CN114990612A - Indium-based perovskite catalyst LaInO 3 Preparation and use of - Google Patents

Indium-based perovskite catalyst LaInO 3 Preparation and use of Download PDF

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CN114990612A
CN114990612A CN202210805553.9A CN202210805553A CN114990612A CN 114990612 A CN114990612 A CN 114990612A CN 202210805553 A CN202210805553 A CN 202210805553A CN 114990612 A CN114990612 A CN 114990612A
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laino
indium
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周微
刘立成
朱昱晓
董子超
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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Abstract

The invention provides an indium-based perovskite catalyst LaInO 3 Preparation of (1) and electrochemical reduction of CO 2 Application in the preparation of formic acid. The application provides an indium-based perovskite catalyst LaInO 3 The preparation method can obtain the catalyst with the particle size of 60-80nm and uniform dispersion through a simple hydrothermal-calcination two-step method, has simple synthesis process, controllable conditions and smaller particle size, and solves the technical problem of small current density caused by larger particle size of the perovskite catalyst in the prior art. Compared with the prior catalyst, the indium-based perovskite catalyst LaInO 3 Electrochemical reduction of CO 2 In the application of preparing formic acid, the better electrocatalytic reduction of CO is shown 2 The activity and current density of the produced formic acid fill up the research blank of the perovskite catalyst in the field, and the catalyst has good stability and wide market application prospect.

Description

Indium-based perovskite catalyst LaInO 3 Preparation and use of
Technical Field
The invention belongs to the field of electrochemistry, and relates to a method for reducing CO by electrochemistry 2 A catalyst for preparing formic acid, in particular to an indium-based perovskite catalyst LaInO 3 And their use in electrochemical reduction of CO 2 Application in the preparation of formic acid.
Background
Since the industrial revolution of the 19 th century, the massive combustion of fossil fuels has resulted in atmospheric CO 2 The concentration of the compound is continuously increased, thereby bringing a series of environmental problems, threatening the living environment of human beings and causing huge influence on the global climate and ecological balance. In this context, how to reduce atmospheric CO 2 The concentration of (A) becomes an issue to be solved, which makes CO to be in a state of high necessity 2 The capture and reuse techniques of are becoming increasingly important. CO 2 2 Electrochemical reduction can reduce the carbon content in the atmosphere to a certain extent and produce valuable chemical products, thereby gaining increasing attention of researchers. CO 2 2 The reduced products are various, and the alcohol products (mainly methanol and ethanol) and formic acid are easy to store and have high energy density, and can be used as raw materials of Direct Alcohol Fuel Cells (DAFCs). It can be seen from this that electrochemical reduction of CO 2 (CO 2 RR) are advantageous in that: (1) the reaction condition is mild, and the utilization rate of energy is high; (2) renewable energy can be used as an energy source, so that not only is fossil energy consumption reduced, but also the renewable energy is stored in a chemical energy form, and the method is economical, feasible and environment-friendly.
However, due to CO 2 The molecule has higher thermodynamic stability, and the competitive reaction of electrolyzing water to generate hydrogen, CO, exists 2 The reduction reaction of (A) is a coupling reaction involving multiple electrons and multiple protons, resulting in CO 2 The products of RR are often very complex. In CO 2 Among the numerous products of RR, formic acid (HCOOH), a valuable liquid fuel, is an important chemical intermediate in many industrial processes, has wide application in pharmaceutical, leather and textile industries, and has good researchThe prospect is good. Among numerous catalysts for generating formic acid (In, Bi, Sn, Pb-based metal catalysts), indium-based catalysts have been widely studied because of their superior formic acid selectivity. In (In) 2 O 3 As a simple indium-based catalyst, the catalyst has better electrochemical reduction of CO 2 Is formic acid selectivity, but has complex preparation process and low current density, which greatly limits the development of the indium-based catalyst.
