CN115763852A - Rhodium-bismuth anode catalyst and preparation method and application thereof - Google Patents

Rhodium-bismuth anode catalyst and preparation method and application thereof Download PDF

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CN115763852A
CN115763852A CN202211182013.6A CN202211182013A CN115763852A CN 115763852 A CN115763852 A CN 115763852A CN 202211182013 A CN202211182013 A CN 202211182013A CN 115763852 A CN115763852 A CN 115763852A
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rhodium
bismuth
anode catalyst
salt
water
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马亮
肖文贵
陈润
梁洁
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China University of Geosciences
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China University of Geosciences
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a rhodium-bismuth anode catalyst and a preparation method and application thereof. The invention utilizes different reduction orders to regulate and control the synthesis of different Bi components, and constructs the rhodium bismuth alloy and the rhodium-bismuth hydroxide heterojunction by the method. Bismuth is utilized to generate a unique third body effect on noble metal rhodium so as to reduce the poisoning of rhodium and greatly improve the ethanol oxidation activity of rhodium. The invention directionally constructs a rhodium-bismuth alloy structure and a rhodium-bismuth hydroxide interface structure by regulating the adding sequence of alkali and a reducing agent, and improves the ethanol electrooxidation activity of rhodium by regulating the density of rhodium d-band electron cloud by bismuth and the bifunctional mechanism and the synergistic effect generated by the rhodium-bismuth hydroxide interface. The method is simple, easy to operate and suitable for industrial preparation. According to the invention, a small amount of Bi component is introduced to the surface of the Rh-based catalyst, so that the work of the Rh surface component is expected to be effectively regulated and controlled, and the problem of low reaction activity of the Rh-based catalyst for EOR is solved.

Description

Rhodium-bismuth anode catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of fuel cells and energy materials, in particular to a rhodium-bismuth anode catalyst and a preparation method and application thereof.
Background
In recent years, the negative influence of the energy crisis on enterprise production and resident life is increasingly expanded, and a clean and efficient fuel is urgently needed to replace non-renewable fossil energy. The fuel cell is used as a new energy technology, can directly convert chemical energy into electric energy, and greatly reduces the loss in the energy conversion process. The polymer dielectric film fuel cell PEMFC is one of the PEMFCs, and the direct liquid fuel cell DLFC has the characteristics of simple structure, convenient transportation and storage of fuel, and safer use, compared with the PEMFC, and is suitable for being used as a mobile portable power source, and has received much attention.
Among direct liquid fuel cells DLFC, direct Ethanol Fuel Cells (DEFCs) have a very broad application prospect due to their advantages of high specific energy (8.0 kwlkg), wide fuel sources, etc. Although the complete mechanism of the Ethanol Oxidation Reaction (EOR) has not been clarified, a general consensus on the two-pathway mechanism has been reached.
Studies have shown that the dual pathway mechanism comprises C 1 Pathway and C 2 (ii) a pathway. A highly efficient catalyst requires the cleavage of C-C bonds in ethanol via surface hydroxyl groups (OH) ads ) The intermediate species are oxidized to complete the electro-oxidation catalysis of ethanol. Studies have shown that the existing Pt is also Pd, its ethanol oxidation activity and C 1 The selectivity of the pathway is difficult to meet the requirement. At present, how to develop an efficient ethanol electro-oxidation catalyst remains a very challenging topic. Researchers have found that Rh possesses the ability to break the C-C bond of organic molecules, indicating that Rh-based catalysts have the potential to completely catalyze the oxidation of ethanol. However, the activity of Rh itself for the oxidation of ethanol is too low, and since the surface energy of Rh is too high, there is no good method for the regulation of Rh surface components.
Based on the drawbacks of the current Rh-based catalysts, there is a need to improve this.
Disclosure of Invention
In view of the above, the present invention provides a rhodium-bismuth anode catalyst, and a preparation method and an application thereof, so as to solve the defects of the Rh-based catalyst in the prior art.
