CN111632607A - Preparation of iron-doped bismuth sulfide nanotube catalyst and nitrogen reduction application thereof - Google Patents

Preparation of iron-doped bismuth sulfide nanotube catalyst and nitrogen reduction application thereof Download PDF

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CN111632607A
CN111632607A CN202010624731.9A CN202010624731A CN111632607A CN 111632607 A CN111632607 A CN 111632607A CN 202010624731 A CN202010624731 A CN 202010624731A CN 111632607 A CN111632607 A CN 111632607A
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iron
bismuth
bismuth sulfide
doped bismuth
sulfide nanotube
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赵磊
魏琴
任祥
徐晓龙
杨兴龙
王欢
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University of Jinan
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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Abstract

Along with the development of modern industry, the demand of people on energy sources is higher and higher, the synthetic ammonia technology becomes the fate of industrial development, the urgent demand of nitrogen fertilizer and the over-harsh reaction conditions and low conversion rate of the Haber-Bosch method make the preparation of ammonia become a major problem which must be solved in the development of the world at present. Because the heavy metal catalyst is expensive and has scarce resources, the catalyst for producing non-noble metal is used for the electrocatalytic decomposition of N2The research on the realization of nitrogen reduction to produce ammonia by saturated electrolyte is concerned, and is always the most popular in the energy field in recent years. The invention provides a preparation method of an iron-doped bismuth sulfide nanotube catalyst and application of the iron-doped bismuth sulfide nanotube catalyst in electrocatalytic nitrogen reduction.

Description

Preparation of iron-doped bismuth sulfide nanotube catalyst and nitrogen reduction application thereof
Technical Field
The invention relates to the field of preparation of inorganic nano powder and application of electrocatalytic nitrogen reduction, in particular to a preparation method of an iron-doped bismuth sulfide nano catalyst based on a hydrothermal method and application research of the catalyst in electrocatalytic nitrogen reduction reaction.
Background
Ammonia, as an important component of all foods and fertilizers, plays an essential role in maintaining the existence of earth life. Meanwhile, the ammonia molecule is rich in hydrogen, is considered as a promising energy storage intermediate, and is a clean energy carrier. The current traditional industrial synthetic ammonia scheme employs the haber-bosch process, through which over 500 tons of ammonia are produced and used each year. However, the scheme needs to be carried out under the conditions of high pressure of 150-350 atm and high temperature of 300-500 ℃, which not only has serious energy consumption, but also brings serious environmental pollution, and statistics shows that about 3 million tons of carbon dioxide are discharged into the atmosphere every year in the preparation process, which causes serious greenhouse effect and brings serious barrier to the development of national economy. Therefore, after one hundred years of industrial synthesis of ammonia by the Haber-Bosch method, a resource-saving and environment-friendly artificial ammonia synthesis strategy is found, and the realization of the reduction of nitrogen into ammonia under normal temperature and pressure is a research hotspot in the energy field at present.
In recent years, with continuous research on methods for synthesizing ammonia, such as photocatalytic synthesis ammonia, electrocatalytic synthesis ammonia, and biosynthetic ammonia, which have low energy consumption and pollutant discharge, the technology for artificially synthesizing ammonia has been advanced greatly. In view of the existing infrastructure, mild reaction conditions, safe process flow and green, pollution-free process, the electrocatalytic nitrogen reduction reaction has become one of the most promising alternatives to the haber-bosch process. However, the existing electrocatalytic nitrogen reduction ammonia production process still faces a series of problems which are difficult to solve, and the industrial production of the electrocatalytic nitrogen reduction ammonia production process still faces huge challenges due to the low ammonia gas generation rate and the Faraday efficiency. Therefore, the reasonable design of the high-efficiency and stable electro-catalytic nitrogen reduction reaction catalyst is very important. Electrocatalytic nitrogen reduction reactions have similar potentials to hydrogen evolution reactions, so that generally, electrocatalytic nitrogen reduction processes are accompanied by non-negligible competing hydrogen evolution reactions, resulting in poor faradaic efficiency and low electron utilization of electrocatalytic nitrogen reduction reactions. According to the calculation result of the density functional theory, the bismuth semiconductor has weak hydrogen adsorption, reasonable hydrogen evolution reaction activity, can selectively promote nitrogen adsorption on the surface of the catalyst and promote the formation of N2H by limiting the accessibility of electrons on the surface of the hydrogen evolution reaction, and the 6p orbit of bismuth and the 2p orbit of nitrogen have strong interaction, thereby being beneficial to giving electrons to nitrogen molecules and promoting the dissociation of nitrogen-nitrogen triple bonds. Therefore, the bismuth-based metal nano-catalyst prepared is very hopeful to realize high activity and high selectivity of the electro-catalytic nitrogen reduction reaction, and makes great contribution to the industrial production of the electro-catalytic nitrogen reduction reaction.
