CN108855112A - Perovskite oxygen-separating catalyst with high-specific surface area and preparation method thereof - Google Patents
Perovskite oxygen-separating catalyst with high-specific surface area and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 29
- 239000001301 oxygen Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 59
- 239000002994 raw material Substances 0.000 claims description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229960001484 edetic acid Drugs 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 235000015895 biscuits Nutrition 0.000 claims description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000011236 particulate material Substances 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- 235000005979 Citrus limon Nutrition 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 244000248349 Citrus limon Species 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002321 LaFeO3 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PRIDBSCVFUQJMN-UHFFFAOYSA-L [Ag+].Cl(=O)(=O)[O-].[Ag+].Cl(=O)(=O)[O-] Chemical compound [Ag+].Cl(=O)(=O)[O-].[Ag+].Cl(=O)(=O)[O-] PRIDBSCVFUQJMN-UHFFFAOYSA-L 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8474—Niobium
-
- 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
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/56—
-
- B01J35/613—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
-
- 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
Abstract
The invention discloses a kind of perovskite oxygen-separating catalyst and preparation method thereof with high-specific surface area, is the catalyst using perovskite as active component.First using solid reaction process or sol-gal process preparation synthesis perovskite catalyst SrCoxFe0.9‑ xNb0.1O3‑δ, wherein 0.4≤x≤0.6 or x=0.8, and δ indicates SrCoxFe0.9‑xNb0.1O3‑δThe Lacking oxygen of oxide, then reuses H2O2Processing.Compared with the perovskite catalyst of conventional method synthesis, have the characteristics that large specific surface area, catalytic activity are high.The method of the present invention easy realization easy to operate, the single no miscellaneous phase of the mesoporous perovskite of synthesis, can significantly decrease overpotential for oxygen evolution and take-off potential, have a good application prospect.
Description
Technical field
The present invention relates to a kind of perovskite catalysts and preparation method thereof, more particularly to a kind of perovskite oxygen-separating catalyst
And preparation method thereof, it is applied to catalysis water dissociation technology field.
Background technique
Environmental pollution and energy shortage, it has also become two hang-ups of face of mankind nowadays.All doing one's utmost to find in countries in the world
Clean energy resource and renewable energy.Hydrogen Energy because have many advantages, such as cleaning, renewable, calorific value is high, convenient for storage and transport, and it is general
All over being considered most there is prospect, can be used on a large scale as renewable energy source carrier.Water electrolysis hydrogen production existing more than 100 years
Developing history, simple process not high to equipment requirement, environmentally friendly and hydrogen purity obtained are high, be current hydrogen manufacturing are most
Feasible and environmentally friendly mode.
Electro-catalysis water decomposition reaction can be divided into evolving hydrogen reaction and oxygen evolution reaction, and wherein oxygen evolution reaction is four electronics transfer mistakes
Journey, it is the bottleneck of electrocatalytic decomposition water that more complicated and difficult than evolving hydrogen reaction two-electron shift process is more, and dynamics is slow.
Therefore the oxygen-separating catalyst of high activity must be designed to accelerate oxygen evolution reaction.Perovskite oxide is because of cheap and oxygen evolution activity
Height is considered as one of ideal oxygen-separating catalyst.
Shao's ancestor's equality uses the perovskite SrNb of solid reaction process preparation0.1Co0.7Fe0.2O3-δ, more excellent electrification is presented
Learn analysis oxygen performance.But to reach the requirement of commercial applications, it is also necessary to further increase its performance.
Improving catalyst electrochemical active surface is to improve the active effective way of Electrochemical oxygen evolution.
