CN108786828A - Redox reaction catalyst with perovskite structure and its preparation method and application - Google Patents
Redox reaction catalyst with perovskite structure and its preparation method and application Download PDFInfo
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- 238000006479 redox reaction Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 14
- 229910003047 LaxSr1 − xCoO3 − δ Inorganic materials 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 229910002449 CoO3−δ Inorganic materials 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 11
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 239000000446 fuel Substances 0.000 claims abstract description 8
- 238000004549 pulsed laser deposition Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 229910018307 LaxSr1−x Inorganic materials 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 46
- 239000001301 oxygen Substances 0.000 claims description 46
- 229910019653 Mg1/3Nb2/3 Inorganic materials 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 229910002244 LaAlO3 Inorganic materials 0.000 claims description 27
- 238000000151 deposition Methods 0.000 claims description 24
- 230000008021 deposition Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000004062 sedimentation Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 11
- 238000011946 reduction process Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 229910003781 PbTiO3 Inorganic materials 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 6
- 229910002902 BiFeO3 Inorganic materials 0.000 claims description 5
- 229910002534 DyScO3 Inorganic materials 0.000 claims description 5
- 229910003200 NdGaO3 Inorganic materials 0.000 claims description 5
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 5
- 229910002113 barium titanate Inorganic materials 0.000 claims description 5
- 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 5
- 238000005516 engineering process Methods 0.000 claims description 5
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 5
- 229910002938 (Ba,Sr)TiO3 Inorganic materials 0.000 claims description 4
- 229910002340 LaNiO3 Inorganic materials 0.000 claims description 4
- 229910020294 Pb(Zr,Ti)O3 Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 1
- 229910052571 earthenware Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 160
- 239000010409 thin film Substances 0.000 description 21
- 150000002500 ions Chemical class 0.000 description 14
- 238000006722 reduction reaction Methods 0.000 description 14
- 230000032258 transport Effects 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005389 magnetism Effects 0.000 description 4
- GPAAEXYTRXIWHR-UHFFFAOYSA-N (1-methylpiperidin-1-ium-1-yl)methanesulfonate Chemical compound [O-]S(=O)(=O)C[N+]1(C)CCCCC1 GPAAEXYTRXIWHR-UHFFFAOYSA-N 0.000 description 3
- 241000238366 Cephalopoda Species 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002183 La0.7Sr0.3CoO3-δ Inorganic materials 0.000 description 1
- 229910002341 LaNiO3(001) Inorganic materials 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910002398 SrCoOx Inorganic materials 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 239000013589 supplement Substances 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
- 210000003462 vein Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J23/83—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 rare earths or actinides
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- 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
- B01J23/835—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 germanium, tin or lead
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- 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
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- B01J23/8437—Bismuth
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Abstract
The present invention provides a kind of redox reaction catalyst and its preparation method and application with perovskite structure, and the catalyst is the La being deposited on substratexSr1‑xCoO3‑δFilm, wherein 0.5≤x≤0.9,0<δ<1.5.The preparation method includes:Prepare LaxSr1‑xCoO3Target;Using pulsed laser deposition, so that target made from step 1) is orientated in (001) face of substrate, (011) face or its beveling and deposit, form LaxSr1‑xCoO3‑δFilm.Advantage of the invention is that:Perovskite oxide reduction temperature is down to room temperature, perovskite oxide oxidizing temperature is decreased to less than 100 DEG C.Preparation method is simple with design, operability is strong, low in energy consumption, manufacturing cost is low, is conducive to the practical application of material.Such controllable redox reaction material has specific use and significance in the fields such as redox reaction catalysis, fuel cell, chemical sensor.
Description
Technical field
The present invention relates to a kind of novel redox reaction catalyst with perovskite structure and preparation method thereof and answer
With.
Background technology
With the development of human society, problem of environmental pollution and energy shortage problem are more and more severeer.The oxygen of carbon monoxide
Change and water decomposition is most important for the exploration of environmental Kuznets Curves and regenerative resource.Currently, rare metal is because of its higher catalysis
Activity and be widely studied.However in practical applications, high cost and the factors such as rare metal resources are rare, constrain such material
The business application of material.We are badly in need of developing a kind of high catalytic activity and low-cost catalyst.
In recent years, perovskite oxide is due to its high catalytic activity, low cost, extensive element selection and environmental-friendly etc.
Plurality of advantages causes the extensive concern of people, becomes a kind of emerging redox reaction catalyst.As perovskite knot
The SrCoO of structure redox material research hotspot3-δThe difference of middle Co ionic oxide formations state shows apparent magneto-electric behavior difference.Tool
There is the SrCoO of perovskite structure3-δMetallic character is presented, restores the SrCoO with brownmillerite structure of generation2.5It shows good
Insulation behavior, but its reduction temperature is up to 700 DEG C.In SrCoOxAfter part Sr is replaced with La in material, generating has calcium titanium
The La of mine structure0.5Sr0.5CoO3(LSCO) material, by mixing (LSCO with a high proportion of urea:Urea=1:2) and in 550-
After being calcined through a large amount of Lacking oxygens of chemical reaction introducing at 650 DEG C, this La can be made0.5Sr0.5CoO3-δThe oxidation activity of mixture
Temperature is down to 150-200 DEG C.
La with perovskite structurexSr1-xCoO3-δFor oxide under theoretical stoichiometric ratio, Electrical transport embodies gold
Category behavior, with the reduction of oxygen atom ratio, oxygen vacancy concentration is gradually increasing, and Electrical transport embodies semiconductor behavior.?
