CN117753980A - Electrocatalytic reduction carbon dioxide anti-perovskite catalyst - Google Patents
Electrocatalytic reduction carbon dioxide anti-perovskite catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 34
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 34
- 230000009467 reduction Effects 0.000 title claims abstract description 29
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- 238000002360 preparation method Methods 0.000 claims abstract description 21
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- 238000000034 method Methods 0.000 claims description 16
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
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- YZZFBYAKINKKFM-UHFFFAOYSA-N dinitrooxyindiganyl nitrate;hydrate Chemical group O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZZFBYAKINKKFM-UHFFFAOYSA-N 0.000 claims description 7
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- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 7
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 7
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- 229910052738 indium Inorganic materials 0.000 abstract description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 11
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- 238000002441 X-ray diffraction Methods 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an electrocatalytic reduction carbon dioxide anti-perovskite catalyst, which is prepared by the following steps: (1) Dissolving nickel salt, indium salt, metavanadate and a molecular activator into water, performing ultrasonic dispersion, and performing magnetic stirring; (2) hydrothermal reaction; (3) Centrifuging, collecting precipitate, cleaning, and drying; and (4) annealing treatment to obtain the product. The molecular formula of the anti-perovskite catalyst is InNNi 3‑x V x . The preparation method of the working electrode comprises the following steps: (1) Mixing 10mg of anti-perovskite catalyst, 5mg of carbon black, 50 mu L of nafion solution, 500 mu L of ethanol and 450 mu L of deionized water, placing the mixture into a 2mL closed container, and continuing to carry out ultrasonic treatment for 1h; and (2) uniformly spraying to obtain the product. The anti-perovskite catalyst has rich indium active site support and good conductivity and magnetism, and can be used as a catalyst for electrocatalytic reduction of carbon dioxide into formic acid.
Description
Technical Field
The invention relates to the technical field of electrocatalytic reduction of carbon dioxide, in particular to an electrocatalytic reduction carbon dioxide anti-perovskite catalyst.
Background
Carbon dioxide (CO) 2 ) The emissions exceeding the standard cause serious environmental pollution problems, and the massive consumption of fossil energy also causes a plurality of potential irreversible energy crisis in human society. To solve the above problems, scientists have proposed a number of reduction processes for converting carbon dioxide into valuable chemicals, such as thermocatalysis, photocatalysis, bioconversion, electrocatalysis, etc. The electrocatalytic reduction method can control reduction products through voltage, catalyst components, electrolyte concentration and the like, and the electrolytic cell has a simple structure, and electrolyte is easy to recycle, so that the electrocatalytic reduction method has great potential to assist global energy storage and achieve the aim of carbon neutralization more quickly.
In the course of the electrocatalytic reduction of carbon dioxide, by transferring 2, 4, 6, 8 or 12 electrons, various valuable products can be obtained, the most common products being carbon monoxide (CO), methane (CH) 4 ) Formic acid (HCOOH), methanol (CH) 3 OH, ethylene (C) 2 H 4 ) Ethanol (C) 2 H 5 OH), and the like. However, carbon dioxide molecules have extremely high chemical stability because of the highly oxidizing nature of carbon dioxide. In addition, CO 2 Is challenged by competing Hydrogen Evolution Reactions (HER), has high thermodynamic and kinetic barriers, and has limited selectivity for specific products. In view of the above, the choice of catalyst is critical. At present, the high-selectivity catalyst is still a noble metal catalyst such as platinum, gold, silver and the like. Therefore, the development of low-cost, high-selectivity and long-stability catalysts is a key to practical application of electrocatalytic reduction of carbon dioxide.
Currently, non-noble metal catalysts, such as Cu, ni, in, bi, have been developed which are partially excellent in performance and inexpensive. Of these catalysts, in has a high selectivity to formic acid, but few indium-based catalysts can operate for a long period of time without deactivation. Therefore, it is a difficulty of current research to be able to maintain long-term stability while improving the selectivity of indium-based materials.
Currently, some researchers begin to design indium-based materials into ore structures with stable structures. Inverse perovskite is a face-centered cubic structure material that has been similar to perovskite structures, but positive and negative particles occupy opposite positions in the structure. The inverse perovskite has the same structural tolerance and diversity as the perovskite, and has unique "cation-rich" properties and good electrical conductivity. These advantages of inverse perovskite are a great advantage in electrocatalysis, which may be a tunable selectivity catalyst.