In addition, recent cases report that heteroatom doping can well promote the improvement of the activity of the electrocatalytic nitrogen reduction reaction. The doping strategy is expected to make a great contribution to the electrocatalytic nitrogen reduction reaction by adjusting the competitive reaction in the reaction process and influencing the aspects of active sites, electronic structures and the like. Considering the high activity of the iron atom in the electrocatalytic nitrogen reduction reaction, the electrocatalytic nitrogen reduction activity and selectivity of the material can be greatly improved after the iron atom is introduced. In view of the above, the invention provides a preparation method of the iron-doped bismuth sulfide nano-catalyst and application research of the catalyst in electrocatalysis of nitrogen gas reduction to ammonia, and provides a new idea for improving selectivity and yield of the electrocatalysis of nitrogen gas reduction to ammonia reaction.
Disclosure of Invention
One of the objectives of the present invention is to explore a novel preparation method of an iron-doped bismuth sulfide nanotube catalyst.
The invention also aims to apply the synthesized iron-doped bismuth sulfide nanotube catalyst to an electro-catalytic nitrogen reduction system at normal temperature and normal pressure, and explore a novel resource-saving and environment-friendly scheme for artificially synthesizing ammonia.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
1. a preparation method of an iron-doped bismuth sulfide nanotube catalyst is characterized by comprising the following preparation steps: adding an iron and bismuth source reagent, 0-10 mmol of urea, a certain amount of reaction solution, 0-30 mmol of surfactant and 0-15 mmol of sulfur source into a reaction kettle with a polytetrafluoroethylene lining, stirring, heating for a certain time by a hydrothermal synthesis method, naturally cooling, standing for 1-15 days at room temperature, centrifuging, washing and vacuum drying to obtain the iron-doped bismuth sulfide nanotube.
2. The surfactant is added in the synthesis process, so that the interface state of a solution system of the synthesis process is obviously changed, the controllable regulation and control of the morphology of the nanotube are realized, meanwhile, the synthesis process is placed at room temperature for a plurality of days, the regulation and control of the tubular morphology can be realized through the slow ion exchange effect, and compared with the traditional method of carrying out morphology control through other modes, the synthesis process has the advantages that the good effect is obtained through the synergistic effect of the surfactant and the ion exchange, and the preparation process is energy-saving and environment-friendly.
3. In the preparation method of the iron-doped bismuth sulfide nanotube catalyst, a reaction solution is an aqueous solution of dimethylformamide and ethylene glycol, wherein the molar ratio of the dimethylformamide to the ethylene glycol is 3: 4.
4. In the preparation method of the iron-doped bismuth sulfide nanotube catalyst, an iron source reagent is one or a combination of several of ferric nitrate nonahydrate, ferric acetylacetonate, ferric trichloride hexahydrate and ferrous sulfate hexahydrate; the concentration of iron in the iron bismuth pre-reaction liquid is 0.005-0.03 mol/L; the bismuth source is one or a combination of more of bismuth chloride hexahydrate, bismuth sulfate hexahydrate, bismuth nitrate hexahydrate, bismuth acetylacetonate and bismuth acetate; the bismuth concentration in the iron bismuth pre-reaction liquid is 0.005-0.02 mol/L; the sulfur source reagent is one or a combination of several of thioacetamide, sodium sulfide, sublimed sulfur and thiourea; the surfactant is one or more of sodium octadecyl benzene sulfonate, cetyl trimethyl ammonium bromide, stearic acid, alkyl glucoside and sodium glycocholate.
5. The preparation method of the iron-doped bismuth sulfide nanotube catalyst is characterized in that the heating temperature of the hydrothermal synthesis method in the step is 150 DEGoC~ 200oAnd C, the reaction time is 6-15 h.
6. The preparation method of the iron-doped bismuth sulfide nanotube catalyst and the nitrogen reduction application of the iron-doped bismuth sulfide nanotube catalyst are characterized in that a three-electrode system is adopted for testing, an electro-catalytic nitrogen reduction performance test is carried out on an electrochemical workstation, carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst is taken as a working electrode, a carbon rod is taken as a counter electrode, and an Ag/AgCl electrode is taken as a reference electrode; taking 0.1mol/L sodium sulfate solution as electrolyte; an H-shaped glass electrolytic tank is used as an electrolytic reaction device.
Detailed description of the preferred embodiments
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and to the accompanying drawings, which are included to further illustrate features and advantages of the invention, and not to limit the scope of the invention as claimed.