In recent years, the general formula ABO 3 The perovskite metal oxide is widely researched in the fields of photoelectricity and catalysis. This is because most of the metallic elements in the periodic table constitute a stable perovskite structure, so that it exhibits high flexibility and diversity of properties. Based on this, significant progress has been made in the use of perovskite catalysts in electrocatalytic Oxygen Evolution Reactions (OERs) and Oxygen Reduction Reactions (ORRs). However, the indium-based perovskite catalyst of which the product is formic acid has poor conductivity and large particle size due to the sintering effect in the preparation process, so that the current density in the reaction process is low. In order to solve these problems, it is necessary to develop a highly efficient and stable catalyst for improving the product selectivity, suppressing the hydrogen evolution reaction, and increasing the current density. At present, no relevant report is found.
Disclosure of Invention
Aiming at the electrochemical reduction of CO in the prior art 2 The invention provides an indium-based perovskite catalyst LaInO, which has the current situation that the preparation method is complicated or the current density is too low in the preparation of a formic acid catalyst 3 Preparation of (2) and its use in electrochemical catalytic reduction of CO 2 Application in the preparation of formic acid. The indium-based perovskite catalyst LaInO prepared by the invention 3 The method has the advantages of simple synthesis process, controllable conditions and small particle size. Therefore, it is used for electrochemical reduction of CO 2 The catalyst for preparing formic acid has high selectivity and high current density, and fills the blank of research of perovskite catalysts in the field.
The technical scheme of the invention is as follows:
indium-based perovskite catalyst LaInO 3 The preparation method comprises the following steps:
(1) weighing proper amount of In(NO 3 ) 3 、La(NO 3 ) 3 ·6H 2 And (3) adding O and glycine into water, stirring until the O and the glycine are completely dissolved and uniformly mixed, and then slowly dropwise adding an alkaline solution until the pH value of the solution is 8-9 to obtain a mixed solution. Wherein, the In (NO) 3 ) 3 、La(NO 3 ) 3 ·6H 2 The molar ratio of O to glycine is 1: 1: (3-6). The alkaline solution is 25-28% ammonia water, NaOH solution or KOH solution. In (NO) In the mixed solution 3 ) 3 And La (NO) 3 ) 3 ·6H 2 The concentration of O is 0.015-0.02 mol/L, and the concentration of glycine is 0.045-0.12 mol/L. The glycine is added, so that a certain adjusting effect is achieved on the preparation of the final appearance of the catalyst.
(2) Carrying out hydrothermal reaction on the mixed solution obtained in the step (1) at the temperature of 170-200 ℃ for 10-14h, cleaning and drying the precipitate after the reaction is finished to obtain in (OH) 3 And La (OH) 3 A precursor of perovskite;
(3) calcining the precursor at the temperature of 600-800 ℃ for 2-3 h to obtain the indium-based perovskite catalyst LaInO 3 . The glycine is added in the step (1), and the hydrothermal reaction and the appropriate calcination condition are combined, so that the prepared catalyst is uniform and granular, and the particle size distribution of the particles is 60-80 nm. Compared with the perovskite catalyst with the grain diameter as high as hundreds of nanometers in the prior art, the indium-based perovskite catalyst prepared by the method not only remarkably reduces the grain diameter and improves the current density, but also can be obtained by a simple hydrothermal-calcining two-step method, the synthesis process is simpler, and the synthesis conditions are controllable.
The indium-based perovskite catalyst LaInO 3 Electrochemical reduction of CO 2 Application in the preparation of formic acid. The application is as follows: the indium-based perovskite catalyst LaInO is added 3 Coating the powder on a substrate material to prepare a working electrode; the substrate material is hydrophobic carbon cloth or carbon paper. Wherein the loading amount of the catalyst on the working electrode is 1-2mg/cm 2 . The indium-based perovskite catalyst LaInO 3 The powder has a particle size of 60-80nAnd m is selected. The specific method for preparing the working electrode comprises the following steps: the indium-based perovskite catalyst LaInO is added 3 The powder is uniformly mixed with a proper amount of Nafion solution and alcohol solvent to obtain mixed solution; and then uniformly coating the mixed solution on a substrate material, and drying to obtain the working electrode. The alcohol solvent is isopropanol, ethanol or ethanol water solution. Compared with indium-based oxide, the indium-based perovskite catalyst LaInO prepared by the method 3 Shows higher electrochemical reduction of CO 2 The activity of formic acid production, the maximum Faraday efficiency can reach 91 percent, and CO is filled 2 Study blank for RR reaction.