The report hard template method such as Oana Mihai prepares perovskite LaFeO3, specific surface area reaches 30m2g-1；Zhang Xiaohua
La is prepared for using soft template method0.6Pr0.4NiO3, specific surface area reaches 17m2g-1.But alkaline earth element is rich in for preparation
Pure phase multiple metallic element perovskite oxide (such as：AxA'1-xByB'1-yO3-δ) it is still a huge challenge, because of hard mold
The dissolution of plate can also destroy the crystal structure of perovskite.And the burning of soft template also results in form carbonate byproduct.It is rich in
The multiple metallic element perovskite oxide of alkaline earth element is difficult to prepare the perovskite with high-specific surface area, this, which becomes, urgently solves
Certainly the technical issues of.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
Perovskite oxygen-separating catalyst with high-specific surface area and preparation method thereof, using H2O2Processing analysis oxygen catalytic activity is higher
SrCoxFe0.9-xNb0.1O3-δPerovskite catalyst obtains mesoporous SrCoxFe0.9-xNb0.1O3-δ, improve its electro-chemical activity surface
Product, and then increase its Electrochemical oxygen evolution activity, to significantly decrease overpotential for oxygen evolution and take-off potential, before realizing preferably application
Scape.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of perovskite oxygen-separating catalyst with high-specific surface area has following element composition：SrCoxFe0.9- xNb0.1O3-δ, wherein 0.4≤x≤0.6 or x=0.8, and δ indicates SrCoxFe0.9-xNb0.1O3-δThe Lacking oxygen of oxide.
It is preferred that SrCoxFe0.9-xNb0.1O3-δOxide particulate material has meso-hole structure.
It is preferred that SrCoxFe0.9-xNb0.1O3-δOxide particle size is at 0.1~10 μm, and preferably specific grain surface product is not low
In 11m2g-1。
A kind of preparation method of perovskite oxygen-separating catalyst of the present invention with high-specific surface area, includes the following steps：
A. solid reaction process or sol-gal process are used, perovskite catalyst SrCo is synthesizedxFe0.9-xNb0.1O3-δPowder,
Wherein 0.4≤x≤0.6 or x=0.8, and δ indicates SrCoxFe0.9-xNb0.1O3-δThe Lacking oxygen of oxide；
B. H is used2O2Handle the SrCo prepared in the step axFe0.9-xNb0.1O3-δPowder takes in part steps a
Obtained SrCoxFe0.9-xNb0.1O3-δPowder is added to H2O2In solution, to H2O2After decomposition reaction is completed and cooled down, it will mix
Liquid is filtered, washed, dries, i.e. acquisition high-specific surface area SrCoxFe0.9-xNb0.1O3-δPowder is denoted as SrCoxFe0.9-xNb0.1O3-δ-
1；It is preferred that the H used2O2The mass fraction of solution is 20~30wt.%；It is preferred that control H2O2The decomposition reaction time is 5~30 points
Clock；Use H2O2Handle SrCoxFe0.9-xNb0.1O3-δWhen powder, preferably control SrCoxFe0.9-xNb0.1O3-δThe concentration of catalyst is not
Lower than 10g/L；
C. circulate operation is carried out by the method for the step b, can be obtained the SrCo with high-specific surface areaxFe0.9- xNb0.1O3-δ- n powder, wherein n-1 indicates the number of circulate operation, and n >=1.H is used every time2O2Handle SrCoxFe0.9- xNb0.1O3-δWhen powder, preferably control SrCoxFe0.9-xNb0.1O3-δThe concentration of catalyst is not less than 10g/L.Preferred cycle behaviour
The frequency n -1 of work is 1~6 time.
It is preferred that using solid reaction process, perovskite catalyst SrCo is synthesizedxFe0.9-xNb0.1O3-δPowder, its step are as follows：
According to SrCoxFe0.9-xNb0.1O3-δThe atomic mole fraction ratio of each component element weighs analysis pure raw material in chemical expression
SrCO3、Co3O4、Fe2O3And Nb2O5As raw material, ingredient is carried out according to certain mass ratio, i.e., according to raw material：The quality of alcohol
Than being 1：0.4, and according to raw material：The mass ratio of zirconia ball is 1：2.5 ratio measures alcohol respectively and weighs zirconia ball
As ball milling decentralized medium and fine grinding rotor, carry out the full and uniform wet-mixing of at least 48h, first ball milling, after drying 200~
250MPa depresses to circular film, then roasts biscuit at 1100~1200 DEG C, is fired into mutually laggard powder of crossing and screens, then
Secondary ball milling at least for 24 hours is carried out using planetary ball mill, diameter of particle is maintained at no more than 1um, then powder is carried out
After drying, SrCo is obtainedxFe0.9-xNb0.1O3-δPerovskite Phase powder.