Example 1
The first step is as follows: sequentially adding ferrous sulfate heptahydrate (0.5 mmol, 0.139 g), bismuth sulfate (0.25 mmol, 0.176 g), urea (5 mmol,0.3 g), 15 mL of dimethylformamide and 20 mL of ethylene glycol into a laboratory reaction kettle with a polytetrafluoroethylene lining, adding sublimed sulfur (12 mmol,0.385 g) under magnetic stirring, continuously stirring for one hour until the materials are dissolved, placing the reaction kettle in an oven at 180 ℃ for reaction for 12 hours, respectively centrifugally washing the reaction kettle for several times by deionized water and absolute ethyl alcohol after natural cooling, and finally placing the reaction kettle in a place of 60 mLoC, in vacuum drying, obtaining the black iron-doped bismuth sulfide nanotube after 12 hours;
the second step is that: application of iron-doped bismuth sulfide nanotube in preparing ammonia by electrocatalysis
1. Weighing 5 mg of iron-doped bismuth sulfide nanotube, adding the iron-doped bismuth sulfide nanotube into 1 mL of mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 5: 5), simultaneously adding 50 mu L of Nafion solution, and carrying out ultrasonic treatment for 1 h to obtain uniform dispersion liquid. Dripping 20 μ L of the dispersion solution on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 1 cm × 1 cm, and naturally drying;
2. a three-electrode system is adopted to perform electro-catalytic ammonia production performance test on a Chenghua 660E electrochemical workstation. The carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. Taking 0.1mol/L sodium sulfate solution as electrolyte and an H-shaped glass electrolytic tank as a reaction device;
3. and (2) taking carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst as a working electrode, and performing cyclic voltammetry in a three-electrode system to activate the sample, wherein the cyclic voltammetry voltage interval is-1.0V to-1.6V (relative to an Ag/AgCl electrode), the highest potential is-1.6V, the lowest potential is-1.0V, the starting potential is-1.0V, the ending potential is-1.6V, and the scanning rate is 0.05V/s. The sampling interval is 0.001V, the standing time is 2 s, and the number of scanning segments is 500;
4. after cyclic voltammetry, a carbon paper coated with an iron-doped bismuth sulfide nanotube catalyst is used as a working electrode, and a linear voltage scanning test is carried out in a three-electrode system, wherein the voltage interval is-1.0 to-1.6V (relative to an Ag/AgCl electrode). The initial potential was-1.0V and the final potential was-1.6V. The scan rate was 5 mV/s. The sampling interval was 0.001V. The standing time was 2 s. Firstly, argon is introduced into the electrolyte for 30 min to discharge nitrogen dissolved in the electrolyte, and a first linear voltage scanning test is carried out after the argon is saturated. Then introducing nitrogen into the electrolyte for 30 min, and carrying out a second linear voltage scanning test after the nitrogen is saturated;
5. taking carbon paper coated with an iron-doped bismuth sulfide nanotube catalyst as a working electrode, and carrying out a long-time electro-catalysis ammonia production test on the catalyst, wherein the potentials are respectively set to be-1.0V, -1.1V, -1.2V, -1.3V, -1.4V and-1.5V (relative to Ag/AgCl), and the running time is 7200 s;
the third step: ammonia production test
1. Drawing a working curve: 0.0. mu.g/mL, 0.1. mu.g/mL, 0.2. mu.g/mL, 0.3. mu.g/mL, 0.4. mu.g/mL, 0.5. mu.g/mL, 0.6. mu.g/mL, 0.7. mu.g/mL, 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL of a standard solution was prepared in 0.1mol/L of a sodium sulfate solution using ammonium chloride as a standard reagent, and the absorbance was measured by subjecting it to a color reaction. Adding 4mL of standard solution into 50 muL of oxidation solution containing sodium hypochlorite (rho Cl = 4-4.9) and sodium hydroxide (0.75M), then further sequentially adding 500 muL of coloring solution containing 0.4M sodium salicylate and 0.32M sodium hydroxide, finally adding 50 muL of catalyst solution (0.1 g sodium nitroprusside is diluted to 10 mL by deionized water), standing and developing for 1 h under the condition of room temperature and light shading, performing spectral scanning in the wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording the value of absorbance at 655 nm, and drawing with the concentration to obtain a working curve;
2. and (3) testing the yield of ammonia: respectively taking 4mL of electrolyte which runs for 7200 s at each potential, adding the electrolyte into 50 muL of oxidation solution containing sodium hypochlorite (rho Cl = 4-4.9) and sodium hydroxide (0.75M), further sequentially adding 500 muL of coloring solution containing 0.4M sodium salicylate and 0.32M sodium hydroxide, finally adding 50 muL of catalyst solution (0.1 g of sodium nitroprusside is diluted to 10 mL by deionized water), standing and developing for 1 h under the condition of room temperature and light shading, performing spectral scanning in the wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording the absorbance value at 655 nm, and combining with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the iron-doped bismuth sulfide nanotube has excellent effect when being applied to the electrocatalysis ammonia preparation, and the ammonia yield reaches 32.83 mu g h under minus 0.5V (relative to a standard hydrogen electrode)-1mg-1 cat.The Faraday efficiency reaches 4.32%.
