CN111646516A - Preparation of Prussian-like blue sulfur-vanadium co-doped iron oxide and application of iron oxide in electrocatalytic nitrogen reduction - Google Patents

Preparation of Prussian-like blue sulfur-vanadium co-doped iron oxide and application of iron oxide in electrocatalytic nitrogen reduction Download PDF

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CN111646516A
CN111646516A CN202010571699.2A CN202010571699A CN111646516A CN 111646516 A CN111646516 A CN 111646516A CN 202010571699 A CN202010571699 A CN 202010571699A CN 111646516 A CN111646516 A CN 111646516A
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vanadium
iron oxide
sulfur
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prussian
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孙旭
赵明珠
高令峰
郭成英
马晓晶
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University of Jinan
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Abstract

The invention provides a preparation method of Prussian-like blue sulfur and vanadium co-doped iron oxide nano powder and application of the Prussian-like blue sulfur and vanadium co-doped iron oxide nano powder in electrocatalytic nitrogen reduction. Firstly, adding a vanadium source and an iron source into a high-temperature high-pressure reaction kettle to prepare a pre-reaction liquid, heating the pre-reaction liquid to react for a certain time, cooling, washing, drying in vacuum and collecting to obtain ferrovanadium precursor nano powder, and then placing the ferrovanadium precursor nano powder into a tubular furnace to carry out a vulcanization reaction under the protection of inert gas to obtain prussian-like blue sulfur-vanadium co-doped iron oxide nano powder. The sulfur-vanadium co-doped iron oxide shows excellent catalytic activity in the field of electrocatalytic nitrogen reduction (NRR), and ammonia is produced under-0.1V (relative to a standard hydrogen electrode)The high rate reaches 80.0 mu g h–1mg–1 cat.Meanwhile, the Faraday efficiency reaches 4.5 percent.

Description

Preparation of Prussian-like blue sulfur-vanadium co-doped iron oxide and application of iron oxide in electrocatalytic nitrogen reduction
Technical Field
The invention relates to the field of preparation of inorganic nano powder and application of electrocatalytic nitrogen reduction, in particular to a method for preparing prussian-like blue sulfur-vanadium co-doped iron oxide nano powder based on a hydrothermal method and application of the prussian-like blue sulfur-vanadium co-doped iron oxide nano powder in the field of electrocatalytic nitrogen reduction.
Background
The yield of ammonia, which is a high-efficiency pollution-free energy carrier and a main raw material of chemical fertilizers, greatly influences the development of society and the progress of human beings. With the dramatic increase in the population of today's world, the world's demand for chemical fertilizers is increasing. In addition, the limited availability of fossil fuels as a main energy source and environmental pollution have made further development of mankind to be a major problem. Therefore, the development of clean, efficient and recyclable new energy sources and energy storage materials is receiving much attention. In conclusion, the efficient conversion of nitrogen into ammonia is an important part of maintaining the normal life of human beings on earth. At present, the industrial classical ammonia production method (haber-bosch method) has huge production scale and high energy consumption, and a large amount of greenhouse gases are released in the production process, which has great influence on the environment and is one of the reasons causing the non-negligible greenhouse effect. For this reason, extensive researchers have been devoted to exploring the reduction of nitrogen under mild, pollution-free conditions to produce ammonia.
