CN112144111A - Method for regulating electrocatalytic activity of iron-based perovskite oxide film through phase change process - Google Patents
Method for regulating electrocatalytic activity of iron-based perovskite oxide film through phase change process Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 230000000694 effects Effects 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 27
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- 229910052742 iron Inorganic materials 0.000 title claims abstract description 24
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- 239000013078 crystal Substances 0.000 claims abstract description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 230000008021 deposition Effects 0.000 claims abstract description 21
- 230000001276 controlling effect Effects 0.000 claims abstract description 14
- 229910002406 SrFeO2.5 Inorganic materials 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 51
- 239000010409 thin film Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 20
- 238000005137 deposition process Methods 0.000 claims description 8
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims description 7
- 229910002182 La0.7Sr0.3MnO3 Inorganic materials 0.000 claims description 2
- 239000013077 target material Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 3
- 238000000151 deposition Methods 0.000 description 21
- 238000004549 pulsed laser deposition Methods 0.000 description 18
- 229910002372 SrTiO3(001) Inorganic materials 0.000 description 6
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- C30B23/00—Single-crystal growth by condensing evaporated or sublimed materials
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Abstract
The invention discloses a method for regulating and controlling electrocatalytic activity of an iron-based perovskite oxide film by a phase change process, and relates to the technical field of electrocatalytic materials. The invention utilizes the pulse laser deposition technology to accurately regulate and control the oxygen pressure in the deposition processSmall SrFeO with different phase structures3‑x(0<x is less than or equal to 0.5) single crystal film to realize SrFeO3‑x(0<x is less than or equal to 0.5) single crystal film is formed by SrFeO2.97(perovskite phase, PV) to SrFeO2.5Structural phase change of (perovskite phase, BM) to regulate SrFeO3‑x(0<x is less than or equal to 0.5) electrocatalytic activity of the single crystal film electrode to obtain the single crystal film with high electrocatalytic activity.
Description
Technical Field
The invention relates to the technical field of electrocatalytic materials, in particular to a method for regulating electrocatalytic activity of an iron-based perovskite oxide film by using a phase change process.
Background
With the gradual consumption and reduction of fossil fuels, the development of new energy capable of being continuously utilized is a major challenge in modern society, hydrogen energy is taken as clean and environment-friendly novel energy with great prospect and is being put into use in large quantity, and the hydrogen production by electrolyzing water is considered to be the most scientific and efficient method at present. In order to improve the reaction kinetics, a high-efficiency active catalyst must be added in the water electrolysis process. Synthetic materials such as noble metals have been developed as electrocatalysts (e.g., IrO)2，RuO2Pt, Au, etc.), but their large-scale commercial application is limited due to their excessive cost and low content. Therefore, the development of a novel electrocatalyst with low cost and high efficiency is of great significance.
In recent years, many transition metal oxides begin to gradually replace noble metals to become research hotspots of novel electrocatalysts, perovskite oxides show great potential in the field of electrocatalysts due to low cost, high activity, simple preparation method and strong reaction kinetics, and most representative novel catalysts belong to Fe, Co and Ni type perovskite oxide catalysts. At present, the regulation and control of the electrocatalytic activity of the perovskite Strontium Ferrite (SFO) mainly focus on the aspects of powder-based element composition, morphological characteristics, particle size, oxygen vacancy and the like. In particular, oxygen vacancies play an important role in the whole process of electrocatalytic reaction, but the regulation of electrocatalytic activity based on oxygen channels under the microstructure is rarely reported.
Disclosure of Invention
The technical problem to be solved by the invention is some defects mentioned in the background technology, and the electrocatalytic activity is regulated and controlled through a fine microscopic oxygen channel so as to provide a method for regulating the electrocatalytic activity of an iron-based perovskite oxide film in a phase-change process.
