CN115522223A - Fluorine-doped non-noble metal electrocatalyst and preparation method and application thereof - Google Patents
Fluorine-doped non-noble metal electrocatalyst and preparation method and application thereof Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 46
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 45
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- -1 fluoride ions Chemical class 0.000 claims description 28
- 239000011737 fluorine Substances 0.000 claims description 27
- 229910052731 fluorine Inorganic materials 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000012876 carrier material Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012018 catalyst precursor Substances 0.000 claims description 4
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- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000007743 anodising Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 239000002055 nanoplate Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 65
- 230000000694 effects Effects 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 49
- 229910002640 NiOOH Inorganic materials 0.000 description 30
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- 239000000523 sample Substances 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 238000002048 anodisation reaction Methods 0.000 description 14
- 229910018916 CoOOH Inorganic materials 0.000 description 13
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- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
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- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000004506 ultrasonic cleaning Methods 0.000 description 8
- 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 7
- 238000011161 development Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 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 5
- 238000005516 engineering process Methods 0.000 description 5
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 4
- 229910018661 Ni(OH) Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
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- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- 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
- WTFUTSCZYYCBAY-SXBRIOAWSA-N 6-[(E)-C-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-N-hydroxycarbonimidoyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C/C(=N/O)/C1=CC2=C(NC(O2)=O)C=C1 WTFUTSCZYYCBAY-SXBRIOAWSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 238000002253 near-edge X-ray absorption fine structure spectrum Methods 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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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
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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
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Abstract
The invention discloses a fluorine-doped non-noble metal electrocatalyst and a preparation method and application thereof. The electrocatalyst comprises an active amorphous layer and a substrate, wherein the active amorphous layer is distributed on the surface of the substrate and is fluorine-doped non-noble metal oxyhydroxide. The invention converts the surface of the substrate into oxyhydroxide by an electrochemical anode oxidation method and simultaneously dopes fluorinion, thereby improving the oxygen evolution electrocatalytic activity. The method has the advantages of easily available raw materials, simple and convenient operation and convenient mass production. The prepared catalyst has high intrinsic performance and rich active sites, can efficiently and stably catalyze the electrolytic water oxygen evolution reaction under the alkaline condition, and has better catalytic performance than the single metal oxide/oxyhydroxide oxygen evolution electrocatalyst catalyst reported at present.
Description
Technical Field
The invention belongs to the technical field of hydrogen production technology and materials, and particularly relates to a fluorine-doped non-noble metal electrocatalyst, and a preparation method and application thereof.
Background
The growing world demand for energy and the consumption of fossil fuels are major challenges for sustainable development. Hydrogen is widely considered as a clean and efficient secondary energy carrier, and the large-scale industrial application of the secondary energy carrier is expected to fundamentally solve the global problems of energy shortage, environmental pollution and the like, so the development of the hydrogen energy utilization technology becomes the key point of the energy development strategy of all countries in the world. Promoting the industrial application of hydrogen energy requires constructing a complete hydrogen energy industrial chain including the links of hydrogen production, hydrogen storage, hydrogen fuel cells and the like, wherein the hydrogen production is a source. In the existing hydrogen production mode, the coupling of water electrolysis hydrogen production and primary renewable energy sources such as solar energy, wind energy and the like can become an ideal large-scale hydrogen production technology, and is an optimal way to 'hydrogen economy'. The electrolysis of water involves two half reactions of cathodic hydrogen evolution and anodic oxygen evolution, and the reduction of overpotential of the two reactions, namely the reduction of energy consumption of electrolysis reaction, is the core of the development of water electrolysis technology. In the process, the Oxygen Evolution (OER) process at the anode involves four-electron transfer reaction and becomes a main rate-limiting step for hydrogen production by water electrolysis, so that the development of a high-activity electrocatalyst, namely an oxygen evolution electrocatalyst is very important for the technical development of water electrolysis.
