CN116470076A - Alkaline system direct methanol fuel cell anode catalyst and preparation method thereof - Google Patents
Alkaline system direct methanol fuel cell anode catalyst and preparation method thereof Download PDFInfo
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- CN116470076A CN116470076A CN202310517262.4A CN202310517262A CN116470076A CN 116470076 A CN116470076 A CN 116470076A CN 202310517262 A CN202310517262 A CN 202310517262A CN 116470076 A CN116470076 A CN 116470076A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000000446 fuel Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 150000000703 Cerium Chemical class 0.000 claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010668 complexation reaction Methods 0.000 claims abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008139 complexing agent Substances 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 36
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 34
- 230000000694 effects Effects 0.000 abstract description 16
- 229910052759 nickel Inorganic materials 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 239000011149 active material Substances 0.000 abstract description 5
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 238000007254 oxidation reaction Methods 0.000 description 17
- 230000003647 oxidation Effects 0.000 description 13
- 239000013078 crystal Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006056 electrooxidation reaction Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012353 t test Methods 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Classifications
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- 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
-
- 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
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- 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
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- 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
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- H—ELECTRICITY
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- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H01M4/9041—Metals or alloys
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to an anode catalyst of an alkaline system direct methanol fuel cell, which is a nickel-cerium coexisting composite catalyst Ni/CeO wrapped by a nitrogen-containing carbon material and obtained by adopting a citric acid complexation method, taking citric acid as a complexing agent, providing metal ions by nickel salt and cerium salt, uniformly mixing in water, drying to form nickel-cerium gel, and calcining at 600 ℃ in an inert atmosphere 2 @CN-600. The invention adopts the active material nickel and the catalyst promoter cerium oxide obtained after calcination to replace the traditional noble metal, and adjusts and controls the electronic structure of the catalyst by doping hetero atoms, thereby improving the catalytic activity and the electricity of the catalystThe anode is extremely conductive, and has excellent electrochemical reaction activity when being used as an anode catalyst of an alkaline system direct methanol fuel cell.
Description
Technical Field
The invention belongs to the technical field of electrochemical catalytic oxidation, relates to a fuel cell anode catalyst, and in particular relates to a non-noble metal-based carbon material anode catalyst of a direct methanol fuel cell under an alkaline system and a preparation method thereof. The catalyst prepared by the invention can be used for electrochemical catalytic oxidation of methanol fuel.
Background
Direct Methanol Fuel Cells (DMFCs) have been widely studied as a promising portable power supply device due to their excellent energy conversion efficiency and no pollutant emissions. In DMFCs, the key process that determines cell efficiency is the Methanol Oxidation Reaction (MOR) at the anode, requiring the use of an electrocatalyst to accelerate the MOR process.
Noble metal-based catalysts (such as Ru and Pt) exhibit excellent electrocatalytic activity towards MOR, but are limited by their scarcity and poor resistance to CO poisoning. Thus, MOR electrocatalysts based on non-noble transition metals, such as Co, cu, ni and Mn, have been widely studied. In addition to single metal-based catalysts, alloying of different metals can improve the catalytic activity of the catalyst by adjusting the electronic properties of the catalyst.
Currently, different nanocomposite materials have been widely studied, especially noble metal alloy materials. For example, pt-Pd hollow nanocubes obtained by etching Pt with Pd have an enhanced alloying effect; the Pt-Ni nanocrystals have a multi-layered framework and a good self-supporting structure that can promote electron transport and prevent morphology changes in long-term electrochemical testing. All of these show excellent electrocatalytic activity and durability to methanol oxidation. However, non-noble metal-based nanocrystals have been rarely studied due to their instability and oxidation susceptibility, and it is necessary to develop non-noble metal nanocrystals with high stability.
Among the numerous non-noble metal-based catalysts, nickel is abundant in the crust and inexpensive, and has been widely used in many conventional industrial catalytic processes, such as methane reforming, additionHydrogen reaction, hydrocracking and oxidation reactions. Nickel-based materials have also been extensively studied in electrochemical energy storage and electrocatalysis processes, thanks to their low cost and high activity. Based on the easily reversible redox state of Ni-based materials (Ni 2+ /Ni 3+ ) And an empty d-orbital, is expected to become a non-platinum catalyst for electrocatalytic oxidation of methanol and ethanol in alkaline medium.