Therefore, how to develop an anti-perovskite catalyst having both high selectivity and long-term stability is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention aims to provide an electrocatalytic reduction carbon dioxide anti-perovskite catalyst, which solves the disadvantages in the prior art.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the anti-perovskite catalyst specifically comprises the following steps:
(1) Dissolving nickel salt, indium salt, metavanadate and a molecular activator into water, performing ultrasonic dispersion, and magnetically stirring to obtain a mixed solution;
(2) Carrying out hydrothermal reaction on the mixed solution to obtain a suspension;
(3) Centrifuging the suspension, collecting precipitate, cleaning, and drying to obtain a precursor;
(4) And (3) annealing the precursor to obtain the anti-perovskite catalyst.
Further, in the step (1), the nickel salt is nickel acetate tetrahydrate; the indium salt is indium nitrate hydrate; the metavanadate is ammonium metavanadate; the molecular activator is hexamethylenetetramine; the water is deionized water; the dosage ratio of nickel salt, indium salt, metavanadate, molecular activator and water is (1.1-1.4) mmol to 0.5mmol (0.1-0.4) mmol to 4mmol to 40mL, preferably 1.2mmol to 0.5mmol to 0.3mmol to 4mmol to 40mL.
The adoption of the method has the further beneficial effects that the nickel acetate tetrahydrate is used for providing a nickel source; the function of the indium nitrate hydrate is to provide a source of indium; the ammonium metavanadate serves to provide a vanadium source; the role of Hexamethylenetetramine (HMT) is to activate the metal precursor.
Further, in the step (1), the ultrasonic dispersion time is 30min; the rotation speed of the magnetic stirring is 550r/min, and the time is 30min.
The adoption of the ultrasonic dispersing device has the further beneficial effects that the metal ions are better dissolved and uniformly dispersed through ultrasonic dispersion and magnetic stirring.
Further, in the step (2), the temperature of the hydrothermal reaction is 120 ℃ and the time is 12 hours. Further, the hydrothermal reaction specifically includes: and transferring the mixed solution into a polytetrafluoroethylene liner with the capacity of 100mL, loading the polytetrafluoroethylene liner into a stainless steel water heating reaction kettle, and then placing the stainless steel water heating reaction kettle in a blast drying oven, and keeping the temperature at 120 ℃ for 12 hours.
The adoption of the method has the further beneficial effect that the catalyst precursor can be uniformly generated through hydrothermal reaction.
Further, in the step (3), the rotational speed of centrifugation is 7000r/min, and the time is 15min; the cleaning is specifically as follows: respectively cleaning with water and ethanol alternately for three times; the drying temperature was 60℃and the time was 12 hours.
The precursor and the waste liquid can be separated by centrifugation. Organic impurities can be washed off by washing; by drying, moisture in the precursor can be removed, and generation of impurities during the annealing treatment can be avoided.
Further, in the step (4), the annealing treatment specifically includes: and placing the precursor in a tube furnace, continuously ventilating for 30min at room temperature by taking ammonia gas as carrier gas, continuously heating up to 550 ℃ at 5 ℃/min, keeping the temperature for 5h, switching the carrier gas to nitrogen gas when the tube furnace is naturally cooled to 200 ℃, and naturally cooling to room temperature.
The adoption of the method has the further beneficial effects that the ammonia gas is firstly taken as carrier gas, and the purpose of continuously ventilating for 30min at room temperature is to manufacture ammonia atmosphere, so that a nitrogen source is provided for the anti-perovskite catalyst. The purpose of switching the carrier gas to nitrogen when the tube furnace is naturally cooled to 200 ℃ is to remove the residual ammonia in the tube furnace.
The molecular formula of the anti-perovskite catalyst prepared by the preparation method is InNNi 3-x V x Where x=0.2, 0.4, 0.6 or 0.8.