Example 2
The first step is as follows: sequentially adding 0.8mmol (0.224 g) of ferrous sulfate heptahydrate, 0.4 mmol (0.071 g) of bismuth sulfate, 5mmol (0.3 g) of urea, 15 mL of dimethylformamide and 20 mL of ethylene glycol into a laboratory reaction kettle with a polytetrafluoroethylene lining, adding 12 mmol (0.385 g) of sublimed sulfur under magnetic stirring, continuously stirring for one hour until the sublimed sulfur is dissolved, placing the reaction kettle in an oven at 180 ℃ for reaction for 12 hours, after natural cooling, respectively centrifugally washing the reaction kettle for several times by using deionized water and absolute ethyl alcohol, and finally placing the reaction kettle in a reaction kettle with a 60 mL polytetrafluoroethylene liningoC, in vacuum drying, obtaining the black iron-doped bismuth sulfide nanotube after 12 hours;
the second step is that: application of iron-doped bismuth sulfide nanotube in preparing ammonia by electrocatalysis
1. Weighing 5 mg of iron-doped bismuth sulfide nanotube, adding the iron-doped bismuth sulfide nanotube into 1 mL of mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 5: 5), simultaneously adding 50 mu L of Nafion solution, and carrying out ultrasonic treatment for 1 h to obtain uniform dispersion liquid. Dripping 20 μ L of the dispersion solution on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 1 cm × 1 cm, and naturally drying;
2. a three-electrode system is adopted to perform electro-catalytic ammonia production performance test on a Chenghua 660E electrochemical workstation. The carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. Taking 0.1mol/L sodium sulfate solution as electrolyte and an H-shaped glass electrolytic tank as a reaction device;
3. and (2) taking carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst as a working electrode, and performing cyclic voltammetry in a three-electrode system to activate the sample, wherein the cyclic voltammetry voltage interval is-1.0V to-1.6V (relative to an Ag/AgCl electrode), the highest potential is-1.6V, the lowest potential is-1.0V, the starting potential is-1.0V, the ending potential is-1.6V, and the scanning rate is 0.05V/s. The sampling interval is 0.001V, the standing time is 2 s, and the number of scanning segments is 500;
4. after cyclic voltammetry, a carbon paper coated with an iron-doped bismuth sulfide nanotube catalyst is used as a working electrode, and a linear voltage scanning test is carried out in a three-electrode system, wherein the voltage interval is-1.0 to-1.6V (relative to an Ag/AgCl electrode). The initial potential was-1.0V and the final potential was-1.6V. The scan rate was 5 mV/s. The sampling interval was 0.001V. The standing time was 2 s. Firstly, argon is introduced into the electrolyte for 30 min to discharge nitrogen dissolved in the electrolyte, and a first linear voltage scanning test is carried out after the argon is saturated. Then introducing nitrogen into the electrolyte for 30 min, and carrying out a second linear voltage scanning test after the nitrogen is saturated;
5. taking carbon paper coated with an iron-doped bismuth sulfide nanotube catalyst as a working electrode, and carrying out a long-time electro-catalysis ammonia production test on the catalyst, wherein the potentials are respectively set to be-1.0V, -1.1V, -1.2V, -1.3V, -1.4V and-1.5V (relative to Ag/AgCl), and the running time is 7200 s;
the third step: ammonia production test
1. Drawing a working curve: 0.0. mu.g/mL, 0.1. mu.g/mL, 0.2. mu.g/mL, 0.3. mu.g/mL, 0.4. mu.g/mL, 0.5. mu.g/mL, 0.6. mu.g/mL, 0.7. mu.g/mL, 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL of a standard solution was prepared in 0.1mol/L of a sodium sulfate solution using ammonium chloride as a standard reagent, and the absorbance was measured by subjecting it to a color reaction. Adding 4mL of standard solution into 50 muL of oxidation solution containing sodium hypochlorite (rho Cl = 4-4.9) and sodium hydroxide (0.75M), then further sequentially adding 500 muL of coloring solution containing 0.4M sodium salicylate and 0.32M sodium hydroxide, finally adding 50 muL of catalyst solution (0.1 g sodium nitroprusside is diluted to 10 mL by deionized water), standing and developing for 1 h under the condition of room temperature and light shading, performing spectral scanning in the wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording the value of absorbance at 655 nm, and drawing with the concentration to obtain a working curve;
2. and (3) testing the yield of ammonia: respectively taking 4mL of electrolyte which runs for 7200 s at each potential, adding the electrolyte into 50 muL of oxidation solution containing sodium hypochlorite (rho Cl = 4-4.9) and sodium hydroxide (0.75M), further sequentially adding 500 muL of coloring solution containing 0.4M sodium salicylate and 0.32M sodium hydroxide, finally adding 50 muL of catalyst solution (0.1 g of sodium nitroprusside is diluted to 10 mL by deionized water), standing and developing for 1 h under the condition of room temperature and light shading, performing spectral scanning in the wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording the absorbance value at 655 nm, and combining with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the iron-doped bismuth sulfide nanotube has excellent effect when being applied to the electrocatalysis ammonia preparation, and the ammonia yield reaches 40.57 mu g h under-0.5V (relative to a standard hydrogen electrode)-1mg-1 cat.The Faraday efficiency reaches 6.17%.