In recent years, the development of novel non-noble metal catalysts, which are intended to reduce material costs and to achieve excellent catalytic performance, has become a mainstream trend in the field of electrolytic water technology. It is reported in the literature that many types of materials such as oxides/hydroxides, nitrides, phosphides, sulfides, borides, etc. of 3d transition metal compounds have good basic electrocatalytic oxygen evolution activity, but overall, non-noble transition metal oxygen evolution electrocatalysts can minimize the overpotential of the oxygen evolution reaction because they are four-electron reactions and have only the appropriate adsorption energy of the active sites for the oxygen intermediates (OH, O, and OOH). (t.h.lee, s.a.lee, h.patk, m.j.choi, d.lee, h.w.jang, ACS appl.energy mater.2020,3, 1634-1643.). And the hetero atom doping can optimize the electronic structure of the active site of the oxygen evolution catalyst, thereby optimizing the binding energy of the active site and an oxygen intermediate, and is considered as an important means for obtaining a high-performance catalyst.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a fluorine-doped non-noble metal electrocatalyst, and a preparation method and application thereof. Due to the extremely high electron affinity and electronegativity, the fluorine ions can affect the electronic structure and physicochemical properties of the metal catalyst, so that the intrinsic activity of the catalyst is changed. Thus allowing passage of fluoride ionsDoping modifies the non-noble metal catalyst and improves the OER activity of the catalyst. The catalyst prepared by the invention has high intrinsic activity, can efficiently catalyze the electrolytic water oxygen evolution reaction under the alkaline condition, and has the catalytic performance close to that of noble metal RuO 2 A catalyst.
The purpose of the invention is realized by the following technical scheme:
the utility model provides a non-noble metal electro-catalysis oxygen evolution catalyst of fluorine doping, the electrocatalyst includes active amorphous layer and base member, active amorphous layer distributes on the base member surface, active amorphous layer is fluorine doped non-noble metal oxyhydroxide. The active amorphous layer is an amorphous oxyhydroxide compound.
Preferably, the non-noble metal in the fluorine-doped non-noble metal oxyhydroxide is at least one of Fe, co and Ni.
Preferably, the substrate is a non-noble metal oxide or metal hydroxide, and the non-noble metal is at least one of Fe, co, ni and Mo.
Preferably, the thickness of the active amorphous layer is 2-5 nm; the active amorphous layer is obtained by the conversion of a substrate under electrochemical anodic oxidation in an alkaline solution containing fluoride ions.
Preferably, the matrix is present in the form of nanoplates;
preferably, the electrocatalyst further comprises a support on which the substrate is supported; the carrier is one of foam metal, metal mesh, ion exchange resin and molecular sieve.
Preferably, the matrix is Ni (OH) 2 、Co(OH) 2 Or NiMoO 4 。
The preparation method of the fluorine-doped non-noble metal electrocatalyst comprises the following steps:
(1) Adding a carrier material into a solution containing non-noble metal salt, carrying out hydrothermal reaction, growing a nano-structure catalyst precursor on the surface of the carrier material,
(2) And (2) electrochemically anodizing the catalyst precursor in the step (1) in an alkaline solution containing fluoride ions to obtain the fluorine-doped non-noble metal electrocatalyst.
Preferably, the non-noble metal salt in step (1) comprises at least one of a halide and an oxysalt of a non-noble metal, and the non-noble metal comprises at least one of Fe, ni, co and Mo;
further preferably, the halide is chloride; the oxysalt is nitrate, carbonate, acetate and sulfate;
preferably, the support material in step (1) is selected from one of a foamed metal, a metal mesh, an ion exchange resin and a molecular sieve.
Preferably, the concentration of the non-noble metal salt in the step (1) is 0.01 to 0.1M (when the non-noble metal salt is a plurality of, the total concentration is obtained); the solvent of the solution is water; the temperature of the hydrothermal reaction is 120-180 ℃; the time of the hydrothermal reaction is 6-12 hours.
Preferably, the solution in the step (1) also contains a precipitating agent; the precipitant is CO (NH) 2 ) 2 (ii) a The concentration of the precipitant is 0.1-1M.
Preferably, the fluoride ion in the step (2) is at least one of sodium fluoride and potassium fluoride; the time of the electrochemical anode oxidation is 0.5 to 1.5h, and the current density is 5 to 20mA cm -2 The concentration of the fluorine ions is 0.25-0.75M; the concentration of the alkaline solution is 0.5M-1.5M.
