CN111545208A - Cobalt-nickel bimetallic catalyst and preparation method thereof - Google Patents
Cobalt-nickel bimetallic catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- UYTPUPDQBNUYGX-UHFFFAOYSA-N guanine Chemical compound O=C1NC(N)=NC2=C1N=CN2 UYTPUPDQBNUYGX-UHFFFAOYSA-N 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 7
- 239000013110 organic ligand Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 claims description 2
- 229930024421 Adenine Natural products 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229960000643 adenine Drugs 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 2
- 239000002773 nucleotide Substances 0.000 claims description 2
- 125000003729 nucleotide group Chemical group 0.000 claims description 2
- 150000003904 phospholipids Chemical class 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 229930003231 vitamin Natural products 0.000 claims description 2
- 239000011782 vitamin Substances 0.000 claims description 2
- 229940088594 vitamin Drugs 0.000 claims description 2
- 235000013343 vitamin Nutrition 0.000 claims description 2
- 150000003722 vitamin derivatives Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 claims 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims 1
- UKDHSAZUXNLNLV-UHFFFAOYSA-N nickel(2+) dinitrate tetrahydrate Chemical compound O.O.O.O.[Ni++].[O-][N+]([O-])=O.[O-][N+]([O-])=O UKDHSAZUXNLNLV-UHFFFAOYSA-N 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000003575 carbonaceous material Substances 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/33—
-
- B01J35/60—
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
Abstract
The invention discloses a cobalt-nickel bimetallic catalyst and a preparation method thereof. The raw materials are easy to obtain and low in price, and a new nitrogen source is not required to be introduced for preparing the nitrogen-doped porous carbon material; the catalytic performance of the material can be further improved by the synergistic effect of the cobalt and nickel double metals. Provides a good method for exploring a new method for preparing non-noble metal catalyst material and provides basis for further experimental optimization and industrial production.
Description
Technical Field
The invention belongs to the field of metal catalyst synthesis, and particularly relates to a cobalt-nickel bimetallic catalyst and a preparation method thereof.
Technical Field
With the continuous progress and development of human society, the consumption of fossil energy is increasing, and simultaneously, a series of problems such as resource shortage, environmental pollution and the like are caused, so that the development of green and clean renewable energy is urgently needed. Oxygen Reduction Reactions (ORR) are one of the most critical reactions in energy conversion systems such as fuel cells (r. Bashyam, p.a Zelenay, optics of non-preferred Metal complex catalysts for fuel cells. Nature 443(2006) 63-66.) when combined with their reverse process hydrogen evolution reactions (OER), rechargeable Metal-air cells can be assembled, both of which belong to the core process for preparing clean renewable energy sources (f.y. Cheng and j. Chen, Metal-air catalysts: from oxygen reduction chemistry to catalysts. chem.soc. rev., 2012, 41, 2172-. It is well known that Pt-based catalysts are quite effective for catalyzing ORR, while Ru-based catalysts are ideal materials for catalyzing OER (J.B. Wu, H. Yang, Platinum-based oxygen reduction catalysts. Acc. chem. Res. 46 (2013) 1848-1857.). However, these noble metal-based catalysts have a number of fatal disadvantages such as limited reserves, poor stability, and extreme sensitivity to ethanol. Therefore, there is a need to find alternatives to noble metal-based catalysts.
One of the prerequisites for a high efficiency electrocatalyst is its porosity (e.g., specific surface area and porous structure), which provides a channel for ion and mass transport. The research finds that the transition metal organic complex has the advantages of good conductivity, good stability, structural and functional diversity, unsaturated metal containing sites and the like, and is widely researched (C, Han, J, Wang, Y, et al, Nitrogen-doped halogen carbon semiconductors as effective metal-free electrolytes for oxygen reduction reaction in alkali metal medium J, mater, chem. A, 2014, 2, 605-. Meanwhile, doping of hetero atoms (nitrogen, phosphine, sulfur, etc.) with a carbon material containing a metal element exhibits excellent performance in electrocatalysis. Some biological micromolecules are rich in nitrogen elements, a nitrogen source does not need to be introduced secondarily, products obtained after pyrolysis of the biological micromolecules are two-dimensional flaky materials with surface defects, partial metal atoms can be well fixed through high-temperature pyrolysis after the biological micromolecules are compounded with a metal organic framework material, and meanwhile, the catalytic performance can be further improved through the synergistic effect of double metals.
