CN111250076A - Nano bismuth catalyst and preparation method and application thereof - Google Patents

Nano bismuth catalyst and preparation method and application thereof Download PDF

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CN111250076A
CN111250076A CN202010217747.8A CN202010217747A CN111250076A CN 111250076 A CN111250076 A CN 111250076A CN 202010217747 A CN202010217747 A CN 202010217747A CN 111250076 A CN111250076 A CN 111250076A
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bismuth
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bismuth catalyst
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CN111250076B (en
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康毅进
付先彪
李辉
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University of Electronic Science and Technology of China
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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract

The invention provides a nano bismuth catalyst and a preparation method and application thereof, wherein the nano bismuth catalyst comprises a substrate and an active agent loaded on the substrate, and the active agent is nano bismuth with an exposed (001), (012), (104) or (110) crystal face. The invention prepares the nano bismuth catalyst by the interface limited-domain reduction method, the prepared nano bismuth catalyst has the Faraday efficiency as high as 18.3 percent when being used as a cathode catalyst of a flow electrolytic cell to carry out electrocatalytic reduction on nitrogen to synthesize ammonia, and the ammonia yield is 605.5 mu g mg‑1 Bih‑1The method overcomes the limitations of low efficiency, low current efficiency and the like of the electrochemical synthesis of ammonia at the present stage, and has commercial value.

Description

Nano bismuth catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a nano bismuth catalyst and a preparation method and application thereof.
Background
In 2017, it was determined that 1.42 million tons of ammonia were produced by global ammonia plants using the haber process, in which 77% of the hydrogen required for ammonia synthesis was produced by steam reforming of methane, and the use of the hydrogen source was a carbon-intensive process with an average release of 2.1 tons of carbon dioxide per 1 ton of ammonia produced; the haber process must be carried out under conditions of high temperature of 500 ℃ and high pressure of 200atm, which is severe, and energy intensive conditions mean that more fossil fuels are consumed and more carbon dioxide is emitted. The synthetic ammonia consumes 1-2% of the global annual energy supply, and the amount of discharged carbon dioxide accounts for 1% of the global annual emission.
Renewable electricity, which continues to drop in price, provides a very competitive route to ammonia production by electrochemical reduction of nitrogen gas using water as a sustainable hydrogen source at low temperature and pressure conditions. However, two major challenges exist so far: (1) most of the researches on the electrochemical synthesis of ammonia are carried out in a two-chamber electrochemical cell (H-cell), the solubility of nitrogen in an aqueous solution is extremely low, and the mass transfer of raw material gas can be limited in the electrolytic process; (2) the chemical reaction inertness of nitrogen, and a high-activity ammonia synthesis catalyst has not been developed yet. These two problems make the ammonia yield and current efficiency very low, which greatly limits the industrial application of electrochemical synthesis of ammonia.
Therefore, the exploration of a catalyst which has low energy consumption and low pollution and can improve the yield and the activity of the electrochemical synthesis ammonia has practical application value.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nano bismuth catalyst and a preparation method and application thereof, and the nano bismuth catalyst is prepared by an interface limited reduction method, so that the problems of high energy consumption and high pollution of the traditional Haber method ammonia synthesis, low efficiency of the electroreduction synthesis of ammonia in a traditional electrolytic cell, low activity of the catalyst and the like can be effectively solved.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a nanometer bismuth catalyst comprises a substrate and an active agent loaded on the substrate, wherein the active agent is nanometer bismuth with a specific crystal face exposed at high selectivity, the crystal face is (001), (012), (104) or (110), particularly, 90% of the nanometer bismuth is highly selectively exposed at the (001) crystal face, the average size of the nanometer bismuth is 1.5 microns, and the crystal face has an obvious promotion effect on the electrocatalytic synthesis of ammonia.
