CN115872460A - Method for effectively improving catalytic performance of perovskite catalyst - Google Patents
Method for effectively improving catalytic performance of perovskite catalyst Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 93
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001354 calcination Methods 0.000 claims description 18
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 14
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- 239000000243 solution Substances 0.000 description 14
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a method for effectively improving the catalytic performance of a perovskite catalyst, which is characterized by comprising the following steps: doping transition metal nickel in the perovskite structure material by adopting a sol-gel technology; doping non-metal nitrogen in the perovskite structure substance by adopting a chemical vapor deposition technology to obtain the transition metal and non-metal modified perovskite-based catalyst. According to the invention, the object aimed by the lifting method and the overall process of the lifting method are controlled, and the perovskite catalyst is doped with transition metal and non-metal elements, so that the technical problems of complex process, high cost, low efficiency and low stability of the obtained catalyst in the prior art are solved, and the catalytic performance, especially the oxygen evolution catalytic performance, of the perovskite-based catalyst can be improved; the amount of the transition metal nickel element modified on the perovskite substance component is preferably controlled, and the effect of improving the catalytic performance of the perovskite-based catalyst can be further ensured.
Description
Technical Field
The invention belongs to the technical field of materials and electrochemical energy storage new energy, and particularly relates to a method for effectively improving the catalytic performance of a perovskite catalyst.
Background
The Hydrogen production process by water electrolysis consists of two half reactions, namely, an Oxygen Evolution Reaction (OER) at the anode and a Hydrogen Evolution Reaction (HER) at the cathode. HER and OER occur simultaneously during water electrolysis, but due to H in the electrolyte + And OH - Concentration difference ([ H ] + ]·[OH - ]＝10 -14 ) Resulting in difficulty in obtaining high activity of the catalyst at the same time. However, the OER reaction, one of the half reactions of electrolysis of water, has slower kinetics than the HER reaction, limiting its high conversion efficiency, which is one of the reasons why electrocatalytic decomposition of water still cannot be used on a large scale, and thus high conversion rate and high efficiency OER electrocatalysts are required to improve energy conversion efficiency.
Oxygen Evolution Reaction (OER) is a key and essential step in a variety of energy storage (fuel cells, rechargeable metal air cells, etc.) conversion devices. Most of the catalysts selected at present are noble metals and oxides with high cost and low reserves. Despite the tremendous efforts of researchers to do so, it remains a significant challenge to develop power generation catalyst materials at low cost. The noble metals iridium dioxide and ruthenium dioxide are recognized electrocatalysts having very good oxygen evolution catalytic properties, however iridium dioxide and ruthenium dioxide are less stable in the electrocatalysis process. In addition, iridium and ruthenium are rare and precious metals, and the expensive cost price and the limited content of iridium and ruthenium in the crust severely restrict the large-area commercial promotion of iridium and ruthenium. Therefore, it is necessary to develop a catalyst with high activity, low cost, abundant reserves and good stability to improve efficiency and reduce cost, wherein the Perovskite oxide (Perovskite Oxides) electrocatalyst is rapidly in the recent years popular research due to its cheap and easily available, simple preparation and controllable structure.
Based on the method, the transition metal iron-based perovskite type oxide rich in earth reserves is selected for research, and the electrochemical properties of the transition metal iron-based perovskite type oxide are improved by electronic regulation and surface modification of the transition metal iron-based perovskite type oxide. LaFeO 3 Is a typical simple perovskite and has many applications, for example: catalytic oxidation, sensors, solid oxide fuel cells, and the like. However, as an electrocatalyst, laFeO 3 Perovskites exhibit poor OER performance in alkaline solutions.
To address these problems, various strategies have been proposed for increasing the amount of LaFeO 3 OER performance of (2). Wherein the staff pass through La 0.95 FeO 3-δ Incorporation of suitable a-site cation deficiency in perovskites to enhance electrocatalytic OER activity, and even preparation of ultra-thin LaFeO on niobium-doped strontium titanate by pulsed laser deposition 3 A film. However, the above-mentioned preparation processes require complicated process flows.
