CN110055555A - Oxygen evolution reaction catalysts and its preparation method and application - Google Patents
Oxygen evolution reaction catalysts and its preparation method and application Download PDFInfo
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- CN110055555A CN110055555A CN201810373870.1A CN201810373870A CN110055555A CN 110055555 A CN110055555 A CN 110055555A CN 201810373870 A CN201810373870 A CN 201810373870A CN 110055555 A CN110055555 A CN 110055555A
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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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- 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
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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
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of oxygen evolution reaction catalysts preparation method and applications.The oxygen evolution reaction catalysts are Y2‑xMxRu2O7, wherein M is Pr or Zn, and 0 < x < 2.Preparation method includes preparing including Y salt, the mixed solution of M salt and Ru salt, metal ion match progress ligand reaction preparation Y being added into mixed solution2Ru2O7Presoma, to the Y2Ru2O7Presoma calcination processing and etc..The oxygen evolution reaction catalysts precious metal content is low, and conductivity is high, and analysis oxygen catalytic activity is high, stable in catalytic performance.And preparation method process conditions are easily-controllable, favorable repeatability, high production efficiency.The oxygen evolution reaction catalysts can prepare oxygen evolution reaction electrode, electrochemical appliance and hydrogen and oxygen is generated by water method in apply, so that improving water generates the high-efficient of hydrogen and oxygen, reduce economic cost.
Description
Technical field
The invention belongs to electrochemical catalysis technical fields, and in particular to a kind of oxygen evolution reaction catalysts and preparation method thereof and
Using.
Background technique
Hydrogen is with a wide range of applications in human society future source of energy pattern as important secondary energy sources.Hydrogen
Gas itself is the energy carrier of clean and effective, turns gas technology as obs network node using the electricity of fuel cell, utilizes wind energy, solar energy etc.
Batch-type renewable energy power generation carries out hydrogen preparation, can satisfy the conversion of extensive clean energy resource and storage demand needed.
Electricity turns gas technology (Power to gas, be often abbreviated as P2G or PtG), is to utilize electrical power conversion for gaseous fuel
Technology is that a kind of and clean energy resource of rising in recent years is especially the novel big rule that intermittent renewable energy power generation is combined closely
Mould industrializes water electrolysis hydrogen production technology.Electricity turn gas technology key be by electric power by way of electrolysis by water decomposition be oxygen and
Hydrogen.Hydrogen can be used as the means of storage energy, so this purposes is also known as hydrogen energy storage.With wind power hydrogen production energy storage technology
For, core concept is that hydrogen and oxygen is made in water electrolysis using wind-powered electricity generation when wind-powered electricity generation is sufficient but can not surf the Internet, need abandonment
Gas, and stored hydrogen as energy carrier；When needing electric energy, by the hydrogen of storage by different modes (internal combustion engine,
Fuel cell or other modes) be converted to electrical energy transportation online.Compared to traditional electrolyzed alkaline water hydrogen producing technology, proton exchange membrane
(PEM) there is electrolysis water big high-efficient, rapid dynamic response speed, current density operation range, modularized design, scale can greatly may be used
The advantages that small, is more suitable for smart grid energy storage technology.
Oxygen evolution reaction (OER) plays a key effect during water decomposition produces hydrogen.Although passing through researcher's
Effort improves the performance of electrolysis water, but oxygen evolution reaction elctro-catalyst still has kinetics slowly and in acidity
The low problem of stability in environment.It is most of to have the oxide of catalytic activity all unstable under harsh acid condition.Ruthenium
(Ru) and iridium (Ir) oxide is two kinds of OER catalyst best in acid medium.Ruthenium-oxide although activity with higher, but
Its long-time stability is bad, and the business OER catalyst of mainstream mostly uses greatly yttrium oxide at present.But ruthenium and iridium are all noble metal, valence
Lattice are expensive, a large amount of to use the reduction for being unfavorable for water electrolysis hydrogen production technical costs.For the industrialization hair for accelerating PEM water electrolysis hydrogen production
Exhibition, the content for reducing noble metal in membrane electrode are particularly important.Currently, the ultimate challenge of oxygen evolution reaction elctro-catalyst research is to find
One kind having high electrocatalytic active, the simultaneously uncorroded electrocatalysis material under acid and oxygen evolution potential.