Among the existing methods for synthesizing ammonia, the electrocatalytic nitrogen reduction (NRR) has the advantages of mild reaction conditions (normal temperature and normal pressure), safe and easily-controlled reaction process and the like, and becomes a novel ammonia production method which is most hopeful to replace the Haber-Bosch method. However, up to now electrocatalytic ammonia production has met with major difficulties for its large-scale industrial production due to low yields and the concomitant strong competing reaction (hydrogen evolution, HER). Therefore, the exploration and development of suitable catalysts to increase the rate and selectivity of electrocatalytic nitrogen reduction for ammonia production are not always feasible. The transition metal compound is expected to become a high-efficiency electro-catalytic nitrogen reduction catalyst and even realize the industrial production of ammonia due to the advantages of low price, rich content, easy adjustment of electronic structure, no toxicity, no harm and the like reported by the literature. For example, the Suxuping topic group reports: both density functional calculation (DFT) and experimental results prove that the molybdenum disulfide can be used as an excellent electro-catalytic nitrogen reduction catalyst for 0.1M Na2SO4In an electrolyte, molybdenum disulfideThe high HER activity inhibits the promotion of the electrocatalytic nitrogen reduction catalytic selectivity. The electrocatalytic nitrogen reduction process has a bottleneck in further exploration and development of catalysts due to the inedible competitive reaction (HER). Therefore, the search for effective regulation means to improve selectivity and the synthesis of novel electrocatalytic nitrogen reduction catalysts is urgent.
The doping method can successfully improve the carrier concentration near the Fermi surface level through the fine adjustment effect on local electrons of the intrinsic material, so that the catalytic activity is greatly improved. Meanwhile, the introduction of the hetero atoms also has great influence on the morphological structure of the material, and a favorable morphological structure is obtained by regulating and controlling the doping amount, so that the further improvement of the catalytic activity is realized. Recent research shows that sulfur atom doping is used as an important means for anion doping, and the electronic property of the material can be efficiently regulated and optimized, and active sites are activated, so that the efficient electrocatalytic nitrogen reduction performance is realized. In addition, cationic doping has also achieved significant breakthroughs in numerous areas. Diatomic co-doping approaches are increasingly well known. In view of the above, the invention provides prussian-like blue sulfur and vanadium co-doped iron oxide nano powder as a high-efficiency electrocatalyst.
Disclosure of Invention
The invention aims to provide preparation of Prussian-like blue sulfur and vanadium co-doped iron oxide nano powder and application of the Prussian-like blue sulfur and vanadium co-doped iron oxide nano powder in preparing ammonia through electrocatalysis. In order to solve the problems, the technical scheme of the invention is as follows:
1. a preparation method of Prussian-like blue sulfur and vanadium co-doped iron oxide nano powder comprises the following preparation steps: (1) sequentially adding vanadium and iron sources into the reaction solution to prepare reaction solution, stirring until the vanadium and iron sources are fully dissolved, heating the reaction solution for a certain time, naturally cooling, washing and collecting to obtain vanadium-iron precursor nano powder. (2) And (3) putting the ferrovanadium precursor into a tubular furnace, introducing inert gas, and carrying out a vulcanization reaction at a certain temperature to finally obtain the prussian-like blue sulfur-vanadium co-doped iron oxide nano powder.
2. A preparation method of Prussian blue-like sulfur and vanadium co-doped iron oxide nano powder comprises the following steps of (1), wherein a reaction solution is an ammonia water solution, and the concentration of ammonia water is 0.4-1.0 mol/L; wherein the optimal concentration of the ammonia water is 0.5 mol/L.
3. In the step (1), the vanadium source reagent is one or a combination of sodium metavanadate, sodium orthovanadate, ammonium metavanadate, vanadyl acetylacetonate, sodium pyrovanadate and potassium metavanadate. The most preferred vanadium sources are sodium metavanadate and potassium metavanadate.
4. A preparation method of Prussian-blue-like sulfur and vanadium co-doped iron oxide nano powder is disclosed, wherein in the step (1), the concentration of a vanadium source solution is as follows: 0.002-0.006 mol/L, the optimal concentration is: 0.003 to 0.005 mol/L.
5. In the step (1), an iron source is one or a combination of several of ferric nitrate nonahydrate, ferric trichloride hexahydrate and ferric sulfate, and the optimal iron source is as follows: ferric nitrate nonahydrate.
6. A preparation method of Prussian-blue-like sulfur and vanadium co-doped iron oxide nano powder is provided, wherein in the step (1), the concentration of an iron source solution is as follows: 0.01-0.02 mol/L, and the optimal iron source concentration is 0.013-0.016 mol/L.
