CN110975877A - Quenching modification method for improving electrocatalytic performance of metal oxide, prepared metal oxide electrocatalyst and application - Google Patents
Quenching modification method for improving electrocatalytic performance of metal oxide, prepared metal oxide electrocatalyst and application Download PDFInfo
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- CN110975877A CN110975877A CN201911164916.XA CN201911164916A CN110975877A CN 110975877 A CN110975877 A CN 110975877A CN 201911164916 A CN201911164916 A CN 201911164916A CN 110975877 A CN110975877 A CN 110975877A
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- metal oxide
- metal
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 41
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 41
- 238000010791 quenching Methods 0.000 title claims abstract description 31
- 230000000171 quenching effect Effects 0.000 title claims abstract description 29
- 238000002715 modification method Methods 0.000 title claims abstract description 26
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 239000012266 salt solution Substances 0.000 claims abstract description 13
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 238000003837 high-temperature calcination Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 150000004692 metal hydroxides Chemical class 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000000593 microemulsion method Methods 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 22
- 238000001816 cooling Methods 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000001354 calcination Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 230000005595 deprotonation Effects 0.000 abstract description 2
- 238000010537 deprotonation reaction Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000000840 electrochemical analysis Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- 239000000843 powder Substances 0.000 description 36
- 239000008367 deionised water Substances 0.000 description 29
- 229910021641 deionized water Inorganic materials 0.000 description 29
- 239000005457 ice water Substances 0.000 description 20
- 239000002243 precursor Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 229910005809 NiMoO4 Inorganic materials 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 11
- 239000004202 carbamide Substances 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 11
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 238000003917 TEM image Methods 0.000 description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000007605 air drying Methods 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 6
- 235000018660 ammonium molybdate Nutrition 0.000 description 6
- 239000011609 ammonium molybdate Substances 0.000 description 6
- 229940010552 ammonium molybdate Drugs 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 5
- 239000002073 nanorod Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229940075397 calomel Drugs 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- C25B11/095—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 at least one of the compounds being organic
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- 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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Abstract
The invention discloses a quenching modification method for improving electrocatalysis performance of metal oxides and application thereof. The method comprises the following steps: and calcining the synthesized metal oxide precursor at high temperature, quickly taking out, and quickly cooling in an ice salt solution with a certain concentration. The method provided by the invention not only can dope metal ions into the metal oxide, but also can carry out structural modification on the surface of the metal oxide. The valence state of elements in the catalyst is changed by doping metal ions, so that the surface adsorption of oxygen is facilitated, and OOH deprotonation is promoted; meanwhile, the catalyst has different crystal structures on the surface, and has lower crystallinity and more defects. Electrochemical tests show that the metal oxide catalyst prepared by the quenching modification method has better electrocatalysis performance, lowers overpotential and has better catalytic stability. Meanwhile, the method has the advantages of simple process, low cost and wide application range, and is beneficial to promoting the manufacturing and development of the electro-catalyst.
Description
Technical Field
The invention relates to the field of modification of a metal catalyst manufacturing process, in particular to a quenching modification method for improving the electrocatalytic performance of a metal oxide, the prepared metal oxide electrocatalyst and application.
Background
The increasing concern over energy crisis and environmental pollution has prompted the urgent search for renewable energy alternatives to fossil fuels and, accordingly, for efficient energy storage devices. Among various energy storage devices, rechargeable Metal-air batteries are an ideal and promising electrochemical energy storage device (Wang S, Qin J, Meng T, et al, Metal-organic frame-induced transformation of action-like carbon nano-structural as an advanced multi-functional electrochemical energy storage for over-working and Zn-air batteries [ J-air batteries ]]Nano Energy, 2017, 39: 626-. However, Oxygen Evolution (OER) and oxygen reduction (ORR) are key reactions for metal-air battery cathodes, and their efficiency is hampered by multi-step proton coupled electron transfer and slow kinetic processes (Kim J S, Kim B, Kim H, et)al. Recentprogress on multimetaloxide catalysts for the oxygen evolution reaction[J]Advanced Energy Materials, 2018, 8(11): 1702774). Therefore, in order to increase the electrochemical reaction rate of the negative electrode and promote the development of the metal-air battery, it is important to design and develop a high-efficiency electrocatalyst. Although noble metals such as Ir and Ru and their oxides have been used as highly efficient electrocatalysts, their high cost and scarcity have certainly hindered their large-scale practical application to some extent (Wu T, Sun S, Song J, et al2O4with self-termination ofsurface reconstruction for water oxidation[J]Nature Catalysis, 2019, 2(9): 763-772.). Therefore, in order to replace these scarce noble metal catalysts, much effort has been devoted to the design and synthesis of inexpensive, resource-rich and efficient electrocatalysts.