In order to reduce the content of precious metal to realize the economic cost of oxygen evolution reaction elctro-catalyst, also there is trial at present
The elctro-catalyst of precious metal content is reduced, but in the middle discovery of practical application, as the content of precious metal reduces, oxygen analysis
Reaction elctro-catalyst occurs that conductivity is lower accordingly out, is unfavorable for the electronic transfer process of catalytic reaction process, so as to cause
The not high problem of catalytic activity occurs.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of oxygen evolution reaction catalysts and its preparation are provided
Methods and applications cause at high cost to solve existing oxygen evolution reaction catalysts using noble metal, and stability is undesirable or existing
Precious metal content, but the technical problem that conductivity is lower.
In order to achieve the above-mentioned object of the invention, one aspect of the present invention provides a kind of oxygen evolution reaction catalysts.The analysis oxygen is anti-
Answering catalyst is Y2-xMxRu2O7, wherein M is Pr or Zn, and 0 < x < 2.
Another aspect of the present invention provides a kind of preparation method of oxygen evolution reaction catalysts.The oxygen evolution reaction catalysts
Preparation method include the following steps:
According to Y2-xMxRu2O7The molar ratio of middle Y, M and Ru element dissolves Y salt, M salt and Ru salt, and it is molten to prepare mixing
Liquid；Wherein, M is Pr or Zn, and 0 < x < 2；
Metal ion match is added into the mixed solution and carries out ligand reaction, is then removed molten in mixed solution
Agent obtains solid mixture；
Calcination processing is carried out in oxygen-containing atmosphere after the solid mixture is carried out dusting processing.
Further aspect of the present invention provides a kind of oxygen evolution reaction electrode.The oxygen evolution reaction electrode includes present invention analysis oxygen
Catalysts or by oxygen evolution reaction catalysts prepared by preparation method of the present invention.
Another aspect of the invention provides a kind of electrochemical appliance, and the electrochemical appliance includes anode and cathode, described
Anode is oxygen evolution reaction electrode of the present invention.
Further aspect of the present invention provides a kind of method that hydrogen and oxygen is generated by water.The method includes walking as follows
It is rapid:
Water with the positive contact contained by electrochemical appliance of the present invention is provided；
It is powered to the electrochemical appliance, respectively to convert at least part of the water on the cathode and anode
At hydrogen and oxygen.
Oxygen evolution reaction catalysts of the present invention use Y2-xMxRu2O7As elctro-catalyst, pyrochlore knot is specifically adulterated using M
The Y of structure2Ru2O7, on the one hand the oxygen evolution reaction catalysts conductivity is good, effectively increases its catalytic activity, and in acidity
Environmental stability is high；On the other hand, the content of Y is effectively reduced, effectively reduces the content of precious metal, reduce its it is economical at
This.
The preparation method of oxygen evolution reaction catalysts of the present invention will be prepared containing Y, M and Ru solion using sol-gal process
The presoma of the oxygen evolution reaction catalysts directly carries out calcination processing afterwards.Therefore, the preparation method obtains calcining
Oxygen evolution reaction catalysts precious metal content is low, and conductivity is high, analyses oxygen catalytic activity, and can guarantee oxygen evolution reaction catalysts
Stable in catalytic performance.In addition, the preparation method process conditions are easily-controllable, favorable repeatability, high production efficiency effectively reduces life
Produce cost.
Oxygen evolution reaction electrode and electrochemical appliance of the present invention are due to containing oxygen evolution reaction catalysts of the present invention or system of the present invention
The oxygen evolution reaction catalysts of Preparation Method preparation, therefore, oxygen evolution reaction electrode and electrochemical appliance analysis oxygen rate of the present invention are high, Er Qiecheng
This is low.