Further, the molecular formula of the anti-perovskite catalyst is InNNi 2.4 V 0.6 。
The preparation method of the working electrode containing the anti-perovskite catalyst prepared by the preparation method specifically comprises the following steps:
(1) Mixing 10mg of anti-perovskite catalyst, 5mg of carbon black, 50 mu L of nafion solution, 500 mu L of ethanol and 450 mu L of deionized water, and placing the mixture in a 2mL closed container, and continuing to carry out ultrasonic treatment for 1h to obtain catalytic ink;
(2) And uniformly spraying the catalytic ink on carbon paper or foam nickel by using a spray gun to obtain the working electrode.
The use of carbon black has the further beneficial effect that the purpose of adding the carbon black is to enhance conductivity; the purpose of adding nafion (perfluorosulfonic acid polymer) solution is to enhance the adhesion of the catalytic ink; the purpose of adding ethanol is to enhance volatility; the purpose of the deionized water addition is to increase the solubility of the inverse perovskite catalyst.
An anti-perovskite catalyst prepared by the preparation method, an application of the anti-perovskite catalyst and a working electrode prepared by the preparation method in preparing formic acid by electrocatalytic reduction of carbon dioxide.
Compared with the prior art, the invention has the following beneficial effects:
1. the anti-perovskite catalyst has rich indium active site support and good conductivity and magnetism, and can be used as a catalyst for electrocatalytic reduction of carbon dioxide into formic acid.
2. The invention is doped with InNNi by vanadium 3 Is constructed by regulating Ni 3 The structural distortion of the N-octahedron changes the local electronic state inside the catalyst and exposes more indium catalytic active sites, thereby improving the faraday efficiency and catalytic activity of the catalyst. The face-centered cubic structure formed by the inverse perovskite greatly improves the stability of the catalyst and realizes a great breakthrough in the aspects of service life and selectivity of the indium-based catalyst.
3. According to the invention, the stability of the indium-based material is improved by selecting the catalyst structure, and the catalyst structure is modified by doping metal vanadium, so that more indium active sites are exposed, the selectivity and electrochemical activity of the catalyst for electrocatalytic reduction of carbon dioxide are improved, and efficient and stable electrocatalytic reduction of carbon dioxide into formic acid can be realized.
4. The catalyst of the invention is prepared from inverse perovskite InNNi 3 The material is obtained by doping metal V on the X position, adopts a two-step method (hydrothermal reaction and annealing treatment) and is prepared by modifying InNNi 3 The metal V with different proportions is doped, so that the doping proportion with the best performance is screened out.
5. According to the invention, through material design and strategy design, an electrocatalytic carbon dioxide reduction catalyst with high selectivity and long-time stability is synthesized, the problems of low selectivity and poor stability of the conventional indium-based catalyst are solved, and the actual application of electrocatalytic carbon dioxide reduction is greatly promoted.
Drawings
FIG. 1 is a process flow diagram of a method for preparing an inverse perovskite catalyst of examples 1-4;
FIG. 2 is an X-ray diffraction pattern of the inverse perovskite catalysts of comparative example 1 and examples 1-4;
FIG. 3 is an InNNi of the anti-perovskite catalyst of example 3 2.4 V 0.6 Scanning electron microscope images of (2);
FIG. 4 is an InNNi of the anti-perovskite catalyst of example 3 2.4 V 0.6 Is a high power transmission electron microscope image;
FIG. 5 is an X-ray photoelectron spectrum of the anti-perovskite catalysts of comparative example 1 and example 3;
FIG. 6 is a graph of electrocatalytic reduction carbon dioxide polarization for working electrodes of comparative example 2 and examples 5-8;
FIG. 7 is a graph of the Faraday efficiency of electrocatalytic reduction of carbon dioxide for working electrodes of comparative example 2 and examples 5-8;
FIG. 8 is a graph of electrocatalytic reduction carbon dioxide stability test i-t for the working electrode of example 7.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the anti-perovskite catalyst, as shown in fig. 1, specifically comprises the following steps:
(1) 1.4mmol of nickel acetate tetrahydrate, 0.5mmol of indium nitrate hydrate, 0.1mmol of ammonium metavanadate and 4mmol of hexamethylenetetramine are dissolved in 40mL of deionized water, dispersed for 30min by ultrasonic, and magnetically stirred for 30min at a rotating speed of 550r/min to obtain a mixed solution;
(2) Transferring the mixed solution into a polytetrafluoroethylene liner with the capacity of 100mL, loading into a stainless steel water heating reaction kettle, and then placing into a blast drying oven for hydrothermal reaction at the constant temperature of 120 ℃ for 12 hours to obtain a suspension;
(3) Adding the suspension into a centrifuge, centrifuging at 7000r/min for 15min, collecting precipitate, cleaning with water and ethanol respectively, and drying in a blast drying oven at 60deg.C for 12 hr to obtain precursor;
(4) Placing the precursor in a tube furnace, continuously ventilating for 30min at room temperature by taking ammonia gas as carrier gas, continuously heating up to 550 ℃ at 5 ℃/min, keeping the temperature for 5h, switching the carrier gas to nitrogen gas when the tube furnace is naturally cooled to 200 ℃, and naturally cooling to room temperature to obtain the inverse perovskite catalyst InNNi 2.8 V 0.2 。
Example 2
The preparation method of the anti-perovskite catalyst, as shown in fig. 1, specifically comprises the following steps:
(1) 1.3mmol of nickel acetate tetrahydrate, 0.5mmol of indium nitrate hydrate, 0.2mmol of ammonium metavanadate and 4mmol of hexamethylenetetramine are dissolved in 40mL of deionized water, dispersed for 30min by ultrasonic, and magnetically stirred for 30min at a rotating speed of 550r/min to obtain a mixed solution;
(2) Transferring the mixed solution into a polytetrafluoroethylene liner with the capacity of 100mL, loading into a stainless steel water heating reaction kettle, and then placing into a blast drying oven for hydrothermal reaction at the constant temperature of 120 ℃ for 12 hours to obtain a suspension;
(3) Adding the suspension into a centrifuge, centrifuging at 7000r/min for 15min, collecting precipitate, cleaning with water and ethanol respectively, and drying in a blast drying oven at 60deg.C for 12 hr to obtain precursor;
(4) Placing the precursor in a tube furnace, continuously ventilating for 30min at room temperature by taking ammonia gas as carrier gas, continuously heating up to 550 ℃ at 5 ℃/min, keeping the temperature for 5h, switching the carrier gas to nitrogen gas when the tube furnace is naturally cooled to 200 ℃, and naturally cooling to room temperature to obtain the inverse perovskite catalyst InNNi 2.6 V 0.4 。
Example 3
The preparation method of the anti-perovskite catalyst, as shown in fig. 1, specifically comprises the following steps:
(1) 1.2mmol of nickel acetate tetrahydrate, 0.5mmol of indium nitrate hydrate, 0.3mmol of ammonium metavanadate and 4mmol of hexamethylenetetramine are dissolved in 40mL of deionized water, dispersed for 30min by ultrasonic, and magnetically stirred for 30min at a rotating speed of 550r/min to obtain a mixed solution;
(2) Transferring the mixed solution into a polytetrafluoroethylene liner with the capacity of 100mL, loading into a stainless steel water heating reaction kettle, and then placing into a blast drying oven for hydrothermal reaction at the constant temperature of 120 ℃ for 12 hours to obtain a suspension;
(3) Adding the suspension into a centrifuge, centrifuging at 7000r/min for 15min, collecting precipitate, cleaning with water and ethanol respectively, and drying in a blast drying oven at 60deg.C for 12 hr to obtain precursor;
(4) Placing the precursor in a tube furnace, continuously ventilating for 30min at room temperature by taking ammonia gas as carrier gas, continuously heating up to 550 ℃ at 5 ℃/min, keeping the temperature for 5h, switching the carrier gas to nitrogen gas when the tube furnace is naturally cooled to 200 ℃, and naturally cooling to room temperature to obtain the inverse perovskite catalyst InNNi 2.4 V 0.6 。
Example 4
The preparation method of the anti-perovskite catalyst, as shown in fig. 1, specifically comprises the following steps:
(1) 1.1mmol of nickel acetate tetrahydrate, 0.5mmol of indium nitrate hydrate, 0.4mmol of ammonium metavanadate and 4mmol of hexamethylenetetramine are dissolved in 40mL of deionized water, dispersed for 30min by ultrasonic, and magnetically stirred for 30min at a rotating speed of 550r/min to obtain a mixed solution;
