CN110280237A - A kind of perovskite oxide for hydrogen reduction catalysis reaction of microwave method preparation - Google Patents
A kind of perovskite oxide for hydrogen reduction catalysis reaction of microwave method preparation Download PDFInfo
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- CN110280237A CN110280237A CN201910628058.3A CN201910628058A CN110280237A CN 110280237 A CN110280237 A CN 110280237A CN 201910628058 A CN201910628058 A CN 201910628058A CN 110280237 A CN110280237 A CN 110280237A
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- hydrogen reduction
- perovskite oxide
- method preparation
- catalysis reaction
- microwave method
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000009467 reduction Effects 0.000 title claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000001257 hydrogen Substances 0.000 title claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000008139 complexing agent Substances 0.000 claims abstract description 7
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 6
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 5
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 27
- 238000009768 microwave sintering Methods 0.000 abstract description 7
- 239000008151 electrolyte solution Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- 238000010924 continuous production Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910002075 lanthanum strontium manganite Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000009770 conventional sintering Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910003417 La0.2Sr0.8 Inorganic materials 0.000 description 2
- 229910003367 La0.5Sr0.5MnO3 Inorganic materials 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000452 restraining effect Effects 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B01J35/33—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of perovskite oxides for hydrogen reduction catalysis reaction of microwave method preparation, the following steps are included: deionized water is added in beaker, open stirring, sequentially add metal salt, organic complexing agent is stirred to after being completely dissolved, pH adjusting agent is added, mixed solution, heating, stirring is until gel-forming, by gel drying, solid matter is obtained, is sintered 1~10 minute using 600 DEG C in microwave agglomerating furnace, can be prepared by the perovskite oxide for hydrogen reduction catalysis reaction of the microwave method preparation.Compared with traditional sintering processing, microwave sintering not only reduces sintering time, sintering temperature is reduced by a larger margin, 200 DEG C are reduced at phase temperature, it is energy saving, more conducively automation, continuous production, and the hydrogen reduction performance of perovskite oxide is higher than 800 DEG C of resulting properties of sample of sintering of tradition in alkaline electrolyte solution.
Description
Technical field
The invention belongs to electro-catalysis field, the hydrogen reduction that is used for for relating in particular to a kind of microwave method preparation is catalyzed reaction
Perovskite oxide.
Background technique
Modern society, the crises day such as shortage of resources, environmental pollution such as haze, acid rain, greenhouse effects that fossil energy causes
Become obvious, in order to solve this kind of crisis, is badly in need of exploitation cleaning, environmental protection, the efficient energy.Currently available clean energy resource is main
Including wind energy, water energy, solar energy, nuclear energy.However, the deterioration of the serious ecological environment of hydroelectric generation bring, nuclear energy there is
The risk of leakage, wind energy, the intermittence of solar energy and the excessive utilization rate of occupied area are too low, these all hinder this kind of energy
Further development.Therefore developing novel energy storage and converting system is necessary.Metal-air battery has
The energy density of superelevation, fuel cell are not limited the energy conversion efficiency with superelevation by Carnot cycle, these two types of batteries by
More and more concerns are arrived.Although the mechanism of these two types of batteries is different, oxygen reduction reaction all occurs for their cathodes.
Oxygen reduction reaction is that cathode surface oxygen reduction is water (acidic electrolyte bath) or hydroxyl (alkalinity during discharge
Electrolyte) process.Oxygen reduction reaction is extremely complex, and dynamics is sluggish, is fuel cell and metal-air battery into one
Walk one of the most important restraining factors of development.Therefore, research oxygen reduction reaction to fuel cell and metal-air battery be to
It closes important.Generally acknowledged best oxygen reduction reaction catalyst is precious metal based catalysts at present, but precious metal based catalysts
Expensive, resource scarcity, and easily occur catalyst poisoning phenomena such as, therefore, research base metal class hydrogen reduction catalysis
Agent material just becomes very significant.