7. A preparation method of Prussian-blue-like sulfur and vanadium co-doped iron oxide nano powder is characterized in that in the step (1), the molar ratio of a vanadium source to an iron source is 1-3: 2-5, and the optimal molar ratio is 1-2: 3-5.
8. A preparation method of Prussian-blue-like sulfur and vanadium co-doped iron oxide nano powder is disclosed, wherein in the step (1), the reaction temperature of a ferrovanadium pre-reaction liquid is as follows: 100 to 200oC, the reaction time is as follows: 20-30 h, optimally: 160-200 ofoC，20~ 25 h。
9. The method for preparing prussian blue-like sulfur and vanadium co-doped iron oxide nano powder according to claim 1, wherein in the step (2), the sulfur source reagent is one or a combination of thioacetamide, sodium sulfide, potassium thiocyanate and thiourea, and the optimal sulfur source is: thiourea and thioacetamide.
10. A preparation method of Prussian-blue-like sulfur and vanadium co-doped iron oxide nano powder is characterized in that in the step (2), the mass ratio of the vanadium and iron precursor nano powder to a sulfur source reagent is as follows: 1-2: 20-30.
11. The method for preparing prussian-like blue-like sulfur and vanadium co-doped iron oxide nano powder according to claim 1, wherein in the step (2), the inert gas is: nitrogen, argon. The optimal method is as follows: nitrogen, argon.
12. The method for preparing prussian-like blue-like sulfur and vanadium co-doped iron oxide nano powder according to claim 1, wherein in the step (2), the reaction temperature is 200%oC ~ 400oAnd C, the reaction time is 1-3 h. The optimal method is as follows: 250oC~ 300oC，1 ~ 2 h。
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: a50 mL hydrothermal reaction kettle for a laboratory is taken, and the hydrothermal reaction kettle is provided with a stainless steel shell and a polytetrafluoroethylene inner container. Adding 1.5 mL of ammonia water into a 50 mL polytetrafluoroethylene inner container filled with 40 mL of water, sequentially adding sodium metavanadate (0.023 g and 0.2 mmol) and ferric nitrate nonahydrate (0.145 g and 0.6 mmol) under magnetic stirring, stirring until the sodium metavanadate and the ferric nitrate nonahydrate are fully dissolved, sealing a hydrothermal autoclave, and placing the hydrothermal autoclave in an oven at 160 ℃ for reaction for 20 hours. After natural cooling, respectively centrifugally washing with deionized water and absolute ethyl alcohol for several times, and finally placing at 60 deg.CoAnd C, drying in vacuum for 12 hours to obtain red vanadium-doped ferric oxide nano powder.
The second step is that: 50 mg vanadium-doped iron oxide precursor nano powder is placed in a quartz boat, 1 g of sublimed sulfur is placed in a cupel, the cupel and the quartz boat are sequentially placed in the center of a tube furnace in the airflow direction, and 300 g of the sublimed sulfur is placed under the protection of nitrogen gasoC, annealing for 1h, and naturally cooling to room temperature to obtain the Prussian-like blue sulfur and vanadium co-doped iron oxide nano powder.
The third step: application of sulfur-vanadium co-doped iron oxide nano powder in electrocatalysis ammonia preparation
1. Weighing 5 mg of sulfur-vanadium co-doped iron oxide nano powder, adding the powder 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 1h to obtain uniform dispersion liquid. And (3) taking 20 mu L of the dispersion liquid, dripping the dispersion liquid on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 1 cm multiplied by 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. Carbon paper coated with sulfur-doped iron oxide nano powder 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. 0.1 mol/L hydrochloric acid solution is used as electrolyte, and an H-shaped glass electrolytic tank is used as a reaction device.