LaxSr1-xCoO3-δDue to La in oxide3+And Sr2+Presence, there are Co in material3+And Co4+The ion of two kinds of valence states, Co4+
Ion is in low spin state (t2g 5eg 0), it is unfavorable for and O2-Ions binding, O2-Ion is thus from LaxSr1-xCoO3-δIn oxide
Flowing abjection, forms and is in middle spin (t2g 5eg 1) or high-spin (t2g 4eg 2) Co3+Ion, the Co of upper state4+Ion tends to
To more stable Co3+Ion or Co2+Ion transit.Therefore LaxSr1-xCoO3-δOxide is easy to happen redox reaction,
All there is huge application value in numerous areas such as redox reaction catalysis, fuel cell, chemical sensors.
However currently, redox reaction catalyst there are still catalytic activity low, poor controllability, manufacturing cost height etc. lacks
The application range of point, many catalysis materials is extremely restricted.LaxSr1-xCoO3-δAs the catalyst of redox reaction, tool
There are catalytic activity height, the selection of the high and low cost of controllability, stable structure, extensive element and many advantages such as environmental-friendly, if right
Its redox reaction warm area extends to more low temperature even room temperature and finds its preferable control method, LaxSr1-xCoO3-δMaterial
It is potential that there is more wide application prospect in fields such as redox catalysis, fuel cell, chemical sensors.
Invention content
Inventor has found by a lot of research work, mixes excessive La, prepares having for generation and stablizes perovskite structure
LaxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) film shows the characteristic extremely sensitive to stress, membrane stress tune
Oxygen mobility in the lower material of control substantially enhances, to make redox reaction temperature further decrease.
Inventor is by depositing LaxSr1-xCoO3-δThe mode of epitaxial film answers material introducing using thin film technique
Power, discovery apply electric current under the temperature cycles environment of room temperature to low temperature (20K), and with the process O can occur for material2-Ion
Flowing and abjection, to realize LaxSr1-xCoO3-δReduction reaction occurs at room temperature for material.The Electrical transport of material also by
Metal behavior is to semiconductor behaviorism theory.In LaxSr1-xCoO3-δIn perovskite oxide, there are Co3+And Co4+Two kinds of valence states
Ion.However Co4+Ion energy higher, it is intended to more stable Co3+Ion transit.In LaxSr1-xCoO3-δPerovskite structure
Oxide in, O2-Ionic radius is minimum, and mobility is most strong.System can pass through O2-Ion flow or the mode of abjection make Co4+
Ion transit is Co3+Ion, to reduce maximum system energy.Due to energy very little needed for the process, by the film of substrate stress
CoO occurs6Octahedra lattice field distortion can also occur, La at room temperature so as to cause the reduction processxSr1-xCoO3-δOxide
Also it is gradually converted into oxygen debt reduction-state.Accordingly, due to O2-Ion good mobility in the film, LaxSr1-xCoO3-δIt is thin
(≤100 DEG C) can be realized the oxidation process of film at a lower temperature.In the environment of 100 DEG C of pure oxygens, it is in reduction-state
LaxSr1-xCoO3-δFilm can be oxidized to original state, to realize primary complete redox reaction process.
The present invention passes through to LaxSr1-xCoO3-δThe method that perovskite oxide introduces stress using thin film technique, is gone back
Former reaction temperature is adjusted to room temperature, can accurately and easily be regulated and controled to reduction reaction process by electric current, for actually answering
With being of great significance.
Therefore, the purpose of the present invention is to provide a kind of novel redox reaction catalysis material with perovskite structure and
The application of preparation method and the material in the fields such as redox catalysis, fuel cell, chemical sensor.
In order to help to understand the present invention, some terms are defined below.Other terms used herein have this hair
The bright normally understood meaning of those of ordinary skill in the related art.
Unstable state Electrical transport of the present invention refers to film when carrying out temperature cycles electronic transport and measuring, with survey
The increase of number is measured, film resistor gradually increases, and metal behavior corresponds to warm area and becomes narrow gradually, metal-to-semiconductor transition temperature
Gradually to high-temperature mobile.
The purpose of the present invention is what is realized by the following technical solutions.
The present invention provides a kind of redox reaction catalyst with perovskite structure, the catalyst is to be deposited on
La on substratexSr1-xCoO3-δFilm, wherein 0.5≤x≤0.9,0<δ<1.5.
According to catalyst provided by the invention, wherein the thickness of the film can be 1~500nm, preferably 10~
200nm。
According to catalyst provided by the invention, wherein the substrate is (LaAlO3)0.3(SrAl0.5TaO3)0.7、yPb
(Mg1/3Nb2/3)O3-(1-y)PbTiO3(0.8<y<0.5)、LaAlO3、SrTiO3、NdGaO3、LaNiO3、DyScO3、NdScO3、
MgO、Pb(Zr,Ti)O3、(Ba,Sr)TiO3、BiFeO3、BaTiO3And PbTiO3In one kind.
According to catalyst provided by the invention, wherein the film be deposited on (001) face of the substrate, (011) face or
It, which chamfers, is orientated.
According to catalyst provided by the invention, wherein the thickness of the substrate can be 0.05~1mm.
In addition the present invention also provides the preparation method of above-mentioned redox reaction catalyst, the preparation method includes:
1) La is preparedxSr1-xCoO3Target, wherein 0.5≤x≤0.9;
2) apply pulsed laser deposition, make target made from step 1) (001) face of substrate, (011) face or its tiltedly
Upward deposition is cut, La is formedxSr1-xCoO3-δFilm, wherein 0.5≤x≤0.9,0<δ<1.5.
According to preparation method provided by the invention, wherein step 1) prepares La using solid sintering technologyxSr1-xCoO3Target.