Therefore, a heteroatom-doped cobalt-nickel bimetallic catalyst is prepared by preparing porous carbon by using biological micromolecules as nitrogen sources, carrying or coating a metal organic framework complex in situ and carrying out high-temperature pyrolysis. Because the catalyst has higher specific surface area, a hierarchical porous structure and unsaturated metal sites, compared with the similar catalyst, the activity of catalyzing ORR and OER is obviously increased, the catalyst is close to the commercialized noble metal catalyst, and the application prospect is wide.
Disclosure of Invention
The invention aims to overcome the technical problems in the prior art and provides a method for preparing a cobalt-nickel bimetallic catalyst by using small biological molecules as a nitrogen source, wherein the catalyst has certain ORR and OER catalytic activities.
The invention is realized by the following technical scheme, a method for preparing a cobalt-nickel bimetallic catalyst by using small biological molecules as a nitrogen source comprises the following steps:
(1) and (3) placing a certain amount of biological micromolecules in a tube furnace, carrying out high-temperature carbonization in inert gas, naturally cooling the tube furnace to room temperature, taking out a sample, and grinding to obtain the porous carbon.
(2) Ultrasonically dispersing porous carbon prepared from biological micromolecules in a certain solvent, adding a proper amount of surfactant, adding a certain amount of organic ligand, and uniformly stirring.
(3) Weighing a certain amount of cobalt salt, adding the cobalt salt into the solution obtained in the step 1), stirring for 0.5 hour to ensure that the solution is uniform, then weighing a certain amount of nickel salt, adding the nickel salt into the solution, and continuously stirring for 0.5-4 hours, preferably 1-2 hours.
And after stirring, standing at room temperature for 12-48 hours, preferably 24-36 hours, centrifuging, washing, and drying at 60 ℃ in a vacuum environment overnight to obtain a solid product.
(4) Grinding the solid product obtained in the step 3), placing the solid product in a tube furnace, carrying out high-temperature carbonization in inert gas, taking out a sample after the tube furnace is naturally cooled to room temperature, and grinding to obtain the cobalt-nickel bimetallic catalyst material.
Further, the high-temperature carbonization conditions in the step (1) are as follows: keeping the temperature at 700-1200 ℃ for 1-4 hours, preferably at 800-1000 ℃ for 2-3 hours, and raising the temperature at 2-10 ℃/min.
Further, the biological small molecule in the step (1) is guanine, adenine, amino acid, nucleotide, fructose, vitamin, phospholipid, polysaccharide or deoxynucleotide.
Further, the solvent in the step (2) is deionized water, methanol, ethanol, dimethyl sulfoxide or N, N-dimethylformamide; the surfactant is polyoxyethylene polyoxypropylene ether block copolymer (F127) or polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123); the organic ligand is 2-methylimidazole, 4-biphenyldicarboxylic acid, terephthalic acid or formic acid.
Further, in the step (3), the cobalt salt is cobalt nitrate hexahydrate, cobalt acetate tetrahydrate, cobalt chloride hexahydrate or cobalt sulfate, and the nickel salt is nickel nitrate hexahydrate, nickel acetate tetrahydrate, nickel chloride hexahydrate or nickel sulfate hexahydrate; the molar ratio of porous carbon prepared from the biological micromolecules to the cobalt salt is 1:1-1:6, and the optimal ratio is as follows: 1:1, 1:2, 1:4 or 1: 6; the molar ratio of the nickel salt to the cobalt salt is 1:1-1:4, preferably: 1:1, 1:2 or 1:4, the molar ratio of the cobalt salt to the organic ligand being 1:4 to 1:10, preferably 1:4, 1:5, 1:6, 1:8 or 1: 10.
Further, the high-temperature carbonization conditions in the step (4) are as follows: the temperature is kept at 1300 ℃ of 550-1300 ℃ for 2-4 hours, the carbonization temperature is preferably 700-900 ℃, and the heating rate is 2-20 ℃/min.
