CN109759115A - Nanometer cobalt/cobalt sulfide is carried on porous carbon composite catalyst of Heteroatom doping and its preparation method and application - Google Patents
Nanometer cobalt/cobalt sulfide is carried on porous carbon composite catalyst of Heteroatom doping and its preparation method and application Download PDFInfo
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- CN109759115A CN109759115A CN201910110022.6A CN201910110022A CN109759115A CN 109759115 A CN109759115 A CN 109759115A CN 201910110022 A CN201910110022 A CN 201910110022A CN 109759115 A CN109759115 A CN 109759115A
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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
The invention discloses the porous carbon composite catalysts and its preparation method and application that nanometer cobalt/cobalt sulfide is carried on Heteroatom doping, are related to nano composite catalyst and electro-catalysis technical field.The composite catalyst is obtained with three hetero atom mixed matching cobalt-based metal-organic framework materials (writing a Chinese character in simplified form are as follows: Co-NSOMOF) of nitrogen sulphur oxygen for precursor preparation, is used for high-efficient electrolytic water.In the potassium hydroxide electrolyte of 1 mol L-1, when current density reaches 10 mA cm-2, have lower cell voltage (1.56 V).And the catalyst is still able to maintain higher catalytic activity after long-time loop test, there is stronger stability, practical application value with higher.
Description
Technical field
The present invention relates to nano composite catalyst and electro-catalysis technical field, and in particular to a kind of nanometer cobalt/cobalt sulfide
Be carried on porous carbon composite catalyst of Heteroatom doping and preparation method thereof and its in terms of electro-catalysis integrally decomposes water
Using.
Background technique
The development of today's society global industryization, the excessive of fossil energy use the ring for resulting in energy crisis and getting worse
Border pollution problem.Hydrogen energy density with higher, it is the renewable energy of clean and environmental protection that unique product, which is water, after burning
Carrier will get a good chance of the replacer as fossil energy in future.Electrochemical decomposition water is one of most promising production hydrogen technology,
It is made of Oxygen anodic evolution and cathode hydrogen evolution reaction, but biggish overpotential limits the large-scale business application of this technology.
Currently, mature commercial liberation of hydrogen and oxygen-separating catalyst is mainly precious metal material (such as: platinum and ruthenium-oxide etc.), however its low storage
Amount and fancy price limit the extensive use of this kind of precious metal material.
The porous carbon that transition metal/composite nano metal sulfide particle is carried on Heteroatom doping is a kind of excellent function material
Material.In recent years, the transient metal chalcogenide chalcogenide (TMCs) containing sulfide and selenides is living due to its excellent catalysis
Property and stability and be concerned.In all transient metal sulfides, cobalt-based sulfide has been proved to possess excellent electricity
Catalytic performance and outstanding chemical stability.In addition, Heteroatom doping can be caused to adjustment and the electricity of structure into carbon material
The variation of son arrangement, this can promote the electron-transport between catalyst surface and reaction intermediate to make electrocatalysis characteristic obtain
To be promoted.In addition, porous carbon is because of its unique porous structure, high conductivity, high-specific surface area and excellent electrochemically stable
Property etc. advantages be widely used in the research fields such as catalysis, adsorbing separation and energy storage.By transition metal/nano metal sulfide
Particulate load can produce the electrocatalysis of collaboration on the porous carbon of Heteroatom doping, greatly promote electrocatalysis characteristic, expand
Open up its application range.
The pyrolysis of metal organic frame (MOFs) can produce diversified nano material, including carbon-based material, metal
Oxide, metal sulfide, metal phosphide and metal carbides etc..The derivative of these MOFs specific surface with higher
Product, the features such as adjustable pore structure are sensing them, and gas storage, catalysis and the energy etc. present very big application
Prospect.However in the research that the MOFs of report prepares catalysis material as presoma and from template is sacrificed, selected MOF
Presoma is mainly that ZIF series and MIL series etc. are tied by some classics MOFs that single ligand and metal ion are self-assembly of
Structure.In addition, some additional is blended with MOFs containing heteroatomic precursor (for example, thiocarbamide or glyphosine) needs as precursor,
Composite carbon Base Metal/metallic compound nano material that there is hetero atom to mix is formed through carbonization.This undoubtedly will increase and prepared
The complexity of journey.Therefore, in addition to further investigation it has been reported that common MOFs various nanostructures are prepared as presoma
Carbon material outside, reasonably select the MOFs that constructs of mixed ligand comprising hetero atom (such as: nitrogen phosphate and sulfur, oxygen) as forerunner
Body is a critically important research side by being pyrolyzed a step to obtain the porous carbon based compound nano material of Heteroatom doping in situ
To.
