CN109847778A - A kind of cobalt disulfide for being electrolysed elutriation oxygen/carbon nitrogen composite material and its synthetic method - Google Patents
A kind of cobalt disulfide for being electrolysed elutriation oxygen/carbon nitrogen composite material and its synthetic method Download PDFInfo
- Publication number
- CN109847778A CN109847778A CN201910009039.2A CN201910009039A CN109847778A CN 109847778 A CN109847778 A CN 109847778A CN 201910009039 A CN201910009039 A CN 201910009039A CN 109847778 A CN109847778 A CN 109847778A
- Authority
- CN
- China
- Prior art keywords
- carbon nitrogen
- composite material
- cobalt
- nitrogen composite
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Cobalt disulfide/carbon nitrogen the composite material and its synthetic method that the present invention relates to a kind of for being electrolysed elutriation oxygen.The material is porous dodecahedron structure, CoS2Nano particle is by graphite carbon coating and is evenly distributed on dodecahedron carbon nitrogen frame.It shows fabulous activity and ultra-long time stability as anode of electrolytic water oxygen-separating catalyst in electrolysis elutriation oxygen, with excellent performance, considerably beyond the catalytic performance of noble metal Ru, Ir, performance is also much better than the non-noble metallic materials catalyst obtained by other methods simultaneously, has very big application prospect in electrolysis elutriation oxygen field.
Description
Technical field
The invention belongs to electrolysis water catalyst technical fields, are related to the new and effective base metal electrolysis elutriation oxygen of one kind and urge
Agent cobalt disulfide/carbon nitrogen composite material and preparation method.
Background technique
Demand with people to the energy is growing, and developing efficient, stable new energy converting system becomes
The research hotspot of scientific circles.Electrolysis water be it is a kind of cleaning, sustainable large scale preparation hydrogen method, be with " water ", " hydrogen "
Energy transfer medium system based on " oxygen " can be regarded as " zero-emission " clean energy resource converting system truly.And it sets
Counting out high performance catalyst material is the core for improving electrolysis water performance.During electrolysis water, since analysis oxygen process is one
Four electronic processes generally require higher overpotential to push its progress, to hinder the smooth of entire electrolysis water process
It carries out, therefore, finds suitable catalyst to reduce the overpotential of analysis oxygen process and have a very big significance.Although ruthenium (Ru) and iridium
(Ir) etc. noble metal catalysts have high analysis oxygen catalytic activity, but since reserves are few on earth for it, price, thus sternly
Electrolysis aquatic products hydrogen is hindered again and produces the large-scale application of oxygen.Therefore, noble metal is replaced to use with non-noble metallic materials in recent years
In the direction that electro-catalysis analysis oxygen is also made great efforts at numerous researchers.
Due to its efficient inherent catalytic activity and natural reserves abundant, 3d transition metals cobalt, nickel are considered as that can replace
For the most promising material of noble metal catalyst.But traditional block or reunion cobalt, nickel metal nanoparticle are due to smaller
Specific surface area and the competitiveness applied in electrochemical catalysis of less active site it is smaller.In addition, exposed cobalt, nickel are golden
Stability of the metal nano-particle in strong alkali solution and under high overpotential is poor.Vulcanizing treatment is carried out to transition metal to be recognized
To be a kind of important means for improving its electro catalytic activity, however, simple vulcanizing treatment, can exist and vulcanize insufficient, conduction
Property poor, the disadvantages of active site is insufficient, and stability is bad.
Metal organic framework compound (MOFs) has big specific surface area, uniform duct and periodic arrangement of elements
The features such as, ZIF-67 is the dodecahedron that is formed with metallic element cobalt and organic ligand bonding as one of MOFs, existing
There is technology to have been reported that: using it as presoma, is modified on its basis to improve catalytic performance, including form LDH using it as template
It structure and is oxidized, phosphatization, the methods of vulcanization is widely used.Jian-Rong Li et al. people (Adv.Energy
Mater.2017,1602643) using ZIF-67 as template, it is aoxidized, is vulcanized, phosphorating treatment is for being catalyzed analysis oxygen, but property
It can need to be improved.
Summary of the invention
The object of the present invention is to provide a kind of base metal electro-catalysis of electrolysis elutriation oxygen to analyse oxygen material, specially one kind two
Cobalt sulfide/carbon nitrogen composite material and its synthetic method.
A kind of cobalt disulfide/carbon nitrogen composite material, the material are porous dodecahedron structure, CoS2Nano particle is by stone
Black carbon coating is simultaneously evenly distributed on dodecahedron carbon nitrogen frame.
According to the above scheme, cobalt disulfide/carbon nitrogen composite material size is at 0.1~1.5 μm, CoS2Particle size is in 5nm
To between 10nm.
Above-mentioned cobalt disulfide/carbon nitrogen composite material answering in electrolysis elutriation oxygen as anode of electrolytic water oxygen-separating catalyst
With.
The application method are as follows: cobalt disulfide/carbon nitrogen composite material is made electrode for active component, then with this electricity
Extremely working electrode analyses oxygen for anode of electrolytic water.
Specific steps are as follows: be configured to dispersion liquid with Nafion solution, be then supported on room temperature in foam nickel carrier and dry, obtain
To containing cobalt disulfide/carbon nitrogen composite active component nickel foam, working electrode is made with it, platinized platinum is to electrode, Hg/
HgO is reference electrode, and using KOH as electrolyte, anode of electrolytic water analyses oxygen.It is with good catalytic performance, in 10mAcm-2
Current density under, overpotential only needs 205mV, when current density reaches 1000mAcm-2When, overpotential 327mV.Much
It has been more than the catalytic performance of noble metal Ru, Ir, while performance is also much better than to urge by the non-noble metallic materials that other methods obtain
Agent.
