CN116351478A - Preparation method of oxygen reduction catalyst, product and application thereof - Google Patents
Preparation method of oxygen reduction catalyst, product and application thereof Download PDFInfo
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- CN116351478A CN116351478A CN202310299226.5A CN202310299226A CN116351478A CN 116351478 A CN116351478 A CN 116351478A CN 202310299226 A CN202310299226 A CN 202310299226A CN 116351478 A CN116351478 A CN 116351478A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 30
- 239000001301 oxygen Substances 0.000 title claims abstract description 30
- 230000009467 reduction Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002608 ionic liquid Substances 0.000 claims abstract description 30
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 30
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 21
- 239000006229 carbon black Substances 0.000 claims abstract description 19
- 238000000197 pyrolysis Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- -1 1-butyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 claims description 4
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims description 4
- NVLDSCWHEUSPCV-UHFFFAOYSA-N [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Co++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O NVLDSCWHEUSPCV-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- YJAHZMNHEWAMNS-UHFFFAOYSA-N CCCCN1C=CN(C)C1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O Chemical group CCCCN1C=CN(C)C1.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O.O=S(C(F)(F)F)(NS(C(F)(F)F)(=O)=O)=O YJAHZMNHEWAMNS-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000010453 quartz Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000010757 Reduction Activity Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- 208000021251 Methanol poisoning Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
-
- B01J35/33—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- 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
The invention discloses a preparation method of an oxygen reduction catalyst, a product and application thereof, wherein the preparation method comprises the steps of mixing MOFs containing transition metal and ionic liquid [ BMIM ]]NTf 2 Mixing with carbon black, and carrying out high-temperature pyrolysis to obtain the catalyst; wherein the mass ratio of MOFs containing transition metal to carbon black is 1:1 to 1.5, the volume mass ratio of the ionic liquid to the MOFs containing transition metal is in mu L: g is 15-30: 0.04; the pyrolysis temperature is 400-800 ℃, the pyrolysis time is 2h,the pyrolysis atmosphere is nitrogen. The invention provides a preparation method of an oxygen reduction catalyst, which comprises MOFs containing transition metal and ionic liquid ([ BMIM)]NTf 2 ) The catalyst is compounded with carbon black to realize good synergistic catalysis effect; meanwhile, the preferable compounding proportion realizes the best effect of oxygen reduction performance.
Description
Technical Field
The invention belongs to the technical field of oxygen reduction catalysis, and particularly relates to a preparation method of an oxygen reduction catalyst, a product and application thereof.
Background
With the increasing consumption of energy and environmental deterioration, the development of alternative energy and green energy has become urgent. In addition, the greenhouse effect, a serious shortage of renewable fossil energy sources, further exaggerates the need for cleaner, more efficient energy conversion technologies. Under the current energy transformation background, solar energy and wind energy are the main forces of the current energy development due to the characteristics of wide distribution, huge reserves, extremely clean and the like. However, the two are limited by the influence of natural environment, so that the energy supply is unstable, the cost is high, the conversion efficiency is low, and the social requirement cannot be completely met.
Therefore, the battery is used as a device with high-efficiency energy conversion and storage, has the advantages of high efficiency, low cost and environmental protection compared with fossil energy, and well solves most of the problems in energy development.
The oxygen reduction reaction that occurs at the cathode is an important reaction process for electrochemical cells, and commercial platinum-based catalysts are typically used. However, commercial platinum-based catalysts have limited use due to their poor long-term stability and susceptibility to methanol poisoning. In addition, the low reserves and high price of platinum also limit the large-scale use of such catalysts. Therefore, it is highly desirable to develop efficient, economical ORR electrocatalysts. In recent years, transition metal-based catalysts have been widely studied for application in Oxygen Reduction Reactions (ORR) to replace platinum-based catalysts, with their ideal catalytic activity.
Co 9 S 8 Similar to Pt electrodes, although much promising work has been done in research as a bifunctional catalyst, conventional Co 9 S 8 Low conductivity, poor stability and low surface area still severely limit its practical application.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
Therefore, the invention aims to overcome the defects in the prior art and provide a preparation method of an oxygen reduction catalyst.