In order to solve the above problems, the present invention proposes the following technical solutions:
the invention provides a phase-change engineering controlled electrocatalytic activity of an iron-based perovskite oxide filmThe method comprises bombarding a target material on a substrate layer by using pulse laser, and adjusting the dynamic oxygen partial pressure to 1.0-30.0 Pa in the deposition process to obtain SrFeO with different phase structures3-x(0<x is less than or equal to 0.5), and the target is SrFeO2.97。
The different phase structure refers to SrFeO2.97(perovskite phase, PV) to SrFeO2.5Structural phase change of (perovskite phase, BM) to realize SrFeO3-x(0<x is less than or equal to 0.5) the regulation and control of the electrocatalytic activity of the film.
The further technical proposal is that the vacuum degree of the back bottom in the cavity of the pulse laser deposition system is less than 2 multiplied by 10-5Pa, and the deposition temperature is 600-800 ℃.
The further technical proposal is that the laser light source is KrF excimer laser, the laser wavelength is 248nm, the pulse width is 10ns, and the laser energy density is 1.0J/cm2～4.0J/cm2The frequency is 1 Hz-10 Hz.
The further technical proposal is that SrFeO is obtained when the dynamic oxygen partial pressure is 5.0Pa in the deposition process2.5A single crystal thin film.
Namely, SrFeO when the critical dynamic oxygen partial pressure in the deposition process is 5Pa3-x(0<x is less than or equal to 0.5) the structural phase change from PV to BM of the single crystal film to obtain SrFeO2.5A single crystal thin film.
The further technical proposal is that the SrFeO2.5The single crystal film is of a brownmillerite phase structure.
The further technical proposal is that the SrFeO3-x(0<x is less than or equal to 0.5) the thickness of the single crystal film is 10-40 nm.
The further technical scheme is that the substrate layer comprises a single crystal substrate and La0.7Sr0.3MnO3A conductive network.
The specific scheme of the substrate layer is that SrTiO3(001) Depositing La on single crystal substrate by pulsed laser deposition0.7Sr0.3MnO3The bottom electrode acts as a conductive network.
The further technical proposal is that the La is0.7Sr0.3MnO3Thickness of the conductive networkIs 10-15 nm.
The invention provides a method for regulating and controlling the electrocatalytic activity of an iron-based perovskite oxide film by phase change engineering, which is used for preparing SrFeO with different phase structures3-x(0<x is less than or equal to 0.5) application of the single crystal film.
The invention also provides SrFeO with different phase structures3-x(0<x is less than or equal to 0.5), and is prepared by the method for regulating and controlling the electrocatalytic activity of the iron-based perovskite oxide film by the phase change engineering.
The principle of the invention is as follows: by using the pulse laser deposition technology and accurately regulating and controlling the oxygen partial pressure in the deposition process, the method can be used for preparing SrTiO3(001) SrFeO with different phase structures deposited on a single crystal substrate3-x(0<x is less than or equal to 0.5) single crystal film. The fine regulation and control of an oxygen channel under a microstructure are utilized to realize SrFeO2.97(PV) to SrFeO2.5(BM) structural transition. Experiments prove that SrFeO has oxygen precipitation activity2.5(BM) having an oxygen channel more favorable for the oxygen evolution reaction; compared with SrFeO2.97(PV)，SrFeO2.5The oxygen evolution activity of (BM) is significantly improved.
Compared with the prior art, the invention can achieve the following technical effects:
(1) the invention utilizes the pulse laser deposition technology to accurately regulate and control the oxygen pressure in the deposition process to obtain SrFeO with different phase structures3-x(0<x is less than or equal to 0.5) single crystal film, thereby regulating and controlling SrFeO3-x(0<x is less than or equal to 0.5) electrocatalytic activity of the single crystal film electrode to obtain the single crystal film with high electrocatalytic activity.
(2) The Pulsed Laser Deposition (PLD) used in the invention realizes SrFeO3-x(0<x is less than or equal to 0.5) the regulation and control of the electrocatalytic activity of the thin film structure phase change engineering can be used for the performance regulation and modification of almost all oxide materials.