(2) Transferring the mixed solution into a polytetrafluoroethylene liner with the capacity of 100mL, loading into a stainless steel water heating reaction kettle, and then placing into a blast drying oven for hydrothermal reaction at the constant temperature of 120 ℃ for 12 hours to obtain a suspension;
(3) Adding the suspension into a centrifuge, centrifuging at 7000r/min for 15min, collecting precipitate, cleaning with water and ethanol respectively, and drying in a blast drying oven at 60deg.C for 12 hr to obtain precursor;
(4) Placing the precursor in a tube furnace, continuously ventilating for 30min at room temperature by taking ammonia gas as carrier gas, continuously heating up to 550 ℃ at 5 ℃/min, keeping the temperature for 5h, switching the carrier gas to nitrogen gas when the tube furnace is naturally cooled to 200 ℃, and naturally cooling to room temperature to obtain the inverse perovskite catalyst InNNi 2.2 V 0.8 。
Example 5
The preparation method of the working electrode containing the anti-perovskite catalyst specifically comprises the following steps:
(1) Mixing 10mg of the anti-perovskite catalyst prepared in the example 1, 5mg of carbon black, 50 mu L of nafion solution, 500 mu L of ethanol and 450 mu L of deionized water, and placing the mixture in a 2mL closed container, and continuing ultrasonic treatment for 1h to obtain catalytic ink;
(2) And uniformly spraying the catalytic ink on carbon paper or foam nickel by using a spray gun to obtain the working electrode.
Example 6
The preparation method of the working electrode containing the anti-perovskite catalyst specifically comprises the following steps:
(1) Mixing 10mg of the anti-perovskite catalyst prepared in example 2, 5mg of carbon black, 50 mu L of nafion solution, 500 mu L of ethanol and 450 mu L of deionized water, and placing the mixture in a 2mL closed container, and continuing ultrasonic treatment for 1h to obtain catalytic ink;
(2) And uniformly spraying the catalytic ink on carbon paper or foam nickel by using a spray gun to obtain the working electrode.
Example 7
The preparation method of the working electrode containing the anti-perovskite catalyst specifically comprises the following steps:
(1) Mixing 10mg of the anti-perovskite catalyst prepared in example 3, 5mg of carbon black, 50 mu L of nafion solution, 500 mu L of ethanol and 450 mu L of deionized water, and placing the mixture in a 2mL closed container, and continuing ultrasonic treatment for 1h to obtain catalytic ink;
(2) And uniformly spraying the catalytic ink on carbon paper or foam nickel by using a spray gun to obtain the working electrode.
Example 8
The preparation method of the working electrode containing the anti-perovskite catalyst specifically comprises the following steps:
(1) Mixing 10mg of the anti-perovskite catalyst prepared in example 4, 5mg of carbon black, 50 mu L of nafion solution, 500 mu L of ethanol and 450 mu L of deionized water, and placing the mixture in a 2mL closed container, and continuing ultrasonic treatment for 1h to obtain catalytic ink;
(2) And uniformly spraying the catalytic ink on carbon paper or foam nickel by using a spray gun to obtain the working electrode.
Comparative example 1
Inverse perovskite catalyst InNNi 3 The preparation process of (2) differs from that of example 3 only in that it does not contain ammonium metavanadate.
Comparative example 2
The preparation method of the working electrode containing the anti-perovskite catalyst specifically comprises the following steps:
(1) Mixing 10mg of the anti-perovskite catalyst prepared in the comparative example 1, 5mg of carbon black, 50 mu L of nafion solution, 500 mu L of ethanol and 450 mu L of deionized water, and placing the mixture in a 2mL closed container, and continuing ultrasonic treatment for 1h to obtain catalytic ink;
(2) And uniformly spraying the catalytic ink on carbon paper or foam nickel by using a spray gun to obtain the working electrode.
Performance testing
1. Characterization of
The anti-perovskite catalysts prepared in comparative example 1 and examples 1 to 4 were each tested for an X-ray diffraction pattern, a scanning electron microscope, a high-power transmission electron microscope, and an X-ray photoelectron spectrum, respectively.