In order to solve the technical problems, the invention provides the following technical scheme: MOFs and ionic liquid [ BMIM ] containing transition metal]NTf 2 Mixing with carbon black, and carrying out high-temperature pyrolysis to obtain the catalyst; wherein the mass ratio of MOFs containing transition metal to carbon black is 1:1 to 1.5, the volume mass ratio of the ionic liquid to the MOFs containing transition metal is in mu L: g is 15-30: 0.04;
the pyrolysis temperature is 400-800 ℃, the pyrolysis time is 2h, and the pyrolysis atmosphere is nitrogen.
As a preferred embodiment of the preparation process according to the invention, there is provided: the MOFs containing transition metal include ZIF-67 and MOFs (Fe, co).
As a preferred embodiment of the preparation process according to the invention, there is provided: the ZIF-67 synthesis method comprises the following steps of,
respectively dissolving 2-methylimidazole and cobalt nitrate in absolute methanol, and uniformly stirring;
slowly dripping the cobalt nitrate methanol solution into the 2-methylimidazole methanol solution, and continuously stirring for 12 hours;
and then centrifugally washing the supernatant with methanol to be colorless, and drying the obtained product at 60 ℃ for 12 hours to obtain the ZIF-67.
As a preferred embodiment of the preparation process according to the invention, there is provided: the MOFs (Fe, co) and the synthesis method thereof comprise,
respectively dissolving 2-methylimidazole and cobalt nitrate in absolute methanol, and uniformly stirring;
slowly dripping the cobalt nitrate methanol solution into the 2-methylimidazole methanol solution, and continuously stirring for 2 hours;
adding ferric acetylacetonate, stirring for 12h, centrifuging with methanol for 3 times, washing to obtain colorless supernatant, and drying at 60deg.C for 12h to obtain orange powder (MOFs (Fe, co)).
As a preferred embodiment of the preparation process according to the invention, there is provided: said ionic liquid [ BMIM ]]NTf 2 The synthesis method comprises the steps of,
dissolving lithium bistrifluoromethylsulfonylimide and 1-butyl-3-methylimidazole hexafluorophosphate into deionized water, and stirring at room temperature for 6 hours;
separating the upper and lower liquid layers with a separating funnel, wherein the lower liquid layer is 1-butyl-3-methylimidazole bis (trifluoro methanesulfonimide) ([ BMIM)]NTf 2 ) And (3) an ionic liquid.
As a preferred embodiment of the preparation process according to the invention, there is provided: the high-temperature pyrolysis is carried out, wherein the heating rate is 5 ℃/min.
As a preferred embodiment of the preparation process according to the invention, there is provided: the mass ratio of the MOFs containing the transition metal to the carbon black is 1:1.5.
As a preferred embodiment of the preparation process according to the invention, there is provided: said ionic liquid [ BMIM ]]NTf 2 The volume-mass ratio to MOFs containing transition metal was 30. Mu.L: 0.04g.
It is still another object of the present invention to overcome the deficiencies of the prior art and to provide a product made by a process for preparing an oxygen reduction catalyst.
It is a further object of the present invention to overcome the deficiencies in the prior art and to provide the use of said product as an oxygen reduction catalyst.
The invention has the beneficial effects that:
(1) The invention pyrolyzes MOFs and ionic liquid ([ BMIM) containing transition metal at high temperature]NTf 2 ) And carbon black to prepare a high-efficiency oxygen reduction catalyst, the catalyst synthesis process is simple, and the repetition is convenient; meanwhile, the prepared catalyst particles are not easy to agglomerate, and the oxygen reduction performance of the catalyst is improved.
(2) The invention provides a preparation method of an oxygen reduction catalyst, which comprises MOFs containing transition metal and ionic liquid ([ BMIM)]NTf 2 ) And carbon black to perform compoundingThe preparation realizes good synergistic catalysis effect; meanwhile, the preferable compounding proportion realizes the best effect of oxygen reduction performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
fig. 1 is an XRD pattern of the catalyst in example 1 of the present invention.
FIG. 2 is an XPS chart of the catalyst in example 1 of the present invention.
