CN111203206A - CeO (CeO)2Base electro-catalysis oxygen production catalyst and preparation method and application thereof - Google Patents
CeO (CeO)2Base electro-catalysis oxygen production catalyst and preparation method and application thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000001301 oxygen Substances 0.000 title claims abstract description 89
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 239000004744 fabric Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 238000000151 deposition Methods 0.000 claims description 17
- 238000011282 treatment Methods 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 13
- 238000009832 plasma treatment Methods 0.000 claims description 10
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims description 5
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000004005 microsphere Substances 0.000 claims description 5
- 239000002073 nanorod Substances 0.000 claims description 5
- 239000002135 nanosheet Substances 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
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Abstract
The invention relates to CeO2A base electro-catalysis oxygen-generating catalyst, a preparation method and application thereof. The invention discovers through a large amount of experiments that CeO is improved2Middle Ce3+Can remarkably improve the content of CeO2Thereby activating CeO2. CeO prepared by the invention2The catalytic oxygen production performance of the electro-catalytic oxygen production catalyst can be comparable to that of the traditional noble metal catalyst RuO2And even more efficient catalytic performance. The invention is through the use of CeO2Activation of (D) to obtain CeO2The electro-catalysis oxygen production catalyst has the advantages of lower preparation cost, simpler process and obvious economic benefit, and is very suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the field of electrocatalysis, and relates to an anode reaction catalyst for producing oxygen, in particular to CeO2A base electro-catalysis oxygen-generating catalyst, a preparation method and application thereof.
Background
The high-speed development of the society has higher and higher energy consumption, and the problems of the limited reserves of traditional fossil fuels such as petroleum, natural gas and coal, environmental pollution caused in the using process and the like force researchers to develop sustainable clean energy.
Hydrogen energy is a highly favored clean energy due to its high heat value of combustion and essentially zero pollution during use. The most environmentally friendly and promising of the hydrogen energy production technologies is hydrogen production by water electrolysis from sustainable energy sources such as wind energy and solar energy. The hydrogen production process by water electrolysis comprises a cathode reaction for producing hydrogen and an anode reaction for producing oxygen, and the oxygen production reaction involves the transfer of 4 electrons, so that more energy needs to be consumed, which is also the main reason for higher energy consumption in the hydrogen production process by water electrolysis.
In the prior art, whether the oxygen production reaction catalyst can realize industrial production mainly depends on the catalytic performance and stability of the catalyst, the material cost and the preparation cost. It is presently recognized that a relatively good oxygen-generating catalyst is the noble metal oxide RuO2And IrO2However, the high price and poor stability have restricted the use of these catalysts on a large scale.
Cerium oxide (CeO)2) Middle Ce3+And Ce4+And easily converted with each other, so that it has excellent redox properties. At the same time, oxygen vacancies will accompany the Ce3+And is formed so that it has better oxygen storage and oxygen transfer capabilities. These excellent properties have led to their widespread use including CO oxidation and NO x Thermal catalysis including selective catalytic reduction of (a). In recent years, more and more researchers have begun to apply this to electrocatalytic oxygen production reactions, and have made good progress. But CeO2Is mainly used as one component of the whole catalyst rather than being directly used as an oxygen generating catalyst, and the single component CeO2The electrocatalytic oxygen production performance of (a) is almost negligible.
Thus, only by finding CeO2To improve the intrinsic catalytic activity of CeO2Can be independently applied to electrocatalytic oxygen generation and activated CeO2When the catalyst is compounded with other oxygen producing catalysts, the overall performance of the catalyst can be further improved.
Disclosure of Invention
The invention aims to solve the problem of CeO in the prior art2The problem of no catalytic activity or weak catalytic activity in the electrocatalytic oxygen production process is solved, thereby obviously improving the CeO2So that it can be applied alone to electrocatalytic oxygen production.
In order to solve the above technical problems, the present invention is achieved by the following technical solutions.
The first aspect of the present invention provides a CeO2Based on electrocatalytic oxygen-generating catalysts comprising CeO2In which CeO is present2The following treatments were performed: adding CeO2Depositing on the surface of the carbon cloth, and activating.
Preferably, the CeO2The structure of (a) is selected from one or more of a planar structure, a porous structure, a nanosheet, a nanowire, a nanorod and a microsphere structure.
Preferably, the CeO2And depositing the carbon cloth on the surface of the carbon cloth by one or more methods selected from electroplating, hydrothermal method, coprecipitation, sol-gel and high-temperature calcination.