Above-mentioned electrolysis water oxygen-separating catalyst cobalt disulfide/carbon nitrogen composite material synthetic method, which is characterized in that including with
Lower step:
It will anneal in two steps under ZIF-67 inert gas, the annealing in two steps are as follows: be first by ZIF-67 in inertia
280~400 DEG C of calcinings under atmosphere, then 600~1000 DEG C of calcinings in an inert atmosphere again；
Then the product after above-mentioned annealing is fully ground to mix and anneal under an inert atmosphere with S powder and is vulcanized
Reaction, obtains cobalt disulfide/carbon nitrogen composite material.
According to the above scheme, the time of 280~400 DEG C of first step calcinings is 1.5~3h, temperature in first step calcining
More preferably 300 DEG C, the preferred 2h of duration；The time of 600~1000 DEG C of the second step calcinings is 3.5~5h, and second step is forged
Preferably 800 DEG C of temperature in burning, the preferred 4h of duration.
According to the above scheme, the mixed proportion of the product after the annealing and S powder is calculated as 10:1~1 according to mass ratio:
10。
According to the above scheme, the vulcanization reaction temperature is 280~350 DEG C, and the time is 10~15h, temperature preferably 300
DEG C, the preferred 12h of duration.
According to the above scheme, the preparation method of the ZIF-67:
(1) by 2-methylimidazole, it is dissolved in the in the mixed solvent being made of methanol and ethyl alcohol, it is molten to prepare 2-methylimidazole
The volume ratio of liquid, 0.05~1M of concentration, methanol and ethyl alcohol is any ratio, preferably 1:1；
(2) cobalt source substance is dissolved in the solvent being mixed to get by methanol and ethanol solution, prepares cobalt source solution, concentration
In 0.01~0.2M, the volume ratio of methanol and ethyl alcohol is any ratio, preferably 1:1；
(3) solution that step (1) obtains is quickly poured into the solution of step (2) while stirring, continues one section of stirring
Time is then allowed to stand, and obtains purple precipitated product, with organic solvent ethyl alcohol and methanol alternately centrifuge washing, filtering, 40~
6~15h is dried at 80 DEG C.
According to the above scheme, the temperature that two solution are stirred in step (3) is within the scope of 0~50 DEG C, and preferably 25 DEG C, stirring
Time, dwell temperature was within the scope of 0~50 DEG C in 5s~1h, preferably 10min, preferably 25 DEG C, the time in 5~36h, preferably for 24 hours.
The ratio of the amount of the substance of the amount and cobalt source substance of the substance of 2-methylimidazole is 0.005~0.5 in step (3):
1。
According to the above scheme, the cobalt source substance of step (3) is selected from Co (NO3)2·6H2O、CoCl2·6H2O、CoSO4·6H2O、
C15H21CoO6。
The present invention it is innovative for the first time nanoscale, pattern have been obtained by two steps calcining carbonizatin method and one-step calcination vulcanization
Together with " sulfur-rich " type elctro-catalyst of high oxygen separated performance, i.e., by the carbon-coated CoS of graphite2Nano particle is evenly distributed on
Using metal organic frame as the electrolysis water oxygen-separating catalyst on the carbon nitrogen frame that template obtains.It is excellent with good electric conductivity
Different hydrophilic ability, can effectively activated water molecule, there is active site abundant, so as to efficiently decompose aquatic products oxygen.
It shows fabulous activity and ultra-long time stability, tool as anode of electrolytic water oxygen-separating catalyst in electrolysis elutriation oxygen
There is excellent performance (in 10mAcm-2Current density under, overpotential only needs 205mV, when current density reaches 1000mA
cm-2When, overpotential 327mV.Considerably beyond the catalytic performance of noble metal Ru, Ir, while performance is also much better than to pass through other
The non-noble metallic materials catalyst that method obtains has very big application prospect in electrolysis elutriation oxygen field.
Detailed description of the invention
Fig. 1 is the X-ray diffraction spectrogram (abbreviation XRD) of sample: (a) ZIF-67；(b) Co/NC: cobalt/carbon nitrogen composite material；
CoS2/ NC: cobalt disulfide/carbon nitrogen composite material.
Fig. 2 is the scanning electron microscope image (abbreviation SEM) of sample: (a) ZIF-67 that step (3) obtains；(b) cobalt/
Carbon nitrogen composite material；(c) cobalt disulfide/carbon nitrogen composite material.
Fig. 3 is cobalt/carbon nitrogen composite material transmission electron microscope figure (abbreviation TEM)；(a) (b) is under low range
TEM；(c) figure is the enlarged drawing of boxed area in (b) figure, is high-resolution-ration transmission electric-lens figure (abbreviation HRTEM)；It (d) is cobalt/carbon nitrogen
High angle annular dark field-scanning transmission electron microscope figure (abbreviation HAADF-STEM) of composite material；(e), (f) divide with (g)
It is not C, N and Co distribution diagram of element.
Fig. 4 is cobalt disulfide/carbon nitrogen composite material transmission electron microscope figure (abbreviation TEM)；(a) (b) is low range
Under TEM；(c) figure is the enlarged drawing of boxed area in (b) figure, is high-resolution-ration transmission electric-lens figure (abbreviation HRTEM)；(d) for cobalt/
High angle annular dark field-scanning transmission electron microscope figure (abbreviation HAADF-STEM) of carbon nitrogen composite material；(e), (f), (g)
It (h) is C, N, the distribution map of Co and S element respectively.
Fig. 5 is sample ZIF-67, cobalt/carbon nitrogen composite material (Co/NC), cobalt disulfide/carbon nitrogen composite material (CoS2/NC)
Raman spectrogram (abbreviation Raman).