It is preferred that using sol-gal process, perovskite catalyst SrCo is synthesizedxFe0.9-xNb0.1O3-δPowder, its step are as follows：
(1) according to SrCoxFe0.9-xNb0.1O3-δThe atomic mole fraction ratio of each component element weighs Sr in chemical expression
(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2O and C10H5NbO20As raw material, deionized water is added, by heating, stirring
It mixes to accelerate to and be completely dissolved, obtain metal ion solution；
(2) according to the metal ion in the metal ion solution prepared in the step (1)：Ethylenediamine tetra-acetic acid：Lemon
The molar ratio 1 of lemon acid：1：1.5 ratio weighs ethylenediamine tetra-acetic acid and citric acid and deionized water is added, heat and stir to
Organic matter dissolution, obtains organic solution；
(3) metal ion solution that will be prepared in the step (1) and and the middle organic solution prepared of the step (2)
It is mixed, and mixed liquor is moved in the water-bath not less than 85 DEG C and is stirred, then ammonia spirit is added dropwise, by the pH value of mixed liquor
7~8 are adjusted to, keeps the temperature of water-bath not less than 85 DEG C, mixed liquor is continued stirring until and is evaporated and become bronzing colloidal sol, then is put
Enter into the baking oven not less than 160 DEG C and be dried, after colloidal sol becomes spongy porosu solid, colloidal sol is moved into resistance furnace
In, temperature is risen to from room temperature not less than 380 DEG C with the heating rate not less than 2 DEG C/min, and keep the temperature at least 5 hours, then
Furnace cooling obtains presoma；Then presoma mortar grinder is uniform, it places into resistance furnace, to be not less than 2 DEG C/min
Heating rate temperature is risen to from room temperature not less than 900 DEG C, and keep the temperature at least 5 hours, subsequent furnace cooling obtains
SrCo0.8Fe0.1Nb0.1O3-δPowder.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage：
1. the present invention uses H2O2Handle the SrCo of solid reaction process or sol-gal process preparationxFe0.9-xNb0.1O3-δPowder
End makes SrCoxFe0.9-xNb0.1O3-δCatalyst surface forms porous structure, and then significantly increases its specific surface area, and synthesis has
The SrCo of high-specific surface areaxFe0.9-xNb0.1O3-δCatalyst, preparation process simply easily realize that cost of material is low, active site
Increased significantly, oxygen evolution kinetic be improved significantly, oxygen evolution activity is obviously improved；
2. the single no miscellaneous phase of the mesoporous perovskite that the present invention synthesizes, can significantly decrease overpotential for oxygen evolution and take-off potential,
It has a good application prospect；
3. the present invention is that the multiple metallic element perovskite oxide rich in alkaline earth element is prepared with high-specific surface area
Perovskite provides a kind of approach.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of perovskite catalyst in one~embodiment of case study on implementation three.
Fig. 2 is that H is used in case study on implementation one of the present invention2O2The N of the perovskite catalyst prepared after processing2Adsorption desorption curve.
Fig. 3 is that H is used in case study on implementation two of the present invention2O2The N of the perovskite catalyst prepared after processing2Adsorption desorption curve.
Fig. 4 is the N that sol-gal process prepares perovskite powder in case study on implementation three of the present invention2Adsorption desorption curve.
Fig. 5 is that H is used in case study on implementation three of the present invention2O2The N of the perovskite catalyst prepared after processing2Adsorption desorption curve.
Fig. 6 is the linear sweep voltammetry curve of one perovskite catalyst of the preferred embodiment of the present invention.
Fig. 7 is the linear sweep voltammetry curve of two perovskite catalyst of the preferred embodiment of the present invention.
Fig. 8 is the linear sweep voltammetry curve of three perovskite catalyst of the preferred embodiment of the present invention.
