CN113430555A - Iridium oxide-platinum composite nano catalyst, preparation method and application thereof - Google Patents
Iridium oxide-platinum composite nano catalyst, preparation method and application thereof Download PDFInfo
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- CN113430555A CN113430555A CN202110722425.3A CN202110722425A CN113430555A CN 113430555 A CN113430555 A CN 113430555A CN 202110722425 A CN202110722425 A CN 202110722425A CN 113430555 A CN113430555 A CN 113430555A
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- 239000002131 composite material Substances 0.000 title claims abstract description 90
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 79
- DYXZHJQUDGKPDJ-UHFFFAOYSA-N iridium;oxoplatinum Chemical compound [Ir].[Pt]=O DYXZHJQUDGKPDJ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 53
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000001301 oxygen Substances 0.000 claims abstract description 52
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910000457 iridium oxide Inorganic materials 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 229910052697 platinum Inorganic materials 0.000 claims description 34
- 238000005868 electrolysis reaction Methods 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 29
- 229910052741 iridium Inorganic materials 0.000 claims description 28
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 21
- 238000009792 diffusion process Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
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- 239000002184 metal Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
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- 239000007787 solid Substances 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 9
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- 150000001875 compounds Chemical class 0.000 claims description 5
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- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 claims description 2
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
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- 238000012360 testing method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
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- 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 6
- 239000000843 powder Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
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- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 230000007797 corrosion Effects 0.000 description 3
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- 239000007772 electrode material Substances 0.000 description 3
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- 239000007788 liquid Substances 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
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- 239000011733 molybdenum Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- 239000010937 tungsten Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
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- 206010021143 Hypoxia Diseases 0.000 description 1
- 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 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229910000487 osmium oxide Inorganic materials 0.000 description 1
- JIWAALDUIFCBLV-UHFFFAOYSA-N oxoosmium Chemical compound [Os]=O JIWAALDUIFCBLV-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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
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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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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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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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- 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 provides an iridium oxide-platinum composite nano catalyst, which comprises iridium oxide and metallic platinum, wherein the oxygen evolution overpotential of the catalyst is obviously lower than that of an iridium oxide electrode, and the catalyst has good catalytic activity and electrolytic stability, good comprehensive performance and can meet the requirement of actual production. In addition, the preparation method of the catalyst is simple and easy to implement and easy to control, and the obtained product has high purity and is beneficial to large-scale production and application.
Description
Technical Field
The invention belongs to the technical field of water electrolysis, and particularly relates to an iridium oxide and platinum composite anodic oxygen evolution nano catalyst, and a preparation method and application thereof.
Background
Hydrogen energy is an environment-friendly energy source, and is more environment-friendly and efficient compared with fossil energy. The method for producing hydrogen by utilizing water electrolysis is a safe and green method with high practical value for obtaining hydrogen, and is widely applied to various fields in industry. The Solid Polymer Electrolyte (SPE) water electrolysis hydrogen production technology has the advantages of high purity of the prepared gas product, less process maintenance, low hydrogen production cost and the like.
Water electrolysis relates to two electrode reactions, the reversibility of a hydrogen electrode (cathode) reaction is good, the research is relatively mature, the overpotential of a hydrogen electrode material is reported to be reduced to dozens of millivolts, the reaction process of an oxygen electrode (anode) is slow, the number of intermediate processes and intermediate products is large, the overpotential of the hydrogen electrode material is often hundreds of millivolts, the oxygen evolution potential is high, and the catalysis condition is harsh. Therefore, the anode has high requirements on the stability of the catalyst, and even the noble metal materials are in high potential and acidic environment, the anode is in the problems of corrosion and dissolution, which makes the anode catalyst in great challenge and is also a key link for limiting the development of water electrolysis. Therefore, the depolarization of the anode has important significance for reducing the energy consumption of the whole water electrolysis hydrogen production process, and the oxygen evolution depolarization of the anode mainly depends on an anode catalyst.