Fig. 6 is the catalytic performance figure of sample: (a) being sample foams nickel, ZIF-67, RuO2, cobalt/carbon nitrogen composite material, two
Cobalt sulfide/carbon nitrogen composite material linear sweep voltammetry figure (LSV), cobalt disulfide/carbon nitrogen composite material present minimum mistake
Potential；(b) scheme for cobalt disulfide/carbon nitrogen composite material LSV under high current density；It (c) is cobalt disulfide/carbon nitrogen composite material
Stability test figure.
Specific embodiment
Below with reference to specific example, the present invention is further elaborated, but the present invention is not limited to following embodiments.
Embodiment 1
(1) 1.746g Co (NO is weighed3)2·6H2O is stirred in the in the mixed solvent of 40ml ethyl alcohol and 40mL methanol with magnetic force
Device stirring 10min is mixed, then ultrasound 10min.Equally, 1.97g 2-methylimidazole is weighed in the mixed of 40ml ethyl alcohol and 40ml methanol
In bonding solvent, with magnetic stirrer 10min, then ultrasound 10min.Above-mentioned organic solution is rapid while agitating
Salting liquid is poured into, and continues to be stored at room temperature for 24 hours after stirring 10min, obtained violet precipitate ethyl alcohol and methanol are alternately washed
It washs, is centrifuged, 60 DEG C of 12h drying obtain metal organic framework compound ZIF-67.Fig. 1 (a) gives the ZIF-67's prepared
The peak of XRD diagram, characteristic peak and fitting corresponds, and the electron microscope in Fig. 2 (a) shows that ZIF-67 is of uniform size and outer mass color
Sliding dodecahedron structure.The Raman peaks of ZIF are also all the peaks of corresponding organic matter in Fig. 5.
(2) ZIF-67 in step (1) is placed in magnetic boat in the first 300 DEG C of annealing 2h of nitrogen atmosphere in tube furnace, then
800 DEG C of annealing 4h, the sample taken out after cooling is porous dodecahedron cobalt/carbon nitrogen composite material.XRD diagram in Fig. 1 (b)
Display cobalt/carbon nitrogen composite material only remains the characteristic peak of three apparent metallic cobalts, and the electron microscope in Fig. 2 (b) shows cobalt/carbon
Nitrogen composite material maintains original dodecahedron structure but surface becomes coarse, and cobalt particle is exposed, and the TEM of Fig. 3 is aobvious
After showing annealing, cobalt/carbon nitrogen composite material becomes porous structure by original smooth surface, and metallic cobalt is by graphite carbon coating, graphite
It is unbodied carbon N structure outside carbon, and cobalt particle is generally evenly distributed in entire dodecahedron, wherein d=
0.21nm corresponds to the lattice fringe of cobalt, and d=0.34nm corresponds to the lattice fringe of graphitic carbon, and distribution diagram of element shows C, and N, Co are equal
Even is dispersed in entire dodecahedron.Fig. 5 is ZIF-67, cobalt/carbon nitrogen composite material (Co/NC), cobalt disulfide/carbon nitrogen are compound
Material (CoS2/ NC) Raman spectrogram, wherein cobalt/carbon nitrogen composite material (CoS2/ NC) Raman spectrogram in: the peak D represents C
The defect of atomic lattice, and what the peak G represented is stretching vibration in the face of C atom sp2 hydridization.
(3) alcohol is added in the cobalt in step (2)/carbon nitrogen composite material and sulphur powder 1:3 to pass through repeatedly sufficiently in mortar
Wet grinding mixing, then in magnetic boat in tube furnace 300 DEG C of annealing 12h under nitrogen atmosphere, the sample collected after cooling down is i.e.
For high-efficient electrolytic water oxygen-separating catalyst cobalt disulfide/carbon nitrogen composite material.Fig. 1 (b) is examined in cobalt disulfide/carbon nitrogen composite material
The characteristic peak of cobalt disulfide is measured, it is original that the electron microscope in Fig. 2 (c) shows that cobalt disulfide/carbon nitrogen composite material maintains
Dodecahedron structure and surface become more coarse.After the TEM of Fig. 4 shows vulcanization, the cobalt disulfide of generation is by graphitic carbon packet
It covers, is unbodied carbon N structure outside graphitic carbon, and cobalt disulfide uniform particle is distributed in entire dodecahedron,
In, d=0.28nm corresponds to the lattice fringe of cobalt disulfide, and d=0.34nm corresponds to the lattice fringe of graphitic carbon, and distribution diagram of element
Show that C, N, Co, S are uniformly dispersed in entire dodecahedron.Cobalt disulfide/carbon nitrogen composite material Raman peaks are shown in Fig. 5
The corresponding peak D, the peak G.
(4) it weighs above-mentioned catalyst 5mg to be added in the ethyl alcohol of 400 μ L, ultrasonic 30min, then is added dropwise into above-mentioned solution
The isopropanol ultrasound 30min of 100 μ L, is finally added dropwise the Nafion solution of the 50 commercially available 5wt% of μ L thereto, after ultrasonic 30min
It drops evenly in 1 × 1cm-2Nickel foam on room temperature drying.Using the KOH of 1mol/L as electrolyte, with the bubble containing catalyst
Foam nickel is working electrode, and platinized platinum is to electrode, and Hg/HgO is that reference electrode carries out electro-chemical test.The result measured such as Fig. 6,
(a) chart is bright: cobalt disulfide/carbon nitrogen composite material shows absolute electrolysis water oxygen evolution activity with respect to other materials,
10mA·cm-2Current density under, overpotential only needs 205mV.Considerably beyond noble metal RuO2Catalytic performance.(b) figure
Display reaches 1000mAcm when current density-2When, overpotential is only 327mV.
(c) figure is respectively 10mAcm in current density-2And 1000mAcm-2After continued electrolysis 10h, catalyst is kept
Good stability.