Therefore, the prior art still has the technical problems of complex preparation process, high cost, low efficiency and low stability of the prepared catalyst.
Therefore, in order to solve the above problems, a method for effectively improving the catalytic performance of a perovskite catalyst is proposed herein.
Disclosure of Invention
In order to solve the technical problems, the invention designs a method for effectively improving the catalytic performance of a perovskite catalyst, wherein an object aimed at by the improvement method and the overall process of the improvement method are controlled, an iron-based perovskite catalyst is taken as the object, and transition metal and non-metal elements are doped in the iron-based perovskite catalyst, so that the technical problems of complex preparation process, high cost, low efficiency and low stability of the obtained catalyst in the prior art are solved, and the catalytic performance, especially the oxygen evolution catalytic performance, of the perovskite-based catalyst can be improved; in addition, the invention also preferably controls the amount of the transition metal nickel element modified on the perovskite substance component, and can further ensure the effect of improving the catalytic performance of the perovskite-based catalyst.
In order to achieve the technical effects, the invention is realized by the following technical scheme: a method for effectively improving the catalytic performance of a perovskite catalyst is characterized by comprising the following steps:
step1, doping transition metal nickel in the perovskite structure substance by adopting a sol-gel technology;
and Step2, doping non-metal nitrogen in the perovskite structure substance by adopting a chemical vapor deposition technology to obtain the transition metal and non-metal modified perovskite-based catalyst.
Further, the sol-gel technology comprises the following steps:
step1.1, mixing La (NO) 3 ) 3 、(1-x)Fe(NO 3 ) 3 、x Ni(NO 3 ) 2 Dissolving in deionized water, and adding acidic substances;
step1.2, placing the solution in a water bath, heating and stirring by adopting a magnetic heating stirrer until gel is formed;
step1.3, placing the gel in a constant-temperature drying oven for low-temperature calcination;
grinding a sample subjected to low-temperature calcination by Step1.4, then putting the sample into a muffle furnace to be calcined to form a perovskite structure, heating, and naturally cooling to obtain a perovskite oxide LaFe 1-x Ni x O 3 。
Further, x =0 to 1 in Step1.1; the ratio of the amounts of the target metals Fe, ni and the acidic substance is 5:2 to 4;
the temperature of water bath heating in Step1.2 is 65-85 ℃;
the temperature of the low-temperature calcination in the Step1.3 is 100-150 ℃;
the calcining temperature in Step1.4 is 400-600 ℃, and the heating rate is 1-3 ℃/min.
Further, x =0.5 in step1.1; the ratio of the amounts of the target metals Fe and Ni to the amount of the acidic substance is 5:3;
the temperature of water bath heating in Step1.2 is 80 ℃;
the temperature of the low-temperature calcination in the Step1.3 is 120 ℃;
the calcining temperature in Step1.4 is 600 ℃, and the heating rate is 2 ℃/min.
Further, the chemical vapor deposition technology comprises the following specific steps:
step2.1 preparation of perovskite oxide LaFe 0.5 Ni 0.5 O 3 Placing the mixture into a porcelain container, placing the porcelain container into a tubular furnace for calcination, adding carrier gas for doping of non-metal element nitrogen, and finally cooling to room temperature to obtain the non-metal element nitrogen-doped LaFe 0.5 Ni 0.5 O 3 A perovskite type oxide.
Further, in Step2.1, the perovskite oxide LaFe 0.5 Ni 0.5 O 3 Placing in a porcelain container, and placing in a tube furnace at 5 deg.C for 5 min -1 Heating to 450 ℃ at the rate of (1) and keeping for 2h, adding ammonia gas for doping of non-metal element nitrogen, and finally cooling to room temperature to obtain LaFe 0.5 Ni 0.5 O 3 -NH 3 。
Further, the LaFe 0.5 Ni 0.5 O 3 -NH 3 Can be used as an oxygen evolution catalyst.
