CN111686727B - Preparation method of supported oxygen evolution catalyst and water electrolyzer membrane electrode - Google Patents
Preparation method of supported oxygen evolution catalyst and water electrolyzer membrane electrode Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000001301 oxygen Substances 0.000 title claims abstract description 39
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 39
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 54
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 43
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 23
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- 229920005597 polymer membrane Polymers 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002504 iridium compounds Chemical class 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 24
- 239000003513 alkali Substances 0.000 abstract 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical group O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 15
- 229910000457 iridium oxide Inorganic materials 0.000 description 15
- 229910052741 iridium Inorganic materials 0.000 description 12
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 12
- 238000011056 performance test Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6486—Tantalum
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- B01J35/23—
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- B01J35/33—
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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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a preparation method of a supported oxygen evolution catalyst and a membrane electrode of a water electrolyzer. A supported oxygen evolution catalyst comprises transition metal oxide carrier nanoparticles subjected to conductive treatment at room temperature and alkali metal-doped noble metal oxide nanoparticles supported on the surface of the transition metal oxide carrier nanoparticles, wherein the mass of alkali metal is 1% -20% of that of the transition metal oxide, and the mass of noble metal is 5% -30% of that of the transition metal oxide. According to the invention, the active nano-particles of the high-activity noble metal are loaded on the surface of the oxide carrier with high conductivity and high specific surface area, so that the purposes of increasing the utilization rate of the noble metal and improving the activity of the catalyst are achieved.
Description
Technical Field
The invention relates to the technical field of electrochemical oxygen evolution materials and hydrogen energy, in particular to a preparation method of a supported oxygen evolution catalyst and a water electrolyzer membrane electrode.
Background
The polymer water electrolyzer is a technology for converting electric energy into hydrogen and oxygen, and has wide application prospects in the aspects of renewable energy storage, hydrogen production and oxygen production. At present, the technology is the most importantA large limiting factor is their high manufacturing costs. At present, a great amount of noble metal materials such as platinum, iridium, ruthenium and the like are still used in the membrane electrode of the water electrolyzer, and the dosage of the noble metals is large and is generally 0.5-3mg/cm 2 Therefore, it is desired to reduce the cost by reducing the amount of the catalyst. In a proton exchange membrane water electrolyzer, a membrane electrode is in an acid system, and the anode catalyst with the optimal comprehensive performance at present is iridium oxide and ruthenium oxide. However, the use of a large amount of noble metal brings the cost of the membrane electrode to increase, so that the development of a novel catalytic material to improve the specific activity of the noble metal is urgently needed. In the development of a novel catalyst, a transition oxide is generally used as a carrier to support a noble metal active material. However, most of the transition metal oxides are wide bandgap semiconductors, and therefore, the electron conductivity is poor, and the activity of the supported catalyst cannot be improved. The conductivity of the transition metal oxide can be improved by doping, but the specific surface area of the oxide material obtained in the sintering process is low, so that the utilization rate of the noble metal material loaded and on the surface is not high, and the requirement of a high-activity catalyst cannot be met. Meanwhile, the activity of the crystalline iridium oxide obtained by sintering by the conventional method is still insufficient, and the quality activity needs to be improved. In the actual preparation process, the currently adopted preparation method of the supported oxygen evolution catalyst is divided into a treatment step for a carrier and a synthesis step for a noble metal oxide, multiple steps such as adsorption, drying, sintering, washing, separation and the like are required in the preparation process, the preparation process is complex, and the cost is high.
In addition, in the application link, some high-activity catalysts do not actually show their performances in the membrane electrode, so that the amount of noble metal is high, and therefore, the development of a corresponding membrane electrode preparation process aiming at the characteristics of the catalysts is still needed.
Disclosure of Invention
The invention provides a supported oxygen evolution catalyst and a preparation method of a membrane electrode of a water electrolyzer.
The invention aims to provide a supported oxygen evolution catalyst, which consists of transition metal oxide carrier nanoparticles subjected to conductive treatment at room temperature and alkali metal doped noble metal oxide nanoparticles loaded on the surfaces of the transition metal oxide carrier nanoparticles, wherein the mass of the alkali metal is 1-20% of that of the transition metal oxide, and the mass of the noble metal is 5-30% of that of the transition metal oxide. According to the invention, the high-activity noble metal active nano particles are loaded on the surface of the transition metal oxide carrier with high conductivity and high specific surface area, so that the purposes of increasing the utilization rate of noble metal and improving the activity of the catalyst are achieved.