Embodiment 2
(1) 1.746g Co (NO is weighed3)2·6H2O is stirred in the in the mixed solvent of 40ml ethyl alcohol and 40ml methanol with magnetic force
Device stirring 10min is mixed, then ultrasound 10min.Equally, 1.97g 2-methylimidazole is weighed in the mixed of 40ml ethyl alcohol and 40ml methanol
In bonding solvent, with magnetic stirrer 10min, then ultrasound 10min.Above-mentioned organic solution is rapid while agitating
Salting liquid is poured into, and continues to be stored at room temperature 18h after stirring 5min, obtained violet precipitate ethyl alcohol and methanol are alternately washed
It washs, is centrifuged, 60 DEG C of 12h drying obtain metal organic frame ZIF-67.
(2) ZIF-67 in step (1) is placed in magnetic boat in the first 300 DEG C of annealing 2h of nitrogen atmosphere in tube furnace, then
1000 DEG C of annealing 3.5h, the sample taken out after cooling is porous dodecahedron cobalt/carbon nitrogen composite material.
(3) alcohol is added in the cobalt in step (2)/carbon nitrogen composite material and sulphur powder 3:1 to pass through repeatedly sufficiently in mortar
Wet grinding mixing, then 350 DEG C of annealing 10h, the sample collected after cooling are under nitrogen atmosphere in tube furnace in magnetic boat
High-efficient electrolytic water oxygen-separating catalyst cobalt disulfide/carbon nitrogen composite material.
(4) it weighs above-mentioned 5 ㎎ of catalyst to be added in the ethyl alcohol of 400 μ L, ultrasonic 30min, then is added dropwise into above-mentioned solution
The isopropanol ultrasound 30min of 100 μ L, is finally added dropwise the Nafion solution of the 50 commercially available 5wt% of μ L thereto, after ultrasonic 30min
It drops evenly in 1 × 1cm-2Nickel foam on room temperature drying.Using the KOH of 1mol/L as electrolyte, with the bubble containing catalyst
Foam nickel is working electrode, and platinized platinum is to electrode, and Hg/HgO is that reference electrode carries out electro-chemical test.When current density is 10mA
cm-2And 100mAcm-2When overpotential respectively referring to table 1.
Embodiment 3
(1) 1.746g Co (NO is weighed3)2·6H2O is stirred in the in the mixed solvent of 40ml ethyl alcohol and 40ml methanol with magnetic force
Device stirring 10min is mixed, then ultrasound 10min.Equally, 1.97g 2-methylimidazole is weighed in the mixed of 50ml ethyl alcohol and 40ml methanol
In bonding solvent, with magnetic stirrer 10min, then ultrasound 10min.Above-mentioned organic solution is rapid while agitating
Salting liquid is poured into, and continues to be stored at room temperature for 24 hours after stirring 20min, obtained violet precipitate ethyl alcohol and methanol are alternately washed
It washs, is centrifuged, 60 DEG C of 12h drying obtain metal organic frame ZIF-67.
(2) ZIF-67 in step (1) is placed in magnetic boat in the first 300 DEG C of annealing 2h of nitrogen atmosphere in tube furnace, then
800 DEG C of annealing 4h, the sample taken out after cooling is porous dodecahedron cobalt/carbon nitrogen composite material.
(3) alcohol is added in the cobalt in step (2)/carbon nitrogen composite material and sulphur powder 1:6 to pass through repeatedly sufficiently in mortar
Wet grinding mixing, then 280 DEG C of annealing 15h, the sample collected after cooling are under nitrogen atmosphere in tube furnace in magnetic boat
High-efficient electrolytic water oxygen-separating catalyst cobalt disulfide/carbon nitrogen composite material.
(4) it weighs above-mentioned 5 ㎎ of catalyst to be added in the ethyl alcohol of 400 μ L, ultrasonic 30min, then is added dropwise into above-mentioned solution
The isopropanol ultrasound 30min of 100 μ L, is finally added dropwise the Nafion solution of the 50 commercially available 5wt% of μ L thereto, after ultrasonic 30min
It drops evenly in 1 × 1cm-2Nickel foam on room temperature drying.Using the KOH of 1mol/L as electrolyte, with the bubble containing catalyst
Foam nickel is working electrode, and platinized platinum is to electrode, and Hg/HgO is that reference electrode carries out electro-chemical test.When current density is 10mA
cm-2And 100mAcm-2When overpotential respectively referring to table 1.
Embodiment 4
(1) 1.746g Co (NO is weighed3)2·6H2O is stirred in the in the mixed solvent of 40ml ethyl alcohol and 40ml methanol with magnetic force
Device stirring 10min is mixed, then ultrasound 10min.Equally, 1.97g 2-methylimidazole is weighed in the mixed of 40ml ethyl alcohol and 40ml methanol
In bonding solvent, with magnetic stirrer 10min, then ultrasound 10min.Above-mentioned organic solution is rapid while agitating
Salting liquid is poured into, and continues to be stored at room temperature for 24 hours after stirring 30min, obtained violet precipitate ethyl alcohol and methanol are alternately washed
It washs, is centrifuged, 60 DEG C of 12h drying obtain metal organic frame ZIF-67.
(2) ZIF-67 in step (1) is placed in magnetic boat in the first 280 DEG C of annealing 3h of nitrogen atmosphere in tube furnace, then
600 DEG C of annealing 5h, the sample taken out after cooling is porous dodecahedron cobalt/carbon nitrogen composite material.
(3) alcohol is added in the cobalt in step (2)/carbon nitrogen composite material and sulphur powder 1:3 to pass through repeatedly sufficiently in mortar
Wet grinding mixing, then 300 DEG C of annealing 12h, the sample collected after cooling are under nitrogen atmosphere in tube furnace in magnetic boat
High-efficient electrolytic water oxygen-separating catalyst cobalt disulfide/carbon nitrogen composite material.
