CN112824326A - A-site-deficient oxide of titanium-based perovskite structure without alkaline earth elements and preparation and application thereof - Google Patents
A-site-deficient oxide of titanium-based perovskite structure without alkaline earth elements and preparation and application thereof Download PDFInfo
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Abstract
The invention provides a titanium-based oxide which is free of alkaline earth elements and has an A-site vacancy and can maintain a perovskite structure at a temperature of more than 1000 ℃, and the oxide structure comprises the following components: laxTi1‑yFey‑ zMzO3‑δWherein x is more than or equal to 0.66 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 2z and less than or equal to 0, delta represents non-stoichiometric oxygen, delta is more than or equal to-0.2 and less than or equal to 0.4, and M is selected from one of Co, Ni, Mn, Zn, Cu and V; when the titanium-based perovskite oxide is prepared into the cathode material and used in the field of carbon dioxide electroreduction, the cathode material shows good electrochemical performance and is superior to partial cathode materials in the prior art, and the invention also finds that the B-site doped Fe is helpful for keeping the perovskite structure rule of the titanium-based perovskite structure oxide under the high-temperature condition, so that the invention has important significance for further and widely applying the A-site deficient alkali-earth-element-free perovskite structure oxide.
Description
Technical Field
The invention relates to the field of solid oxide electrolytic cells, in particular to an oxide with a titanium-based perovskite structure, and preparation and application thereof.
Background
The dependence of human society on fossil energy development leads to the increase of carbon dioxide concentration in the atmosphere year by year, and the intensification of greenhouse effect brings unprecedented pressure to the ecological environment. The carbon dioxide is converted into high value-added products (carbon monoxide, methane, ethylene and the like) by utilizing renewable energy sources to realize carbon neutral circulation, and the carbon neutral circulation has a positive promotion effect on alleviating greenhouse effect.
As one of the carbon dioxide conversion and utilization techniques, the solid oxide electrolytic cell technique has attracted attention because of its advantages of high reaction rate, high product selectivity, high faraday efficiency, and the like. However, various problems still exist with the cathode materials of solid oxide electrolysis cells for the electroreduction of carbon dioxide. The traditional Ni-based cermet electrode is easy to oxidize and carbon deposit, while the perovskite oxide electrode can avoid the problems, on one hand, the intrinsic catalytic activity of the perovskite oxide is low; on the other hand, most of reported perovskites contain alkaline earth elements, and under high temperature conditions, the alkaline earth elements are segregated on the surface and further react with CO2The reaction generates carbonate, occupies surface active sites, and reduces the performance of the electrode. Therefore, the search for high performance cathode catalysts remains a focus in the current research field.
Titanium-based perovskite oxides (e.g., SrTiO)3) The cathode material used as a solid oxide electrolytic cell is used for carbon dioxide electroreduction, has better catalytic performance,however, most titanium-based perovskites contain alkaline earth elements, and the oxides of titanium-based perovskites without alkaline earth elements (e.g., LaTiO)3+δ) The synthesis is difficult, mainly because under the A-site vacancy state, the valence state of the oxide is not easy to keep balance; the thermodynamic stability of the product can be reduced by controlling the vacancy of the A position to regulate the valence balance of anions and cations. The perovskite oxide needs to be sintered at high temperature (1000-1200 ℃) when being used for preparing a cathode material, but the oxide of the titanium-based perovskite structure with the A-site lacking alkaline earth elements, which is synthesized by the prior art, is difficult to maintain the perovskite structure (ceramic. int.45(2016)1698 1704) at the temperature higher than 800 ℃ because of thermodynamic instability. The above disadvantages prevent the wide application of the oxide in the field of cathode material electrolytic cells, and the oxide is not reported at present for cathode materials of solid oxidation electrolytic cells. In conclusion, the development of the titanium-based perovskite oxide which can keep stable at high temperature and does not contain alkaline earth elements and the application thereof in the field of electrolytic cells have great significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a titanium-based oxide which has no alkaline earth element at the A site and can maintain the perovskite structure at the temperature of more than 1000 ℃ and a preparation method thereof by simultaneously regulating and controlling the A site non-stoichiometry and B site doping elements of the perovskite, and the key point is that the B site doped Fe is beneficial to the oxide to maintain the perovskite structure under the temperature condition. The solid oxide is further applied to the fields of preparation of cathode materials of electrolytic cells and carbon dioxide electroreduction, and the cathode materials are low in cost and show good electrochemical performance and excellent stability.