Summary of the invention
The porous carbon for being carried on Heteroatom doping the purpose of the present invention is to provide a kind of novel nanometer cobalt/cobalt sulfide is multiple
Mould assembly electrocatalytic decomposition water catalyst is (referred to as: Co/Co9S8@NSOC)；Another object is to provide the preparation method of the catalyst
And application.
To achieve the purpose of the present invention, the present invention selects 2,5- thiophene dicarboxylic acid and 1 cheap and easy to get, bis- (the 4- pyridines of 3-
Base) three hetero atom mixed matching cobalt-based metal-organic framework materials of the nitrogen sulphur oxygen (letter constructed of two kinds of ligands of propane and soluble cobalt
It is written as: Co-NSOMOF) it is compound electrocatalytic decomposition water catalyst described in precursor preparation, it is used for efficient overall moisture solution.
The compound electrocatalytic decomposition water catalyst the preparation method is as follows:
(1) bis- (4- pyridyl group) propane of 2,5- thiophene dicarboxylic acid, 1,3-, soluble cobalt are dissolved in N, N- dimethyl respectively
It in formamide, is stirred at room temperature, 110-120 DEG C of isothermal reaction, after reaction, is cooled to room temperature to obtain to system temperature muddy
Turbid solution.
(2) solid is obtained by filtration in turbid solution obtained in step (1), through drying, grinding obtains Co-NSOMOF forerunner
Body.
(3) the resulting Co-NSOMOF presoma of step (2) is calcined under nitrogen atmosphere and obtains solid powder, through dilute salt
Then sour supersound washing is centrifuged repeatedly washing with deionized water and ethyl alcohol, obtains target product after drying and grinding.
The molar ratio of bis- (4- pyridyl group) propane of 2,5- thiophene dicarboxylic acid, 1,3- and soluble cobalt is 1 in step (1):
1:1.5~1.8.The preferred cabaltous nitrate hexahydrate of soluble cobalt.
Step (3) heating rate is 5~10 DEG C/min, and the temperature of presoma calcining is 600-900 DEG C.
Application of the composite material as catalyst, mainly in terms of electrocatalytic hydrogen evolution, analysis oxygen and overall moisture solution.
Application method is as follows: 1. are carried on the porous carbon of Heteroatom doping with nanometer cobalt/cobalt sulfide prepared by the present invention
Catalyst of the composite material as working electrode is used for the survey of its electrocatalytic hydrogen evolution and oxygen evolution reaction performance using three-electrode system
Examination.It take reference electrode, platinum filament as auxiliary electrode, 1mol L of silver-silver chloride (Ag/AgCl) electrode-1Potassium hydroxide aqueous solution is
Electrolyte.
2. overall moisture solution electrolytic cell is tested: being carried on the more of Heteroatom doping with nanometer cobalt/cobalt sulfide prepared by the present invention
Hole carbon composite is catalyst drop coating in the cathode and anode that are used separately as electrolytic cell on glass-carbon electrode, electrolyte 1mol
L-1Potassium hydroxide aqueous solution.
The invention has the advantages that:
The compound electrocatalytic decomposition water catalyst is with novel three hetero atom mixed matching cobalt-based metal-organic framework of nitrogen sulphur oxygen
Material (Co-NSOMOF) is presoma, and nanometer cobalt/eight nine cobalts of vulcanization are prepared by step carbonization and is carried on nitrogen sulphur oxygen three and mixes
The compound catalysis material of miscellaneous porous carbon.Carbon-based frame has micropore, mesoporous, macropore and the multistage pore property deposited, and can be to urge
Agent provides bigger contact surface, and more active sites is enable to expose, and provides better mass transfer channel, accelerates electricity
Son transmission.In addition, three kinds of nitrogen, sulphur and oxygen Heteroatom dopings enter in carbon-based frame, more defect sites are provided, accelerate electronics
Conduction is to make its electro catalytic activity be improved.In addition, the porous carbon structure and nanometer cobalt of more Heteroatom dopings/eight vulcanizations nine
Cobalt phase combines the synergistic effect generated further to promote the electro catalytic activity of material, has weight in electro-catalysis overall moisture solution field
It is worth and realistic meaning.