(4) it weighs above-mentioned 5 ㎎ of catalyst to be added in the ethyl alcohol of 400 μ L, ultrasonic 30min, then is added dropwise into above-mentioned solution
The isopropanol ultrasound 30min of 100 μ L, is finally added dropwise the Nafion solution of the 50 commercially available 5wt% of μ L thereto, after ultrasonic 30min
It drops evenly in 1 × 1cm-2Nickel foam on room temperature drying.Using the KOH of 1mol/L as electrolyte, with the bubble containing catalyst
Foam nickel is working electrode, and platinized platinum is to electrode, and Hg/HgO is that reference electrode carries out electro-chemical test.When current density is 10mA
cm-2And 100mAcm-2When overpotential respectively referring to table 1.
Embodiment 5
(1) 1.746g Co (NO is weighed3)2·6H2O is stirred in the in the mixed solvent of 30ml ethyl alcohol and 40ml methanol with magnetic force
Device stirring 10min is mixed, then ultrasound 10min.Equally, 1.97g 2-methylimidazole is weighed in the mixed of 30ml ethyl alcohol and 40ml methanol
In bonding solvent, with magnetic stirrer 10min, then ultrasound 10min.Above-mentioned organic solution is rapid while agitating
Salting liquid is poured into, and continues to be stored at room temperature for 24 hours after stirring 1h, obtained violet precipitate ethyl alcohol and methanol are alternately washed,
Centrifugation, 60 DEG C of 12h drying, obtains metal organic frame ZIF-67.
(2) ZIF-67 in step (1) is placed in magnetic boat in the first 300 DEG C of annealing 2h of nitrogen atmosphere in tube furnace, then
1000 DEG C of annealing 3.5h, the sample taken out after cooling is porous dodecahedron cobalt/carbon nitrogen composite material.
(3) alcohol is added in the cobalt in step (2)/carbon nitrogen composite material and sulphur powder 1:3 to pass through repeatedly sufficiently in mortar
Wet grinding mixing, then 350 DEG C of annealing 12h, the sample collected after cooling are under nitrogen atmosphere in tube furnace in magnetic boat
High-efficient electrolytic water oxygen-separating catalyst cobalt disulfide/carbon nitrogen composite material.
(4) it weighs above-mentioned catalyst 5mg to be added in the ethyl alcohol of 400 μ L, ultrasonic 30min, then is added dropwise into above-mentioned solution
The isopropanol ultrasound 30min of 100 μ L, is finally added dropwise the Nafion solution of the 50 commercially available 5wt% of μ L thereto, after ultrasonic 30min
It drops evenly in 1 × 1cm-2Nickel foam on room temperature drying.Using the KOH of 1mol/L as electrolyte, with the bubble containing catalyst
Foam nickel is working electrode, and platinized platinum is to electrode, and Hg/HgO is that reference electrode carries out electro-chemical test.When current density is 10mA
cm-2And 100mAcm-2When overpotential respectively referring to table 1.
Embodiment 6
(1) 1.746g Co (NO is weighed3)2·6H2O is stirred in the in the mixed solvent of 40ml ethyl alcohol and 40ml methanol with magnetic force
Device stirring 10min is mixed, then ultrasound 10min.Equally, 1.97g 2-methylimidazole is weighed in the mixed of 40ml ethyl alcohol and 20ml methanol
In bonding solvent, with magnetic stirrer 10min, then ultrasound 10min.Above-mentioned organic solution is rapid while agitating
Salting liquid is poured into, and continues to be stored at room temperature for 24 hours after stirring 10s, obtained violet precipitate ethyl alcohol and methanol are alternately washed,
Centrifugation, 60 DEG C of 18h drying, obtains metal organic frame ZIF-67.
(2) ZIF-67 in step (1) is placed in magnetic boat in the first 400 DEG C of annealing 2h of nitrogen atmosphere in tube furnace, then
800 DEG C of annealing 4h, the sample taken out after cooling is porous dodecahedron cobalt/carbon nitrogen composite material.
(3) alcohol is added in the cobalt in step (2)/carbon nitrogen composite material and sulphur powder 1:3 to pass through repeatedly sufficiently in mortar
Wet grinding mixing, then 280 DEG C of annealing 12h, the sample collected after cooling are under nitrogen atmosphere in tube furnace in magnetic boat
High-efficient electrolytic water oxygen-separating catalyst cobalt disulfide/carbon nitrogen composite material.
(4) it weighs above-mentioned catalyst 5mg to be added in the ethyl alcohol of 400 μ L, ultrasonic 30min, then is added dropwise into above-mentioned solution
The isopropanol ultrasound 30min of 100 μ L, is finally added dropwise the Nafion solution of the 50 commercially available 5wt% of μ L thereto, after ultrasonic 30min
It drops evenly in 1 × 1cm-2Nickel foam on room temperature drying.Using the KOH of 1mol/L as electrolyte, with the bubble containing catalyst
Foam nickel is working electrode, and platinized platinum is to electrode, and Hg/HgO is that reference electrode carries out electro-chemical test.When current density is 10mA
cm-2And 100mAcm-2When overpotential respectively referring to table 1.
Table 1
Claims (10)
1. a kind of cobalt disulfide/carbon nitrogen composite material, it is characterised in that: the material is porous dodecahedron structure, CoS2Nanometer
Particle is by graphite carbon coating and is evenly distributed on dodecahedron carbon nitrogen frame.
2. cobalt disulfide according to claim 1/carbon nitrogen composite material, it is characterised in that: cobalt disulfide/carbon nitrogen composite wood
The size of material is at 0.1~1.5 μm, CoS2Particle size is in 5nm between 10nm.
3. cobalt disulfide described in claim 1/carbon nitrogen composite material is as anode of electrolytic water oxygen-separating catalyst in electrolysis elutriation
Application in oxygen.