The invention has the beneficial effects that:
(1) The invention adopts the sol-gel technology to realize the iron-based perovskite catalyst doped with the transition metal element nickel to further improve the oxygen evolution capability, and also preferably adopts the sol-gel technology which is environment-friendly and low in cost to prepare the perovskite oxide precursor; the practical transition metal nickel-doped iron-based perovskite oxide is provided to obtain the high-efficiency oxygen evolution electrocatalytic material, so that the cost is low, and the environment is not polluted;
by doping transition metal nickel into the iron-based perovskite structure material, the oxygen evolution performance of the perovskite-based catalyst can be effectively improved; the perovskite type oxide precursor can be prepared by adopting a sol-gel technology, the mixture ratio of organic complex and the like in the preparation process of the perovskite type oxide precursor is controlled, and the conditions such as temperature and the like in the preparation process are strictly controlled, so that the prepared perovskite structure substance has more active sites, the promotion effect of oxygen evolution performance is ensured, and the preparation method of the perovskite type oxide precursor has low cost and no environmental pollution.
Due to adsorption of OH by a metal oxide of perovskite structure (e.g., fe-based perovskite oxide) - Has stronger ability, and Ni-based material adsorbs OH - The prepared nickel-iron-based perovskite oxide can absorb OH by combining the nickel-iron-based perovskite oxide and the nickel-iron-based perovskite oxide - Ability to react with OH in the reaction - The adsorption capacity is moderate, and the adsorption capacity is neither too strong nor too weak, so that the adsorption catalyst is suitable for improving the catalytic performance of the composite catalytic reaction.
(2) The method adopts the chemical vapor deposition technology to realize nitrogen doping of nickel-iron-based perovskite type oxides with non-metallic elements, and controls the doping amount of nitrogen by controlling the calcination time of a tubular furnace so as to adjust the oxygen evolution performance; excessive or too little nitrogen content is not beneficial to adsorption and desorption in the intermediate step of oxygen evolution, and the improvement of the catalytic performance is negatively affected; the calcination temperature for preparing the nonmetal-doped nickel-iron-based perovskite type oxide is 450 ℃, the reaction time is 1h, and the oxygen evolution performance of the obtained nonmetal-doped nickel-iron-based perovskite type catalyst is obviously improved compared with that of an undoped nickel-iron-based perovskite type catalyst; and the oxygen evolution catalytic performance of the perovskite is obviously improved by adopting a simple chemical vapor deposition technology, the cost is greatly reduced, and the commercialization requirement is met.
The invention also adopts the chemical vapor deposition technology to prepare the non-metal nitrogen-doped nickel-iron-based perovskite catalyst to improve the oxygen evolution reaction capability and stability, and correspondingly provides a preparation method of the doping process; the method is simple and easy to operate, short in preparation period, environment-friendly and pollution-free, and can be used for replacing a noble metal catalyst to prepare the electrode material on a large scale.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows LaFe prepared by the present invention 1-x Ni x O 3 (x =0, 0.25, 0.5, 0.75, 1) and LaFe 0.5 Ni 0.5 O 3 -NH 3 Schematic XRD of (1);
FIG. 2 shows LaFe prepared by the present invention 1-x Ni x O 3 (x =0, 0.25, 0.5, 0.75, 1) and LaFe 0.5 Ni 0.5 O 3 -NH 3 SEM and EDS spectra of (a);
FIG. 3 shows LaFe prepared by the present invention 0.5 Ni 0.5 O 3 Schematic HRTEM of (1);
FIG. 4 shows LaFe prepared by the present invention 0.5 Ni 0.5 O 3 -NH 3 Schematic HRTEM of (1);
FIG. 5 shows LaFe prepared by the present invention 1-x Ni x O 3 (x =0, 0.25, 0.5, 0.75, 1) and LaFe 0.5 Ni 0.5 O 3 -NH 3 Schematic diagram of the LSV polarization curve of (1);
FIG. 6 shows LaFe prepared by the present invention 1-x Ni x O 3 (x =0, 0.25, 0.5, 0.75, 1) and LaFe 0.5 Ni 0.5 O 3 -NH 3 Tafel slope of (1);
FIG. 7 shows LaFe prepared by the present invention 1-x Ni x O 3 (x =0, 0.25, 0.5, 0.75, 1) and LaFe 0.5 Ni 0.5 O 3 -NH 3 Schematic diagram of electric double layer capacitance of (a);
FIG. 8 shows LaFe prepared by the present invention 1-x Ni x O 3 (x =0, 0.25, 0.5, 0.75, 1) and LaFe 0.5 Ni 0.5 O 3 -NH 3 At a current density of 10mA cm -2 The following overpotential diagram;
FIG. 9 shows LaFe prepared by the present invention 0.5 Ni 0.5 O 3 -NH 3 Schematic stability diagram of (a).