Example 3
The first step is as follows: taking a laboratory 50 mL reaction kettle with a polytetrafluoroethylene lining, sequentially adding ferrous sulfate heptahydrate (0.5 mmol, 0.139 g), bismuth sulfate (0.25 mmol, 0.176 g), urea (9 mmol, 0.45 g), sodium dodecyl benzene sulfonate (0-10 mmol), 15 mL of dimethylformamide and 20 mL of ethylene glycol, adding sublimed sulfur (6 mmol,0.192 g) under magnetic stirring, continuously stirring for one hour until the sublimed sulfur is dissolved, placing the reaction kettle in an oven at 180 ℃ for reaction for 12 hours, after natural cooling, respectively centrifuging and washing the reaction kettle for several times by deionized water and absolute ethyl alcohol, and finally placing the reaction kettle in a 60 mL reaction kettle with a polytetrafluoroethylene liningoC in vacuum drying for 12 h to obtain blackIron-doped bismuth sulfide nanotubes;
the second step is that: application of iron-doped bismuth sulfide nanotube in preparing ammonia by electrocatalysis
1. Weighing 5 mg of iron-doped bismuth sulfide nanotube, adding the iron-doped bismuth sulfide nanotube into 1 mL of mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 5: 5), simultaneously adding 50 mu L of Nafion solution, and carrying out ultrasonic treatment for 1 h to obtain uniform dispersion liquid. Dripping 20 μ L of the dispersion solution on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 1 cm × 1 cm, and naturally drying;
2. a three-electrode system is adopted to perform electro-catalytic ammonia production performance test on a Chenghua 660E electrochemical workstation. The carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. Taking 0.1mol/L sodium sulfate solution as electrolyte and an H-shaped glass electrolytic tank as a reaction device;
3. and (2) taking carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst as a working electrode, and performing cyclic voltammetry in a three-electrode system to activate the sample, wherein the cyclic voltammetry voltage interval is-1.0V to-1.6V (relative to an Ag/AgCl electrode), the highest potential is-1.6V, the lowest potential is-1.0V, the starting potential is-1.0V, the ending potential is-1.6V, and the scanning rate is 0.05V/s. The sampling interval is 0.001V, the standing time is 2 s, and the number of scanning segments is 500;
4. after cyclic voltammetry, a carbon paper coated with an iron-doped bismuth sulfide nanotube catalyst is used as a working electrode, and a linear voltage scanning test is carried out in a three-electrode system, wherein the voltage interval is-1.0 to-1.6V (relative to an Ag/AgCl electrode). The initial potential was-1.0V and the final potential was-1.6V. The scan rate was 5 mV/s. The sampling interval was 0.001V. The standing time was 2 s. Firstly, argon is introduced into the electrolyte for 30 min to discharge nitrogen dissolved in the electrolyte, and a first linear voltage scanning test is carried out after the argon is saturated. Then introducing nitrogen into the electrolyte for 30 min, and carrying out a second linear voltage scanning test after the nitrogen is saturated;
5. taking carbon paper coated with an iron-doped bismuth sulfide nanotube catalyst as a working electrode, and carrying out a long-time electro-catalysis ammonia production test on the catalyst, wherein the potentials are respectively set to be-1.0V, -1.1V, -1.2V, -1.3V, -1.4V and-1.5V (relative to Ag/AgCl), and the running time is 7200 s;
the third step: ammonia production test
1. Drawing a working curve: 0.0. mu.g/mL, 0.1. mu.g/mL, 0.2. mu.g/mL, 0.3. mu.g/mL, 0.4. mu.g/mL, 0.5. mu.g/mL, 0.6. mu.g/mL, 0.7. mu.g/mL, 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL of a standard solution was prepared in 0.1mol/L of a sodium sulfate solution using ammonium chloride as a standard reagent, and the absorbance was measured by subjecting it to a color reaction. Adding 4mL of standard solution into 50 muL of oxidation solution containing sodium hypochlorite (rho Cl = 4-4.9) and sodium hydroxide (0.75M), then further sequentially adding 500 muL of coloring solution containing 0.4M sodium salicylate and 0.32M sodium hydroxide, finally adding 50 muL of catalyst solution (0.1 g sodium nitroprusside is diluted to 10 mL by deionized water), standing and developing for 1 h under the condition of room temperature and light shading, performing spectral scanning in the wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording the value of absorbance at 655 nm, and drawing with the concentration to obtain a working curve;
2. and (3) testing the yield of ammonia: respectively taking 4mL of electrolyte which runs for 7200 s at each potential, adding the electrolyte into 50 muL of oxidation solution containing sodium hypochlorite (rho Cl = 4-4.9) and sodium hydroxide (0.75M), further sequentially adding 500 muL of coloring solution containing 0.4M sodium salicylate and 0.32M sodium hydroxide, finally adding 50 muL of catalyst solution (0.1 g of sodium nitroprusside is diluted to 10 mL by deionized water), standing and developing for 1 h under the condition of room temperature and light shading, performing spectral scanning in the wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording the absorbance value at 655 nm, and combining with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the iron-doped bismuth sulfide nanotube has excellent effect when being applied to the electrocatalysis ammonia preparation, and the ammonia yield reaches 30.25 mu g h under minus 0.5V (relative to a standard hydrogen electrode)-1mg-1 cat.The Faraday efficiency reaches 4.02 percent.