3. And (3) taking carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder as a working electrode, and carrying out cyclic voltammetry test in a three-electrode system to activate a sample. The cyclic voltammetry test voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode), the highest potential is 0V, the lowest potential is-1.0V, the initial potential is 0V, and the final potential is-1.0V. The scanning rate was 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 test, taking carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder as a working electrode, and performing linear voltage scanning test in a three-electrode system, wherein the voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode). The initial potential was 0V and the final potential was-1.0V. 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. And then introducing nitrogen into the electrolyte for 30 min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
5. The carbon paper coated with the sulfur-vanadium co-doped iron oxide nano powder is used as a working electrode, a long-time electro-catalysis ammonia production test is carried out on the catalyst, and the potential is respectively set to be-0.35V, -0.45V, -0.55V, -0.65V, -0.75V and-0.85V (relative to Ag/AgCl), and the running time is 7200 s.
The fourth 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 a hydrochloric acid solution of 0.1 mol/L using ammonium chloride as a standard reagent and subjected to a color reaction to test the absorbance. 2mL of the standard solution was added with 2mL of 1 mol/L sodium hydroxide solution (containing 5wt% salicylic acid and 5wt% sodium citrate dihydrate), then 1 mL of 0.05 mol/L sodium hypochlorite solution was added,
finally, 0.2 mL of 5wt% sodium nitroprusside dihydrate solution was added. Standing and developing for 2 h at room temperature in a dark place, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet-visible spectrophotometer, recording an absorbance value at 655 nm, and drawing with concentration to obtain a working curve.
2. And (3) testing the yield of ammonia: 2mL of the electrolyte after running for 2 hours at each potential is taken, 2mL of 1 mol/L sodium hydroxide solution (containing 5wt% of salicylic acid and 5wt% of sodium citrate dihydrate) is added, 1 mL of 0.05 mol/L sodium hypochlorite solution is added, and 0.2 mL of 5wt% sodium nitroprusside dihydrate is added. Standing and developing for 2 h at room temperature in a dark place, performing spectrum scanning within 550-800 nm by using an ultraviolet spectrum, recording an absorbance value at 655 nm, and combining with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the sulfur-doped iron oxide nano powder has excellent effect when being applied to the electrocatalysis ammonia preparation, and the ammonia yield reaches 80 mu g h under minus 0.1V (relative to a standard hydrogen electrode)–1mg–1 cat.The Faraday efficiency reaches 4.5%.
Example 2
The first step is as follows: a50 mL hydrothermal reaction kettle for a laboratory is taken, and the hydrothermal reaction kettle is provided with a stainless steel shell and a polytetrafluoroethylene inner container. Adding 1.5 mL of ammonia water into a 50 mL polytetrafluoroethylene inner container filled with 40 mL of water, sequentially adding vanadyl acetylacetonate (0.0583 g, 0.22 mmol) and ferric trichloride hexahydrate (0.105 g, 0.65 mmol) under magnetic stirring, stirring until the vanadyl acetylacetonate and ferric trichloride hexahydrate are fully dissolved, sealing the hydrothermal autoclave, and placing the hydrothermal autoclave in an oven at 180 ℃ for reaction for 22 hours. After natural cooling, respectively using deionized water and absolute ethyl alcohol to centrifugally wash for a plurality of times, finally placing the materials in a vacuum drying oven at 60 ℃ for 12 hours to obtain the red sulfur vanadium co-doped ferric oxide nano powder.
The second step is that: 50 mg vanadium-doped iron oxide precursor nano powder is placed in a quartz boat, 0.8 g thiourea is placed in a cupel, the cupel and the quartz boat are sequentially placed in the center of a tube furnace in the direction of air flow, and 280 g of the vanadium-doped iron oxide precursor nano powder is placed in the quartz boat under the protection of nitrogen gasoC, annealing for 1h, and naturally cooling to room temperature to obtain the Prussian-like blue sulfur and vanadium co-doped iron oxide nano powder.