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 of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
Example 1
A universal method for effectively improving the catalytic performance of a perovskite catalyst comprises the following steps:
(1) Perovskite oxide precursor is prepared by a sol-gel method, and 0.01mol of La (NO) is weighed 3 ) 3 ·6H 2 0 and 0.01mol of Fe (NO) 3 ) 3 ·9H 2 Dissolving 0 in 100ml of deionized water, and stirring until the solution is dissolved; then 0.012mol of citric acid is added; the ratio of the amounts of the target metal element and the acidic substance is 5:3;
(2) Putting the solution in the step (1) in a water bath, and heating and stirring at 80 ℃ by adopting a magnetic heating stirrer until gel is formed;
(3) Drying the gel obtained in the step (2) in a constant-temperature drying oven at 120 ℃ for one night;
(4) Grinding the sample obtained in the step (3), then putting the sample into a muffle furnace at 600 ℃ to be calcined for 2h to form a perovskite structure, wherein the heating rate is 2 ℃/min, and naturally cooling to obtain perovskite oxide LaFeO 3 。
Example 2
A universal method for effectively improving the catalytic performance of a perovskite catalyst comprises the following steps:
(1) Perovskite oxide precursor is prepared by a sol-gel method, and 0.01mol of La (NO) is weighed 3 ) 3 ·6H 2 0,0.0075mol of Fe (NO) 3 ) 3 ·9H 2 0 and 0.0025mol of Ni (NO) 3 ) 2 ·6H 2 Dissolving 0 in 100ml of deionized water, and stirring until the solution is dissolved; then 0.012mol of citric acid is added; the ratio of the amounts of the target metal element and the acidic substance is 5:3;
(2) Putting the solution in the step (1) in a water bath, and heating and stirring at 80 ℃ by adopting a magnetic heating stirrer until gel is formed;
(3) Drying the gel obtained in the step (2) in a constant-temperature drying oven at 120 ℃ for one night;
(4) Grinding the sample obtained in the step (3), then putting the sample into a muffle furnace at 600 ℃ to be calcined for 2h to form a perovskite structure, wherein the heating rate is 2 ℃/min, and naturally cooling to obtain a perovskite oxide LaFe 0.75 Ni 0.25 O 3 。
Example 3
A universal method for effectively improving the catalytic performance of a perovskite catalyst comprises the following steps:
(1) Perovskite oxide precursor is prepared by a sol-gel method, and 0.01mol of La (NO) is weighed 3 ) 3 ·6H 2 0,0.0025mol of Fe (NO) 3 ) 3 ·9H 2 0 and 0.0075mol of Ni (NO) 3 ) 2 ·6H 2 Dissolving 0 in 100ml of deionized water, and stirring until the solution is dissolved; then 0.012mol of citric acid is added; the ratio of the amounts of the target metal element and the acidic substance is 5:3;
(2) Putting the solution in the step (1) in a water bath, and heating and stirring at 80 ℃ by adopting a magnetic heating stirrer until gel is formed;
(3) Drying the gel obtained in the step (2) in a constant-temperature drying oven at 120 ℃ for one night;
(4) Grinding the sample obtained in the step (3), then putting the sample into a muffle furnace at 600 ℃ to be calcined for 2h to form a perovskite structure, wherein the heating rate is 2 ℃/min, and naturally cooling to obtain a perovskite oxide LaFe 0.25 Ni 0.75 O 3 。