Among the electrocatalysts, transition metal oxides and their derivatives have become a promising catalytic material for water oxidation catalysis [ J ] because of their advantages of adjustability, abundant resources, low cost and potential stability]Science, 2013, 340(6128): 60-63.). However, such metal catalysts also have the disadvantages of poor conductivity, insufficient catalytic performance, etc., resulting in higher overpotential and limited kinetics for OER/ORR. Therefore, in order to meet the catalytic requirements of the metal-air battery, the metal catalyst is continuously modified, so that the metal catalyst has the advantages of low overpotential, stability and the like, the electrocatalytic performance of the metal catalyst is improved, and the metal catalyst becomes one of the current research hotspots. Ion doping, interface structure reforming and morphology design regulation are modification methods which are researched more, and effectively promote the development of metal catalysts (Bergmann A, Jones T E, Moreno E M, et al. Unifield structural mol of the catalytic active state of Co (oxide) oxidative catalyst [ J]Nature Catalysis,2018, 1(9): 711.). For example, Shaoyang Zhang et al utilize NaH2PO2For NiMoO4The surface is phosphatized to improve NiMoO4OER performance (Zhang S, She G, Li S, et al. Enhancing the electrophoretic activity of NiMoO)4through a post-phosphorization processfor oxygen evolution reaction[J]Catalysis Communications, 2019: 105725.). However, the above modification methods all involve complicated synthesis steps, are cumbersome, even require high-temperature calcination again, consume resources, and have yet to be improved in electrocatalytic properties. Therefore, it is very important to develop and design a novel metal catalyst modification method with simple steps and high efficiency.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a quenching modification method for improving the electrocatalytic performance of metal oxides.
The quenching modification method provided by the invention can dope metal ions into the metal oxide, can perform structural rearrangement on the surface of the oxide, can produce more defects, effectively improves the electrocatalytic activity of the catalyst, has better catalytic stability, and has positive effects on promoting the development of electrolytic water oxygen production and metal air batteries.
The quenching modification method of the electrocatalytic performance of the metal oxide can be applied to electrolytic water and oxygen reduction reactions and high-efficiency metal catalysts for metal-air batteries.
It is a secondary object of the present invention to provide a novel metal oxide electrocatalyst.
The final purpose of the invention is to provide the application of the metal oxide catalyst prepared by the quenching modification method in electrolytic water oxygen evolution and oxygen reduction reaction.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a quenching modification method for improving electrocatalytic performance of a metal oxide, which comprises the following steps: and heating the metal oxide precursor to perform high-temperature calcination treatment, quickly taking out the metal oxide precursor, soaking the metal oxide precursor in an ice salt solution to perform quick cooling treatment, and then stirring, filtering, cleaning and drying to obtain the quenched and modified metal oxide electrocatalyst.
Further, the metal oxide precursor is one or more of a metal hydroxide, a metal carbonate, and a metal bicarbonate.
Further, the synthesis method of the metal oxide precursor is more than one of a hydrothermal method, a solvothermal method, a coprecipitation method, a sol-gel method, a solid-phase reaction method and a microemulsion method.
Preferably, the synthesis method of the metal oxide precursor is a hydrothermal method. The hydrothermal process comprises: adding metal salt, urea and ammonium fluoride into a reaction kettle, adding water, heating for heating, centrifuging to obtain precipitate, washing with water and ethanol, and vacuum drying to obtain metal hydroxide.
Further, the temperature of the high-temperature calcination treatment is 300-900 ℃.
Preferably, the temperature of the high-temperature calcination treatment is 400-600 ℃.
Further, the time of the high-temperature calcination treatment is 1-15 h.
Preferably, the time of the high-temperature calcination treatment is 2 to 6 hours.