Fig. 3 is a TEM image of the catalyst in example 1 of the present invention.
FIG. 4 is a LSV plot at 1600rpm of samples prepared with varying amounts of carbon black addition in example 1 of the present invention.
FIG. 5 is a LSV plot at 1600rpm for samples of different ionic liquid additions in example 1 of the present invention.
FIG. 6 shows 500-ZIF-67-C, 500-ZIF-67-C- [ BMIM according to the invention prepared in example 1]BF 4 And 500-ZIF-67-C- [ BMIM]NTf 2 Oxygen reduction activity profile.
FIG. 7 is a 500℃ZIF-67-Fe-C- [ BMIM according to the invention prepared in example 2]NTf 2 And 500-ZIF-67-C- [ BMIM]NTf 2 Oxygen reduction activity profile.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The raw materials in the invention are all common commercial products.
Example 1
(1) Preparation of a metal organic framework ZIF-67 material:
8.32g of 2-methylimidazole is dissolved in 30mL of methanol and stirred uniformly by a magnetic stirrer to obtain colorless transparent solution A;
2.94g Co(NO 3 ) 2 ·6H 2 o is dissolved in 30mL of methanol and stirred uniformly to obtain dark red transparent solution B;
and then putting the solution B into a constant pressure funnel, slowly dripping the solution B into the solution A, stirring for 12 hours, standing for 5 hours, centrifuging by a centrifuge, collecting a purple precipitate, repeatedly washing with methanol for three times until the supernatant is colorless, putting into an oven, and drying at 60 ℃ overnight to obtain purple powder which is ZIF-67.
(2) Ionic liquids ([ BMIM)]NTf 2 ) Preparation of materials:
2.90g of lithium bistrifluoromethylsulfonylimide and 2.87g of 1-butyl-3-methylimidazole hexafluorophosphate are dissolved in 50mL of deionized water and stirred at room temperature for 6h;
separating the upper and lower liquid layers with a separating funnel, wherein the lower liquid layer is 1-butyl-3-methylimidazole bis (trifluoro methanesulfonimide) ([ BMIM)]NTf 2 ) And (3) an ionic liquid.
(3)Co 9 S 8 -preparation of SNC material:
weighing ZIF-67 and carbon black in a certain mass ratio, putting into an agate mortar (ZIF-670.04 g for example with the ratio of 1:1.5 and 0.06g of carbon black), grinding uniformly, and dripping a certain amount of [ BMIM ] into the mixed powder]NTf 2 (30. Mu.L for example) grinding again to mix the ionic liquid and powder homogeneously;
then collecting the ground product, putting the product into a quartz boat, putting the quartz boat into a tube furnace, and calcining the quartz boat for 2 hours at different temperatures (400, 500, 600, 700 and 800 ℃) in a nitrogen atmosphere;
after calcining, waiting for the tube furnace to cool, collecting calcined products, grinding and weighing to obtain Co 9 S 8 -SNC。
Under the same conditions, a sample prepared without adding an ionic liquid and an equivalent amount of 1-butyl-3-methylimidazole hexafluorophosphate ionic liquid (purchased from Aladin) are taken as a comparison sample, and the sample is taken as an example at 500 ℃ and named as T-ZIF-67-C-ionic liquid.
(4) Evaluation of oxygen reduction reaction Performance:
a three-electrode system is adopted: the working electrode is a glassy carbon electrode connected to RDE, the counter electrode is a carbon rod, the reference electrode is a saturated Ag/AgCl electrode, and the electrolyte is 0.1M KOH. Catalyst loading was 24mgcm -2 。
The voltage range of the CV test curve is 0.2 to-1V, and the sweeping speed is 50mV/s.
The RDE rotation speed of the LSV test is 400-2500rpm, the test voltage range is 0.2-1V, and the scanning speed is 5mV/s. Initiation potential (E) 0 ) And half-wave potential (E) 1/2 ) Is two important parameters for qualitatively evaluating the oxygen reduction electrocatalytic performance of a catalyst, wherein E 0 And E is 1/2 The more positive the value of (c) indicates that the catalyst has higher electrocatalytic oxygen reduction activity. E (E) 1/2 The value of the potential corresponding to half the ORR limit diffusion current in the LSV graph at 1600 rpm.
