CN111389411A - Perovskite electrocatalyst and preparation method and application thereof - Google Patents
Perovskite electrocatalyst and preparation method and application thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910001868 water Inorganic materials 0.000 claims abstract description 32
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 90
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 34
- 239000011240 wet gel Substances 0.000 claims description 22
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 9
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000499 gel Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 229960001484 edetic acid Drugs 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention provides a perovskite electrocatalyst and a preparation method and application thereof, wherein the chemical expression of the perovskite electrocatalyst is L aCo1‑xPtxO3‑Wherein x is 0-0.08. the invention adopts sol-gel method to prepare perovskite electrocatalyst (L aCo)1‑ xPtxO3‑) Doping trace noble metal Pt at the B site to ensure that the overpotential of the sample for catalyzing water decomposition Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER) is 0.42-0.48V and 0.26-0.32V respectively (the current density is 10 mA/cm)2) Compared to undoped L aCoO3The catalytic performance of the platinum-doped electrocatalyst is improved to a certain extent.
Description
Technical Field
The invention relates to the technical field of electrocatalytic water decomposition, in particular to a perovskite electrocatalyst and a preparation method and application thereof.
Background
With the dramatic decrease in fossil fuels in the world, energy issues have attracted widespread attention. Hydrogen energy is a clean renewable energy source which has been recently approved, and hydrogen can be produced by water decomposition, but the normal water decomposition process has low efficiency and low yield. Therefore, the yield of hydrogen energy can be greatly improved by using the electrocatalyst in the water splitting process. Noble metal simple substance platinum, ruthenium oxide and the like have excellent electrocatalytic performance on water decomposition, but due to the defects of low reserves, high cost, poor stability and the like, the application of the noble metal catalyst in the aspect of water decomposition is limited to a certain extent. Some alternative catalysts, such as transition metal oxides, alkali metal oxides, and perovskite oxides, play an important role in electrocatalytic water decomposition due to their advantages of low cost, good chemical stability, high thermal stability, and the like.
Perovskite type oxide (ABO)3) The type of the transition metal ion at the middle B position determines the oxidation-reduction characteristic and the catalytic activity of the oxide, and the alkali metal ion at the A position mainly plays the roles of a crystal framework and a stable structure. The electrocatalytic activity of perovskite materials can be affected by partial substitution or defect treatment of the a-site or B-site.
Disclosure of Invention
The invention overcomes the defects in the prior art, the catalytic activity of the existing perovskite electrocatalyst is low, and the perovskite electrocatalyst, the preparation method and the application thereof are provided.
The purpose of the invention is realized by the following technical scheme.
A perovskite electrocatalyst and a preparation method thereof, wherein the chemical expression of the perovskite electrocatalyst is L aCo1- xPtxO3-Wherein x is 0 to 0.08, is material L aCoO3The number of oxygen vacancies caused by the principle of electric neutrality after doping trace noble metal Pt is carried out according to the following steps:
and 2, transferring the wet gel obtained in the step 1 into a crucible, placing the crucible into a forced air drying box for drying at the drying temperature of 150 ℃ and the drying time of 20-30h to obtain dry gel, placing the dry gel into a muffle furnace for sintering, raising the temperature from the room temperature of 20-25 ℃ to 400 ℃ at the speed of 2-6 ℃/min, keeping the temperature for 2-4h to completely decompose the nitrate in the precursor, raising the temperature to 800 ℃ at the speed of 6-12 ℃/min, calcining for 3-5h, and then cooling to the room temperature of 20-25 ℃ along with the furnace to finally obtain the perovskite electrocatalyst.
In step 1, the molar ratio of metal ions (the sum of metal lanthanum, metal cobalt and metal platinum), ethylenediamine tetraacetic acid and citric acid is 1:1:2, and the concentration of the perovskite solution is 0.10 mol/L.
In step 1, after ultrasonic dispersion, the aqueous solution is placed in a water bath device with a water bath temperature of 70-90 ℃, preferably 80 ℃, and stirred under magnetic force at a speed of 300-.
In step 2, the wet gel was dried at 120 ℃ for 24 h.
In step 2, the atmosphere in which the xerogel is calcined in the muffle furnace is air.
In the step 2, the temperature is increased from 20-25 ℃ to 450 ℃ at the rate of 3-5 ℃/min, the temperature is kept for 2-3h to completely decompose the nitrate in the precursor, and then the temperature is increased to 800-850 ℃ at the rate of 8-10 ℃/min, and the calcination is carried out for 4-5 h.