The third step: application of sulfur-vanadium co-doped iron oxide nano powder in electrocatalysis ammonia preparation
1. Weighing 5 mg of sulfur-vanadium co-doped iron oxide nano powder, adding the powder 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 1h to obtain uniform dispersion liquid. And (3) taking 20 mu L of the dispersion liquid, dripping the dispersion liquid on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 1 cm multiplied by 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. Carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder 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. 0.1 mol/L hydrochloric acid solution is used as electrolyte, and an H-shaped glass electrolytic tank is used as a reaction device.
3. And (3) taking carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder as a working electrode, and carrying out cyclic voltammetry test in a three-electrode system to activate a sample. The cyclic voltammetry test voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode), the highest potential is 0V, the lowest potential is-1.0V, the initial potential is 0V, and the final potential is-1.0V. The scanning rate was 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 test, taking carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder as a working electrode, and performing linear voltage scanning test in a three-electrode system, wherein the voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode). The initial potential was 0V and the final potential was-1.0V. 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. And then introducing nitrogen into the electrolyte for 30 min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
5. The carbon paper coated with the sulfur-vanadium co-doped iron oxide nano powder is used as a working electrode, a long-time electro-catalysis ammonia production test is carried out on the catalyst, and the potential is respectively set to be-0.35V, -0.45V, -0.55V, -0.65V, -0.75V and-0.85V (relative to Ag/AgCl), and the running time is 7200 s.
The fourth 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 a hydrochloric acid solution of 0.1 mol/L using ammonium chloride as a standard reagent and subjected to a color reaction to test the absorbance. 2mL of the standard solution was added with 2mL of 1 mol/L sodium hydroxide solution (containing 5wt% salicylic acid and 5wt% sodium citrate dihydrate), 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5wt% sodium nitroprusside dihydrate solution was added. Standing and developing for 2 h at room temperature in a dark place, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet-visible spectrophotometer, recording an absorbance value at 655 nm, and drawing with concentration to obtain a working curve.
2. And (3) testing the yield of ammonia: 2mL of the electrolyte after running for 2 hours at each potential is taken, 2mL of 1 mol/L sodium hydroxide solution (containing 5wt% of salicylic acid and 5wt% of sodium citrate dihydrate) is added, 1 mL of 0.05 mol/L sodium hypochlorite solution is added, and 0.2 mL of 5wt% sodium nitroprusside dihydrate is added. Standing and developing for 2 h at room temperature in a dark place, performing spectrum scanning within 550-800 nm by using an ultraviolet spectrum, recording an absorbance value at 655 nm, and combining with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the sulfur-vanadium co-doped ferric oxide nano powder has excellent effect of-0.1V (in-0.1V) when being applied to the electrocatalysis ammonia preparationRelative standard hydrogen electrode) the yield of ammonia reaches 81.2 mu g h–1mg–1 cat.The Faraday efficiency reaches 4.3%.
Example 3
The first step is as follows: a50 mL hydrothermal reaction kettle for a laboratory is taken, and the hydrothermal reaction kettle is provided with a stainless steel shell and a polytetrafluoroethylene inner container. Adding 1.5 mL of ammonia water into a 50 mL polytetrafluoroethylene inner container filled with 40 mL of water, sequentially adding sodium pyrovanadate (0.0765 g, 0.25 mmol) and ferric sulfate (0.2479 g, 0.62 mmol) under magnetic stirring, continuing to fully dissolve, sealing the hydrothermal autoclave, and placing the hydrothermal autoclave in an oven at 150 ℃ for heat preservation for 24 hours. After natural cooling, respectively using deionized water and absolute ethyl alcohol to centrifugally wash for a plurality of times, finally placing the materials in a vacuum drying oven at 60 ℃ for 12 hours to obtain the red sulfur and vanadium co-doped ferric oxide nano powder.
The second step is that: 50 mg of sulfur-vanadium co-doped iron oxide precursor nano powder is placed in a quartz boat, 1.5 g of sublimed sulfur is placed in a cupel, the cupel and the quartz boat are sequentially placed in the center of a tube furnace in the airflow direction, and 280 g of sulfur-vanadium co-doped iron oxide precursor nano powder is placed under the protection of argon gasoC, annealing for 1h, and naturally cooling to room temperature to obtain the Prussian-like blue sulfur and vanadium co-doped iron oxide nano powder.