Preferably, the activation is selected from one or more of electrochemical treatment, hydrogen atmosphere heat treatment, oxygen atmosphere heat treatment, air atmosphere plasma treatment, and nitrogen atmosphere plasma treatment.
Preferably, the activation is performed by an oxygen atmosphere heat treatment and then a hydrogen atmosphere heat treatment.
In a second aspect, the present invention provides a CeO2The preparation method of the base electrocatalytic oxygen production catalyst comprises the following steps:
(1) adding CeO2Depositing on the surface of carbon cloth to obtain CeO2-f；
(2) For CeO2-f carrying out an activation treatment to obtain CeO2An electrocatalytic oxygen producing catalyst.
Preferably, the CeO2The structure of (a) is selected from one or more of a planar structure, a porous structure, a nanosheet, a nanowire, a nanorod and a microsphere structure.
Preferably, the CeO in the step (1)2And depositing the carbon cloth on the surface of the carbon cloth by one or more methods selected from electroplating, hydrothermal method, coprecipitation, sol-gel and high-temperature calcination.
Preferably, the activation in step (2) is selected from one or more of electrochemical treatment, hydrogen atmosphere heat treatment, oxygen atmosphere heat treatment, air atmosphere plasma treatment, and nitrogen atmosphere plasma treatment.
Preferably, the activation in step (2) is performed by first performing heat treatment in an oxygen atmosphere and then performing heat treatment in a hydrogen atmosphere.
In a third aspect, the present invention provides a CeO2Application of electro-catalytic oxygen production catalyst in electro-catalytic oxygen production, wherein the electro-catalytic oxygen production catalyst comprises CeO2In which CeO is present2The following treatments were performed: adding CeO2Depositing on the surface of the carbon cloth, and activating.
Preferably, the CeO2The structure of (a) is selected from one or more of a planar structure, a porous structure, a nanosheet, a nanowire, a nanorod and a microsphere structure.
Preferably, the CeO2And depositing the carbon cloth on the surface of the carbon cloth by one or more methods selected from electroplating, hydrothermal method, coprecipitation, sol-gel and high-temperature calcination.
Preferably, the activation is selected from one or more of electrochemical treatment, hydrogen atmosphere heat treatment, oxygen atmosphere heat treatment, air atmosphere plasma treatment, and nitrogen atmosphere plasma treatment.
Preferably, the activation is performed by an oxygen atmosphere heat treatment and then a hydrogen atmosphere heat treatment.
Generally, the method of increasing the activity of a catalyst can be achieved by increasing the number of active sites of the catalyst in addition to the intrinsic activity of the catalyst. It is a common practice to prepare nanostructures with large specific surface areas so as to expose more catalytically active sites. The invention is prepared by mixing CeO2Depositing on the surface of carbon cloth to obtain CeO2Fresh sample (CeO)2-f）；Then, for CeO2F a series of post-treatments, different modes of post-treatment giving compositions of different chemical composition (Ce)3+And Ce4+) And cerium oxides of the defect type (oxygen vacancy and cerium vacancy) having different electrocatalytic oxygen-generating intrinsic activities, the essence of which is to increase CeO2Middle Ce3+The content of (a).
Other characteristics and theoretical calculation show that Ce in cerium oxide3+The increase of the content can not only improve the conductivity of the catalyst, but also optimize the adsorption energy of an intermediate substance OH in the oxygen production reaction, thereby greatly improving the intrinsic oxygen production catalytic activity of the catalyst.
In order to further improve the oxygen generating activity, the inventors of the present invention have obtained CeO2-f calcination in an oxygen atmosphere and subsequent heat treatment in a hydrogen atmosphere to give CeO2-O2-H2The porous structure of (3). Through the treatment, the intrinsic activity of the cerium dioxide can be further improved, and more active sites are exposed, so that the oxygen generation catalytic activity of the cerium dioxide is even better than that of a precious metal catalyst RuO2. It should be understood that the above-mentioned modifications are preferred embodiments of the present invention for more significant technical effects, and are not intended to limit the present invention. The oxygen-generating catalytic activity results are shown in FIG. 5, CeO2-O2-H2The oxygen generating performance of the alloy is superior to that of CeO2-H2And also slightly higher than the noble metal catalyst RuO2。
Compared with the prior art, the invention has the following technical effects:
(1) conventional CeO2Because of poor conductivity and the like, it cannot be applied alone to electrocatalytic oxygen generation reaction, and is mainly used as one of components of the entire catalyst rather than being directly used as an oxygen generation catalyst. The invention finds CeO through a large number of experiments2By increasing CeO2Middle Ce3+Can remarkably improve the content of CeO2Further activating CeO2So that the electrocatalytic oxygen production performance is greatly improved.