The working electrode can be used for electrochemical reduction of CO in an H-type electrolytic cell or a flow electrolytic cell 2 And (4) preparing formic acid. When the catalyst is used in an H-type electrolytic cell, the catalyst is coated on the front side and the back side of the substrate material; when used in a flow cell, the catalyst is coated on one side of a microporous diffusion layer of a base material. Electrochemical reduction of CO with indium-based perovskite catalyst in a flow cell 2 The current density of the formic acid preparation reaction reaches 107mA/cm 2 -1.1V vs. rhe, solving the problem of low current density of the perovskite catalyst.
The invention has the beneficial effects that:
(1) the application provides an indium-based perovskite catalyst LaInO 3 The preparation method can obtain the catalyst with the particle size of 60-80nm and uniform dispersion by a simple hydrothermal-calcination two-step method, has simple synthesis process, controllable conditions and smaller particle size, and solves the technical problem of small current density caused by larger particle size of the perovskite catalyst in the prior art.
(2) Indium-based perovskite catalyst LaInO prepared by the method 3 Compared with the existing catalyst, the catalyst shows better electro-catalytic reduction of CO 2 The activity and current density of the produced formic acid fill the blank of the research of the perovskite catalyst in the field. Wherein, the Faraday efficiency can reach 91 percent at most, and the selectivity is high; the current density is high, and the current density in the flow cell can reach 107mA/cm 2 In an H-type cell, the current density is also higher than for the other catalysts.
(3) The system of the present applicationPrepared indium-based perovskite catalyst LaInO 3 The method has good stability, and the faradaic efficiency and the current density of the formic acid product are basically kept stable after 12 hours of electrolysis.
Drawings
FIG. 1 shows LaInO prepared according to the present invention 3 XRD spectra of the perovskite catalyst and comparison with standard card data.
FIG. 2 shows LaInO prepared according to the present invention 3 SEM image (1) and particle size statistical distribution graph (2) of perovskite.
FIG. 3 shows LaInO in an H-type electrolytic cell 3 、In 2 O 3 、La 2 O 3 And In La mix Electrocatalytic reduction of CO 2 Graph of faradaic efficiency and current density of formic acid production as a function of catalytic potential.
FIG. 4 shows LaInO 3 Total current density at-1.0V vs. rhe potential and change in formic acid faradaic efficiency versus electrolysis time.
FIG. 5 shows LaInO in a flow cell 3 Electrocatalytic reduction of CO 2 Graph of faradaic efficiency and current density of formic acid production as a function of catalytic potential.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1: indium-based perovskite catalyst LaInO 3 Preparation and use of
1. Indium-based perovskite catalyst LaInO 3 Preparation of
In (NO) 3 ) 3 、La(NO 3 ) 3 ·6H 2 O and glycine are mixed according to a molar ratio of 1: 1: 3, stirring until the mixture is completely dissolved and uniformly mixed, and then slowly dropwise adding an alkaline solution until the pH value of the solution is 8-9. In (NO) therein 3 ) 3 And La (NO) 3 ) 3 ·6H 2 The concentration of O was 0.015mol/L and the concentration of glycine was 0.045 mol/L. The alkaline solution is NaOH solution (1M). Continuously stirring until the solution is completely dissolved and uniformly mixed, transferring the solution into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a reaction kettle, and putting the reaction kettle into an ovenCarrying out hydrothermal reaction at 170 ℃ for 14 h; to obtain in (OH) 3 And La (OH) 3 I.e. a precursor of the perovskite catalyst. After the reaction is finished, collecting the precipitate, washing for a plurality of times, and drying in an oven to obtain white precursor powder. And finally, putting the precursor powder into a muffle furnace, and calcining for 3h at 650 ℃ to obtain the product. Comparison of the XRD spectra of the product with the data of a standard card (as shown in FIG. 1) confirms that the product is an indium-based perovskite catalyst LaInO 3 。
Para indium base perovskite catalyst LaInO 3 SEM characterization was performed and the results are shown in FIG. 2. As can be seen from FIG. 2, the synthesized catalyst was in the form of uniform particles, and the particle size of most particles was 60 to 80 nm.