Compared with the prior art, the invention has the following advantages: the used biological micromolecule raw materials have wide sources and low price, and the whole preparation process is simple; the porous carbon prepared from the biological micromolecules is in a flaky shape, has defects on the surface and can be used as a site for anchoring an active center; the use of the surfactant enhances the interaction between the metal organic framework and the porous carbon; the decomposition of the organic ligand can leave pore channels on the surface of the material, further increase the specific surface area, and is beneficial to mass transfer and electron transfer; the synergistic effect between the cobalt and the nickel can prevent the single metal species from agglomerating in the high-temperature pyrolysis process, retain the dispersed metal species and be beneficial to improving the catalytic activity; the prepared heteroatom-doped cobalt-nickel metal catalyst has higher specific surface area, rich porous structure and rich active centers, compared with raw materials and similar catalysts, the ORR performance of the material is obviously improved, and the catalyst has good methanol resistance and stability, so that a good method is provided for exploring a non-noble metal catalyst, and an effective basis is provided for further experimental optimization and industrial production.
Drawings
FIG. 1 is an SEM image of CoNi-C-1 prepared in example 1;
FIG. 2 is the XRD pattern of CoNi-C-1 prepared in example 1 before pyrolysis;
FIG. 3 is an XPS nitrogen peak plot for CoNi-C-1 prepared in example 1;
FIG. 4 is an ORR performance CV curve of CoNi-C-1 prepared in example 1;
FIG. 5 is an LSV curve of ORR performance of CoNi-C-1 prepared in example 1.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the present invention is not limited to the following examples.
Example 1
Weighing 1g of guanine, placing the guanine in a 30mL ceramic crucible, placing the ceramic crucible in a high-temperature tube furnace, heating the guanine to 1000 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 2 hours, and naturally cooling the guanine to the room temperature to obtain the porous carbon material. 150mg of porous carbon is weighed and added into a mixed solution of 40mL of methanol and 40mL of ethanol, 50mg of F127 is added as a surfactant, and the mixture is uniformly dispersed through ultrasonic treatment. 328mg of 2-methylimidazole was added under magnetic stirring, and after stirring for 0.5 hour, 292mg of cobalt nitrate hexahydrate was added, the stirring was continued for 0.5 hour, 146mg of nickel nitrate hexahydrate was added, and the mixture was allowed to stand at room temperature for 24 hours. The product was collected by centrifugation, washing. The product was then dried in a vacuum oven at 60 ℃ overnight to give a black powdery solid. And finally, putting the product into a 30mL ceramic crucible, putting the ceramic crucible into a high-temperature tube furnace, heating the ceramic crucible to 800 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 2 hours, and naturally cooling the ceramic crucible to room temperature to obtain the nitrogen-doped cobalt-nickel bimetallic nitrogen-doped catalyst which is named as CoNi-C-1.
Example 2
Weighing 1g of guanine, placing the guanine in a 30mL ceramic crucible, placing the ceramic crucible in a high-temperature tube furnace, heating the guanine to 1000 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 2 hours, and naturally cooling the guanine to the room temperature to obtain the porous carbon material. 150mg of porous carbon is weighed, added into a mixed solution of 40mL of dimethyl sulfoxide and 40mL of ethanol, and 50mg of F127 serving as a surfactant is added and uniformly dispersed through ultrasonic treatment. 328mg of 2-methylimidazole was added under magnetic stirring, and after stirring for 0.5 hour, 292mg of cobalt nitrate hexahydrate was added, the stirring was continued for 0.5 hour, 146mg of nickel nitrate hexahydrate was added, and the mixture was allowed to stand at room temperature for 24 hours. The product was collected by centrifugation, washing. The product was then dried in a vacuum oven at 60 ℃ overnight to give a black powdery solid. And finally, putting the product into a 30mL ceramic crucible, putting the ceramic crucible into a high-temperature tube furnace, heating the ceramic crucible to 800 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, keeping the temperature for 2 hours, and naturally cooling the ceramic crucible to room temperature to obtain the nitrogen-doped cobalt-nickel bimetallic nitrogen-doped catalyst named as CoNi-C-2.
FIG. 1 is an SEM image of CoNi-C-1. From the images, it can be seen that the material, while maintaining the original MOF morphology, derives many carbon nanotubes, and at the same time, many channels are formed on the surface. In addition, many metal particles are added, which can be used as active centers for catalytic reactions.