The application of the fluorine-doped non-noble metal electrocatalyst in electrocatalysis of water decomposition and oxygen analysis.
The design principle of the invention is as follows:
the principle of the invention is as follows: for an electrocatalyst, intrinsic activity, number of active sites, electrical conductivity are three factors that affect its apparent catalytic activity. While the intrinsic activity can be increased by doping with an element, the range of choice of the metal element is limited due to the phase separation that can occur in many compounds doped with transition metal elements during the oxygen evolution reaction. In order to improve the activity of the catalyst and expand the exploration range of doped elements, the intrinsic activity of the catalyst is improved by doping the anionic fluorine element on the design idea of the catalyst, and a simple and easy preparation method is provided for realizing the method. Firstly, a nanosheet precursor containing a catalyst active component and having a high specific surface area is grown on the surface of a carrier material by a hydrothermal method, so that a material composition and a structural foundation are laid for synthesizing a high-performance catalyst; subsequently, the surface of the nanosheet is converted into oxyhydroxide with high catalytic activity by electrochemical anodic oxidation in a solution containing fluorine ions, and the intrinsic activity of the catalyst is improved by doping the fluorine ions into the surface of the catalyst while the oxyhydroxide is formed; in conclusion, the electrochemical oxygen evolution catalyst provided by the invention has high intrinsic activity and abundant active sites.
The invention has the advantages and beneficial effects that:
(1) The method is different from the traditional method in that the catalyst is prepared by electrochemical anodic oxidation in a fluorine-containing solution, so that fluorine ions can be doped into the catalyst to improve the intrinsic activity of the catalyst while active-phase oxyhydroxide is formed on the surface of the catalyst; in addition, a large number of active sites are exposed out of the ultra-thin nano sheet synthesized by the hydrothermal method, so that high oxygen evolution reaction catalytic activity is obtained.
(2) The novel preparation method of the fluorine ion doped non-noble metal oxygen evolution electrocatalyst provided by the invention has the advantages of easily available raw materials, simple process, convenience for mass production and no pollution in the whole process.
(3) The invention provides a fluoride ion-doped non-noble metal oxygen evolution electrocatalyst catalyst which can efficiently catalyze electrolyzed water oxygen evolution reaction under alkaline condition, and has comprehensive catalytic performance close to that of noble metal RuO 2 A catalyst.
Drawings
FIG. 1 shows a hydrothermal sample Ni (OH) of example 1 2 /NF, niOOH/Ni (OH) after electrochemical anodic oxidation 2 NF and F-NiOOH/Ni (OH) after doping fluorine ions in electrochemical anodic oxidation 2 X-ray diffraction pattern of/NF.
FIG. 2 shows the hydrothermal Ni (OH) state of example 1 (a) 2 /NF and (b) sample F-NiOOH/Ni (OH) after electrochemical anodic oxidation doping with fluorine ions 2 the/NF is a shape picture of a scanning electron microscope.
FIG. 3 shows the hydrothermal Ni (OH) state in example 1 2 (a) selected region electron diffraction pattern (b) high fraction of NFPhotograph taken by electron microscope, and F-NiOOH/Ni (OH) after doping fluorine ions in electrochemical anodic oxidation 2 The (c) selected area electron diffraction pattern of/NF (d) high resolution electron micrograph.
FIG. 4 shows Ni (OH) in example 1 2 /NF、NiOOH/Ni(OH) 2 /NF and sample F-NiOOH/Ni (OH) after doping fluorine ions for electrochemical anodic oxidation 2 The X-ray photoelectron spectrum of/NF.
FIG. 5 shows NiOOH/Ni (OH) in example 1 2 /NF and sample F-NiOOH/Ni (OH) after doping with fluoride ions by electrochemical anodic oxidation 2 XANES spectrum (a) of/NF and EXAFS analysis result (b).
FIG. 6 shows NiOOH/Ni (OH) in example 1 2 /NF and sample F-NiOOH/Ni (OH) after doping with fluoride ions by electrochemical anodic oxidation 2 /NF、RuO 2 The polarization curves of the NF and NF oxygen evolution reactions are compared.
