CN110176606A - A kind of Co@NC high dispersive catalyst with core-casing structure, preparation method and applications - Google Patents
A kind of Co@NC high dispersive catalyst with core-casing structure, preparation method and applications Download PDFInfo
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- CN110176606A CN110176606A CN201910423441.5A CN201910423441A CN110176606A CN 110176606 A CN110176606 A CN 110176606A CN 201910423441 A CN201910423441 A CN 201910423441A CN 110176606 A CN110176606 A CN 110176606A
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- dicyanodiamine
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 27
- 239000008103 glucose Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 239000002105 nanoparticle Substances 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 239000010411 electrocatalyst Substances 0.000 claims abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- -1 dicyan Diamines Chemical class 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 30
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000003780 insertion Methods 0.000 abstract 1
- 230000037431 insertion Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- 239000011258 core-shell material Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229910018874 CoNx Inorganic materials 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002133 porous carbon nanofiber Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/396—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- Y02E60/50—Fuel cells
Abstract
A kind of Co@NC high dispersive catalyst with core-casing structure, preparation method and applications, belong to energy and material and electrochemical technology field.Catalyst with glucose be the source C, dicyanodiamine C, N source, Co (NO3)·6H2O is the source Co, is made using high-temperature calcination；The g-C of dicyanodiamine pyrolytic generation two-dimensional sheet3N4, the intermediate carbon and metal species that glucose pyrolytic generates, insertion g-C3N4Sheet in；It is dispersed on graphene carbon-coating in the catalyst by the Co nanoparticle that N-C layers coat.The catalyst may be used as metal-air battery, fuel battery negative pole oxygen reduction electro-catalyst.Low in raw material price of the present invention is easy to get, and preparation process is simple, is easy to amplify production；The decomposition in situ of dicyanodiamine provides N abundant for catalyst and adulterates active site, forms abundant meso-hole structure, improves catalyst activity, and the transmitting transport for reaction partner matter during ORR provides channel, meets the mass transfer demand of reaction process；Catalyst stability is good, methanol tolerance is strong.
Description
Technical field
The invention belongs to energy and material and electrochemical technology fields, are related to a kind of Cathodic oxygen reduction elctro-catalyst, tool
Body is related to a kind of Co@NC high dispersive catalyst with core-casing structure, preparation method and applications.
Background technique
In recent years fuel cell because economical and efficient, it is environmentally protective the advantages that cause the extensive concern of domestic and foreign scholars.
However the Cathodic oxygen reduction of fuel cell (ORR) has that dynamic process is slow.Pt base catalyst is current property
Best, the most popular fuel cell ORR catalyst of energy, but Pt base elctro-catalyst stability is poor, at high price, limits combustion
Expect that the large-scale commercial of battery uses, thus develops there is higher catalytic activity and stability, corrosion-resistant, low-cost urge
Agent has important practical significance and application value.
Transition metal (such as Fe, Co, Ni, Mn) catalyst is at low cost, chemical stability is good, high catalytic efficiency, environment friend
Good and reactive specy multiplicity, most potential substitution Pt base catalyst.Especially metal-nitrogen-carbon (M-N-C) catalyst is due to tool
There is efficient active site, there is important research significance to ORR catalytic performance is improved.However, there is activity in M-N-C catalyst
The problems such as site is easily dissociated in the electrolytic solution, poor catalyst stability.Using the corrosion resistance of carbon, better than metallic, this is special
Active sites are coated in carbon-coating structure and prepare cladded type M-N-C and can effectively solve the above problems by point.This structure not only may be used
To improve catalyst electric conductivity, the dispersion of metallic can also be promoted, prevent metal nanoparticle from reuniting, guard catalyst
Active sites, while the carbon material of metallic and Heteroatom doping is it is also possible to occurring synergistic effect and further increasing catalyst
ORR catalytic performance.