FIG. 2 is an XRD image of CoNi-C-1 before pyrolysis. The image shows the typical peak of ZIF-67 (already indicated in the figure), while the peak around 25 ° corresponds to the (002) crystal plane of graphitic carbon, indicating that ZIF-67 is well supported on porous carbon made of small biological molecules.
FIG. 3 is an XPS nitrogen peak plot of CoNi-C-1. It is evident that the nitrogen element is divided into four peaks, corresponding to pyridine nitrogen, pyrrole nitrogen, metal nitrogen and graphite nitrogen, respectively. Wherein the relative content of pyridine nitrogen and graphite nitrogen is very key to improving the catalytic activity of ORR.
FIG. 4 is an ORR performance CV curve for CoNi-C-1. An obvious oxidation reduction peak can be seen at 0.8V, which indicates that the material has the performance of catalyzing ORR; while the redox peak of the nickel-only catalyst is around 0.7V, which is much lower than CoNi-C-1, indicating that the synergy of the bimetallic does play a role in improving the performance of ORR catalysis.
FIG. 5 is an ORR performance LSV curve of CoNi-C-1. The half-wave potential of 0.83V and the initial potential of 0.95V both indicate that the material catalyzes ORR with excellent performance.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A preparation method of a cobalt-nickel bimetallic catalyst is characterized by comprising the following steps: the method comprises the following steps:
1) placing the biological micromolecules in a tube furnace, carrying out high-temperature carbonization in inert gas, and grinding to obtain porous carbon after the tube furnace is naturally cooled to room temperature;
2) ultrasonically dispersing porous carbon prepared from biomass micromolecules in a solvent, adding a surfactant and an organic ligand, and uniformly stirring to obtain a mixed solution; firstly, adding cobalt salt into the mixed solution, stirring for 0.5h to make the solution uniform, then adding nickel salt, and continuously stirring for 0.5-4 h;
3) standing at room temperature for 12-48 h, and carrying out centrifugal washing and vacuum drying to obtain a solid product;
4) grinding the solid product obtained in the step 3), placing the solid product in a tubular furnace, carrying out high-temperature carbonization in inert gas, naturally cooling to room temperature, taking out a sample, and grinding to obtain the cobalt-nickel bimetallic catalyst.
2. The method of preparing a cobalt-nickel bimetallic catalyst as in claim 1, wherein: the biological micromolecules are guanine, adenine, amino acid, nucleotide, fructose, vitamin, phospholipid, polysaccharide or deoxynucleotide.
3. The method of preparing a cobalt-nickel bimetallic catalyst as in claim 1, wherein: the high-temperature carbonization conditions in the step 1) are as follows: keeping the temperature at 700-.
4. The method of preparing a cobalt-nickel bimetallic catalyst as in claim 1, wherein: the solvent in the step 2) is deionized water, methanol, ethanol, dimethyl sulfoxide or N, N-dimethylformamide.
5. The method of preparing a cobalt-nickel bimetallic catalyst as in claim 1, wherein: the surfactant in the step 2) is polyoxyethylene polyoxypropylene ether block copolymer or polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
6. The method of preparing a cobalt-nickel bimetallic catalyst as in claim 1, wherein: the organic ligand in the step 2) is 2-methylimidazole, 4-biphenyldicarboxylic acid, terephthalic acid or formic acid.
7. The method of preparing a cobalt-nickel bimetallic catalyst as in claim 1, wherein: the cobalt salt in the step 3) is cobalt nitrate hexahydrate, cobalt acetate tetrahydrate, cobalt chloride hexahydrate or cobalt sulfate; the nickel salt is nickel nitrate hexahydrate, nickel nitrate tetrahydrate, nickel chloride hexahydrate or nickel sulfate hexahydrate.
8. The method of preparing a cobalt-nickel bimetallic catalyst as in claim 1, wherein: the molar ratio of porous carbon prepared from the biological micromolecules to the cobalt salt is 1:1-1: 6; the molar ratio of the nickel salt to the cobalt salt is 1:1-1: 4; the molar ratio of the cobalt salt to the organic ligand is 1:4-1: 10.
9. A cobalt-nickel bimetallic catalyst prepared by the preparation method according to any one of claims 1 to 8, characterized in that: the nickel-cobalt bimetallic catalyst has oxygen reduction reaction catalytic activity.
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