1. X-ray diffraction pattern
The anti-perovskite catalysts prepared in comparative example 1 and examples 1 to 4 were each tested for their X-ray diffraction patterns. The results are shown in FIG. 2.
As can be seen from FIG. 2, the anti-perovskite catalysts of comparative example 1 and examples 1 to 4 each have anti-perovskite characteristic peaks. The doping of vanadium in the anti-perovskite catalysts of examples 1-4 resulted in a characteristic shift of the characteristic peak-to-low angle compared to the comparative example, which demonstrates that the doping of vanadium changes the lattice spacing and also demonstrates successful synthesis of the anti-perovskite catalysts of examples 1-4.
2. Scanning electron microscope image
Taking the anti-perovskite catalyst InNNi prepared in example 3 2.4 V 0.6 And testing the scanning electron microscope image. The results are shown in FIG. 3.
As can be seen from FIG. 3, example 3 anti-perovskite catalyst InNNi 2.4 V 0.6 Is a nano cluster, and the EDS mapping shows that In, N, ni, V and other elements are uniformly distributed.
3. High power transmission electron microscope image
Taking the anti-perovskite catalyst InNNi prepared in example 3 2.4 V 0.6 And testing the high-power transmission electron microscope image. The results are shown in FIG. 4.
As can be seen from FIG. 4, example 3 anti-perovskite catalyst InNNi 2.4 V 0.6 With uniform lattice fringes, d=0.224 nm is attributed to InNNi 2.4 V 0.6 (111)。
4. X-ray photoelectron spectrogram
The anti-perovskite catalysts prepared in comparative example 1 and example 3 were each tested for their X-ray photoelectron spectra. The results are shown in FIG. 5.
As can be seen from FIG. 5, in element exists mainly as 3-valent In and is the same as comparative example 1 anti-perovskite catalyst InNNi 3 Example 3 inverse perovskite catalyst InNNi 2.4 V 0.6 Characteristic peaks of V appear, also demonstrating that V is successfully doped into the anti-perovskite structure.
2. Electrochemical testing
Working electrodes prepared in comparative example 2 and examples 5 to 8 were each taken to have an area of 1.0cm -2 Electrochemical tests are carried out by adopting an electrochemical workstation of CHI760E of Shanghai Chen Hua instruments, and a polarization curve graph, a Faraday efficiency graph and a stability test i-t curve graph of the electrocatalytic reduction carbon dioxide are respectively tested.
The test conditions were as follows: the platinum sheet electrode was used as a counter electrode, the Ag/AgCl electrode was used as a reference electrode, and a three-electrode system was formed by combining the working electrodes of comparative example 2 and examples 5 to 8 above, respectively, with an electrolyte of 1.0M KHCO 3 An aqueous solution.
1. Electrocatalytic reduction carbon dioxide polarization curve graph
The working electrodes prepared in comparative example 2 and examples 5-8 were each tested for their electrocatalytic reduction carbon dioxide polarization profiles. The results are shown in FIG. 6.
As can be seen from FIG. 6, the anti-perovskite catalyst InNNi of comparative example 1 3 In comparison, V doping greatly improves the activity of the anti-perovskite catalysts of examples 1-4, and the anti-perovskite catalyst InNNi of example 3 2.4 V 0.6 The performance improvement of (2) is the greatest.
2. Faraday efficiency graph of electrocatalytic reduction of carbon dioxide
Working electrodes prepared in comparative example 2 and examples 5-8 were each tested for their electrocatalytic reduction carbon dioxide faradaic efficiency profile. The results are shown in FIG. 7.
As can be seen from FIG. 7, the anti-perovskite catalyst InNNi of comparative example 1 3 In comparison, V doping greatly improves the selectivity of the anti-perovskite catalysts of examples 1-4, and example 3 anti-perovskiteTitanium ore catalyst InNNi 2.4 V 0.6 The performance improvement of (2) is the greatest.
3. Stability test i-t curve graph of electrocatalytic reduction carbon dioxide
The working electrode prepared in example 7 was used to test its electrocatalytic reduction carbon dioxide stability test i-t graph. The results are shown in FIG. 8.