In a first aspect, the present invention provides a method for preparing a rhodium-bismuth anode catalyst, comprising the steps of:
adding rhodium salt and bismuth salt into water, then adding a carbon source, dispersing, and then adding sodium citrate and/or sodium oxalate to obtain a mixed solution;
reacting NaBH 4 And/or KBH 4 Dissolving NaOH in water to prepare an alkaline aqueous solution;
dropwise adding the alkaline aqueous solution into the mixed solution, reacting for 4-8 h at 70-90 ℃, filtering to obtain a solid product, and calcining the solid product to obtain the rhodium-bismuth anode catalyst;
or, adding Na into the mixed solution 2 CO 3 Reacting for 1-2 h at 70-90 ℃, adding NaOH to adjust the pH value of the solution to 11-12, and finally adding NaBH 4 And (3) reacting the solution at 70-90 ℃ for 4-8 h, filtering to obtain a solid product, and calcining the solid product to obtain the rhodium-bismuth anode catalyst.
Preferably, in the preparation method of the rhodium-bismuth anode catalyst, the rhodium salt comprises at least one of rhodium trichloride, rhodium nitrate, rhodium sulfate and sodium chlororhodate.
Preferably, in the preparation method of the rhodium-bismuth anode catalyst, the bismuth salt comprises at least one of bismuth nitrate, bismuth chloride and bismuth citrate.
Preferably, in the preparation method of the rhodium-bismuth anode catalyst, the carbon source comprises at least one of activated carbon and carbon powder.
Preferably, the preparation method of the rhodium-bismuth anode catalyst comprises the steps of adding rhodium salt and bismuth salt into water, then adding a carbon source, dispersing, and then adding sodium citrate to obtain a mixed solution; adding Na into the mixed solution 2 CO 3 In the step (2), rhodium salt, bismuth salt and carbonSource, sodium citrate, na 2 CO 3 The mass ratio of the water to the water is (5-20), (0.5-2), (10-30), (150-250), (5-20) and (20-100).
Preferably, in the preparation method of the rhodium-bismuth anode catalyst, in the step of calcining the solid product, the calcining temperature is 90-110 ℃ and the time is 1-3 h.
Preferably, the preparation method of the rhodium-bismuth anode catalyst comprises the step of mixing NaBH 4 And/or KBH 4 In the step of dissolving NaOH in water, naBH 4 And/or KBH 4 The mass ratio of NaOH to water is (1-5) to (1-3) to (800-1200).
Preferably, the preparation method of the rhodium-bismuth anode catalyst comprises the steps of adding rhodium salt and bismuth salt into water, then adding a carbon source, dispersing, and then adding sodium citrate and/or sodium oxalate to obtain a mixed solution, wherein the mass ratio of the rhodium salt, the bismuth salt, the carbon source, the sodium citrate and/or sodium oxalate to the water is (5-20): (0.5-2): (10-30): 150-250): 20-100.
And (3) dropwise adding an alkaline aqueous solution into the mixed solution, wherein the mass ratio of the alkaline aqueous solution to the mixed solution is (2-6) to (3-7).
In a second aspect, the invention also provides a rhodium-bismuth anode catalyst prepared by the preparation method.
In a third aspect, the invention also provides the rhodium-bismuth anode catalyst prepared by the preparation method or the application of the rhodium-bismuth anode catalyst in the catalytic oxidation of ethanol in an ethanol fuel cell.
Compared with the prior art, the preparation method of the rhodium-bismuth anode catalyst has the following beneficial effects:
the preparation method of the rhodium-bismuth anode catalyst utilizes different reduction sequences to regulate and control the synthesis of different Bi components, and constructs the rhodium-bismuth alloy and the rhodium-bismuth hydroxide heterojunction through the method. Bismuth is utilized to generate a unique third body effect on noble metal rhodium so as to reduce the poisoning of rhodium and greatly improve the ethanol oxidation activity of rhodium. The invention can directionally construct a rhodium-bismuth alloy structure and a rhodium-bismuth hydroxide interface structure by regulating the adding sequence of alkali and a reducing agent, and improve the ethanol electrooxidation activity of rhodium by regulating the density of rhodium d-band electron cloud by bismuth and the bifunctional mechanism and the synergistic effect generated by a rhodium-bismuth hydroxide interface. The method is simple, easy to operate, suitable for industrial preparation and can also be used for research work of other systems. According to the invention, a small amount of Bi component is introduced to the surface of the Rh-based catalyst, so that the work of the Rh surface component is expected to be effectively regulated and controlled, and the problem of low reaction activity of the Rh-based catalyst for EOR is solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is an X-ray diffraction (XRD) pattern of a rhodium-bismuth anode catalyst prepared in example 1 of the present invention;
FIG. 2 is a transmission electron micrograph of a rhodium-bismuth anode catalyst prepared in example 1 of the present invention;
FIG. 3 is a graph showing the electrooxidation activity of ethanol under alkaline conditions of catalysts prepared in examples 1 to 2 of the present invention and comparative example 1;
FIG. 4 is a graph showing stability tests of catalysts prepared in examples 1 to 2 of the present invention and comparative example 1 under an alkaline condition;
fig. 5 is a graph showing the durability test of the rhodium-bismuth anode catalyst prepared in example 1 of the present invention for thousands of cycles under alkaline conditions.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides a rhodium-bismuth anode catalyst and a preparation method and application thereof. The following are detailed below. It should be noted that the following description of the embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of the present application, the term "including" means "including but not limited to". Various embodiments of the invention may exist in a range of versions; it is to be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges such as, for example, from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within a range such as, for example, 1, 2, 3, 4, 5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the range so indicated.