Detailed description of the invention
Fig. 1 is powder x-ray diffraction (PXRD) map and the monocrystalline simulation of Co-NSOMOF presoma synthesized by the present invention
PXRD map comparison diagram；Wherein, the 1 PXRD spectrogram to be simulated by single crystal data；2 be synthesis Co-NSOMOF PXRD spectrum
Figure.
Fig. 2 is catalyst Co/Co prepared by the present invention9S8Powder x-ray diffraction (PXRD) phenogram of@NSOC, wherein
1 is by the resulting Co in inorganic crystal data library9S8The PXRD spectrum that standard card is simulated；2 be resulting by inorganic crystal data library
The PXRD spectrum that Co standard card is simulated；3 be catalyst Co/Co prepared by the present invention9S8The PXRD of@NSOC is composed.
Fig. 3 is the transmission electron microscope picture (a) of catalyst prepared by the present invention, (b) is the high-resolution-ration transmission electric-lens of catalyst
Scheme, the 1 lattice diffraction fringes for vulcanizing nine cobalt nano-particles for eight in figure, 2 be the lattice diffraction fringe of cobalt nano-particle, (c) is
The constituency Elemental redistribution of catalyst scans (Mapping) electron microscope.
Fig. 4 is nitrogen adsorption isotherm of catalyst at a temperature of 77K prepared by the present invention, and illustration is according to absorption etc.
The pore size distribution curve for the catalyst that warm line computation goes out.
Fig. 5 is for catalyst prepared by the present invention as working electrode active material in 1mol L-1In potassium hydroxide solution
OER linear scan polarization curve.
Fig. 6 is the Tafel slope curve of the prepared catalyst of the present invention fitted by Fig. 5 OER polarization curve.
Fig. 7 is for catalyst prepared by the present invention as working electrode active material in 1mol L-1In potassium hydroxide solution
Stability time-testing current figure.
Fig. 8 is for catalyst prepared by the present invention as working electrode active material in 1mol L-1In potassium hydroxide solution
HER linear scan polarization curve.
Fig. 9 is the Tafel slope curve of the prepared catalyst of the present invention fitted by Fig. 8 HER polarization curve.
Figure 10 is the overall moisture electrolytic cell that catalyst prepared by the present invention is assembled as cathode and anode material.
Figure 11 is the line for the overall moisture electrolytic cell that catalyst prepared by the present invention is assembled as cathode and anode material
Property scanning polarization curve, electrolyte be 1mol L-1Potassium hydroxide solution.
Figure 12 be the present invention prepared by catalyst as cathode and anode material assembling overall moisture electrolytic cell it is steady
Characteristic time-testing current figure.
Specific embodiment
Below by example, the present invention is described further:
Embodiment 1: synthesis nanometer cobalt/cobalt sulfide is carried on the compound electro-catalysis overall moisture of porous carbon of Heteroatom doping
Solve catalyst
(1) by 0.435g cabaltous nitrate hexahydrate and bis- (the 4- pyrroles of 0.172g 2,5- thiophene dicarboxylic acid and 0.198g 1,3-
Piperidinyl) propane is dissolved in 30mL n,N-Dimethylformamide, 2h is stirred at room temperature.Then it is stirred back under the conditions of 120 DEG C
Stream 12h obtains purple turbid solution.It is filtered, after washing and being dried in vacuo, it is solid that grinding obtains presoma (Co-NSOMOF) purple
Body powder.The PXRD of presoma is as shown in Figure 1, prepared presoma and the peak PXRD simulated with single crystal data are almost complete
It is complete to coincide, show that prepared presoma has very high crystallinity and purity.