The third step: application of sulfur-vanadium co-doped iron oxide nano powder in electrocatalysis ammonia preparation
1. Weighing 5 mg of sulfur-vanadium co-doped iron oxide nano powder, adding the powder 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 an Afion solution, and performing ultrasonic treatment for 1h to obtain a uniform dispersion liquid. And (3) taking 20 mu L of the dispersion liquid, dripping the dispersion liquid on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 1 cm multiplied by 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. Carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder 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. 0.1 mol/L hydrochloric acid solution is used as electrolyte, and an H-shaped glass electrolytic tank is used as a reaction device.
3. And (3) taking carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder as a working electrode, and carrying out cyclic voltammetry test in a three-electrode system to activate a sample. The cyclic voltammetry test voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode), the highest potential is 0V, the lowest potential is-1.0V, the initial potential is 0V, and the final potential is-1.0V. The scanning rate was 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 test, taking carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder as a working electrode, and performing linear voltage scanning test in a three-electrode system, wherein the voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode). The initial potential was 0V and the final potential was-1.0V. 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. And then introducing nitrogen into the electrolyte for 30 min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
5. The carbon paper coated with the sulfur-vanadium co-doped iron oxide nano powder is used as a working electrode, a long-time electro-catalysis ammonia production test is carried out on the catalyst, and the potential is respectively set to be-0.35V, -0.45V, -0.55V, -0.65V, -0.75V and-0.85V (relative to Ag/AgCl), and the running time is 7200 s.
The fourth 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 a hydrochloric acid solution of 0.1 mol/L using ammonium chloride as a standard reagent and subjected to a color reaction to test the absorbance. 2mL of the standard solution was added with 2mL of 1 mol/L sodium hydroxide solution (containing 5wt% salicylic acid and 5wt% sodium citrate dihydrate), 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5wt% sodium nitroprusside dihydrate solution was added. Standing and developing for 2 h at room temperature in a dark place, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet-visible spectrophotometer, recording an absorbance value at 655 nm, and drawing with concentration to obtain a working curve.
2. AmmoniaAnd (3) yield testing: 2mL of the electrolyte after running for 2 hours at each potential is taken, 2mL of 1 mol/L sodium hydroxide solution (containing 5wt% of salicylic acid and 5wt% of sodium citrate dihydrate) is added, 1 mL of 0.05 mol/L sodium hypochlorite solution is added, and 0.2 mL of 5wt% sodium nitroprusside dihydrate is added. Standing and developing for 2 h at room temperature in a dark place, performing spectrum scanning within 550-800 nm by using an ultraviolet spectrum, recording an absorbance value at 655 nm, and combining with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the sulfur-vanadium co-doped iron oxide nano powder has excellent effect when being applied to the electrocatalysis ammonia preparation, and the ammonia yield reaches 79.63 mu g h under-0.1V (relative to a standard hydrogen electrode)–1mg–1 cat.The Faraday efficiency reaches 4.3%.
Example 4
The first step is as follows: a50 mL hydrothermal reaction kettle for a laboratory is taken, and the hydrothermal reaction kettle is provided with a stainless steel shell and a polytetrafluoroethylene inner container. Adding 1.5 mL of ammonia water into a 50 mL polytetrafluoroethylene inner container filled with 40 mL of water, sequentially adding potassium metavanadate (0.0359 g and 0.26 mmol) and ferric nitrate nonahydrate (0.1669 g and 0.69 mmol) under magnetic stirring, stirring until the potassium metavanadate and the ferric nitrate nonahydrate are fully dissolved, sealing the hydrothermal autoclave, and placing the hydrothermal autoclave in an oven at 160 ℃ for reaction for 22 hours. After natural cooling, respectively using deionized water and absolute ethyl alcohol to centrifugally wash for a plurality of times, finally placing the materials in a vacuum drying oven at 60 ℃ for 12 hours to obtain the red sulfur and vanadium co-doped ferric oxide nano powder.