Specific embodiment
Above scheme is described further below in conjunction with specific implementation example, the preferred embodiment of the present invention is described in detail such as
Under：
Embodiment one
In the present embodiment, a kind of perovskite oxygen-separating catalyst with high-specific surface area has following element composition：
SrCo0.6Fe0.3Nb0.1O3-δ, δ expression SrCo0.6Fe0.3Nb0.1O3-δThe Lacking oxygen of oxide.SrCo0.6Fe0.3Nb0.1O3-δOxidation
Composition granule material has meso-hole structure.SrCo0.6Fe0.3Nb0.1O3-δOxide particle size is 5.5 μm, and specific grain surface product is
11.28m2g-1。
A kind of preparation method of perovskite oxygen-separating catalyst of the present embodiment with high-specific surface area, using solid reaction process
Synthesize perovskite catalyst SrCo0.6Fe0.3Nb0.1O3-δ, then reuse H2O2Processing obtains mesoporous perovskite, obtains Gao Bibiao
Area includes the following steps：
A. solid reaction process is used, perovskite catalyst SrCo is synthesized0.6Fe0.3Nb0.1O3-δPowder, its step are as follows：It presses
According to SrCo0.6Fe0.3Nb0.1O3-δThe atomic mole fraction ratio of each component element weighs analysis pure raw material SrCO in chemical expression3、
Co3O4、Fe2O3And Nb2O5As raw material, ingredient is carried out according to certain mass ratio, i.e., according to raw material：The mass ratio of alcohol is 1：
0.4, and according to raw material：The mass ratio of zirconia ball is 1：2.5 ratio measures alcohol respectively and weighs zirconia ball as ball
Decentralized medium and fine grinding rotor are ground, is pushed after carrying out the full and uniform wet-mixing of 48h, first ball milling, drying in 200~250MPa
At circular film, then biscuit is roasted at 1100 DEG C, be fired into it is mutually laggard cross powder screening, recycle planetary ball mill into
The secondary ball milling of row for 24 hours, is maintained at diameter of particle no more than 1um, after then powder is dried, obtains
SrCo0.6Fe0.3Nb0.1O3-δPerovskite Phase powder；
B. taking 100ml mass percent concentration is the H of 30wt.%2O2Solution is added into the beaker of 1000ml, uses
H2O2Handle the SrCo prepared in the step a0.6Fe0.3Nb0.1O3-δPowder takes obtained in 1g step a
SrCo0.6Fe0.3Nb0.1O3-δPowder is added to H2O2In solution, to H2O2It is more with circulating water type after decomposition reaction is completed and cooled down
It is washed with vacuum pump suction filtration, deionized water, places into drying 1 hour in 100 DEG C of baking ovens, i.e. acquisition high-specific surface area
SrCo0.6Fe0.3Nb0.1O3-δPowder is denoted as SrCo0.6Fe0.3Nb0.1O3-δ-1。
Embodiment two
The present embodiment is basically the same as the first embodiment, and is particular in that：
In the present embodiment, a kind of perovskite oxygen-separating catalyst with high-specific surface area has following element composition：
SrCo0.4Fe0.5Nb0.1O3-δ, δ expression SrCo0.4Fe0.5Nb0.1O3-δThe Lacking oxygen of oxide.SrCo0.4Fe0.5Nb0.1O3-δOxidation
Composition granule material has meso-hole structure.SrCo0.4Fe0.5Nb0.1O3-δOxide particle size is 4.7 μm, and specific grain surface product is
13.46m2g-1。
A kind of preparation method of perovskite oxygen-separating catalyst of the present embodiment with high-specific surface area, using solid reaction process
Synthesize perovskite catalyst SrCo0.4Fe0.5Nb0.1O3-δ, then reuse H2O2Processing obtains mesoporous perovskite, obtains Gao Bibiao
Area includes the following steps：
A. solid reaction process is used, perovskite catalyst SrCo is synthesized0.4Fe0.5Nb0.1O3-δPowder, its step are as follows：It presses
According to SrCo0.4Fe0.5Nb0.1O3-δThe atomic mole fraction ratio of each component element weighs analysis pure raw material SrCO in chemical expression3、
Co3O4、Fe2O3And Nb2O5As raw material, ingredient is carried out according to certain mass ratio, i.e., according to raw material：The mass ratio of alcohol is 1：
0.4, and according to raw material：The mass ratio of zirconia ball is 1：2.5 ratio measures alcohol respectively and weighs zirconia ball as ball