Preferably, the noble metal oxide nanoparticles have a particle size of 0.8 to 2.5 nm.
The invention also provides a preparation method of the supported oxygen evolution catalyst, which comprises the following steps:
(1) Mixing transition metal oxide and alkali metal powder, and performing ball milling reaction for 1-5 hours at room temperature, wherein the mass of alkali metal is 1% -20% of that of the transition metal oxide, so as to obtain a mixture of the transition metal oxide and the alkali metal oxide;
(2) Adding water into the mixture of the transition metal oxide and the alkali metal oxide obtained in the step (1), stirring, adding a noble metal precursor in an argon atmosphere, and stirring at 25-80 ℃ for 1-2 hours to obtain a suspension;
(3) And (3) drying the suspension obtained in the step (2), and sintering the powder obtained after drying at 250-500 ℃ for 1-4 hours in an inert atmosphere to obtain the supported oxygen evolution catalyst.
The invention firstly uses alkali metal to treat the oxide carrier at room temperature, adds noble metal precursor into the obtained product and synthesizes the high-efficiency oxygen evolution catalyst by a one-pot method. On one hand, the addition of the alkali metal can react with the transition metal oxide particles to generate conductive transition metal oxide, so that the enhancement of the conductive capability of the transition metal oxide at room temperature is realized, and the defect of reduction of the specific surface area of the oxide caused by reduction under the traditional high-temperature condition is avoided; on the other hand, the alkali metal oxide obtained after the reaction of the alkali metal and the transition metal oxide in the previous step can continuously react with the noble metal precursor, and alkali metal ions are doped into the noble metal oxide (iridium oxide) to further improve the catalytic activity of the noble metal oxide (iridium oxide), so that the purpose of strengthening the intrinsic activity of the noble metal is achieved. In the process, alkali metal substances do not need to be separated, and the synthesis process is simple and pollution-free.
Preferably, the specific steps in step (1) are: mixing a transition metal oxide and alkali metal powder, sequentially adding dimethyl carbonate and an acetone solution, and carrying out ball milling at room temperature for 1-5 hours to obtain a mixture of the transition metal oxide and the alkali metal oxide, wherein the mass of the alkali metal is 1-20% of that of the transition metal oxide, the solid-to-liquid ratio of the transition metal oxide to the dimethyl carbonate is 1-25-1.
Preferably, the transition metal is selected from one or more of titanium, niobium, tantalum, tungsten and cerium.
Preferably, the alkali metal is selected from one or more of lithium, sodium and potassium.
Preferably, the noble metal precursor is an iridium compound and/or a ruthenium compound, and the mass of the noble metal is 5-30% of that of the transition metal oxide. The iridium compound and/or ruthenium compound are both soluble salts or acids, such as ruthenium oxide or chloroiridic acid, and when the noble metal is a mixture of an iridium compound and a ruthenium compound, the mass ratio of the iridium compound to the ruthenium compound is 1:2.
The invention also provides a preparation method of the membrane electrode of the water electrolyzer, which adopts the supported oxygen evolution catalyst as an anode catalyst and comprises the following steps: adding water, isopropanol and membrane solution into an anode catalyst, preparing catalyst ink by ultrasonic treatment, and spraying the catalyst ink on the surface of a polymer membrane; adding water, isopropanol and membrane solution into the cathode catalyst, ultrasonically preparing catalyst ink, spraying the catalyst ink on the other surface of the polymer membrane, and drying to obtain the membrane electrode of the water electrolyzer.
Preferably, the preparation method of the membrane electrode of the water electrolyzer specifically comprises the following steps: adding water, isopropanol and a membrane solution into a supported oxygen evolution catalyst, ultrasonically preparing a catalyst ink, and spraying the catalyst ink on the surface of a polymer membrane, wherein the mass ratio of the water to the isopropanol to the supported oxygen evolution catalyst is 5; adding water, isopropanol and a membrane solution into a platinum-carbon catalyst, ultrasonically preparing a catalyst ink, spraying the catalyst ink on the other surface of the polymer membrane, wherein the mass ratio of the water to the isopropanol to the platinum-carbon catalyst is 5.