Example 4
The first step is as follows: a laboratory 50 mL polytetrafluoroethylene-lined reaction kettle was charged with ferrous sulfate heptahydrate (0.5 mmol, 0.139 g), bismuth sulfate (0.25 mmol, 0.17 g)6 g) Adding sublimed sulfur (12 mmol,0.385 g) into 15 ml of dimethylformamide and 20 ml of ethylene glycol under magnetic stirring, continuously stirring for one hour until the sublimed sulfur is dissolved, placing the mixture into a 120 ℃ oven for reaction for 12 hours, after natural cooling, respectively centrifugally washing the mixture for a plurality of times by using deionized water and absolute ethyl alcohol, and finally placing the mixture into a 60-degree flaskoC, in vacuum drying, obtaining the black iron-doped bismuth sulfide nanotube after 12 hours;
the second step is that: application of iron-doped bismuth sulfide nanotube in preparing ammonia by electrocatalysis
1. Weighing 5 mg of iron-doped bismuth sulfide nanotube, adding the iron-doped bismuth sulfide nanotube into 1 mL of mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 5: 5), simultaneously adding 50 mu L of Nafion solution, and carrying out ultrasonic treatment for 1 h to obtain uniform dispersion liquid. Dripping 20 μ L of the dispersion solution on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 1 cm × 1 cm, and naturally drying;
2. a three-electrode system is adopted to perform electro-catalytic ammonia production performance test on a Chenghua 660E electrochemical workstation. The carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. Taking 0.1mol/L sodium sulfate solution as electrolyte and an H-shaped glass electrolytic tank as a reaction device;
3. and (2) taking carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst as a working electrode, and performing cyclic voltammetry in a three-electrode system to activate the sample, wherein the cyclic voltammetry voltage interval is-1.0V to-1.6V (relative to an Ag/AgCl electrode), the highest potential is-1.6V, the lowest potential is-1.0V, the starting potential is-1.0V, the ending potential is-1.6V, and the scanning rate is 0.05V/s. The sampling interval is 0.001V, the standing time is 2 s, and the number of scanning segments is 500;
4. after cyclic voltammetry, a carbon paper coated with an iron-doped bismuth sulfide nanotube catalyst is used as a working electrode, and a linear voltage scanning test is carried out in a three-electrode system, wherein the voltage interval is-1.0 to-1.6V (relative to an Ag/AgCl electrode). The initial potential was-1.0V and the final potential was-1.6V. The scan rate was 5 mV/s. The sampling interval was 0.001V. The standing time was 2 s. Firstly, argon is introduced into the electrolyte for 30 min to discharge nitrogen dissolved in the electrolyte, and a first linear voltage scanning test is carried out after the argon is saturated. Then introducing nitrogen into the electrolyte for 30 min, and carrying out a second linear voltage scanning test after the nitrogen is saturated;
5. taking carbon paper coated with an iron-doped bismuth sulfide nanotube catalyst as a working electrode, and carrying out a long-time electro-catalysis ammonia production test on the catalyst, wherein the potentials are respectively set to be-1.0V, -1.1V, -1.2V, -1.3V, -1.4V and-1.5V (relative to Ag/AgCl), and the running time is 7200 s;
the third step: ammonia production test
1. Drawing a working curve: 0.0. mu.g/mL, 0.1. mu.g/mL, 0.2. mu.g/mL, 0.3. mu.g/mL, 0.4. mu.g/mL, 0.5. mu.g/mL, 0.6. mu.g/mL, 0.7. mu.g/mL, 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL of a standard solution was prepared in 0.1mol/L of a sodium sulfate solution using ammonium chloride as a standard reagent, and the absorbance was measured by subjecting it to a color reaction. Adding 4mL of standard solution into 50 muL of oxidation solution containing sodium hypochlorite (rho Cl = 4-4.9) and sodium hydroxide (0.75M), then further sequentially adding 500 muL of coloring solution containing 0.4M sodium salicylate and 0.32M sodium hydroxide, finally adding 50 muL of catalyst solution (0.1 g sodium nitroprusside is diluted to 10 mL by deionized water), standing and developing for 1 h under the condition of room temperature and light shading, performing spectral scanning in the wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording the value of absorbance at 655 nm, and drawing with the concentration to obtain a working curve;
2. and (3) testing the yield of ammonia: respectively taking 4mL of electrolyte which runs for 7200 s at each potential, adding the electrolyte into 50 muL of oxidation solution containing sodium hypochlorite (rho Cl = 4-4.9) and sodium hydroxide (0.75M), further sequentially adding 500 muL of coloring solution containing 0.4M sodium salicylate and 0.32M sodium hydroxide, finally adding 50 muL of catalyst solution (0.1 g of sodium nitroprusside is diluted to 10 mL by deionized water), standing and developing for 1 h under the condition of room temperature and light shading, performing spectral scanning in the wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording the absorbance value at 655 nm, and combining with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the Fe-doped bismuth sulfide nanotubeThe electro-catalysis ammonia preparation method has excellent effect when used for preparing ammonia under-0.5V (relative to a standard hydrogen electrode), and the yield of ammonia reaches 28.20 mu g h-1mg-1 cat.The Faraday efficiency reaches 3.98 percent.