Drawings
FIG. 1 shows SrFeO obtained in examples 1 to 3 of the present invention3-x(0<x is less than or equal to 0.5) XRD pattern of the single crystal film.
FIG. 2 shows SrFeO obtained in examples 1 to 3 of the present invention3-x(0<x is less than or equal to 0.5) preparing the single crystal film into a linear voltammogram of the single crystal film electrode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments. It is apparent that the embodiments to be described below are only a part of the embodiments of the present invention, and not all of them. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
To explore SrFeO with different phase structures3-x(0<x is less than or equal to 0.5), and the method for regulating the electrocatalytic activity of the iron-based perovskite oxide film by applying the phase change engineering provided by the invention to prepare SrFeO with different phase structures3-x(0<x is less than or equal to 0.5), and SrFeO3-x(0<x is less than or equal to 0.5) preparing a single crystal film electrode to carry out an electrocatalytic activity test, wherein the specific preparation method of the single crystal film electrode is as follows:
(1) in SrTiO3(001) Depositing La with the thickness of 10-15nm on a single crystal substrate by a pulse laser deposition technology0.7Sr0.3MnO3The bottom electrode is used as a conductive network;
(2) adjusting the dynamic oxygen partial pressure in the deposition process on the conductive network obtained in the step (1) by a pulse laser deposition technology to obtain SrFeO with different structures3-x(0<x is less than or equal to 0.5) film, SrFeO3-x(0<x is less than or equal to 0.5) the thickness of the film is 10-40 nm;
the parameters of the pulsed laser deposition technology (PLD) in the step (2) are as follows: the dynamic oxygen partial pressure is 1.0-30.0 Pa, the substrate temperature is 600-800 ℃, the laser light source is KrF excimer laser, the laser wavelength is 248nm, the laser pulse width is 10ns, and the laser energy density is 1.0J/cm2～4.0J/cm2The laser frequency is 1 Hz-10 Hz.
(3) SrFeO obtained in the step (2)3-x(0<x is less than or equal to 0.5) connecting the silver wires with the film and coating the silver wires with epoxy resinCoating SrFeO3-x(0<x is less than or equal to 0.5) all parts except the film to obtain the single crystal film electrode;
(4) performing 1.2-1.8V linear voltammetry test on the single crystal thin film electrode obtained in the step (3) in 1moL/L KOH electrolyte to obtain SrFeO with different phase structures3-x(0<x is less than or equal to 0.5), and carrying out research test on the oxygen precipitation performance of the film electrode.
The specific embodiment is as follows:
example 1
In the embodiment, the single crystal thin film electrode is prepared by a method for regulating and controlling the electrocatalytic activity of the iron-based perovskite oxide through phase change engineering, and the method comprises the following specific steps:
(1) in SrTiO3(001) Deposition of 10nm La by pulsed laser sputtering on single crystal substrates0.7Sr0.3MnO3A bottom electrode; the parameters of PLD are: the substrate temperature is 720 ℃, the dynamic oxygen partial pressure is 30Pa, the laser energy is 200mJ, the laser frequency is 3Hz, and the deposition time is 5 min;
(2) with SrFeO2.97Continuing to obtain SrFeO with different ferrite coordination numbers on the bottom electrode obtained in the step (1) by using a Pulsed Laser Deposition (PLD) technology for the target3-x(0<x is less than or equal to 0.5) thin film; the parameters of PLD are that the dynamic oxygen partial pressure is 20Pa, the substrate temperature is 700 ℃, the laser energy is 200mJ, the laser frequency is 3Hz, the deposition time is 15min, and the obtained SrFeO3-xThe film structure is SrFeO2.97The thickness of the film is 20 nm; lattice constant of the resulting thin film structure
(3) SrFeO obtained in the step (2)2.97The film part is connected with a silver wire, and then the SrFeO is coated by epoxy resin2.97And obtaining a single crystal thin film electrode at the part except the thin film.