The method of hydrogen and oxygen is generated by water due to using electrochemical appliance of the present invention in the present invention, water generation hydrogen
Gas and oxygen it is high-efficient, economic cost is low.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples, in attached drawing:
Fig. 1 is the Y that the embodiment 11 that embodiment 11 provides provides1.8Pr0.2Ru2O7The Y prepared with comparative example 112Ru2O7X
Ray powder diffraction curve graph；
Fig. 2 is the Y that EXAMPLE Example 11 provides1.8Pr0.2Ru2O7, comparative example 11 provide Y2Ru2O7Catalyst and comparison
The business IrO that example 12 provides2Polarization curve；
Fig. 3 is the Y that EXAMPLE Example 13 provides1.85Zn0.15Ru2O7, comparative example 11 provide Y2Ru2O7Catalyst and right
The business IrO that ratio 12 provides2Polarization curve；
Fig. 4 is the Y that embodiment 11 provides1.8Pr0.2Ru2O7, comparative example 11 provide Y2Ru2O7Catalyst and comparative example 12 mention
The business IrO of confession2Stability test figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
On the one hand, the embodiment of the invention provides a kind of oxygen evolution reaction catalysts.The oxygen evolution reaction catalysts are Y2- xMxRu2O7, wherein M is Pr or Zn, and 0 < x < 2.In this way, the oxygen evolution reaction catalysts are with the Y of pyrochlore constitution2Ru2O7For
Basis is doped using Pr or Zn, on the one hand effectively increases Y2Ru2O7Conductivity, be the Y2-xMxRu2O7Have
Excellent conductivity, improves the electronic transfer process of its catalytic reaction process, to improve the oxygen evolution reaction catalysts
Catalytic performance, and acidic environment stability is high, and therefore, significantly reducing in equivalent performance reduces the analysis oxygen
The usage amount of catalysts reduces the cost of water electrolysis hydrogen production；On the other hand, due to the presence of M element, contained by it
Element species and relation with contents, content containing yttrium is substantially reduced, and is far below IrO2(86%wt) and RuO2Your gold in (76%wt)
The content of category effectively reduces the content of precious metal, reduces its economic cost.
In one embodiment, the Y is controlled2-xMxRu2O7Partial size be 100nm-800nm.By controlling partial size, to realize
Further increase analysis oxygen catalytic activity.
On the other hand, the embodiment of the invention also provides the preparation methods of oxygen evolution reaction catalysts described above.The analysis
Oxygen catalysts preparation method includes the following steps:
S01: according to Y2-xMxRu2O7The molar ratio of middle Y, M and Ru element dissolves Y salt, M salt and Ru salt, prepares mixed
Close solution；
Metal ion match is added in S02: Xiang Suoshu mixed solution and carries out complex reaction, is then removed in mixed solution
Solvent, obtain solid mixture；
S03: calcination processing is carried out in oxygen-containing atmosphere after the solid mixture is carried out dusting processing.
Wherein, in the step S01, Y2-xMxRu2O7Y as described above2-xMxRu2O7, therefore, Y, M and Ru element rub
You are than as described above, specifically, if M is Pr or Zn, 0 < x < 2.The Y salt, M salt and Ru salt, which carry out dissolution, can be can
It dissolves in the solvent of those salt, such as but not just for water.The specific can be that it is molten that Y salt, M salt and Ru salt are first configured to salt respectively
Then liquid is proportionally mixed, directly Y salt, M salt and Ru salt can also be directly dissolved in same solvent, is directly prepared
At mixed solution.In the mixed solution of preparation, the dispersion of Y, M and Ru uniform ion.In one embodiment, the Y salt can select
With including Y (NO3)3·6H2O, anhydrous YCl3、YCl3·6H2At least one of O, the Ru salt can be selected including RuCl3、
(NH4)2RuCl6、K2RuCl5(H2At least one of O).About the M salt, since the M can be Pr or Zn, institute
Stating M salt can be Pr salt or Zn salt.When the M salt is Pr salt, the Pr salt is Pr (NO3)3、PrCl3At least one of；
When the M salt is Zn salt, the Zn salt be zinc nitrate hexahydrate, zinc citrate, acetic anhydride zinc, in two water zinc acetates at least
It is a kind of.There is good dissolubility therefore can conveniently be configured to stable solution for those Y salt, M salt and Ru salt；In addition, should
A little salt impurity are few, so that the oxygen evolution reaction catalysts purity is high finally prepared, to effectively increase oxygen evolution reaction catalysts
Catalytic activity and stability.In addition,
In a particular embodiment, described in the mixed solution, the concentration of the Y salt is 0.001~0.1molL-1, institute
The concentration for stating Ru salt is 0.001~0.1mol L-1, the concentration of the Pr salt is 0.001~0.1mol L-1, the Zn salt it is dense
Degree is 0.001~0.1mol L-1。
In the step S02, metal ion match is added in Xiang Suoshu mixed solution, it can effectively and metal ion
Y, M and Ru ion forms ligand.Therefore, the metal ion match is added amount should relatively described Y, M and Ru ion
Amount be it is enough, be achieved and be sufficiently formed ligand with Y, M and Ru ion.In one embodiment, the metal ion complexation
It is Y, M and Ru metal ion in the metal ion match and the mixed solution that the amount in the mixed solution, which is added, in object
The molar ratio of total amount is (1~10): 1.In a particular embodiment, the metal ion match is citric acid, ethylenediamine tetrem
At least one of acid.Select those types the metal ion match have excellent ion complexation, with Y, M and
Ru metal ion forms stable ligand, and does not bring impurity element into subsequent calcination.