Further, the concentration of the ice salt solution is 0-5M.
Preferably, the concentration of the ice salt solution is 0-2M.
Further, the ice salt solution is more than one of carbonate solution, bicarbonate solution, nitrate solution, chloride solution, sulfate solution and phosphate solution.
Preferably, the metal salt is one or more of iron nitrate, cobalt nitrate, chromium nitrate and manganese sulfate.
Further, the temperature of the ice salt solution is-10 ℃ to 10 ℃.
Preferably, the temperature of the ice salt solution is 0 ℃.
Further, the stirring speed of the stirring treatment is 100-1000 rpm, and the stirring treatment time is 0.5-12 h.
Preferably, the stirring rate of the stirring treatment is 700 rpm, and the stirring treatment time is 1 h.
The invention provides a metal oxide electrocatalyst prepared by using the quenching modification method for improving the electrocatalysis performance of metal oxides.
The metal oxide electrocatalyst provided by the invention can be applied to metal-air batteries, electrolyte water hydrogen production, electrolyte water oxygen production and oxygen reduction reaction.
The invention also provides a preparation method of the novel metal oxide electrocatalyst. The method comprises the following steps:
(1) preparing synthetic metal hydroxide by adopting a hydrothermal reaction: adding metal salt, urea and ammonium fluoride into a reaction kettle, adding water, heating for hydrothermal reaction, centrifuging to obtain precipitate (powder) after the reaction is finished, separating the powder, alternately cleaning with deionized water and ethanol, and then drying in vacuum to obtain metal hydroxide;
(2) taking metal hydroxide, placing the metal hydroxide in a muffle furnace, and heating for calcining; then taking out the powder (calcined product), soaking the powder in an ice water solution containing metal salt, and stirring; and then carrying out suction filtration, taking the precipitate, washing the precipitate with deionized water, and finally carrying out forced air drying and drying to obtain the novel metal oxide electrocatalyst.
Further, the metal salt in the step (1) is ammonium molybdate, nickel nitrate or cobalt nitrate.
Further, the mass ratio of the metal salt to the urea in the step (1) is 5:1 to 10: 1.
Further, the mass ratio of the metal salt to the ammonium fluoride in the step (1) is 15:1 to 3:1
Further, the mass-volume ratio of the metal salt to the water in the step (1) is 5-100: 1 mg/mL
Further, the temperature of the hydrothermal reaction in the step (1) is 100-.
Further, the temperature of the calcination treatment in the step (2) is 400-600 ℃, and the time of the calcination treatment is 2-5 h.
Further, the metal salt in the step (2) is one of ferric nitrate, cobalt nitrate, chromium nitrate and manganese sulfate.
Further, in the ice water solution containing the metal salt in the step (2), the concentration of the metal salt is 0 to 2M.
Further, the temperature of the ice water solution containing the metal salt in the step (2) is-10 DEG C
Preferably, the temperature of the ice-water solution containing the metal salt in the step (2) is 0 ℃.
Further, the stirring speed of the stirring treatment in the step (2) is 100-1000 rpm, and the stirring treatment time is 0.5-12 h.
The invention finally provides the application of the metal oxide electrocatalyst prepared based on the quenching modification method in electrolysis water oxygen evolution and oxygen reduction reaction, which comprises the following steps:
(1) dispersing metal oxide in a mixed solution of ethanol and water, adding a perfluorosulfonic acid polymer solution, and performing ultrasonic dispersion to obtain a dispersion liquid;
(2) and (3) dripping the dispersion liquid on the surface of a smooth glassy carbon electrode, and drying by using nitrogen.
(3) In aqueous KOH, linear scan testing was performed using a rotating disk electrode.
Further, in the mixed solution of ethanol and water in the step (1), the volume percentage concentration of the ethanol is 0-100%.
Further, the mass-to-volume ratio of the metal oxide to the mixed solution of ethanol and water in the step (1) is 1-10 mg/ml.
Further, the mass concentration of the perfluorosulfonic acid polymer solution in the step (1) is 1-10%.
Further, the volume ratio of the perfluorosulfonic acid polymer solution in the step (1) to the mixed solution of ethanol and water is 0-10%.
Further, the concentration of the KOH aqueous solution in the step (3) is 0.1-1M.