The technical scheme of the invention is as follows:
in a first aspect, the present invention provides a titanium-based perovskite structure oxide which is free of alkaline earth elements, has a vacancy at the a-position, and can maintain a perovskite structure at a temperature of more than 1000 ℃, the oxide having a composition of: laxTi1-yFey- zMzO3-δWherein x is 0.66-0.7, y is 0.1-0.5, y is 0-2 z, delta is non-stoichiometric oxygen, delta is-0.2-0.4, and M is selected from Co, Ni, Mn, Zn, Cu and VOne kind of the medicine.
In the structural composition expression, x is preferably 0.66. ltoreq. x.ltoreq.0.7, y is preferably 0.1. ltoreq. y.ltoreq.0.5, and y is preferably 0. ltoreq.2 z.ltoreq.y.
In the structural composition expression, 0.66. ltoreq. x.ltoreq.0.7 and 0.2. ltoreq. y.ltoreq.0.4 are preferred.
In the structural composition expression, M is preferably one of Co, Ni, Mn or V.
In a second aspect, the invention provides a preparation method of the titanium-based perovskite oxide, which comprises the following steps:
a. and (3) according to the structural composition expression: laxTi1-yFey-zMzO3-δLanthanum nitrate and butyl titanate are weighed according to the stoichiometric ratio, at least one of ferric nitrate, cobalt nitrate, nickel nitrate, manganese nitrate, zinc nitrate, copper nitrate and ammonium metavanadate is dissolved in 1.5-2.0 mol/L nitric acid aqueous solution;
b. respectively weighing citric acid and ethylenediamine tetraacetic acid, and adding the citric acid and the ethylenediamine tetraacetic acid into the nitrate solution, wherein the total molar number of the citric acid and the metal cations is 1.5: 1-2.0: 1, and the total molar number of the ethylenediamine tetraacetic acid and the metal cations is 1: 1-1.5: 1;
c. dropwise adding ammonia water, and adjusting the pH of the mixed solution to 7-8;
d. stirring at 80 deg.C for 2 hr, and heating at 200 deg.C to form gel;
e. and heating the gel to spontaneous combustion, collecting powder, and calcining for 2-10 hours at the temperature of 800-1200 ℃ to obtain the perovskite structure oxide.
In a third aspect, the invention provides an electrolytic cell cathode material prepared using the titanium-based perovskite oxide.
In a fourth aspect, the invention provides a preparation method of the cathode material of the electrolytic cell, which comprises the following steps:
preparing a titanium-based perovskite structure oxide according to the steps a-e, grinding the prepared titanium-based perovskite structure oxide, and adding 6-10 wt.% of terpineol solution of ethyl cellulose to prepare electrode slurry, wherein the mass ratio of the terpineol solution of the ethyl cellulose to the oxide is 0.6: 1-1: 1; and scraping the electrode slurry on a strontium and magnesium co-doped lanthanum gallate electrolyte sheet coated with a lanthanum-doped cerium oxide transition layer, and calcining for 2-5 h at 1000-1200 ℃.
In a fifth aspect, the present invention provides an electrolytic cell system having said cathode material made of an oxide of titanium-based perovskite structure.
In a sixth aspect, the present invention provides an electrochemical testing method using the electrolytic cell system described herein.
Has the advantages that:
1. the invention provides a series of titanium-based perovskite structure oxides by simultaneously regulating and controlling A-site non-stoichiometry and B-site doping elements of perovskite and controlling the proportion of the elements in each component, wherein the oxides have no alkaline earth elements, have A-site vacancy and can maintain the perovskite structure at the temperature of more than 1000 ℃.
2. The oxide with the titanium-based perovskite structure can be prepared into an electrolytic cell cathode material to be applied to the field of carbon dioxide electroreduction, and the electrolytic cell cathode material prepared by the oxide has excellent catalytic performance and good stability, and is superior to partial cathode materials in the prior art.
3. The invention discovers that the B-site doped Fe is helpful for keeping the rule of the perovskite structure of the titanium-based perovskite structure oxide under the high-temperature condition, and the invention has important significance for further and widely applying the A-site vacancy-free perovskite structure oxide.