After the metal ion match to be added carries out ligand reaction, the pH value of the mixed solution containing ligand is adjusted
In alkalinity, to increase the stability of ligand, to form stable colloidal sol.In one embodiment, the mixing containing ligand is molten
The pH value of liquid is adjusted to 8.5~9.In addition, the reagent for adjusting mixed solution pH value can be but not just for ammonium hydroxide, preferably
Ammonium hydroxide, to avoid the difficult foreign ion in sintering volatilization is mixed into mixed solution.The method of solvent in mixed solution is removed at this time
It can be direct vacuum drying treatment, be also possible to heat heating water bath solvent flashing such as and remove solvent, acquisition solid mixture.
The mixed solution containing ligand directly can certainly be subjected to standing aging process, so that ligand generates precipitating,
Then it carries out being separated by solid-liquid separation and removes solvent, obtain solid mixture.
The solid mixture obtained after solvent in mixed solution is removed, that is to say Y2-xMxRu2O7Presoma.It is excellent
Choosing, further include that solid is passed through to such as 120 DEG C to be dried in vacuo, dry is also adequately, as done after solvent seasoning processing to be removed
Dry 6~for 24 hours, sufficiently remove solvent.
In above-mentioned steps S03, the solid mixture prepared in step S02 is subjected to dusting processing, on the one hand
The partial size of calcined product can effectively be controlled；On the other hand the solid mixture is enabled to carry out fully calcined.To described
The method that solid mixture carries out dusting processing can be but be not only the methods of grinding.
In oxygen-containing atmosphere will through dusting, treated after the solid mixture calcined, the solid mixture exists
Y is generated in high temperature2-xMxRu2O7.In one embodiment, 800~1200 DEG C of the calcination processing, time are 6~20h.Having
In body embodiment, when M is Pr, 800~1200 DEG C of the calcination processing, the time is 6~20h；It is described to forge when M is Zn
1100~1200 DEG C for burning processing, time are 6~20h.By the temperature and time of optimization calcining, so that calcined product is sufficiently burnt
Knot, and form Y2-xMxRu2O7。
Therefore, the oxygen evolution reaction catalysts precious metal content of the preparation method preparation of oxygen evolution reaction catalysts described above
It is low, but still there is high analysis oxygen catalytic activity, and can guarantee oxygen evolution reaction catalysts stable in catalytic performance, Er Qiehan
There is M doped chemical, assigns Y2-xMxRu2O7Excellent conductivity.In addition, the preparation method process conditions are easily-controllable, repeatability
Good, high production efficiency effectively reduces production cost.In addition, through detecting prepared by the preparation method of the oxygen evolution reaction catalysts
Oxygen evolution reaction catalysts Y2-xMxRu2O7Partial size be 100-800nm.
In another aspect, present aspect embodiment is also on the basis of oxygen evolution reaction catalysts described above and preparation method thereof
Provide a kind of oxygen evolution reaction electrode.The oxygen evolution reaction electrode includes oxygen evolution reaction catalysts described above.In this way, due to
The content of the oxygen evolution reaction catalysts precious metal is low, and conductivity is high, and analysis oxygen catalytic activity is high, acidic environment stability
Height, and preparation method process conditions are easily-controllable, favorable repeatability.Therefore, the oxygen evolution reaction electrode economic cost is low, and analyses
Oxygen rate is high.
Further, the embodiment of the invention also provides a kind of electrochemical appliances.The electrochemical appliance includes necessary
Component such as includes anode and cathode.Wherein, the anode is oxygen evolution reaction of embodiment of the present invention electrode.Since the analysis oxygen is anti-
It answers electrode economic cost low, and analyses oxygen rate height, therefore, the cost of the electrochemical appliance water electrolysis hydrogen production is low, and efficiency
It is high.In a particular embodiment, the electrochemical appliance can be proton exchange membrane (PEM) apparatus for electrolyzing.