In a preferred embodiment, the solid sintering technology includes:Raw material La is weighed according to atomic molar ratio2O3、
SrCO3And Co3O4, it is put into crucible and carries out baking material;It is taken out while hot after baking, being fully ground makes it uniformly mix;It then will grinding
Obtained powder, which is put into crucible, to be placed in Muffle furnace, in 800~1000 DEG C of 5~15h of pre-burning;Products therefrom is through abundant again
24~36h is calcined after grinding at 1100~1300 DEG C;It carries out third time again to be fully ground, then die mould, and 1200~1400
DEG C 32~40h of sintering obtains the LaxSr1-xCoO3Target.
According to preparation method provided by the invention, wherein the substrate is (LaAlO3)0.3(SrAl0.5TaO3)0.7、yPb
(Mg1/3Nb2/3)O3-(1-y)PbTiO3(0.8<y<0.5)、LaAlO3、SrTiO3、NdGaO3、LaNiO3、DyScO3、NdScO3、
MgO、Pb(Zr,Ti)O3、(Ba,Sr)TiO3、BiFeO3、BaTiO3And PbTiO3In one kind.
According to preparation method provided by the invention, wherein the condition of pulsed laser deposition described in step 2) includes:Arteries and veins
Impulse light energy is 50~800mJ;The distance between substrate and target are 20~80mm;Film deposition temperature is 600~900
℃;Back end vacuum degree is less than 5 × 10-4Pa;Oxygen pressure is 10-2~200Pa;Preferably, the pulsed laser deposition is heavy
The product time is 1~60 minute, more preferably 5~45 minutes;Pulse laser frequency can be 1~12Hz, preferably 2~8Hz.Its
In, the back end vacuum degree refers to:The front cavity of film growth vacuumizes the corresponding air pressure of reached maximum vacuum.
Preferably, the step 2) further includes:To the end of film is grown, 10-4~105In the oxygen or air atmosphere of Pa
It is cooled to room temperature.Oxygen pressure by controlling film growth and temperature-fall period controls LaxSr1-xCoO3-δThe oxygen content of film,
Make 0<δ<1.5.
The present invention also provides above-mentioned redox reaction catalyst or according to redox made from the method for the present invention
Application of the catalysts in the fields such as redox reaction catalysis, fuel cell, chemical sensor.
According to application provided by the invention, wherein the oxide-reduction method of the catalyst is respectively:
Reduction process:In LaxSr1-xCoO3-δElectrode is prepared on film, later to film 1~10 μ A electric current 20~
Temperature cycles are carried out in 320K warm areas, you can realize LaxSr1-xCoO3-δThe reduction of film.Can by observe resistance variations can
Monitor LaxSr1-xCoO3-δThe reduction process of film;
Oxidation process:Using tube furnace by the La in reduction-statexSr1-xCoO3-δFilm moves back under air or pure oxygen
Fire, you can make film oxidation to original state.Preferably, annealing conditions include:Atmospheric condition is the standard atmospheric pressures of 0.01Pa~1
Pure oxygen or air, oxidizing temperature≤100 DEG C, oxidization time≤1 hour.
Compared with prior art, advantage of the invention is that:Perovskite oxide reduction temperature is down to room temperature, by calcium titanium
Mine oxides temperature is decreased to less than 100 DEG C.La is deposited on monocrystal chip using impulse laser deposition systemxSr1- xCoO3-δFilm, the substrate with different lattice constants can be to LaxSr1-xCoO3-δFilm applies the stress of different type and degree,
The membrane stress of introducing leads to CoO6Octahedra crystal field generates corresponding distortion, accelerated material O2-Ion deviates from process.Pass through control
Electric current processed can accurately and easily regulate and control redox reaction process, LaxSr1-xCoO3-δThe preparation method of thin-film material
With design is simple, operability is strong, low in energy consumption, manufacturing cost is low, be conducive to the practical application of material.Such controllable oxidation
Reduction reaction material has specific use and important in the fields such as redox reaction catalysis, fuel cell, chemical sensor
Meaning.
Description of the drawings
Hereinafter, carry out the embodiment that the present invention will be described in detail in conjunction with attached drawing, wherein:
Fig. 1 is La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film
The XRD spectral lines acquired at room temperature;
Fig. 2 is La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film
(222) the crystal face reciprocal space collection of illustrative plates (RSM) acquired at room temperature;
Fig. 3 is La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film
(013) the crystal face reciprocal space collection of illustrative plates (RSM) acquired at room temperature;
Fig. 4 is La made from embodiment 20.7Sr0.3CoO2.75/(LaAlO3)0.3(SrAl0.5TaO3)0.7(100) film is in room
The lower XRD spectral lines acquired of temperature;
Fig. 5 is La made from embodiment 30.7Sr0.3CoO2.89/LaAlO3(100) the XRD spectral lines that film acquires at room temperature;
Fig. 6 is La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film
Intensity of magnetization at a temperature of 10K is with change of magnetic field strength curve;
Fig. 7 is La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film
Heating thermomagnetization curve under 500Oe magnetic field intensities;
Fig. 8 is La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film
The direction [01-1] resistance varies with temperature curve;
Fig. 9 is La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film
[100] direction resistance varies with temperature curve;
Figure 10 is La made from embodiment 20.7Sr0.3CoO2.75/(LaAlO3)0.3(SrAl0.5TaO3)0.7(100) film
[001] direction resistance varies with temperature curve;
Figure 11 is La made from embodiment 30.7Sr0.3CoO2.89/LaAlO3(100) film [001] direction resistance becomes with temperature
Change curve;
Figure 12 is La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film
Before annealing (rectangular) direction (circle) [01-1] resistivity varies with temperature correlation curve afterwards;
Figure 13 is La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film
The direction [01-1] resistivity varies with temperature curve after annealing.
Specific implementation mode
The present invention is further described in detail With reference to embodiment, the embodiment provided is only for explaining
The bright present invention, the range being not intended to be limiting of the invention.