FIG. 7 shows NiOOH/Ni (OH) in example 1 2 /NF and sample F-NiOOH/Ni (OH) after doping fluorine ions for electrochemical anodic oxidation 2 The current density of/NF (a) is related to the potential sweep rate, and the impedance spectrum test result of (b) under the open-circuit potential.
FIG. 8 is a graph showing F-NiOOH/Ni (OH) samples after doping with fluoride ions in the electrochemical anodization of example 1 2 Durability test results of/NF in a 1M KOH electrolyte containing 0.01M KF.
FIG. 9 is a sample F-CoOOH/Co (OH) after doping with fluoride ions by electrochemical anodization in example 2 2 The shape and appearance of NF are shown by a scanning electron microscope.
FIG. 10 is a graph showing samples F-CoOOH/Co (OH) after doping with fluoride ions for electrochemical anodization in example 2 2 X-ray diffraction pattern of/NF.
FIG. 11 is a graph showing samples F-CoOOH/Co (OH) after doping with fluoride ions for electrochemical anodization in example 2 2 High resolution electron micrograph of/NF.
FIG. 12 is a sample F-CoOOH/Co (OH) after doping with fluoride ions for electrochemical anodization in example 2 2 The X-ray photoelectron spectrum of/NF.
FIG. 13 is a sample F-CoOOH/Co (OH) after doping with fluoride ions for electrochemical anodization in example 2 2 /NF and RuO 2 Polarization curve of oxygen evolution reaction of/NFCompare the figures.
FIG. 14 shows the sample F-CoOOH/Co (OH) after doping with fluoride ions by electrochemical anodization in example 3 2 /CF、CoOOH/Co(OH) 2 /CF and RuO 2 Comparative plot of oxygen evolution reaction polarization curve of/NF.
FIG. 15 is a graph showing F-NiOOH/NiMoO samples after doping fluorine ions for electrochemical anodization in example 4 4 /NF、NiOOH/NiMoO 4 /NF and RuO 2 Comparative plot of oxygen evolution reaction polarization curve of/NF.
FIG. 16 is a graph showing F-NiOOH/NiMoO samples after doping with fluoride ions in the electrochemical anodization of example 5 4 /CF、NiOOH/NiMoO 4 /CF and RuO 2 Comparative plot of oxygen evolution reaction polarization curve for/CF.
FIG. 17 shows F-Ni samples after doping with fluoride ions for electrochemical anodization in example 6 1-x Fe x OOH/NiFeLDH/NF、Ni 1-x Fe x And 4, an oxygen evolution reaction polarization curve comparison graph of OOH/NiFe LDH/NF.
Detailed Description
The present invention is specifically described below with reference to examples, but the embodiments and the scope of the present invention are not limited to the following examples.
The present invention is described in detail below with reference to specific examples.
Example 1
F-NiOOH/Ni(OH) 2 Synthesis, structure and catalytic performance of/NF catalyst
Preparing a catalyst:
(1) Using foam Nickel (NF) as carrier, its thickness is 1.80mm, and its surface density is 650g/m 2 The aperture is 0.20-0.80 mm. Foamed nickel (1X 4 cm) 2 ) Ultrasonic cleaning with ethanol for 10 min, activating with 1M hydrochloric acid solution for 5 min, ultrasonic cleaning with deionized water for 10 min, and ultrasonic cleaning with 30mL of NiSO 4 ·6H 2 Placing O (0.02M) deionized water solution in a hydrothermal kettle with volume of 50mL, treating at 140 deg.C for 6 hr, naturally cooling to room temperature, cleaning the obtained sample, and vacuum drying at 60 deg.C for 2 hr to obtain hydrothermal Ni (OH) sample 2 /NF。
(2) Mixing 1X 2cm 2 Is prepared by preparing a hydrothermal sampleThe counter electrode is a carbon plate, the reference electrode is Hg/HgO, electrochemical anodic oxidation doping is carried out in a mixed solution of 1M KOH and 0.5M KF, and the current density is 15mA cm -2 . Obtaining the target catalyst F-NiOOH/Ni (OH) after electrochemical anodic oxidation for 1h 2 /NF。
NiOOH/Ni(OH) 2 Preparation of/NF with F-NiOOH/Ni (OH) 2 The difference of/NF: carrying out electrochemical anodic oxidation doping in a 1MKOH solution; the others are the same.