Example 5
The first step is as follows: taking a reaction kettle which is used in a laboratory and is lined with 50 mL of polytetrafluoroethylene, sequentially adding ferrous sulfate heptahydrate (0.5 mmol, 0.139 g), bismuth sulfate (0.25 mmol, 0.176 g), urea (5 mmol,0.3 g), sodium octadecylbenzenesulfonate (0-10 mmol), 15 mL of dimethylformamide and 20 mL of ethylene glycol, adding sublimed sulfur (12 mmol,0.385 g) under magnetic stirring, continuously stirring for one hour until the sublimed sulfur is dissolved, placing the reaction kettle in an oven at 180 ℃ for reaction for 6 hours, placing the reaction kettle at room temperature for 7 days after natural cooling, then respectively carrying out centrifugal washing for a plurality of times by deionized water and absolute ethyl alcohol, and finally placing the reaction kettle at 60 mL of the reaction kettle for centrifugal washing for a plurality ofoC, in vacuum drying, obtaining the black iron-doped bismuth sulfide nanotube after 12 hours;
the second step is that: application of iron-doped bismuth sulfide nanotube in preparing ammonia by electrocatalysis
1. Weighing 5 mg of iron-doped bismuth sulfide nanotube, adding the iron-doped bismuth sulfide nanotube into 1 mL of mixed solvent of ethanol and water (the volume ratio of the ethanol to the water is 5: 5), simultaneously adding 50 mu L of Nafion solution, and carrying out ultrasonic treatment for 1 h to obtain uniform dispersion liquid. Dripping 20 μ L of the dispersion solution on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 1 cm × 1 cm, and naturally drying;
2. a three-electrode system is adopted to perform electro-catalytic ammonia production performance test on a Chenghua 660E electrochemical workstation. The carbon paper coated with the iron-doped bismuth sulfide nanotube is used as a working electrode, a carbon rod is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode. Taking 0.1mol/L sodium sulfate solution as electrolyte and an H-shaped glass electrolytic tank as a reaction device;
3. and (2) taking carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst as a working electrode, and performing cyclic voltammetry in a three-electrode system to activate the sample, wherein the cyclic voltammetry voltage interval is-1.0V to-1.6V (relative to an Ag/AgCl electrode), the highest potential is-1.6V, the lowest potential is-1.0V, the starting potential is-1.0V, the ending potential is-1.6V, and the scanning rate is 0.05V/s. The sampling interval is 0.001V, the standing time is 2 s, and the number of scanning segments is 500;
4. after cyclic voltammetry, a carbon paper coated with an iron-doped bismuth sulfide nanotube catalyst is used as a working electrode, and a linear voltage scanning test is carried out in a three-electrode system, wherein the voltage interval is-1.0 to-1.6V (relative to an Ag/AgCl electrode). The initial potential was-1.0V and the final potential was-1.6V. The scan rate was 5 mV/s. The sampling interval was 0.001V. The standing time was 2 s. Firstly, argon is introduced into the electrolyte for 30 min to discharge nitrogen dissolved in the electrolyte, and a first linear voltage scanning test is carried out after the argon is saturated. Then introducing nitrogen into the electrolyte for 30 min, and carrying out a second linear voltage scanning test after the nitrogen is saturated;
5. taking carbon paper coated with an iron-doped bismuth sulfide nanotube catalyst as a working electrode, and carrying out a long-time electro-catalysis ammonia production test on the catalyst, wherein the potentials are respectively set to be-1.0V, -1.1V, -1.2V, -1.3V, -1.4V and-1.5V (relative to Ag/AgCl), and the running time is 7200 s;
the third step: ammonia production test
1. Drawing a working curve: 0.0. mu.g/mL, 0.1. mu.g/mL, 0.2. mu.g/mL, 0.3. mu.g/mL, 0.4. mu.g/mL, 0.5. mu.g/mL, 0.6. mu.g/mL, 0.7. mu.g/mL, 0.8. mu.g/mL, 0.9. mu.g/mL, 1.0. mu.g/mL of a standard solution was prepared in 0.1mol/L of a sodium sulfate solution using ammonium chloride as a standard reagent, and the absorbance was measured by subjecting it to a color reaction. Adding 4mL of standard solution into 50 muL of oxidation solution containing sodium hypochlorite (rho Cl = 4-4.9) and sodium hydroxide (0.75M), then further sequentially adding 500 muL of coloring solution containing 0.4M sodium salicylate and 0.32M sodium hydroxide, finally adding 50 muL of catalyst solution (0.1 g sodium nitroprusside is diluted to 10 mL by deionized water), standing and developing for 1 h under the condition of room temperature and light shading, performing spectral scanning in the wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording the value of absorbance at 655 nm, and drawing with the concentration to obtain a working curve;
2. and (3) testing the yield of ammonia: 4mL of the electrolyte solution after 7200 s of operation at each potential was taken, added to 50. mu.L of an oxidizing solution containing sodium hypochlorite (. rho.Cl = 4-4.9) and sodium hydroxide (0.75M), and then further added in sequence by 5And (3) adding 50 muL of catalyst solution (0.1 g of sodium nitroprusside is diluted to 10 mL by deionized water) into 00 muL of coloring solution containing 0.4M of sodium salicylate and 0.32M of sodium hydroxide, standing and developing for 1 h under the condition of room temperature and light shading, performing spectral scanning in the wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording the value of absorbance at 655 nm, and combining with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the iron-doped bismuth sulfide nanotube has excellent effect when being applied to the electrocatalysis ammonia preparation, and the ammonia yield reaches 39.58 mu g h under minus 0.5V (relative to a standard hydrogen electrode)-1mg-1 cat.The Faraday efficiency reaches 5.62 percent.
Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (5)

1. A preparation method of an iron-doped bismuth sulfide nanotube catalyst is characterized by comprising the following preparation steps: adding an iron and bismuth source reagent, 0-10 mmol of urea, a certain amount of reaction solution, 0-30 mmol of surfactant and 0-15 mmol of sulfur source into a reaction kettle with a polytetrafluoroethylene lining, stirring, heating for a certain time by a hydrothermal synthesis method, naturally cooling, standing for 1-15 days at room temperature, centrifuging, washing and vacuum drying to obtain the iron-doped bismuth sulfide nanotube.