At present, the anode catalyst mainly adopts metal, metal oxide and alloy catalyst with oxygen evolution capability and corrosion resistance, such as Ir, Ru, Pt, Ir oxide, Ru oxide and the like. In a strong oxidation environment in which the catalyst is contacted with a strong-acid Nafion proton conductor and oxygen atoms exist, non-noble metals such as Ni, Co and the like are easily oxidized or corroded and dissolved, and although a non-noble metal-doped composite catalyst is researched, the catalyst actually applied to large-scale production is few at present. Therefore, the SPE water electrolysis oxygen evolution electrode still uses noble metal catalytic materials at present.
Wherein, RuO2And IrO2The oxide is a semiconductor type oxide, has metal conductivity, can be used for oxygen evolution reaction, and is a better oxygen evolution catalyst. In water electrolysis, the overpotential Ru ═ Ir of the anode in the anodic Oxygen Evolution Reaction (OER) under acidic conditions<Pd<Rh<Pt<Au<Nb, which indicates that among the metal catalysts of the anode, Ru and Ir are the main catalysts for catalyzing OER. From a stability perspective, pyrolyzed RuO2The performance was stable before 400h and then dropped rapidly. In the unit oxygen evolution catalyst, RuO2And IrO2Is the best oxygen evolution catalyst. However, iridium is expensive and too costly for large-scale production; RuO2The oxygen evolution potential is lower under acidic conditions, but is unstable and not suitable for long-term electrolysis. Therefore, the unit noble metal catalyst is too expensive and has high cost; or poor stability and short life. Thus, binary noble metal oxygen evolution catalysts have naturally been brought to the researchers' disposalAttention and research.
In the study of binary noble metal catalysts, RuO was the first choice2And IrO2In an attempt to solve the RuO while maintaining the original activity2The long-term electrolytic stability is reduced quickly. XRD analysis showed RuO2And IrO2Both oxides are non-stoichiometric, with RuO2Is a hypoxia structure (RuO)2-x) And IrO2Is an oxygen-rich structure (IrO)2+x). Their mixed oxides have a synergistic effect on the mutual ratio, so that in RuO2In which IrO is added2Can improve RuO2And (4) stability. Furthermore, RuO2And IrO2May also be separately reacted with Ta2O5、TiO2、SnO2The inert components are combined to obtain a stable structure. However, the binary composite catalyst with non-noble metal has not been satisfactory in oxygen evolution activity and stability, although the cost is reduced.
Therefore, in the field of water electrolysis, further optimization of the anode catalyst is still needed, so that a water electrolysis anode with good conductivity, high oxygen evolution catalytic activity, good selectivity, good mechanical property and electrochemical stability can be obtained, and the requirement of actual production can be met.
Disclosure of Invention
In order to solve the problems, the inventor of the present invention has made extensive studies and prepares a composite nano catalyst containing iridium oxide and platinum metal by a sol-gel method, wherein phases in the composite nano catalyst powder are uniformly distributed, the particle size of the powder is 20-100nm, the dispersibility is good, the purity is high, the process is simple, the catalyst activity and stability are good, the overpotential of an anode layer is further reduced, the preparation process is simple, and the composite nano catalyst is suitable for industrial application.
The first aspect of the invention aims to provide an iridium oxide-platinum composite nano catalyst, which comprises iridium oxide and metallic platinum, wherein the iridium oxide and the metallic platinum are uniformly distributed in nano particles, the oxygen evolution overpotential of the catalyst is lower than that of the nano iridium oxide, and the particle size of the nano iridium oxide is 20-100 nm.
In the iridium oxide-platinum composite nano-catalyst, the mass ratio of iridium oxide to platinum is (1-15):1, preferably (5-12):1, and more preferably (8-10): 1.
The second aspect of the present invention is directed to provide a method for preparing the iridium oxide-platinum composite nano-catalyst, in which raw materials including an iridium source and a platinum source are added to a solvent to form a uniform solution, so as to ensure uniform distribution of phases in the nano-composite catalyst. And precipitating and calcining to obtain the iridium oxide-platinum composite nano catalyst. The method comprises the following steps:
and 3, calcining the precursor to obtain the iridium oxide-platinum composite nano catalyst.
An object of a third aspect of the present invention is to provide the use of the iridium oxide-platinum composite nanocatalyst for the electrolysis of water, in particular for the anode in a pure water electrolysis cell, preferably for the preparation of a membrane electrode in a solid polymer electrolyte water electrolysis cell, in particular for the preparation of an anode catalytic layer and/or an anode gas diffusion layer in a membrane electrode.