La1-xSrxMnO3(0 < x < 1) (LSM) is a kind of deficiency perovskite oxygen of Typical cations non-stoichiometric
Compound has efficient hydrogen reduction catalytic performance in alkaline electrolyte solution, is that one kind has promising base metal very much
Catalyst.But the sintering of usually LSM is carried out in traditional calcining furnace, sintering temperature is generally at 800 DEG C or more, sintering
2~10h of time, the sintering of long-time high temperature lead to the contact of LSM with electrolyte solution and oxygen so that the crystal grain of LSM becomes larger
Area becomes smaller, and reduces the oxygen reduction activity of material.The loss that another aspect high temperature is sintered electric energy for a long time is very big.
Microwave sintering is a kind of new material sintering process, it has the advantages that heating rate is fast, energy utilization rate is high.It passes
Unite sintering processing be to transfer heat to be heated sample by modes such as convection current, conduction or radiation, the process of heating be by
Outside in, therefore, sintering time is long, and crystallite dimension is big.Microwave sintering is the subtle knot of the special wave band and material using microwave
Structure couples and generates the sintering processing of heat, is a kind of whole heating method.And the presence of microwave reduces the work of reaction
Change can, thereby reduce material at Xiang Wendu, be easy to get the crystal grain of small size.
For these reasons, the present invention is prepared for hydrogen reduction used in alkaline electrolyte solution using microwave sintering method and urges
Change material La1-xSrxMnO3(0 < x < 1).Compared with traditional sintering processing, microwave sintering not only reduces sintering time, more
Sintering temperature is considerably reduced, energy saving at 200 DEG C of phase temperature reduction, more conducively automation, continuous production, and
The hydrogen reduction performance of perovskite oxide is higher than 800 DEG C of resulting properties of sample of sintering of tradition in alkaline electrolyte solution.
Summary of the invention
For various deficiencies of the prior art, the perovskite oxide for hydrogen reduction catalysis reaction is now disclosed, with tradition
Sintering processing compare, microwave sintering not only reduces sintering time, reduce sintering temperature by a larger margin, at phase temperature reduce
It is 200 DEG C, energy saving, more conducively automation, continuous production, and in alkaline electrolyte solution perovskite oxide oxygen also
Originality can be higher than 800 DEG C of resulting properties of sample of sintering of tradition.
To achieve the above object, the invention provides the following technical scheme:
A kind of perovskite oxide for hydrogen reduction catalysis reaction of microwave method preparation, comprising the following steps:
(1) deionized water is added in beaker, opens stirring and sequentially adds metal after revolving speed is 150~500 revs/min
Salt, organic complexing agent are stirred to after being completely dissolved, and pH adjusting agent is added, and are adjusted pH value as 7~10 and are obtained mixed solution；
(2) mixed solution that step (1) obtains is warming up to 70~100 DEG C, revolving speed is adjusted to 400~800 revs/min, stirs
It mixes until gel-forming, by gel, the drying at 160~190 DEG C, obtains solid matter；
(3) step (2) resulting solid matter is sintered 1~10 minute using 600 DEG C in microwave agglomerating furnace
The perovskite oxide for hydrogen reduction catalysis reaction of the microwave method preparation is made.
The additional amount of metal salt is 0.1~1mol in the step (1), and the additional amount of organic complexing agent is 0.1~3mol,
The additional amount of deionized water is 100-10000g.
As a kind of embodiment of the invention, the metal salt in the step (1) is lanthanum nitrate, strontium nitrate and manganese nitrate
Mixture.
As an alternate embodiment of the invention, the metal salt in the step (1) is lanthanum acetate, strontium acetate and second
The mixture of sour manganese.
Organic complexing agent in the step (1) is one of citric acid, ethanedioic acid tetraacethyl, tartaric acid and malic acid
Or two kinds.
PH adjusting agent is one or both of ammonium hydroxide, sodium hydroxide, potassium hydroxide and ethylenediamine in the step (1).
The beneficial effects of the present invention are:
Using microwave-assisted sintering, sintering time is not only reduced, reduces sintering temperature by a larger margin, it is energy saving,
More conducively automation, continuous production, and the crystallite dimension of products obtained therefrom is small, by a relatively large margin to improve alkaline electrolyte molten
The hydrogen reduction performance of perovskite oxide in liquid.