The porous carbon of N doping has been made using the method for fractional steps by Bai et al. [Small Methods 2018,1800049,1-8]
Nano fiber coated Co particle catalyst.They are first by Zn (NO3)2·6H2O and Co (NO3)2·6H2O and 2-methylimidazole are first
Then Zn is made in magnetic agitation under aged at room temperaturexCo1-x- ZIFs precursor；Then by ZnxCo1-x- ZIFs precursor and N- bis-
Methylformamide and polyacrylonitrile are using the obtained Zn of method of electrostatic spinningxCo1-x- ZIF@PAN fiber；Final high temperature calcined catalyst
The porous carbon nanofiber that N doping is made in precursor coats Co particle catalyst.The experimental results showed that the catalyst is with excellent
ORR catalytic performance, good stability and methanol tolerant performance.However, the catalyst preparation process is many and diverse, step is more, experiment
Condition needs further improvement.
Song et al. [Carbon.2018 (138) 300-308] is wrapped in using the carbon-coating that Co-N doping is made in two-step method
Co/CoNxThe catalyst with core-casing structure (Co-N-PC) of@C nano particle.Firstly, trisodium citrate is used to pass through high temperature for carbon source
Porous carbon PC is made in calcining and pickling；Then with CoCl2·6H2O is the source Co, the source melamine C, N, 1,10- phenanthroline soft mode
Core-shell structure Co-N-PC catalyst is made using high-temperature calcination in plate.The experimental results showed that the catalyst shows under alkaline condition
Out to O2Efficient catalytic, and show good stability.However, catalyst metal particle size model during the preparation process
It encloses greatly, process is many and diverse, is unfavorable for large scale preparation.
In conclusion M-N-C catalyst has good ORR catalytic performance, but preparation process is up for being further simplified.
Therefore, design preparation process is simple, raw material is cheap and the efficient M-N-C catalyst of abundance has important practical significance and
Application value.
The present invention uses cheap glucose for the source C, the source dicyanodiamine C, N, Co (NO3)·6H2O is source metal,
The Co NC catalyst that N doping carbon nanometer layer cladding Co nanoparticle core-shell structure is prepared using one step of high temperature pyrolytic cracking (HTP), for urging
Change ORR reaction.
Summary of the invention
The present invention provides a kind of Co NC catalyst of N doping carbon nanometer layer cladding Co nanoparticle core-shell structure, preparation side
Method and application, the catalyst use cheap glucose for the source C, the source dicyanodiamine C, N, Co (NO3)·6H2O is metal
The source Co is made using one step of high-temperature calcination.Compared with common Pt base catalyst, take-off potential and quotient in alkaline medium
The performance that product Pt/C is catalyzed ORR is suitable, positive 38mV of the half wave potential than commodity Pt/C, and has higher stability and resistance to first
Alcohol performance, low in raw material price and abundance, preparation process is simple, is conducive to large-scale production, practical valence with higher
Value.
In order to achieve the above object, The technical solution adopted by the invention is as follows:
A kind of Co@NC high dispersive catalyst with core-casing structure, the catalyst with cheap glucose be the source C, dicyan two
Amine is the source C, N, Co (NO3)·6H2O is the source Co, is made using one step of high-temperature calcination, and it is 2-30nm which, which has aperture,
Meso-hole structure.The g-C of dicyanodiamine pyrolytic generation two-dimensional sheet3N4, glucose pyrolytic generate intermediate carbon and
Metal species are inserted into g-C3N4Sheet in, facilitate g-C3N4Grow into graphene sheet layer and non-carbonic nanotube.The catalyst
Middle to be dispersed on graphene carbon-coating by the Co nanoparticle that N-C layers coat, Co metal nanoparticle is uniform in size, passes through tune
The feed ratio for controlling calcination temperature and precursor, can control the pattern of catalyst, optimal screening goes out the catalyst that ORR is had excellent performance.