2. Indium-based perovskite catalyst LaInO 3 Application of
Adopts the indium-based perovskite catalyst LaInO 3 Electrochemical reduction of CO 2 The method for preparing the formic acid specifically comprises the following steps:
(1) grinding the prepared catalyst powder until the particles are uniformly dispersed, weighing a proper amount of catalyst powder, mixing the catalyst powder with Nafion solution and isopropanol, and performing ultrasonic dispersion until the mixture is uniformly mixed to obtain a mixed solution. And uniformly coating the mixed solution on a substrate material for a plurality of times in a small amount, and drying overnight to obtain the working electrode. Wherein the loading amount of the catalyst on the working electrode is 1mg/cm 2 And the substrate material is carbon paper.
(2) Electrochemical reduction of CO in H-type electrolytic cell 2 The reaction of (2); the electrolyte is a potassium bicarbonate solution with the concentration of 0.1-1M, and CO is introduced 2 The flow rate of (2) is 30 ml/min. Adopting the working electrode prepared in the step (1), wherein the reference electrode is Ag/AgCl, the counter electrode is a high-purity platinum sheet, and the diaphragm is a proton exchange membrane; the applied potential is-0.8 to-1.3V (vs. RHE). In the working electrode, the catalyst is coated on the front side and the back side of the carbon paper.
(3) Electrochemical reduction of CO in a flow cell 2 The reaction of (1); the electrolyte is a potassium hydroxide solution with the concentration of 0.5-1.5M, and the circulating flow rate of the electrolyte is 20-30 mL/min; prepared by the step (1)Preparing the obtained working electrode, wherein the reference electrode is Ag/AgCl, the counter electrode is foamed nickel or a platinum sheet, and the diaphragm is an anion exchange membrane; the applied potential is-0.7 to-1.3V (vs. RHE). In the working electrode, the catalyst is coated on one side of the microporous diffusion layer of the substrate material.
Example 2: indium-based perovskite catalyst LaInO 3 Preparation and use of
In contrast to the embodiment 1, the process,
1. indium-based perovskite catalyst LaInO 3 Preparation of (2)
In (NO) 3 ) 3 、La(NO 3 ) 3 ·6H 2 O and glycine are mixed according to a molar ratio of 1: 1: and 5, dissolving the mixture in a proper amount of water, stirring the mixture until the mixture is completely dissolved and uniformly mixed, and then slowly dropwise adding an alkaline solution until the pH value of the solution is 8-9. In (NO) therein 3 ) 3 And La (NO) 3 ) 3 ·6H 2 The concentration of O is 0.018mol/L, and the concentration of glycine is 0.09 mol/L. The alkaline solution is ammonia (25-28%). Stirring to dissolve completely, mixing, and performing hydrothermal reaction at 180 deg.C for 12h to obtain in (OH) 3 And La (OH) 3 I.e. a precursor of the perovskite catalyst. After the reaction is finished, collecting the precipitate, washing for a plurality of times, and drying to obtain white precursor powder. And finally, putting the precursor powder into a muffle furnace, and calcining for 2h at 750 ℃ to obtain a product. Comparing the XRD spectrogram of the product with the data of a standard card to confirm that the product is the LaInO catalyst of the indium-based perovskite 3 . Para indium base perovskite catalyst LaInO 3 SEM characterization proves that the particles are uniform particles, and the particle size of most particles is 60-80 nm.