Various nickel-based catalysts have been developed for use in the electrocatalytic oxidation of methanol, such as Ni nanoparticles (High Electrocatalytic Behaviour of Ni Impregnated Conducting Polymer Coated Platinum and Graphite Electrodes for Electrooxidation of Methanol,Electrochim. Acta224 (2017): 468-474.) NiO film (Facile synthesis of a mechanically robust and highly porous NiO film with excellent electrocatalytic activity towards methanol oxidation,Nanoscale, 8(2016): 11256-63.），Ni-P-O （Three-dimensional astrocyte-network Ni-P-O compound with superior electrocatalytic activity and stability for methanol oxidation in alkaline environments, J. Mater. Chem. A 3(2015): 4669-4678.），NiCoPO（Nickel phosphate materials regulated by doping cobalt for urea and methanol electro-oxidation, Int. J. Hydrogen Energy44 (2019): 16305-16314), etc. Although a great deal of research has been conducted on nickel-based catalysts, there is a long way to develop nickel-based catalysts that meet the practical application requirements.
Cerium oxide (CeO) 2 ) Is an important rare earth metal oxide, the cation of which can be switched between +3 and +4 oxidation states, thus having the ability to store, transport and release oxygen, ceO 2 Are widely used as supports and promoters in conventional catalysis. Such as Tao et al (Interface engineering of Pt and CeO) 2 nanorods with unique interaction for methanol oxidation, Nano Energy53 (2018): 604-612.) Pt/CeO prepared by plasma irradiation 2 P catalyst, exhibiting excellent catalytic activity and durability towards MOR. Meanwhile, dao et al (Pt-loaded Au@CeO 2 core–shell nanocatalysts for improving methanol oxidation reaction activity, J. Mater. Chem. AAu@CeO prepared from 7 (2019): 26996-27006.) 2 Stability and activity of @ Pt/C exceeded that of Pt/C because of CeO 2 The introduction of (3) alters the electronic structure of the catalyst.
Disclosure of Invention
The invention aims to provide an anode catalyst of an alkaline system direct methanol fuel cell and a preparation method thereof, and the electronic structure of the catalyst is regulated and controlled by doping hetero atoms, so that the catalytic activity of the catalyst and the conductivity of an electrode are improved.
The Ni-based catalyst has excellent electrocatalytic activity, ceO 2 Is a catalyst promoter for improving the electrocatalytic activity, so the invention uses Ni and CeO 2 A platinum-free catalyst for electrochemical oxidation of methanol in alkaline medium is prepared in order to increase the electrocatalytic activity of Ni.
The alkaline system direct methanol fuel cell anode catalyst adopts a citric acid complexation method, takes citric acid as a complexing agent, provides metal ions for nickel salt and cerium salt, is uniformly mixed in water and then dried to form nickel-cerium gel, and is obtained by calcining at 600 ℃ in an inert atmosphere, wherein the nickel-cerium coexisting composite catalyst is coated by a nitrogen-containing carbon material, namely Ni/CeO 2 @CN-600。
Specifically, the invention also provides a preparation method of the alkaline system direct methanol fuel cell anode catalyst, which comprises the steps of preparing a metal precursor solution by dissolving nickel salt and cerium salt in water, adding citric acid solution for complexing to form nickel-cerium composite material, removing water to obtain nickel-cerium gel, and calcining at 600 ℃ in an inert atmosphere to prepare Ni/CeO 2 Catalyst @ CN-600.
Wherein, the mass ratio of the citric acid to the nickel salt and the cerium salt is preferably 2:1-4:0.5-2.
The invention preferably adopts a drying mode to remove the moisture in the nickel-cerium composite material to obtain nickel-cerium gel.
More specifically, the method comprises the steps of evaporating water in the nickel-cerium composite material at room temperature, and drying in an oven at 60-100 ℃ to obtain nickel-cerium gel.
More specifically, the invention is to calcine the nickel cerium gel at a rate of 1-5 ℃/min from room temperature to 600 ℃ under an inert atmosphere.
Wherein the calcination time is preferably 1 to 5 hours.
The invention adopts a brand new citric acid complexation method, and forms gel by complexing nickel element and cerium element through simple complexation reaction, and the nitrogen-containing carbon material coated nickel-cerium composite material is obtained after calcination, and the nitrogen-containing carbon material is used as an anode catalyst of an alkaline system direct methanol fuel cell, thereby having excellent electrochemical reaction activity.
The anode catalyst prepared by the invention is directly coated on the surface of hydrophilic conductive carbon cloth after being dispersed by absolute ethyl alcohol, and can be used as a working electrode after being dried, any binder is not used, the existence of an inactive area can be avoided, and the working electrode has better conductivity.