The embodiment of the application provides a preparation method of a rhodium-bismuth anode catalyst, which comprises the following steps:
s1, adding rhodium salt and bismuth salt into water, then adding a carbon source, dispersing, and then adding sodium citrate and/or sodium oxalate to obtain a mixed solution;
s2, adding NaBH 4 and/KBH 4 Dissolving NaOH in water to prepare an alkaline aqueous solution;
s3, dropwise adding the alkaline aqueous solution into the mixed solution, reacting for 4-8 h at 70-90 ℃, filtering to obtain a solid product, and calcining the solid product to obtain the rhodium-bismuth anode catalyst;
or, adding Na into the mixed solution 2 CO 3 Reacting for 1-2 h at 70-90 ℃, adding NaOH to adjust the pH value of the solution to 11-12, and finally adding NaBH 4 And (3) reacting the solution at 70-90 ℃ for 4-8 h, filtering to obtain a solid product, and calcining the solid product to obtain the rhodium-bismuth anode catalyst.
The preparation method of the rhodium-bismuth anode catalyst comprises the steps of dropwise adding an alkaline aqueous solution into a mixed solution, reacting for 4-8 hours at 70-90 ℃, filtering to obtain a solid product, and calcining the solid product to obtain the rhodium-bismuth anode catalyst, wherein the catalyst is a RhBi/C catalyst; adding Na into the mixed solution 2 CO 3 Reacting for 1-2 h at 70-90 ℃, adding NaOH to adjust the pH value of the solution to 11-12, and finally adding NaBH 4 Reacting the solution at 70-90 ℃ for 4-8 h, filtering to obtain a solid product, and calcining the solid product to obtain the rhodium-bismuth anode catalyst which is Rh-Bi (OH) 3 a/C catalyst.
The rhodium-bismuth anode catalyst is prepared by adopting a liquid phase synthesis method, specifically, synthesis of different Bi components is regulated and controlled by utilizing different reduction sequences, and a rhodium-bismuth alloy and a rhodium-bismuth hydroxide heterojunction are constructed by the method. The bismuth is utilized to generate a unique third body effect on the noble metal rhodium so as to reduce the poisoning of the rhodium and greatly improve the ethanol oxidation activity of the rhodium. The rhodium-bismuth alloy structure and the rhodium-bismuth hydroxide interface structure can be directionally constructed by regulating the addition sequence of alkali and a reducing agent, and the ethanol electrooxidation activity of rhodium is improved by regulating the electron cloud density of rhodium d-band by bismuth and the bifunctional mechanism and the synergistic effect generated by the rhodium-bismuth hydroxide interface. The method is simple, easy to operate, suitable for industrial preparation and can also be used for research work of other systems. According to the application, a small amount of Bi components are introduced to the surface of the Rh-based catalyst, so that the work of the Rh surface components is expected to be effectively regulated and controlled, and the problem of low reaction activity of the Rh-based catalyst for EOR is solved.
In some embodiments, the rhodium salt comprises at least one of rhodium trichloride, rhodium nitrate, rhodium sulfate, sodium chlororhodate.
In some embodiments, the bismuth salt includes at least one of bismuth nitrate, bismuth chloride, bismuth citrate.
In some embodiments, the carbon source comprises at least one of activated carbon, carbon powder.
In some embodiments, the water used is ultrapure water.
Preferably, the rhodium salt is RhCl 3 ·3H 2 O, bismuth salt is Bi (NO) 3 ) 3 ·5H 2 And the carbon source of O adopts XC-72 carbon powder.