Example 4
A universal method for effectively improving the catalytic performance of a perovskite catalyst comprises the following steps:
(1) Perovskite oxide precursor is prepared by a sol-gel method, and 0.01mol of La (NO) is weighed 3 ) 3 ·6H 2 0 and 0.01mol of Ni (NO) 3 ) 2 ·6H 2 Dissolving 0 in 100ml of deionized water, and stirring until the solution is dissolved; then 0.012mol of citric acid is added; ratio of amounts of the target metal element and the acidic substance5:3;
(2) Putting the solution in the step (1) in a water bath, and heating and stirring at 80 ℃ by adopting a magnetic heating stirrer until gel is formed;
(3) Drying the gel obtained in the step (2) in a constant-temperature drying oven at 120 ℃ for one night;
(4) Grinding the sample obtained in the step (3), then putting the sample into a muffle furnace at 600 ℃ to be calcined for 2h to form a perovskite structure, wherein the heating rate is 2 ℃/min, and naturally cooling to obtain a perovskite oxide LaNiO 3 。
Example 5
A universal method for effectively improving the catalytic performance of a perovskite catalyst comprises the following steps:
(1) Perovskite oxide precursor is prepared by a sol-gel method, and 0.01mol of La (NO) is weighed 3 ) 3 ·6H 2 0,0.005mol of Fe (NO) 3 ) 3 ·9H 2 0 and 0.005mol of Ni (NO) 3 ) 2 ·6H 2 0 is dissolved in 100ml of deionized water and stirred until the solution is dissolved; then 0.012mol of citric acid is added; the ratio of the amounts of the target metal element and the acidic substance is 5:3;
(2) Putting the solution in the step (1) in a water bath, and heating and stirring at 80 ℃ by adopting a magnetic heating stirrer until gel is formed;
(3) Drying the gel obtained in the step (2) in a constant-temperature drying oven at 120 ℃ for one night;
(4) Grinding the sample obtained in the step (3), then placing the sample into a muffle furnace at 600 ℃ for calcining for 2h to form a perovskite structure, wherein the heating rate is 2 ℃/min, and naturally cooling to obtain a perovskite oxide LaFe 0.5 Ni 0.5 O 3 ；
(5) Weighing 100mg of the nickel-based perovskite oxide obtained in the step (4), introducing ammonia gas into a tubular furnace by adopting a chemical vapor deposition technology, calcining for 2 hours at 450 ℃, heating up at a rate of 5 ℃/min, and naturally cooling to obtain the nonmetallic nitrogen-doped nickel-iron-based perovskite catalyst LaFe 0.5 Ni 0.5 O 3 -NH 3 。
LaFe can be prepared through the steps (1) to (5) 0.5 Ni 0.5 O 3 -NH 3 . By contrast, only performing the steps (1) to (4) without performing the step (5) can obtain LaFe 0.5 Ni 0.5 O 3 。
Example 6
FIG. 1 shows LaFe prepared in example 5 0.5 Ni 0.5 O 3 The XRD pattern of the invention shows that the LaFe prepared by the invention 0.5 Ni 0.5 O 3 And LaFe 0.5 Ni 0.5 O 3 -NH 3 Are pure phases and as the content of the transition metal nickel increases, laFe 1-x Ni x O 3 Since the radius of Ni element is smaller than that of Fe element, when Ni element is substituted for Fe element, lattice contraction occurs, causing the characteristic peaks thereof to move in the direction of increasing 2 θ.