Detailed description of the invention
Fig. 1 is the M-La that embodiment three provides0.5Sr0.5MnO3- 3 and T-La0.5Sr0.5MnO3-1、T-La0.5Sr0.5MnO3-
2、T-La0.5Sr0.5MnO3The XRD spectra of -3 XRD spectra.
Fig. 2 is the M-La that embodiment three provides0.5Sr0.5MnO3- 3 and T-La0.5Sr0.5MnO3-1、T-La0.5Sr0.5MnO3-
2、T-La0.5Sr0.5MnO3- 3 LSV curve.
Fig. 3 is the M-La that embodiment three provides0.5Sr0.5MnO3- 3 and T-La0.5Sr0.5MnO3-1、T-La0.5Sr0.5MnO3-
2、T-La0.5Sr0.5MnO3- 3 electronics transfer number curve.
Fig. 4 is the M-La that embodiment three provides0.5Sr0.5MnO3- 3 and T-La0.5Sr0.5MnO3-1、T-La0.5Sr0.5MnO3-
2、T-La0.5Sr0.5MnO3- 3 hydrogen peroxide generation rate curve.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
A kind of perovskite oxide for hydrogen reduction catalysis reaction of the microwave method of embodiment one preparation
The following steps are included:
(1) 100g is gone to be added in beaker from water, opens stirring and is sequentially added after revolving speed is 300 revs/min
The lanthanum nitrate of 0.01mol, the strontium nitrate of 0.04mol, the manganese nitrate of 0.05mol and 0.15mol citric acid stir to completely molten
Ammonium hydroxide is added in Xie Hou, adjusts pH value as 8 and obtains mixed solution；
(2) mixed solution that step (1) obtains is warming up to 80 DEG C, revolving speed is adjusted to 600 revs/min, and stirring is until gel
It is formed, gel is dry at 160 DEG C, obtain solid matter；
(3) step (2) resulting solid matter is carried out 600 DEG C using microwave agglomerating furnace to be sintered 1 minute, can be prepared by institute
The perovskite oxide for stating microwave method preparation, is denoted as M-La0.2Sr0.8MnO3-1。
A kind of perovskite oxide for hydrogen reduction catalysis reaction of the microwave method of embodiment two preparation
The following steps are included:
(1) 100g is gone to be added in beaker from water, opens stirring and is sequentially added after revolving speed is 300 revs/min
The lanthanum nitrate of 0.015mol, 0.035mol strontium nitrate, the nitric acid of 0.05mol and 0.3mol tartaric acid stir to being completely dissolved
Afterwards, ammonium hydroxide is added, adjusts pH value as 8 and obtains mixed solution；
(2) mixed solution that step (1) obtains being warming up to 80 DEG C, revolving speed is adjusted to 600 revs/min, until gel-forming,
Gel is dry at 160 DEG C, obtain solid matter；
(3) step (2) resulting solid matter is carried out 600 DEG C using microwave agglomerating furnace to be sintered 3 minutes, can be prepared by institute
The perovskite oxide for stating microwave method preparation, is denoted as M-La0.3Sr0.7MnO3-2。
A kind of perovskite oxide for hydrogen reduction catalysis reaction of the microwave method of embodiment three preparation
The following steps are included:
(1) 100g is gone to be added in beaker from water, opens stirring and is sequentially added after revolving speed is 300 revs/min
The lanthanum nitrate of 0.02mol, the strontium nitrate of 0.02mol, the manganese nitrate of 0.04mol and 0.2mol citric acid stir to being completely dissolved
Afterwards, ammonium hydroxide is added, adjusts pH value as 8 and obtains mixed solution；
(2) mixed solution that step (1) obtains being warming up to 80 DEG C, revolving speed is adjusted to 600 revs/min, until gel-forming,
Gel is dry at 160 DEG C, obtain solid matter；
(3) step (2) resulting solid matter is carried out 600 DEG C using microwave agglomerating furnace to be sintered 10 minutes, can be prepared by
The perovskite oxide of the microwave method preparation, is denoted as M-La0.5Sr0.5MnO3-3。
A kind of perovskite oxide for hydrogen reduction catalysis reaction of microwave method preparation of example IV
The following steps are included:
(1) 100g is gone to be added in beaker from water, opens stirring and is sequentially added after revolving speed is 300 revs/min
