is molten to obtain khaki
Liquid, and aging for 24 hours, finally filters final product at room temperature, is rinsed with the mixed solution (1:10v/v) and water of HCl and water
For several times to obtain GO, it is configured to the GO suspension of 2mg/L.
Three FeSe of embodiment2The preparation of nano particle
Present embodiments provide a kind of FeSe2The preparation method of nano particle, i.e., improved Hummers method, including it is as follows
Step: by 0.2703g (0.001mol) FeCl3·6H2O and 0.07289g (0.0002mol) CTAB are dispersed in 30mL water, so
0.15792g (0.002mol) selenium powder is added under magnetic stirring afterwards, is slowly added to 20mL N later2H4·H2O simultaneously stirs 0.5h,
Mixture is transferred in autoclave later and handles 12h at 150 DEG C, after reaction kettle is cooling, gained mixture is centrifuged
Separate and use water and ethanol washing for several times after, black precipitate dry 2h at 80 DEG C obtains FeSe2Nano particle.
The material that the present embodiment is prepared is scanned through x-ray diffractometer, as shown in Figure 1.
Example IV FeSe2-Co3O4Composite material and preparation method
Present embodiments provide a kind of FeSe2-Co3O4Composite material, including FeSe2And Co3O4, the FeSe2Modification exists
Co3O4FeSe is obtained on surface2-Co3O4, FeSe2-Co3O4FeSe in composite material2And Co3O4Molar ratio be 5:3.
FeSe provided in this embodiment2-Co3O4The preparation method of composite material includes the following steps: (1) according to embodiment
One method prepares Co3O4Nano material；
(2) by 0.2703g (0.001mol) FeCl3·6H2O and 0.07289g (0.0002mol) CTAB are dispersed in 30mL water
In, 0.15792g (0.002mol) Se powder is then added under magnetic stirring, is slowly added to 20mL N later2H4·H2O is simultaneously stirred
0.5h, then by 0.1426g (0.0006mol) Co3O4Powder is added in mixture and stirs 0.5h, later turns mixture
It moves on in autoclave and handles 12h at 150 DEG C, after reaction kettle is cooling, gained mixture is centrifugated and uses water and second
After alcohol washing for several times, black precipitate dry 2h at 80 DEG C obtains FeSe2-Co3O4Composite material.
The composite material that the present embodiment is prepared is scanned through x-ray diffractometer, as shown in Figure 1.
It will be seen from figure 1 that discovery FeSe2And Co3O4Characteristic diffraction peak, the characterization show preparation material be
FeSe2-Co3O4Composite material.
The composite material that the present embodiment is prepared is scanned Electronic Speculum characterization (shown in such as Fig. 2 (a)) and transmitted electron
Microscopic characterization (shown in such as Fig. 3 (a)).
From Fig. 2 (a) and 3 (a) as can be seen that there are spherical particles, it was demonstrated that FeSe2-Co3O4Composite material is successfully prepared.
Five FeSe of embodiment2-Co3O4Composite material and preparation method
Present embodiments provide a kind of FeSe2-Co3O4Composite material, unlike example IV, FeSe2-Co3O4It is multiple
FeSe in condensation material2And Co3O4Molar ratio be 5:5.
FeSe provided in this embodiment2-Co3O4The preparation method of composite material, the hydro-thermal reaction unlike example IV
Temperature is 145 DEG C, the hydro-thermal reaction time 14h.
Six FeSe of embodiment2-Co3O4Composite material and preparation method
Present embodiments provide a kind of FeSe2-Co3O4Composite material, unlike example IV, FeSe2-Co3O4It is multiple
FeSe in condensation material2And Co3O4Molar ratio be 7:5.
FeSe provided in this embodiment2-Co3O4The preparation method of composite material, the hydro-thermal reaction unlike example IV
Temperature is 155 DEG C, the hydro-thermal reaction time 11h.
Seven FeSe of embodiment2-Co3O4Composite material and preparation method
Present embodiments provide a kind of FeSe2-Co3O4Composite material, unlike example IV, FeSe2-Co3O4It is multiple
FeSe in condensation material2And Co3O4Molar ratio be 7:3.
FeSe provided in this embodiment2-Co3O4The preparation method of composite material, the hydro-thermal reaction unlike example IV
Temperature is 140 DEG C, the hydro-thermal reaction time 15h.