Compared with Typical precious metal catalyst (Pt yl), the catalyst raw material is at low cost and abundance, and preparation process is simple, activity and
Stability is prominent, and is conducive to large-scale production.
A kind of preparation method of Co@NC high dispersive catalyst with core-casing structure, comprising the following steps:
(1) by cobalt metal salt Co (NO3)·6H2O, glucose, dicyanodiamine are added separately in water, in 50~100 DEG C of temperature
The lower stirring 0.1-48h of degree obtains solution A.The molar ratio of the dicyanodiamine and cobalt metal salt is 50~200:1~10；It is described
Glucose and dicyanodiamine mass ratio be 1~30:1~30.
(2) step (1) acquired solution A is dry, obtain catalyst precarsor B.
(3) calcined catalyst precursor B under inert atmosphere, calcination temperature are 500-1500 DEG C, and heating rate is 1-30 DEG C
min-1, calcination time 0.5-48h obtains Co@NC catalyst after cooling.
Co (NO described in step (1)3)·6H2O can be replaced one of Co transition metal salt or a variety of.Dicyanodiamine
Alternatively at g-C3N4, urea, melamine, one of thiocarbamide etc. or a variety of.
Drying means described in step (2) is vacuum drying, air atmosphere is dry, inert atmosphere is dry, is freeze-dried etc.,
Drying temperature is -40~200 DEG C, and drying time is 1~100h.
Inert gas used in step (3) is the one or more of nitrogen or argon gas, and inert gas flow velocity is 1~30mL
min-1。
Above-mentioned Co (NO3)·6H2O catalyst with core-casing structure is used as metal-air battery, fuel battery negative pole hydrogen reduction electricity
Catalyst.
Compared with prior art, Co@NC high dispersive catalyst with core-casing structure of the present invention and preparation method have following
Advantage:
It 1) is the source C using glucose using the Co@NC high dispersive catalyst with core-casing structure of the method for the invention preparation,
Dicyanodiamine is the source C, N, Co (NO3)·6H2O is source metal, is prepared using " a step pyrolysismethod ", raw materials used price is low
Honest and clean to be easy to get, preparation process is simple, is easy to amplify production；
2) using the Co@NC high dispersive catalyst with core-casing structure of the method for the invention preparation, Co nanoparticle is wrapped by
In N doping carbon-coating, core-shell structure is formed, metallic particle size is close, is uniformly dispersed.Unique core-shell structure can be kept away
Exempt from Co nanoparticle and directly contacted with electrolyte, inhibits the growth and reunion of metal nanoparticle, and Co nanoparticle is in height
The electric conductivity of catalyst can be improved in the graphitization for facilitating carbon-coating in warm calcination process, these are conducive to the electricity for improving catalyst
Chemical activity and stability；
3) using the Co@NC high dispersive catalyst with core-casing structure of the method for the invention preparation, having aperture is 2-30nm
Meso-hole structure, can for during ORR reaction partner matter transmitting transport channel be provided, meet the mass transfer need of reaction process
It asks；
4) using the Co@NC high dispersive catalyst with core-casing structure of the method for the invention preparation, N-C layers of cladding Co nucleocapsid are received
Rice corpuscles is dispersed in graphene film layer surface, and it is a large amount of that the graphene sheet layer of high conductivity and high-specific surface area is conducive to exposure
Active site, improve material ORR activity；
5) using the Co@NC high dispersive catalyst with core-casing structure of the method for the invention preparation, by regulating and controlling preparation condition,
The controllable preparation of the achievable catalyst of molar feed ratio, calcination temperature, calcination time of such as dicyanodiamine and source metal；
6) using the Co@NC high dispersive catalyst with core-casing structure of the method for the invention preparation, pass through x-ray photoelectron energy
The content of hetero atom nitrogen is up to 8.81% known to spectrum (XPS) test, can enrich the active site and defective bit of material surface
Point is conducive to improve material ORR activity；
7) using the Co@NC high dispersive catalyst with core-casing structure of the method for the invention preparation, ORR under alkaline condition
Take-off potential is close to commercialization Pt/C catalyst, and half wave potential is far just in commercialization Pt/C catalyst, and stability is good, methanol tolerance
Property is strong.It can be used as the cathodic oxygen reduction catalyst of a variety of devices such as metal-air battery, fuel cell.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) spectrogram that sample is made according to embodiment 1.