The iridium oxide-platinum composite nano catalyst provided by the invention has the following beneficial effects:
(1) the overpotential of the iridium oxide-platinum composite nano catalyst is lower than that of nano iridium oxide, and the iridium oxide-platinum composite nano catalyst has better anode catalyst performance. And after the composite catalyst is continuously electrolyzed by pure water for 3000 hours, the overpotential is only increased by 4.4 percent, which shows that the composite catalyst has good stability and meets the requirement of industrial use.
(2) Compared with a pure iridium oxide anode, the invention not only reduces the material cost, but also improves the catalytic performance, and has obvious comprehensive benefit. In addition, other auxiliary doping elements can be utilized to obtain the polynary iridium oxide-platinum composite nano-catalyst, so that the purposes of further reducing the cost of raw materials and improving the activity of the catalyst are achieved.
(3) The preparation process of the iridium oxide-platinum composite nano catalyst is simple and easy to operate and control, and the obtained composite nano catalyst has uniform component distribution and high product purity, so that the comprehensive performance of the composite nano catalyst is greatly improved, and the preparation method is favorable for developing industrial application.
(4) The iridium oxide-platinum composite nano catalyst prepared by the invention is applied to an anode catalyst layer in a membrane electrode of SPE, and can also attach a composite electrode to an anode gas diffusion layer so as to reduce the resistance among components in the membrane electrode and improve the performance of an SPE electrolytic cell and the water electrolysis efficiency.
Drawings
FIG. 1 shows an XRD test pattern of an iridium oxide-platinum composite nano-catalyst I prepared in example 1 of the present invention;
FIG. 2 shows an SEM test chart of the iridium oxide-platinum composite nano-catalyst I prepared in example 1 of the invention;
FIG. 3 shows a side view of the EDS of the iridium oxide-platinum composite nanocatalyst I prepared in example 1 of the present invention;
FIG. 4 shows the IrO of the present invention2Oxygen evolution polarization curves of the iridium oxide-platinum composite nano catalyst I and the iridium oxide-platinum composite nano catalyst III;
FIG. 5 shows the oxygen evolution polarization curves of the electrode prepared from the iridium oxide-platinum composite nanocatalyst I prepared in example 1 of the present invention after Initial (Initial) and 5000 cycles (5000 CV);
FIG. 6 shows the evolution of oxygen evolution over-potential after the electrode electrolysis prepared from the iridium oxide-platinum composite nanocatalyst I prepared in example 1 of the present invention was continuously performed for 1000 hours, 2000 hours and 3000 hours;
fig. 7 shows a schematic view of the structure of the solid polymer electrolyte membrane 1 and the gas diffusion layer 2 in the membrane electrode of the present invention.
Description of the reference numerals
1-a solid polymer electrolyte membrane;
11-a proton exchange membrane;
12-a cathode catalyst layer;
13-anode catalyst layer;
2-a gas diffusion layer;
21-anode gas diffusion layer;
22-cathode gas diffusion layer.
Detailed Description
The present invention will now be described in detail by way of specific embodiments, and features and advantages of the present invention will become more apparent and apparent from the following description.
The invention utilizes a sol-gel method to prepare the oxygen evolution composite nano catalyst for water electrolysis, the iridium oxide is compounded with metal platinum in the catalyst to obtain the nano composite catalyst, the overpotential of the oxygen evolution catalyst is further reduced, the iridium oxide and the metal platinum are uniformly distributed, and the nano composite catalyst has good stability, good comprehensive performance and simple preparation method and is beneficial to large-scale production and application.
The invention provides an iridium oxide-platinum composite nano catalyst, which comprises iridium oxide and metallic platinum, wherein the oxygen evolution overpotential of the catalyst is lower than that of nano iridium oxide, and the particle size of the nano iridium oxide is 20-100 nm.
In the iridium oxide-platinum composite nano-catalyst, the mass ratio of iridium oxide to platinum is (1-15):1, preferably (5-12):1, and more preferably (8-10): 1.