Decentralized medium and fine grinding rotor are ground, is pushed after carrying out the full and uniform wet-mixing of 48h, first ball milling, drying in 200~250MPa
At circular film, then biscuit is roasted at 1100 DEG C, be fired into it is mutually laggard cross powder screening, recycle planetary ball mill into
The secondary ball milling of row for 24 hours, is maintained at diameter of particle no more than 1um, after then powder is dried, obtains
SrCo0.4Fe0.5Nb0.1O3-δPerovskite Phase powder；
B. taking 100ml mass percent concentration is the H of 30wt.%2O2Solution is added into the beaker of 1000ml, uses
H2O2Handle the SrCo prepared in the step a0.6Fe0.3Nb0.1O3-δPowder takes obtained in 1g step a
SrCo0.4Fe0.5Nb0.1O3-δPowder is added to H2O2In solution, to H2O2It is more with circulating water type after decomposition reaction is completed and cooled down
It is washed with vacuum pump suction filtration, deionized water, places into drying 1 hour in 100 DEG C of baking ovens, i.e. acquisition high-specific surface area
SrCo0.4Fe0.5Nb0.1O3-δPowder；
C. it is carried out again circulate operation 1 time by the method for the step b, that is, obtaining has high-specific surface area
SrCo0.4Fe0.5Nb0.1O3-δPowder, and each H2O2Handle SrCo0.4Fe0.5Nb0.1O3-δWhen powder,
SrCo0.4Fe0.5Nb0.1O3-δAnd H2O2Mixed system in SrCo0.4Fe0.5Nb0.1O3-δConcentration be 10g/L, obtain Gao Bibiao
Area SrCo0.4Fe0.5Nb0.1O3-δ- 2 powder.
Embodiment three
The present embodiment is basically the same as the first embodiment, and is particular in that：
In the present embodiment, a kind of perovskite oxygen-separating catalyst with high-specific surface area has following element composition：
SrCo0.8Fe0.1Nb0.1O3-δPowder, δ indicate SrCo0.8Fe0.1Nb0.1O3-δThe Lacking oxygen of powder oxide.SrCo0.8Fe0.1Nb0.1O3-δ
Powder oxide particulate material has meso-hole structure.SrCo0.8Fe0.1Nb0.1O3-δPowder oxide particle size is 0.2 μm, particle ratio
Surface area is 20.94m2g-1。
A kind of preparation method of perovskite oxygen-separating catalyst of the present embodiment with high-specific surface area, using collosol and gel
Method synthesizes perovskite catalyst SrCo0.8Fe0.1Nb0.1O3-δThen powder reuses H2O2Processing obtains mesoporous perovskite, obtains
High-specific surface area, its step are as follows：
(1) according to SrCo0.8Fe0.1Nb0.1O3-δThe atomic mole fraction ratio of each component element weighs in chemical expression
21.417g Sr(NO3)2、23.562g Co(NO3)2·6H2O、4.088g Fe(NO3)3·9H2O and 5.445g C10H5NbO20
It is put into the beaker of 800ml as raw material, 200ml deionized water is added, is completely dissolved, is obtained by heating, stirring to accelerate to
To metal ion solution；
(2) according to the metal ion in the metal ion solution prepared in the step (1)：Ethylenediamine tetra-acetic acid：Lemon
The molar ratio 1 of lemon acid：1：1.5 ratio, weighs 59.149g ethylenediamine tetra-acetic acid and 58.334g citric acid is added to another
In the beaker of 800ml, and 200ml deionized water is added, heats and stir to organic matter and dissolve, obtain organic solution；
(3) metal ion solution that will be prepared in the step (1) and and the middle organic solution prepared of the step (2)
It is mixed, and mixed liquor is moved in 85 DEG C of water-bath and stirred, then ammonia spirit is added dropwise, the pH value of mixed liquor is adjusted to 7
~8,85 DEG C of temperature of water-bath are kept, mixed liquor is continued stirring until and is evaporated and become bronzing colloidal sol, are placed into 160 DEG C
It is dried in baking oven, after colloidal sol becomes spongy porosu solid, colloidal sol is moved in resistance furnace, with the heating of 2 DEG C/min
Temperature is risen to 380 DEG C from room temperature by rate, and keeps the temperature 5 hours, and subsequent furnace cooling obtains presoma；Then by presoma with grinding
Alms bowl grinding uniformly, places into resistance furnace, temperature is risen to 900 DEG C from room temperature with the heating rate of 2 DEG C/min, and it is small to keep the temperature 5
When, subsequent furnace cooling, i.e. acquisition SrCo0.8Fe0.1Nb0.1O3-δPowder.