Another aspect, on the basis of oxygen evolution reaction electrode described above and electrochemical appliance, the embodiment of the present invention is provided
A kind of method that hydrogen and oxygen is generated by water.Described method includes following steps:
S04: the water with positive contact contained by electrochemical appliance is provided；
S05: it is powered to the electrochemical appliance, respectively on the cathode and anode of the electrochemical appliance by the water
At least part be converted to hydrogen and oxygen.
Wherein, the electrochemical appliance in step S04 is electrochemical appliance of the embodiment of the present invention above, therefore, contained by
Anode is oxygen evolution reaction of embodiment of the present invention electrode above.In this way, the anode of the electrochemical appliance contains analysis described above
Oxygen catalysts.In this way, since the method that hydrogen and oxygen is generated by water is due to using electrochemistry of the embodiment of the present invention
Device, therefore, water generate the high-efficient of hydrogen and oxygen, and economic cost is low.
Now providing multiple specific embodiments, the present invention will be described in further detail.
1. oxygen evolution reaction catalysts and preparation method thereof embodiment
Embodiment 11
Present embodiments provide a kind of oxygen evolution reaction catalysts and preparation method thereof.The oxygen evolution reaction catalysts are that burning is green
The Y of stone structure1.8Pr0.2Ru2O7。
The oxygen evolution reaction catalysts preparation method includes the following steps:
S11. by Y (NO3)3·6H2O is dissolved in deionized water, obtains the first solution, concentration 0.045molL-1。
S12. by Pr (NO3)3·6H2O is dissolved in deionized water, obtains the second solution, concentration 0.005molL-1；
S13. by RuCl3The second solution of S12 is added, obtains third solution, RuCl3Concentration be 0.05molL-1, stirring
10 minutes；
S14., citric acid is dissolved in the third solution of S13, is stirred 30 minutes, the concentration of citric acid is 0.20molL-1；
S15. by 80 DEG C of heating water baths of the solvent of S14, solvent evaporated, obtained product is put into vacuum oven, and 120 DEG C
Dry 10h；
S16. dried powder obtained in S15 is ground 20 minutes, is put into crucible, 10h, calcination temperature is calcined in air
It is 1000 DEG C.
Embodiment 12
Present embodiments provide a kind of oxygen evolution reaction catalysts and preparation method thereof.The oxygen evolution reaction catalysts are that burning is green
The Y of stone structure1.85Zn0.15Ru2O7。
The oxygen evolution reaction catalysts preparation method includes the following steps:
S11. by Y (NO3)3·6H2O is dissolved in deionized water, obtains the first solution, concentration 0.04625molL-1。
S12. by Zn (NO3)3·6H2O is dissolved in deionized water, obtains the second solution, concentration 0.00375molL-1；
S13. by RuCl3The second solution of S12 is added, obtains third solution, RuCl3Concentration be 0.05molL-1, stirring
10 minutes；
S14., citric acid is dissolved in the third solution of S13, is stirred 30 minutes, the concentration of citric acid is 0.30molL-1；
S15. by 80 DEG C of heating water baths of the solvent of S14, solvent evaporated, obtained product is put into vacuum oven, and 120 DEG C
Dry 10h；
S16. dried powder obtained in S15 is ground 20 minutes, is put into crucible, 10h, calcination temperature is calcined in air
It is 1000 DEG C.
Embodiment 13
Present embodiments provide a kind of oxygen evolution reaction catalysts and preparation method thereof.The oxygen evolution reaction catalysts are that burning is green
The Y of stone structure1.8Pr0.2Ru2O7。
The oxygen evolution reaction catalysts preparation method includes the following steps:
S11. by YCl3It is dissolved in deionized water, obtains the first solution, concentration is 0.045mol L-1。
S12. by PrCl3It is dissolved in deionized water, obtains the second solution, concentration is 0.005mol L-1；
S13. by (NH4)2RuCl6The second solution of S12 is added, obtains third solution, (NH4)2RuCl6Concentration be
0.05mol L-1, stir 10 minutes；
S14., citric acid is dissolved in the third solution of S13, is stirred 30 minutes, the concentration of ethylenediamine tetra-acetic acid is 0.20mol
L-1；
S15. by 80 DEG C of heating water baths of the solvent of S14, solvent evaporated, obtained product is put into vacuum oven, and 120 DEG C
Dry 10h；
S16. dried powder obtained in S15 is ground 20 minutes, is put into crucible, 10h, calcination temperature is calcined in air
It is 1000 DEG C.