Eight FeSe of embodiment2-Co3O4Composite material and preparation method
Present embodiments provide a kind of FeSe2-Co3O4Composite material, unlike example IV, FeSe2-Co3O4It is multiple
FeSe in condensation material2And Co3O4Molar ratio be 6:4.
FeSe provided in this embodiment2-Co3O4The preparation method of composite material, the hydro-thermal reaction unlike example IV
Temperature is 160 DEG C, the hydro-thermal reaction time 10h.
Nine FeSe of embodiment2-Co3O4- rGO composite material and preparation method
Present embodiments provide a kind of FeSe2-Co3O4- rGO composite material, including FeSe2、Co3O4And rGO, it is described
FeSe2And Co3O4It is supported on the rGO and obtains FeSe2-Co3O4- rGO, FeSe2-Co3O4FeSe in-rGO composite material2With
Co3O4Molar ratio be 5:3.
FeSe provided in this embodiment2-Co3O4The preparation method of-rGO composite material includes the following steps: (1) according to reality
Apply the method preparation Co of example one3O4Nano material；
(2) GO suspension is prepared according to the method for embodiment two；
(3) by 0.2703g (0.001mol) FeCl3·6H2O and 0.07289g (0.0002mol) CTAB are dispersed in 30mL water
In, 0.15792g (0.002mol) Se powder is then added under magnetic stirring, is slowly added to 20mL N later2H4·H2O is simultaneously stirred
0.5h, then by 0.1426g (0.0006mol) Co3O4Powder is added in mixture and stirs 0.5h, backward mixture in
Injection 26.74mL GO suspension simultaneously stirs 0.5h, mixture is transferred in autoclave later and handles 12h at 150 DEG C,
After reaction kettle is cooling, by gained mixture be centrifugated and use water and ethanol washing for several times after, black precipitate is at 80 DEG C
Dry 2h obtains FeSe2-Co3O4- rGO composite material.
The composite material that the present embodiment is prepared is scanned through x-ray diffractometer, as shown in Figure 1.
It will be seen from figure 1 that discovery FeSe2And Co3O4Characteristic diffraction peak, but since the content of rGO is less, in addition
Lower diffracted intensity does not observe the characteristic diffraction peak of rGO, which shows that the material of preparation is FeSe2-Co3O4Composite wood
Material.
The composite material that the present embodiment is prepared is scanned Electronic Speculum characterization (shown in such as Fig. 2 (b)) and transmitted electron
Microscopic characterization (shown in such as Fig. 3 (b)).
From Fig. 2 (b) and 3 (b) as can be seen that there are spherical particle and rGO lamella, show FeSe2-Co3O4Successfully adhere to
On rGO lamella, it was demonstrated that nanometer Fe Se2-Co3O4- rGO composite material is successfully prepared.
The composite material that the present embodiment is prepared is characterized into magnetism through VSM and externally-applied magnetic field test, as shown in Figure 4.
From fig. 4, it can be seen that FeSe2-Co3O4The magnetism of-rGO composite material is stronger, and saturation magnetization is about 19.84emu/
G, therefore can be separated nano material from liquid phase by externally-applied magnetic field, it is sharp again convenient for the recycling of catalyst in application aspect
With.
Ten FeSe of embodiment2-Co3O4- rGO composite material and preparation method
Present embodiments provide a kind of FeSe2-Co3O4- rGO composite material, unlike embodiment nine, FeSe2-
Co3O4FeSe in-rGO composite material2And Co3O4Molar ratio be 5:5.
FeSe provided in this embodiment2-Co3O4The preparation method of composite material, the hydro-thermal reaction unlike embodiment nine
Temperature is 145 DEG C, the hydro-thermal reaction time 14h.
11 FeSe of embodiment2-Co3O4- rGO composite material and preparation method
Present embodiments provide a kind of FeSe2-Co3O4- rGO composite material, unlike embodiment nine, FeSe2-
Co3O4FeSe in-rGO composite material2And Co3O4Molar ratio be 7:5.
FeSe provided in this embodiment2-Co3O4The preparation method of-rGO composite material, the hydro-thermal unlike example IV
Reaction temperature is 155 DEG C, the hydro-thermal reaction time 11h.