(4) taking 100ml mass percent concentration is the H of 30wt.%2O2Solution is added into the beaker of 1000ml, uses
H2O2Handle the SrCo prepared in the step (3)0.8Fe0.1Nb0.1O3-δPowder takes obtained in 1g step (3)
SrCo0.8Fe0.1Nb0.1O3-δPowder is added to H2O2In solution, to H2O2It is more with circulating water type after decomposition reaction is completed and cooled down
It is washed with vacuum pump suction filtration, deionized water, places into drying 1 hour in 100 DEG C of baking ovens, i.e. acquisition high-specific surface area
SrCo0.8Fe0.1Nb0.1O3-δPowder；
(5) it is carried out again circulate operation 5 times by the method for the step (4), that is, obtaining has high-specific surface area
SrCo0.8Fe0.1Nb0.1O3-δPowder, and each H2O2Handle SrCo0.8Fe0.1Nb0.1O3-δWhen powder,
SrCo0.8Fe0.1Nb0.1O3-δAnd H2O2Mixed system in SrCo0.8Fe0.1Nb0.1O3-δConcentration be 10g/L, obtain Gao Bibiao
Area SrCo0.8Fe0.1Nb0.1O3-δ- 5 powder.
Experimental test and analysis：
The intermediate products Perovskite Phase powder prepared to the above embodiment of the present invention and the high-specific surface area calcium finally prepared
Titanium ore powder carries out experimental test and analysis, referring to X-ray diffraction (XRD) map of Fig. 1 perovskite catalyst it is found that H2O2Processing
Front and back perovskite powders still remain single perovskite structure, have no miscellaneous phase generation.
One, perovskite specific surface area evaluation experimental：
At -196 DEG C, using N2Adsorption desorption instrument (Micromeritics ASAP 2020), uses Brunauer-Emmett-
Teller (BET) method calculates the specific surface area of catalyst；As shown in Fig. 2, H2O2One perovskite of Processing Example
SrCo0.6Fe0.3Nb0.1O3-δAfter catalyst, the specific surface area of perovskite has reached 11.28m2g-1.As shown in figure 3, H2O2Processing is real
Apply two perovskite SrCo of example0.4Fe0.5Nb0.1O3-δAfter catalyst 2 times, the specific surface area of perovskite has reached 13.46m2g-1.Such as figure
Shown in 4-5, H2O2Three perovskite SrCo of Processing Example0.8Fe0.1Nb0.1O3-δAfter catalyst 5 times, the specific surface area of perovskite is aobvious
It writes and increases, specific surface area reaches 20.94m2g-1, reach 10 times before handling.Using in one~implementation of case study on implementation three of the present invention
Perovskite catalyst, then reuse H2O2Processing obtains mesoporous perovskite, obtains high-specific surface area.
Two, perovskite analyses oxygen henchnmrk test：
1. the preparation of catalyst pulp：The catalyst fines of equivalent and conductive carbon are taken to be distributed to ethyl alcohol and concentration as 5wt.%
Nafion mixed liquor in, then ultrasonic vibration makes it be uniformly dispersed to obtain catalyst pulp；
2. electric grade preparation：A certain amount of black liquid is taken to be supported on rotation glass carbon electricity with micropipettor in the slurry of above-mentioned preparation
In grade, natural air drying；
The oxygen evolution activity of catalyst is tested：The electric grade prepared is subjected to electro-chemical test in rotating circular disk electricity grade.
Three, electrochemistry experiment：
Electrochemical Test Procedure is as follows：
1. electrochemical measurement system is three-electrode system, i.e., glass carbon electricity grade is working electrode, and platinized platinum electricity grade is to electrode, silver
Silver chlorate is reference electrode, and electrolyte is 0.1M KOH solution；
2. being passed through oxygen before electro-chemical test into electrolyte reaches oxygen saturation state into electrolyte, and is testing
It is all carried out under oxygen atmosphere in journey；
The oxygen evolution activity of catalyst is tested to evaluate using linear sweep voltammetry, and voltage scan range is 0.2~1.0V, sweeps
Retouching speed is 5mv/s, rotation speed 1600rmp.