The invention adopts a one-step quenching strategy to realize the doping of metal impurity ions in the metal oxide catalyst; meanwhile, the structure of the metal oxide is changed, and the surface of the metal oxide has a thin structure with a layer of different crystalline phases. The valence state of elements in the catalyst is changed by doping metal ions, so that the surface adsorption of oxygen is facilitated, and OOH deprotonation is promoted; meanwhile, the different crystal structures on the surface of the catalyst have lower crystallinity, and more defects improve the electrocatalytic activity. The metal oxide catalyst prepared by the quenching modification method has better OER and ORR performances, lower overpotential and better catalytic stability. Meanwhile, the method has simpler process, and the metal ion doping and the surface structure adjustment are completed simultaneously; and the cost is low, the application range is wide, and the manufacture and development of the electro-catalyst are promoted.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the quenching modification method for improving the electrocatalytic performance of the metal oxide, provided by the invention, adopts in-situ one-step synthesis, is simple in method and low in cost, and can realize industrial production.
(2) The quenching modification method for improving the electrocatalytic performance of the metal oxide provided by the invention simultaneously completes metal ion doping and surface structure adjustment.
(3) The catalyst prepared by the quenching modification method has excellent electro-catalytic performance, lower overpotential and better stability.
Drawings
Fig. 1 is an SEM image and a TEM image of NMO-NC material particles prepared in comparative example 1, wherein (a) is a part of the SEM image, and (b) is a part of the TEM image;
FIG. 2 is an SEM image and a TEM image of NMO-Fe-1 material particles prepared in example 1, wherein (a) is a partial SEM image and (b) is a partial TEM image;
FIG. 3 is a linear scan of samples from examples 1-4 and comparative example 1;
FIG. 4 is a linear scan of samples from examples 5-7 and comparative example 2.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Comparative example 1
(1) 2.622 g of ammonium molybdate, 4.362 g of nickel nitrate and 0.45 g of urea were charged into a 100 ml reaction vessel, 70ml of deionized water was further added thereto, stirred for 30 minutes and then reacted at 160 ℃ for 12 hours. Cooling, separating the powder with a centrifuge, alternately cleaning with deionized water and ethanol, and vacuum drying at 60 deg.C to obtain NiMoO4And (3) precursor.
(2) Taking 200 mg of NiMoO4Placing the precursor in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min for 2 hours, and naturally cooling to room temperature to obtain NiMoO4And the nano rod is marked as NMO-NC.
(3) 5 mg of NMO-NC is dispersed in a mixed solution of 200 mu L of ethanol and 750 mu L of deionized water, 50 mu L of perfluorosulfonic acid type polymer solution is added, and ultrasonic dispersion is carried out for 2 hours. 10 μ L of the dispersion was dropped onto a smooth glassy carbon electrode surface and blown dry with nitrogen. In a 1M KOH aqueous solution, a Pt sheet is taken as a counter electrode, a calomel electrode is taken as a reference electrode, a rotating disk electrode is utilized to carry out linear scanning test, the rotating speed is 1600 rpm, the voltage range is 0.1-0.9V (relative to the calomel electrode), and the scanning speed is 5 mV/s.
Fig. 1 is SEM and TEM images of NMO-NC particles prepared in comparative example 1, and (a) part is an SEM image and (b) part is a TEM image. The SEM image shows that NMO-NC is in the shape of a nanorod and the length of the nanorod is about 3-5 um. The TEM image shows that NMO-NC has better crystallinity.
Comparative example 2
(1) 0.291 g of cobalt nitrate, 0.093 g of ammonium fluoride and 0.30 g of urea were charged into a 50 ml reaction vessel, and 35 ml of deionized water was further added, stirred for 30 minutes and then reacted at 120 ℃ for 12 hours. Cooling, separating powder with centrifuge, alternately cleaning with deionized water and ethanol, and vacuum drying at 60 deg.CDrying and drying to obtain Co3O4And (3) precursor.