The raw material that is used in embodiment and equipment are described as follows:
1) impulse laser deposition system used in the embodiment of the present invention produces for Shenyang scientific instrument manufactory, model:
PLD-IV type impulse laser deposition systems;Cu-K α target X-ray diffractometers are respectively the RINT2400 types X of Rigaku companies production
The four circular single crystal X-ray diffractometer of D8Discover types of x ray diffractometer x and the production of German Brooker company;Superconductive quantum interference
Vibrating specimen magnetometer (MPMS (SQUID) VSM) produces, model MPMS for Quantum Design (USA) company
(SQUID)VSM。
2) raw materials used La in the embodiment of the present invention2O3、SrCO3、Co3O4It is commercialization oxide.La2O3Purity is
99.999wt%;SrCO3Purity is 99.99wt%;Co3O4Purity is 99.9985wt%, and the above raw material is purchased from A Faai
Sha (China) Chemical Co., Ltd..
La in embodimentxSr1-xCoO3-δThe preparation method of film is as follows:
1) La is preparedxSr1-xCoO3(0.5≤x≤0.9) target.
LaxSr1-xCoO3(0.5≤x≤0.9) target is prepared by high temperature solid-phase sintering method, first by raw material La2O3、
SrCO3And Co3O4, the required quality of each raw material is calculated than the purity with raw material according to atomic molar, is counted according to aforementioned proportion
The quality calculated weighs raw material, is respectively put into the crucible cleaned up and carries out baking material.It is taken out while hot after having toasted, fully
Grinding makes it uniformly mix.Then it puts the powder into the crucible cleaned up and is placed in Muffle furnace, at 900 DEG C first
Secondary pre-burning 10h.Products therefrom calcines 30h after being fully ground again at 1200 DEG C.It carries out third time again to be fully ground, then root
Die mould is carried out according to required size, the target diameter about 30mm that we use, thickness about 3.5mm are obtained after being sintered 36h in 1300 DEG C
Target needed for obtaining.
2) La is preparedxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) film.
With acetone and washes of absolute alcohol 2) described in substrate, polishing wiping chip bench, substrate is pasted onto base with elargol
On piece platform, it is placed on warm table and toasts 15 minutes.By baked chip bench (posting substrate) and 1) in obtained LaxSr1- xCoO3Target is fitted into deposition chamber, is opened mechanical pump and molecular pump successively, is waited for that air pressure is down to 10-4When Pa, heating system is opened
System, target temperature is heated to by chip bench.It is then filled with oxygen, it is 10 to make oxygen pressure in cavity-2~200Pa, utilizes pulse laser
Deposition technique on the substrate described in 2), deposits LaxSr1-xCoO3-δFilm.To the end of film is grown, 10-4~105Pa's
It is cooled to room temperature in oxygen or air atmosphere.Oxygen pressure by controlling film growth and temperature-fall period controls LaxSr1- xCoO3-δThe oxygen content of film, makes 0<δ<1.5.
The condition of the pulsed laser deposition technique includes:Pulsed laser energy is 50~800mJ;Pulse laser frequency is
1~12Hz;The distance between monocrystal chip and target are 20~80mm;Film deposition temperature is 600~900 DEG C;Back end vacuum
Degree is less than 5 × 10-4Pa;Oxygen pressure is 10-2~200Pa;Sedimentation time is 1~60 minute.
Oxidation-reduction process and method are as follows:
1) reduction process
In the La preparedxSr1-xCoO3-δElectrode is prepared on film, later to film under certain applied current a constant temperature
Temperature cycles are carried out in area, you can realize LaxSr1-xCoO3-δThe reduction of film can monitor La by observing resistance variationsxSr1- xCoO3-δThe reduction process of film.Temperature cycles section is 20~320K, and applied current is 1~10 μ A.
2) oxidation process
Using tube furnace by the La in reduction-statexSr1-xCoO3-δFilm is annealed under air or pure oxygen, you can is made thin
Film is oxidizing to original state.Annealing conditions:Atmospheric condition be the standard atmospheric pressures of 0.01Pa~1 pure oxygen or air, oxidizing temperature≤
100 DEG C, oxidization time≤1 hour.
Embodiment 1
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.7, δ=0.25), substrate for use are that (011) is orientated
0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3, pulsed laser energy is 295mJ in step 2);Pulse laser frequency is 3Hz;Monocrystalline
The distance between substrate and target are 55mm;Film deposition temperature is 740 DEG C;Back end vacuum degree 2 × 10-4Pa;Oxygen pressure is
1Pa;Sedimentation time is 15 minutes;To the end of film is grown, it is cooled to room temperature in the oxygen atmosphere of 1Pa.The thickness of film is
50nm。
Embodiment 2
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.7, δ=0.25), substrate for use are that (001) is orientated
(LaAlO3)0.3(SrAl0.5TaO3)0.7, pulsed laser energy is 295mJ in step 2);Pulse laser frequency is 3Hz;Monocrystalline base
The distance between piece and target are 55mm;Film deposition temperature is 740 DEG C;Back end vacuum degree 2 × 10-4Pa;Oxygen pressure is
1Pa;Sedimentation time is 15 minutes;To the end of film is grown, it is cooled to room temperature in the oxygen atmosphere of 1Pa.The thickness of film is
50nm。
Embodiment 3
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.7, δ=0.11), substrate for use are that (001) is orientated
LaAlO3, pulsed laser energy is 295mJ in step 2);Pulse laser frequency is 3Hz;The distance between monocrystal chip and target
For 55mm;Film deposition temperature is 740 DEG C;Back end vacuum degree 2 × 10-4Pa;Oxygen pressure is 10Pa;Sedimentation time is 15 points
Clock;To the end of film is grown, it is cooled to room temperature in the oxygen atmosphere of 10Pa.The thickness of film is 30nm.