Characterization of phase/structure/elemental chemistry of the catalyst:
the X-ray diffraction and scanning electron microscope images of the hydrothermal sample and the sample after electrochemical anodization obtained in this example are shown in fig. 1 and fig. 2, respectively. According to XRD analysis (FIG. 1), the synthesized hydrothermal sample and the sample after electrochemical anodization are Ni (OH) 2 A crystalline phase. The observation of a scanning electron microscope (a and b in figure 2) shows that the hydrothermal sample has a nanosheet structure, and the morphology of the nanosheet is not obviously changed after electrochemical anodic oxidation. Transmission electron microscopy (c, d in FIG. 3) further confirmed that the target catalyst surface was covered with an amorphous phase and the substrate remained Ni (OH) 2 。
According to X-ray photoelectron spectroscopy (FIG. 4), ni appeared in the sample after electrochemical anodization 3+ Signal, and after fluorine doping, ni 3+ The binding energy of (a) is shifted towards a high binding energy. From the results of the EXAFS analysis of b in FIG. 5, it can be seen that the bond length of Ni-O (OH) is shortened after F doping, and F - Substitute O in NiOOH 2 -or OH - And it can be known from a in FIG. 5 that the valence of F is increased after doping, and F-is excluded from replacing O 2- Thus F replaces OH in NiOOH - The position of (a). It is thus demonstrated that the F ions dope into the nickel oxyhydroxide and replace the OH "sites in the nickel oxyhydroxide. The above analysis confirmed that the target catalyst was foam nickel supported F-NiOOH/Ni (OH) 2 A catalyst.
Electrocatalytic performance test of the catalyst:
the oxygen evolution reaction polarization curve test result (figure 6) shows that the oxygen evolution reaction electrocatalytic activity of the catalyst after fluorine doping by using the method is improved, and the hydrogen content is 1.0M10mA cm in potassium oxide lye -2 The over potential under the current density is reduced by 30mV compared with that without fluorine doping, and the catalytic activity is superior to that of a noble metal RuO 2 A catalyst; 10mA cm -2 Respectively, niOOH/Ni (OH) 2 /NF：300mV，F-NiOOH/Ni(OH) 2 /NF：268mV，RuO 2 /NF：272mV，NF：340mV。
The target catalyst F-NiOOH/Ni (OH) is given in FIG. 7 2 The current density and potential sweep rate of the/NF and the reference sample are shown in a graph and the impedance spectrum test result is obtained. The electrochemical specific surface area and the charge transfer resistance of the sample which is not doped with the fluorine element and the target catalyst are not obviously changed, namely the number of active sites and the conductivity of the catalyst are not obviously changed. For electrocatalysts, however, the three elements that affect their apparent catalytic activity are: intrinsic activity, number of active sites and conductivity. Therefore, the reason for the increased activity of the catalyst is the increase in the intrinsic activity of the catalyst after fluorine doping.
FIG. 8 shows F-NiOOH/Ni (OH) 2 The stability test result of the/NF catalyst shows that the activity of the catalyst is not obviously declined after being measured in a 1M KOH solution containing 0.01M KF for 100 hours at constant current, which indicates that the catalyst has excellent stability.
Example 2
F-CoOOH/Co(OH) 2 Synthesis, structure and catalytic performance of/NF catalyst
Preparing a catalyst:
in the synthesis method of this example, similarly to example 1, the difference is that the synthesis of the precursor is different.
The hydroxide precursor is synthesized by the following method: foamed nickel (1X 4 cm) 2 ) Ultrasonic cleaning with ethanol for 10 min, activating with 1M hydrochloric acid solution for 5 min, and ultrasonic cleaning with deionized water for 10 min, and mixing with 30mL of solution containing Co (NO) 3 ) 2 ·6H 2 O(3mmol)、CO(NH 2 ) 2 (12 mmol) of deionized water solution is placed in a hydrothermal kettle with the volume of 50mL, the mixture is naturally cooled to the room temperature after being processed at the constant temperature of 120 ℃ for 8 hours, the prepared sample is fully cleaned and then is dried in vacuum at the temperature of 60 ℃ for 2 hours, and a hydroxide precursor Co (OH) is obtained 2 /NF。
Characterization of phase/structure/elemental chemistry of the catalyst:
the observation of a scanning electron microscope (figure 9) shows that the target catalyst is a 3D nano flower ball structure consisting of nano sheets.