Compared with the prior art, the invention has the beneficial effects that:
1. the content of noble metal in the membrane electrode of the existing polymer water electrolyzer is generally 0.8-3mg/cm 2 The total amount of noble metal in the membrane electrode can be reduced to 0.2mg/cm by using the method provided by the invention 2 The performance is not reduced, so the cost of the membrane electrode can be obviously reduced;
2. the invention develops a simple and feasible technology for preparing the supported oxygen evolution catalyst by a one-pot method, the treatment of the oxide material and the hydrolysis and the loading of the noble metal precursor are completed in the same container, the precursor material is not wasted, the preparation process does not need a separation step, and the preparation method is simple and convenient to operate and is suitable for large-scale preparation;
3. the modification treatment of the transition metal oxide material is carried out at room temperature, so that the reduction process under the traditional high-temperature condition is avoided, the specific surface area of the carrier material is not reduced, the formation of high-dispersion active sites is facilitated, and the energy consumption in the preparation process is reduced;
4. alkali metal oxide formed after the alkali metal particles react with the transition metal oxide carrier material does not need to be separated, and can be directly used as a preparation raw material of a subsequent noble metal active oxide material to react with the raw material to obtain a noble metal oxide active substance; the active substance can obtain higher activity than the traditional noble metal oxide due to the addition of alkali metal ions, and the performance of the catalyst is further improved.
Drawings
FIG. 1 is a flow diagram of the present invention for preparing a supported oxygen evolution catalyst;
FIG. 2 is a transmission electron microscope image of the supported oxygen evolution catalyst prepared in example 1 of the present invention;
FIG. 3 is a graph of the mass activity of supported oxygen evolution catalysts prepared in examples 1 and 2 of the present invention;
FIG. 4 is a graph showing the polarization curves of the polymer water electrolyzers according to example 1 of the present invention and comparative example 1.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
Example 1
As shown in figure 1, the preparation method of the supported oxygen evolution catalyst and the membrane electrode of the water electrolyzer comprises the following steps:
(1) Taking 1g of titanium dioxide powder, adding 0.05g of metal lithium powder, 50mL of dimethyl carbonate and 15mL of acetone solution, adding the mixture into a ball milling tank, carrying out ball milling for 1h at room temperature, taking out and drying to obtain grayish blue oxide particles;
(2) Adding 100mL of pure water into the product obtained in the step (1), stirring at room temperature for 15min, continuously introducing argon, adding a chloroiridic acid solution to ensure that the iridium content is 0.1g, and stirring the solution at 60 ℃ for 2h to obtain a suspension;
(3) Drying the suspension obtained in the step (2) at 80 ℃, carrying out heat treatment on the powder obtained by drying at 250 ℃ for 1h in an argon atmosphere, and filtering and washing the powder after the heat treatment to obtain the final oxygen evolution catalyst with 10% iridium load;
(4) Taking 20mg of the oxygen evolution catalyst obtained in the step (3), adding water and isopropanol, wherein the mass ratio of the water to the isopropanol to the catalyst is 5 2 ；
(5) Taking 10mg of a platinum-carbon catalyst, adding water and isopropanol, wherein the mass ratio of the water to the isopropanol to the platinum-carbon catalyst is 530 percent, obtaining catalyst ink after ultrasonic treatment for 15min, spraying the catalyst ink on the other surface of the proton exchange membrane, wherein the spraying area is 8cm 2 And vacuum drying at 80 ℃ for 12h to finally obtain the membrane electrode with ultralow noble metal loading.
FIG. 2 is a transmission electron microscope image of the supported oxygen evolution catalyst prepared in the present example, and it can be seen from FIG. 2 that the particle size of the prepared titanium oxide carrier is in the range of 20-50nm, and the particle size of the iridium oxide is about 1-1.5nm, which indicates that the catalyst has a higher electrochemical active area.
Fig. 3 is an electrochemical activity of commercial iridium oxide and the composite catalyst obtained in this example tested using an electrochemical workstation, wherein the noble metal mass activity of the supported oxygen evolution catalyst prepared in this example was 7.3 times that of the commercial iridium oxide catalyst.
The catalyst loading capacity in the prepared membrane electrode is obtained by using weight measurement, and the total noble metal consumption in the membrane electrode is determined to be 0.2mg/cm 2 . The water electrolyzer is operated in a bidirectional water supply and constant current electrolysis mode at 80 ℃ and 1A/cm 2 The polarization curve was determined after 12 hours of operation at atmospheric pressure, as shown in FIG. 4.
The polarization curve of the water electrolyzer of FIG. 4 shows that at 1A/cm 2 The single-bath voltage is 1.718V at 80 ℃, and the electrolytic efficiency reaches more than 72 percent (LHV).