4. application according to claim 2, which is characterized in that application method are as follows: be by cobalt disulfide/carbon nitrogen composite material
Active component is made electrode, then using this electrode as working electrode, analyses oxygen, specific steps for anode of electrolytic water are as follows: use
Nafion solution is configured to dispersion liquid, is then supported on room temperature in foam nickel carrier and dries, obtains multiple containing cobalt disulfide/carbon nitrogen
The nickel foam of condensation material active component makees working electrode with it, and platinized platinum is to electrode, and Hg/HgO is reference electrode, using KOH as
Electrolyte, anode of electrolytic water analyse oxygen.
5. cobalt disulfide described in claim 1/carbon nitrogen composite material synthetic method, which comprises the following steps:
It will anneal in two steps under ZIF-67 inert gas, the annealing in two steps are as follows: be first by ZIF-67 in inert atmosphere
Lower 280~400 DEG C of calcinings, then 600~1000 DEG C of calcinings in an inert atmosphere again；
Then the product after above-mentioned annealing is fully ground to mix and anneal under an inert atmosphere with S powder and vulcanize instead
It answers, obtains cobalt disulfide/carbon nitrogen composite material.
6. synthetic method according to claim 5, it is characterised in that: the time of 280~400 DEG C of the first step calcinings
For 1.5~3h；The time of 600~1000 DEG C of the second step calcinings is 3.5~5h.
7. synthetic method according to claim 5, it is characterised in that: the mixing of product and S powder after the annealing
Ratio is calculated as 10:1~1:10 according to mass ratio.
8. synthetic method according to claim 5, it is characterised in that: the vulcanization reaction temperature is 280~350 DEG C,
Time is 10~15h.
9. synthetic method according to claim 5, it is characterised in that: the preparation method of the ZIF-67:
(1) by 2-methylimidazole, it is dissolved in the in the mixed solvent being made of methanol and ethyl alcohol, prepares 2-methylimidazole solution, it is dense
Spend 0.05~1M；
(2) cobalt source substance is dissolved in the solvent being mixed to get by methanol and ethanol solution, prepares cobalt source solution, concentration exists
0.01~0.2M；
(3) solution that step (1) obtains is quickly poured into the solution of step (2) while stirring, continues stirring a period of time,
It is then allowed to stand, obtains purple precipitated product, with organic solvent ethyl alcohol and methanol alternately centrifuge washing, filtering, 40~80 DEG C
6~15h of lower drying.
10. synthetic method according to claim 5, it is characterised in that: the temperature that two solution are stirred in step (3) exists
Within the scope of 0~50 DEG C, mixing time is in 5s~1h, and dwell temperature is within the scope of 0~50 DEG C, and the time is in 5~36h；In step (3)
The ratio of the amount of the substance of the amount and cobalt source substance of the substance of 2-methylimidazole is 0.005~0.5:1；The cobalt source object of step (3)
Matter is selected from Co (NO3)2·6H2O、CoCl2·6H2O、CoSO4·6H2O、C15H21CoO6。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910009039.2A CN109847778B (en) | 2019-01-04 | 2019-01-04 | Cobalt disulfide/carbon nitrogen composite material for oxygen evolution by electrolyzing water and synthetic method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910009039.2A CN109847778B (en) | 2019-01-04 | 2019-01-04 | Cobalt disulfide/carbon nitrogen composite material for oxygen evolution by electrolyzing water and synthetic method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109847778A true CN109847778A (en) | 2019-06-07 |
| CN109847778B CN109847778B (en) | 2022-07-01 |
Family
ID=66893967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910009039.2A Active CN109847778B (en) | 2019-01-04 | 2019-01-04 | Cobalt disulfide/carbon nitrogen composite material for oxygen evolution by electrolyzing water and synthetic method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109847778B (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534739A (en) * | 2019-08-19 | 2019-12-03 | 中南大学 | Amorphous carbon-coated metal sulfide of one kind and preparation method thereof |
| CN110697782A (en) * | 2019-11-01 | 2020-01-17 | 宁波大学 | Co3S4@MoS2Preparation method and application of core-shell structure nanosheet array material |
| CN110813334A (en) * | 2019-10-16 | 2020-02-21 | 武汉工程大学 | Preparation method and application of foam nickel-loaded iron-nickel-based composite material |
| CN111155145A (en) * | 2020-01-15 | 2020-05-15 | 浙江农林大学 | Bifunctional electrolytic water electrode with super-wettability and preparation method thereof |
| CN111370707A (en) * | 2020-03-17 | 2020-07-03 | 东北大学秦皇岛分校 | Cobalt sulfide-based composite material and preparation method and application thereof |
| CN111389430A (en) * | 2020-05-15 | 2020-07-10 | 郑州大学 | Catalyst CoP for hydrogen production by water electrolysisxSyMWCNTs and preparation method thereof |
| CN111468165A (en) * | 2020-05-22 | 2020-07-31 | 青岛品泰新材料技术有限责任公司 | Nitrogen-doped nano CoS2Preparation method and application of graphene photocatalytic material |
| CN111697213A (en) * | 2020-05-06 | 2020-09-22 | 广州大学 | Cobalt disulfide-tin disulfide composite particle and preparation method and application thereof |
| CN111841598A (en) * | 2020-06-23 | 2020-10-30 | 合肥师范学院 | S-doped Co @ NC composite material with high oxygen evolution catalytic activity and preparation method thereof |