As shown in figs 6-8, H2O2Treated all perovskite catalysts are 10mA/cm in current density2When overpotential
It is substantially reduced with take-off potential, this shows H2O2Treated, and above-described embodiment perovskite can significantly improve its Electrochemical oxygen evolution
Energy.
In short, the above embodiment of the present invention has the perovskite oxygen-separating catalyst of high-specific surface area, it is with perovskite for work
The catalyst of property component.First using solid reaction process or sol-gal process preparation synthesis perovskite catalyst SrCoxFe0.9- xNb0.1O3-δ, then x=0.4,0.6 or 0.8 reuses H2O2Processing.Compared with the perovskite catalyst of conventional method synthesis,
Have the characteristics that large specific surface area, catalytic activity are high.The method of the present invention easy realization easy to operate, the mesoporous perovskite of synthesis are single
Without miscellaneous phase, overpotential for oxygen evolution and take-off potential can be significantly decreased, is had a good application prospect.
The embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can also be according to this hair
The purpose of bright innovation and creation makes a variety of variations, and that does under the Spirit Essence and principle of all technical solutions according to the present invention changes
Become, modification, substitution, combination or simplified, should be equivalent substitute mode, as long as meeting goal of the invention of the invention, as long as not
There is the technical principle and inventive concept of perovskite oxygen-separating catalyst of high-specific surface area and preparation method thereof away from the present invention, all
It belongs to the scope of protection of the present invention.
Claims (10)
1. a kind of perovskite oxygen-separating catalyst with high-specific surface area, which is characterized in that have following element composition：
SrCoxFe0.9-xNb0.1O3-δ, wherein 0.4≤x≤0.6 or x=0.8, and δ indicates SrCoxFe0.9-xNb0.1O3-δOxide
Lacking oxygen.
2. according to claim 1 with the perovskite oxygen-separating catalyst of high-specific surface area, it is characterised in that：SrCoxFe0.9- xNb0.1O3-δOxide particulate material has meso-hole structure.
3. according to claim 1 with the perovskite oxygen-separating catalyst of high-specific surface area, it is characterised in that：SrCoxFe0.9- xNb0.1O3-δFor oxide particle size at 0.1~10 μm, specific grain surface product is not less than 11m2g-1。
4. a kind of preparation method of the perovskite oxygen-separating catalyst with high-specific surface area, which is characterized in that include the following steps：
A. solid reaction process or sol-gal process are used, perovskite catalyst SrCo is synthesizedxFe0.9-xNb0.1O3-δPowder, wherein
0.4≤x≤0.6 or x=0.8, and δ indicates SrCoxFe0.9-xNb0.1O3-δThe Lacking oxygen of oxide；
B. H is used2O2Handle the SrCo prepared in the step axFe0.9-xNb0.1O3-δPowder takes in part steps a and obtains
SrCoxFe0.9-xNb0.1O3-δPowder is added to H2O2In solution, to H2O2After decomposition reaction is completed and cooled down, by mixed liquor mistake
Filter, washing, dry, i.e. acquisition high-specific surface area SrCoxFe0.9-xNb0.1O3-δPowder is denoted as SrCoxFe0.9-xNb0.1O3-δ-1；
C. circulate operation is carried out by the method for the step b, can be obtained the SrCo with high-specific surface areaxFe0.9- xNb0.1O3-δ- n powder, wherein n-1 indicates the number of circulate operation, and n >=1.
5. the preparation method of the perovskite oxygen-separating catalyst with high-specific surface area according to claim 4, it is characterised in that：
In the step b, the H of use2O2The mass fraction of solution is 20~30wt.%.
6. the preparation method of the perovskite oxygen-separating catalyst with high-specific surface area according to claim 4, it is characterised in that：
In the step b, H is controlled2O2The decomposition reaction time is 5~30 minutes.