(2) violet solid powder obtained in 400mg step (1) is placed in quartz boat, quartz boat is placed on tubular type
In furnace, first leads to nitrogen 30min and exhaust furnace air, then tube furnace is warming up under nitrogen atmosphere with the rate of 10 DEG C/min
800 DEG C, and in 800 DEG C of calcining at constant temperature 3h.After cooled to room temperature, by obtained black solid through dilute hydrochloric acid supersound washing,
Then washing is centrifuged repeatedly for several times with deionized water and ethyl alcohol, black solid powder is obtained after drying and grinding.
(3) nanometer cobalt/cobalt sulfide is carried on the characterization of the porous carbon composite of Heteroatom doping:
The PXRD of prepared composite material is as shown in Fig. 2, the characteristic peak of resulting materials and JCPDS standard card in map
The Co of No.86-22739S8And the Co of No.89-4307 is consistent, and belongs to cubic crystal structure.Transmission electron microscope and high-resolution
Transmission electron microscope and Elemental redistribution scanning (Mapping) are as shown in figure 3, gained carbon material is porous structure, and has cobalt and eight
Vulcanize nine cobalt nano-particles to be supported in porous carbon matrix.Distribution diagram of element shows carbon in resulting materials, nitrogen, sulphur, oxygen and cobalt
Element exists and is uniformly distributed.Nitrogen adsorption result as shown in figure 4, show resulting materials nitrogen adsorption capacity with higher,
Specific surface area is larger, and has micropore, mesoporous, macropore and the hierarchical porous structure deposited.
Embodiment 2: the porous carbon compound material that nanometer cobalt/cobalt sulfide of the present invention is carried on Heteroatom doping is urged as electricity
The performance test of agent
The preparation of elctro-catalyst working electrode:
By by 2mg Co/Co produced by the present invention9S8@NSOC catalyst is dispersed in 220 μ L and contains 100 μ L water, 100 μ L DMF
In the Nafion solution of 20 μ L mass percentages 5%, then it is ultrasonically treated 30 minutes and obtains the finely dispersed slurry of catalyst
Liquid.Then, 5 μ L slurry drops are coated in glassy carbon electrode surface using micropipettor, be then dried at room temperature for stand-by.Electro-catalysis
Agent performance test uses three-electrode system, and electrolyte is 1mol L-1Potassium hydroxide aqueous solution.Test equipment is Shanghai morning China
CHI660E electrochemical workstation.
Fig. 5 is that oxygen property test chart is analysed in the electro-catalysis of catalyst of the present invention, as shown, in 1mol L-1Potassium hydroxide
In electrolyte, load has the electrode of catalyst that there is apparent electro-catalysis to analyse oxygen property.When current density reaches 10mA cm-2When,
Its overpotential for oxygen evolution is 373mV, has lower analysis oxygen overpotential.
Fig. 6 is that the corresponding Tafel slope figure of oxygen test is analysed in electro-catalysis, as shown, the catalyst has lower tower luxuriant and rich with fragrance
That slope (80mv/dec).
Fig. 7 is that oxidative stability test chart is analysed in the electro-catalysis of resulting materials, as shown, in the chronoamperometry by 10h
After test, correlated current does not change substantially, has excellent chemical stability, practical application value with higher.
Fig. 8 is the electrocatalytic hydrogen evolution property test chart of catalyst of the present invention, as shown, in 1mol L-1Potassium hydroxide
In electrolyte, load has the electrode of catalyst to have apparent electrocatalytic hydrogen evolution property.When current density reaches 10mA cm-2When,
Its overpotential of hydrogen evolution is 216mV, has lower liberation of hydrogen overpotential under alkaline condition.
Fig. 9 is that electrocatalytic hydrogen evolution tests corresponding Tafel slope figure, as shown, the catalyst has lower tower luxuriant and rich with fragrance
That slope (149mv/dec).
Embodiment 3: nanometer cobalt/cobalt sulfide prepared by the present invention is carried on the compound catalysis of porous carbon of Heteroatom doping
Application of the agent in overall moisture solution electrolytic cell
Using catalyst produced by the present invention as the cathode and anode of overall moisture solution electrolytic cell, electrolyte is Figure 10
1mol L-1Potassium hydroxide aqueous solution, apparent hydrogen and oxygen can be observed and generate.