(2) Taking 50 mg of Co3O4Placing the precursor in a muffle furnace, heating to 400 ℃ at the heating rate of 5 ℃/min for 3 hours, and naturally cooling to room temperature to obtain Co3O4Nanorods, denoted as Co3O4-NC。
(3) 5 mg of Co are taken3O4-NC is dispersed in a mixed solution of 200. mu.L ethanol and 750. mu.L deionized water, 50. mu.L perfluorosulfonic acid type polymer solution is added, and ultrasonic dispersion is carried out for 1 hour. 10 μ L of the dispersion was dropped onto a smooth glassy carbon electrode surface and blown dry with nitrogen. In a 1M KOH aqueous solution, a Pt sheet is taken as a counter electrode, a calomel electrode is taken as a reference electrode, a rotating disk electrode is utilized to carry out linear scanning test, the rotating speed is 1600 rpm, the voltage range is 0.1-0.9V (relative to the calomel electrode), and the scanning speed is 5 mV/s.
Example 1
(1) 2.622 g of ammonium molybdate, 4.362 g of nickel nitrate and 0.45 g of urea were charged into a 100 ml reaction vessel, 70ml of deionized water was further added thereto, stirred for 30 minutes and then reacted at 160 ℃ for 12 hours. Cooling, separating the powder with a centrifuge, alternately cleaning with deionized water and ethanol, and vacuum drying at 60 deg.C to obtain NiMoO4And (3) precursor.
(2) Taking 200 mg of NiMoO4Placing the precursor in a muffle furnace, heating to 500 deg.C at a heating rate of 5 deg.C/min for 2 hr, quickly taking out the powder, and placing into a furnace containing 1M Fe (NO)3)3In an ice-water solution of (2), the Fe (NO)3)3The temperature of the ice-water solution of (2) was 0 ℃ and stirred for 1 hour at a stirring rate of 700 rpm. And then, carrying out suction filtration to separate the powder, washing the powder by using a large amount of deionized water, and finally carrying out forced air drying and drying at 60 ℃ to obtain NMO-Fe-1.
(3) The working electrode was prepared in the same manner as in comparative example 1, and the same test conditions were used for the linear scan test.
FIG. 2 is an SEM image and a TEM image of NMO-Fe-1 particles prepared in example 1, in which (a) part is an SEM image and (b) part is a TEM image. SEM image displayAfter high-temperature quench cooling, the NMO particles (NiMoO)4Particles) still maintain the shape of the nanorods, and the shape is hardly changed. TEM shows that after quenching, NMO particles have a crystalline phase interface, and the surface of the NMO particles has a thin structure with an amorphous phase of about 5 nm, which indicates that the quenching process carries out structural reformation on the surface of the NMO particles, thereby causing poor crystallinity.
Example 2
(1) 2.622 g of ammonium molybdate, 4.362 g of nickel nitrate and 0.45 g of urea were charged into a 100 ml reaction vessel, 70ml of deionized water was further added thereto, stirred for 30 minutes and then reacted at 160 ℃ for 12 hours. Cooling, separating the powder with a centrifuge, alternately cleaning with deionized water and ethanol, and vacuum drying at 60 deg.C to obtain NiMoO4And (3) precursor.
(2) Taking 200 mg of NiMoO4Placing the precursor in a muffle furnace, heating to 500 deg.C at a heating rate of 5 deg.C/min for 2 hr, quickly taking out the powder, and placing into a furnace containing 1M Co (NO)3)2In an ice-water solution of (2), the Co (NO)3)2The temperature of the ice-water solution of (2) was 0 ℃ and stirred for 1 hour at a stirring rate of 700 rpm. And then carrying out suction filtration to separate the powder, washing the powder by using a large amount of deionized water, and finally carrying out forced air drying and drying at 60 ℃ to obtain NMO-Co-1.
(3) The working electrode was prepared in the same manner as in comparative example 1, and the same test conditions were used for the linear scan test.
Example 3
(1) 2.622 g of ammonium molybdate, 4.362 g of nickel nitrate and 0.45 g of urea were charged into a 100 ml reaction vessel, 70ml of deionized water was further added thereto, stirred for 30 minutes and then reacted at 160 ℃ for 12 hours. Cooling, separating the powder with a centrifuge, alternately cleaning with deionized water and ethanol, and vacuum drying at 60 deg.C to obtain NiMoO4And (3) precursor.