Fig. 2 (a) is transmission electron microscope (TEM) photo that sample is made according to embodiment 1.
Fig. 2 (b) is high power transmission electron microscope (RHTEM) picture that sample is made according to embodiment 1.
Fig. 3 (a) is the nitrogen adsorption desorption curve that sample is made according to embodiment 1.
Fig. 3 (b) is the pore size distribution curve that sample is made according to embodiment 1.
Fig. 4 (a) is the total spectrogram of x-ray photoelectron spectroscopy that sample is made according to embodiment 1.
Fig. 4 (b) is the high-resolution Co 2p x-ray photoelectron spectroscopy spectrogram that sample is made according to embodiment 1.
Fig. 4 (c) is the high-resolution N 1s x-ray photoelectron spectroscopy spectrogram that sample is made according to embodiment 1.
Fig. 5 is according to embodiment 1, and sample made from 2,3 and comparative example 1 are in room temperature, O2The 0.1mol L of saturation-1KOH electricity
Cyclic voltammetric (CV) curve in liquid is solved, sweeps speed: 10mV s-1, revolving speed: 1600rpm.
Fig. 6 (a) is the sample according to made from embodiment 1 in room temperature, O2The 0.1mol L of saturation-1Line in KOH electrolyte
Property scanning volt-ampere (LSV) curve, sweep speed: 10mV s-1, revolving speed: 400rpm, 900rpm, 1600rpm, 2500rpm；Fig. 6 (b) is
Koutecky-Levich (K-L) curve corresponding with the LSV curve of Fig. 6 (a).
Fig. 7 is the sample according to made from embodiment 1 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electrolyte
In chronoamperogram, sweep speed: 100mV s-1, revolving speed: 400rpm, voltage are constant at 0.56V (vs.RHE).
Fig. 8 is sample made from embodiment 1 respectively in room temperature, O2The 0.1mol L of saturation-1KOH electrolyte, O2Saturation
3mol L-1CH3OH+0.1mol L-1CV curve in KOH electrolyte, sweeps speed: 10mV s-1。
Fig. 9 is comparative example 1 respectively in room temperature, O2The 0.1mol L of saturation-1KOH electrolyte, O2The 3mol L of saturation- 1CH3OH+0.1mol L-1CV curve in KOH electrolyte, sweeps speed: 10mV s-1.The present invention tests reference electrode used
The Ag/AgCl electrode of KCl saturation.Potential is carried out by V (vs.RHE)=V (vs.Ag/AgCl)+0.059pH+0.26 formula to turn
It changes.
Specific embodiment
The present invention is explained in detail below with reference to specific example, but the present invention is not limited only to these specific implementations
Example.
Embodiment 1:Co@NC1:104(Co refers to Co (NO in raw material to-C-8003)·6H2O, NC are dicyanodiamine, 1:104 Co
(NO3)·6H2The molar ratio of O and dicyanodiamine, C are glucose, and the mass ratio of NC and C are 15:1, and 800 refer to that pyrolysis temperatures are 800
℃)
By 0.05g Co (NO3)·6H2O, 1.5g dicyanodiamine and 0.1g glucose are dissolved in 20ml deionized water, obtain solution
A；3h is stirred at 80 DEG C of oil bath, is uniformly mixed with abundant dissolution and obtains solution B；By uniformly mixed solution in air drying cabinet
In 80 DEG C of dry 12h, obtain catalyst precarsor；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat,
30 DEG C of min under nitrogen protection-1Temperature programming obtains Co@NC after natural cooling to 800 DEG C of calcining 2h1:104- C-800 catalysis
Agent.