In the process of water electrolysis oxygen evolution reaction, the intermediate process is complex, so that a plurality of intermediate products are generated, the dynamic process is slow, the overpotential of the anode is high, and the catalytic condition is severe, so that the requirement on the anode is very strict. In the SPE electrode structure, the used proton exchange membrane has strong acidity after being soaked in water, and the anode material is easy to dissolve or passivate in an oxygen evolution environment. Platinum and platinum group metals have been employed in large quantities due to their remarkable catalytic activity and stability. However, most of the existing water electrolysis anodes are repeatedly sprayed, dried and sintered, or an iridium dioxide layer is prepared on a platinum electrode, and the obtained anodes have the defects of cracking, uneven distribution, poor performance stability and the like, and are complex to operate and long in process preparation time.
In the present invention, IrO2Pt forms a composite catalyst in which iridium is present as an oxide phase and platinum is present as a metal phase, the two being homogeneously distributed, the particlesThe size is 20-100nm, the specific surface catalytic sites are rich, the oxygen evolution activity of the catalyst is good, the uniformity of the distribution of the composite phase and the matching property of iridium oxide and platinum particles are good, the oxygen evolution overpotential of the obtained iridium oxide-platinum composite nano catalyst is further reduced, and the iridium oxide-platinum composite nano catalyst has good stability.
In the platinum group metals, the oxygen evolution overpotential sequence is RuO2＜IrO2PdO < Pt, and the order of the acid media corrosion resistance is IrO2＞Pt＞RuO2PdO. Under acidic conditions, IrO2Second to RuO in electrocatalytic activity2While in the oxygen evolution environment, the stability can be kept very high, and the service life is RuO under the same condition2More than 20 times, becomes an ideal catalytic material of the anode for oxygen evolution.
In the invention, Pt and IrO are adopted2The composite phase forms uniformly distributed catalyst, so that the composite catalyst is compared with nano IrO under the same other conditions2The catalyst has lower oxygen evolution overpotential which can be reduced by 10-15%, and has good stability in an acid oxygen evolution environment, and after 3000 hours of pure water electrolysis, the electrode overpotential is only increased by 4.4%, so that the comprehensive performance of the oxygen evolution catalyst is effectively improved, and the catalyst has good application prospect in the industrial field of SPE water electrolysis.
In one embodiment of the present invention, the iridium oxide-platinum composite nanocatalyst further comprises an auxiliary doping element selected from one or more transition metal elements other than platinum and iridium, preferably one or more of titanium, ruthenium, rubidium, osmium, niobium, rhodium, tungsten, molybdenum, rhenium, chromium and palladium, and more preferably one or more of titanium and chromium. The auxiliary doping element is in a metal state or an oxidation state.
The molar ratio of the iridium element to the auxiliary doping element is (80-180):1, preferably (95-160):1, and more preferably (110): 135): 1.
According to the requirements of actual production environment and production condition, auxiliary doping elements can be added into the iridium oxide-platinum composite nano catalyst. The composite titanium or titanium oxide in the iridium oxide-platinum composite nano catalyst can reduce the raw material cost of the anode on the premise of not reducing the performance of the anode; the composite ruthenium oxide, osmium, palladium, tungsten, molybdenum, chromium and osmium oxide is beneficial to the stability of an electrode in the electrolytic process and further improves the performance of the anode.
The particle size of the iridium oxide-platinum composite nano catalyst is 20-100nm, preferably 25-80nm, and more preferably 30-60 nm.
The second aspect of the invention provides a preparation method of the iridium oxide-platinum composite nano-catalyst, which comprises the steps of adding raw materials including an iridium source and a platinum source into a solvent, precipitating, and then calcining to obtain the iridium oxide-platinum composite nano-catalyst. The method comprises the following steps:
The iridium source is selected from iridium-containing compounds, such as iridium trichloride, iridium tetrachloride, chloroiridic acid and the like, and is preferably iridium trichloride or chloroiridic acid, such as iridium trichloride.
The platinum source is selected from platinum-containing compounds, such as chloroplatinic acid.
The solvent is water. And (3) selecting acid water or neutral water according to the solubility of the iridium source and the platinum source in the solvent, dissolving the iridium source and the platinum source in the solvent, and uniformly mixing. The preparation method of the invention adopts water phase for reaction, has low cost and little pollution, and is beneficial to industrial production.