The invention has the beneficial effects that the perovskite electrocatalyst (L aCo) is prepared by adopting a sol-gel method1- xPtxO3-) The sample is doped with trace precious metal Pt at the B site to catalyze moistureThe overpotential of the Oxygen Evolution Reaction (OER) and the Hydrogen Evolution Reaction (HER) is 0.42-0.48V and 0.26-0.32V (current density is 10 mA/cm)2) Compared to undoped L aCoO3The catalytic performance of the platinum-doped electrocatalyst is improved to a certain extent.
Drawings
FIG. 1 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-) Has an XRD spectrum of (1), wherein L C is L aCoO3L CP2 is L aCo0.98Pt0.02O3-L CP4 is L aCo0.96Pt0.04O3-L CP6 is L aCo0.94Pt0.06O3-L CP8 is L aCo0.92Pt0.08O3-。
FIG. 2 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-) Has an XRD spectrum of (2), wherein L C is L aCoO3L CP2 is L aCo0.98Pt0.02O3-L CP4 is L aCo0.96Pt0.04O3-L CP6 is L aCo0.94Pt0.06O3-L CP8 is L aCo0.92Pt0.08O3-。
FIG. 3 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-And x ═ 0).
FIG. 4 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-And x ═ 0.06).
FIG. 5 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-) The OER linear sweep voltammogram of (1), wherein the electrolyte is 0.1M KOH aqueous solution, L C is L aCoO3L CP2 is L aCo0.98Pt0.02O3-L CP4 is L aCo0.96Pt0.04O3-L CP6 is L aCo0.94Pt0.06O3-L CP8 is L aCo0.92Pt0.08O3-。
FIG. 6 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-) HER linear sweep ofPlotting voltammogram, wherein the electrolyte is 0.1M KOH aqueous solution, L C is L aCoO3L CP2 is L aCo0.98Pt0.02O3-L CP4 is L aCo0.96Pt0.04O3-L CP6 is L aCo0.94Pt0.06O3-L CP8 is L aCo0.92Pt0.08O3-。
FIG. 7 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-) In which L C is L aCoO3L CP2 is L aCo0.98Pt0.02O3-L CP4 is L aCo0.96Pt0.04O3-L CP6 is L aCo0.94Pt0.06O3-L CP8 is L aCo0.92Pt0.08O3-。
FIG. 8 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-) Has a HER tafel slope of (1), wherein L C is L aCoO3L CP2 is L aCo0.98Pt0.02O3-L CP4 is L aCo0.96Pt0.04O3-L CP6 is L aCo0.94Pt0.06O3-L CP8 is L aCo0.92Pt0.08O3-。
FIG. 9 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-) The OER electrochemical impedance spectroscopy of (1), wherein L C is L aCoO3L CP2 is L aCo0.98Pt0.02O3-L CP4 is L aCo0.96Pt0.04O3-L CP6 is L aCo0.94Pt0.06O3-L CP8 is L aCo0.92Pt0.08O3-。
FIG. 10 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-) HER electrochemical impedance spectroscopy of (1), wherein L C is L aCoO3L CP2 is L aCo0.98Pt0.02O3-L CP4 is L aCo0.96Pt0.04O3-L CP6 is L aCo0.94Pt0.06O3-L CP8 is L aCo0.92Pt0.08O3-。
FIG. 11 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-And x ═ 0.06) OER linear sweep voltammogram before and after cycling.
FIG. 12 shows perovskite electrocatalyst (L aCo) prepared by the present invention1-xPtxO3-X ═ 0.06) HER linear sweep voltammogram before and after cycling.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Lanthanum nitrate, cobalt nitrate, ethylene diamine tetraacetic acid, citric acid and ammonia water are purchased from chemical reagents ltd of miuiou, tianjin, and a platinum nitrate solution (containing 13.29 mass percent of Pt) is purchased from alatin, shanghai.