(2) The electrocatalytic oxygen production catalyst prepared by the invention has catalytic productionThe oxygen performance can be compared with that of the prior noble metal catalyst RuO2And even more efficient catalytic performance.
(3) The invention is through the use of CeO2The electrocatalytic oxygen production catalyst prepared by the activation has the advantages of lower preparation cost, simpler process and obvious economic benefit, and is very suitable for industrial large-scale production.
Drawings
FIG. 1 shows CeO according to the present invention2A flow chart for preparing the electro-catalysis oxygen-generating catalyst.
FIG. 2 shows CeO prepared by different activation methods2Schematic representation of the electrocatalytic oxygen generating activity (a) and the intrinsic oxygen generating activity (b) of the base electrocatalytic oxygen generating catalyst.
FIG. 3 shows CeO2-H2Schematic plan structure under different magnification microscope.
FIG. 4 is a view of porous CeO2-O2-H2Structural schematic diagram of catalyst under different multiplying power microscope.
FIG. 5 shows CeO2Catalyst and noble metal catalyst RuO2And comparing the performance of the oxygen generation catalyst.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
CeO2-f preparation comprising the steps of:
(1) ultrasonically rinsing a commercial carbon cloth substrate in a mixed solution (30 percent by weight) of sulfuric acid and nitric acid (the volume ratio is 1: 1) for 2 hours, rinsing the rinsed carbon cloth for multiple times by using ultrapure water, and naturally drying in the air;
(2) making washed carbon cloth into electrode and soaking in CeO2Heating the solution to 70 ℃ and applying a constant current of 0.25 milliampere per square centimeter for 20 minutes, CeO2Will be generated in situ on the surface of the carbon cloth.
The CeO2The precursor solution of (2) is a mixed solution of 2 mmol of cerium nitrate and 10 mmol of sodium chloride.
Example 2
CeO (CeO)2The preparation method of the electro-catalysis oxygen generation catalyst comprises the following steps:
(1) CeO was added in the same manner as in example 12Depositing a fresh sample on the surface of the carbon cloth to obtain CeO2-f；
(2) A three-electrode system is adopted, the reference electrode is silver/silver chloride, the counter electrode is a platinum wire, and fresh CeO is adopted2(CeO2-f) as working electrode, electrolyte is 1M KOH solution;
(3) using an electrochemical workstation, CeO2-f performing 30 Cyclic Voltammetry (CV) scans at a voltage range of 1 to-0.5V relative to the reversible hydrogen electrode to produce CeO2An electrocatalytic oxygen producing catalyst;
（4）CeO2the electro-catalytic oxygen production catalyst is taken out of the solution and washed by ultrapure water for multiple times, and then is placed in the air for natural drying, and the name of the electro-catalytic oxygen production catalyst is CeO2。
Example 3
CeO (CeO)2The preparation method of the electro-catalysis oxygen generation catalyst comprises the following steps:
(1) CeO was added in the same manner as in example 12Depositing a fresh sample on the surface of the carbon cloth to obtain CeO2-f；
(2) Adding CeO2-f, placing the quartz tube in a tube furnace, and introducing 5% hydrogen/argon gas for 30 minutes to remove air in the quartz tube so that the quartz tube is filled with 5% hydrogen/argon gas;
(3) continuously introducing 5% hydrogen/argon, raising the temperature to 500 ℃ at a heating rate of 10 ℃/min, and preserving the temperature for 2 hours;
(4) after the heat preservation is finished, the sample in the quartz tube is naturally cooled to the room temperature along with the furnace, the sample is taken out after the ventilation is closed, and the sample is named as CeO2-H2。
Prepared CeO2-H2Plane junction under electron microscope with different multiplying powersAs shown in fig. 3.