The invention further improves the Ni/CeO by adopting a mode of doping heteroatom N in the catalyst to regulate the electronic structure of the catalyst 2 Catalytic Activity of the @ CN-T composite catalyst, the Ni/CeO of the invention was tested by cyclic voltammetry 2 Methanol oxidation reactivity of the @ CN-600 composite catalyst, at a scan rate of 50mV/s, 1M KOH and 1M CH 3 The peak current density of 1.642V vs RHE in the OH solution mixed electrolyte reaches 229.56mA cm -2 Has obvious catalytic effect on methanol. Meanwhile, under the voltage of 1.542V vs RHE, the current density is only 169.04mA cm after the i-t test of a 12h timing current method -2 Drop to 155.02mA cm -2 The current density retention was 91.7%.
Drawings
FIG. 1 is a drawing of the preparation of Ni/CeO according to example 1 2 X-ray diffraction pattern of the @ CN-600 catalyst powder.
FIG. 2 is a drawing of the preparation of Ni/CeO according to example 2 2 X-ray diffraction pattern of the @ CN-500 catalyst powder.
FIG. 3 is a schematic illustration of the preparation of Ni-NiO/CeO in example 3 2 X-ray diffraction pattern of the @ CN-700 catalyst powder.
FIG. 4 is a drawing of the preparation of Ni/CeO according to example 1 2 Catalyst @ CN-600 in 1M KOH and 1M KOH+1M CH 3 Cyclic voltammogram in OH solutionA drawing.
FIG. 5 is a drawing of the preparation of Ni/CeO according to example 1 2 12h chronoamperometric i-t test pattern for the @ CN-600 catalyst.
FIG. 6 is a graph comparing the catalytic activities of example 1 with those of examples 2 and 3.
Description of the embodiments
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples. The following examples are presented only to more clearly illustrate the technical aspects of the present invention so that those skilled in the art can better understand and utilize the present invention without limiting the scope of the present invention.
The production process, the experimental method or the detection method related to the embodiment of the invention are all conventional methods in the prior art unless otherwise specified, and the names and/or the abbreviations thereof are all conventional names in the field, so that the related application fields are very clear and definite, and a person skilled in the art can understand the conventional process steps according to the names and apply corresponding equipment to implement according to conventional conditions or conditions suggested by manufacturers.
The various instruments, equipment, materials or reagents used in the examples of the present invention are not particularly limited in source, and may be conventional products commercially available through regular commercial routes or may be prepared according to conventional methods well known to those skilled in the art.
Examples
Example 1
2g of nickel nitrate and 1g of cerium nitrate were weighed and dissolved in 15mL of deionized water to prepare a metal precursor solution.
2g of citric acid is weighed and dissolved in 15mL of deionized water, the solution is added into the metal precursor solution under stirring to obtain a homogeneous solution, the solution is stirred for 0.5h at room temperature, and then the solution is dried in an oven at 80 ℃ to obtain the nickel cerium gel.
Putting nickel cerium gel into a tubular reaction furnace, N 2 Raising the temperature from room temperature to 600 ℃ at a rate of 2 ℃/min under the atmosphere, and keeping for 120min, and then N 2 Cooled to room temperature under protection.
Taking out the reaction product, grinding uniformly to obtainNi/CeO 2 Catalyst @ CN-600.
The active material and the corresponding crystal face in the prepared catalyst are tested by adopting an X-ray diffraction analysis technology, and the diffraction pattern shown in figure 1 is obtained.
It was combined with powder diffraction Standard Commission Standard cards Ni (PDF#04-0850) and CeO 2 (PDF # 34-0394) diffraction angles 2θ=44.5 °, 51.8 ° and 76.3 ° correspond to the (111), (200) and (220) crystal planes of nickel, respectively, 2θ= 28.554 °, 33.081 °, 47.478 °, 56.334 ° and 76.698 ° correspond to the (111), (200), (220), (311) and (331) crystal planes of cerium oxide, respectively.
Based on CeO alone 2 Has no catalytic performance, and the active substances in the catalyst are proved to be Ni and CeO 2 The presence of (2) can slow down the oxidation rate of Ni, so CeO 2 Can be used as a cocatalyst to improve the catalytic performance of the catalyst.
Example 2
2g of nickel nitrate and 1g of cerium nitrate were weighed and dissolved in 15mL of deionized water to prepare a metal precursor solution.