As can be seen from FIG. 8, example 3 anti-perovskite catalyst InNNi 2.4 V 0.6 The faraday efficiency remains high after a steady operation of 100 hours.
The experiment shows that the selectivity of the anti-perovskite catalyst for electrocatalytically reducing carbon dioxide into formic acid is as high as 93.6%, and in the reaction process, the liquid phase product only contains formate ions, and the gas phase product only contains side reaction hydrogen.
The current density of the anti-perovskite catalyst of the invention at-0.8V vs RHE is up to 100mA/mg, the current density at-1.1V vs RHE is up to 200mA/mg, and the stability is up to more than 100 h.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the anti-perovskite catalyst is characterized by comprising the following steps of:
(1) Dissolving nickel salt, indium salt, metavanadate and a molecular activator into water, performing ultrasonic dispersion, and magnetically stirring to obtain a mixed solution;
(2) Carrying out hydrothermal reaction on the mixed solution to obtain a suspension;
(3) Centrifuging the suspension, collecting precipitate, cleaning, and drying to obtain a precursor;
(4) And (3) annealing the precursor to obtain the anti-perovskite catalyst.
2. The method for preparing an inverse perovskite catalyst according to claim 1, wherein in the step (1), the nickel salt is nickel acetate tetrahydrate; the indium salt is indium nitrate hydrate; the metavanadate is ammonium metavanadate; the molecular activator is hexamethylenetetramine; the water is deionized water; the dosage ratio of the nickel salt, the indium salt, the metavanadate, the molecular activator and the water is (1.1-1.4) mmol to 0.5mmol (0.1-0.4) mmol to 4mmol to 40mL.
3. The method for preparing an inverse perovskite catalyst according to claim 1, wherein in the step (1), the ultrasonic dispersion time is 30min; the rotating speed of the magnetic stirring is 550r/min, and the time is 30min.
4. The method for preparing an inverse perovskite catalyst according to claim 1, wherein in the step (2), the hydrothermal reaction is performed at 120 ℃ for 12 hours.
5. The method for preparing an inverse perovskite catalyst according to claim 4, wherein the hydrothermal reaction is specifically: and transferring the mixed solution into a polytetrafluoroethylene liner with the capacity of 100mL, loading the polytetrafluoroethylene liner into a stainless steel water heating reaction kettle, and then placing the stainless steel water heating reaction kettle in a blast drying oven, and keeping the temperature at 120 ℃ for 12 hours.
6. The method for preparing an inverse perovskite catalyst according to claim 1, wherein in the step (3), the centrifugal rotation speed is 7000r/min, and the time is 15min; the cleaning is specifically as follows: respectively cleaning with water and ethanol alternately for three times; the drying temperature is 60 ℃ and the drying time is 12 hours.
7. The method for preparing an inverse perovskite catalyst according to claim 1, wherein in the step (4), the annealing treatment is specifically: and placing the precursor in a tube furnace, continuously ventilating for 30min at room temperature by taking ammonia gas as carrier gas, continuously heating up to 550 ℃ at 5 ℃/min, keeping the temperature for 5h, switching the carrier gas to nitrogen gas when the tube furnace is naturally cooled to 200 ℃, and naturally cooling to room temperature.
8. An inverse perovskite catalyst as claimed in any one of claims 1 to 7, wherein the molecular formula is InNNi 3-x V x Where x=0.2, 0.4, 0.6 or 0.8.
9. A process for the preparation of a working electrode comprising an anti-perovskite catalyst prepared by a process as claimed in any one of claims 1 to 7, comprising in particular the steps of:
(1) Mixing 10mg of anti-perovskite catalyst, 5mg of carbon black, 50 mu L of nafion solution, 500 mu L of ethanol and 450 mu L of deionized water, and placing the mixture in a 2mL closed container, and continuing to carry out ultrasonic treatment for 1h to obtain catalytic ink;
(2) And uniformly spraying catalytic ink on carbon paper or foam nickel by using a spray gun to obtain the working electrode.
10. Use of an anti-perovskite catalyst prepared by a preparation method according to any one of claims 1 to 7, an anti-perovskite catalyst according to claim 8 and a working electrode prepared by a preparation method according to claim 9 in the electrocatalytic reduction of carbon dioxide to formic acid.
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