Embodiment 14
Present embodiments provide a kind of oxygen evolution reaction catalysts and preparation method thereof.The oxygen evolution reaction catalysts are that burning is green
The Y of stone structure1.85Zn0.15Ru2O7。
S11. by Y (NO3)3·6H2O is dissolved in deionized water, obtains the first solution, concentration 0.04625molL-1。
S12. zinc acetate is dissolved in deionized water, obtains the second solution, concentration is 0.00375mol L-1；
S13. by K2RuCl5(H2O the second solution of S12) is added, obtains third solution, K2RuCl5(H2O concentration) is
0.05mol L-1, stir 10 minutes；
S14., citric acid is dissolved in the third solution of S13, is stirred 30 minutes, the concentration of citric acid is 0.30molL-1；
S15. by 80 DEG C of heating water baths of the solvent of S14, solvent evaporated, obtained product is put into vacuum oven, and 120 DEG C
Dry 10h；
S16. dried powder obtained in S15 is ground 20 minutes, is put into crucible, 8h, calcination temperature is calcined in air
It is 1200 DEG C.
Embodiment 15
Present embodiments provide a kind of oxygen evolution reaction catalysts and preparation method thereof.The oxygen evolution reaction catalysts are that burning is green
The Y of stone structure0.8Pr1.2Ru2O7。
The oxygen evolution reaction catalysts preparation method includes the following steps:
S11. by Y (NO3)3·6H2O is dissolved in deionized water, obtains the first solution, concentration 0.005molL-1。
S12. by Pr (NO3)3·6H2O is dissolved in deionized water, obtains the second solution, concentration 0.0075molL-1；
S13. by RuCl3The second solution of S12 is added, obtains third solution, RuCl3Concentration be 0.05molL-1, stirring
10 minutes；
S14., citric acid is dissolved in the third solution of S13, is stirred 30 minutes, the concentration of citric acid is 0.20molL-1；
S15. by 80 DEG C of heating water baths of the solvent of S14, solvent evaporated, obtained product is put into vacuum oven, and 120 DEG C
Dry 10h；
S16. dried powder obtained in S15 is ground 20 minutes, is put into crucible, 10h, calcination temperature is calcined in air
It is 1000 DEG C.
Comparative example 11
This comparative example provides a kind of oxygen evolution reaction catalysts and preparation method thereof.The oxygen evolution reaction catalysts are that burning is green
The Y of stone structure2Ru2O7。
The Y2Ru2O7It is prepared as follows:
S11. by Y (NO3)3·6H2O is dissolved in deionized water, obtains the first solution, concentration 0.005molL-1；
S12. by RuCl3Solution described in S11 is added, obtains the second solution, RuCl3Concentration be 0.005molL-1, stirring
10 minutes；
S13., citric acid is dissolved in the second solution of step S12, is stirred 30 minutes, the concentration of citric acid is 0.022mol L-1；
S14. by 80 DEG C of heating water baths of the solvent of S13, solvent evaporated, obtained product is put into vacuum oven, and 120 DEG C
Dry 10h；
S15. dried powder S14 obtained is ground 20 minutes, is put into crucible, 12h is calcined in air, calcination temperature is
1000℃。
Comparative example 12
Existing business IrO2Catalyst.
2. oxygen evolution reaction electrode and electrochemical appliance embodiment
Embodiment 21
The oxygen evolution reaction catalysts Y that Example 11 provides1.8Pr0.2Ru2O7Catalyst 5mg takes acetylene black 1mg, is dissolved in
In 0.7mL isopropanol and 0.3mL deionized water solution, ultrasonic 10min, the Nafion for measuring the 5wt% of 30uL with liquid-transfering gun are molten
Liquid continues ice bath and disperses 1h.8uL is taken to be coated on the glass-carbon electrode that diameter is 5mm, naturally dry.It is ginseng with standard hydrogen electrode
Than electrode, platinum guaze is three-electrode electro Chemical system to be formed, in 0.5M H to electrode2SO4In solution, lead under the conditions of nitrogen, carries out electricity
Chemical property test.