| CN112403503A (en) * | 2020-11-27 | 2021-02-26 | 电子科技大学 | Preparation method of nitrogen-doped MOF structure modified two-phase sulfide material |
| CN113471455A (en) * | 2021-07-01 | 2021-10-01 | 湖南理工学院 | Cobalt disulfide/nitrogen and sulfur co-doped mesoporous carbon composite catalyst for zinc-air battery and preparation method thereof |
| CN114392757A (en) * | 2022-01-21 | 2022-04-26 | 海南大学 | Preparation method and application of transition metal compound catalyst |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105552392A (en) * | 2016-01-06 | 2016-05-04 | 复旦大学 | Cobalt diselenide/graphite carbon composite material, namely oxygen reduction catalyst, and preparation method thereof |
| CN106384675A (en) * | 2016-10-17 | 2017-02-08 | 江苏大学 | Carbon nitride/cobalt sulfide super capacitor electrode material, preparation method thereof, and application thereof |
| CN107159297A (en) * | 2017-06-21 | 2017-09-15 | 黑龙江大学 | A kind of difunctional VPO catalysts cobalt/cobaltosic oxide/nitrogen carbon composite and preparation method thereof |
| CN107447231A (en) * | 2017-08-02 | 2017-12-08 | 中国石油大学(华东) | A kind of two cobaltous telluride electro-catalysis analysis O compoiste material and its preparation method and application |
| CN107871875A (en) * | 2016-09-26 | 2018-04-03 | 中国科学院大连化学物理研究所 | A kind of oxygen evolution reaction elctro-catalyst, its preparation method and application |
| CN108048866A (en) * | 2017-11-29 | 2018-05-18 | 华南理工大学 | The preparation of the porous carbon-coated cobalt iridium Core-shell Structure Nanoparticles of N doping and its catalysis water-splitting application |
| CN108461763A (en) * | 2018-03-12 | 2018-08-28 | 华南理工大学 | A kind of cobalt disulfide/sulfur and nitrogen co-doped graphene catalysis material and preparation and application |
| CN108796551A (en) * | 2018-06-04 | 2018-11-13 | 佛山市利元合创科技有限公司 | It is supported on sea urchin shape vulcanization Co catalysts in nickel foam and preparation method thereof, as the application of electrolysis water oxygen-separating catalyst |
-
2019
- 2019-01-04 CN CN201910009039.2A patent/CN109847778B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105552392A (en) * | 2016-01-06 | 2016-05-04 | 复旦大学 | Cobalt diselenide/graphite carbon composite material, namely oxygen reduction catalyst, and preparation method thereof |
| CN107871875A (en) * | 2016-09-26 | 2018-04-03 | 中国科学院大连化学物理研究所 | A kind of oxygen evolution reaction elctro-catalyst, its preparation method and application |
| CN106384675A (en) * | 2016-10-17 | 2017-02-08 | 江苏大学 | Carbon nitride/cobalt sulfide super capacitor electrode material, preparation method thereof, and application thereof |
| CN107159297A (en) * | 2017-06-21 | 2017-09-15 | 黑龙江大学 | A kind of difunctional VPO catalysts cobalt/cobaltosic oxide/nitrogen carbon composite and preparation method thereof |
| CN107447231A (en) * | 2017-08-02 | 2017-12-08 | 中国石油大学(华东) | A kind of two cobaltous telluride electro-catalysis analysis O compoiste material and its preparation method and application |
| CN108048866A (en) * | 2017-11-29 | 2018-05-18 | 华南理工大学 | The preparation of the porous carbon-coated cobalt iridium Core-shell Structure Nanoparticles of N doping and its catalysis water-splitting application |
| CN108461763A (en) * | 2018-03-12 | 2018-08-28 | 华南理工大学 | A kind of cobalt disulfide/sulfur and nitrogen co-doped graphene catalysis material and preparation and application |
| CN108796551A (en) * | 2018-06-04 | 2018-11-13 | 佛山市利元合创科技有限公司 | It is supported on sea urchin shape vulcanization Co catalysts in nickel foam and preparation method thereof, as the application of electrolysis water oxygen-separating catalyst |
Non-Patent Citations (6)
| Title |
|---|
| JIAN ZHOU ET AL.: "MOF Template-Directed Fabrication of Hierarchically Structured Electrocatalysts for Efficient Oxygen Evolution Reaction"", 《ADV. ENERGY MATER.》 * |
| JING YAN ET AL.: ""Metal organic framework (ZIF-67)-derived hollow CoS2/N-doped carbon nanotube composites for extraordinary electromagnetic wave absorption"", 《COMPOSITES PART B》 * |
| JINTAO ZHANG ET AL.: ""Embedding CoS2 nanoparticles in N-doped carbon nanotube hollow frameworks for enhanced lithium storage properties"", 《NANO RESEARCH》 * |
| JUNHUI CAO ET AL.: ""Zeolitic Imidazolate Framework-Derived Core-Shell-Structured CoS2/CoS2-N-C Supported on Electrochemically Exfoliated Graphene Foil for Efficient Oxygen Evolution"", 《BATTERIES& SUPERCAPS》 * |
| WANG GUANLONG ET AL.: ""Encapsulation of Co metal by nitrogen doped porous carbon for catalytic removal of organic pollutants"", 《大连理工大学学报》 * |
| 杨颖，叶雅杰，赵艳丽等编著: "《碳纳米管的结构、性能、合成及其应用》", 31 August 2013, 哈尔滨：黑龙江大学出版社 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534739A (en) * | 2019-08-19 | 2019-12-03 | 中南大学 | Amorphous carbon-coated metal sulfide of one kind and preparation method thereof |
| CN110813334A (en) * | 2019-10-16 | 2020-02-21 | 武汉工程大学 | Preparation method and application of foam nickel-loaded iron-nickel-based composite material |
| CN110813334B (en) * | 2019-10-16 | 2023-01-10 | 武汉工程大学 | Preparation method and application of foam nickel loaded iron-nickel based composite material |
| CN110697782A (en) * | 2019-11-01 | 2020-01-17 | 宁波大学 | Co3S4@MoS2Preparation method and application of core-shell structure nanosheet array material |
| CN111155145A (en) * | 2020-01-15 | 2020-05-15 | 浙江农林大学 | Bifunctional electrolytic water electrode with super-wettability and preparation method thereof |