2. The method for preparing the iron-doped bismuth sulfide nanotube catalyst according to claim 1, wherein the reaction solution is an aqueous solution of dimethylformamide and ethylene glycol, wherein the molar ratio of dimethylformamide to ethylene glycol is 3: 4.
3. The method for preparing the iron-doped bismuth sulfide nanotube catalyst according to claim 1, wherein in the step, the iron source reagent is one or a combination of several of ferric nitrate nonahydrate, ferric acetylacetonate, ferric trichloride hexahydrate and ferrous sulfate hexahydrate; the concentration of iron in the iron bismuth pre-reaction liquid is 0.005-0.03 mol/L; the bismuth source is one or a combination of more of bismuth chloride hexahydrate, bismuth sulfate hexahydrate, bismuth nitrate hexahydrate, bismuth acetylacetonate and bismuth acetate; the bismuth concentration in the iron bismuth pre-reaction liquid is 0.005-0.02 mol/L; the sulfur source reagent is one or a combination of several of thioacetamide, sodium sulfide, sublimed sulfur and thiourea; the surfactant is one or more of sodium octadecyl benzene sulfonate, cetyl trimethyl ammonium bromide, stearic acid, alkyl glucoside and sodium glycocholate.
4. The method for preparing the iron-doped bismuth sulfide nanotube catalyst according to claim 1, wherein the heating temperature of the hydrothermal synthesis method in the step is 150 degrees centigradeoC~ 200oAnd C, the reaction time is 6-15 h.
5. The preparation method of the iron-doped bismuth sulfide nanotube catalyst and the nitrogen reduction application of the iron-doped bismuth sulfide nanotube catalyst are characterized in that a three-electrode system is adopted for testing, an electro-catalytic nitrogen reduction performance test is carried out on an electrochemical workstation, carbon paper coated with the iron-doped bismuth sulfide nanotube catalyst is taken as a working electrode, a carbon rod is taken as a counter electrode, and an Ag/AgCl electrode is taken as a reference electrode; taking 0.1mol/L sodium sulfate solution as electrolyte; an H-shaped glass electrolytic tank is used as an electrolytic reaction device.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112663076A (en) * 2020-12-24 2021-04-16 华南理工大学 Iron-doped molybdenum diselenide nano material with hollow structure, preparation method thereof and application of iron-doped molybdenum diselenide nano material in electrocatalytic nitrogen reduction

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120162320A1 (en) * 2010-12-28 2012-06-28 Seiko Epson Corporation Piezoelectric element, liquid ejecting head, and liquid ejecting apparatus
CN105056973A (en) * 2015-07-16 2015-11-18 南昌航空大学 Efficient Bi2S3-BiFeO3 composite visible-light-driven photocatalyst prepared through in-situ growth with chemical corrosion method and application of Bi2S3-BiFeO3 composite visible-light-driven photocatalyst
CN109967095A (en) * 2019-04-17 2019-07-05 南昌航空大学 A kind of holocrystalline bulk heterojunction catalysis material and its preparation method and application
CN110201683A (en) * 2019-07-02 2019-09-06 济南大学 A kind of preparation method and the reduction application of electro-catalysis nitrogen of vanadium doping ferrous sulfide
CN111068718A (en) * 2020-01-08 2020-04-28 济南大学 Preparation of nano spherical sulfur-doped iron oxide and application of nano spherical sulfur-doped iron oxide in electrocatalytic nitrogen reduction

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120162320A1 (en) * 2010-12-28 2012-06-28 Seiko Epson Corporation Piezoelectric element, liquid ejecting head, and liquid ejecting apparatus
CN105056973A (en) * 2015-07-16 2015-11-18 南昌航空大学 Efficient Bi2S3-BiFeO3 composite visible-light-driven photocatalyst prepared through in-situ growth with chemical corrosion method and application of Bi2S3-BiFeO3 composite visible-light-driven photocatalyst
CN109967095A (en) * 2019-04-17 2019-07-05 南昌航空大学 A kind of holocrystalline bulk heterojunction catalysis material and its preparation method and application
CN110201683A (en) * 2019-07-02 2019-09-06 济南大学 A kind of preparation method and the reduction application of electro-catalysis nitrogen of vanadium doping ferrous sulfide
CN111068718A (en) * 2020-01-08 2020-04-28 济南大学 Preparation of nano spherical sulfur-doped iron oxide and application of nano spherical sulfur-doped iron oxide in electrocatalytic nitrogen reduction

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张小敏等: "硫化铋纳米管的制备及性能研究", 《人工晶体学报》, no. 06, 15 June 2013 (2013-06-15), pages 1070 - 1076 *
袁新松等: "一维纳米硫化铋制备工艺的研究进展", 《稀有金属与硬质合金》, no. 04, 20 December 2009 (2009-12-20), pages 48 - 52 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112663076A (en) * 2020-12-24 2021-04-16 华南理工大学 Iron-doped molybdenum diselenide nano material with hollow structure, preparation method thereof and application of iron-doped molybdenum diselenide nano material in electrocatalytic nitrogen reduction

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