In some embodiments, a small amount of HCl may be added to facilitate dissolution when dissolving the bismuth salt.
In some embodiments, rhodium salt and bismuth salt are added into water, then a carbon source is added, and after dispersion, sodium citrate and/or sodium oxalate are added to obtain a mixed solution; adding Na into the mixed solution 2 CO 3 In the step (a), rhodium salt, bismuth salt, carbon source, sodium citrate and/or sodium oxalate, na 2 CO 3 The mass ratio of the water to the water is (5-20), (0.5-2), (10-30), (150-250), (5-20) and (20-100).
In some embodiments, the step of calcining the solid product is carried out at a temperature of 90 to 110 ℃ for a time of 1 to 3 hours.
In some embodiments, the NaBH is added to the reaction mixture 4 And/or KBH 4 In the step of dissolving NaOH in water, naBH 4 And/or KBH 4 The mass ratio of NaOH to water is (1-5) to (1-3) to (800-1200).
In some embodiments, in the step of adding rhodium salt and bismuth salt into water, then adding a carbon source, dispersing, and then adding sodium citrate to obtain a mixed solution, the mass ratio of the rhodium salt, the bismuth salt, the carbon source, the sodium citrate and/or the sodium oxalate to the water is (5-20): 0.5-2): 10-30): 150-250): 20-100;
reacting NaBH 4 In the step of dropwise adding the aqueous alkaline solution to the mixed solution, naBH 4 The mass ratio of the alkaline aqueous solution to the mixed solution is (2-6) to (3-7).
In some embodiments, after filtering to obtain a solid product, drying the solid product for 12-24 hours, and then calcining the solid product to obtain the rhodium-bismuth anode catalyst.
Based on the same inventive concept, the embodiment of the application also provides a rhodium-bismuth anode catalyst which is prepared by adopting the preparation method.
The catalytic activity, stability and durability of the optimal rhodium-bismuth anode catalyst (example 1) obtained by the invention to ethanol electrooxidation are greatly improved. The best rhodium-bismuth anode catalyst has an ethanol oxidation catalytic activity as high as 850mA/mgRh (FIG. 3), which is 17 times higher than that of the carbon-supported rhodium catalyst (example 3) at the same potential. After 1 hour stability test (potential: 0.5V vs RHE), the catalytic activity remained 170mA/mgRh, which was 35 times the steady-state current of the carbon-supported rhodium catalyst under the same conditions (FIG. 4). At the same time, the catalyst still has higher catalytic activity after 1000 cycles of CV (fig. 5). The catalyst has low preparation investment, less flow and easy operation, and can be used for industrial production. The preparation and research method for directionally constructing different structures is also suitable for researching other systems.
Based on the same inventive concept, the embodiment of the application also provides a rhodium-bismuth anode catalyst prepared by the preparation method or an application of the rhodium-bismuth anode catalyst in catalytic oxidation of ethanol in an ethanol fuel cell.
The preparation and use of the rhodium-bismuth anode catalysts of the present application are further illustrated by the following specific examples. This section further illustrates the present invention with reference to specific examples, which should not be construed as limiting the invention. The technical means employed in the examples are conventional means well known to those skilled in the art, unless otherwise specified. Reagents, methods and apparatus employed in the present invention are conventional in the art unless otherwise indicated.
Example 1
The embodiment of the application provides a preparation method of a rhodium-bismuth anode catalyst, which comprises the following steps:
s1, mixing 14mg of RhCl 3 ·3H 2 O、1mg Bi(NO 3 ) 3 ·5H 2 Adding O into 50ml of ultrapure water, then adding 20mg of XC-72 carbon powder, performing ultrasonic dispersion for 1h to form a uniform dispersion system, then adding 200mg of sodium citrate, and stirring to obtain a mixed solution;
s2, adding 10mg of Na into the mixed solution in the step S1 2 CO 3 Reacting at 80 ℃ for 2h, adding NaOH to adjust the pH value of the solution to 11, and finally adding 40ml of 3g/L NaBH 4 Solution (NaBH) 4 Adding into water to obtain NaBH 4 Solution) inReacting at 80 deg.C for 6h, filtering to obtain solid product, drying for 20h, and calcining at 100 deg.C for 1h to obtain rhodium-bismuth anode catalyst (Rh-Bi (OH) 3 a/C catalyst).