(2) Taking 200 mg of NiMoO4Placing the precursor in a muffle furnace, heating to 500 deg.C at a heating rate of 5 deg.C/min for 2 hr, quickly taking out the powder, and placing into a furnace containing 0.1M Cr (NO)3)3In an ice water solutionSaid Cr (NO)3)3The temperature of the ice-water solution of (2) was 0 ℃ and stirred for 1 hour at a stirring rate of 700 rpm. And then, carrying out suction filtration to separate the powder, washing the powder by using a large amount of deionized water, and finally carrying out forced air drying and drying at 60 ℃ to obtain NMO-Cr-0.1.
(3) The working electrode was prepared in the same manner as in comparative example 1, and the same test conditions were used for the linear scan test.
Example 4
(1) 2.622 g of ammonium molybdate, 4.362 g of nickel nitrate and 0.45 g of urea were charged into a 100 ml reaction vessel, 70ml of deionized water was further added thereto, stirred for 30 minutes and then reacted at 160 ℃ for 12 hours. Cooling, separating the powder with a centrifuge, alternately cleaning with deionized water and ethanol, and vacuum drying at 60 deg.C to obtain NiMoO4And (3) precursor.
(2) Taking 200 mg of NiMoO4Placing the precursor in a muffle furnace, heating to 500 deg.C at a heating rate of 5 deg.C/min for 2 hr, quickly taking out the powder, and placing in a furnace containing 0.5M MnSO4In an ice-water solution of the said MnSO4The temperature of the ice-water solution of (2) was 0 ℃ and stirred for 1 hour at a stirring rate of 700 rpm. And then, carrying out suction filtration to separate the powder, washing the powder by using a large amount of deionized water, and finally carrying out forced air drying and drying at 60 ℃ to obtain NMO-Mn-0.5.
(3) The working electrode was prepared in the same manner as in comparative example 1, and the same test conditions were used for the linear scan test.
FIG. 3 is a linear scan of samples from examples 1-4 and comparative example 1. It can be seen that the overpotential is 460 mV compared to natural cooling; whereas after quenching in an ice-water salt solution the overpotential decreases significantly. Wherein, in 1M Fe (NO)3)3After quenching in the solution, the overpotential is reduced by 98 mV, the OER performance is obviously improved, and the electrocatalytic activity is higher.
Example 5
(1) 0.291 g of cobalt nitrate, 0.093 g of ammonium fluoride and 0.30 g of urea were charged into a 50 ml reaction vessel, and 35 ml of deionized water was further added, stirred for 30 minutes and then reacted at 120 ℃ for 12 hours. After cooling downSeparating the powder by a centrifuge, alternately cleaning the powder by deionized water and ethanol, and then drying the powder in vacuum at 60 ℃ to obtain Co3O4And (3) precursor.
(2) Taking 50 mg of Co3O4Placing the precursor in a muffle furnace, heating to 400 deg.C at a heating rate of 5 deg.C/min for 3 hr, quickly taking out the powder, and placing into a furnace containing 1M Fe (NO)3)3In an ice-water solution of (2), the Fe (NO)3)3The temperature of the ice-water solution of (2) was 0 ℃ and stirred for 1 hour at a stirring rate of 700 rpm. Then, carrying out suction filtration to separate the powder, washing the powder by using a large amount of deionized water, and finally carrying out forced air drying and drying at 60 ℃ to obtain Co3O4-Fe-1。
(3) The working electrode was prepared in the same manner as in comparative example 2, and the same test conditions were used for the linear scan test.
Example 6
(1) 0.291 g of cobalt nitrate, 0.093 g of ammonium fluoride and 0.30 g of urea were charged into a 50 ml reaction vessel, and 35 ml of deionized water was further added, stirred for 30 minutes and then reacted at 120 ℃ for 12 hours. Cooling, separating the powder by a centrifugal machine, alternately cleaning by deionized water and ethanol, and then drying in vacuum at 60 ℃ to obtain Co3O4And (3) precursor.