7. the preparation method of the perovskite oxygen-separating catalyst with high-specific surface area according to claim 4, it is characterised in that：
In the step b or in the step c, H is used every time2O2Handle SrCoxFe0.9-xNb0.1O3-δWhen powder, control
SrCoxFe0.9-xNb0.1O3-δThe concentration of catalyst is not less than 10g/L.
8. the preparation method of the perovskite oxygen-separating catalyst with high-specific surface area according to claim 4, it is characterised in that：
In the step c, the frequency n -1 of the circulate operation is 1~6 time.
9. the preparation method of the perovskite oxygen-separating catalyst with high-specific surface area according to claim 4, which is characterized in that
In the step c, using solid reaction process, perovskite catalyst SrCo is synthesizedxFe0.9-xNb0.1O3-δPowder, step is such as
Under：According to SrCoxFe0.9-xNb0.1O3-δThe atomic mole fraction ratio of each component element weighs analysis pure raw material in chemical expression
SrCO3、Co3O4、Fe2O3And Nb2O5As raw material, ingredient is carried out according to certain mass ratio, i.e., according to raw material：The quality of alcohol
Than being 1：0.4, and according to raw material：The mass ratio of zirconia ball is 1：2.5 ratio measures alcohol respectively and weighs zirconia ball
As ball milling decentralized medium and fine grinding rotor, carry out the full and uniform wet-mixing of at least 48h, first ball milling, after drying 200~
250MPa depresses to circular film, then roasts biscuit at 1100~1200 DEG C, is fired into mutually laggard powder of crossing and screens, then
Secondary ball milling at least for 24 hours is carried out using planetary ball mill, diameter of particle is maintained at no more than 1um, then powder is carried out
After drying, SrCo is obtainedxFe0.9-xNb0.1O3-δPerovskite Phase powder.
10. the preparation method of the perovskite oxygen-separating catalyst with high-specific surface area, feature exist according to claim 4
In in the step c, using sol-gal process, synthesis perovskite catalyst SrCoxFe0.9-xNb0.1O3-δPowder, step
It is as follows：
(1) according to SrCoxFe0.9-xNb0.1O3-δThe atomic mole fraction ratio of each component element weighs Sr in chemical expression
(NO3)2、Co(NO3)2·6H2O、Fe(NO3)3·9H2O and C10H5NbO20As raw material, deionized water is added, by heating, stirring
It mixes to accelerate to and be completely dissolved, obtain metal ion solution；
(2) according to the metal ion in the metal ion solution prepared in the step (1)：Ethylenediamine tetra-acetic acid：Citric acid
Molar ratio 1：1：1.5 ratio weighs ethylenediamine tetra-acetic acid and citric acid and deionized water is added, and heats and stirs to organic
Object dissolution, obtains organic solution；
(3) it the metal ion solution of preparation will be carried out with the organic solution prepared in the step (2) in the step (1)
Mixing, and mixed liquor is moved in the water-bath not less than 85 DEG C and is stirred, then ammonia spirit is added dropwise, the pH value of mixed liquor is adjusted to
7~8, it keeps the temperature of water-bath not less than 85 DEG C, continues stirring until mixed liquor and be evaporated and become bronzing colloidal sol, place into
It is dried in baking oven not less than 160 DEG C, after colloidal sol becomes spongy porosu solid, colloidal sol is moved in resistance furnace, with
Heating rate not less than 2 DEG C/min rises to temperature not less than 380 DEG C from room temperature, and keeps the temperature at least 5 hours, then cold with furnace
But presoma is obtained；Then presoma mortar grinder is uniform, it places into resistance furnace, to be not less than the heating of 2 DEG C/min
Rate rises to temperature not less than 900 DEG C from room temperature, and keeps the temperature at least 5 hours, subsequent furnace cooling obtains
SrCo0.8Fe0.1Nb0.1O3-δPowder.
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| CN109745987A (en) * | 2018-12-13 | 2019-05-14 | 大连海事大学 | The preparation method and application of strontium cobalt-based properties of perovskite mixed-oxide oxygen carrier |
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| CN115074747A (en) * | 2021-03-12 | 2022-09-20 | 中国科学院物理研究所 | Quadruple perovskite oxide, preparation method and application thereof, and method for electrolyzing water |
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