Example 1
12.9900g of lanthanum nitrate (L a (NO) were weighed out3)3·6H2O), 8.7309g of cobalt nitrate (Co (NO)3)2·6H2O) dissolving the mixture in 300m L deionized water to prepare a solution with the concentration of 0.1 mol/L, then adding 17.5344g of ethylenediamine tetraacetic acid and 25.2168g of citric acid into the mixed solution, stirring the mixture until the mixture is uniformly mixed, then adjusting the pH of the solution to 6-7 by using 25% ammonia water, and placing the mixed solution in a water bath at the temperature of 80 ℃ for magnetic stirring (the stirring speed is 400r/min) until a honey-like wet gel is formed;
then transferring the wet gel into a crucible, and placing the crucible in an oven to dry for 24 hours at 120 ℃ (air atmosphere) to obtain fluffy, fragile and purplish red xerogel;
heating to 400 ℃ at a speed of 3 ℃/min in the air atmosphere of a muffle furnace, keeping for 3h to completely decompose nitrate in the precursor, heating to 800 ℃ at a speed of 10 ℃/min, and calcining for 5h to obtain the perovskite electrocatalyst L aCoO not doped with platinum element3。
Example 2
12.9900g of lanthanum nitrate (L a (NO) were weighed out3)3·6H2O), 8.5563g of cobalt nitrate (Co (NO)3)2·6H2O), 0.8807g of platinum nitrate (Pt (NO)3)2) Dissolving in deionized water to obtain the final productAdding 17.5344g of ethylenediamine tetraacetic acid and 25.2168g of citric acid into the mixed solution, stirring until the mixed solution is uniformly mixed, adjusting the pH of the solution to 6-7 by using 20% ammonia water, and placing the mixed solution in a water bath at 70 ℃ for magnetic stirring (the stirring speed is 300r/min) until honey-shaped wet gel is formed;
then transferring the wet gel into a crucible, and drying the wet gel in an oven at 100 ℃ (air atmosphere) for 30h to obtain fluffy, fragile and purplish red xerogel;
heating to 450 ℃ at the temperature of 5 ℃/min in the air atmosphere of a muffle furnace, keeping the temperature for 2h to completely decompose the nitrate in the precursor, heating to 850 ℃ at the temperature of 8 ℃/min, and calcining for 4h to obtain the perovskite electrocatalyst L aCo doped with the platinum element0.98Pt0.02O3-。
Example 3
12.9900g of lanthanum nitrate (L a (NO) were weighed out3)3·6H2O), 8.3817g of cobalt nitrate (Co (NO)3)2·6H2O), 1.7614g of platinum nitrate (Pt (NO)3)2) Dissolving in deionized water to prepare a solution with the concentration of 0.12 mol/L, then adding 17.5344g of ethylenediamine tetraacetic acid and 25.2168g of citric acid into the mixed solution, stirring until the mixture is uniformly mixed, then adjusting the pH of the solution to 6-7 by using 30% ammonia water, and placing the mixed solution in a water bath at 90 ℃ for magnetic stirring (the stirring speed is 500r/min) until honey-like wet gel is formed;
then transferring the wet gel into a crucible, and drying the wet gel in an oven at 150 ℃ (air atmosphere) for 20h to obtain fluffy, fragile and purplish red xerogel;
heating to 420 ℃ at a temperature of 4 ℃/min in the air atmosphere of a muffle furnace, keeping the temperature for 2.5h to completely decompose the nitrate in the precursor, heating to 820 ℃ at a temperature of 9 ℃/min, and calcining for 4.5h to obtain the perovskite electrocatalyst L aCo doped with the platinum element0.96Pt0.04O3-。
Example 4
12.9900g of lanthanum nitrate (L a (NO) were weighed out3)3·6H2O), 8.2070g of cobalt nitrate (Co (NO)3)2·6H2O), 2.6422g of platinum nitrate (Pt (NO)3)2) Dissolved in 300m L deionized waterPreparing a solution with the concentration of 0.1 mol/L, adding 17.5344g of ethylenediamine tetraacetic acid and 25.2168g of citric acid into the mixed solution, stirring until the mixture is uniformly mixed, adjusting the pH of the solution to 6-7 by using 24% ammonia water, and placing the mixed solution in a water bath at the temperature of 75 ℃ for magnetic stirring (the stirring speed is 450r/min) until honey-shaped wet gel is formed;
then transferring the wet gel into a crucible, and drying the wet gel in an oven at 110 ℃ (air atmosphere) for 26h to obtain fluffy, fragile and purplish red xerogel;
heating to 50 deg.C at 6 deg.C/min in the air atmosphere of muffle furnace, maintaining for 2 hr to completely decompose nitrate in the precursor, heating to 1000 deg.C at 12 deg.C/min, and calcining for 3 hr to obtain platinum-doped perovskite electrocatalyst L aCo0.94Pt0.06O3-。
Example 5