Figure 11 is the line for the overall moisture solution electrolytic cell for using prepared catalyst to assemble as cathode and anode material
Property scanning polarization curve, when current density be 10mA cm-2When, having lower cell voltage is 1.56V.
As shown in figure 12, the overall moisture solution electrolytic cell assembled with prepared catalyst of the present invention is electric by the timing of 10h
After the test of stream method, correlated current shows that prepared catalyst has excellent stability, has there is no significantly changing
Higher practical application value.
Claims (5)
1. the porous carbon composite catalyst that a kind of nanometer cobalt/cobalt sulfide is carried on Heteroatom doping, which is characterized in that by such as
Lower section method is prepared:
(1) bis- (4- pyridyl group) propane of 2,5- thiophene dicarboxylic acid, 1,3-, cabaltous nitrate hexahydrate are dissolved in N, N- dimethyl methyl respectively
It in amide, is stirred at room temperature, later in 110-120 DEG C of isothermal reaction, after reaction, is cooled to room temperature to system temperature
Obtain turbid solution；
(2) solid is obtained by filtration in turbid solution obtained in step (1), through drying, grinding obtains Co-NSOMOF presoma；
(3) the resulting Co-NSOMOF presoma of step (2) is calcined under nitrogen atmosphere and obtains solid powder, it is super through dilute hydrochloric acid
Sound washing, is then centrifuged repeatedly washing with deionized water and ethyl alcohol, obtains target product after drying and grinding.
2. nanometer cobalt/cobalt sulfide as described in claim 1 is carried on the porous carbon composite catalyst of Heteroatom doping, feature
It is, the molar ratio of bis- (4- pyridyl group) propane of 2,5- thiophene dicarboxylic acid, 1,3- and cabaltous nitrate hexahydrate is 1:1 in step (1):
1.5~1.8。
3. nanometer cobalt/cobalt sulfide as described in claim 1 is carried on the porous carbon composite catalyst of Heteroatom doping, feature
It is, step (3) heating rate is 5 ~ 10 DEG C/min, and the temperature of presoma calcining is 600-900 DEG C.
4. nanometer cobalt/cobalt sulfide described in claim 1-3 is carried on the application of the porous carbon composite catalyst of Heteroatom doping,
It is characterized in that, as follows as elctro-catalyst working electrode application method: (1) nanometer cobalt/cobalt sulfide being carried on hetero atom and mixed
Miscellaneous porous carbon composite catalyst Co/Co9S8@NSOC is added in the mixed solution of n,N-Dimethylformamide and deionized water,
Nafion solution is added, obtains finely dispersed catalyst slurry after ultrasonic disperse；By catalyst slurry drop-coated in glass-carbon electrode
It goes up and is dried at room temperature for；(2) three-electrode system is used, is using silver-silver chloride (Ag/AgCl) electrode as reference electrode, platinum filament
Auxiliary electrode, 1 mol L-1Potassium hydroxide aqueous solution is that electrolyte carries out electro-catalysis production hydrogen respectively and produces oxygen.
5. nanometer cobalt/cobalt sulfide as described in claim 1-3 is carried on answering for the porous carbon composite catalyst of Heteroatom doping
With, which is characterized in that the application of water decomposition electrolytic cell is as follows as a whole, is carried on hetero atom respectively with nanometer cobalt/cobalt sulfide and mixes
Miscellaneous porous carbon composite catalyst Co/Co9S8For@NSOC as cathode and anode, electrolyte is 1 mol L-1Potassium hydroxide water
Solution.
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| CN114990567A (en) * | 2022-05-13 | 2022-09-02 | 北京理工大学 | Preparation method and application of sulfur coordination cobalt monoatomic catalyst loaded on carbon-based carrier |
| CN113134394B (en) * | 2021-03-27 | 2022-11-15 | 上海应用技术大学 | Method for modifying ZIF-67 through vulcanization and application |
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| CN112264046A (en) * | 2020-09-15 | 2021-01-26 | 金陵科技学院 | Co derived from coordination compound9S8Porous carbon composite catalyst and preparation method thereof |
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Application publication date: 20190517 |