The lanthanum acetate of 0.02mol, the strontium acetate of 0.02mol, the manganese acetate of 0.04mol and 0.2mol citric acid stir to being completely dissolved
Afterwards, ammonium hydroxide is added, adjusts pH value as 8 and obtains mixed solution；
(2) mixed solution that step (1) obtains being warming up to 80 DEG C, revolving speed is adjusted to 600 revs/min, until gel-forming,
Gel is dry at 160 DEG C, obtain solid matter；
(3) step (2) obtained solid matter utilization microwave agglomerating furnace is carried out 600 DEG C to be sintered 6 minutes, is can be prepared by described
The perovskite oxide of microwave method preparation, is denoted as M-La0.5Sr0.5MnO3-4。
A kind of perovskite oxide for hydrogen reduction catalysis reaction of the microwave method of embodiment five preparation
The following steps are included:
(1) 100g is gone to be added in beaker from water, opens stirring and is sequentially added after revolving speed is 300 revs/min
The lanthanum acetate of 0.03mol, the strontium acetate of 0.02mol, the manganese acetate of 0.05mol and 0.3mol tartaric acid stir to being completely dissolved
Afterwards, ammonium hydroxide is added, adjusts pH value as 8 and obtains mixed solution；
(2) mixed solution that step (1) obtains being warming up to 80 DEG C, revolving speed is adjusted to 600 revs/min, until gel-forming,
Gel is dry at 160 DEG C, obtain solid matter；
(3) step (2) resulting solid matter is carried out 600 DEG C using microwave agglomerating furnace to be sintered 10 minutes, can be prepared by
The perovskite oxide of the microwave method preparation, is denoted as M-La0.6Sr0.4MnO3-5。
A kind of perovskite oxide for hydrogen reduction catalysis reaction of the microwave method of embodiment six preparation
The following steps are included:
(1) 100g is gone to be added in beaker from water, opens stirring and is sequentially added after revolving speed is 300 revs/min
The lanthanum acetate of 0.01mol, the strontium acetate of 0.04mol, the manganese acetate of 0.05mol and 0.15mol citric acid stir to completely molten
Sodium hydroxide is added in Xie Hou, adjusts pH value as 8 and obtains mixed solution；
(2) mixed solution that step (1) obtains being warming up to 80 DEG C, revolving speed is adjusted to 600 revs/min, until gel-forming,
Gel is dry at 160 DEG C, obtain solid matter；
(3) step (1) resulting solid matter is carried out 600 DEG C using microwave agglomerating furnace to be sintered 10 minutes, can be prepared by
The perovskite oxide of the microwave method preparation, is denoted as M-La0.2Sr0.8MnO3-6。
A kind of perovskite oxide of comparative example one
Conventional sintering method specific steps:
(1) 100g is gone to be added in beaker from water, opens stirring and is sequentially added after revolving speed is 300 revs/min
The lanthanum nitrate of 0.02mol, the strontium nitrate of 0.02mol, the manganese nitrate of 0.04mol and 0.2mol citric acid stir to being completely dissolved
Afterwards, ammonium hydroxide is added, adjusts pH value as 8 and obtains mixed solution；
(2) mixed solution that step (1) obtains being warming up to 80 DEG C, revolving speed is adjusted to 600 revs/min, until gel-forming,
Gel is dry at 160 DEG C, obtain solid matter；
(3) step (2) resulting solid matter is carried out 600 DEG C using Muffle furnace to be sintered 2 hours, is denoted as T-
La0.5Sr0.5MnO3-1。
A kind of perovskite oxide of comparative example two
Preparation method is substantially with comparative example one, and with being a difference in that for comparative example one: sintering temperature is 700 DEG C, is denoted as T-
La0.5Sr0.5MnO3-2。
A kind of perovskite oxide of comparative example three