Embodiment 22
The oxygen evolution reaction catalysts Y that Example 13 provides1.85Zn0.15Ru2O7Catalyst 5mg takes acetylene black 1mg, is dissolved in
In 0.7mL isopropanol and 0.3mL deionized water solution, ultrasonic 10min, the Nafion for measuring the 5wt% of 30uL with liquid-transfering gun are molten
Liquid continues ice bath and disperses 1h.8uL is taken to be coated on the glass-carbon electrode that diameter is 5mm, naturally dry.It is ginseng with standard hydrogen electrode
Than electrode, platinum guaze is three-electrode electro Chemical system to be formed, in 0.5M H to electrode2SO4In solution, lead under the conditions of nitrogen, carries out electricity
Chemical property test.
Comparative example 21
Take Y in comparative example 112Ru2O7Catalyst 5mg takes acetylene black 1mg, is dissolved in 0.7mL isopropanol and 0.3mL deionization
In aqueous solution, ultrasonic 10min measures the Nafion solution of the 5wt% of 30uL with liquid-transfering gun, continues ice bath and disperses 1h.8uL is taken to apply
It is overlying on the glass-carbon electrode that diameter is 5mm, naturally dry.Using standard hydrogen electrode as reference electrode, platinum guaze is to electrode, composition three
Electrode electro Chemical system, in 0.5MH2SO4In solution, lead under the conditions of nitrogen, carries out electrochemical property test.
Comparative example 22
Take 12 business IrO of comparative example2Catalyst 5mg takes acetylene black 1mg, is dissolved in 0.7mL isopropanol and 0.3mL deionization
In aqueous solution, ultrasonic 10min measures the Nafion solution of the 5wt% of 30uL with liquid-transfering gun, continues ice bath and disperses 1h.8uL is taken to apply
It is overlying on the glass-carbon electrode that diameter is 5mm, naturally dry.Using standard hydrogen electrode as reference electrode, platinum guaze is to electrode, composition three
Electrode electro Chemical system, in 0.5MH2SO4In solution, lead under the conditions of nitrogen, carries out electrochemical property test.In this, as comparative sample
Product.
3. the test of correlated performance
The Y that the present embodiment 11 is provided1.8Pr0.2Ru2O7The Y prepared with comparative example 112Ru2O7Catalyst carries out X-ray powder
Last diffraction, wherein the diffraction curve of 11 product of described the present embodiment 11 and comparative example is as shown in Figure 1.As shown in Figure 1, product is urged
Agent has identical characteristic peak, is really Y1.8Pr0.2Ru2O7、Y2Ru2O7, and purity is high.Embodiment 12 is provided
Y1.85Zn0.15Ru2O7And the doped catalyst that other embodiments provide also carries out X-ray analysis, learns what each embodiment provided
Doped catalyst also has corresponding characteristic peak, is also proved to catalyst described in its corresponding molecular formula, and purity is high.
Y prepared by the present embodiment 111.8Pr0.2Ru2O7The Y that catalyst, embodiment 12 provide1.85Zn0.15Ru2O7, comparison
The Y that example 11 provides2Ru2O7The business IrO provided with comparative example 122Oxygen-separating catalyst carries out polarization test respectively, stability is surveyed
Examination, wherein the scan frequency of polarization test is 10mV s-1；The cyclic voltammetry scan number of stability test is 2000 times, scanning
Voltage range is 1.35V-1.6V, and scanning speed is 100mV s-1。
After tested, the Y that embodiment 11 provides1.8Pr0.2Ru2O7, comparative example provide Y2Ru2O7Catalyst and business IrO2's
Polarization curve is as shown in Fig. 2, as shown in Figure 2, under identical application current potential, Y1.8Pr0.2Ru2O7Current density be substantially better than
Y2Ru2O7And IrO2, and Y2Ru2O7Current density be substantially better than IrO again2.Illustrate Y1.8Pr0.2Ru2O7Chemical property ratio
Y2Ru2O7、IrO2It is excellent, but Y2Ru2O7Chemical property is better than IrO again2。
The Y that embodiment 12 provides1.85Zn0.15Ru2O7, comparative example provide Y2Ru2O7Catalyst and business IrO2Polarization it is bent
Line chart is as shown in figure 3, from the figure 3, it may be seen that under identical application current potential, Y1.85Zn0.15Ru2O7Current density be substantially better than
Y2Ru2O7And IrO2, and Y2Ru2O7Current density be substantially better than IrO again2.Illustrate Y1.85Zn0.15Ru2O7Chemical property ratio
Y2Ru2O7、IrO2It is excellent, but Y2Ru2O7Chemical property is better than IrO again2。
The Y that embodiment 11 provides1.8Pr0.2Ru2O7, comparative example provide Y2Ru2O7Catalyst and business IrO2Stability
As shown in figure 4, as shown in Figure 4, under 2000 cyclic voltammetry scans (voltage scan range: 1.1~1.6V, sweep speed:
100mV/s), Y1.8Pr0.2Ru2O7Stability be substantially better than Y2Ru2O7、IrO2, and Y2Ru2O7Stability be substantially better than again
IrO2.Illustrate Y1.8Pr0.2Ru2O7Stability ratio Y2Ru2O7、IrO2It is excellent, but Y2Ru2O7Stability is better than IrO again2。
Each catalyst that other embodiments provide is tested referring to the method for the polarization of 11 catalyst test of embodiment and stability
Corresponding polarization and stability, the characteristic close that the catalyst that each embodiment provides is presented with Fig. 2-4 respectively.