Example 2
The embodiment of the application provides a preparation method of a rhodium-bismuth anode catalyst, which comprises the following steps:
s1, mixing 14mg of RhCl 3 ·3H 2 O、1mg Bi(NO 3 ) 3 ·5H 2 Adding O into 50ml of ultrapure water, then adding 20mg of XC-72 carbon powder, performing ultrasonic dispersion for 1h to form a uniform dispersion system, then adding 200mg of sodium citrate, and stirring to obtain a mixed solution;
s2, mixing 120mg NaBH 4 And 40mg NaOH dissolved in 40ml water to prepare NaBH 4 An alkaline aqueous solution of (a);
s3, naBH in the step S2 4 And (2) dropwise adding the alkaline aqueous solution into the mixed solution in the step (S1), reacting for 6 hours at 80 ℃, filtering to obtain a solid product, drying the solid product for 20 hours, and calcining for 1 hour at 100 ℃ to obtain the rhodium-bismuth anode catalyst (namely the RhBi/C catalyst).
Comparative example 1
The comparative example provides a method for preparing a carbon-supported rhodium catalyst, comprising the steps of:
s1, mixing 14mg of RhCl 3 ·3H 2 Adding O into 50ml of ultrapure water, then adding 20mg of XC-72 carbon powder, performing ultrasonic dispersion for 1h to form a uniform dispersion system, then adding 200mg of sodium citrate, and stirring to obtain a mixed solution;
s2, mixing 120mg NaBH 4 And 40mg NaOH dissolved in 40ml water to prepare NaBH 4 An alkaline aqueous solution of (a);
s3, naBH in the step S2 4 And (2) dropwise adding the alkaline aqueous solution into the mixed solution in the step (S1), reacting for 6 hours at 80 ℃, filtering to obtain a solid product, drying the solid product for 20 hours, and calcining for 1 hour at 100 ℃ to obtain the carbon-supported rhodium catalyst (namely the Rh/C catalyst).
Performance characterization
FIG. 1 shows a rhodium-bismuth cation prepared in example 1Polar catalyst (i.e. Rh-Bi (OH) 3 X-ray diffraction (XRD) pattern of/C catalyst).
As can be seen from fig. 1, the rhodium-bismuth anode catalyst prepared in example 1 is mainly rhodium, and no peak of bismuth hydroxide is observed, which may be amorphous bismuth hydroxide with a small amount of bismuth hydroxide.
FIG. 2 is a transmission electron micrograph of the rhodium-bismuth anode catalyst prepared in example 1. The average particle size of the catalyst is 2.05 nm as shown in FIG. 2.
FIG. 3 shows Rh-Bi (OH) prepared in example 1 3 Ethanol electrooxidation activity test plots for the/C catalyst, the RhBi/C catalyst prepared in example 2, and the Rh/C catalyst prepared in comparative example 1 under alkaline conditions (all electrochemical tests below used a three-electrode system covered with catalyst material (catalyst loading of 0.285mg cm) -2 ) The glassy carbon electrode is used as a working electrode, a carbon rod and a mercury/mercury oxide electrode are respectively used as a counter electrode and a reference electrode, and 1mol/L NaOH +1mol/L C is selected 2 H 5 OH solution is used as electrolyte, and cyclic voltammetry is carried out on the electrode at room temperature, the scanning speed is 50mv/s, and the scanning potential is 0-1.2V relative to the reversible hydrogen electrode).
As can be seen from FIG. 3, rh-Bi (OH) prepared in example 1 3 The mass activity of the/C catalyst was 850mA/mg Rh 17 times that of the Rh/C catalyst of comparative example 1, while its initial potential was about 80mv lower than that of the Rh/C catalyst. The RhBi/C catalyst prepared in example 2 is a carbon-supported rhodium-bismuth alloy catalyst having only Rh-Bi (OH) activity 3 75% of the/C catalyst, but the activity was also 12 times improved compared to the Rh/C catalyst prepared in comparative example 1.
FIG. 4 shows Rh-Bi (OH) prepared in example 1 3 Stability test plots (scan potential of 0.5V vs. reversible hydrogen electrode) of the/C catalyst, the RhBi/C catalyst prepared in example 2, and the Rh/C catalyst prepared in comparative example 1 under alkaline conditions.
The RhBi/C catalyst prepared in example 2 had poor stability and a large reduction in activity after 1 hour of cycling, but also showed a slight improvement over the Rh/C catalyst prepared in comparative example 1.