Embodiment 4
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.9, δ=0.01), substrate for use are that (111) are orientated
SrTiO3, pulsed laser energy is 800mJ in step 2);Pulse laser frequency is 12Hz;Between monocrystal chip and target away from
From for 20mm;Film deposition temperature is 900 DEG C;Back end vacuum degree 5 × 10-4Pa;Oxygen pressure is 200Pa;Sedimentation time is 1
Minute;To the end of film is grown, 105It is cooled to room temperature in the oxygen atmosphere of Pa.The thickness of film is 20nm.
Embodiment 5
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.8, δ=0.03), substrate for use are that (001) is orientated
NdGaO3, pulsed laser energy is 650mJ in step 2);Pulse laser frequency is 8Hz;The distance between monocrystal chip and target
For 30mm;Film deposition temperature is 800 DEG C;Back end vacuum degree 2 × 10-4Pa;Oxygen pressure is 100Pa;Sedimentation time is 3 points
Clock;To the end of film is grown, 105It is cooled to room temperature in the air atmosphere of Pa.The thickness of film is 350nm.
Embodiment 6
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.7, δ=0.36), selected substrate are that (001) is orientated
LaNiO3, pulsed laser energy is 215mJ in step 2);Pulse laser frequency is 2Hz;The distance between monocrystal chip and target
For 45mm;Film deposition temperature is 750 DEG C;Back end vacuum degree 2 × 10-4Pa;Oxygen pressure is 0.1Pa;Sedimentation time is 30 points
Clock;To the end of film is grown, it is cooled to room temperature in the oxygen atmosphere of 0.1Pa.The thickness of film is 500nm.
Embodiment 7
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.6, δ=0.39), selected substrate are that (001) is orientated
DyScO3, pulsed laser energy is 215mJ in step 2);Pulse laser frequency is 2Hz;The distance between monocrystal chip and target
For 45mm;Film deposition temperature is 750 DEG C;Back end vacuum degree 2 × 10-4Pa;Oxygen pressure is 0.1Pa;Sedimentation time is 30 points
Clock;To the end of film is grown, it is cooled to room temperature in the oxygen atmosphere of 0.1Pa.The thickness of film is 400nm.
Embodiment 8
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.6, δ=0.45), selected substrate are that (001) is orientated
NdScO3, pulsed laser energy is 215mJ in step 2);Pulse laser frequency is 2Hz;The distance between monocrystal chip and target
For 45mm;Film deposition temperature is 600 DEG C;Back end vacuum degree 2 × 10-4Pa;Oxygen pressure is 0.1Pa;Sedimentation time is 30 points
Clock;To the end of film is grown, it is cooled to room temperature in the oxygen atmosphere of 0.1Pa.The thickness of film is 80nm.
Embodiment 9
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.5, δ=1.49), selected substrate are the MgO that (001) is orientated,
Pulsed laser energy is 50mJ;Pulse laser frequency is 1Hz;The distance between monocrystal chip and target are 80mm;Film deposits
Temperature is 750 DEG C;Back end vacuum degree 5 × 10-5Pa;Oxygen pressure is 10-2Pa;Sedimentation time is 60 minutes;Wait for film grown junction
Beam, 10-4It is cooled to room temperature in the oxygen atmosphere of Pa.The thickness of film is 2nm.
Embodiment 10
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.5, δ=0.97), selected substrate are the Pb that (001) is orientated
(Zr,Ti)O3, pulsed laser energy is 215mJ in step 2);Pulse laser frequency is 2Hz;Between monocrystal chip and target
Distance is 50mm;Film deposition temperature is 750 DEG C;Back end vacuum degree 1 × 10-4Pa;Oxygen pressure is 10-2Pa;Sedimentation time is
45 minutes;To the end of film is grown, 10-3It is cooled to room temperature in the oxygen atmosphere of Pa.The thickness of film is 150nm.
Embodiment 11
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.5, δ=0.63), selected substrate be (001) be orientated (Ba,
Sr)TiO3, pulsed laser energy is 255mJ in step 2);Pulse laser frequency is 2Hz;Between monocrystal chip and target away from
From for 50mm;Film deposition temperature is 750 DEG C;Back end vacuum degree 1 × 10-4Pa;Oxygen pressure is 10-2Pa;Sedimentation time is 45
Minute;To the end of film is grown, 10-2It is cooled to room temperature in the oxygen atmosphere of Pa.The thickness of film is 1nm.
Embodiment 12
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.7, δ=0.24), selected substrate are that (001) is orientated
BiFeO3, pulsed laser energy is 275mJ in step 2);Pulse laser frequency is 2Hz;The distance between monocrystal chip and target
For 50mm;Film deposition temperature is 750 DEG C;Back end vacuum degree 2 × 10-4Pa;Oxygen pressure is 1Pa;Sedimentation time is 30 points
Clock;To the end of film is grown, it is cooled to room temperature in the oxygen atmosphere of 1Pa.The thickness of film is 5nm.
Embodiment 13
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.8, δ=0.16), selected substrate are that (001) is orientated
BaTiO3, pulsed laser energy is 305mJ in step 2);Pulse laser frequency is 2Hz;The distance between monocrystal chip and target
For 45mm;Film deposition temperature is 750 DEG C;Back end vacuum degree 2 × 10-4Pa;Oxygen pressure is 10Pa;Sedimentation time is 30 points
Clock;To the end of film is grown, it is cooled to room temperature in the oxygen atmosphere of 10Pa.The thickness of film is 10nm.