Further, the loading amount of the active agent on the substrate is 0.1-5.0mg/cm2(ii) a Preferably, the loading of the active agent on the substrate is 0.8mg/cm2。
Furthermore, the nano bismuth is a bismuth porous nano sheet, a bismuth nano polyhedron, a bismuth nanowire or a bismuth nano spherical particle, and the like, and the invention is not limited to the forms, as long as the exposed crystal face is (001), (012), (104) or (110) and the bismuth has a nano particle size; when the bismuth nano-polyhedron is used, at least one of bismuth regular tetrahedron, bismuth regular octahedron and bismuth icosahedron can be used.
Further, the substrate is carbon paper, carbon cloth, carbon fiber or conductive ceramic.
The preparation method of the nano bismuth catalyst comprises the following steps:
(1) uniformly mixing ethanol and deionized water according to a volume ratio of 10-90:90-10 to obtain a detergent, adding an active agent into the detergent, placing the detergent in an ultrasonic cleaning machine for ultrasonic cleaning for 2-5min, and then drying in vacuum; the preferred ultrasonic frequency is 4X 104Hz～8×104Hz。
(2) Carrying out ultrasonic dispersion on the active agent and the conductive adhesive which are subjected to vacuum drying in the step (1) according to the mass ratio of 1-19:9-1 to obtain slurry; during ultrasonic dispersion, ethanol, isopropanol and the like are added as dispersing agents;
(3) and (3) uniformly spraying the slurry obtained in the step (2) on a substrate, and drying by using inert gases such as argon, nitrogen and the like to obtain the nano bismuth catalyst.
Further, the active agent is prepared by the following method: mixing and stirring 1-10mg/mL active agent precursor dispersion liquid and 2-8mg/mL reducing liquid according to the volume ratio of 1:3-10 for 0.5-3h, then cleaning, centrifuging and drying to obtain an active agent; wherein the active agent precursor dispersion liquid is a bismuth-containing solution, preferably a bismuth oxybromide dispersion liquid, a bismuth oxychloride dispersion liquid, a bismuth oxyiodide dispersion liquid and derivatives thereof; the reducing solution is a solution obtained by dissolving a reducing agent in a solvent, and the reducing agent is a water-soluble reducing agent, preferably sodium borohydride; the solvent of the active agent precursor dispersion liquid and the solvent in the reducing liquid are not mutually soluble, and the solvent of the active agent precursor dispersion liquid is preferably a solvent with lower polarity, such as n-hexane, toluene and the like; the solvent of the reducing solution is deionized water. Further, taking a bismuth oxybromide dispersion as an example to illustrate the preparation process of the active agent precursor dispersion: mixing bismuth nitrate pentahydrate and hexadecyl trimethyl ammonium bromide according to the molar ratio of 0.1-1:1, placing the mixture in a solvent, performing ultrasonic dispersion for 1-3h to form a uniform solution, then transferring the uniform solution into a reaction kettle, stirring and reacting for 6-24h at the temperature of 180 ℃ with the stirring rate of 200-800r/min, and washing after the reaction is finished to obtain the bismuth nitrate/cetyl trimethyl ammonium bromide aqueous solution; wherein the solvent is oleylamine, octadecylamine and derivatives thereof, mixed solution of glycol and water and the like; washing is carried out with a low-polarity solvent, preferably n-hexane.
Other types of active agent precursor dispersions are prepared similar to the bismuth oxybromide dispersion, simply by replacing the corresponding cetyltrimethylammonium bromide, e.g., cetyltrimethylammonium bromide is replaced by cetyltrimethylammonium chloride when the active agent precursor dispersion is a bismuth oxychloride dispersion.
Further, the conductive adhesive is Nafion, and the mass ratio of the active agent to the conductive adhesive is 9: 1.
The nano bismuth catalyst can be used for electrocatalytic synthesis of ammonia, namely the application of the nano bismuth catalyst in the aspect of electrocatalytic synthesis of ammonia.
A flow electrolytic cell comprises the nano catalyst, and the nano catalyst is used as a cathode catalyst for electrocatalytic synthesis of ammonia.