XRD results showed (FIG. 10) that the synthesized hydrothermal sample and the sample after electrochemical anodization were Co (OH) 2 A crystalline phase.
Transmission electron microscopy (fig. 11) further confirmed the presence of a surface amorphous phase in the target catalyst.
XPS results showed (fig. 12) that the surface was generated CoOOH and that F was doped into CoOOH.
Electrocatalytic performance test of the catalyst:
the oxygen evolution reaction polarization curve test results (FIG. 13) show that F-CoOOH/Co (OH) 2 the/NF catalyst has excellent oxygen evolution reaction electrocatalytic activity, and can reach 10mA cm in 1.0M potassium hydroxide alkaline solution only by 245mV of oxygen evolution overpotential -2 The current density of (1).
Example 3
F-CoOOH/Co(OH) 2 Synthesis, structure and catalytic performance of/CF catalyst
Preparing a catalyst:
in the synthesis of this example, similar to example 2, the only difference is that Nickel Foam (NF) is replaced with Cobalt Foam (CF).
Electrocatalytic performance test of the catalyst:
the oxygen evolution reaction polarization curve test results (FIG. 14) show that F-CoOOH/Co (OH) 2 the/CF catalyst has excellent oxygen evolution reaction electrocatalytic activity, and can reach 10mA cm in 1.0M potassium hydroxide alkali solution only by the oxygen evolution overpotential of 248mV -2 The current density of (2).
Example 4
F-NiOOH/NiMoO 4 Synthesis, structure and catalytic performance of/NF catalyst
Preparing a catalyst:
in the synthesis method of this example, similar to example 1, the only difference is the hydroxide/oxide precursor.
Oxide precursorThe body was synthesized by the following method: foamed nickel (1X 4 cm) 2 ) Ultrasonic cleaning with ethanol for 10 min, activating with 1M hydrochloric acid solution for 5 min, and ultrasonic cleaning with deionized water for 10 min, and mixing with 36mL Ni (NO) 3 ) 2 ·6H 2 O(4mmol)、(NH 4 ) 6 Mo 7 O 24 ·4H 2 O(1mmol)、CO(NH 2 ) 2 Putting (10 mmol) deionized water solution into a hydrothermal kettle with the volume of 50mL, carrying out constant temperature treatment at 150 ℃ for 18 hours, naturally cooling to room temperature, fully cleaning the prepared sample, and carrying out vacuum drying at 60 ℃ for 2 hours to obtain an oxide precursor NiMoO 4 /NF。
Electrocatalytic performance test of the catalyst:
the oxygen evolution reaction polarization curve test result (FIG. 15) shows that F-NiOOH/NiMoO 4 the/NF catalyst has excellent oxygen evolution reaction electrocatalytic activity, and can reach 10mA cm in 1.0M potassium hydroxide alkali solution only with the oxygen evolution overpotential of 252mV -2 The current density of (1).
Example 5
F-NiOOH/NiMoO 4 Synthesis, structure and catalytic performance of/CF catalyst
Preparing a catalyst:
in the synthesis process of this example, similar to example 4, only Nickel Foam (NF) was replaced with Cobalt Foam (CF).
The oxygen evolution reaction polarization curve test result (FIG. 16) shows that F-NiOOH/NiMoO 4 the/CF catalyst has excellent oxygen evolution reaction electrocatalytic activity, and can reach 10mA cm in 1.0M potassium hydroxide alkali solution with the oxygen evolution overpotential of 253mV -2 The current density of (1).
Example 6
F-Ni 1-x Fe x Synthesis, structure and catalytic performance of OOH/NiFe LDH/NF catalyst
Preparing a catalyst:
in the synthesis method of this example, similar to example 1, the only difference is the hydroxide/oxide precursor.