Example 4
CeO (CeO)2The preparation method of the electro-catalysis oxygen generation catalyst comprises the following steps:
(1) CeO was added in the same manner as in example 12Depositing a fresh sample on the surface of the carbon cloth to obtain CeO2-f；
(2) Adding CeO2-f, placing the quartz tube in a tube furnace, and introducing high-purity oxygen for 30 minutes to remove air in the quartz tube so that the quartz tube is filled with oxygen;
(3) continuously introducing high-purity oxygen, raising the temperature to 500 ℃ at a heating rate of 10 ℃/min, and preserving the temperature for 2 hours;
(4) after the heat preservation is finished, the sample in the quartz tube is naturally cooled to the room temperature along with the furnace, the sample is taken out after the ventilation is closed, and the sample is named as CeO2-O2。
Example 5
CeO (CeO)2The preparation method of the electro-catalysis oxygen generation catalyst comprises the following steps:
(1) CeO was added in the same manner as in example 12Depositing a fresh sample on the surface of the carbon cloth to obtain CeO2-f；
(2) Adding CeO2F, placing the plasma cleaning instrument in a cavity, and vacuumizing to be lower than 300 pa;
(3) opening an air inlet valve while keeping the operation of a vacuum pump, and adjusting the vacuum degree to 400 pa;
(4) turning on the plasma and modulating the intensity to 18W, and continuing the treatment for 20 minutes; finally, the plasma and the vacuum pump are closed, and the sample is taken out after the air pressure is recovered to the standard atmospheric pressure to prepare CeO2Electrocatalytic oxygen-producing catalyst named CeO2-PL-Air。
Example 6
CeO (CeO)2The preparation method of the electro-catalysis oxygen generation catalyst comprises the following steps:
(1) CeO was added in the same manner as in example 12Depositing a fresh sample on the surface of the carbon cloth to obtain CeO2-f；
(2) C is to beeO2Placing the vacuum pump in a cavity of a plasma cleaning instrument, introducing nitrogen to purge the plasma cavity for 30 minutes, closing a nitrogen inlet valve, vacuumizing to be lower than 300pa, opening the nitrogen inlet valve, keeping the vacuum pump running, and adjusting the vacuum degree to 400 pa;
(3) turning on the plasma and modulating the intensity to 18W, and continuing the treatment for 20 minutes;
(4) closing the plasma and the vacuum pump, taking out the sample after the air pressure is recovered to the standard atmospheric pressure, and obtaining CeO2Electrocatalytic oxygen-producing catalyst named CeO2-PL-N2。
Example 7
CeO (CeO)2The preparation method of the electro-catalysis oxygen generation catalyst comprises the following steps:
(1) CeO was added in the same manner as in example 12Depositing a fresh sample on the surface of the carbon cloth to obtain CeO2-f；
(2) Referring to example 4, CeO2-f heat treatment in a tube furnace in an oxygen atmosphere for 2 hours, wherein the heat treatment temperature is 500 ℃ to obtain CeO2-O2A catalyst;
(3) referring to example 3, CeO2-O2Heat treating the catalyst in a tubular furnace in 5% hydrogen/argon atmosphere at 500 deg.c for 2 hr to obtain CeO2Electrocatalytic oxygen-producing catalyst named CeO2-O2-H2. In which porous CeO is present2-O2-H2The structural schematic diagram of the catalyst under different magnification electron microscopes is shown in fig. 4.
Verification example 1
The CeO obtained in examples 1 to 6 were taken2Detecting the oxygen production catalytic activity of the electro-catalysis oxygen production catalyst. Adopting a three-electrode test system, taking silver/silver chloride as a reference electrode, taking a platinum wire as a counter electrode, and taking fresh CeO2(CeO2CeO obtained in accordance with-f) and examples 2 to 62The electro-catalysis oxygen production catalysts are respectively used as working electrodes, the electrolyte is 1M KOH solution, an electrochemical workstation is utilized to carry out linear scanning of current along with voltage change, and the scanning speed is10 mV/s. The higher the current at the same voltage, the better the oxygen production effect of the electrolyzed water. The results of the detection are shown in FIG. 2.
The results show that CeO prepared by the present invention2，CeO2-H2And CeO2-O2Compared with the conventional CeO2An activity of almost zero, the oxygen-generating catalytic activity of which is significantly enhanced (FIG. 2 a). Especially CeO2-H2The intrinsic oxygen-generating catalytic activity (fig. 2b, activity per electrochemically active surface area) of the sample was most pronounced. Other characteristics and theoretical calculation show that Ce in cerium oxide3+The increase of the content can not only improve the conductivity of the catalyst, but also optimize the adsorption energy of an intermediate substance OH in the oxygen production reaction, thereby greatly improving the intrinsic oxygen production catalytic activity of the catalyst. CeO (CeO)2-H2It is due to the heat treatment of the hydrogen atmosphere that part of the Ce is present4+Is converted into Ce3+Thereby greatly improving the intrinsic oxygen generating performance.