The second step is that: 50 mg of sulfur-vanadium co-doped iron oxide precursor nano powder is placed in a quartz boat, 1.5 g of sublimed sulfur is placed in a cupel, the cupel and the quartz boat are sequentially placed in the center of a tube furnace in the direction of air flow, and 300 g of sulfur-vanadium co-doped iron oxide precursor nano powder is protected by nitrogen gasoC, annealing for 1h, and naturally cooling to room temperature to obtain the Prussian-like blue sulfur and vanadium co-doped iron oxide nano powder.
The third step: application of sulfur-vanadium co-doped iron oxide nano powder in electrocatalysis ammonia preparation
1. Weighing 5 mg of sulfur-vanadium co-doped iron oxide nano powder, adding the powder 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 1h to obtain uniform dispersion liquid. And (3) taking 20 mu L of the dispersion liquid, dripping the dispersion liquid on the surface of clean and dry carbon paper, wherein the surface area of the carbon paper is controlled to be 1 cm multiplied by 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. Carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder 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. 0.1 mol/L hydrochloric acid solution is used as electrolyte, and an H-shaped glass electrolytic tank is used as a reaction device.
3. And (3) taking carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder as a working electrode, and carrying out cyclic voltammetry test in a three-electrode system to activate a sample. The cyclic voltammetry test voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode), the highest potential is 0V, the lowest potential is-1.0V, the initial potential is 0V, and the final potential is-1.0V. The scanning rate was 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 test, taking carbon paper coated with sulfur-vanadium co-doped iron oxide nano powder as a working electrode, and performing linear voltage scanning test in a three-electrode system, wherein the voltage interval is 0 to-1.0V (relative to an Ag/AgCl electrode). The initial potential was 0V and the final potential was-1.0V. 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. And then introducing nitrogen into the electrolyte for 30 min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
5. The carbon paper coated with the sulfur-vanadium co-doped iron oxide nano powder is used as a working electrode, a long-time electro-catalysis ammonia production test is carried out on the catalyst, and the potential is respectively set to be-0.35V, -0.45V, -0.55V, -0.65V, -0.75V and-0.85V (relative to Ag/AgCl), and the running time is 7200 s.
The fifth 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 a hydrochloric acid solution of 0.1 mol/L using ammonium chloride as a standard reagent and subjected to a color reaction to test the absorbance. 2mL of the standard solution was added with 2mL of 1 mol/L sodium hydroxide solution (containing 5wt% salicylic acid and 5wt% sodium citrate dihydrate), 1 mL of 0.05 mol/L sodium hypochlorite solution was added, and 0.2 mL of 5wt% sodium nitroprusside dihydrate solution was added. Standing and developing for 2 h at room temperature in a dark place, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet-visible spectrophotometer, recording an absorbance value at 655 nm, and drawing with concentration to obtain a working curve.
2. And (3) testing the yield of ammonia: 2mL of the electrolyte after running for 2 hours at each potential is taken, 2mL of 1 mol/L sodium hydroxide solution (containing 5wt% of salicylic acid and 5wt% of sodium citrate dihydrate) is added, 1 mL of 0.05 mol/L sodium hypochlorite solution is added, and 0.2 mL of 5wt% sodium nitroprusside dihydrate is added. Standing and developing for 2 h at room temperature in a dark place, performing spectrum scanning within 550-800 nm by using an ultraviolet spectrum, recording an absorbance value at 655 nm, and combining with a working curve to finally obtain the concentration of ammonia. After data processing and calculation, the sulfur-vanadium co-doped iron oxide nano powder has excellent effect when being applied to the electrocatalysis ammonia preparation, and the ammonia yield reaches 80.45 mu g h under minus 0.1V (relative to a standard hydrogen electrode)–1mg–1 cat.The Faraday efficiency reaches 4.55 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 (7)

1. The preparation method of Prussian-like blue sulfur and vanadium co-doped iron oxide is characterized by comprising the following preparation steps: (1) adding a vanadium source and an iron source reagent into the reaction solution to obtain a pre-reaction solution, heating the pre-reaction solution for a period of time, naturally cooling, washing, centrifuging, drying, and collecting to obtain vanadium-iron precursor nano powder; (2) and (3) putting the ferrovanadium precursor nano powder into a tubular furnace, and vulcanizing at a certain temperature under the protection of inert gas argon to obtain prussian-like blue sulfur-vanadium co-doped iron oxide nano powder.