2. Indium-based perovskite catalyst LaInO 3 Application of
Adopts the indium-based perovskite catalyst LaInO 3 Electrochemical reduction of CO 2 The method for preparing the formic acid specifically comprises the following steps:
(1) grinding the prepared catalyst powder until the particles are dispersed relatively uniformly, weighing a proper amount of catalyst powder, mixing the catalyst powder with Nafion solution and ethanol, and ultrasonically dispersing until the catalyst powder is uniformly mixedAnd obtaining a mixed solution. And uniformly coating the mixed solution on hydrophobic carbon cloth for a plurality of times in a small amount, and drying overnight to obtain the working electrode. Wherein the loading amount of the catalyst on the working electrode is 1.5mg/cm 2 。
(2) The same as in example 1.
(3) The same as in example 1.
Example 3: indium-based perovskite catalyst LaInO 3 Preparation and use of
In contrast to the embodiment 1, the process of the invention,
1. indium-based perovskite catalyst LaInO 3 Preparation of
In (NO) 3 ) 3 、La(NO 3 ) 3 ·6H 2 O and glycine are mixed according to a molar ratio of 1: 1: and 6, dissolving in a proper amount of water, stirring until the solution is completely dissolved and uniformly mixed, and then slowly dropwise adding an alkaline solution until the pH value of the solution is 8-9. In (NO) therein 3 ) 3 And La (NO) 3 ) 3 ·6H 2 The concentration of O is 0.02mol/L, and the concentration of glycine is 0.12 mol/L. The alkaline solution is KOH (1M). Stirring to dissolve completely, mixing, and performing hydrothermal reaction at 200 deg.C for 10 hr to obtain in (OH) 3 And La (OH) 3 I.e. a precursor of the perovskite catalyst. After the reaction is finished, collecting the precipitate, washing for a plurality of times, and drying to obtain white precursor powder. And finally, putting the precursor powder into a muffle furnace, and calcining for 2h at 800 ℃ to obtain the product. Comparing the XRD spectrogram of the product with the data of a standard card to confirm that the product is the LaInO catalyst of the indium-based perovskite 3 . Para indium base perovskite catalyst LaInO 3 SEM characterization proves that the particles are uniform particles, and the particle size of most particles is 60-80 nm.
2. Indium-based perovskite catalyst LaInO 3 Application of
Adopts the indium-based perovskite catalyst LaInO 3 Electrochemical reduction of CO 2 The method for preparing the formic acid specifically comprises the following steps:
(1) grinding the prepared catalyst powder until the particles are dispersed relatively uniformly, and weighing a proper amount of the catalyst powder andmixing the Nafion solution and the ethanol-water solution, and performing ultrasonic dispersion until the mixture is uniformly mixed to obtain a mixed solution. And uniformly coating the mixed solution on hydrophobic carbon cloth for a plurality of times in a small amount, and drying overnight to obtain the working electrode. Wherein the loading amount of the catalyst on the working electrode is 2mg/cm 2 。
(2) The same as in example 1.
(3) The same as in example 1.
Comparative example 1: in 2 O 3 Synthesis and application of catalyst
In (NO) 3 ) 3 And glycine in a molar ratio of 1: 5, dissolving the mixture in a proper amount of water, stirring until the mixture is completely dissolved and uniformly mixed; then slowly dropwise adding an alkaline solution until the pH value of the solution is 8-9; in (NO) among them 3 ) 3 The concentration of (2) was 0.018mol/L, and the concentration of glycine was 0.09 mol/L. The alkaline solution is ammonia (25-28%). Continuously stirring until the mixture is completely dissolved and uniformly mixed, and then carrying out hydrothermal reaction for 12 hours at the temperature of 180 ℃; after the reaction is finished, collecting the precipitate, washing for a plurality of times, and drying in a drying oven to obtain white precursor powder; finally, the mixture is placed into a muffle furnace to be calcined for 2 hours at 750 ℃ to obtain In 2 O 3 A catalyst.