Verification example 2
CeO obtained in the present invention in example 1, example 3 and example 7 was collected2Based on electrocatalytic oxygen-generating catalysts, with commercially available RuO2The catalysts were used as controls, and the oxygen production catalytic performance of each of the four catalysts was measured. Adopting a three-electrode test system, taking silver/silver chloride as a reference electrode, taking a platinum wire as a counter electrode, and taking fresh CeO2(CeO2-f) CeO prepared in examples 3 and 72Electrocatalytic oxygen generation catalyst and commercially available RuO2The catalysts are respectively used as working electrodes, the electrolyte is 1M KOH solution, an electrochemical workstation is utilized to carry out linear scanning of current along with voltage change, and the scanning speed is 10 mV/s. The higher the current at the same voltage, the better the oxygen production effect of the electrolyzed water. The results of the detection are shown in FIG. 5.
The results show that CeO prepared by the present invention2Based electrocatalytic oxygen production catalyst with RuO approximating the traditional noble metal catalyst2Electrocatalytic oxygen generating activity of (1), and CeO prepared in example 72The catalytic activity of the electro-catalysis oxygen generation catalyst is even better than RuO2Catalyst and process for preparing same. It is apparent that CeO is prepared by the present invention2The electro-catalysis oxygen production catalyst can replace the traditional noble metal catalyst to be used for electro-catalysis oxygen production reaction, and meanwhile, the preparation process is simple and the cost is low, so that the electro-catalysis oxygen production catalyst has extremely high social and economic benefits and can be suitable for industrial large-scale production.
The above detailed description section specifically describes the analysis method according to the present invention. It should be noted that the above description is only for the purpose of helping those skilled in the art better understand the method and idea of the present invention, and not for the limitation of the related contents. The present invention may be appropriately adjusted or modified by those skilled in the art without departing from the principle of the present invention, and the adjustment and modification also fall within the scope of the present invention.
Claims (10)
1. CeO (CeO)2Based on electrocatalytic oxygen-generating catalysts comprising CeO2Characterized in that the CeO2The following treatments were performed: adding CeO2Depositing on the surface of the carbon cloth, and activating.
2. The CeO of claim 12Based on an electrocatalytic oxygen-generating catalyst, characterized in that said CeO2The structure of (a) is selected from one or more of a planar structure, a porous structure, a nanosheet, a nanowire, a nanorod and a microsphere structure.
3. The CeO of claim 12Based on an electrocatalytic oxygen-generating catalyst, characterized in that said CeO2And depositing the carbon cloth on the surface of the carbon cloth by one or more methods selected from electroplating, hydrothermal method, coprecipitation, sol-gel and high-temperature calcination.
4. The CeO of claim 12The electro-catalysis oxygen generation catalyst is characterized in that the activation is selected from one or more of electrochemical treatment, hydrogen atmosphere heat treatment, oxygen atmosphere heat treatment, air atmosphere plasma treatment and nitrogen atmosphere plasma treatment.
5. The CeO of claim 42The electro-catalysis oxygen generation catalyst is characterized in that the activation is carried out by firstly carrying out heat treatment in an oxygen atmosphere and then carrying out heat treatment in a hydrogen atmosphere.
6. CeO according to any one of claims 1 to 52The preparation method of the base electrocatalytic oxygen production catalyst is characterized by comprising the following steps:
(1) adding CeO2Depositing on the surface of carbon cloth to obtain CeO2-f；
(2) For CeO2-f carrying out an activation treatment to obtain CeO2An electrocatalytic oxygen producing catalyst.
7. The method for preparing according to claim 6, wherein the CeO2The structure of (a) is selected from one or more of a planar structure, a porous structure, a nanosheet, a nanowire, a nanorod and a microsphere structure.
8. The method according to claim 6, wherein the CeO in the step (1)2And depositing the carbon cloth on the surface of the carbon cloth by one or more methods selected from electroplating, hydrothermal method, coprecipitation, sol-gel and high-temperature calcination.
9. The production method according to claim 6, wherein the activation in the step (2) is one or more selected from the group consisting of electrochemical treatment, hydrogen atmosphere heat treatment, oxygen atmosphere heat treatment, air atmosphere plasma treatment, and nitrogen atmosphere plasma treatment.
10. CeO according to any one of claims 1 to 52CeO prepared based on an electrocatalytic oxygen production catalyst or according to the preparation method of any one of claims 6 to 92Application of the base electro-catalysis oxygen generation catalyst in electro-catalysis oxygen generation.
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