CN115925005A - Layered Sr 4 Ir 3 O 10 Preparation of low iridium catalyst and application of catalyst in hydrogen production by acidic electrolyzed water - Google Patents
Layered Sr 4 Ir 3 O 10 Preparation of low iridium catalyst and application of catalyst in hydrogen production by acidic electrolyzed water Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 94
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 48
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 44
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- 230000002378 acidificating effect Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000001257 hydrogen Substances 0.000 title abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
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- 150000001768 cations Chemical class 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000002503 iridium Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- 159000000008 strontium salts Chemical class 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 claims description 5
- 229910021639 Iridium tetrachloride Inorganic materials 0.000 claims description 5
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 claims description 5
- 235000010703 Modiola caroliniana Nutrition 0.000 claims description 5
- 244000038561 Modiola caroliniana Species 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 5
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 claims description 5
- 230000000536 complexating effect Effects 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
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- 238000010668 complexation reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 69
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 229910000457 iridium oxide Inorganic materials 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 239000002028 Biomass Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- -1 alkaline earth metal cation Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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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
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Abstract
Layered Sr 4 Ir 3 O 10 Preparation of low iridium catalyst and application in hydrogen production by acidic electrolyzed water, belonging to the field of electrolyzed water catalyst, and the Sr with R-P type perovskite structure is obtained by combining metal cation complexation, sol-gel method, heat treatment for removing complexing agent and high-temperature sintering 4 Ir 3 O 10 Low iridium catalyst, realizes Sr with laminated structure 4 Ir 3 O 10 And (3) preparing a catalyst. The obtained catalyst microscopically forms pseudo perovskite type low iridium catalyst nano particles with similar R-P structures by alternately arranging a layer of rock salt structure and a three-layer perovskite structure, and the actual load or the content of Ir is less than the theoretical load or the content. Increase the benefit of iridium atomThe catalyst has high activity and stability.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy materials, and particularly relates to Sr with high catalytic activity and high stability 4 Ir 3 O 10 A low iridium catalyst and its application in the electrolysis of acidic water to produce hydrogen.
Background
In recent years, with the increasing prominence of energy crisis and environmental problems, hydrogen energy has been developed, and the use of fossil energy has been gradually reduced and replaced. The global energy pattern is undergoing a deep transition from relying on traditional fossil energy to pursuing clean and efficient energy, and China is also developing clean energy vigorously, reducing the use of traditional fossil energy and actively searching for alternative energy.
The hydrogen is taken as an ideal secondary energy carrier, and only water is discharged during the use process, and other harmful gases or solid particles are not discharged. Hydrogen (H) 2 ) As a zero-emission renewable energy carrier, the energy-saving biomass fuel has high energy density (142 MJ/kg, which is about 4.5 times of coke, 3 times of gasoline and 3.9 times of alcohol with the same mass), excellent energy conversion efficiency and no pollution (the combustion product is water and no greenhouse gas CO is generated) 2 Emission, almost zero emission in the true sense), and the like, can be regarded as an ideal fuel for dealing with energy exhaustion and environmental problems in the later petroleum era, and can effectively alleviate the increasingly serious environmental problems. In the face of the potential large-scale hydrogen demand, the development of efficient and green hydrogen production technology is urgently needed. Hydrogen production by electrolysis of water is considered to be the most viable clean hydrogen production technology, where water can be split into high-purity green hydrogen by electricity generated from waste heat or renewable intermittent energy sources (wind or solar). However, the overpotential of the anodic Oxygen Evolution (OER) reaction in the hydrogen production process by acidic water electrolysis causes excessive energy loss of electrolysis water, and the excessive consumption of noble metals in the catalyst and the short service life of the catalyst become one of the bottleneck problems restricting the large-scale commercial application of the catalyst. Therefore, the preparation of the anode catalyst for the electrolyzed water with high activity, long service life and low precious metal consumption becomes the key for improving the efficiency of the electrolyzed water and reducing the cost.
However, there is no advantage in the prior art in using a novel layered structure Sr 4 Ir 3 O 10 The method realizes the activation effect of lattice oxygen in a perovskite layer and interstitial oxygen in a salt rock layer in the catalyst on oxygen precipitation sites generated by water decomposition and the stabilization effect of the catalyst structure, and realizes the great improvement of the activity and the stability of the catalyst. Thus, sr 4 Ir 3 O 10 As a new generation of high-efficiency low-iridium catalyst, the electrocatalytic performance of the acid water electrolysis anode oxygen precipitation reaction comprehensively surpasses that of commercial iridium dioxide (IrO) 2 ). The catalyst synthesis process is simple and easy to implement, and the preparation conditions are mildAnd is easy for industrial scale-up production.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide Sr with high catalytic activity and high stability 4 Ir 3 O 10 A preparation method of a low iridium catalyst and application of the low iridium catalyst in acidic electrolyzed water. The prepared iridium catalyst has a layered crystal structure of R-P type perovskite, and has the advantages of high oxygen precipitation electrocatalytic activity, long-term stability and low iridium loading capacity. Based on Sr 4 Ir 3 O 10 The low iridium catalyst has lattice oxygen activating effect and interstitial oxygen stabilizing effect, so that the catalyst has very high oxygen evolution electrocatalytic activity and electrochemical stability. The electrocatalytic performance comprehensively surpasses that of commercial iridium dioxide (IrO) 2 ) Can replace commercial iridium dioxide to be a catalyst for the anodic oxygen evolution reaction under the acidic medium of electrolytic water. The synthesis process of the catalyst is simple and easy to implement, the preparation condition is mild, and the industrial scale-up production is easy to realize.
In order to realize the purpose of the invention, the invention adopts the following technical scheme: sr with laminated structure 4 Ir 3 O 10 The preparation method of the low iridium catalyst comprises the step of preparing the low iridium catalyst from black solid powder, wherein the crystal structure of the low iridium catalyst is a pseudo perovskite type iridium oxide nano particle with an R-P type layer structure.
In a preferred embodiment of the present invention, the Sr is 4 Ir 3 O 10 The actual loading or content of Ir of the low iridium catalyst is less than the theoretical loading or content, i.e. Sr: the molar ratio of Ir is greater than or equal to 4; the particle size of the catalyst particles is 50-100nm.
In a preferred embodiment of the present invention, the strontium element in the iridium catalyst may be replaced with an element such as calcium or barium.
The invention also protects the Sr 4 Ir 3 O 10 The preparation method of the low iridium catalyst adopts the method of combining metal cation complexation, sol-gel method, heat treatment to remove complexing agent and high temperature sintering to obtain Sr with R-P type perovskite structure 4 Ir 3 O 10 The low-iridium catalyst is a low-iridium catalyst,realize Sr having a layered structure 4 Ir 3 O 10 And (3) preparing a catalyst.
Further, the preparation method comprises the following steps:
(1) Metal cation complexing step: at room temperature, adding metal salt into the prepared citric acid aqueous solution, performing ultrasonic dispersion for 0.5h, and then performing magnetic stirring reaction for 2h;
(2) A gel forming step: putting the mixed solution obtained in the step (1) on a heating table, and evaporating to remove water to obtain mixed gel with metal cations embedded in citric acid molecular frameworks;
(3) Gel modification treatment: putting the mauve gel obtained in the step (2) into a porcelain boat, and carrying out heat treatment for 10-14h under a certain atmosphere to remove a complexing agent and residual water in the gel;
(4) And (3) high-temperature sintering: sintering the powder obtained in the step (3) at a high temperature for 10-14h in a certain atmosphere to obtain the Sr 4 Ir 3 O 10 A low iridium catalyst.
In a preferred embodiment of the present invention, in step (1), the concentration of the aqueous citric acid solution is from 8wt.% to 12wt.%, the concentration of the strontium salt is from 0.04 to 0.12mM, the concentration of the iridium salt is from 0.02 to 0.1mM, and the molar ratio of the strontium salt to the iridium salt is from 1 to 1. 80-120ml of citric acid aqueous solution is used for every 0.004mol of strontium.
In a preferred embodiment of the present invention, in the step (1), the strontium salt and the iridium salt are selected from strontium carbonate, strontium nitrate, iridium trichloride, iridium tetrachloride and the like.
In a preferred embodiment of the present invention, in the step (2), the heating temperature is controlled at 80-90 ℃ until the water is evaporated to dryness to form a gel.
In a preferred embodiment of the present invention, in the step (3), the certain atmosphere is an oxygen or air atmosphere, the heat treatment temperature is 600 ℃, and the temperature increase rate is 2 ℃/min.
In a preferred embodiment of the present invention, in the step (4), the certain atmosphere is an oxygen or air atmosphere, the heat treatment temperature is 900 to 1000 ℃, and the temperature rise rate is 3 ℃/min.
The invention also protects the Sr 4 Ir 3 O 10 Low iridium catalysts are used as anodic oxygen evolution catalysts for acidic and PEM electrolyzed waters.
Compared with the existing electrolytic water electrocatalyst synthesis technology, the invention has the following advantages:
the invention provides Sr with a laminated structure 4 Ir 3 O 10 The obtained catalyst is a pseudo perovskite type low iridium catalyst with a Ruddlesden-Popper (R-P) structure, which is formed by alternately arranging a layer of rock salt structure and a three-layer perovskite structure on a microstructure.
The size of the catalyst particles prepared by the method is controlled to be 50-100 nanometers, so that the active specific surface area of the catalyst is greatly improved, and the use amount of the catalyst is favorably reduced.
The invention makes the alkaline earth metal cation and the noble metal cation fully mixed by utilizing a metal cation complexing method and a sol-gel method. And then, carrying out heat treatment on the gel after complexing, effectively removing the complexing agent, obtaining metal powder which is uniformly mixed, and providing conditions for the subsequent formation of an R-P type perovskite structure.
Sr prepared by the invention 4 Ir 3 O 10 The low iridium catalyst is used for obtaining the low iridium-loaded oxygen precipitation catalyst with excellent electrocatalytic activity and stability.
The catalyst prepared by the invention is 10mA/cm in an acid environment 2 The overpotential at the current density of (2 mV) is only much lower than that of commercial iridium dioxide (IrO) 2 ) 370mV of catalyst and at 10mA/cm 2 Has almost no attenuation after constant current is stabilized for 25h under the current density of (1), while commercial iridium dioxide (IrO) 2 ) Under the same conditions, the catalyst is completely inactivated within less than 5 hours.
Sr obtained by the invention 4 Ir 3 O 10 The low-iridium catalyst has lower iridium content than commercial iridium dioxide, improves the utilization rate of iridium atoms, has more excellent electrocatalytic activity and stability, and can replace the commercial iridium dioxide to become a catalyst for the anode oxygen precipitation reaction under the acidic medium of electrolyzed water.
Drawings
The invention will be further described with reference to the accompanying drawings, which are only schematic illustrations and illustrations of the invention, and do not limit the scope of the invention.
FIG. 1 shows Sr obtained in example 1 4 Ir 3 O 10 Transmission Electron Microscopy (TEM) images and X-ray diffraction (XRD) patterns of the low iridium catalysts.
FIG. 2 shows the catalyst obtained in example 1 and commercial iridium dioxide (IrO) 2 ) Polarization curve comparison graph of catalyst in acid medium and 10mA/cm 2 Comparative plot of galvanostatic test at current density.
FIG. 3 is a Scanning Electron Microscope (SEM) picture, X-ray diffraction (XRD) pattern of the catalyst obtained in example 2, and its reaction product with commercial iridium dioxide (IrO) 2 ) Polarization curves of the catalyst in acidic medium are compared.
FIG. 4 is a Scanning Electron Microscope (SEM) picture, X-ray diffraction (XRD) pattern of the catalyst obtained in example 3, and its reaction product with commercial iridium dioxide (IrO) 2 ) Polarization curves of the catalyst in acidic medium are compared.
Fig. 5 is a Transmission Electron Microscope (TEM) image and a schematic view of the crystal structure of the catalyst obtained in example 1.
Detailed Description
The following detailed description is given with reference to specific examples, but the scope of the present invention is not limited by the specific embodiments.
Example 1 (batch ratio Sr: ir =2
The method combining metal cation complexation, sol-gel method, gel modification and high-temperature sintering is adopted, and the Sr is prepared according to the charging ratio of Sr to Ir =2 4 Ir 3 O 10 The low iridium catalyst comprises the following steps:
(1) Preparing 100mL of 10wt.% citric acid aqueous solution, performing ultrasonic dispersion uniformly, adding 0.004mol of strontium carbonate and 0.002mol of iridium tetrachloride, performing ultrasonic dispersion uniformly for 0.5h, and performing magnetic stirring for 2h;
(2) Carrying out open evaporation on the mixed solution in the step (1) on a heating table at the temperature of 80-90 ℃ until water is evaporated to dryness to form gel-state materials;
(3) Putting the mauve gel obtained in the step (2) into a porcelain boat, performing heat treatment in an air atmosphere by using a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 12 hours;
(4) And (4) taking out and grinding the powder obtained in the step (3), putting the powder into a porcelain boat, sintering the powder at a high temperature in an air atmosphere by using a muffle furnace, raising the temperature to 900 ℃ at a heating rate of 3 ℃/min, and preserving the temperature for 12 hours to obtain the iridium oxide catalyst with the R-P type perovskite crystal structure.
Sr produced in example 1 4 Ir 3 O 10 As shown in fig. 1a, a Transmission Electron Microscope (TEM) image of the low iridium catalyst shows that iridium oxide is in the form of particles and has a size distribution of about 50 to 100nm, and a lattice fringe is clearly seen in fig. 1a, whereby an iridium catalyst having good crystallinity is obtained.
Said Sr 4 Ir 3 O 10 The actual loading of Ir for the low iridium catalyst was 30wt.%;
FIG. 1b shows the X-ray diffraction pattern of the catalyst obtained in example 1, after sol-gel processing and high-temperature sintering, with Sr 4 Ir 3 O 10 The PDF standard card has good correspondence and accords with A n+1 B n O 3n+1 The iridium catalyst has a general formula, has no obvious miscellaneous peak, and obtains an R-P type perovskite structure iridium catalyst with the perovskite layer number n = 3.
FIG. 2a shows the catalyst obtained in example 1 and commercial iridium dioxide (IrO) 2 ) Polarization curves of the catalyst in acidic medium are compared. Wherein the electrolyte solution: 0.1M HClO 4 An aqueous solution; scanning rate: 10mV/s; scanning voltage range: 0.8-1.4V. The Linear Sweep Voltammetry (LSV) after i-R compensation shows that the prepared iridium catalyst with the R-P type perovskite structure is at 10mA/cm 2 Has an overpotential lower than that of commercial iridium dioxide (IrO) 2 )。
FIG. 2b shows the catalyst obtained in example 1 and commercial iridium dioxide (IrO) 2 ) Comparative plot of galvanostatic testing of the catalyst in acidic medium. Wherein the electrolyte solution: 0.1M HClO 4 An aqueous solution; current density: 10mA/cm 2 . The prepared iridium catalyst with the R-P type perovskite structure hardly attenuates after constant current is stabilized for 35 hoursAnd commercial iridium dioxide (IrO) 2 ) The catalyst is completely deactivated in less than 5h under the same conditions.
Example 2 (batch ratio Sr: ir =4
The method combining metal cation complexation, a sol-gel method, gel modification and high-temperature sintering is adopted, and the Sr is prepared according to the charge ratio of Sr to Ir =4 4 Ir 3 O 10 The low iridium catalyst comprises the following steps:
(1) Preparing 100mL of 10wt.% citric acid aqueous solution, performing ultrasonic dispersion uniformly, adding 0.004mol of strontium carbonate and 0.003mol of iridium tetrachloride, performing ultrasonic dispersion uniformly for 0.5h, and performing magnetic stirring for 2h;
(2) Carrying out open evaporation on the mixed solution in the step (1) on a heating table at the temperature of 80-90 ℃ until water is evaporated to dryness to form gel-state materials;
(3) Putting the mauve gel obtained in the step (2) into a porcelain boat, performing heat treatment in an air atmosphere by using a muffle furnace, raising the temperature to 600 ℃ at a heating rate of 2 ℃/min, and preserving the temperature for 12 hours;
(4) And (4) taking out and grinding the powder obtained in the step (3), putting the powder into a porcelain boat, sintering the powder at a high temperature in an air atmosphere by using a muffle furnace, raising the temperature to 900 ℃ at a heating rate of 3 ℃/min, and preserving the temperature for 12 hours to obtain the iridium oxide catalyst with the R-P type perovskite crystal structure.
Example 2 preparation of Sr 4 Ir 3 O 10 Scanning Electron Microscope (SEM) images, X-ray diffraction (XRD) patterns of low iridium catalysts, and their use with commercial iridium dioxide (IrO) 2 ) As shown in figure 3, the OER performance of the catalyst in an acid medium is that the iridium oxide is granular and has the size distribution of about 50-200 nm; XRD pattern and Sr 4 Ir 3 O 10 The PDF standard card has good correspondence and conforms to A n+1 B n O 3n+1 General formula (I), and no obvious hetero-peak; its OER performance is superior to commercial IrO 2 。
Example 3 (batch ratio Sr: ir =1
The method combining metal cation complexation, a sol-gel method, gel modification and high-temperature sintering is adopted, and the Sr is prepared according to the charge ratio of Sr to Ir =1 4 Ir 3 O 10 The low iridium catalyst comprises the following steps:
(1) Preparing 100mL of 10wt.% citric acid aqueous solution, performing ultrasonic dispersion uniformly, adding 0.004mol of strontium carbonate and 0.004mol of iridium tetrachloride, performing ultrasonic dispersion uniformly for 0.5h, and performing magnetic stirring for 2h;
(2) Carrying out open evaporation on the mixed solution in the step (1) on a heating table at the temperature of 80-90 ℃ until water is evaporated to dryness to form gel-state materials;
(3) Putting the mauve gel obtained in the step (2) into a porcelain boat, performing heat treatment in an air atmosphere by using a muffle furnace, heating to 600 ℃ at a heating rate of 2 ℃/min, and preserving heat for 12 hours;
(4) And (4) taking out and grinding the powder obtained in the step (3), placing the powder into a porcelain boat, sintering the powder at a high temperature in an air atmosphere by using a muffle furnace, raising the temperature to 900 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 12 hours to obtain the iridium oxide catalyst with the R-P type perovskite crystal structure.
Sr produced in example 3 4 Ir 3 O 10 Scanning Electron Microscope (SEM) images, X-ray diffraction (XRD) patterns of low iridium catalysts, and their use with commercial iridium dioxide (IrO) 2 ) The OER performance of the catalyst in an acid medium is shown in figure 4, wherein the iridium oxide is granular and has the size distribution of about 200-300 nm; XRD pattern and Sr 4 Ir 3 O 10 The PDF standard card has good correspondence and conforms to A n+1 B n O 3n+1 General formula (I), and no obvious hetero-peak; its OER performance is superior to commercial IrO 2 。
The foregoing detailed description has described the basic principles and principal features of the invention. It should be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and any changes or modifications which do not occur to the inventive concept are intended to be included within the scope of the present invention. The present invention is subject to various changes and modifications without departing from the scope of the invention, which will fall within the scope of the claims.
Claims (9)
1. Layered Sr 4 Ir 3 O 10 The low iridium catalyst is characterized by being black solid powderThe catalyst is formed by alternately arranging a layer of rock salt structure and three layers of perovskite structures on a microstructure to form pseudo-perovskite type low-iridium catalyst nano particles with a structure similar to Ruddlesden-Popper (R-P), wherein the actual load or content of Ir is less than or equal to the theoretical load or content, namely Sr: the molar ratio of Ir is less than or equal to 4; the particle size of the catalyst particles is 50-100nm.
2. A layered Sr as in claim 1 4 Ir 3 O 10 The low iridium catalyst is characterized in that the molar ratio of strontium salt to iridium salt is 1 to 1, and the particle size of the catalyst can be regulated and controlled by adjusting the molar ratio of strontium salt to iridium salt, so that the catalyst with larger specific surface area is obtained.
3. Preparation of the layered Sr as claimed in claim 1 or 2 4 Ir 3 O 10 A process for the production of a low iridium catalyst, comprising the steps of:
(1) Metal cation complexing step: adding metal salt into the prepared citric acid aqueous solution at room temperature, performing ultrasonic dispersion for 0.5h, and performing magnetic stirring reaction for 2h;
(2) A gel forming step: putting the mixed solution in the step (1) on a heating table, and evaporating water to obtain mixed gel with metal cations embedded in citric acid molecular frameworks;
(3) Gel modification treatment: putting the mauve gel obtained in the step (2) into a porcelain boat, and carrying out heat treatment for 10-14h under a certain atmosphere to remove a complexing agent and residual water in the gel;
(4) And (3) high-temperature sintering: sintering the powder obtained in the step (3) at a high temperature for 10-14h in a certain atmosphere to obtain the Sr 4 Ir 3 O 10 A low iridium catalyst.
4. The process of claim 3, wherein in step (1), the aqueous citric acid solution concentration is from 8wt.% to 12wt.%, the strontium salt concentration is from 0.04 to 0.12mM, the iridium salt concentration is from 0.02 to 0.1mM, the molar ratio of strontium salt to iridium salt is from 1 to 2; 80-120ml of citric acid aqueous solution is used for every 0.004mol of strontium.
5. The method according to claim 3, wherein in the step (1), the strontium salt and the iridium salt are selected from strontium carbonate, strontium nitrate, iridium trichloride and iridium tetrachloride.
6. The method according to claim 3, wherein in the step (2), the heating temperature is controlled to 80-90 ℃ until the water is evaporated to dryness to form a gel.
7. The method according to claim 3, wherein in the step (3), the atmosphere is oxygen or air, the heat treatment temperature is 600 ℃, and the temperature increase rate is 2 ℃/min.
8. The method according to claim 3, wherein in the step (4), the atmosphere is oxygen or air, the heat treatment temperature is 900 to 1000 ℃, and the temperature rising speed is 3 ℃/min.
9. The layered Sr as in claim 1 or 2 4 Ir 3 O 10 Use of a low iridium catalyst for anodic oxygen evolution of acidic water and Proton Exchange Membrane (PEM) electrolyzed water.
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