The mixing temperature is 40-70 ℃, preferably 45-65 ℃, more preferably 50-60 ℃. Under the heating condition, the dissolution of the platinum source and the iridium source is promoted, so that the iridium and the platinum in the solution are fully contacted and uniformly mixed.
The iridium source and the platinum source are added in such an amount that the mass ratio of iridium oxide to platinum in the iridium oxide-platinum composite nano catalyst is (1-15):1, preferably (5-12):1, and more preferably (8-10): 1.
In one embodiment of the present invention, an auxiliary doping element source is further added, which is selected from compounds containing auxiliary doping elements, such as titanium sulfate, titanium tetrachloride, water-soluble ruthenium trichloride, sodium hexachloroosmate, sodium tetrachloropalladate, ammonium tungstate, sodium molybdate, chromium nitrate, and the like, preferably titanium tetrachloride, chromium nitrate.
The iridium source, the platinum source and the auxiliary doping element source are added into the solvent, so that the solution is fully mixed, the metal elements can be fully contacted and uniformly distributed, the uniformity of each component in the catalyst is improved, the metal elements have better synergistic action, and the performance and the stability of the catalyst are enhanced.
The molar ratio of the iridium source to the auxiliary doping element source is (80-180):1, preferably (95-160):1, more preferably (110): 135): 1. Wherein the molar amount of the iridium source is based on the molar amount of iridium element therein, and the molar amount of the auxiliary doping element source is based on the molar amount of doping element therein.
And 2, adjusting the pH value of the reaction solution to enable the reaction solution to generate precipitate and age to obtain a precursor.
Adding alkaline substance into the reaction solution, adjusting pH value to precipitate the metal ions in the solution from the reaction solution. The pH is 6.5 to 13, preferably a pH at which the metal ions can be sufficiently precipitated, for example 9 to 10.
The alkaline substance is an inorganic or organic base, preferably an inorganic strong base, such as sodium hydroxide.
Preferably, the aging is carried out under heat preservation conditions, the aging temperature being from 50 to 60 ℃ and preferably 55 ℃. The ageing time is 2-7h, preferably 3.5-5.5 h.
Washing the precursor for 3-7 times, wherein the washing solvent is water or alcohol solvent.
And 3, calcining the precursor to obtain the iridium oxide-platinum composite nano catalyst.
And drying the precursor and then calcining.
The calcination temperature is 600-1100 ℃, preferably 700-1000 ℃, and more preferably 800-900 ℃; the calcination time is 0.5 to 7 hours, preferably 1.0 to 5 hours, and more preferably 1.5 to 3 hours. The calcination temperature can directly affect the phase and performance of the composite catalyst. When the temperature is lower than 600 ℃, the metal phase platinum is difficult to form, and above 800 ℃, all platinum is ensured to form a metal phase state, and the method is also beneficial to the crystallinity of the nano catalytic material. However, the calcination temperature is too high, and the crystal grains are easy to grow, which is not favorable for the nano-crystallization of the material. In addition, when the calcination time is less than 0.5h, the phase transformation is incomplete, and when the calcination time is more than 3h, crystal grains are easy to grow up and shrink on the specific surface, so that the catalytic activity is reduced.
The third aspect of the invention provides the use of the iridium oxide-platinum composite nano-catalyst for oxygen production by electrolysis of water, in particular for preparing an anode in a pure water electrolytic cell, preferably for preparing a membrane electrode in a solid polymer electrolyte water electrolytic cell, in particular for preparing an anode catalytic layer and/or an anode gas diffusion layer in a membrane electrode.
The membrane electrode comprises a solid polymer electrolyte membrane 1 and a gas diffusion layer 2. The two sides of the solid polymer electrolyte membrane 1 are respectively provided with a cathode catalyst layer 12 and an anode catalyst layer 13, and the middle part is provided with a proton exchange membrane 11. The gas diffusion layer 2 includes a cathode gas diffusion layer 22 and an anode gas diffusion layer 21, which are respectively disposed on the sides of the solid polymer electrolyte membrane 1 having the cathode catalytic layer 12 and the anode catalytic layer 13, as shown in fig. 7. The solid polymer electrolyte membrane 1 and the gas diffusion layer 2 are formed into membrane electrodes by hot pressing.