12.9900g of lanthanum nitrate (L a (NO) were weighed out3)3·6H2O), 8.0324g of cobalt nitrate (Co (NO)3)2·6H2O), 3.5229g of platinum nitrate (Pt (NO)3)2) Dissolving in 300m L deionized water to prepare a solution with the concentration of 0.1 mol/L, then adding 17.5344g of ethylenediamine tetraacetic acid and 25.2168g of citric acid into the mixed solution, stirring until the mixture is uniformly mixed, then adjusting the pH of the solution to 6-7 by using 27% ammonia water, placing the mixed solution in a water bath at 85 ℃ and magnetically stirring (the stirring speed is 450r/min) until honey-shaped wet gel is formed;
then transferring the wet gel into a crucible and placing the crucible in an oven for drying for 27h at 130 ℃ (air atmosphere) to obtain fluffy, fragile and purplish red xerogel;
heating to 400 ℃ at a speed of 2 ℃/min in the air atmosphere of a muffle furnace, keeping the temperature for 4h to completely decompose the nitrate in the precursor, heating to 800 ℃ at a speed of 6 ℃/min, and calcining for 5h to obtain the perovskite electrocatalyst L aCo doped with platinum element0.92Pt0.08O3-。
As shown in FIG. 1, the peaks in the graph correspond to L aCo respectively1-xO3The characteristic peak crystal phase of (JCPDSNo.84-0848) is relatively pure.
As shown in fig. 2, as the doping amount of the noble metal Pt increases, the main peaks at about 32.9 ° and 33.3 ° are shifted to the left due to the fact that the ionic radius of the doped Pt is larger than that of Co.
As shown in FIGS. 3 and 4, the spacing of the lattice fringes for the product was about 0.27nm, corresponding to L aCo1-xO3(JCPDSNo.84-0848)
Interplanar spacing, indicating successful noble metal incorporation of L aCoO3。
As shown in FIGS. 5 and 6, overpotentials (current density of 10 mA/cm) of electrocatalytic water-producing oxygen OER and hydrogen-producing HER of platinum-doped perovskite2At corresponding voltage) is lower than that of undoped perovskite L aCoO3It is shown that trace doping of the noble metal Pt does improve the electrocatalytic properties of the perovskite, wherein L aCo0.94Pt0.06O3-The overpotentials for electrocatalytic water oxygen and hydrogen production were the lowest, 0.45V and 0.29V, respectively, indicating that its electrocatalytic water decomposition performance was best compared to other products.
L aCo as shown in FIGS. 7 and 80.94Pt0.06O3-With the smallest tafel slopes of OER and HER.
L aCo as shown in FIGS. 9 and 100.94Pt0.06O3-The electrochemical impedance values with the smallest OER and HER, the smallest Tafel slope and the smallest electrochemical impedance values are also illustrated L aCo0.94Pt0.06O3-Has better electrocatalytic water decomposition performance than other products.
L aCo as shown in FIGS. 11 and 120.94Pt0.06O3-After 500 cycles, the overpotential increases are small in amplitude, namely 20mV and 28mV respectively, which shows that the overpotential also has good stability.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A perovskite electrocatalyst which is characterized in thatThe chemical expression of the perovskite electrocatalyst is L aCo1-xPtxO3-Wherein x is 0-0.08, the method comprises the following steps:
step 1, lanthanum nitrate (L a (NO)3)3·6H2O), cobalt nitrate (Co (NO)3)2·6H2O) and platinum nitrate (Pt (NO)3)2) Adding into deionized water to obtain solution, adding EDTA and citric acid into the solution, wherein the molar ratio of metal ions (metal lanthanum, metal cobalt and metal platinum) to EDTA and citric acid is (1-2) to (2-4), the concentration of perovskite solution is 0.08-0.12 mol/L, and adding 20-30% ammonia water (NH)3·H2O) adjusting the pH value of the solution to 6-7, ultrasonically dispersing the solution, transferring the solution to a magnetic stirrer with a water bath, and uniformly stirring the solution to obtain wet gel;
and 2, transferring the wet gel obtained in the step 1 into a crucible, placing the crucible into a forced air drying box for drying at the drying temperature of 150 ℃ and the drying time of 20-30h to obtain dry gel, placing the dry gel into a muffle furnace for sintering, raising the temperature from the room temperature of 20-25 ℃ to 400 ℃ at the speed of 2-6 ℃/min, keeping the temperature for 2-4h to completely decompose the nitrate in the precursor, raising the temperature to 800 ℃ at the speed of 6-12 ℃/min, calcining for 3-5h, and then cooling to the room temperature of 20-25 ℃ along with the furnace to finally obtain the perovskite electrocatalyst.