Embodiment 2:Co@NC1:104(Co refers to Co (NO in raw material to-C-7003)·6H2O, NC are dicyanodiamine, 1:104 Co
(NO3)·6H2The molar ratio of O and dicyanodiamine, C are glucose, and the mass ratio of NC and C are 15:1, and 700 refer to that pyrolysis temperatures are 700
℃)
By 0.05g Co (NO3)·6H2O, 1.5g dicyanodiamine and 0.1g glucose are dissolved in 20ml deionized water, obtain solution
A；0.5h is stirred at 100 DEG C of oil bath, is uniformly mixed with abundant dissolution and obtains solution B；Uniformly mixed solution is done in air
80 DEG C of dry 12h, obtain catalyst precarsor in dry case；Drying gained precursor is placed in mortar, grinding is uniformly placed on quartz
In boat, 15 DEG C of min under nitrogen protection-1Temperature programming obtains Co@NC after natural cooling to 700 DEG C of calcining 45h1:104-C-
700 catalyst.
Embodiment 3:Co@NC200:7(Co refers to Co (NO in raw material to-C-9003)·6H2O, NC are dicyanodiamine, 200:7 Co
(NO3)·6H2The molar ratio of O and dicyanodiamine, C are glucose, and the mass ratio of NC and C are 1:30, and 900 refer to that pyrolysis temperatures are 900
℃)
By 0.05g Co (NO3)·6H2O, 1.5g dicyanodiamine and 0.1g glucose are dissolved in 20ml deionized water, obtain solution
A；25h is stirred at 80 DEG C of oil bath, is uniformly mixed with abundant dissolution and obtains solution B；By uniformly mixed solution in inert atmosphere
80 DEG C of dry 12h, obtain catalyst precarsor in drying box；Drying gained precursor is placed in mortar, grinding is uniformly placed on stone
Ying Zhouzhong, under nitrogen protection 15 DEG C of min-1Temperature programming obtains Co@NC after natural cooling to 900 DEG C of calcining 0.5h1:104-
C-900 catalyst.
Embodiment 4:Co@NC50:1(Co refers to Co (NO in raw material to-C-5003)·6H2O, NC are dicyanodiamine, 50:1 Co
(NO3)·6H2The molar ratio of O and dicyanodiamine, C are glucose, and the mass ratio of NC and C are 1:30, and 500 refer to that pyrolysis temperatures are 500
℃)
By 0.57g Co (NO3)·6H2O, 0.33g dicyanodiamine and 0.1g glucose are dissolved in 20ml deionized water, obtain solution
A；3h is stirred at 100 DEG C of oil bath, is uniformly mixed with abundant dissolution and obtains solution B；Uniformly mixed solution is being air-dried
200 DEG C of dry 1h, obtain catalyst precarsor in case；Drying gained precursor is placed in mortar, grinding is uniformly placed on quartz boat
In, 3 DEG C of min under nitrogen protection-1Temperature programming obtains Co@NC after natural cooling to 500 DEG C of calcining 0.5h50:1- C-500 is urged
Agent.
Embodiment 5:Co@NC200:7(Co refers to Co (NO in raw material to-C-15003)·6H2O, NC are dicyanodiamine, and 200:7 is
Co(NO3)·6H2The molar ratio of O and dicyanodiamine, C are glucose, and the mass ratio of NC and C are 1:30, and 1500 finger pyrolysis temperatures are
1500℃)
By 2.3g Co (NO3)·6H2O, 0.0033g dicyanodiamine and 0.1g glucose are dissolved in 20ml deionized water, obtain molten
Liquid A；48h is stirred at 50 DEG C of oil bath, is uniformly mixed with abundant dissolution and obtains solution B；Uniformly mixed solution is dry in freezing
- 40 DEG C of dry 30h, obtain catalyst precarsor in dry case；Drying gained precursor is placed in mortar, grinding is uniformly placed on quartz
In boat, 3 DEG C of min under protection of argon gas-1Temperature programming obtains Co@NC after natural cooling to 1500 DEG C of calcining 2h200:7-C-
1500 catalyst.
