CN117702176A - Preparation method of Nb-based metal doped material and application of Nb-based metal doped material in difunctional oxygen electrochemistry - Google Patents
Preparation method of Nb-based metal doped material and application of Nb-based metal doped material in difunctional oxygen electrochemistry Download PDFInfo
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Abstract
The invention discloses a preparation method of an Nb-based metal doping material and application of difunctional oxygen electrochemistry, which comprises preparation of the Nb-based metal doping material, application of an electrochemical oxygen reduction function and application of an electrochemical ozone precipitation function. Namely preparing a novel metal-doped Nb-based material, preparing the novel material by a hydrothermal method and a high-temperature calcination method, and performing electrochemical double-function reaction, wherein the novel material comprises two reactions of electrochemical oxygen reduction to produce hydrogen peroxide and electrochemical ozone precipitation. The Nb-based metal doped material prepared by the invention is doped by utilizing different La series metals to obtain mixed metal doped materials with different morphologies, and the proper regulation and control of the hydrogen peroxide intermediate produced by oxygen reduction are performed through the metal center, and meanwhile, a novel non-lead system is explored to perform 6e electrolysis of aquatic ozone, so that various materials with double-function oxygen electrochemical functions are finally obtained. The method has important reference significance for the development of the non-lead system catalyst which is used immediately after the electrochemical hydrogen peroxide production and is separated out by the electrochemical ozone, and can promote the application of the double functions.
Description
Technical Field
The invention belongs to the technical field of material preparation and application, and particularly relates to a preparation method of an Nb-based metal doped material and application of the Nb-based metal doped material in difunctional oxygen electrochemistry.
Background
Niobium (Nb) is an important superconductor material, and the superconducting properties can be adjusted by doping niobium. The niobium-based metal doped material, such as Nb3Sn (niobium-tin alloy), is a high-temperature superconducting material, and doped with other metal elements in an alloying mode, so that the superconducting transformation temperature and the current carrying capacity of the niobium-based metal doped material can be regulated and controlled, and the niobium-based metal doped material can be widely applied to the fields of magnets, superconducting cables and the like; niobium-based metal doped materials are also of great interest in the battery and energy storage fields. The compound based on niobium, such as a positive electrode material LiNbO3 in a lithium ion battery, has good electrochemical performance, and improves the cycle life and the charge and discharge efficiency of the battery. Niobium-based catalysts exhibit excellent performance in the field of Oxygen Reduction Reactions (ORR) and the like. The active site of the catalyst is improved through doping of niobium, so that the catalytic activity and stability are improved, and the catalyst has potential of being applied to systems such as fuel cells, metal-air cells and the like. In general, niobium-based metal doped materials have shown extensive research and application in a variety of fields, including superconducting materials, battery and energy storage materials, catalysts, optoelectronic devices, and electronic devices. Researchers are continually seeking to optimize the properties of niobium-based materials by regulating their structure and properties to meet the needs of different fields.
Oxygen electrochemical research has made significant progress in the fields of energy conversion, environmental remediation and novel energy storage. Researchers are continually looking for more efficient, economical, and environmentally friendly oxygen electrochemical technologies to drive the development of renewable and clean energy technologies. Among them, oxygen Reduction Reaction (ORR) is a key oxygen electrochemical reaction, affecting the performance of energy conversion devices such as fuel cells and metal air cells. ORR generates hydrogen peroxide through a 2 e-reaction, which is one route for providing green, safe and low-concentration hydrogen peroxide which can be used in the process of production, and the challenge is to develop an efficient electrocatalyst material for the process of production; another oxygen electrochemical reaction, electrochemical ozone Evolution (EOP), is also a more specific 6 e-Oxygen Evolution (OER). The over-potential of EOP is greater than OER, indicating that the difficulty is also greater. Ozone is a strong oxidizing agent with a high degree of oxidizing properties and is capable of reacting with a wide variety of substances. The electrolysis of water to produce ozone is an important technology and has wide application in the fields of water treatment and wastewater treatment. The challenge is to replace the existing anode lead-based catalyst, develop a lead-free series catalyst, and electrolyze water with high activity and stability to prepare ozone.
The research shows that the niobium-based metal doped material is promising, and oxygen electrochemistry (2 eORR to prepare hydrogen peroxide and 6e EOP to prepare ozone) is a green, safe and efficient method. However, both reactions, oxygen electrochemistry is limited by the choice of catalyst. Therefore, the novel catalyst is developed, and the catalyst is simultaneously used for preparing hydrogen peroxide by 2eORR and preparing ozone by 6eEOP, so that the double-function electrochemical reaction is of great significance.
Disclosure of Invention
The invention aims to provide a preparation method of an Nb-based metal doping material and application of the Nb-based metal doping material in dual-function oxygen electrochemistry.
The invention aims to provide a preparation method of an Nb-based metal doped material and application of difunctional oxygen electrochemistry, wherein the method comprises three steps of preparation of the Nb-based metal doped material, application of an electrochemical oxygen reduction function and application of an electrochemical ozone precipitation function. Preparing a novel metal-doped Nb-based material, and preparing the novel material by a hydrothermal method and a high-temperature calcination method, wherein the novel material is used for electrochemical double-function reaction.