12 FeSe of embodiment2-Co3O4- rGO composite material and preparation method
Present embodiments provide a kind of FeSe2-Co3O4- rGO composite material, unlike embodiment nine, FeSe2-
Co3O4FeSe in-rGO composite material2And Co3O4Molar ratio be 7:3.
FeSe provided in this embodiment2-Co3O4The preparation method of-rGO composite material, the hydro-thermal unlike example IV
Reaction temperature is 140 DEG C, the hydro-thermal reaction time 15h.
13 FeSe of embodiment2-Co3O4- rGO composite material and preparation method
Present embodiments provide a kind of FeSe2-Co3O4- rGO composite material, unlike embodiment nine, FeSe2-
Co3O4FeSe in-rGO composite material2And Co3O4Molar ratio be 6:4.
FeSe provided in this embodiment2-Co3O4The preparation method of-rGO composite material, the hydro-thermal unlike example IV
Reaction temperature is 160 DEG C, the hydro-thermal reaction time 10h.
14 FeSe of embodiment2-Co3O4The application of-rGO composite material electrocatalytic decomposition aquatic products hydrogen production oxygen
(1) glass-carbon electrode (GCE, 3mm) is polished using 0.3 μm and 0.05 μm of alumina powder, then uses water and ethyl alcohol
Carry out continuous ultrasonic cleaning.
(2) use droplet casting method by catalyst deposit on glass-carbon electrode: the FeSe that 5mg embodiment nine is prepared2-
Co3O4- rGO composite material is dispersed in 485 μ L water and 485 μ L isopropanols, continuous ultrasound 20min；Later, by the 5wt% of 30 μ L
Nafion solution, which is added in mixture, is ultrasonically treated 30min to evenly dispersed；Finally, 5 μ L slurries are coated to glass-carbon electrode
Above and at room temperature dry 1h.
(3) in evolving hydrogen reaction, use graphite electrode (GC) and saturated calomel electrode (SCE) as to electrode and ginseng respectively
Than electrode, working electrode is that load has FeSe2-Co3O4The glass-carbon electrode of-rGO composite material, all HER tests are in 0.5M
H2SO4It is carried out in solution, temperature is room temperature.Lsv curve (as shown in Fig. 5 (a)) and tafel slope figure are drawn (such as Fig. 5 (b) institute
Show).
(4) in oxygen evolution reaction, use platinized platinum and Hg/HgO (1M) electrode as to electrode and reference electrode, work respectively
Electrode is that load has FeSe2-Co3O4The glass-carbon electrode of-rGO composite material, meanwhile, use 1M KOH solution as progress OER survey
The electrolyte of examination, temperature are room temperature.Draw lsv curve (shown in such as Fig. 6 (a)) and tafel slope figure (shown in such as Fig. 6 (b)).
All polarization curves are all compensated without iR.
The Co that embodiment one is prepared respectively according to the method described above3O4Nano material, embodiment three are prepared
FeSe2The FeSe that nano particle and example IV are prepared2-Co3O4Composite material is tested.
The result shows that FeSe2-Co3O4Composite material and FeSe2-Co3O4- rGO composite material all has electro-catalysis and produces hydrogen production
Oxygen performance has lesser overpotential and lesser tafel slope, and FeSe compared to other materials2-Co3O4- rGO composite wood
Material is compared with FeSe2-Co3O4The overpotential and tafel slope of composite material are lower, and electro-catalysis production hydrogen production oxygen performance is more excellent, therefore
FeSe2-Co3O4- rGO heterojunction structure can be used as the efficient overall catalyst for decomposing water.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of FeSe2-Co3O4Composite material, which is characterized in that including FeSe2And Co3O4, the FeSe2Modification is in Co3O4Table
FeSe is obtained on face2-Co3O4Composite material；
Preferably, the FeSe2-Co3O4FeSe in composite material2And Co3O4Molar ratio be (5-7): (3-5), further it is excellent
It is selected as (5-6): (3-4).
2. a kind of prepare FeSe described in claim 12-Co3O4The method of composite material, which is characterized in that including walking as follows
It is rapid: in water by trivalent iron salt, selenium powder, reducing agent and optional surfactant-dispersed, Co to be then added3O4, through hydro-thermal reaction
Obtain FeSe2-Co3O4Composite material.