2. The perovskite electrocatalyst as claimed in claim 1, wherein in step 1, the molar ratio of the metal ions (the sum of metal lanthanum, metal cobalt and metal platinum), the ethylenediaminetetraacetic acid and the citric acid is 1:1:2, and the concentration of the perovskite solution is 0.10 mol/L.
3. A perovskite electrocatalyst according to claim 1, wherein: in step 1, after ultrasonic dispersion, the aqueous solution is placed in a water bath device with a water bath temperature of 70-90 ℃, preferably 80 ℃, and stirred under magnetic force at a speed of 300-.
4. A perovskite electrocatalyst according to claim 1, wherein: in the step 2, the drying temperature of the wet gel is 120 ℃, the drying time is 24h, the temperature is increased from the room temperature of 20-25 ℃ to 450 ℃ at the speed of 3-5 ℃/min, the temperature is kept for 2-3h, the nitrate in the precursor is completely decomposed, the temperature is increased to 850 ℃ at the speed of 8-10 ℃/min, and the calcination is carried out for 4-5 h.
5. The preparation method of the perovskite electrocatalyst is characterized in that the chemical expression of the perovskite electrocatalyst is L aCo1-xPtxO3-Wherein x is 0-0.08, the method comprises the following steps:
step 1, lanthanum nitrate (L a (NO)3)3·6H2O), cobalt nitrate (Co (NO)3)2·6H2O) and platinum nitrate (Pt (NO)3)2) Adding into deionized water to obtain solution, adding EDTA and citric acid into the solution, wherein the molar ratio of metal ions (metal lanthanum, metal cobalt and metal platinum) to EDTA and citric acid is (1-2) to (2-4), the concentration of perovskite solution is 0.08-0.12 mol/L, and adding 20-30% ammonia water (NH)3·H2O) adjusting the pH value of the solution to 6-7, ultrasonically dispersing the solution, transferring the solution to a magnetic stirrer with a water bath, and uniformly stirring the solution to obtain wet gel;
and 2, transferring the wet gel obtained in the step 1 into a crucible, placing the crucible into a forced air drying box for drying at the drying temperature of 150 ℃ and the drying time of 20-30h to obtain dry gel, placing the dry gel into a muffle furnace for sintering, raising the temperature from the room temperature of 20-25 ℃ to 400 ℃ at the speed of 2-6 ℃/min, keeping the temperature for 2-4h to completely decompose the nitrate in the precursor, raising the temperature to 800 ℃ at the speed of 6-12 ℃/min, calcining for 3-5h, and then cooling to the room temperature of 20-25 ℃ along with the furnace to finally obtain the perovskite electrocatalyst.
6. The process for preparing a perovskite electrocatalyst as claimed in claim 5, wherein in step 1, the molar ratio of metal ions (metal lanthanum, metal cobalt and metal platinum) to ethylenediaminetetraacetic acid and citric acid is 1:1:2, and the concentration of the perovskite solution is 0.10 mol/L.
7. A process for the preparation of a perovskite electrocatalyst as claimed in claim 5 wherein: in step 1, after ultrasonic dispersion, the aqueous solution is placed in a water bath device with a water bath temperature of 70-90 ℃, preferably 80 ℃, and stirred under magnetic force at a speed of 300-.
8. A process for the preparation of a perovskite electrocatalyst as claimed in claim 5 wherein: in step 2, the wet gel was dried at 120 ℃ for 24 h.
9. A process for the preparation of a perovskite electrocatalyst as claimed in claim 5 wherein: in the step 2, the temperature is increased from 20-25 ℃ to 450 ℃ at the rate of 3-5 ℃/min, the temperature is kept for 2-3h to completely decompose the nitrate in the precursor, and then the temperature is increased to 800-850 ℃ at the rate of 8-10 ℃/min, and the calcination is carried out for 4-5 h.
10. Use of a perovskite electrocatalyst as claimed in claims 1 to 4 for the electrolysis of water wherein: the overpotentials of the perovskite electrocatalyst for catalyzing water decomposition Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER) are 0.42-0.48V and 0.26-0.32V respectively, which shows that the perovskite electrocatalyst has better performance in electrocatalytic water decomposition compared with other existing catalysts.
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