The anode catalyst layer 13 is prepared from the iridium oxide-platinum composite nano-catalyst. The anode catalyst layer 13 is prepared by coating the iridium oxide-platinum composite nano catalyst on an exchange membrane by a hot pressing method, a spraying method, a transfer printing method or a dry powder spraying method, so as to obtain the solid polymer electrolyte membrane 1.
The anode gas diffusion layer 21 is a porous titanium plate, a titanium foam or a titanium mesh, and preferably is a titanium foam. In a preferred embodiment of the present invention, the iridium oxide-platinum composite nanocatalyst is contained in the anode gas diffusion layer 21.
Soaking the porous titanium plate, the foamed titanium or the titanium net in the reaction liquid in the step 1 at the temperature of 45-65 ℃, more preferably at the temperature of 50-60 ℃ for 1-5 hours, preferably for 2-3 hours, and performing ultrasonic assisted soaking.
After the completion of the immersion, the reaction solution in which the anode gas diffusion layer 21 is immersed is subjected to step 2, and the precursor is aged on the surface and/or inside the anode gas diffusion layer 21. And washing and drying the anode gas diffusion layer 21 containing the precursor obtained in the step 2, and performing a step 3 to obtain the anode gas diffusion layer 21 containing the iridium oxide-platinum composite nano-catalyst. The proton exchange membrane 11 and the cathode gas diffusion layer 22 are not particularly limited in the present invention.
The iridium oxide-platinum composite nano catalyst provided by the invention contains uniformly distributed iridium oxide and metal platinum, can reach a lower overpotential than nano iridium oxide, so that the activity of an SPE anode catalyst layer is improved, and the iridium oxide-platinum composite nano catalyst has good stability, can keep a stable overpotential in a water electrolysis environment, and improves the water electrolysis efficiency and the service life of a membrane electrode. In addition, the iridium oxide-platinum composite nano-catalyst is simple in preparation method, can be applied to preparation of an anode or an anode layer in water electrolysis, and is beneficial to large-scale production and application.
Examples
Example 1
1.651g of iridium trichloride trihydrate and 0.265g of chloroplatinic acid (H)2PtCl6·6H2O) was added to 50mL of water and heated to about 55 ℃ to dissolve it. Then adding 0.2M sodium hydroxide solution, adjusting the pH value of the reaction solution to 9-10, preserving heat at 55 ℃, aging for 4 hours, and filtering to obtain a precipitate precursor.
And washing the precursor by using deionized water until a washing liquid is detected by using silver nitrate and no white precipitate is generated, thus obtaining the precursor. And (3) drying the precursor at 80 ℃ for 2h, transferring the precursor to a muffle furnace, calcining the precursor at 800 ℃ for about 2h, cooling the precursor along with the furnace, and taking out the precursor to obtain the iridium oxide-platinum composite nano catalyst I.
Example 2
2.412g of chloroiridic acid (H)2IrCl6·6H2O) and 0.265g of chloroplatinic acid (H)2PtCl6·6H2O) was added to 50mL of water and heated to about 55 ℃ to dissolve it. Then adding 0.2M sodium hydroxide solution, adjusting the pH value of the reaction solution to 9-10, preserving heat at 55 ℃, aging for 4 hours, and filtering to obtain a precipitate precursor.
And washing the precursor by using deionized water until a washing liquid is detected by using silver nitrate and no white precipitate is generated, thus obtaining the precursor. And drying the precursor at 80 ℃ for 2h, transferring the precursor to a muffle furnace, calcining the precursor at 900 ℃ for about 2h, cooling the precursor along with the furnace, and taking out the precursor to obtain the iridium oxide-platinum composite nano catalyst II.