Example 2
In the embodiment, the single crystal thin film electrode is prepared by a method for regulating and controlling the electrocatalytic activity of the iron-based perovskite oxide through phase change engineering, and the method comprises the following specific steps:
(1) in SrTiO3(001) Deposition of 10nm on a single crystal substrate by pulsed laser sputteringLa0.7Sr0.3MnO3A bottom electrode; the parameters of PLD are: the substrate temperature is 720 ℃, the dynamic oxygen partial pressure is 30Pa, the laser energy is 200mJ, the laser frequency is 3Hz, and the deposition time is 5 min;
(2) continuously obtaining SrFeO with different ferrite coordination numbers on the conductive network obtained in the step (1) by a Pulse Laser Deposition (PLD) technology3-x(0<x is less than or equal to 0.5) single crystal film; the parameters of PLD are that the dynamic oxygen partial pressure is 10Pa, the substrate temperature is 700 ℃, the laser energy is 200mJ, the laser frequency is 3Hz, the deposition time is 12min, and the obtained SrFeO3-xThe film structure is SrFeO2.89(ii) a The thickness of the film is 20 nm; lattice constant of the resulting thin film structure
(3) SrFeO obtained in the step (2)2.89The film part is connected with a silver wire, and then the SrFeO is coated by epoxy resin3-x(0<x is less than or equal to 0.5) outside the thin film, and obtaining the single crystal thin film electrode.
Example 3
In the embodiment, the single crystal thin film electrode is prepared by a method for regulating and controlling the electrocatalytic activity of the iron-based perovskite oxide through phase change engineering, and the method comprises the following specific steps:
(1) in SrTiO3(001) Deposition of 10nm La by pulsed laser sputtering on single crystal substrates0.7Sr0.3MnO3A conductive network; the parameters of PLD are: the substrate temperature is 720 ℃, the dynamic oxygen partial pressure is 30Pa, the laser energy is 200mJ, the laser frequency is 3Hz, and the deposition time is 5 min;
(2) with SrFeO2.97Continuously obtaining SrFeO with different ferrite coordination numbers on the conductive network obtained in the step (1) by the target through a Pulse Laser Deposition (PLD) technology3-x(0<x is less than or equal to 0.5) single crystal film; the parameters of PLD are that the dynamic oxygen partial pressure is 5Pa, the substrate temperature is 700 ℃, the laser energy is 200mJ, the laser frequency is 3Hz, the deposition time is 10min, and the obtained SrFeO3-xThe film structure is SrFeO2.5The thickness of the film is 20 nm; lattice constant of the resulting thin film structure
(3) SrFeO obtained in the step (2)2.5The film part is connected with a silver wire, and then the SrFeO is coated by epoxy resin2.5And obtaining the single crystal thin film electrode except the thin film.
XRD verification of the single crystal thin film electrodes obtained in examples 1 to 3 was carried out, and the results are shown in FIG. 1.
The result shows that the SrFeO can be obtained by accurately regulating the oxygen partial pressure by using the Pulsed Laser Deposition (PLD) technology2.97Single crystal thin film (PV) to SrFeO2.5Structural phase change of the single crystal thin film (BM). SrFeO with decreasing oxygen pressure for deposition3-x(0<x is less than or equal to 0.5) film lattice constant cfilmGradually increased, when the oxygen pressure is reduced to 5Pa, SrFeO3-x(0<x is less than or equal to 0.5) film is converted from PV phase to BM phase, and lattice constant cfilmIncrease to
The single crystal thin film electrodes obtained in the above examples 1 to 3 were subjected to a catalytic performance test by the following method:
(1) preparing 1moL/L electrolyte from analytically pure KOH and high-purity water, and introducing high-purity oxygen until the electrolyte is saturated;
(2) and (2) putting the single crystal thin film electrode obtained in the above example 1-3 into the KOH electrolyte prepared in the step (1), and performing a linear voltammetry test in a voltage range of 1.2-1.8V.