FIG. 1 is a synthetic Co in example 4 of the present invention 9 S 8 XRD pattern of SNC, from which it can be seen that the diffraction peaks correspond to C and Co 9 S 8 Is a standard spectrogram of (2).
FIG. 2 is an XPS spectrum of C1S of the catalyst of example 4 of the invention, demonstrating the formation of S, N-doped carbon; FIG. 3 is a TEM image of the catalyst of example 4 of the present invention, showing Co 9 S 8 The nano particles are coated by S and N doped carbon and are uniformly distributed.
FIGS. 4 and 5 are LSV plots at 1600rpm for samples with varying amounts of carbon black and varying amounts of ionic liquid added, respectively, demonstrating the presence of ZIF67: the mass ratio of C is 1:1.5 (0.04 g:0.06 g), the initial potential and half-wave potential of the catalyst were the largest and the ORR catalytic activity was the highest when the ionic liquid addition amount was 30. Mu.L (see Table 1 for specific values).
TABLE 1
FIG. 6 is a 500-ZIF-67-C, 500-ZIF-67-C- [ BMIM]BF 4 And 500-ZIF-67-C- [ BMIM]NTf 2 LSV at 1600rpm, 500-ZIF-67-C- [ BMIM can be seen]NTf 2 The initial potential and half-wave potential of the catalyst are far higher than those of the catalyst added with other ionic liquids and the catalyst not added with ionic liquids (specific numerical values are shown in table 2), the limiting diffusion current density is also improved, and the optimized catalyst has higher oxygen reduction performance.
TABLE 2
Example 2
(1) Preparation of metal organic frameworks MOFs (Fe, co) materials:
8.32g of 2-methylimidazole was dissolved in 30mL of methanol and stirred uniformly with a magnetic stirrer to obtain colorless transparent solution A,2.94g of Co (NO) 3 ) 2 ·6H 2 O and 3.35g Fe (acac) 3 Dissolving in 60mL of methanol, stirring uniformly to obtain dark red transparent solution B, then placing the solution B into a constant pressure funnel, slowly dripping the solution B into the solution A, stirring for 12h, standing for 5h, centrifuging by a centrifuge, collecting orange precipitate, repeatedly washing with methanol for three times until the supernatant is colorless, placing into an oven, and drying at 60 ℃ overnight to obtain orange powder which is MOFs (Fe, co).
(2)Co 9 S 8 Preparation of Fe-SNC material:
weighing a certain mass ratioMOFs (Fe, co) and carbon black were put into an agate mortar (ZIF-670.04 g, 1:1.5 as an example, carbon black 0.06 g) and ground uniformly, and 30. Mu.L of [ BMIM ] was added dropwise to the mixed powder]NTf 2 Grinding again to uniformly mix the ionic liquid and the powder;
then collecting the ground product, putting the product into a quartz boat, putting the quartz boat into a tube furnace, and calcining the quartz boat for 2 hours at different temperatures (400, 500, 600, 700 and 800 ℃) in a nitrogen atmosphere;
after calcining, waiting for the tube furnace to cool, collecting calcined products, grinding and weighing to obtain Co 9 S 8 Fe-SNC, named T-ZIF-67-Fe-C-ionic liquid.
FIG. 7 is a 500℃ZIF-67-Fe-C- [ BMIM according to the invention prepared in example 2]NTf 2 And 500-ZIF-67-C- [ BMIM]NTf 2 Oxygen reduction Activity (again, 500 ℃ C. For example) is shown, 500 ℃ C. ZIF-67-Fe-C- [ BMIM can be seen]NTf 2 The initial potential and half-wave potential of the catalyst are higher than 500-ZIF-67-C- [ BMIM]NTf 2 (specific numerical values are shown in table 3), the limiting diffusion current density is also improved, and the optimized catalyst has higher oxygen reduction performance.
TABLE 3 Table 3
The invention pyrolyzes MOFs and ionic liquid ([ BMIM) containing transition metal at high temperature]NTf 2 ) And carbon black to prepare a high-efficiency oxygen reduction catalyst, the catalyst synthesis process is simple and is convenient to repeat; the prepared catalyst particles are not easy to agglomerate, and have high oxygen reduction catalytic activity and conductivity.