FIG. 2 shows LaFe prepared in example 5 0.5 Ni 0.5 O 3 And LaFe 0.5 Ni 0.5 O 3 -NH 3 SEM picture and EDS spectrum of the same, from which the prepared LaFe can be seen 0.5 Ni 0.5 O 3 The inner side contains La, fe, ni and O elements, while LaFe 0.5 Ni 0.5 O 3 -NH 3 The chemical vapor deposition method is characterized in that the chemical vapor deposition method also contains N elements besides La, fe, ni and O elements, which indicates that the chemical vapor deposition method successfully dopes non-metallic element nitrogen on the nickel-iron-based perovskite type oxide.
FIG. 3 shows LaFe prepared in example 5 0.5 Ni 0.5 O 3 The HRTEM image shows obvious lattice stripes, and the measured lattice spacing is 0.2728nm and 0.3825nm respectively corresponding to LaFe 0.5 Ni 0.5 O 3 The (020) and (110) crystal planes of (A); FIG. 4 shows LaFe prepared in example 1 0.5 Ni 0.5 O 3 -NH 3 The HRTEM image shows obvious lattice stripes, and the measured lattice spacing is respectively 0.3748nm and 0.3801nm, which correspond to LaFe 0.5 Ni 0.5 O 3 -NH 3 (110) crystal plane of (iii).
FIG. 5 is prepared as in example 5Of LaFe 0.5 Ni 0.5 O 3 And LaFe 0.5 Ni 0.5 O 3 -NH 3 LSV polarization plot of (a). As can be seen from the figure, the addition of the transition metal Ni makes the iron-based perovskite LaFeO 3 The OER performance is improved to a certain extent, and the OER performance is further improved by adding nonmetal on the basis.
FIG. 6 shows LaFe prepared in example 5 0.5 Ni 0.5 O 3 And LaFe 0.5 Ni 0.5 O 3 -NH 3 Tafel slope plot of (1). As can be seen from the figure, laFe 0.5 Ni 0.5 O 3 -NH 3 Has a minimum Tafel slope of 65mV dec -1 And superior to the commercial catalyst IrO 2 (86mV dec -1 ) This further illustrates LaFe 0.5 Ni 0.5 O 3 -NH 3 Has faster oxygen ion exchange capacity and good kinetic reaction process in the OER process.
FIG. 7 shows LaFe prepared in example 5 0.5 Ni 0.5 O 3 And LaFe 0.5 Ni 0.5 O 3 -NH 3 The electric double layer capacitance diagram of (1), wherein the scanning voltage is in the range of 0.2 to 0.3V. From the figure, laFe can be seen 0.5 Ni 0.5 O 3 -NH 3 The current density of (A) is maximum, which indicates that LaFe 0.5 Ni 0.5 O 3 -NH 3 The catalyst possesses more catalytically active sites than other catalysts.
FIG. 8 shows LaFe prepared in example 5 0.5 Ni 0.5 O 3 And LaFe 0.5 Ni 0.5 O 3 -NH 3 At a current density of 10mA cm -2 Lower overpotential map. It can be seen from the figure that doping with different Ni contents has a significantly different effect on OER performance, when the doping amount of Ni is 0.5 (LaFe) 0.5 Ni 0.5 O 3 ) The result shows that the doping of Ni can obviously improve the OER catalytic activity of the single iron-based perovskite. This is due to the synergistic effect of Ni and Fe. In addition, the perovskite doped with non-metals is overpotentialThe one-step reduction is 270.6mV vs. RHE, and the result shows that the doping of non-metal elements obviously improves the catalytic performance of the perovskite.
FIG. 9 shows LaFe prepared in example 5 0.5 Ni 0.5 O 3 -NH 3 Stability chart of (2). Setting the current density to 10mA cm in 1M KOH solution -2 For LaFe 0.5 Ni 0.5 O 3 -NH 3 The catalyst was subjected to a 35h stability test. As can be seen from the figure, after the continuous operation for 35h, the overpotential hardly changes. It is noted that the partial relief in the curve is due to the accumulation and elimination of air bubbles during the test.