Embodiment 6:Co@NC100:3(Co refers to Co (NO in raw material to-C-8003)·6H2O, NC are dicyanodiamine, 100:3 Co
(NO3)·6H2The molar ratio of O and dicyanodiamine, C are glucose, and the mass ratio of NC and C are 10:1, and 800 refer to that pyrolysis temperatures are 800
℃)
By 173g Co (NO3)·6H2O, 1.5g dicyanodiamine and 0.15g glucose are dissolved in 20ml deionized water, obtain solution
A；0.1h is stirred at 10 0 DEG C of oil bath, is uniformly mixed with abundant dissolution and obtains solution B；Uniformly mixed solution is done in air
100 DEG C of dry 2h, obtain catalyst precarsor in dry case；Drying gained precursor is placed in mortar, grinding is uniformly placed on quartz
In boat, 30 DEG C of min under nitrogen protection-1Temperature programming obtains Co@NC after natural cooling to 800 DEG C of calcining 48h100:3-C-
800 catalyst.
Embodiment 7:Co@NC80:3(Co refers to CoCl in raw material to-C-8002, NC is melamine, and 80:3 is Co (NO3)·
6H2The molar ratio of O and melamine, C are glucose, and the mass ratio of NC and C are 15:7, and 800 refer to that pyrolysis temperatures are 800 DEG C)
By 41.2g CoCl2, 1.5g melamine and 0.7g glucose are dissolved in 20ml deionized water, obtain solution A；In oil bath
35h is stirred at 70 DEG C, is uniformly mixed with abundant dissolution and obtains solution B；By uniformly mixed solution 130 DEG C in air drying cabinet
Dry 40h, obtains catalyst precarsor；Drying gained precursor is placed in mortar, grinding is uniformly placed in quartz boat, in argon gas
Protect lower 10 DEG C of min-1Temperature programming obtains Co@NC after natural cooling to 800 DEG C of calcining 35h80:3- C-800 catalyst.
Comparative example 1: commercialization 20wt.%Pt/C catalyst (JM).
Fig. 1 is X-ray diffraction (XRD) spectrogram that sample is made according to embodiment 1.It is analyzed by the PCPDF card of XRD spectra
Known to the metal species that are made in sample of embodiment 1 be cubic Co (PCPDF#89-7093).Peak position 44.2 °,
The crystal face of Co (111), Co (200), Co (220) are respectively corresponded at 51.5 °, 75.8 °.In addition, 2 θ=26 ° or so are graphene
(002) characteristic diffraction peak of crystal face shows embodiment 1 sample is made and contains high-graphitized carbon.
Fig. 2 (a) is that transmission electron microscope (TEM) photo of sample is made according to embodiment 1 under the conditions of 200nm.Fig. 2 (b) is
Under the conditions of 10nm, high power transmission electron microscope (RHTEM) picture of sample is made according to embodiment 1.By Fig. 2 (a) it is found that metal Co
Nanoparticle is evenly distributed on carbon-coating surface, by NANO software by measuring the diameter of 200 multiple particles it is found that metal at random
The diameter of particle is about 10nm.Metal Co nanoparticle is by the nano-sized carbon of about 2~5nm thickness known to high power electron microscope 2 (b)
Layer cladding, learns from the calculating of lattice fringe, and the spacing of lattice of Co nanoparticle is 0.204nm, corresponds to Cubic Co
(111) crystal face of [PCPDF#89-7093], matches with the test result of XRD.This clad structure also can avoid metallic
With directly contacting for electrolyte solution, the stability of material is improved.