Drawings
FIG. 1 is La prepared in comparative example 10.66TiO2.99X-ray diffraction (XRD) spectrum of (a);
FIG. 2 is La prepared in comparative example 20.66Ti0.8Ni0.2O2.79X-ray diffraction (XRD) spectrum of (a);
FIG. 3 is La prepared in comparative example 30.66Ti0.8Co0.2O2.79X-ray diffraction (XRD) spectrum of (a);
FIG. 4 is La prepared in example 100.66Ti0.9Fe0.1O2.94X-ray diffraction (XRD) spectrum of (a);
FIG. 5 is La prepared in example 110.66Ti0.8Fe0.2O2.89X-ray diffraction (XRD) spectrum of (a);
FIG. 6 is La prepared in example 110.66Ti0.8Fe0.2O2.89Electrolysis of CO2The polarization curve of (a);
Detailed Description
The following detailed description of the present invention is provided to illustrate and explain the present invention and is not intended to limit the present invention
Comparative example 1
La0.66TiO2.99Preparation of
According to La0.66TiO2.99By accurately weighing lanthanum nitrate (28.5787g) and butyl titanate (34.034g) in a stoichiometric ratio and dissolving them in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuing heating and stirring to volatilize water until gel is formed, then transferring to a ceramic bowl to heat and spontaneously combust, collecting the powder, placing the powder in a muffle furnace to roast at 1000 ℃ for 5h to obtain a composite oxide, wherein an XRD (X-ray diffraction) spectrogram is shown in figure 1, and the analysis of the spectrogram shows that La after high-temperature roasting0.66TiO2.99Does not have a perovskite structure.
Comparative example 2
La0.66Ti0.8Ni0.2O2.79Preparation of
According to La0.66Ti0.8Ni0.2O2.79By accurately weighing lanthanum nitrate (28.57866g), butyl titanate (27.2272g) and nickel nitrate (5.8158g) in stoichiometric ratio in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water until gel is formed, then transferring to a ceramic bowl to heat and spontaneously combust, collecting the powder, placing in a muffle furnace to roast at 1000 ℃ for 5h to obtain a composite oxide, wherein an XRD spectrogram is shown in figure 2, and analysis on the spectrogram shows that the oxide does not have a perovskite structure.
Comparative example 3
La0.66Ti0.8Co0.2O2.79Preparation of
According to La0.66Ti0.8Co0.2O2.79By accurately weighing lanthanum nitrate (28.57866g), butyl titanate (27.2272g) and cobalt nitrate (5.8206g) in stoichiometric ratio in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water until gel is formed, then transferring to a ceramic bowl to heat and spontaneously combust, collecting the powder, placing in a muffle furnace to roast at 1000 ℃ for 5h to obtain a composite oxide, wherein an XRD spectrogram is shown in figure 3, and analysis on the spectrogram shows that the oxide does not have a perovskite structure.
Example 1
La0.66Ti0.8Fe0.1Ni0.1O2.84Preparation of
According to La0.66Ti0.8Fe0.1Ni0.1O2.84By accurately weighing lanthanum nitrate (28.57866g), butyl titanate (27.2272g), iron nitrate (4.04g) and cobalt nitrate (2.9079g) in stoichiometric ratio in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, the total mole ratio of the nitrate to the metal cation is respectively determinedWeighing citric acid and ethylenediamine diacetic acid according to the ratio of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting powder, placing the powder in a muffle furnace, and roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.66Ti0.8Fe0.1Ni0.1O2.84。
La obtained by the same production method as in comparative example 20.66Ti0.8Ni0.2O2.84Without the perovskite structure, it is known from the comparison of comparative example 2 with example 1 that the B-site doped Fe contributes to the formation of the perovskite structure of the titanium-based oxide under high temperature conditions.
Example 2
La0.66Ti0.8Fe0.1Co0.1O2.84Preparation of
According to La0.66Ti0.8Fe0.1Co0.1O2.84By accurately weighing lanthanum nitrate (28.5786g), butyl titanate (27.2272g), iron nitrate (4.04g) and cobalt nitrate (2.9103g) in stoichiometric ratio in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.66Ti0.8Fe0.1Co0.1O2.84。
La obtained by the same production method as in comparative example 30.66Ti0.8Co0.2O2.84Without perovskite structure, as also obtained by comparing comparative example 3 with example 2, the B-site doped Fe contributes to the formation of perovskite structure of titanium-based oxide under high temperature conditions.