Example 3
An iridium oxide-platinum composite nanocatalyst iii was prepared according to the method of example 1, with the only difference that: 0.027g of chloroplatinic acid (H) was added2PtCl6·6H2O)。
Example 4
2.412g of chloroiridic acid (H)2IrCl6·6H2O), 0.027g of chloroplatinic acid (H)2PtCl6·6H2O) and 0.015g of chromium nitrate (Cr (NO)3)3·9H2O) was added to 60mL of water and heated to about 55 ℃ to dissolve it. Then adding 0.2M sodium hydroxide solution, adjusting the pH value of the reaction solution to 9-10, preserving heat at 55 ℃, aging for 4 hours, and filtering to obtain a precipitate precursor.
And washing the precursor by using deionized water until the washing liquid does not generate white precipitate when detected by using silver nitrate, and drying for 2 hours at 80 ℃. And transferring the precursor to a muffle furnace, calcining for about 2 hours at 900 ℃, cooling along with the furnace, and taking out to obtain the chromium-doped iridium oxide-platinum composite nano catalyst IV.
Examples of the experiments
Experimental example 1
The iridium oxide-platinum composite nanocatalyst i prepared in example 1 was subjected to an X-ray diffraction test (XRD), and the test results are shown in fig. 1.
In fig. 1, peaks having large intensity such as 27.9, 34.7, 39.9, 53.9 ° and the like at 2 θ correspond to IrO, respectively2The (110), (101), (200), (211) crystal planes of (A); and 2 θ is 39.7, 46.2, 67.4 ° corresponding to the (111), (200), (220) crystal planes of Pt, respectively. The unit cell parameters are a 4.52, b 4.52, c 3.15, α β γ 90 °, tetragonal phase, unit cell volume V64.7A 3, Z2, grain size 4410 angstrom. The result shows that the iridium oxide-platinum composite nano catalyst consists of metal Pt and IrO2And (4) forming.
Experimental example 2
SEM test was performed on the iridium oxide-platinum composite nanocatalyst i prepared in example 1, and the test results are shown in fig. 2. As is apparent from FIG. 2, the electrode material is composed of particles having a particle size of 30-50nm, and has uniform distribution and good uniformity of particle size.
The iridium oxide-platinum composite nanocatalyst i prepared in example 1 was subjected to X-ray energy spectrum (EDS) analysis, and the test results are shown in fig. 3.
It is evident from fig. 3 that the Ir, Pt and O elements are uniformly distributed throughout the powder material, facilitating uniform dispersion of the active sites.
Experimental example 3
Deionized water is used as electrolyte, and sulfuric acid is added to prepare 0.5M H2SO4Solution (simulating SPE electrolyzer environment), test IrO2Oxygen evolution overpotential of (commercial nanometer iridium oxide powder, particle size 20-100nm), iridium oxide-platinum composite nano catalyst I and iridium oxide-platinum composite nano catalyst III is shown in figure 4.
And loading the powder to be tested on a glassy carbon electrode and testing in the same electrochemical workstation.
From FIG. 4, it can be seen that the nano IrO2The oxygen evolution overpotential of the electrode is 320mV, the oxygen evolution overpotential of the iridium oxide-platinum composite nano catalyst I electrode is 274mV, and the oxygen evolution overpotential of the iridium oxide-platinum composite nano catalyst III electrode is 310 mV. As can be seen, the oxygen evolution overpotential of the iridium oxide-platinum composite nano catalyst I electrode is obviously reduced, and the superiority of the iridium oxide-platinum composite nano catalyst I electrode as an anode catalytic material is shown. (when the overpotential test is compared, the oxygen evolution overpotential is a current density of 10mA/cm2The overpotential value of time. )
Experimental example 4
An electrode prepared using the iridium oxide-platinum composite nanocatalyst i prepared in example 1 was at 0.5M H2SO4The cyclic voltammetry curve test was performed in deionized water solution, and after 5000 cycles, the Initial (Initial) and 5000 cycles (5000CV) oxygen evolution polarization curves were measured, and the test results are shown in fig. 5.
As can be seen from FIG. 5, the initial oxygen evolution polarization curve overpotential of the electrode prepared from the iridium oxide-platinum composite nano-catalyst I is 272mV, and after 5000 cycles, the overpotential is 280mV with 2.94% of the rising amplitude, which indicates that the electrode has good stability in the anode environment of electrolyzed water.