The flow electrolytic cell is composed of a cathode chamber and an anode chamber, wherein an electrolyte flow chamber of polytetrafluoroethylene is arranged between the cathode chamber and the anode chamber, and the electrolyte flow chamber is also a chamber where a reference electrode is arranged, wherein the flow grooves of the cathode chamber and the anode chamber are of a serpentine structure, and the purpose is to increase the contact time of a catalyst and a reaction substrate and improve the ammonia synthesis efficiency; the cathode catalyst is arranged between the cathode chamber and the electrolyte flowing chamber, the anode catalyst is arranged between the anode chamber and the electrolyte flowing chamber, and the anode catalyst and the electrolyte flowing chamber are separated by an ion exchange membrane. The current collectors of the cathode and the anode are titanium metal or copper metal plates.
Further, the anode catalyst is a commercial iridium dioxide modified carbon cloth.
Further, when the nano bismuth catalyst is adopted for electrocatalytic synthesis of ammonia, the electrolyte is continuously introduced into the anode, the pure nitrogen is continuously introduced into the cathode, and the electrolyte is continuously introduced into the electrolyte flowing chamber; wherein the electrolyte is 0.1-10M potassium hydroxide aqueous solution.
The nano bismuth catalyst provided by the invention and the preparation method and the application thereof have the following beneficial effects:
the invention uses the interface of two solution phases which are not mutually soluble as a limited domain soft template, and conformally reduces the precursor of an active agent, and prepares the nano bismuth catalyst by an interface limited domain reduction method. The prepared nano bismuth catalyst has the Faraday efficiency as high as 18.3 percent when being used as a cathode catalyst of a flow electrolytic cell to carry out electrocatalytic reduction on nitrogen to synthesize ammonia, and the ammonia yield is 605.5 mu g mg-1 Bih-1The method overcomes the limitations of low efficiency, low current efficiency and the like of the electrochemical synthesis of ammonia at the present stage, and has commercial value.
Drawings
FIG. 1 is a schematic diagram of an interfacial confinement reduction process.
FIG. 2 is a structural representation diagram of precursor bismuth oxybromide nanosheets and bismuth porous nanosheets.
Figure 3 is a schematic diagram of a membrane electrode assembly flow cell.
FIG. 4 shows the results of testing the electrochemical reduction of nitrogen to ammonia.
Detailed Description
Example 1
A nano bismuth catalyst comprises a carbon cloth substrate and bismuth porous nanosheets (001) coated on the carbon cloth, wherein the loading capacity of the bismuth porous nanosheets is 0.8mg/cm2。
The preparation method of the nano bismuth catalyst comprises the following steps:
(1) preparation of precursor bismuth oxybromide dispersion
Mixing bismuth nitrate pentahydrate and hexadecyl trimethyl ammonium bromide according to a molar ratio of 0.25:1, placing the mixture into oleylamine, performing ultrasonic dispersion for 2 hours to form a uniform solution, transferring the uniform solution into a solvothermal reaction kettle, stirring and reacting for 12 hours at 170 ℃, wherein the stirring speed is 350r/min, washing by using n-hexane after the reaction is finished, and finally dispersing the mixture into the n-hexane to obtain the bismuth nitrate pentahydrate;
(2) preparation of active agent bismuth porous nanosheet
Mixing 20mL of precursor bismuth oxybromide dispersion liquid with 60mL of reducing liquid, stirring for 1h, after the reaction is finished, cleaning with an absolute ethyl alcohol/deionized water detergent (the volume ratio of the absolute ethyl alcohol to the deionized water is 1:1), centrifuging, and drying the precipitate in vacuum to obtain an active agent; wherein the reducing solution is 4mg/mL sodium borohydride aqueous solution;
(3) bismuth porous nanosheet cleaning active agent
Adding an active agent into the detergent in the step (2), and placing the detergent in an ultrasonic cleaning machine for ultrasonic cleaning for 5min, wherein the ultrasonic frequency is 6 multiplied by 104Hz, then centrifuging, repeating the cleaning and centrifuging processes for 3 times, and finally drying in vacuum to obtain the cleaned bismuth porous nanosheet active agent;
(4) preparation of the slurry
Mixing an active agent and 5% of Nafion conductive adhesive according to a mass ratio of 9:1, and performing ultrasonic dispersion for 20min by using isopropanol as a dispersing agent to form uniform slurry;
(5) preparation of the catalyst
And uniformly spraying the slurry on a carbon cloth substrate, and blow-drying by using argon to obtain the carbon cloth.