Embodiment 14
Thin-film material group becomes:LaxSr1-xCoO3-δ(x=0.9, δ=0.05), selected substrate are that (001) is orientated
PbTiO3, pulsed laser energy is 345mJ in step 2);Pulse laser frequency is 2Hz;The distance between monocrystal chip and target
For 45mm;Film deposition temperature is 750 DEG C;Back end vacuum degree 2 × 10-4Pa;Oxygen pressure is 50Pa;Sedimentation time is 30 points
Clock;To the end of film is grown, it is cooled to room temperature in the oxygen atmosphere of 50Pa.The thickness of film is 100nm.
Performance characterization
1、LaxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) characterization of membrane structure
La is determined using Cu target X-ray diffractometers0.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3
(011) film, La0.7Sr0.3CoO2.75/(LaAlO3)0.3(SrAl0.5TaO3)0.7(001) film, La0.7Sr0.3CoO2.89/
LaAlO3(001) film, La0.9Sr0.1CoO2.99/SrTiO3(111) film, La0.8Sr0.2CoO2.97/NdGaO3(001) film,
La0.7Sr0.3CoO2.64/LaNiO3(001) film, La0.6Sr0.4CoO2.61/DyScO3(001) film, La0.6Sr0.4CoO2.55/
NdScO3(001) film, La0.5Sr0.5CoO1.51/ MgO (001) film, La0.5Sr0.5CoO2.03/Pb(Zr,Ti)O3(001) thin
Film, La0.5Sr0.5CoO2.37/(Ba,Sr)TiO3(001) film, La0.7Sr0.3CoO2.76/BiFeO3(001) film,
La0.8Sr0.2CoO2.84/BaTiO3(001) film and La0.9Sr0.1CoO2.95/PbTiO3(001) film room temperature X-ray diffraction
(XRD) collection of illustrative plates and reciprocal space figure (RSM) find that all samples are the epitaxial growth of high quality.
Further, La is calculated according to X-ray diffraction (XRD) collection of illustrative plates and reciprocal space figure (RSM)xSr1-xCoO3-δ
(0.5≤x≤0.9,0<δ<1.5) lattice constant in pellicular front outside knead dough and suffered strained situation.
Typically, Fig. 1 provides La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3
(011) X-ray diffraction under film room temperature (XRD) collection of illustrative plates.It can be found that in addition to 0.7Pb (Mg1/3Nb2/3)O3-0.3PbTiO3Base
Piece and La0.7Sr0.3CoO2.75Other than (011) and (022) diffraction maximum of film, occur without other peaks.Show
La0.7Sr0.3CoO3-δFilm is high quality epitaxial growth.The result of calculation of collection of illustrative plates shows, La0.7Sr0.3CoO2.75/0.7Pb
(Mg1/3Nb2/3)O3-0.3PbTiO3(011) outer [011] direction lattice constant of pellicular frontReceive 0.092% pressure
Strain.
Fig. 2 and Fig. 3 provides La made from embodiment 1 respectively0.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-
0.3PbTiO3(011) under film room temperature (222) face and (013) face reciprocal space figure (RSM).The result of calculation of collection of illustrative plates shows,
La0.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film [100] and [01-1] both direction in face
Lattice constant is respectivelyWithRespectively by 2.88% and 1.11% tensile strain, reciprocal space figure result table
Bright La0.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) there are lattice anisotropies to answer in face for film
Variable field.
Fig. 4 provides La made from embodiment 20.7Sr0.3CoO2.75/(LaAlO3)0.3(SrAl0.5TaO3)0.7(001) film chamber
X-ray diffraction (XRD) collection of illustrative plates under temperature.It can be found that in addition to (LaAlO3)0.3(SrAl0.5TaO3)0.7Substrate and
La0.7Sr0.3CoO2.75Other than (001), (002) and (003) diffraction maximum of film, occur without other peaks.Show
La0.7Sr0.3CoO2.75/(LaAlO3)0.3(SrAl0.5TaO3)0.7(100) film is high quality epitaxial growth.The calculating knot of collection of illustrative plates
Fruit shows, La0.7Sr0.3CoO2.75/(LaAlO3)0.3(SrAl0.5TaO3)0.7(001) outer [001] direction lattice constant of pellicular frontThe compressive strain for receiving 0.304%, for isotropism substrate, face internal strain can be rule of thumb outside formula knead dough
It strains estimation to obtain, La0.7Sr0.3CoO2.75/(LaAlO3)0.3(SrAl0.5TaO3)0.7(001) film in face by about
0.228% tensile strain.
Fig. 5 provides La made from embodiment 30.7Sr0.3CoO2.89/LaAlO3(001) X-ray diffraction under film room temperature
(XRD) collection of illustrative plates.It can be found that in addition to LaAlO3Substrate and La0.7Sr0.3CoO2.89(001), (002) and (003) diffraction of film
Other than peak, occur without other peaks.Show La0.7Sr0.3CoO2.75Film is high quality epitaxial growth.The result of calculation of collection of illustrative plates is aobvious
Show, La0.7Sr0.3CoO2.89/LaAlO3(001) outer [001] direction lattice constant of pellicular frontReceive 1.886%
Tensile strain, for isotropism substrate, face internal strain can be obtained rule of thumb in the estimation of formula knead dough external strain,
La0.7Sr0.3CoO2.89/LaAlO3(001) film in face by about 1.414% compressive strain.
2、LaxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) magnetic characterization of film
Utilize superconductive quantum interference vibrating specimen magnetometer【MPMS(SQUID)VSM】Determine the magnetism of above-mentioned film.