The linear voltammogram of the resulting single crystal thin film electrode is shown in FIG. 2.
The results show that SrFeO having a different phase structure3-x(0<x is less than or equal to 0.5) the single crystal film electrodes show different oxygen precipitation activities. In example 3, the oxygen evolution activity potential was lower than that of examples 1 and 2. And at the same potential, the current density is higher in example 3 than in examples 1 and 2, the oxygen yield efficiency is higher, namely when x is 0.5, SrFeO of example 32.5Electrocatalytic activity of (BM) compared to SrFeO of example 1, example 23-xThe electrocatalytic activity of the (PV) is obviously improved. It can be seen that the present invention provides a phaseThe method for regulating and controlling electrocatalytic activity of Fe-based perovskite oxide film by variable engineering realizes SrFeO by using Pulse Laser Deposition (PLD) technology3-x(0<x is less than or equal to 0.5) the electrocatalytic activity of the single crystal film electrode is regulated and controlled.
In the above embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
While the invention has been described with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A method for regulating and controlling electrocatalytic activity of an iron-based perovskite oxide film in a phase change process is characterized in that a target material is bombarded on a substrate layer by using pulse laser, the dynamic oxygen partial pressure in the deposition process is adjusted to be 1.0-30.0 Pa, and SrFeO with a different phase structure is obtained3-x(0<x is less than or equal to 0.5), and the target is SrFeO2.97。
2. The method for regulating and controlling the electrocatalytic activity of the iron-based perovskite oxide film through phase change engineering according to claim 1, wherein the vacuum degree of the back bottom in the cavity is less than 2 x 10-5Pa, and the deposition temperature is 600-800 ℃.
3. The method for regulating and controlling the electrocatalytic activity of the iron-based perovskite oxide thin film in the phase change engineering as claimed in claim 1, wherein the laser light source is KrF excimer laser, the laser wavelength is 248nm, the laser pulse width is 10ns, and the laser energy density is 1.0J/cm2～4.0J/cm2The laser frequency is 1 Hz-10 Hz.
4. The phase change engineered iron-based perovskite oxide thin film of claim 1The method for electrocatalytic activity is characterized in that SrFeO is obtained when the dynamic oxygen partial pressure is 5.0Pa in the deposition process2.5A single crystal thin film.
5. The method for regulating electrocatalytic activity of an iron-based perovskite oxide thin film through phase change engineering according to claim 4, wherein the SrFeO2.5The single crystal film is of a brownmillerite phase structure.
6. The method for regulating electrocatalytic activity of an iron-based perovskite oxide thin film through phase change engineering according to claim 1, wherein the SrFeO3-x(0<x is less than or equal to 0.5) the thickness of the single crystal film is 10-40 nm.
7. The method for regulating electrocatalytic activity of an iron-based perovskite oxide thin film through phase change engineering according to claim 1, wherein the substrate layer comprises a single crystal substrate and La0.7Sr0.3MnO3A conductive network.
8. The method for regulating electrocatalytic activity of an iron-based perovskite oxide thin film through phase change engineering according to claim 7, wherein the La is used for regulating electrocatalytic activity of the iron-based perovskite oxide thin film0.7Sr0.3MnO3The thickness of the conductive network is 10-15 nm.
9. The method for regulating and controlling the electrocatalytic activity of the iron-based perovskite oxide thin film in the phase change engineering according to any one of claims 1 to 8 for preparing SrFeO with different phase structures3-x(0<x is less than or equal to 0.5) application of the single crystal film.
10. SrFeO with different phase structures3-x(0<x is less than or equal to 0.5), which is characterized in that the film is prepared by the method for regulating and controlling the electrocatalytic activity of the iron-based perovskite oxide film by the phase change engineering according to any one of claims 1 to 8.
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