(2) Taking 50 mg of Co3O4Placing the precursor in a muffle furnace, heating to 400 deg.C at a heating rate of 5 deg.C/min for 3 hr, quickly taking out the powder, and placing into a furnace containing 0.5M Ni (NO)3)2In an ice-water solution of (2), the Ni (NO)3)2The temperature of the ice-water solution of (2) was 0 ℃ and stirred for 1 hour at a stirring rate of 700 rpm. Then, carrying out suction filtration to separate the powder, washing the powder by using a large amount of deionized water, and finally carrying out forced air drying and drying at 60 ℃ to obtain Co3O4-Ni-0.5。
(3) The working electrode was prepared in the same manner as in comparative example 2, and the same test conditions were used for the linear scan test.
Example 7
(1) 0.291 g of cobalt nitrate, 0.093 g of ammonium fluoride and 0.30 g of urine were mixed togetherThe extract was added to a 50 ml reaction vessel, followed by addition of 35 ml of deionized water, stirring for 30 minutes, and then reaction at 120 ℃ for 12 hours. Cooling, separating the powder by a centrifugal machine, alternately cleaning by deionized water and ethanol, and then drying in vacuum at 60 ℃ to obtain Co3O4And (3) precursor.
(2) Taking 50 mg of Co3O4Placing the precursor in a muffle furnace, heating to 400 deg.C at a heating rate of 5 deg.C/min for 3 hr, quickly taking out the powder, and placing into a furnace containing 1M Cr (NO)3)3In an ice-water solution of (1), the CuCl2The temperature of the ice-water solution of (2) was 0 ℃ and stirred for 1 hour at a stirring rate of 700 rpm. Then, carrying out suction filtration to separate the powder, washing the powder by using a large amount of deionized water, and finally carrying out forced air drying and drying at 60 ℃ to obtain Co3O4-Cr-1。
(3) The working electrode was prepared in the same manner as in comparative example 2, and the same test conditions were used for the linear scan test.
FIG. 4 is a linear scan of samples from examples 5-7 and comparative example 2. It can be seen that the overpotential is 434 mV compared to natural cooling; whereas after quenching in an ice-water salt solution the overpotential decreases significantly. Wherein, in 1M Fe (NO)3)3After quenching in the solution, the overpotential is reduced by 59 mV, the OER performance is obviously improved, and the electrocatalytic activity is higher.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A quenching modification method for improving the electrocatalytic performance of a metal oxide is characterized by comprising the following steps: and heating the metal oxide precursor to perform high-temperature calcination treatment, and then soaking the metal oxide precursor in an ice salt solution to perform stirring treatment to obtain the quenched and modified metal oxide electrocatalyst.
2. The method of claim 1, wherein the metal oxide precursor is one or more of a metal hydroxide, a metal carbonate, and a metal bicarbonate.
3. The quenching modification method for improving the electrocatalytic performance of a metal oxide according to claim 1, wherein the synthesis method of the metal oxide precursor is at least one of a hydrothermal method, a solvothermal method, a coprecipitation method, a sol-gel method, a solid-phase reaction method and a microemulsion method.
4. The quenching modification method for improving the electrocatalytic performance of a metal oxide as claimed in claim 1, wherein the temperature of the high-temperature calcination treatment is 300-900 ℃; the time of the high-temperature calcination treatment is 1-15 h.
5. The quenching modification method for improving the electrocatalytic performance of a metal oxide as recited in claim 1, wherein the concentration of the ice salt solution is 0-5M.
6. The method of claim 1, wherein the ice salt solution is one or more of a carbonate solution, a bicarbonate solution, a nitrate solution, a chloride solution, a sulfate solution, and a phosphate solution.
7. The quenching modification method for improving the electrocatalytic performance of the metal oxide as claimed in claim 1, wherein the temperature of the ice salt solution is-10 ℃ to 10 ℃.
8. The quenching modification method for improving the electrocatalytic performance of a metal oxide as claimed in claim 1, wherein the stirring rate of the stirring treatment is 100-1000 rpm, and the stirring treatment time is 0.5-12 h.
9. A metal oxide electrocatalyst prepared using the quench modification method to improve the electrocatalytic properties of a metal oxide according to any one of claims 1 to 8.
10. Use of the metal oxide electrocatalyst according to claim 9 in metal-air batteries, in hydrogen production from electrolyte water, in oxygen production from electrolyte water and in oxygen reduction reactions.
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| CN111933957B (en) * | 2020-07-14 | 2022-03-15 | 中北大学 | Preparation method and application of transition metal oxide with controllable aluminum doping amount |
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