2g of citric acid is weighed and dissolved in 15mL of deionized water, the solution is added into the metal precursor solution under stirring to obtain a homogeneous solution, the solution is stirred for 0.5h at room temperature, and then the solution is dried in an oven at 80 ℃ to obtain the nickel cerium gel.
Putting nickel cerium gel into a tubular reaction furnace, N 2 Raising the temperature from room temperature to 500 ℃ at a rate of 2 ℃/min under atmosphere, and keeping for 120min, and then N 2 Cooled to room temperature under protection.
Taking out the reaction product, grinding uniformly to prepare Ni/CeO 2 Catalyst @ CN-500.
The active material and the corresponding crystal face in the catalyst prepared by the method are tested by adopting an X-ray diffraction analysis technology, and the diffraction pattern shown in figure 2 is obtained.
It was combined with powder diffraction Standard Commission Standard cards Ni (PDF#04-0850) and CeO 2 (PDF # 34-0394) in contrast, diffraction angles 2θ=44.5 °, 51.8 ° and 76.3 ° correspond to (111), (200) and (220) crystal planes of nickel, respectively, 2θ= 28.554 °, 33.081 °, 47.478 °, 56.334 ° and 76.698 ° correspond to (11) of cerium oxide, respectively1) The (200), (220), (311) and (331) crystal planes.
Based on CeO alone 2 Has no catalytic performance, and the active substances in the catalyst are proved to be Ni and CeO 2 Is a cocatalyst.
Example 3
2g of nickel nitrate and 1g of cerium nitrate were weighed and dissolved in 15mL of deionized water to prepare a metal precursor solution.
2g of citric acid is weighed and dissolved in 15mL of deionized water, the solution is added into the metal precursor solution under stirring to obtain a homogeneous solution, the solution is stirred for 0.5h at room temperature, and then the solution is dried in an oven at 80 ℃ to obtain the nickel cerium gel.
Putting nickel cerium gel into a tubular reaction furnace, N 2 Raising the temperature from room temperature to 700 ℃ at a rate of 2 ℃/min under atmosphere, and keeping for 120min, and then N 2 Cooled to room temperature under protection.
Taking out the reaction product, grinding uniformly to obtain Ni-NiO/CeO 2 Catalyst @ CN-700.
The active material and the corresponding crystal face in the catalyst prepared by the method are tested by adopting an X-ray diffraction analysis technology, and the diffraction pattern shown in figure 3 is obtained.
It was combined with powder diffraction Standard Commission Standard cards Ni (PDF#04-0850), niO (PDF#47-1049) and CeO 2 The (PDF # 34-0394) controls that diffraction angles 2θ=44.5 °, 51.8 ° and 76.3 ° correspond to the (111), (200) and (220) crystal planes of nickel, respectively, and that the active material in the catalyst is Ni, and 2θ= 37.248 °, 43.275 °, 62.878 ° and 79.407 ° correspond to the (111), (200), (220) and (222) crystal planes of nickel oxide, respectively, and 2θ= 28.554 °, 33.081 °, 47.478 °, 56.334 ° and 76.698 ° correspond to the (111), (200), (220), (311) and (331) crystal planes of cerium oxide, respectively.
The catalyst of this example contained a certain amount of NiO, which was not as catalytically active as Ni.
Application example 1
The Ni/CeO prepared in example 1 was weighed 2 5mg of @ CN-600 catalyst is placed in a centrifuge tube, 30 mu L of absolute ethyl alcohol is added, ultrasonic dispersion is carried out for 15min, 10 mu L of catalyst is sucked by a pipette, the catalyst is evenly dripped on the surface of hydrophilic carbon cloth with the specification of 0.5cm multiplied by 1.5cm, and the hydrophilic carbon cloth is bakedDrying at 60deg.C in a box.
To be coated with Ni/CeO 2 Carbon cloth of a catalyst @ CN-600 is used as a working electrode, a stainless steel sheet with the length of 3cm multiplied by 4cm is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, a three-electrode system is adopted, and a cyclic voltammetry method is used for preparing Ni/CeO 2 The electrochemical performance of the @ CN-600 catalyst was characterized.
With 1M KOH, 1M KOH+1.0M CH respectively 3 And (3) taking the OH mixed solution as an electrolyte solution, and adopting an electrochemical workstation of Shanghai Chenhua CHI 660E to perform methanol electrochemical oxidation (MOR) reactivity test.