Fig. 3 (a) is the nitrogen adsorption desorption curve that sample is made in embodiment 1, from Fig. 3 (a): in relative pressure P/P0
When being 0.4, there is hysteresis loop (adsorpting type IV), this illustrates that catalyst is mesoporous material, specific surface area 352m2g-1；Fig. 3
(b) pore size distribution curve of sample is made for embodiment 1, from Fig. 3 (b): the aperture for the sample that embodiment 1 is prepared
It is mainly distributed on 2-30nm, is conducive to the transmission of ORR reaction partner matter, meets the mass transfer demand of reaction.
Fig. 4 (a) is the total spectrogram of x-ray photoelectron spectroscopy that sample is made according to embodiment 1.System known to from test result
The catalyst nitrogen atom content obtained is up to 8.81%, and the content of metal Co is 1.32%, illustrates the exposed metal of catalyst surface
Particle is few, and most of to be all wrapped in by graphite carbon-coating, this is consistent with TEM result.Fig. 4 (b) is that sample is made according to embodiment 1
High-resolution Co 2p x-ray photoelectron spectroscopy spectrogram, the surface C o of sample catalyst is made mainly with Co in embodiment 13+2p3/2、
Co2+2p3/2、Co3+2p1/2、Co2+2p1/2In the presence of different valence states can provide " donor-receptor " chemisorption site, Ke Yike
Inverse absorption O2, so the catalyst has excellent ORR catalytic activity.Fig. 4 (c) is the height that sample is made according to embodiment 1
N 1s x-ray photoelectron spectroscopy spectrogram is differentiated, can be fitted out the nitrogen species of three types: pyridine N, pyrroles N, graphite N,
And pyridine N, graphite N content is higher, is conducive to be catalyzed ORR.
Fig. 5 is according to embodiment 1, and sample made from 2,3 and comparative example 1 are in room temperature, O2The 0.1mol L of saturation-1KOH electricity
Cyclic voltammetric (CV) curve in liquid is solved, sweeps speed: 10mV s-1, revolving speed: 1600rpm.By Fig. 6, calcination temperature is to catalyst
ORR is affected.When calcination temperature is 800 DEG C, catalyst made from embodiment 1 shows the (starting of excellent ORR catalytic activity
Point 0.97V, half-wave point 0.86V), Pt/C (starting point 0.97V, half-wave point 0.82V) of the catalytic performance better than business.
Fig. 6 (a) is the sample according to made from embodiment 1 in room temperature, O2The 0.1mol L of saturation-1Line in KOH electrolyte
Property scanning volt-ampere (LSV) curve, sweep speed: 10mV s-1, revolving speed: 400rpm, 900rpm, 1600rpm, 2500rpm.Fig. 7 (b) is
Koutecky-Levich (K-L) curve obtained according to the LSV curve (7 (a)) that sample is made in embodiment 1.It can by Fig. 6 (a)
Know, as revolving speed increases, ORR take-off potential is remained unchanged, and Limited diffusion current density constantly increases.It is calculated according to K-L equation
The electron transfer number of 1 surface catalysis ORR of embodiment is 4 or so, shows that catalyst made from embodiment 1 is catalyzed with 4 electronic processes
ORR。
Fig. 7 is the sample according to made from embodiment 1 and comparative example 1 in room temperature, O2The 0.1mol L of saturation-1KOH electrolyte
In chronoa mperometric plot, revolving speed: 400rpm, voltage are constant at 0.56V (vs.RHE).By comparison it is found that passing through 1800s
Chrono-amperometric stability test after, catalyst current density made from embodiment 1 is reduced to original 99.6%, only decay
0.4%；Under the same terms, the current density of 1 catalyst of comparative example is reduced to the 83% of starting, illustrates to urge made from embodiment 1
For agent stability better than catalyst made from comparative example 1, this may be attributed to the fact that the core-shell structure of high dispersive effectively prevents gold
Belong to nanoparticle falling off in catalytic process and assembles.