For the conventional perovskite type electrocatalyst, most researches mainly focus on doping metal elements at the a site and the B site of the perovskite or compounding the metal elements with high-conductivity graphene to improve the electrocatalytic performance of the perovskite type electrocatalyst, such as Oxygen Evolution Reaction (OER), oxygen Reduction Reaction (ORR) and oxygen evolution reaction (HER). The invention adopts sol-gel technology and chemical vapor deposition technology to realize the preparation of the perovskite catalyst doped with transition metal and nonmetal.
Claims (7)
1. A method for effectively improving the catalytic performance of a perovskite catalyst is characterized by comprising the following steps:
step1, doping transition metal nickel in the perovskite structure substance by adopting a sol-gel technology;
and Step2, doping non-metal nitrogen in the perovskite structure substance by adopting a chemical vapor deposition technology to obtain the transition metal and non-metal modified perovskite-based catalyst.
2. The method of claim 1, wherein the sol-gel technique comprises the steps of:
step1.1, mixing La (NO) 3 ) 3 、(1-x)Fe(NO 3 ) 3 、x Ni(NO 3 ) 2 Dissolving in deionized water, and adding acidic substances;
step1.2, putting the solution in a water bath, heating and stirring by adopting a magnetic heating stirrer until gel is formed;
placing the gel in a constant-temperature drying box for low-temperature calcination;
grinding a sample subjected to low-temperature calcination by Step1.4, then putting the sample into a muffle furnace to be calcined to form a perovskite structure, heating, and naturally cooling to obtain a perovskite oxide LaFe 1-x Ni x O 3 。
3. The method of claim 2, wherein the perovskite catalyst has a catalytic performance that is enhanced by:
x =0 to 1 in Step1.1; the ratio of the amounts of the target metals Fe, ni and the acidic substance is 5:2 to 4;
the temperature of water bath heating in the Step1.2 is 65-85 ℃;
the temperature of the low-temperature calcination in the Step1.3 is 100-150 ℃;
the calcining temperature in Step1.4 is 400-600 ℃, and the heating rate is 1-3 ℃/min.
4. A method of effectively enhancing the catalytic performance of a perovskite catalyst as claimed in claim 3, wherein:
x =0.5 in said step1.1; the ratio of the amounts of the target metals Fe, ni and the acidic substance is 5:3;
the temperature of water bath heating in Step1.2 is 80 ℃;
the temperature of the low-temperature calcination in the Step1.3 is 120 ℃;
the calcining temperature in Step1.4 is 600 ℃, and the heating rate is 2 ℃/min.
5. The method for effectively improving the catalytic performance of a perovskite catalyst according to claim 1, wherein the chemical vapor deposition comprises the following steps:
step2.1 preparation of perovskite oxide LaFe 0.5 Ni 0.5 O 3 Placing in a porcelain container, placing in a tube furnace for calcining,adding carrier gas to dope non-metal element nitrogen, and finally cooling to room temperature to obtain the non-metal element nitrogen-doped LaFe 0。5 Ni 0.5 O 3 A perovskite type oxide.
6. The universal method for effectively improving the catalytic performance of a perovskite catalyst as claimed in claim 5, wherein:
in Step2.1, the perovskite oxide LaFe 0.5 Ni 0.5 O 3 Placing in a porcelain container, and placing in a tube furnace at 5 deg.C for min -1 Heating to 450 ℃ at the rate of (1) and keeping for 2h, adding ammonia gas for doping of non-metal element nitrogen, and finally cooling to room temperature to obtain LaFe 0。
5 Ni 0.5 O 3 -NH 3 。
7. The method of any one of claims 1 to 6, wherein the LaFe is effective to enhance the catalytic performance of the perovskite catalyst 0.5 Ni 0.5 O 3 -NH 3 Can be used as an oxygen evolution catalyst.
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