Example 3
La0.66Ti0.5Fe0.5O2.74Preparation of
According to La0.66Ti0.5Fe0.5O2.74By accurately weighing lanthanum nitrate (28.5787g), butyl titanate (17.017g) and iron nitrate (20.2g) in stoichiometric ratio in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.66Ti0.5Fe0.5O2.74。
Example 4
La0.66Ti0.8Fe0.1Mn0.1O2.94Preparation of
According to La0.66Ti0.8Fe0.1Mn0.1O2.94By accurately weighing lanthanum nitrate (28.57866g), butyl titanate (27.2272g), iron nitrate (4.04g) and 50 wt.% manganese nitrate solution (1.7895g) in stoichiometric proportions in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.66Ti0.8Fe0.1Mn0.1O2.94。
Example 5
La0.8Ti0.5Fe0.25Mn0.25O3.075Preparation of
According to La0.8Ti0.5Fe0.25Mn0.25O3.075Expression, lanthanum nitrate (34.6408g), butyl titanate (17.017g), iron nitrate (10.1g) and 50 wt.% manganese nitrate solution (4.4738g) were accurately weighed out from stoichiometric ratios in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.8Ti0.5Fe0.25Mn0.25O3.075。
Example 6
La0.66Ti0.8Fe0.1V0.1O2.99
According to La0.66Ti0.8Fe0.1V0.1O2.99Lanthanum nitrate (28.57866g), butyl titanate (27.2272g), ferric nitrate (4.04g) and ammonium metavanadate (1.1698g) were accurately weighed in stoichiometric proportions and dissolved in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.66Ti0.8Fe0.1V0.1O2.99。
Example 7
La0.8Ti0.5Fe0.25V0.25O3.2
According to La0.8Ti0.5Fe0.25V0.25O3.2By the chemical expression, lanthanum nitrate (34.6408g), butyl titanate (17.017g g), ferric nitrate (10.1g) and ammonium metavanadate (2.9245g) were accurately weighed out from the stoichiometric ratio and dissolved in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, quickly adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.8Ti0.5Fe0.25V0.25O3.2。
Example 8
La0.8Ti0.5Fe0.25Co0.25O2.825
According to La0.8Ti0.5Fe0.25Co0.25O2.825Lanthanum nitrate (34.6408g), butyl titanate (17.017g), iron nitrate (10.1g) and cobalt nitrate (7.2758g) were accurately weighed out from the stoichiometric ratio and dissolved in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.8Ti0.5Fe0.25Co0.25O2.825。
Example 9
La0.8Ti0.5Fe0.25Ni0.25O2.825
According to La0.8Ti0.5Fe0.25Ni0.25O2.825Lanthanum nitrate (34.6408g), butyl titanate (17.017g), ferric nitrate (10.1g) and nickel nitrate (7.26975g) were accurately weighed out from the stoichiometric ratio and dissolved in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.8Ti0.5Fe0.25Ni0.25O2.825。
Example 10
La0.66Ti0.9Fe0.1O2.94
According to La0.66Ti0.9Fe0.1O2.94Lanthanum nitrate (28.5787g), butyl titanate (30.6306g) and iron nitrate (4.04g) were accurately weighed out in stoichiometric proportions and dissolved in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.66Ti0.9Fe0.1O2.94The XRD spectrum is shown in FIG. 4, and the analysis of the spectrum shows that the La after high-temperature roasting0.66Ti0.9Fe0.1O2.94The main phase is perovskite structure with a few impurities.
0.5g of the prepared La0.66Ti0.9Fe0.1O2.94The oxide was ground thoroughly and homogenized, 0.5g of 6 wt.% ethyl fiber was addedAnd preparing the terpineol solution of the element into electrode slurry, coating the electrode slurry on a strontium and magnesium co-doped lanthanum gallate electrolyte sheet coated with a lanthanum-doped cerium oxide transition layer by scraping, and sintering at 1100 ℃ for 2 hours to obtain an electrode with the thickness of about 15 mu m.