Example 2
The nano bismuth catalyst comprises a carbon cloth substrate and bismuth nano spherical particles coated on the carbon cloth, wherein the loading capacity of the bismuth nano spherical particles is 1.0mg/cm2。
The preparation method of the nano bismuth catalyst comprises the following steps:
(1) preparation of bismuth nano spherical particles
Dissolving a certain mass of bismuth nitrate pentahydrate into 1-hexadecyl sulfide and 1-octadecene according to the volume ratio1:1, the total volume of the solution is 10mL, the concentration of the bismuth nitrate pentahydrate in the mixed solution is generally 5-50mg/mL (preferably 15mg/mL), and then the mixed solution is heated to 180 ℃, and the heating rate is 5-6 ℃ min-1The reaction mixture is kept under an inert gas such as argon or nitrogen for 5 minutes. Naturally cooling the reaction solution to room temperature, and centrifuging to collect a product to prepare bismuth nano spherical particles;
the above operations are all carried out in a well ventilated hood.
When bismuth nano spherical particles are prepared, the concentration of bismuth nitrate pentahydrate is in the range of 5-50mg/mL, the structure and the size of the bismuth nano spherical particles are hardly influenced, and the concentration of bismuth nitrate pentahydrate is preferably 15mg/mL in consideration of cost and the like.
(1) Bismuth nano spherical particle cleaning active agent
Mixing absolute ethanol and deionized water at a volume ratio of 1:1 to obtain detergent, adding activator into the detergent, and ultrasonic cleaning in an ultrasonic cleaning machine at ultrasonic frequency of 6 × 10 for 5min4Hz, then centrifuging, repeating the cleaning and centrifuging processes for 3 times, and finally drying in vacuum to obtain the cleaned bismuth porous nanosheet active agent;
(3) preparation of the slurry
Mixing an active agent and 5% of Nafion conductive adhesive according to a mass ratio of 9:1, and performing ultrasonic dispersion for 20min by using isopropanol as a dispersing agent to form uniform slurry;
(4) preparation of the catalyst
And uniformly spraying the slurry on a carbon cloth substrate, and blow-drying by using argon to obtain the carbon cloth.
Comparative example 1
A commercial bismuth catalyst comprises a carbon cloth substrate and commercial bismuth powder (100mesh, 99.99%, Sigma) coated on the carbon cloth, wherein the loading capacity of the commercial bismuth powder is 1.0mg/cm2The preparation method comprises the following specific steps:
(1) preparation of the slurry
Mixing an active agent and 5% of Nafion conductive adhesive according to a mass ratio of 9:1, and performing ultrasonic dispersion for 20min by using isopropanol as a dispersing agent to form uniform slurry;
(2) the preparation of the catalyst is realized by uniformly spraying the slurry on a carbon cloth substrate and blow-drying the slurry by argon.
Test examples
1. Physical characterization
The catalyst is prepared by an interface domain reduction method, taking example 1 as an example, a specific flow chart is shown in fig. 1, and material structure analysis is performed on precursor bismuth oxybromide nanosheets and bismuth porous nanosheets, and the result is shown in fig. 2, wherein a) is an AFM image of the bismuth oxybromide nanosheets, b) is a bismuth oxybromide nanosheet XRD image, c) is a bismuth porous nanosheet XRD image, d) is a bismuth oxybromide nanosheet HAADF-STEM image, e) is a bismuth oxybromide nanosheet HRTEM image, f) is a bismuth oxybromide selected area electron diffraction SAED image, g) is a bismuth nanosheet HAADF-STEM image, h) is a bismuth nanosheet porous HRTEM image, and i) is an FFT image of the bismuth porous nanosheets. The display of FIG. 2 shows that the shapes of the precursor bismuth oxybromide nanosheet and the bismuth porous nanosheet are regular, and the structures are definite.