The invention relates to MOFs and ionic liquid ([ BMIM) containing transition metal]NTf 2 ) The catalyst is compounded with carbon black to realize good synergistic catalysis effect; meanwhile, the preferable compounding proportion realizes the best effect of oxygen reduction performance.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, and it should be covered in the scope of the present invention.
Claims (10)
1. A preparation method of an oxygen reduction catalyst is characterized in that: comprising the steps of (a) a step of,
MOFs and ionic liquid [ BMIM ] containing transition metal]NTf 2 Mixing with carbon black, and carrying out high-temperature pyrolysis to obtain the catalyst; wherein the mass ratio of MOFs containing transition metal to carbon black is 1:1 to 1.5, the volume mass ratio of the ionic liquid to the MOFs containing transition metal is in mu L: g is 15-30: 0.04;
the pyrolysis temperature is 400-800 ℃, the pyrolysis time is 2h, and the pyrolysis atmosphere is nitrogen.
2. The method of manufacturing according to claim 1, wherein: the MOFs containing transition metal include ZIF-67 and MOFs (Fe, co).
3. The method of manufacturing as claimed in claim 2, wherein: the ZIF-67 synthesis method comprises the following steps of,
respectively dissolving 2-methylimidazole and cobalt nitrate in absolute methanol, and uniformly stirring;
slowly dripping the cobalt nitrate methanol solution into the 2-methylimidazole methanol solution, and continuously stirring for 12 hours;
and then centrifugally washing the supernatant with methanol to be colorless, and drying the obtained product at 60 ℃ for 12 hours to obtain the ZIF-67.
4. The method of manufacturing as claimed in claim 2, wherein: the MOFs (Fe, co) and the synthesis method thereof comprise,
respectively dissolving 2-methylimidazole and cobalt nitrate in absolute methanol, and uniformly stirring;
slowly dripping the cobalt nitrate methanol solution into the 2-methylimidazole methanol solution, and continuously stirring for 2 hours;
adding ferric acetylacetonate, stirring for 12h, centrifuging with methanol for 3 times, washing to obtain colorless supernatant, and drying at 60deg.C for 12h to obtain orange powder (MOFs (Fe, co)).
5. The method according to any one of claims 1 to 4, wherein: said ionic liquid [ BMIM ]]NTf 2 The synthesis method comprises the steps of,
dissolving lithium bistrifluoromethylsulfonylimide and 1-butyl-3-methylimidazole hexafluorophosphate into deionized water, and stirring at room temperature for 6 hours;
separating the upper and lower liquid layers with a separating funnel, wherein the lower liquid layer is 1-butyl-3-methylimidazole bis (trifluoro methanesulfonimide) ([ BMIM)]NTf 2 ) And (3) an ionic liquid.
6. The method of manufacturing according to claim 5, wherein: the high-temperature pyrolysis is carried out, wherein the heating rate is 5 ℃/min.
7. The method of manufacturing according to claim 1, wherein: the mass ratio of the MOFs containing the transition metal to the carbon black is 1:1.5-2.
8. The method of manufacturing according to claim 1, wherein: said ionic liquid [ BMIM ]]NTf 2 The volume-mass ratio to MOFs containing transition metal was 30. Mu.L: 0.04g.