FIG. 5 shows Rh-Bi (OH) prepared in example 1 3 Thousand-circle durability test chart under the basic condition of the/C catalyst (1000-circle cyclic voltammetry test, scanning speed of 100mv/s, scanning potential of 0.3V-0.7V relative to a reversible hydrogen electrode).
As can be seen from FIG. 5, rh-Bi (OH) 3 The catalyst of the/C catalyst still retains stronger ethanol oxidation activity after thousands of cycles, and shows better durability.
From the above examples 1-2 and comparative example 1, it can be seen that, compared with the ordinary carbon-supported rhodium Rh/C catalyst in comparative example 1, the addition of a small amount of Bi component can greatly improve the activity and stability of rhodium on ethanol electrooxidation, which proves the feasibility of the method of the present application for regulating the morphology of Rh surface components.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A preparation method of a rhodium-bismuth anode catalyst is characterized by comprising the following steps:
adding rhodium salt and bismuth salt into water, then adding a carbon source, dispersing, and then adding sodium citrate and/or sodium oxalate to obtain a mixed solution;
reacting NaBH 4 And/or KBH 4 Dissolving NaOH in water to prepare an alkaline aqueous solution;
dropwise adding the alkaline aqueous solution into the mixed solution, reacting for 4-8 h at 70-90 ℃, filtering to obtain a solid product, and calcining the solid product to obtain the rhodium-bismuth anode catalyst;
or, adding Na into the mixed solution 2 CO 3 Reacting for 1-2 h at 70-90 ℃, adding NaOH to adjust the pH value of the solution to 11-12, and finally adding NaBH 4 Reacting the solution at 70-90 ℃ for 4-8 h, filtering to obtain a solid product, andand calcining the solid product to obtain the rhodium-bismuth anode catalyst.
2. The method of claim 1, wherein the rhodium salt comprises at least one of rhodium trichloride, rhodium nitrate, rhodium sulfate, and sodium chlororhodate.
3. The method of preparing a rhodium-bismuth anode catalyst according to claim 1, wherein the bismuth salt comprises at least one of bismuth nitrate, bismuth chloride, and bismuth citrate.
4. The method of claim 1, wherein the carbon source comprises at least one of activated carbon and carbon powder.
5. The method for preparing a rhodium-bismuth anode catalyst as claimed in claim 1, wherein the rhodium salt and the bismuth salt are added into water, then the carbon source is added, after dispersion, the sodium citrate is added to obtain a mixed solution; adding Na into the mixed solution 2 CO 3 In the step (2), rhodium salt, bismuth salt, carbon source, sodium citrate and Na 2 CO 3 The mass ratio of the water to the water is (5-20), (0.5-2), (10-30), (150-250), (5-20) and (20-100).
6. The method of preparing a rhodium-bismuth anode catalyst according to claim 1, wherein in the step of calcining the solid product, the calcining temperature is 90 to 110 ℃ and the time is 1 to 3 hours.
7. The method of claim 1, wherein the NaBH is added to the anode rhodium-bismuth anode catalyst 4 And/or KBH 4 In the step of dissolving NaOH in water, naBH 4 And/or KBH 4 The mass ratio of NaOH to water is (1-5) to (1-3) to (800-1200).
8. The method for preparing a rhodium-bismuth anode catalyst as claimed in claim 1, wherein in the step of adding rhodium salt and bismuth salt into water, then adding a carbon source, dispersing, and then adding sodium citrate and/or sodium oxalate to obtain a mixed solution, the mass ratio of rhodium salt, bismuth salt, carbon source, sodium citrate and/or sodium oxalate to water is (5-20): 0.5-2): 10-30): 150-250): 20-100.
And (3) dropwise adding an alkaline aqueous solution into the mixed solution, wherein the mass ratio of the alkaline aqueous solution to the mixed solution is (2-6) to (3-7).
9. A rhodium-bismuth anode catalyst, characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. Use of a rhodium-bismuth anode catalyst prepared by the preparation method according to any one of claims 1 to 8 or a rhodium-bismuth anode catalyst according to claim 9 in catalytic oxidation of ethanol in an ethanol fuel cell.
CN202211182013.6A 2022-09-27 2022-09-27 Rhodium-bismuth anode catalyst and preparation method and application thereof Pending CN115763852A (en)

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