The oxide precursor is synthesized by the following method: foamed nickel (1X 4 cm) 2 ) Sequentially passing through ethanolSonic cleaning for 10 minutes, 1M hydrochloric acid solution activation for 5 minutes and deionized water ultrasonic cleaning for 10 minutes, together with 36mL Ni (NO) 3 ) 2 ·6H 2 O(4mmol)、Fe(NO 3 ) 3 ·9H 2 O(1mmol)、CO(NH 2 ) 2 (10 mmol) deionized water solution is placed in a hydrothermal kettle with the volume of 50mL, is processed at the constant temperature of 150 ℃ for 18 hours, is naturally cooled to the room temperature, and is subjected to vacuum drying at the temperature of 60 ℃ for 2 hours after being fully cleaned to obtain an oxide precursor NiFe LDH/NF.
The oxygen evolution reaction polarization curve test result (FIG. 17) shows that F-Ni 1-x Fe x The OOH/NiFe LDH/NF catalyst has excellent oxygen evolution reaction electrocatalytic activity, and can reach 100mA cm in 1.0M potassium hydroxide alkali solution only by 260mV of oxygen evolution overpotential -2 The current density of (1).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The fluorine-doped non-noble metal electrocatalyst is characterized by comprising an active amorphous layer and a substrate, wherein the active amorphous layer is distributed on the surface of the substrate, and the active amorphous layer is fluorine-doped non-noble metal oxyhydroxide.
2. The fluorine doped non-noble metal electrocatalyst according to claim 1, wherein the non-noble metal in the fluorine doped non-noble metal oxyhydroxide is at least one of Fe, co and Ni;
the base body is non-noble metal oxide or metal hydroxide, and the non-noble metal is at least one of Fe, co, ni and Mo.
3. The fluorine doped non-noble metal electrocatalyst according to claim 1, wherein the thickness of the active amorphous layer is from 2 to 5 nm; the active amorphous layer is obtained by the conversion of a substrate under electrochemical anodic oxidation in an alkaline solution containing fluoride ions.
4. A fluorine doped non-noble metal electrocatalyst according to claim 1, wherein the matrix is present in the form of nanoplates;
the electrocatalyst further comprises a support on which the substrate is supported; the carrier is one of foam metal, metal mesh, ion exchange resin and molecular sieve.
5. The fluorine-doped non-noble metal electrocatalyst according to claim 1, wherein the substrate is Ni (OH) 2 、Co(OH) 2 Or NiMoO 4 。
6. A process for the preparation of a fluorine doped non-noble metal electrocatalyst according to any one of claims 1 to 5, comprising the steps of:
(1) Adding a carrier material into a solution containing non-noble metal salt, carrying out hydrothermal reaction, growing a nano-structure catalyst precursor on the surface of the carrier material,
(2) And (2) electrochemically anodizing the catalyst precursor in the step (1) in an alkaline solution containing fluoride ions to obtain the fluorine-doped non-noble metal electrocatalyst.
7. The method according to claim 6, wherein the non-noble metal salt of step (1) comprises at least one of a halide and an oxysalt of a non-noble metal, the non-noble metal comprising at least one of Fe, ni, co, and Mo; the carrier material is selected from one of foamed metal, metal mesh, ion exchange resin and molecular sieve.
8. The method according to claim 6, wherein the concentration of the non-noble metal salt in the step (1) is 0.01 to 0.1M; the solvent of the solution is water; the temperature of the hydrothermal reaction is 120-180 ℃; the time of the hydrothermal reaction is 6-12 hours.
9. The method according to claim 6, wherein the fluoride ion in the step (2) is at least one of sodium fluoride and potassium fluoride; the time of the electrochemical anode oxidation is 0.5 to 1.5h, and the current density is 5 to 20mA cm -2 The concentration of the fluorine ions is 0.25-0.75M; the concentration of the alkaline solution is 0.5M-1.5M.
10. Use of a fluorine doped non-noble metal electrocatalyst according to any one of claims 1 to 5 for the electrocatalytic decomposition of oxygen from water.
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