In the graph b) in fig. 2, the PDF standard card, i.e. PDF #09-0393, is a vertical line, and the tested bismuth oxybromide nanosheet is a continuous curve; c) in the figure, the PDF standard card, PDF #44-1246, is a vertical line, while the bismuth porous nanoplates tested are continuous curves.
2. Test of Performance of catalyst for preparing Ammonia by electroreduction of Nitrogen
A membrane electrode assembly flow cell, as shown in figure 3, the cell assembly comprising: a cathode current collector 1, a cathode chamber 2, a cathode electrode (the catalysts prepared in examples 1-2 and comparative example are respectively supported on a gas diffusion electrode GDE) 3, an electrolyte flow chamber 4, a reference electrode 5, an ion exchange 6, an anode electrode (the catalyst is a commercial oxygen evolution catalyst RuO)2)7, an anode chamber 8, an anode current collector 9; the circulation grooves of the anode chamber and the cathode chamber are of snake-shaped structures, and the upper part and the lower part of the anode chamber and the cathode chamber are respectively connected with the circulation grooves through conduction pipes; the anode electrode is commercial iridium dioxide modified carbon cloth, and the cathode electrode is the catalyst provided by the application; the upper part and the lower part of the electrolyte flowing chamber are respectively connected by a conduction pipe, and the electrolyte continuously flows; the anode electrode and the cathode electrode are respectively connected with a power supply through an anode current collector and a cathode current collector.
The above flow cell is used for catalytic synthesis of ammonia: continuously introducing 1.0M potassium hydroxide electrolyte into the anode chamber conduction pipe at the flow rate of 10 mL/min; 3.0M potassium hydroxide electrolyte is continuously introduced into the electrolyte flow chamber conduit at the flow rate of 10 mL/min; 99.999 percent ammonia gas is led into the conduction pipe of the cathode chamber, the flow rate is 50mL/min, and the generated ammonia is collected by connecting the lead-out pipe of the cathode chamber with acid liquid.
The catalysts prepared in examples 1 and 2 and comparative example 1 were used to test the performance of ammonia production by electroreduction of nitrogen, the test apparatus is shown in fig. 3, and the test conditions are normal temperature and normal pressure, and the voltage is from-0.2 to-0.8V (vs. The test results are shown in fig. 4, a) are LSV curves of the bismuth porous nanosheets, the bismuth nano spherical particles and the commercialized bismuth powder in nitrogen, b) are total current density graphs of the bismuth catalyst at different potentials, c) are current efficiency graphs at different potentials, and d) are ammonia yield rates at different potentials. As can be seen from the graphs a) and b), the current density of the bismuth porous nanosheet is about 3-4 times that of the commercial bismuth powder, and the reaction current density is obviously improved by using the catalyst disclosed by the invention; graph c) further shows that the bismuth porous nanosheets of the present invention are-0.25V vs RHE, whereas the commercial bismuth powders have an initial potential of-0.6V vs RHE, with a low initial potential meaning that the catalysts of the present invention have higher intrinsic activity. at-0.6V (vs. RHE), the current efficiency of the bismuth porous nanosheet is 18.3%, the current efficiency of the commercial bismuth powder is 1.1%, and the catalyst provided by the invention has higher current utilization efficiency than the commercial bismuth powder. As can be seen from the graph d), the ammonia production rate of the porous bismuth nanosheets at-0.6V (vs. RHE) is 605.5 mug mg-1 Bih-1The ammonia yield of the commercial bismuth powder is 3.0 mu g mg-1 Bih-1The ammonia yield of the catalyst of the invention is 200 times of that of the commercial bismuth powder. Therefore, the catalyst disclosed by the invention overcomes the problems of high energy consumption and high pollution of the traditional Haber method ammonia synthesis, low efficiency of the electroreduction synthesis of ammonia in a traditional electrolytic cell, low activity of the catalyst and the like, and has commercial value.