(1) Grinding the prepared catalyst powder until the particles are dispersed relatively uniformly, weighing a proper amount of catalyst powder, mixing the catalyst powder with a Nafion solution and ethanol, and performing ultrasonic dispersion until the catalyst powder is uniformly mixed to obtain a mixed solution. And uniformly coating the mixed solution on hydrophobic carbon cloth for a plurality of times in a small amount, and drying overnight to obtain the working electrode. Wherein the loading amount of the catalyst on the working electrode is 1.5mg/cm 2 。
(2) The same as in example 1.
(3) The same as in example 1.
Comparative example 2: la 2 O 3 Synthesis and application of catalyst
Adding La (NO) 3 ) 3 ·6H 2 O and glycine are mixed according to a molar ratio of 1: 5 in a proper amount of water, and magnetically stirring for a period of time; then slowly dripping alkaline solution until the pH value of the solution is 8-9; wherein, La (NO) 3 ) 3 In a concentration of0.018mol/L, the concentration of glycine is 0.09 mol/L. The alkaline solution is ammonia (25-28%). Stirring is continued until the mixture is completely dissolved and mixed evenly, and then the hydrothermal reaction is carried out for 12 hours at the temperature of 180 ℃. After the reaction is finished, collecting the precipitate, washing for a plurality of times, and placing the precipitate in a drying oven to be dried to obtain white precursor powder; finally, the mixture is placed into a muffle furnace to be calcined for 2 hours at 750 ℃ to obtain La 2 O 3 A catalyst.
By using In 2 O 3 Electrochemical reduction of CO by catalyst 2 The method for preparing the formic acid specifically comprises the following steps:
(1) grinding the prepared catalyst powder until the particles are dispersed relatively uniformly, weighing a proper amount of catalyst powder, mixing the catalyst powder with a Nafion solution and ethanol, and performing ultrasonic dispersion until the catalyst powder is uniformly mixed to obtain a mixed solution. And uniformly coating the mixed solution on hydrophobic carbon cloth for a plurality of times in a small amount, and drying overnight to obtain the working electrode. The loading amount of the catalyst on the working electrode is 1.5mg/cm 2 。
(2) The same as in example 1.
(3) The same as in example 1.
Comparative example 3: InLa mix Preparation and use of catalysts
In synthesized as described above 2 O 3 And La 2 O 3 The catalyst is prepared from the following components in a molar ratio of 1: 1 In a mortar, fully grinding for a period of time to fully mix the materials to obtain In La mix A catalyst.
Using In La mix Electrochemical reduction of CO by catalyst 2 The method for preparing the formic acid specifically comprises the following steps:
(1) grinding the prepared catalyst powder until the particles are dispersed relatively uniformly, weighing a proper amount of catalyst powder, mixing the catalyst powder with a Nafion solution and ethanol, and performing ultrasonic dispersion until the catalyst powder is uniformly mixed to obtain a mixed solution. And uniformly coating the mixed solution on hydrophobic carbon cloth for a plurality of times in a small amount, and drying overnight to obtain the working electrode. The loading amount of the catalyst on the working electrode is 1.5mg/cm 2 。
(2) The same as in example 1.
(3) The same as in example 1.
Example 4: performance testing of the indium-based perovskite catalysts prepared in examples 1-3 and the catalyst prepared in comparative example
1. Testing of Faraday efficiency and Current Density: measuring the concentration of formate generated by the reaction through high performance liquid chromatography, and calculating the Faraday efficiency according to the formula FE-znF/Q, wherein FE is the Faraday efficiency; z is the number of electrons transferred in the reaction, which is 2 in the present reaction; n is the mole number of formate accumulated in the reaction process; f is the Faraday constant (96485℃ mol) -1 ) (ii) a Q is the number of charges accumulated during the reaction. The current density was calculated by obtaining the number of charges accumulated during the reaction and the reaction time through an electrochemical workstation, and the results are detailed in table 1.