Fig. 8, Fig. 9 are respectively embodiment 1 and comparative example 1 in O2The 0.1mol L of saturation-1KOH electrolyte, O2Saturation
3mol L-1CH3OH+0.1mol L-1CV figure in KOH electrolyte.As shown in Figure 9, catalyst made from embodiment 1 with and without
In the electrolyte solution of methanol, CV curve shows that catalyst made from embodiment 1 is not influenced by methanol fuel without significant change,
It may be used as methanol fuel cell cathode catalyst.As shown in Figure 10, the catalyst of comparative example 1 is in the electrolyte solution for having methanol
In, there is apparent methanol oxidation current (0.4~1.3V), can catalysis methanol oxidation, show selection of the comparative example 1 to fuel
Property it is poor, vulnerable to methanol fire influence.
Embodiment described above only expresses embodiments of the present invention, and but it cannot be understood as to the invention patent
Range limitation, it is noted that for those skilled in the art, without departing from the inventive concept of the premise, also
Several modifications and improvements can be made, these are all belonged to the scope of protection of the present invention.
Claims (8)
1. a kind of Co@NC high dispersive catalyst with core-casing structure, which is characterized in that the catalyst with glucose be the source C, dicyan
Diamines is the source C, N, Co (NO3)·6H2O is the source Co；The g-C of dicyanodiamine pyrolytic generation two-dimensional sheet3N4, glucose height
Temperature decomposes the intermediate carbon generated and metal species are inserted into g-C3N4Sheet in, g-C3N4Grow into graphene sheet layer；The catalysis
It is dispersed on graphene carbon-coating in agent by the Co nanoparticle that N-C layers coat, Co metal nanoparticle is uniform in size.
2. a kind of Co@NC high dispersive catalyst with core-casing structure according to claim 1, which is characterized in that the catalyst
The meso-hole structure for being 2-30nm with aperture.
3. a kind of preparation method of Co@NC high dispersive catalyst with core-casing structure of any of claims 1 or 2, which is characterized in that packet
Include following steps:
(1) by cobalt metal salt Co (NO3)·6H2O, glucose, dicyanodiamine are added separately in water, at a temperature of 50~100 DEG C
It stirs 0.1-48h and obtains solution A；The molar ratio of the dicyanodiamine and cobalt metal salt is 50~200:1~10；The Portugal
Grape sugar and the mass ratio of dicyanodiamine are 1~30:1~30；
(2) step (1) acquired solution A is dry, obtain catalyst precarsor B；
(3) calcined catalyst precursor B under inert atmosphere is warming up to 500-1500 DEG C of calcination temperature, and calcination time handles 0.5-
48h obtains Co@NC catalyst after cooling.
4. the preparation method of Co@NC high dispersive catalyst with core-casing structure according to claim 3, which is characterized in that step
(1) Co (NO described in3)·6H2O can be replaced one of Co transition metal salt or a variety of；Dicyanodiamine is alternatively at g-
C3N4, urea, melamine, one of thiocarbamide etc. or a variety of.
5. the preparation method of Co@NC high dispersive catalyst with core-casing structure according to claim 3, which is characterized in that step
(2) drying means described in is vacuum drying, air atmosphere is dry, inert atmosphere is dry, freeze-drying etc., drying temperature is-
40~200 DEG C, drying time is 1~100h.
6. the preparation method of Co@NC high dispersive catalyst with core-casing structure according to claim 3, which is characterized in that step
(3) inert gas described in is the one or more of nitrogen or argon gas, and inert gas flow velocity is 1~50mL min-1。
7. the preparation method of Co@NC high dispersive catalyst with core-casing structure according to claim 3, which is characterized in that step
(3) heating rate described in is 1-30 DEG C of min-1。
8. a kind of Co@NC high dispersive catalyst with core-casing structure of any of claims 1 or 2 is used as metal-air battery, fuel electricity
Pool cathode oxygen reduction electro-catalyst.
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