9. An oxygen reduction catalyst produced by the production process according to any one of claims 1 to 8.
10. Use of the product of claim 9 as an oxygen reduction catalyst.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013185837A1 (en) * | 2012-06-15 | 2013-12-19 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Method of manufacture of an electrode material and an electrode material |
| US20160064773A1 (en) * | 2014-08-29 | 2016-03-03 | Samsung Electronics Co., Ltd. | Composite, method of preparing the composite, electrolyte comprising the composite, and lithium secondary battery comprising the electrolyte |
| US20160254567A1 (en) * | 2015-02-27 | 2016-09-01 | GM Global Technology Operations LLC | Electrolyte structure for metal batteries |
| CN109307700A (en) * | 2018-10-19 | 2019-02-05 | 海南师范大学 | A kind of method of cobalt-based metal-organic framework material/three-dimensional grapheme nanocomposite modified electrode measurement rutin |
| CN109797405A (en) * | 2019-02-21 | 2019-05-24 | 三峡大学 | A kind of preparation method of cobalt sulfide and nitrogen-doped carbon composite array electrode |
| CN111495350A (en) * | 2020-04-26 | 2020-08-07 | 张大兰 | Nano Co9S8-porous carbon nanofiber oxygen reduction catalyst and preparation method thereof |
| KR20210040673A (en) * | 2019-10-04 | 2021-04-14 | 울산과학기술원 | Method for preparing atomically dispersed catalyst, atomically dispersed catalyst thereby and oxygen reduction reaction catalyst comprising the atomically dispersed catalyst |
| CN114262913A (en) * | 2021-11-26 | 2022-04-01 | 常州大学 | Preparation method of catalyst for producing hydrogen by electrolyzing water with high current density |
| CN115101766A (en) * | 2022-07-19 | 2022-09-23 | 中国科学院过程工程研究所 | Preparation method and application of low-platinum-content cathode oxygen reduction catalyst |
-
2023
- 2023-03-24 CN CN202310299226.5A patent/CN116351478B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013185837A1 (en) * | 2012-06-15 | 2013-12-19 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Method of manufacture of an electrode material and an electrode material |
| US20160064773A1 (en) * | 2014-08-29 | 2016-03-03 | Samsung Electronics Co., Ltd. | Composite, method of preparing the composite, electrolyte comprising the composite, and lithium secondary battery comprising the electrolyte |
| US20160254567A1 (en) * | 2015-02-27 | 2016-09-01 | GM Global Technology Operations LLC | Electrolyte structure for metal batteries |
| CN109307700A (en) * | 2018-10-19 | 2019-02-05 | 海南师范大学 | A kind of method of cobalt-based metal-organic framework material/three-dimensional grapheme nanocomposite modified electrode measurement rutin |
| CN109797405A (en) * | 2019-02-21 | 2019-05-24 | 三峡大学 | A kind of preparation method of cobalt sulfide and nitrogen-doped carbon composite array electrode |
| KR20210040673A (en) * | 2019-10-04 | 2021-04-14 | 울산과학기술원 | Method for preparing atomically dispersed catalyst, atomically dispersed catalyst thereby and oxygen reduction reaction catalyst comprising the atomically dispersed catalyst |
| CN111495350A (en) * | 2020-04-26 | 2020-08-07 | 张大兰 | Nano Co9S8-porous carbon nanofiber oxygen reduction catalyst and preparation method thereof |
| CN114262913A (en) * | 2021-11-26 | 2022-04-01 | 常州大学 | Preparation method of catalyst for producing hydrogen by electrolyzing water with high current density |
| CN115101766A (en) * | 2022-07-19 | 2022-09-23 | 中国科学院过程工程研究所 | Preparation method and application of low-platinum-content cathode oxygen reduction catalyst |
Non-Patent Citations (3)
| Title |
|---|
| GAO QY ET AL., 《CARBON LETTERS》 IONIC LIQUID/ZIF-67 DERIVED CO9S8-SNC CATALYST FOR OXYGEN REDUCTION REACTION IN ALKALINE ELECTROLYTE, 31 October 2023 (2023-10-31) * |
| QUOC CHINH TRAN ET AL., 《APPLIED CATALYSIS B: ENVIRONMENTAL》 PT-BASED ALLOY/CARBON BLACK NANOHYBRID COVERED WITH IONIC LIQUIDSUPRAMOLECULES AS AN EFFICIENT CATALYST FOR OXYGEN REDUCTION REACTIONS, vol. 204, 24 November 2016 (2016-11-24), pages 365 - 373 * |
| XIAOBO HE ET AL., 《CHINESE JOURNAL OF CATALYSIS》 METAL‐ORGANIC FRAMEWORKS FOR HIGHLY EFFICIENT OXYGEN ELECTROCATALYSIS, vol. 39, 5 February 2018 (2018-02-05), pages 207 * |
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