TABLE 1 electrochemical reduction of CO Using the catalysts prepared in examples 1-3 and comparative examples 1-3 2 Performance parameters for formic acid production
Figure BDA0003737116690000071
As can be seen from Table 1, In was used In comparative example 1 2 O 3 Working electrode prepared with catalyst and comparative example 3 with In La mix The Faraday efficiency of the working electrode prepared from the catalyst in an H-shaped electrolytic cell for producing formic acid is 64-65%; the current density of the produced formic acid under the corresponding potential is 3.0-3.2mA/cm 2 (ii) a In a flowing electrolytic cell, the faradaic efficiency of formic acid production is 60-61%, and the current density of formic acid production under corresponding potential is 28.7-30.1mA/cm 2 . Comparative example 2 use of La 2 O 3 In an H-type electrolytic cell, the faradic efficiency of formic acid production of a working electrode prepared from the catalyst is only 6%; the current density of the formic acid produced under the corresponding potential is only 0.1mA/cm 2 (ii) a In a flow electrolytic cell, the faradaic efficiency of formic acid production is only 5%, and the current density of formic acid production at the corresponding potential is 1.9mA/cm 2 。
In addition, LaInO as an indium-based perovskite catalyst prepared in examples 1 to 3 of the present application 3 In an H-type electrolytic cell, the Faraday efficiency of formic acid production is 89-91%, and the current density of formic acid production under corresponding potential is 8.3-9.1mA/cm 2 . Compared with comparative examples 1 and 3, the absolute value of the Faraday efficiency is increased by 25 percent, and the relative Faraday efficiency is increased by 39 percent; the current density of the formic acid produced under the corresponding potential is increased by 4.9-6.1mA/cm 2 And the relative improvement is 153-203%. In a flowing electrolytic cell, the Faraday efficiency of the formic acid production is 88-91%, and the current density of the formic acid production under the corresponding potential can reach 103.5-106.8mA/cm 2 . Compared with comparative examples 1 and 3, the absolute value of the Faraday efficiency is increased by 30 percent, and the Faraday efficiency is relatively increased by 50 percent; the current density of the formic acid is increased by 73.4-78.1mA/cm under the corresponding potential 2 The yield is relatively improved by 244 to 272 percent. It can be seen that the working electrodes prepared in examples 1-3 of the present application use the indium-based perovskite catalyst LaInO prepared in the present application 3 In both H-type electrolytic cells and flow electrolytic cells, the Faraday efficiency and the current density of formic acid produced at corresponding potential are remarkably improved, and unexpected technical effects are generated.
As previously described, the indium-based perovskite catalysts LaInO prepared in examples 1-3 3 The faradaic efficiency of formic acid production is basically consistent with the current density of formic acid production under corresponding potential. Thus, LaInO prepared as in example 2 3 For example, LaInO in an H-cell was investigated 3 、In 2 O 3 、La 2 O 3 And In La mix Electrocatalytic reduction of CO 2 The Faraday efficiency and current density of the methanogenic acid as a function of the catalytic potential (FIG. 3) confirm that the indium-based perovskite catalyst LaInO 3 The faradaic efficiency of formic acid production and the current density of formic acid production at the corresponding potential are significantly due to the other three catalysts. At the same time, the LaInO prepared in example 2 in a flow cell was also investigated 3 Electrocatalytic reduction of CO 2 The faradaic efficiency and current density of formic acid production as a function of catalytic potential (figure 5); obtain LaInO 3 Electrocatalytic reduction of CO 2 The highest Faraday efficiency of formic acid production is 91% (-1.1V vs. RHE), and the current density is 107mA/cm 2 The results are in accordance with Table 1.
2. And (3) stability testing: for the indium-based perovskite catalysts LaInO prepared in examples 1-3 3 Was tested for stability, result oneThus, example 2 is used as an example for explanation. The indium-based perovskite catalyst LaInO prepared in the example was obtained by the foregoing detection method 3 Graph of total current density and change in formic acid faradaic efficiency versus electrolysis time at-1.0V vs. rhe potential (figure 4). As can be seen from FIG. 4, the Faraday efficiency and current density of the formic acid product remained substantially constant after 12h electrolysis, indicating that LaInO 3 The catalyst has good stability.