Comparative example 1
The anode catalyst in the membrane electrode adopts commercial iridium oxide nano catalyst, and the electrochemical performance test, the cathode catalyst dosage, the membrane electrode preparation process, the water electrolyzer assembly process and the performance test method of the rest catalysts are all the same as those in the embodiment 1.
The total noble metal loading of the membrane electrode is determined to be 0.5mg/cm 2 . The polarization curve of FIG. 4 can be seen at 1A/cm 2 The voltage of the single cell at 80 ℃ is 1.806V, which is higher than 1.7V in example 1, and the higher energy consumption of electrolysis is shown. In addition, mass transfer polarization occurs at high current density, indicating that the membrane electrode has poor performance under high current. The above results show that the energy consumption of the water electrolyzer using the commercial catalyst is higher than that of the water electrolyzer using the commercial catalyst even though more noble metals are usedExample 1.
Example 2
The same as in example 1, except that:
the dosage of the lithium metal powder in the step (1) is 0.2g, 25mL of dimethyl carbonic acid and 25mL of acetone, and the ball milling is carried out for 5 hours at room temperature; the mass of the iridium added in the step (2) is 0.3g (the iridium loading is 30 percent), and the iridium is stirred for 1 hour at the temperature of 25 ℃; in the step (3), the heat treatment temperature is 500 ℃ and the time is 4 hours, and the electrochemical performance test methods of the rest catalysts are completely the same as those of the example 1.
From fig. 3 it follows that: the catalyst activity of this example still reached 4 times the activity of the commercial catalyst.
Example 3
The same as example 1, except that:
the dosage of the lithium metal powder in the step (1) is 0.01g, 100mL of dimethyl carbonate and 10mL of acetone, and the ball milling is carried out for 4 hours at room temperature; the mass of iridium added in step (2) was 0.05g (iridium loading of 5%), and the mixture was stirred at 80 ℃ for 2 hours, in step (3), the heat treatment time was 2 hours, and the electrochemical performance test methods of the remaining catalysts were all the same as in example 1.
The mass activity of the noble metal iridium of the present example was measured to be 2.8 times that of commercial iridium oxide.
Example 4
The same as example 1, except that:
using metal sodium powder in the step (1), and carrying out ball milling for 5h at room temperature; adding a mixture of ruthenium trichloride and chloroiridic acid as a noble metal in the step (2), wherein the mass of ruthenium is 0.2g, the mass of iridium is 0.1g (the total noble metal loading is 30%), and stirring for 2 hours at 80 ℃; in the step (3), the heat treatment time is 1h, and the electrochemical performance test methods of the rest of the catalysts are completely the same as those in the example 1.
The mass activity of the noble metal of this example was measured to be 5.6 times that of commercial iridium oxide.
Example 5
The same as in example 1, except that:
using metal potassium powder in the step (1), and performing ball milling for 5 hours at room temperature; adding chloroiridic acid in the step (2), wherein the mass of iridium is 0.2g (the iridium loading is 20%), and stirring for 2h at 80 ℃; in the step (3), the heat treatment time is 1h, and the electrochemical performance test methods of the rest of the catalysts are completely the same as those in the example 1.
The mass activity of the noble metal of this example was measured to be 3.7 times that of commercial iridium oxide.
Example 6
The same as example 1, except that:
niobium pentoxide powder is used in step (1). The electrochemical performance test method of the rest catalysts is completely the same as that of the example 1.
The mass activity of the noble metal of this example was measured to be 3.2 times that of commercial iridium oxide.
Example 7
The same as example 1, except that:
tantalum pentoxide powder is used in step (1). The electrochemical performance test method of the rest catalysts is completely the same as that of the example 1.
The mass activity of the noble metal of this example was measured to be 4.5 times that of commercial iridium oxide.
Example 8
The same as example 1, except that:
tungsten trioxide powder is used in step (1). The electrochemical performance test method of the rest catalysts is completely the same as that of the example 1.
The mass activity of the noble metal of this example was measured to be 5.9 times that of commercial iridium oxide.
Example 9
The same as example 1, except that:
cerium trioxide powder was used in step (1). The electrochemical performance test method of the rest catalysts is completely the same as that of the example 1.