As shown in FIG. 4, the scanning speed in a 1M KOH solution was 50mV/s and the corresponding current density was 66.8mA cm at a voltage of 1.642V vs RHE -2 The method comprises the steps of carrying out a first treatment on the surface of the While at 1M KOH+1.0M CH 3 In the OH mixed solution, the same scanning speed is 50mV/s, and the corresponding current density at the voltage of 1.642V vs RHE is 229.56mA cm -2 The catalyst has obvious catalytic effect on methanol.
Furthermore, according to FIG. 5,1M KOH+1.0M CH 3 In the OH mixed solution, the current density change trend with time is inspected under 1.542V vs RHE voltage by a 12h chronoamperometry i-t test, and the current density is measured from 169.04mA cm after 12h -2 Drop to 155.02mA cm -2 The current density retention rate was 91.7%, indicating that the catalyst had good stability.
Meanwhile, the performance index controls of the nickel-based catalysts reported in some of the literature and the catalysts prepared in example 1, example 2 and example 3 are also provided in the following table 1. Because the traditional nickel-based catalyst has complex preparation method and preparation process and low uniform dispersity of active component nickel, the electrochemical reaction activity of methanol oxidation is directly affected.
As can be seen from the data in Table 1 in combination with the comparative catalytic activity chart of FIG. 6, the current density values of the listed documents and examples 2 and 3 are lower at similar voltage windows of 1.6-1.66V (vs RHE), demonstrating that the methanol oxidation activity is not high. In order to improve the activity of the catalyst, the catalyst prepared by adopting the active nickel component and the cerium oxide capable of providing electron empty orbits and the carbon material with good conductivity and prepared at 600 ℃ can obviously improve the current density value under fixed voltage, namely the activity of catalyzing and oxidizing methanol.
[1] High-performance Bismuth-doped Nickel Aerogel Electrocatalyst for Methanol Oxidation Reaction, Angew. Chem. Int. Ed.,59(2020): 13891-13899.
[2] Selective Methanol-to-Formate Electrocatalytic Conversion on Branched Nickel Carbide, Angew. Chem. Int. Ed., 59(2020): 20826-20830.
[3] I. A. Muhammad, H. Asima, N. Zhang, M. H. Islam, M. M. Ma, G. P. Bruno, ACS Appl. Mater. & Inter., 13(2021): 30603-30613.
The above embodiments of the invention are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Various changes, modifications, substitutions and alterations may be made by those skilled in the art without departing from the principles and spirit of the invention, and it is intended that the invention encompass all such changes, modifications and alterations as fall within the scope of the invention.
Claims (8)
1. An anode catalyst of alkaline system direct methanol fuel cell is prepared by using citric acid complexation method, using citric acid as complexing agent, providing metal ions by nickel salt and cerium salt, mixing uniformly in water, drying to form nickel-cerium gel, calcining at 600 deg.C under inert atmosphere to obtain Ni/CeO composite catalyst coated with nitrogen-containing carbon material 2 @CN-600。
2. The method for preparing anode catalyst of direct methanol fuel cell with alkaline system as claimed in claim 1, wherein nickel salt and cerium salt are dissolved in water to prepare metal precursor solution, citric acid solution is added to complex to form nickel-cerium composite material, water is removed to obtain nickel-cerium gel, and the nickel-cerium gel is calcined at 600 ℃ under inert atmosphere to prepare Ni/CeO 2 Catalyst @ CN-600.
3. The method for preparing the anode catalyst of the direct methanol fuel cell with the alkaline system according to claim 2, wherein the mass ratio of the citric acid to the nickel salt to the cerium salt is 2:1-4:0.5-2.
4. The method for preparing the anode catalyst of the alkaline system direct methanol fuel cell as claimed in claim 2, wherein the nickel-cerium gel is obtained by removing the moisture in the nickel-cerium composite material by adopting a drying mode.
5. The method for preparing the anode catalyst of the direct methanol fuel cell with the alkaline system, as claimed in claim 4, is characterized in that the water in the nickel-cerium composite material is evaporated at room temperature, and then the nickel-cerium gel is obtained by drying in an oven at 60-100 ℃.
6. The method for preparing an anode catalyst of an alkaline system direct methanol fuel cell according to claim 2, wherein the nickel-cerium gel is calcined in an inert atmosphere at a rate of 1-5 ℃/min from room temperature to 600 ℃.
7. The method for preparing an anode catalyst for a direct methanol fuel cell of an alkaline system according to claim 2, wherein the calcination time is 1 to 5 hours.
8. An alkaline system direct methanol fuel cell anode coated with the Ni/CeO of claim 1 2 Catalyst @ CN-600.
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