As can be seen from the above, the indium-based perovskite catalyst LaInO prepared in examples 1 to 3 of the present application was used 3 The working electrode of (2) shows better electrocatalytic reduction of CO 2 The activity and current density of the produced formic acid fill the blank of the research of the perovskite catalyst in the field. In addition, the application provides a hydrothermal-calcination two-step method for preparing the indium-based perovskite catalyst LaInO 3 The method has the advantages of simple synthesis process, controllable conditions, small particle size (60-80nm) and uniform dispersion, and solves the technical problem of small current density caused by large particle size of the perovskite catalyst in the prior art. Meanwhile, the indium-based perovskite catalyst LaInO prepared by the method 3 The method has good stability, the Faraday efficiency and the current density of the formic acid product basically keep stable after 12h of electrolysis, and the method has important practical application value.

Claims (10)

1. Indium-based perovskite catalyst LaInO 3 Electrochemical reduction of CO 2 Application in the preparation of formic acid.
2. Use according to claim 1, characterized in that: the indium-based perovskite catalyst LaInO is added 3 Coating the powder on a substrate material to prepare a working electrode; the substrate material is hydrophobic carbon cloth or carbon paper.
3. Use according to claim 2, characterized in that: the loading amount of the catalyst on the working electrode is 1-2mg/cm 2 。
4. Use according to claim 2, characterized in that: what is needed isThe indium-based perovskite catalyst LaInO 3 The particle size of the powder is 60-80 nm.
5. Use according to any one of claims 2 to 4, characterized in that: the specific method for preparing the working electrode comprises the following steps: the indium-based perovskite catalyst LaInO is added 3 The powder is uniformly mixed with a proper amount of Nafion solution and alcohol solvent to obtain mixed solution; and uniformly coating the mixed solution on a substrate material, and drying to obtain the working electrode.
6. Use according to claim 5, characterized in that: the working electrode is used for electrochemical reduction of CO in an H-type electrolytic cell or a flow electrolytic cell 2 Preparing formic acid; when an H-type electrolytic cell is adopted, the catalyst is coated on the front surface and the back surface of the substrate material; when a flow electrolytic cell is adopted, the catalyst is coated on one side of the microporous diffusion layer of the substrate material.
7. Use according to claim 5, characterized in that: the alcohol solvent is isopropanol, ethanol or ethanol water solution.
8. An indium-based perovskite catalyst LaInO as claimed in any of claims 1 to 7 for use 3 The preparation method is characterized in that: the method comprises the following steps:
(1) weighing proper amount of In (NO) 3 ) 3 、La(NO 3 ) 3 ·6H 2 Dissolving O and glycine in water, stirring until the O and the glycine are completely dissolved and uniformly mixed, and then slowly dropwise adding an alkaline solution until the pH value of the solution is 8-9 to obtain a mixed solution;
(2) carrying out hydrothermal reaction on the mixed solution obtained in the step (1) at the temperature of 170-200 ℃ for 10-14h, cleaning and drying the precipitate after the reaction is finished to obtain in (OH) 3 And La (OH) 3 A precursor of perovskite;
(3) calcining the precursor at the temperature of 600-800 ℃ for 2-3 h to obtain the indium-based perovskite catalyst LaInO 3 。
9. The indium-based perovskite catalyst LaInO of claim 1 3 The preparation method is characterized by comprising the following steps: in (NO) In step (1) 3 ) 3 、La(NO 3 ) 3 ·6H 2 The molar ratio of O to glycine is 1: 1: (3-6).
10. The indium-based perovskite catalyst LaInO as claimed in claim 1 3 The preparation method is characterized by comprising the following steps: the alkaline solution in the step (1) is 25-28% of ammonia water, NaOH solution or KOH solution; in (NO) In the mixed solution 3 ) 3 And La (NO) 3 ) 3 ·6H 2 The concentration of O is 0.015-0.02 mol/L, and the concentration of glycine is 0.045-0.12 mol/L.
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