Claims (10)

1. A nano bismuth catalyst is characterized by comprising a substrate and an active agent loaded on the substrate, wherein the active agent is nano bismuth with an exposed (001), (012), (104) or (110) crystal face.
2. The nano-bismuth catalyst according to claim 1, wherein the loading of the active agent on the substrate is 0.1-5.0mg/cm2。
3. The nano-bismuth catalyst of claim 1, wherein the nano-bismuth is a bismuth porous nanosheet, a bismuth nano-polyhedron, a bismuth nanowire or a bismuth nano-spherical particle.
4. The nano-bismuth catalyst according to claim 1, wherein the substrate is carbon paper, carbon cloth, carbon fiber or conductive ceramic.
5. The method for preparing the nano bismuth catalyst as claimed in any one of claims 1 to 4, comprising the steps of:
(1) uniformly mixing ethanol and deionized water according to the volume ratio of 10-90:90-10 to obtain a detergent, adding an active agent into the detergent to perform ultrasonic cleaning, and then performing vacuum drying;
(2) carrying out ultrasonic dispersion on the active agent and the conductive adhesive which are subjected to vacuum drying in the step (1) according to the mass ratio of 1-19:9-1 to obtain slurry;
(3) and (3) uniformly spraying the slurry obtained in the step (2) on a substrate, and drying by using inert gas to obtain the nano bismuth catalyst.
6. The preparation method of the nano bismuth catalyst according to claim 5, wherein the active agent is prepared by the following method: mixing and stirring 1-10mg/mL active agent precursor dispersion liquid and 2-8mg/mL reducing liquid according to the volume ratio of 1:3-10 for 0.5-3h, then cleaning, centrifuging and drying to obtain the active agent precursor dispersion liquid; wherein the active agent precursor dispersion solution is a bismuth-containing solution, the reducing solution is a sodium borohydride-containing solution, and the solvent of the active agent precursor dispersion solution and the solvent of the reducing solution are immiscible.
7. The method for preparing a nano bismuth catalyst according to claim 6, wherein the active agent precursor dispersion is prepared by the following method: mixing bismuth nitrate pentahydrate and hexadecyl trimethyl ammonium halide according to the molar ratio of 0.1-1:1, placing the mixture into a solvent, ultrasonically dispersing for 1-3h, then stirring and reacting at 160-180 ℃ for 6-24h, and washing after the reaction is finished to obtain the bismuth nitrate/hexadecyl trimethyl ammonium halide composite material.
8. Use of the nano-bismuth catalyst of any one of claims 1 to 4 in the electrocatalytic synthesis of ammonia.
9. The application of claim 8, wherein the nano bismuth catalyst is loaded on a cathode electrode, nitrogen is continuously fed into the cathode electrode, electrolyte is continuously fed into an anode electrode, and 0.1-10M aqueous solution of potassium hydroxide is used as the electrolyte for the electro-catalytic synthesis of ammonia.
10. A flow cell comprising a nano bismuth catalyst according to any one of claims 1 to 4.
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Cited By (4)

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CN112481645A (en) * 2020-10-22 2021-03-12 杭州师范大学 Preparation method of silicon-based catalyst for nitrogen photoelectrochemical reduction
CN113122869A (en) * 2021-03-10 2021-07-16 西南科技大学 Continuous flow electro-catalysis ammonia synthesis device and electro-catalysis ammonia synthesis method
CN114318528A (en) * 2020-09-30 2022-04-12 中国科学院福建物质结构研究所 Bismuth single crystal material and preparation method and application thereof
CN114540882A (en) * 2022-03-25 2022-05-27 四川大学 Metal bismuth nanosheet with rich active sites and preparation method and application thereof

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