3. a kind of FeSe2-Co3O4- rGO composite material, which is characterized in that including FeSe2、Co3O4And rGO, the FeSe2Modification
In Co3O4FeSe is obtained on surface2-Co3O4, the FeSe2-Co3O4It is supported on the rGO and obtains FeSe2-Co3O4- rGO is multiple
Condensation material；
Preferably, the FeSe2-Co3O4FeSe in-rGO composite material2And Co3O4Molar ratio be (5-7): (3-5), into one
Step is preferably (5-6): (3-4).
4. a kind of prepare FeSe as claimed in claim 32-Co3O4The method of-rGO composite material, which is characterized in that including as follows
Step: in water by trivalent iron salt, selenium powder, reducing agent and optional surfactant-dispersed, Co is then added3O4It suspends with GO
Liquid obtains FeSe through hydro-thermal reaction2-Co3O4- rGO composite material.
5. FeSe according to claim 22-Co3O4The preparation method of composite material or FeSe as claimed in claim 42-
Co3O4The preparation method of-rGO composite material, which is characterized in that the reducing agent include in hydrazine hydrate or sodium borohydride at least
One kind, preferably hydrazine hydrate；
And/or the surfactant is cationic surfactant, preferably quaternary cationics, into one
Step is preferably cetyl trimethylammonium bromide.
6. FeSe according to claim 22-Co3O4The preparation method of composite material or FeSe as claimed in claim 42-
Co3O4The preparation method of-rGO composite material, which is characterized in that the hydrothermal temperature is 140-160 DEG C, preferably 145-
155 DEG C, further preferably 150 DEG C；
And/or the hydro-thermal reaction time is 10-15h, preferably 11-14h, further preferably 12h.
7. FeSe according to claim 22-Co3O4The preparation method of composite material or FeSe as claimed in claim 42-
Co3O4The preparation method of-rGO composite material, which is characterized in that the Co3O4Preparation method include the following steps: to divalent
Water is added in cobalt salt, obtains Co through calcining3O4；
Preferably, the calcination temperature is 300-500 DEG C, and further preferably 350-450 DEG C, be still more preferably 400 DEG C；
And/or the calcination time is 1-5h, further preferably 2-4h, is still more preferably 4h；And/or the calcining heating
Rate is 5-15 DEG C/min, and further preferably 8-12 DEG C/min, be still more preferably 10 DEG C/min.
8. FeSe according to claim 22-Co3O4The preparation method of composite material or FeSe as claimed in claim 42-
Co3O4The preparation method of-rGO composite material, which is characterized in that the GO suspension is using modified Hummers method preparation；
Preferably, the preparation method of the GO suspension includes the following steps: graphite, NaNO first3With dense H2SO4Mixing, then according to
Secondary and KMnO4It is reacted with water, obtains GO suspension through aging.
9. a kind of catalyst, which is characterized in that including FeSe described in claim 12-Co3O4Composite material or claim 2,
5, the FeSe that 6,7,8 described in any item preparation methods are prepared2-Co3O4Composite material is as claimed in claim 3
FeSe2-Co3O4The FeSe that-rGO composite material or the described in any item preparation methods of claim 4-8 are prepared2-Co3O4-
RGO composite material.
10. one kind is by FeSe described in claim 12-Co3O4Described in composite material or claim 2,5,6,7 or 8 any one
The FeSe that is prepared of preparation method2-Co3O4Composite material or FeSe as claimed in claim 32-Co3O4- rGO composite material
Or the FeSe that the described in any item preparation methods of claim 4-8 are prepared2-Co3O4- rGO composite material or claim 9
Application of the catalyst in electrocatalytic decomposition water；
Preferably, the electrocatalytic decomposition water includes the following steps: FeSe2-Co3O4Composite material, FeSe2-Co3O4- rGO is multiple
Any one in condensation material or catalyst is coated in as working electrode on electrochemistry glass-carbon electrode, in an acidic solution, with
Graphite electrode is to electrode, and SCE electrode is reference electrode, under electric field-assisted, when testing electrocatalytic decomposition aquatic products hydrogen in solution
Voltage with electric current variation；It is to electrode with Pt in alkaline solution, Hg/HgO electrode is reference electrode, under electric field-assisted,
Test solution in electrocatalytic decomposition aquatic products oxygen when electric current with voltage variation.
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