It can thus be appreciated that oxygen evolution reaction catalysts conductivity provided in an embodiment of the present invention is high, catalytic activity is high, and stability is good,
Purity is high, and preparation method is reproducible.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc. within mind and principle should all include within protection scope of the present invention.
Claims (10)
1. a kind of oxygen evolution reaction catalysts, it is characterised in that: the oxygen evolution reaction catalysts are Y2-xMxRu2O7, wherein M Pr
Or Zn, and 0 < x < 2.
2. oxygen evolution reaction catalysts according to claim 1, it is characterised in that: the Y2-xMxRu2O7Partial size be
100nm-800nm。
3. a kind of preparation method of oxygen evolution reaction catalysts, which comprises the steps of:
According to Y2-xMxRu2O7The molar ratio of middle Y, M and Ru element dissolves Y salt, M salt and Ru salt, prepares mixed solution；
Wherein, M is Pr or Zn, and 0 < x < 2；
Metal ion match is added into the mixed solution and carries out ligand reaction, then removes the solvent in mixed solution,
Obtain solid mixture；
Calcination processing is carried out in oxygen-containing atmosphere after the solid mixture is carried out dusting processing.
4. preparation method according to claim 3, it is characterised in that: the Y salt is Y (NO3)3、·6H2O, anhydrous YCl3、
YCl3·6H2At least one of O；And/or
The Ru salt is RuCl3、(NH4)2RuCl6、K2RuCl5(H2At least one of O)；And/or
When the M salt is Pr salt, the Pr salt is Pr (NO3)3、PrCl3At least one of；It is described when the M salt is Zn salt
Zn salt is at least one of zinc nitrate hexahydrate, zinc citrate, acetic anhydride zinc, two water zinc acetates.
5. preparation method according to claim 3 or 4, it is characterised in that: in the mixed solution, the Y salt it is dense
Degree is 0.001~0.1mol L-1, the concentration of the Ru salt is 0.001~0.1mol L-1, the concentration of the Pr salt is 0.001
~0.1mol L-1, the concentration of the Zn salt is 0.001~0.1mol L-1。
6. preparation method according to claim 3 or 4, it is characterised in that: the metal ion match is citric acid, second
At least one of ethylenediamine tetraacetic acid (EDTA)；And/or
The amount that the metal ion match is added in the mixed solution be the metal ion match with it is described mix it is molten
The molar ratio of Y, M and Ru metal ion total amount in liquid is (1~10): 1.
7. preparation method according to claim 3 or 4, it is characterised in that: 800-1200 DEG C of the calcination processing, time
For 6-20h.
8. a kind of oxygen evolution reaction electrode, it is characterised in that: the oxygen evolution reaction electrode includes claim 1-2 described in any item
Oxygen evolution reaction catalysts or the oxygen evolution reaction catalysts prepared by the described in any item preparation methods of claim 3-7.
9. a kind of electrochemical appliance, including anode and cathode, it is characterised in that: the anode is analysis oxygen according to any one of claims 8
Reaction electrode.
10. a kind of method that hydrogen and oxygen is generated by water, described method includes following steps:
Water with the positive contact contained by electrochemical appliance as claimed in claim 9 is provided；
It is powered to the electrochemical appliance, at least part of the water is converted to hydrogen on the cathode and anode respectively
Gas and oxygen.
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