2. The preparation method of the Prussian-like blue-like sulfur and vanadium co-doped iron oxide nano powder as claimed in claim 1, wherein in the step (1), the reaction solution is ammonia water, and the concentration of the ammonia is 0.4-1.0 mol/L.
3. The method for preparing prussian-like blue-like sulfur and vanadium co-doped iron oxide nanopowder according to claim 1, wherein in the step (1), the vanadium source reagent is one or a combination of more of sodium metavanadate, sodium orthovanadate, ammonium metavanadate, vanadyl acetylacetonate, sodium pyrovanadate and potassium metavanadate, and the concentration of the vanadium source solution is as follows: 0.002-0.006 mol/L; the iron source is ferric nitrate nonahydrate, ferric trichloride hexahydrate and ferric sulfate; one or a combination of several of them, the concentration of the iron source solution is: 0.01-0.02 mol/L; the molar ratio of the vanadium source to the iron source is 1-3: 2-5.
4. The preparation method of the Prussian-like blue sulfur and vanadium co-doped iron oxide nano powder as claimed in claim 1, wherein in the step (1), the reaction temperature of the ferrovanadium pre-reaction solution is 100-200%oAnd C, the reaction time is 20-30 h.
5. The preparation method of the Prussian-like blue-like sulfur and vanadium co-doped iron oxide nano powder as claimed in claim 1, wherein in the step (2), the sulfur source reagent is one or a combination of several of thioacetamide, sodium sulfide, potassium thiocyanate and thiourea, and the mass ratio of the vanadium-nickel precursor to the sulfur source reagent is 1-2: 20-30.
6. The method for preparing prussian-like blue-like sulfur and vanadium co-doped iron oxide nano powder according to claim 1, wherein in the step (2), the reaction temperature is 200%oC ~ 400oAnd C, the reaction time is 1-3 h.
7. The preparation method is 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 Prussian-like blue sulfur-vanadium co-doped iron oxide nano powder 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; 0.1 mol/L hydrochloric acid solution is taken as electrolyte; an H-shaped glass electrolytic tank is used as an electrolytic reaction device.
CN202010571699.2A 2020-06-22 2020-06-22 Preparation of Prussian-like blue sulfur-vanadium co-doped iron oxide and application of iron oxide in electrocatalytic nitrogen reduction Pending CN111646516A (en)

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CN113044894A (en) * 2021-04-06 2021-06-29 济南大学 Preparation of hollow hexahedral F-doped FeVNi hydroxide and application of electrocatalysis ORR
CN114988486A (en) * 2022-04-08 2022-09-02 杭州电子科技大学 Preparation method and application of flower-like cobalt sulfide material derived from growing prussian blue analogue
CN115287671A (en) * 2022-06-29 2022-11-04 西南科技大学 Preparation and application of sulfur-based iron oxide nanowire for extracting uranium from electrochemical seawater
CN115287671B (en) * 2022-06-29 2024-05-10 西南科技大学 Preparation and application of sulfo-ferric oxide nanowire for electrochemical seawater uranium extraction

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113044894A (en) * 2021-04-06 2021-06-29 济南大学 Preparation of hollow hexahedral F-doped FeVNi hydroxide and application of electrocatalysis ORR
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CN115287671B (en) * 2022-06-29 2024-05-10 西南科技大学 Preparation and application of sulfo-ferric oxide nanowire for electrochemical seawater uranium extraction

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