Typically, Fig. 6 provides La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3
(011) under film 10K magnetic moment with change of magnetic field strength curve;Fig. 7 provides La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb
(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film magnetic moment under 500Oe magnetic field intensities varies with temperature curve.Fig. 6's and Fig. 7
The result shows that due to film in face by lattice anisotropy strain field, film in face both direction exist magnetism respectively to different
Property.[100] the born tensile strain in direction is larger, and the coercivity, saturation magnetic moment and remanent magnetism in Fig. 6 (circle) are smaller, Fig. 7 (circle)
In magnetic moment it is smaller, be hard axis;And the born tensile strain in the direction [01-1] is smaller, coercivity, saturation in Fig. 6 (square)
Magnetic moment and remanent magnetism are larger, and the magnetic moment in Fig. 7 (square) is larger, are easy magnetizing axis.
3、LaxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) redox character of film
The characterization of reduction process:
In the La preparedxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) electrode is prepared on film, later to film
Temperature cycles are carried out in a constant temperature area, you can realize La under certain applied currentxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<
1.5) reduction of film can monitor La by observing resistance variationsxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) film
Reduction process.Temperature cycles section is 20K-320K, and applied current is 1 μ A~100mA.
To the La obtained by the present inventionxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) film is under 1 μ A applied currents
Temperature cycles are carried out in 20~320K warm areas, you can realize reduction.
La made from embodiment 1 is set forth in Fig. 8 and Fig. 90.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-
0.3PbTiO3(011) film resistance during [01-1] and [100] direction are in temperature cycles varies with temperature curve, in figure
Number beside curve icon represents the number of loop test.Fig. 8 and Fig. 9's the result shows that La0.7Sr0.3CoO2.75/0.7Pb
(Mg1/3Nb2/3)O3-0.3PbTiO3(011) in [01-1] and [100] both direction there is unstable state Electrical transport in film.
With the increase of loop test number, the resistance value of film gradually increases, and metal-to-semiconductor transition temperature is gradually moved to high temperature
It is dynamic.Due to the presence of anisotropic strain field, the direction [01-1] is strained smaller, is more easy to be magnetized, and metal behavior is preferable, warp
Still in the inner body cash category behavior of certain temperature section after multiple loop test.On the contrary, [100] direction be stressed it is larger, it more difficult to
It is magnetized, metal behavior is poor, and after repeatedly recycling measurement, metal behavior temperature range disappears, and all embodies semiconductor behavior.
The result shows that introducing the La of strain0.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) film, can be in room temperature
Lower carry out redox reaction strains larger [100] direction deoxidation degree bigger.
Figure 10 and Figure 11 provides La made from embodiment 2 and embodiment 3 respectively0.7Sr0.3CoO2.75/(LaAlO3)0.3
(SrAl0.5TaO3)0.7(001) film and La0.7Sr0.3CoO2.89/LaAlO3(001) film resistor varies with temperature curve, in figure
Number beside curve icon represents the number of loop test, applied current:1 μ A recycle warm area:20~320K.The result shows that
La0.7Sr0.3CoO2.75/(LaAlO3)0.3(SrAl0.5TaO3)0.7(001) film and La0.7Sr0.3CoO2.89/LaAlO3(001) thin
Film exists and La0.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) the similar unstable state electricity of film is defeated
Transport characteristic.In addition, applying 10 μ A applied currents to film, there are still the unstable state Electrical transports similar with above-mentioned phenomenon.
Synthetically, film unstable state Electrical transport is existing the reason is that since film is by substrate stress, accelerates O2-From
Subflow is dynamic and deviates from.In LaxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) in material, O2-Ion is the matchmaker for transmitting electronics
It is situated between, O2-The loss of ion hinders the transmission of electronics, and the phenomenon that resistance increases has occurred macroscopically becoming.Above example all tables
It is bright, LaxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) film can occur also under the action of stress and electric current in room temperature
Thin-film material itself reduction is realized in original reaction, while the deoxidation process can also may be used by current control, the reduction process of film
To be monitored by carrying out electronic transport measurement to film.
The characterization of oxidation process:
In order to confirm O2-The loss of ion and the repeatability of material, by the La of above-mentioned hydrogen reductionxSr1-xCoO3-δ(0.5≤
X≤0.9,0<δ<1.5) film is put into pure oxygen anneal.Typically, with La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb
(Mg1/3Nb2/3)O3-0.3PbTiO3(011) for film, the film for undergoing reduction process is put into pure oxygen and is annealed, atmosphere
Environment is 1 standard atmospheric pressure pure oxygen, and annealing temperature is 100 DEG C, annealing time 1 hour.
Figure 12 provides La made from embodiment 10.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) thin
The correlation curve that film reduction-state (rectangular) and the direction oxidation state (circle) [01-1] resistance vary with temperature, shows
La0.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) resistance is apparent after annealing in the direction film [01-1]
Reduce, the corresponding temperature range of metal behavior is broadening.This is because during pure oxygen anneal, the Lacking oxygen in film is by oxygen original
Son filling, the O of film2-Ion is supplemented, and oxidation process, the O as electron transmission medium are undergone2-Ion is supplemented, and is had
Conducive to electronics transfer, macroscopically embodies resistance and reduce phenomenon.The process shows LaxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<
1.5) the oxidation process required temperature of film is relatively low (≤100 DEG C), and the time is shorter (≤1 hour), and material supplements O2-Ion process
It is relatively low to reaction condition requirement, it is easier to realize.
Above-mentioned redox test repeatedly has been carried out to the film after above-mentioned annealing.Figure 13 is to made from embodiment 1
La0.7Sr0.3CoO2.75/0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3(011) after film oxidation the direction [01-1] resistance with temperature
Change curve shows the La after oxidationxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) film is still possessed unstable state and is transported
Redox reaction can still occur at room temperature for characteristic, this also illustrates that oxidation-reduction process has good reproducibility.