The mass activity of the noble metal of this example was measured to be 1.8 times that of commercial iridium oxide.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. A supported oxygen evolution catalyst is characterized by comprising transition metal oxide carrier nanoparticles subjected to conductive treatment at room temperature and alkali metal doped noble metal oxide nanoparticles loaded on the surfaces of the transition metal oxide carrier nanoparticles, wherein the mass of alkali metal is 1% -20% of that of the transition metal oxide, the mass of noble metal is 5% -30% of that of the transition metal oxide, the transition metal is selected from more than one of titanium, niobium, tantalum, tungsten and cerium, the alkali metal is selected from more than one of lithium, sodium and potassium, and the noble metal is an iridium compound and/or a ruthenium compound;
the preparation method of the supported oxygen evolution catalyst comprises the following steps:
(1) Mixing transition metal oxide and alkali metal powder, and performing ball milling reaction for 1-5 hours at room temperature, wherein the mass of alkali metal is 1% -20% of that of the transition metal oxide, so as to obtain a mixture of the transition metal oxide and the alkali metal oxide;
(2) Adding water into the mixture of the transition metal oxide and the alkali metal oxide obtained in the step (1), stirring, adding a noble metal precursor in an argon atmosphere, and stirring at 25-80 ℃ for 1-2 hours to obtain a suspension;
(3) And (3) drying the suspension obtained in the step (2), and sintering the powder obtained after drying at the temperature of 250-500 ℃ for 1-4 hours in an inert atmosphere to obtain the supported oxygen evolution catalyst.
2. The supported oxygen evolution catalyst of claim 1, wherein the noble metal oxide nanoparticles have a particle size of 0.8 to 2.5 nm.
3. A method of preparing the supported oxygen evolution catalyst of claim 1, comprising the steps of:
(1) Mixing transition metal oxide and alkali metal powder, and performing ball milling reaction for 1-5 hours at room temperature, wherein the mass of alkali metal is 1% -20% of that of the transition metal oxide, so as to obtain a mixture of the transition metal oxide and the alkali metal oxide;
(2) Adding water into the mixture of the transition metal oxide and the alkali metal oxide obtained in the step (1) and stirring, then adding a noble metal precursor in an argon atmosphere, and stirring for 1-2 hours at 25-80 ℃ to obtain a suspension;
(3) And (3) drying the suspension obtained in the step (2), and sintering the powder obtained after drying at 250-500 ℃ for 1-4 hours in an inert atmosphere to obtain the supported oxygen evolution catalyst.
4. The method for preparing the supported oxygen evolution catalyst according to claim 3, wherein the specific steps of step (1) are: mixing a transition metal oxide with alkali metal powder, sequentially adding dimethyl carbonate and an acetone solution, and carrying out ball milling reaction for 1-5 hours at room temperature to obtain a mixture of the transition metal oxide and the alkali metal oxide, wherein the mass of the alkali metal is 1-20% of that of the transition metal oxide, the solid-to-liquid ratio of the transition metal oxide to the dimethyl carbonate is 1-25-1.
5. The method for preparing a supported oxygen evolution catalyst according to claim 3 or 4, characterized in that the transition metal is selected from one or more of titanium, niobium, tantalum, tungsten and cerium.
6. The method for preparing a supported oxygen evolution catalyst according to claim 3 or 4, characterized in that the alkali metal is selected from one or more of lithium, sodium and potassium.
7. The method for preparing a supported oxygen evolution catalyst according to claim 3, wherein the noble metal precursor is an iridium compound and/or a ruthenium compound, and the mass of the noble metal is 5 to 30% of the mass of the transition metal oxide.
8. A method for preparing a membrane electrode of a water electrolyzer, which is characterized in that the supported oxygen evolution catalyst of claim 1 is used as an anode catalyst, and comprises the following steps: adding water, isopropanol and membrane solution into an anode catalyst, preparing catalyst ink by ultrasonic treatment, and spraying the catalyst ink on the surface of a polymer membrane; adding water, isopropanol and membrane solution into the cathode catalyst, ultrasonically preparing catalyst ink, spraying the catalyst ink on the other surface of the polymer membrane, and drying to obtain the membrane electrode of the water electrolyzer.
9. The method for preparing a membrane electrode assembly for a water electrolyzer according to claim 8, characterized in that it comprises the following steps: adding water, isopropanol and a membrane solution into a supported oxygen evolution catalyst, ultrasonically preparing a catalyst ink, and spraying the catalyst ink on the surface of a polymer membrane, wherein the mass ratio of the water to the isopropanol to the supported oxygen evolution catalyst is 5; adding water, isopropanol and a membrane solution into a platinum-carbon catalyst, ultrasonically preparing a catalyst ink, spraying the catalyst ink on the other surface of the polymer membrane, wherein the mass ratio of the water to the isopropanol to the platinum-carbon catalyst is (5).
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