CO is carried out by adopting the material2Electroreduction test is carried out, pure carbon dioxide is introduced into the cathode side, and the flow rate is 50mL min-1(ii) a Air is introduced into the anode at a flow rate of 100mL min-1The test temperature is 800 ℃; under the condition of applying 1.4V voltage, the polarization current reaches 0.60A cm-2。
Example 11
La0.66Ti0.8Fe0.2O2.89Preparation of
According to La0.66Ti0.8Fe0.2O2.89By accurately weighing lanthanum nitrate (28.57866g), butyl titanate (27.2272g) and iron nitrate (8.08g) in stoichiometric ratio in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.66Ti0.8Fe0.2O2.89The XRD spectrum is shown in figure 5. With La in example 100.66Ti0.9Fe0.1O2.94In contrast, La0.66Ti0.8Fe0.2O2.89The content of Fe in the composition is increased, impurity diffraction peaks are not seen in an XRD spectrogram, and the prepared oxide forms a pure-phase perovskite structure, so that the Fe is further confirmed to be beneficial to the formation and the stability of the perovskite structure of the titanium-based oxide.
0.5g of the prepared La0.66Ti0.8Fe0.2O2.89The oxide was ground thoroughly and homogenized, and 0.5g of 6 wt.% ethyl cellulose pine oil was addedPreparing an alcohol solution into electrode slurry, coating the electrode slurry on a strontium and magnesium co-doped lanthanum gallate electrolyte sheet coated with a lanthanum-doped cerium oxide transition layer by scraping, and sintering at 1100 ℃ for 2h to obtain an electrode with the thickness of about 15 mu m.
When in electrochemical test, pure carbon dioxide is introduced into the cathode side at the flow rate of 50mL min-1(ii) a Air is introduced into the anode at a flow rate of 100mL min-1The test temperature is 800 ℃; the applied voltage range is 0.2V-1.65V, the electrochemical performance is shown in figure 6, and the current density under the condition of 1.4V can reach 0.80A cm-2。
Example 12
La0.8Ti0.5Fe0.5O2.95Preparation of
According to La0.8Ti0.5Fe0.5O2.95By accurately weighing lanthanum nitrate (34.6408g), butyl titanate (17.017g) and iron nitrate (20.2g) in stoichiometric ratio in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.8Ti0.5Fe0.5O2.95。
0.5g of the prepared La0.8Ti0.5Fe0.5O2.95The oxide was fully and uniformly ground, 0.5g of 6 wt.% terpineol solution of ethyl cellulose was added to make an electrode slurry, the electrode slurry was knife-coated onto a strontium and magnesium co-doped lanthanum gallate electrolyte sheet coated with a lanthanum-doped ceria transition layer, and after sintering at 1100 ℃ for 2h, the electrode thickness was about 15 μm.
CO is carried out by adopting the material2Electroreduction test is carried out, pure carbon dioxide is introduced into the cathode side, and the flow rate is 50mL min-1(ii) a Air is introduced into the anode at a flow rate of 100mL min-1The test temperature is 800 ℃; under the condition of applying 1.4V voltage, the polarization current reaches 1.0A cm-2。
Example 13
La0.7Ti0.7Fe0.3O2.9Preparation of
According to La0.7Ti0.7Fe0.3O2.9By accurately weighing lanthanum nitrate (30.3107g), butyl titanate (23.8238g) and iron nitrate (12.12g) in stoichiometric ratio in 500mL of 1.5mol L-1The total molar concentration of metal cations in the nitric acid aqueous solution is 2mol L-1After the nitrate is dissolved, respectively weighing citric acid and ethylenediamine diacetic acid according to the total molar ratio of the citric acid to metal cations of 1.5:1 and 1:1, dropwise adding ammonia water to adjust the pH value of the solution to 7-8, heating and stirring at 80 ℃ for 1h, raising the temperature to 220 ℃, continuously heating and stirring to volatilize water to form gel, transferring the gel into a ceramic bowl, heating and spontaneous combustion, collecting the powder, placing the powder in a muffle furnace, roasting at 1000 ℃ for 5h to obtain the perovskite structure oxide La0.7Ti0.7Fe0.3O2.9。
0.5g of the prepared La0.7Ti0.7Fe0.3O2.9The oxide was fully and uniformly ground, 0.5g of 6 wt.% terpineol solution of ethyl cellulose was added to make an electrode slurry, the electrode slurry was knife-coated onto a strontium and magnesium co-doped lanthanum gallate electrolyte sheet coated with a lanthanum-doped ceria transition layer, and after sintering at 1100 ℃ for 2h, the electrode thickness was about 15 μm.