| CN111370707A (en) * | 2020-03-17 | 2020-07-03 | 东北大学秦皇岛分校 | Cobalt sulfide-based composite material and preparation method and application thereof |
| CN111697213A (en) * | 2020-05-06 | 2020-09-22 | 广州大学 | Cobalt disulfide-tin disulfide composite particle and preparation method and application thereof |
| CN111389430B (en) * | 2020-05-15 | 2022-10-25 | 郑州大学 | Catalyst CoP for hydrogen production by water electrolysis x S y MWCNTs and preparation method thereof |
| CN111389430A (en) * | 2020-05-15 | 2020-07-10 | 郑州大学 | Catalyst CoP for hydrogen production by water electrolysisxSyMWCNTs and preparation method thereof |
| CN111468165A (en) * | 2020-05-22 | 2020-07-31 | 青岛品泰新材料技术有限责任公司 | Nitrogen-doped nano CoS2Preparation method and application of graphene photocatalytic material |
| CN111841598A (en) * | 2020-06-23 | 2020-10-30 | 合肥师范学院 | S-doped Co @ NC composite material with high oxygen evolution catalytic activity and preparation method thereof |
| CN111841598B (en) * | 2020-06-23 | 2022-10-04 | 合肥师范学院 | S-doped Co @ NC composite material with high oxygen evolution catalytic activity and preparation method thereof |
| CN112403503A (en) * | 2020-11-27 | 2021-02-26 | 电子科技大学 | Preparation method of nitrogen-doped MOF structure modified two-phase sulfide material |
| CN113471455A (en) * | 2021-07-01 | 2021-10-01 | 湖南理工学院 | Cobalt disulfide/nitrogen and sulfur co-doped mesoporous carbon composite catalyst for zinc-air battery and preparation method thereof |
| CN113471455B (en) * | 2021-07-01 | 2022-10-28 | 湖南理工学院 | Cobalt disulfide/nitrogen and sulfur co-doped mesoporous carbon composite catalyst for zinc-air battery and preparation method thereof |
| CN114392757A (en) * | 2022-01-21 | 2022-04-26 | 海南大学 | Preparation method and application of transition metal compound catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109847778B (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109847778A (en) | A kind of cobalt disulfide for being electrolysed elutriation oxygen/carbon nitrogen composite material and its synthetic method | |
| Ma et al. | Ultrafine Rh nanocrystals decorated ultrathin NiO nanosheets for urea electro-oxidation | |
| Liu et al. | Hierarchical nanocomposite electrocatalyst of bimetallic zeolitic imidazolate framework and MoS2 sheets for non-Pt methanol oxidation and water splitting | |
| Wu et al. | Integrating the active OER and HER components as the heterostructures for the efficient overall water splitting | |
| Feng et al. | Core-shell structured ZnCo/NC@ MoS2 electrocatalysts for tunable hydrogen evolution reaction | |
| Wang et al. | Confined growth of porous nitrogen-doped cobalt oxide nanoarrays as bifunctional oxygen electrocatalysts for rechargeable zinc–air batteries | |
| Huang et al. | 3D ordered mesoporous cobalt ferrite phosphides for overall water splitting | |
| Song et al. | Metal-organic framework derived Fe/Fe3C@ N-doped-carbon porous hierarchical polyhedrons as bifunctional electrocatalysts for hydrogen evolution and oxygen-reduction reactions | |
| Yan et al. | Oxygen defect-rich double-layer hierarchical porous Co3O4 arrays as high-efficient oxygen evolution catalyst for overall water splitting | |
| Peng et al. | Zn doped ZIF67-derived porous carbon framework as efficient bifunctional electrocatalyst for water splitting | |
| Qi et al. | Co@ Co3O4 nanoparticle embedded nitrogen-doped carbon architectures as efficient bicatalysts for oxygen reduction and evolution reactions | |
| Gao et al. | Highly active electrocatalysts of CeO2 modified NiMoO4 nanosheet arrays towards water and urea oxidation reactions | |
| CN113235104B (en) | ZIF-67-based lanthanum-doped cobalt oxide catalyst and preparation method and application thereof | |
| CN109603840B (en) | Hierarchical porous nickel oxyhydroxide nanotube array and preparation method and application thereof | |
| Qian et al. | Fe-doped NiCo2S4 catalyst derived from ZIF–67 towards efficient hydrogen evolution reaction | |
| CN110694665B (en) | Preparation method and application of manganese and nitrogen doped octa-sulfur-nonacobalt electrocatalyst | |
| CN110993968A (en) | Preparation method and electrocatalysis application of carbon aerogel single metal atom catalyst | |
| CN113235128B (en) | Triangular nano array assembled by iron-doped cobalt sulfide and molybdenum sulfide nanosheets and preparation method and application thereof | |
| Ye et al. | Reduced graphene oxide supporting hollow bimetallic phosphide nanoparticle hybrids for electrocatalytic oxygen evolution | |
| Li et al. | CoP-anchored high N-doped carbon@ graphene sheet as bifunctional electrocatalyst for efficient overall water splitting | |
| Xiao et al. | Three-dimensional cross-linked Co-MoS 2 catalyst on carbon cloth for efficient hydrogen evolution reaction | |
| CN113881965A (en) | Metal nanoparticle-loaded catalyst taking biomass carbon source as template and preparation method and application thereof | |
| He et al. | Fabrication of MoS2 loaded on expanded graphite matrix for high-efficiency pH-universal hydrogen evolution reaction | |
| Cui et al. | FeNi co-doped electrocatalyst synthesized via binary ligand strategy as a bifunctional catalyst for Zn-air flow battery | |
| Owidah et al. | Metal oxide/carbon nanosheet arrays derivative of stacked metal organic frameworks for triggering oxygen evolution reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |