CN110860292A - Cation co-doped perovskite catalyst for oxygen evolution reaction and preparation method thereof - Google Patents
Cation co-doped perovskite catalyst for oxygen evolution reaction and preparation method thereof Download PDFInfo
- Publication number
- CN110860292A CN110860292A CN201910949639.7A CN201910949639A CN110860292A CN 110860292 A CN110860292 A CN 110860292A CN 201910949639 A CN201910949639 A CN 201910949639A CN 110860292 A CN110860292 A CN 110860292A
- Authority
- CN
- China
- Prior art keywords
- cation
- oxygen evolution
- evolution reaction
- catalyst
- doped perovskite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001301 oxygen Substances 0.000 title claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 34
- 150000001768 cations Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003980 solgel method Methods 0.000 claims abstract description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 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 22
- 239000000243 solution Substances 0.000 claims description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 229960001484 edetic acid Drugs 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000010411 electrocatalyst Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000009841 combustion method Methods 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 description 6
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 4
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012956 testing procedure Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
- C25B11/0773—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide of the perovskite type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- 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
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a cation co-doped perovskite catalyst for oxygen evolution reaction and a preparation method thereof3‑δWherein A is one or more of rare earth metal elements or alkaline earth metal elements, B is transition metal element, and delta is more than or equal to 0 and less than or equal to 1. The cation co-doped perovskite catalyst has excellent oxygen evolution activity (OER) and stability, can be applied to low-temperature oxygen evolution reaction, and has better development prospect in energy storage and conversion technologies relating to the oxygen evolution reaction, such as electrolytic water, metal-air batteries and the like. The invention adopts the processes of sol-gel method, solid phase method and the likeThe preparation method is simple and has the potential of large-scale preparation.
Description
Technical Field
The invention belongs to the field of electrochemical catalysis, and particularly relates to an oxygen evolution reaction electrocatalyst of perovskite oxide, and a preparation method and application thereof.
Background
With the continuous high-speed development of the world economy and the increasing population, the demand of human energy is increasing. Because the traditional energy has great pollution to the environment, people urgently need to find a cleaner energy utilization mode. At present, the main renewable clean energy sources mainly comprise solar energy, wind energy, tidal energy, geothermal energy and the like. However, due to geographical and weather factors, the supply of these renewable clean energy sources is not stable, and often appears intermittent and regional, resulting in a waste of part of the energy sources. Therefore, the development of energy storage and conversion technologies capable of efficiently utilizing these renewable energy sources is of great significance to solve the dilemma of energy shortage.
In recent years, many advanced energy conversion and storage technologies have been developed rapidly. Such as electrolyzed water, metal air cells, fuel cells, etc. The Oxygen Evolution Reaction (OER) is a process of oxidizing water to generate molecular oxygen under the action of an electric field and an electrocatalyst, and is a key link for realizing efficient energy conversion and utilization. The Oxygen Evolution Reaction (OER) involves four electron transfers, the cleavage and formation of metal-oxygen (M-O) and oxygen-oxygen (O-O) bonds, resulting in very slow kinetics. The anodic reaction of water electrolysis is a slow Oxygen Evolution Reaction (OER) with high overvoltage and low oxygen production rate, which indirectly reduces the rate of hydrogen evolution. The slow kinetic process of OER is therefore a major bottleneck limiting the commercial development of this technology. A highly efficient catalyst is generally required to accelerate this reaction. Conventional catalysts often contain noble metals (e.g., RuO)2And IrO2) However, due to the low precious metal inventory, high cost and poor stability, there is a need to develop other non-precious metal Oxygen Evolution (OER) catalysts.
In recent years, ABO has been provided3Perovskite oxides of the general formula have attracted considerable attention because of their structural specificity and component diversity, which exhibit excellent physical and chemical properties. The standard perovskite A site or B site element is replaced by other metal ions or partially replaced to form the perovskite composite oxide with high concentration of ion vacancy or B site ions with different valence states. Among them, Co-based perovskite composite oxides have been widely studied because they exhibit excellent properties in terms of OER electrocatalysis. Regulating and controlling componentAnd a controllable synthesis strategy remains a key issue for preparing highly efficient perovskites.
Disclosure of Invention
An object of the present invention is to provide a cation co-doped perovskite catalyst for oxygen evolution reaction and a preparation method thereof, which can obtain a catalyst with oxygen evolution performance and long-term stability by doping metal cations at the B site.
In order to achieve the purpose, the invention adopts the technical scheme that:
a cation co-doped perovskite catalyst for oxygen evolution reaction is a perovskite structure oxide with a general structural formula ABO3-δWherein A is one or more of rare earth metal elements or alkaline earth metal elements, B is transition metal element, and delta is more than or equal to 0 and less than or equal to 1.
Preferably, the element A is one or more of Sr, La, Ca, Na, K and Ba.
Preferably, the B element is one or more of Nb, Ti, Co, Mn, Fe, Ni, Al, Mo, Cu, Sc and Cr.
Preferably, the perovskite structure oxide is SrTi0.1CoxFe0.9-xO3-δWherein x is more than or equal to 0 and less than or equal to 0.9, and delta is more than or equal to 0 and less than or equal to 1.
A preparation method of a cation co-doped perovskite catalyst for oxygen evolution reaction is characterized in that the perovskite structure oxide is prepared by a solid-phase reaction method, a sol-gel method or a coprecipitation method, a combustion method, a hydrothermal method or a microwave method.
As a preferred technical scheme, the perovskite structure oxide is prepared by adopting a sol-gel method, and the method specifically comprises the following steps:
and 3, stirring and heating the reaction solution obtained in the step 2 until the solution is colloidal, drying, and calcining to finally obtain the perovskite structure oxide.
Preferably, in the steps 1 and 2, the ratio of the total moles of the metal cations to the moles of the citric acid and the moles of the ethylene diamine tetraacetic acid is 1:2: 1.
Preferably, in the step 3, the drying temperature is 100-300 ℃ and the time is 3-8 h; the calcination temperature is 800-1000 ℃ and the time is 3-8 h.
The cation co-doped perovskite catalyst has excellent oxygen evolution activity (OER) and stability, and therefore can be applied to oxygen evolution reaction, particularly as an electrocatalyst of a renewable fuel cell, a rechargeable metal-air battery or water electrolysis.
Has the advantages that: the cation co-doped perovskite catalyst has excellent oxygen evolution activity (OER) and stability, can be applied to low-temperature oxygen evolution reaction, and has better development prospect in energy storage and conversion technologies relating to the oxygen evolution reaction, such as electrolytic water, metal-air batteries and the like. The invention adopts the processes of sol-gel method, solid phase method and the like for preparation, and the method is simple and has the potential of large-scale preparation.
Drawings
FIG. 1 shows SrTi prepared in example0.1CoxFe0.9-xO3-δX-ray diffraction (XRD) profile of a series (X ═ 0.5,0.6,0.7) of perovskite oxides;
FIG. 2 shows SrTi prepared in example 10.1CoxFe0.9-xO3-δPerovskite oxides of the series (x ═ 0.5,0.6,0.7) in O2Polarization profile in saturated 0.1mol/L KOH solution;
FIG. 3 shows SrTi0.1Co0.4Fe0.5O3-δOxygen evolution performance comparison graphs of perovskite oxide and noble metal catalyst IrO 2;
FIG. 4 shows SrTi0.1Co0.4Fe0.5O3-δThe stability curve measured by the CP method of the perovskite oxide;
FIG. 5 shows SrTi0.1CoxFe0.9-xO3-δEIS impedance plots for a series (x ═ 0.5,0.6,0.7) of perovskite oxides;
FIG. 6 shows SrTi0.1CoxFe0.9-xO3-δTafel slope plots for a series (x ═ 0.5,0.6,0.7) of perovskite oxides;
FIG. 7 shows SrTi prepared in example0.1Co0.9O3-δX-ray diffraction (XRD) profile of the perovskite oxide;
FIG. 8 shows SrTi prepared in example0.1Co0.9O3-δPerovskite oxides in O2Polarization profile in saturated 0.1mol/L KOH solution.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
SrTi0.1Co0.4Fe0.5O3-δPreparation of catalyst and evaluation of oxygen evolution Activity
SrTi0.1Co0.4Fe0.5O3-δThe catalyst powder is prepared by a sol-gel method. Respectively taking strontium nitrate, tetrabutyl titanate, cobalt nitrate and ferric nitrate in stoichiometric ratio, adding Citric Acid (CA) and Ethylene Diamine Tetraacetic Acid (EDTA), adding deionized water, heating on a magnetic stirrer to obtain a corresponding solution, adding ammonia water to adjust the pH value to about 7, continuously stirring and heating until the solution becomes colloidal, putting a beaker into a drying oven at 250 ℃, heating for 5 hours to obtain a solid precursor, putting the precursor into a muffle furnace, calcining for 5 hours at 950 ℃ to obtain the required SrTi0.1Co0.4Fe0.5O3-δOxidation of perovskite.
SrTi was prepared in the same manner by repeating the above procedure while changing the corresponding stoichiometric ratio0.1Co0.6Fe0.3O3-δ，SrTi0.1Co0.7Feo0.2O3-δAnd (3) catalyst powder.
FIG. 1 shows SrTi prepared0.1CoxFe0.9-xO3-δX-ray diffraction (XRD) patterns of the perovskite oxides of the series (X ═ 0.5,0.6,0.7) show that, as can be seen from fig. 1, the final products all formed perovskite structures.
The oxygen evolution catalytic activity of the perovskite oxides was tested using a rotating disk electrode. FIG. 2 shows SrTi prepared in example 10.1CoxFe0.9-xO3-δPerovskite oxides of the series (x ═ 0.5,0.6,0.7) in O2Polarization profile in saturated 0.1mol/L KOH solution. From the figure, SrTi can be seen0.1Co0.5Fe0.4O3-δThe perovskite oxide has the best oxygen precipitation performance, the minimum overpotential is 1.60V, and the maximum current density at 1.70V is 30mA/cm2。
FIG. 3 shows SrTi0.1Co0.5Fe0.4O3-δPerovskite oxide and noble metal catalyst IrO2A performance comparison graph of (c). Noble metal catalyst IrO2And SrTi0.1Co0.5Fe0.4O3-δThe catalyst was subjected to electrode preparation and oxygen evolution activity test under the same conditions. From the figure, SrTi can be seen0.1Co0.5Fe0.4O3-δCatalyst and noble metal IrO2Compared with the catalyst, the overpotential is small (1.60V @10 mA/cm)2vs 1.70V@10mA/cm2) High current density (33.5 mA/cm)2@1.71V vs 12.1mA/cm2@ 1.70V). Shows that the oxygen precipitation catalytic activity of the catalyst is higher than that of the noble metal catalyst IrO2And better, has a commercial application foundation.
FIG. 4 shows SrTi0.1Co0.5Fe0.4O3-δThe stability curve of the perovskite oxide measured by the CP method shows SrTi0.1Co0.5Fe0.4O3-δPerovskite oxides have excellent stability. SrTi is shown in FIGS. 5 and 60.1CoxFe0.9-xO3-δEIS impedance profile and Tafel slope profile for a series (x ═ 0.5,0.6,0.7) of perovskite oxides.
Example 2
SrTi0.1Co0.9O3-δPreparation of perovskite oxide and evaluation of oxygen precipitation Activity
SrTi0.1Co0.9O3-δThe catalyst powder is prepared by a sol-gel method. The method comprises the following specific steps: adding strontium nitrate, tetrabutyl titanate and cobalt nitrate according to a stoichiometric ratio, adding Citric Acid (CA) and Ethylene Diamine Tetraacetic Acid (EDTA), adding deionized water, heating on a magnetic stirrer to obtain a corresponding solution, adding ammonia water to adjust the pH value to about 7, continuously stirring and heating until the solution becomes colloidal, putting a beaker into a drying oven at 250 ℃, heating for 5 hours to obtain a solid precursor, putting the precursor into a muffle furnace, calcining at 950 ℃ for 5 hours to obtain the required SrTi0.1Co0.9O3-δOxidation of perovskite.
FIG. 7 shows SrTi0.1Co0.9O3-δXRD pattern of catalyst powder.
And evaluating the oxygen precipitation performance of the catalyst. The electrode preparation and testing procedures were the same as in example 1. FIG. 8 shows SrTi prepared0.1Co0.9O3-δPerovskite oxides in O2Polarization profile in saturated 0.1mol/L KOH solution.
In the prior art, the general formula of the main pair is ABO3The perovskite oxide is subjected to strategies of element doping, defect control, structural change and the like to regulate and optimize the electronic structure of the B-site active metal, so that the aim of improving the performance is fulfilled. In the above embodiment, double doping of metal cations at the B site (Ti and Fe) is employed to improve the activity and stability of the perovskite oxide, and a catalyst with optimized Oxygen Evolution (OER) performance is obtained by adjusting the ratio of the two elements doped at the B site.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. Is used for oxygen evolutionA reactive cation co-doped perovskite catalyst characterized in that: the catalyst is perovskite structure oxide, and the general formula of the structure is ABO3-δWherein A is one or more of rare earth metal elements or alkaline earth metal elements, B is transition metal element, and delta is more than or equal to 0 and less than or equal to 1.
2. The cation co-doped perovskite catalyst for oxygen evolution reaction according to claim 1, characterized in that: the element A is one or more of Sr, La, Ca, Na, K and Ba.
3. The cation co-doped perovskite catalyst for oxygen evolution reaction according to claim 1, characterized in that: the B element is one or more of Nb, Ti, Co, Mn, Fe, Ni, Al, Mo, Cu, Sc and Cr.
4. The cation co-doped perovskite catalyst for oxygen evolution reaction according to claim 1, characterized in that: the perovskite structure oxide is SrTi0.1CoxFe0.9-xO3-δWherein x is more than or equal to 0 and less than or equal to 0.9, and delta is more than or equal to 0 and less than or equal to 1.
5. A method of preparing a cation co-doped perovskite catalyst for oxygen evolution reaction according to any one of claims 1 to 4, characterized in that: the perovskite structure oxide is prepared by a solid-phase reaction method, a sol-gel method or a coprecipitation method, a combustion method, a hydrothermal method or a microwave method.
6. The method of preparing a cation co-doped perovskite catalyst for oxygen evolution reaction according to claim 5, characterized in that: the sol-gel method comprises the following steps:
step 1, mixing nitrate containing an element A and nitrate containing an element B or oxalate or organic matters according to the stoichiometric ratio in the structural formula of the perovskite structure oxide to obtain a mixed solution;
step 2, adding citric acid and ethylenediamine tetraacetic acid serving as complexing agents into the mixed solution obtained in the step 1, and adding ammonia water to adjust the pH value to be neutral to obtain a reaction solution;
and 3, stirring and heating the reaction solution obtained in the step 2 until the solution is colloidal, drying, and calcining to finally obtain the perovskite structure oxide.
7. The method of preparing a cation co-doped perovskite catalyst for oxygen evolution reaction according to claim 6, characterized in that: in the steps 1 and 2, the ratio of the total mole number of the metal cations to the mole number of the citric acid and the mole number of the ethylene diamine tetraacetic acid is 1:2: 1.
8. The method of preparing a cation co-doped perovskite catalyst for oxygen evolution reaction according to claim 6, characterized in that: in the step 3, the drying temperature is 100-300 ℃, and the time is 3-8 h; the calcination temperature is 800-1000 ℃ and the time is 3-8 h.
9. Use of a cation co-doped perovskite catalyst as defined in any one of claims 1 to 4 in an oxygen evolution reaction.
10. Use according to claim 9, characterized in that: the cation co-doped perovskite catalyst is used as an electrocatalyst for a renewable fuel cell, a rechargeable metal-air cell or water electrolysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910949639.7A CN110860292A (en) | 2019-10-08 | 2019-10-08 | Cation co-doped perovskite catalyst for oxygen evolution reaction and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910949639.7A CN110860292A (en) | 2019-10-08 | 2019-10-08 | Cation co-doped perovskite catalyst for oxygen evolution reaction and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110860292A true CN110860292A (en) | 2020-03-06 |
Family
ID=69652109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910949639.7A Pending CN110860292A (en) | 2019-10-08 | 2019-10-08 | Cation co-doped perovskite catalyst for oxygen evolution reaction and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110860292A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112670525A (en) * | 2020-12-01 | 2021-04-16 | 全球能源互联网研究院有限公司 | Solid oxide fuel cell electrode material |
| CN113582240A (en) * | 2020-12-11 | 2021-11-02 | 浙江大学 | Thermochemical heat storage material, thermochemical heat storage module and preparation method |
| CN114797849A (en) * | 2022-02-16 | 2022-07-29 | 南京工业大学 | Bifunctional perovskite oxide catalyst, preparation method and application thereof |
| CN114941151A (en) * | 2022-04-25 | 2022-08-26 | 大连理工大学 | Sc (Sc) 3+ ﹑Al 3+ Doped Ni-based water oxidation catalyst and preparation method thereof |
| CN115845791A (en) * | 2023-02-20 | 2023-03-28 | 农业农村部环境保护科研监测所 | Preparation method and application of Ca/La-based perovskite adsorption material |
| CN116507413A (en) * | 2020-10-15 | 2023-07-28 | 国立大学法人京都大学 | Anode for alkaline water electrolysis and method for producing same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0434480A1 (en) * | 1989-12-01 | 1991-06-26 | Rhone-Poulenc Chimie | Process of electrochemical treatment of oxide materials |
| US20160104926A1 (en) * | 2014-10-09 | 2016-04-14 | Toyota Jidosha Kabushiki Kaisha | Air battery |
| CN108579751A (en) * | 2018-04-12 | 2018-09-28 | 南京工业大学 | Layered perovskite oxide, preparation method and application thereof in oxygen evolution reaction electrocatalysis |
| CN109390598A (en) * | 2018-11-15 | 2019-02-26 | 河北工业大学 | A kind of preparation method and applications of difunctional perofskite type oxide oxygen electrode catalyst |
| CN109759077A (en) * | 2019-01-08 | 2019-05-17 | 南京航空航天大学 | A kind of perovskite oxide catalyst and its preparation method and application |
| CN109967068A (en) * | 2019-03-21 | 2019-07-05 | 深圳先进技术研究院 | A kind of netted doping type perovskite catalyst and its preparation method and application |
-
2019
- 2019-10-08 CN CN201910949639.7A patent/CN110860292A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0434480A1 (en) * | 1989-12-01 | 1991-06-26 | Rhone-Poulenc Chimie | Process of electrochemical treatment of oxide materials |
| US20160104926A1 (en) * | 2014-10-09 | 2016-04-14 | Toyota Jidosha Kabushiki Kaisha | Air battery |
| CN108579751A (en) * | 2018-04-12 | 2018-09-28 | 南京工业大学 | Layered perovskite oxide, preparation method and application thereof in oxygen evolution reaction electrocatalysis |
| CN109390598A (en) * | 2018-11-15 | 2019-02-26 | 河北工业大学 | A kind of preparation method and applications of difunctional perofskite type oxide oxygen electrode catalyst |
| CN109759077A (en) * | 2019-01-08 | 2019-05-17 | 南京航空航天大学 | A kind of perovskite oxide catalyst and its preparation method and application |
| CN109967068A (en) * | 2019-03-21 | 2019-07-05 | 深圳先进技术研究院 | A kind of netted doping type perovskite catalyst and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| CHAO SU等: "SrCo0.9Ti0.1O3-δ As a New Electrocatalyst for the Oxygen Evolution Reaction in Alkaline Electrolyte with Stable Performance", 《ACS APPL MATER INTERFACES》 * |
| M. A. OPAZO等: "Oxygen-vacancy tuning of magnetism in SrTi0.75Fe0.125Co0.125O3-δ perovskite", 《PHYS. REV. MATERIALS》 * |
| 郝恩奇等: "EDTA-柠檬酸复合络合法制备阴极材料La0.4Sr0.6Co0.4Fe0.6O3 粉体", 《佛山陶瓷》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116507413A (en) * | 2020-10-15 | 2023-07-28 | 国立大学法人京都大学 | Anode for alkaline water electrolysis and method for producing same |
| CN116507413B (en) * | 2020-10-15 | 2024-03-22 | 国立大学法人京都大学 | Anode for alkaline water electrolysis and method for producing same |
| CN112670525A (en) * | 2020-12-01 | 2021-04-16 | 全球能源互联网研究院有限公司 | Solid oxide fuel cell electrode material |
| CN112670525B (en) * | 2020-12-01 | 2022-11-25 | 全球能源互联网研究院有限公司 | Solid oxide fuel cell electrode material |
| CN113582240A (en) * | 2020-12-11 | 2021-11-02 | 浙江大学 | Thermochemical heat storage material, thermochemical heat storage module and preparation method |
| CN114797849A (en) * | 2022-02-16 | 2022-07-29 | 南京工业大学 | Bifunctional perovskite oxide catalyst, preparation method and application thereof |
| CN114941151A (en) * | 2022-04-25 | 2022-08-26 | 大连理工大学 | Sc (Sc) 3+ ﹑Al 3+ Doped Ni-based water oxidation catalyst and preparation method thereof |
| CN114941151B (en) * | 2022-04-25 | 2024-04-16 | 大连理工大学 | Sc (Sc)3+﹑Al3+Doped Ni-based water oxidation catalyst and preparation method thereof |
| CN115845791A (en) * | 2023-02-20 | 2023-03-28 | 农业农村部环境保护科研监测所 | Preparation method and application of Ca/La-based perovskite adsorption material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109759077B (en) | Perovskite oxide catalyst and preparation method and application thereof | |
| Plevova et al. | Electrocatalysts for the oxygen evolution reaction in alkaline and neutral media. A comparative review | |
| CN110860292A (en) | Cation co-doped perovskite catalyst for oxygen evolution reaction and preparation method thereof | |
| Wang et al. | The electronic structure of transition metal oxides for oxygen evolution reaction | |
| Li et al. | Amorphous oxide nanostructures for advanced electrocatalysis | |
| Dessie et al. | Recent developments in manganese oxide based nanomaterials with oxygen reduction reaction functionalities for energy conversion and storage applications: A review | |
| CN107268021B (en) | A kind of NiCoAl-LDH modification di-iron trioxide complex light anode material and its preparation method and application | |
| Xu et al. | Toward enhanced oxygen evolution on perovskite oxides synthesized from different approaches: a case study of Ba0. 5Sr0. 5Co0. 8Fe0. 2O3− δ | |
| CN108579751B (en) | Layered perovskite oxide, preparation method and application thereof in oxygen evolution reaction electrocatalysis | |
| Han et al. | Designing oxide catalysts for oxygen electrocatalysis: insights from mechanism to application | |
| Omari et al. | Cu-doped GdFeO3 perovskites as electrocatalysts for the oxygen evolution reaction in alkaline media | |
| CN114808123B (en) | Single crystal porous high entropy hydroxyl oxide and preparation method and application thereof | |
| CN110813361B (en) | Phosphorus-doped cobalt oxide iron nitrogen-doped carbon nanofiber composite material and preparation method and application thereof | |
| CN109295475B (en) | Preparation method of selenium-doped vanadium selenide composite material | |
| CN112593256B (en) | Core-shell FeOOH @ NiFe LDH electro-catalysis material and preparation method thereof | |
| CN111001414A (en) | Structure-controllable hollow nickel cobaltate nanowire/flaky manganese oxide core-shell array material and preparation method thereof | |
| WO2024066179A1 (en) | Surface-modified perovskite oxide electrocatalyst as well as preparation method therefor and use thereof | |
| CN111640953A (en) | Air electrode catalyst of aluminum-air battery and preparation method thereof | |
| CN115872460A (en) | Method for effectively improving catalytic performance of perovskite catalyst | |
| CN115449842A (en) | Lead-doped low-temperature synthesized yttrium ruthenate catalyst and preparation method and application thereof | |
| Munawar et al. | Three-dimensional ordered FeTe-SmCoO3 nanocomposite: As efficient electrocatalyst for water oxidation | |
| CN100490229C (en) | Electro-catalyst of zinc-air battery and method for making same | |
| Nayak et al. | Optimization of Praseodymium-Based Perovskites as Electrocatalysts for Oxygen Reduction Reaction | |
| CN108435178B (en) | Oxide with hexagonal structure, preparation method and application thereof in oxygen evolution reaction | |
| CN113955728A (en) | Preparation of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide and application of hollow-grade-structure cobalt phosphide/cobalt manganese phosphide in electrolytic water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200306 |