CO is carried out by adopting the material2Electroreduction test is carried out, pure carbon dioxide is introduced into the cathode side, and the flow rate is 50mL min-1(ii) a Air is introduced into the anode at a flow rate of 100mL min-1The test temperature is 800 ℃; under the condition of applying 1.4V voltage, the polarization current reaches 1.1Acm-2。
The performances of the cathode material of the electrolytic cell prepared by the invention are compared with the performances of other electrodes reported in the literature, and the specific contents are shown in table 1.
TABLE 1 test of CO electrolysis of various electrode materials at 800 deg.C2Comparison of Performance
The comparison result shows that the catalytic performance of the cathode material prepared by the perovskite oxide without the alkaline earth element with the A-site vacancy provided by the invention is superior to that of part of cathode materials in the prior art.
Any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention should still fall within the protection scope of the technical solution of the present invention for anyone skilled in the art without departing from the technical solution of the present invention.
Claims (9)
1. A titanium-based perovskite structure oxide, characterized in that the perovskite structure oxide has a composition of LaxTi1- yFey-zMzO3-δWherein x is more than or equal to 0.66 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.5, y is more than or equal to 0 and less than or equal to 2z and less than or equal to-0.2 and less than or equal to 0.4, delta represents non-stoichiometric oxygen, and M is selected from one of Co, Ni, Mn, Zn, Cu and V.
2. The titanium-based perovskite structure oxide as claimed in claim 1, wherein x is 0.66. ltoreq. x.ltoreq.0.7, y is 0.1. ltoreq. y.ltoreq.0.5, and y is 0. ltoreq.2 z.ltoreq.y.
3. The titanium-based perovskite structure oxide as claimed in claim 1, wherein x is 0.66. ltoreq. x.ltoreq.0.7, and y is 0.2. ltoreq. y.ltoreq.0.4.
4. The titanium-based perovskite structure oxide according to claim 1, wherein M is one of Co, Ni, Mn and V.
5. A method for producing the titanium-based perovskite structure oxide according to any one of claims 1 to 4, characterized by comprising the steps of:
a. and (3) according to the structural composition expression: la1-xTi1-yFey-zMzO3-δLanthanum nitrate and butyl titanate are weighed according to the stoichiometric ratio, at least one of ferric nitrate, cobalt nitrate, nickel nitrate, manganese nitrate, zinc nitrate, copper nitrate and ammonium metavanadate is dissolved in 1.5-2.0 mol/L nitric acid aqueous solution;
b. respectively weighing citric acid and ethylenediamine tetraacetic acid, and adding the citric acid and the ethylenediamine tetraacetic acid into the nitrate solution, wherein the total molar number of the citric acid and the metal cations is 1.5: 1-2.0: 1, and the total molar number of the ethylenediamine tetraacetic acid and the metal cations is 1: 1-1.5: 1;
c. dropwise adding ammonia water, and adjusting the pH of the mixed solution to 7-8;
d. stirring at 80 deg.C for 2 hr, and heating at 200 deg.C to form gel;
e. and heating the gel to spontaneous combustion, collecting powder, and calcining for 2-10 hours at the temperature of 800-1200 ℃ to obtain the perovskite structure oxide.
6. An electrolytic cell cathode material, characterized in that the cathode material is prepared by using the titanium-based perovskite structure oxide according to any one of claims 1 to 4.
7. A method of making the electrolytic cell cathode material of claim 6, comprising the steps of:
grinding the titanium-based perovskite structure oxide prepared by any one of the claims 5, and then adding 6-10 wt.% terpineol solution of ethyl cellulose to prepare electrode slurry, wherein the mass ratio of the terpineol solution of the ethyl cellulose to the oxide is 0.6: 1-1: 1; and scraping the electrode slurry on a strontium and magnesium co-doped lanthanum gallate electrolyte sheet coated with a lanthanum-doped cerium oxide transition layer, and calcining for 2-5 h at 1000-1200 ℃.
8. An electrolytic cell system characterized in that it has an electrolytic cell cathode material according to any of claim 6.
9. An electrochemical testing method, characterized in that it utilizes the electrolytic cell system of claim 8 for testing.
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