Based on the above results, for LaxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) film, in membrane stress and electricity
Under stream effect, O in film2-Lasting flowing and abjection can occur at room temperature for ion, unstable state Electrical transport occur, generate
Controllable reduction reaction phenomenon.Under pure oxygen after (≤100 DEG C) annealing of lower temperature, the oxygen deviate from film can be obtained benefit
It fills.La after annealingxSr1-xCoO3-δ(0.5≤x≤0.9,0<δ<1.5) film can still be showed by current control generation reduction reaction
As, and there are unstable state transport properties.The perovskite redox reaction catalyst material catalytic temperature having been reported is higher, more
Number does not have the characteristics of controllability, and catalytic temperature is adjusted to room temperature by the present invention by membrane stress and current induced method;
At the same time, operating condition of the invention is easy to implement and manufacturing cost is relatively low.Therefore the present invention exists for perovskite oxide
Application in the fields such as redox reaction catalysis, fuel cell, chemical sensor is of great significance.
Claims (12)
1. a kind of redox reaction catalyst with perovskite structure, the catalyst are the La being deposited on substratexSr1- xCoO3-δFilm, wherein 0.5≤x≤0.9,0<δ<1.5.
2. catalyst according to claim 1, wherein the thickness of the film be 1~500nm, preferably 10~
200nm。
3. catalyst according to claim 1 or 2, wherein the substrate is (LaAlO3)0.3(SrAl0.5TaO3)0.7、yPb
(Mg1/3Nb2/3)O3-(1-y)PbTiO3(0.8<y<0.5)、LaAlO3、SrTiO3、NdGaO3、LaNiO3、DyScO3、NdScO3、
MgO、Pb(Zr,Ti)O3、(Ba,Sr)TiO3、BiFeO3、BaTiO3And PbTiO3In one kind.
4. catalyst according to any one of claim 1 to 3, wherein the film is deposited on (001) of the substrate
Face, (011) face or its beveling are orientated, it is preferable that the thickness of the substrate is 0.05~1mm.
5. the preparation method of redox reaction catalyst any one of Claims 1-4, the preparation method packet
It includes:
1) La is preparedxSr1-xCoO3Target, wherein 0.5≤x≤0.9;
2) pulsed laser deposition is applied, target made from step 1) is made to be taken in (001) face of substrate, (011) face or its beveling
Deposition upwards forms LaxSr1-xCoO3-δFilm, wherein 0.5≤x≤0.9,0<δ<1.5.
6. preparation method according to claim 5, wherein step 1) prepares the La using solid sintering technologyxSr1-xCoO3
Target, it is preferable that the solid sintering technology includes:Raw material La is weighed according to atomic molar ratio2O3、SrCO3And Co3O4, it is put into earthenware
Baking material is carried out in crucible;It is taken out while hot after baking, being fully ground makes it uniformly mix;Then the powder that grinding obtains is put into crucible
It is inside placed in Muffle furnace, in 800~1000 DEG C of 5~15h of pre-burning;Products therefrom after being fully ground 1100~1300 again
DEG C calcining 24~36h;Third time is carried out again to be fully ground, then die mould, and be sintered 32~40h at 1200~1400 DEG C and obtain institute
State LaxSr1-xCoO3Target.
7. preparation method according to claim 5 or 6, wherein the condition packet of pulsed laser deposition described in step 2)
It includes:Pulsed laser energy is 50~800mJ;The distance between substrate and target are 20~80mm;Film deposition temperature be 600~
900℃;Back end vacuum degree is less than 5 × 10-4Pa;Oxygen pressure is 10-2~200Pa.
8. preparation method according to any one of claims 5 to 7, wherein pulsed laser deposition described in step 2)
Sedimentation time be 1~60 minute, preferably 5~45 minutes;Pulse laser frequency is 1~12Hz, preferably 2~8Hz.
9. the preparation method according to any one of claim 5 to 8, wherein the step 2) further includes:Wait for that film is grown
Terminate, 10-4~105It is cooled to room temperature in the oxygen or air atmosphere of Pa.
10. redox reaction catalyst any one of Claims 1-4 or according to any in claim 5 to 9
Redox reaction catalyst is in redox reaction catalysis, fuel cell, chemical sensor made from item the method
Using.
11. application according to claim 10, wherein the oxidation of the catalyst and restoring method are respectively:
Reduction process:In LaxSr1-xCoO3-δElectrode is prepared on film, later to film 1~10 μ A electric current in 20~320K
Temperature cycles are carried out in warm area, you can realize LaxSr1-xCoO3-δThe reduction of film;
Oxidation process:Using tube furnace by the La in reduction-statexSr1-xCoO3-δFilm is annealed under air or pure oxygen, you can
Make film oxidation to original state.
12. application according to claim 11, wherein the condition of the annealing includes:Atmospheric condition is marked for 0.01Pa~1
Quasi- atmospheric pressure pure oxygen or air, oxidizing temperature≤100 DEG C, oxidization time≤1 hour.
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CN111454059A (en) * | 2020-05-20 | 2020-07-28 | 中国科学院重庆绿色智能技术研究院 | Preparation of L axSr1-xCoO3-Method for preparing composite oxide |
CN113522298A (en) * | 2021-07-12 | 2021-10-22 | 南京林业大学 | Perovskite oxide/Ti3C2MXene/foamed nickel composite material and preparation method and application thereof |
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Cited By (3)
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CN111454059A (en) * | 2020-05-20 | 2020-07-28 | 中国科学院重庆绿色智能技术研究院 | Preparation of L axSr1-xCoO3-Method for preparing composite oxide |
CN113522298A (en) * | 2021-07-12 | 2021-10-22 | 南京林业大学 | Perovskite oxide/Ti3C2MXene/foamed nickel composite material and preparation method and application thereof |
CN113522298B (en) * | 2021-07-12 | 2023-09-12 | 南京林业大学 | Perovskite oxide/Ti 3 C 2 MXene/foam nickel composite material and preparation method and application thereof |
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