Preparation method with comparative example one, is 800 DEG C and is denoted as T- with being a difference in that for comparative example one: sintering temperature substantially
La0.5Sr0.5MnO3-3。
Test example
The M-La obtained using embodiment three0.5Sr0.5MnO3-3.600,700 in the way of conventional sintering, burnt at 800 DEG C
Tie obtained T-La0.5Sr0.5MnO3-1、T-La0.5Sr0.5MnO3-2、T-La0.5Sr0.5MnO3-3.Pass through the XRD spectra point of Fig. 1
Analysis is it is known that M-La0.5Sr0.5MnO3- 3 have apparent perovskite structure, and miscellaneous phase is not present.But conventional sintering is 600
℃(T-La0.5Sr0.5MnO3- 1) not at phase.(T-La at 700 DEG C0.5Sr0.5MnO3- 2) there are miscellaneous peak, Xiang Buchun.(T- at 800 DEG C
La0.5Sr0.5MnO3- 3) perovskite oxide of pure phase is just obtained.This illustrates that microwave sintering can significantly reduce perovskite
At Xiang Wendu, reduce sintering time, reduce sintering temperature, can significantly reduce energy consumption.Utilize rotating circular disk electricity
Pole test hydrogen reduction catalytic performance obtains the LSV curve of Fig. 2, finds M-La0.5Sr0.5MnO3- 3 have highest take-off potential and
Limiting current density.Further test discovery M-La0.5Sr0.5MnO3- 3 electron transfer numbers are closest to 4 electronics transfers (Fig. 3), mistake
Hydrogen oxide generation rate is minimum (Fig. 4), this illustrates that microwave method prepares La0.5Sr0.5MnO3Can by a relatively large margin raising material oxygen
Reducing property.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (6)
1. a kind of perovskite oxide for hydrogen reduction catalysis reaction of microwave method preparation, which is characterized in that including following step
It is rapid:
(1) 100~10000g deionized water is added in beaker, opens stirring, after revolving speed is 150~500 revs/min, successively
Addition metal salt, organic complexing agent are stirred to after being completely dissolved, and pH adjusting agent is added, and adjusting pH value obtains mixing molten for 7~10
Liquid；
(2) mixed solution that step (1) obtains is warming up to 70~100 DEG C, revolving speed is adjusted to 400~800 revs/min, and stirring is straight
It is to gel-forming, gel is dry at 160~190 DEG C, obtain solid matter；
(3) step (2) resulting solid matter is sintered 1~10 minute using 600 DEG C in microwave agglomerating furnace, is can be prepared by
The perovskite oxide for hydrogen reduction catalysis reaction of the microwave method preparation.
2. the perovskite oxide for hydrogen reduction catalysis reaction of microwave method preparation according to claim 1, feature
It is, the additional amount of metal salt is 0.1~1mol in the step (2), and the additional amount of organic complexing agent is 0.1~3mol, is gone
The additive amount of ionized water is 100~10000g.
3. the perovskite oxide for hydrogen reduction catalysis reaction of microwave method preparation according to claim 2, feature
It is, metal salt is the mixture of lanthanum nitrate, strontium nitrate and manganese nitrate in the step (2).
4. the perovskite oxide for hydrogen reduction catalysis reaction of microwave method preparation according to claim 2, feature
It is, metal salt is the mixture of lanthanum acetate, strontium acetate and manganese acetate in the step (2).
5. the perovskite oxide for hydrogen reduction catalysis reaction of microwave method preparation according to claim 1, feature
It is, organic complexing agent is one of citric acid, ethanedioic acid tetraacethyl, tartaric acid and malic acid or two in the step (2)
Kind.
6. the perovskite oxide for hydrogen reduction catalysis reaction of microwave method preparation according to claim 1, feature
It is, pH adjusting agent is one or both of ammonium hydroxide, sodium hydroxide, potassium hydroxide and ethylenediamine in the step (3).
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