The catalysts prepared in examples 2 and 4 were subjected to cyclic voltammogram tests using the same test method as that for iridium oxide-platinum composite nanocatalyst i prepared in example 1, and found that:
the overpotential of the oxygen evolution polarization curve of the iridium oxide-platinum composite nano catalyst II prepared in the example 2 is 261 mV;
the overpotential of the oxygen evolution polarization curve of the chromium-doped iridium oxide-platinum composite nano-catalyst IV prepared in example 4 is 293 mV.
Experimental example 5
The iridium oxide-platinum composite nano catalyst I electrode prepared in the example 1 is used for continuously electrolyzing water, oxygen evolution polarization curves are tested after electrolysis is carried out for 1000 hours, 2000 hours and 3000 hours, the oxygen evolution overpotential is respectively 275mV, 280mV and 284mV, the initial oxygen evolution overpotential is 272mV, and the change curve of the oxygen evolution overpotential is shown in figure 6.
It can be found that after 3000 hours of continuous electrolysis, the overpotential amplitude of the iridium oxide-platinum composite nano-catalyst I is 4.4%, which shows that the iridium oxide-platinum composite nano-catalyst I has excellent service life and can meet the requirements of actual production.
The invention has been described in detail with reference to specific embodiments and/or illustrative examples and the accompanying drawings, which, however, should not be construed as limiting the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The iridium oxide-platinum composite nano catalyst is characterized by comprising iridium oxide and metallic platinum, wherein the oxygen evolution overpotential of the catalyst is lower than that of the nano iridium oxide, and the particle size of the nano iridium oxide is 20-100 nm.
2. The catalyst according to claim 1, wherein the iridium oxide-platinum composite nanocatalyst has a mass ratio of iridium to platinum of (1-15): 1.
3. The catalyst of claim 1, wherein the iridium oxide-platinum composite nanocatalyst has an oxygen evolution over potential compared to nano-IrO2The reduction is 10 to 15 percent.
4. The catalyst according to any one of claims 1 to 3, wherein the particle size of the iridium oxide-platinum composite nanocatalyst is in the range of 20-100 nm.
5. The catalyst according to any one of claims 1 to 4, wherein the iridium oxide and the platinum in the form of metal are uniformly mixed and distributed in the catalyst.
6. The preparation method of the iridium oxide-platinum composite nano catalyst is characterized by adding raw materials comprising an iridium source and a platinum source into a solvent, precipitating and calcining to obtain the iridium oxide-platinum composite nano catalyst.
7. The method according to claim 6, characterized in that it comprises the steps of:
step 1, adding an iridium source and a platinum source into a solvent, and mixing to obtain a reaction solution;
step 2, adjusting the pH value of the reaction solution to generate precipitate and aging to obtain a precursor;
and 3, calcining the precursor to obtain the iridium oxide-platinum composite nano catalyst.
8. The method according to claim 7, wherein, in step 1,
the iridium source is selected from iridium-containing compounds, such as iridium trichloride, iridium tetrachloride and chloroiridic acid;
the platinum source is selected from platinum-containing compounds, such as chloroplatinic acid;
the solvent is water.
9. The method of claim 7,
in the step 2, the pH value is 6.5-13, and the aging temperature is 50-60 ℃;
in step 3, the calcination temperature is 600-1100 ℃.
10. Use of an iridium oxide-platinum composite nanocatalyst for the production of oxygen by electrolysis of water, in particular for the production of an anode in a pure water electrolysis cell, preferably for the production of a membrane electrode in a solid polymer electrolyte water electrolysis cell, in particular for the production of an anode catalyst layer and/or an anode gas diffusion layer in a membrane electrode.
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Effective date of registration: 20231025 Address after: Room A033, 2nd Floor, Comprehensive Building, Hunan University Science and Technology Industrial Park, No. 001 Xintian North Road, Ningxiang High tech Industrial Park, Changsha City, Hunan Province, 410600 Patentee after: Hunan Qiwei Hydrogen Energy Technology Co.,Ltd. Address before: 410000 No. 306, building 003, No. 8, Lutian Road, Lugu Base, Changsha high tech Development Zone, Changsha City, Hunan Province Patentee before: Hunan Zixiao New Material Co.,Ltd. |
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