The technical scheme of the invention is realized as follows:
step 1, a preparation method of an Nb-based metal doping material is provided, wherein an Nb precursor, a doped metal precursor, urea and water are mixed and stirred uniformly, after the metal precursor is completely dissolved, the mixture is transferred into a hydrothermal kettle with a tetrafluoro lining, the kettle is placed into an oven with a rotary rod to rotate at a low speed and rotate at a high temperature for a certain time, the hydrothermal kettle is taken out after the temperature is reduced, and the product is subjected to suction filtration and water washing treatment to obtain wet powder. And (3) drying the wet powder in a vacuum drying oven, taking out the dried powder, calcining the powder at a high temperature in a protective atmosphere in a tube furnace, cooling the powder, taking out the powder, and grinding the powder to obtain the corresponding Nb-based metal doping material.
Further, in step 1, the Nb precursor is NbCl 5 、Nb 2 O 5 、NbF 5 Or NbC, the doped metal precursor is lanthanum nitrate (La (NO 3 ) 3 ·6H 2 O), gadolinium nitrate (Gd (NO) 3 ) 3 ·XH 2 O), praseodymium nitrate (PrN 3 O 9 ·6H 2 O), thulium nitrate (Tm (NO) 3 ) 3 ·nH 2 O), europium nitrate (Eu (NO) 3 ) 3 ·6H 2 O) or ytterbium nitrate (Yb (NO) 3 ) 3 ·5H 2 O)。
Further, urea in step 1: water = 10-30:3mg/mL, the amount of Nb precursor is 0.2-3mmol/L, and the amount of doped metal precursor is 0.2-3mmol/L.
Further, in the oven with the rotating rod in step 1, the temperature is set to 150-220 ℃, preferably 200 ℃; the high temperature maintaining time is 5-15 h, preferably 8h; the rotation speed of the rotating rod is set to 2-20rpm, preferably 10rpm; the temperature time of the tube furnace is set to 400-700 ℃ and 1-5 hours, preferably 500 ℃ and 3 hours; the protective atmosphere of the tube furnace is nitrogen or argon.
Step 2 electrochemical oxygen reduction function: the method comprises the steps of performing a test on the selectivity of hydrogen peroxide generated by electrochemical oxygen reduction by adopting a Rotary Ring Disk Electrode (RRDE), wherein slurry prepared by the Nb-based metal doping material is dripped on the RRDE to serve as a working electrode, hg/HgO or Ag/AgCl serves as a reference electrode, a platinum wire serves as a counter electrode, a platinum area on the RRDE serves as a ring electrode, performing a four-electrode test, and performing the test by using a Cyclic Voltammetry (CV) and a Linear Sweep Voltammetry (LSV), wherein the selectivity of hydrogen peroxide can be obtained by formula conversion, and the electrolyte is an acidic, neutral or alkaline electrolyte.
Further, the slurry prepared by Nb-based metal doping materials in the step 2 is prepared by dispersing 1-8mg of catalyst powder in 0.5-0.9mL of solvent dispersing agent, adding 0.1-0.5mL of Nafion solution as an adhesive, and performing ultrasonic dispersion for 10-60min to obtain the catalyst slurry.
Further, the concentration of the Nafion solution in step 2 is 5wt%.
Further, the electrolyte in the step 2 is H with the concentration of 0.1-1.0M 2 SO 4 Aqueous solution, na 0.1-1.0M 2 SO 4 Aqueous solution or 0.01-0.5M NaOH aqueous solution.
Step 3, electrochemical ozone precipitation function: the method is characterized in that the application of the Nb-based metal doped material in the reaction of electrochemical ozone precipitation is carried out by adopting a sealed single electrolytic tank to test the yield of electrochemical ozone precipitation, wherein slurry prepared by the Nb-based metal doped material is dripped on a carrier to serve as a working electrode, ag/AgCl serves as a reference electrode, a platinum sheet serves as a counter electrode, three-electrode test is carried out, the ozone yield can be obtained by utilizing a 2B detection instrument, and the electrolyte is neutral electrolyte.
Further, in the step 3, the carrier is one of a titanium fiber felt, a carbon cloth and a carbon paper, and is preferably a carbon fiber felt.
Further, the slurry prepared by Nb-based metal doping materials in the step 3 is prepared by dispersing 5-20mg of catalyst powder in 0.5-0.9mL of solvent dispersing agent, adding 0.1-0.5mL of Nafion solution as an adhesive, and performing ultrasonic dispersion for 10-60min to obtain the catalyst slurry.
Further, the concentration of the Nafion solution in step 3 is 5wt%.
Further, the electrolyte is Na of 0.1-1.0M 2 SO 4 An aqueous solution.
Compared with the prior art, the invention has the beneficial effects that:
1) The Nb-based metal doped catalyst prepared by the invention adopts two simple and rapid steps of a hydrothermal method and a high-temperature calcination method. The Nb-based metal doping materials with different morphologies are prepared by innovatively combining the Nb-based metal and other lanthanide metals, and the number of active centers is increased by successfully doping the metals. The material of the invention has low temperature required by preparation, low energy consumption, powder catalyst, capability of being used for multifunctional application, smaller particles, reduced cost of the catalyst and good mechanical strength.
2) The Nb-based metal doping material is applied to difunctional oxygen electrochemistry, comprises the steps of preparing hydrogen peroxide by electrochemical oxygen reduction and performing electrochemical ozone separation reaction, and is a high-efficiency green safe material with cathode and anode catalysis effects. Through researches, the selectivity of cathode hydrogen peroxide is up to 93.50%, the yield of anode ozone is 3500ppb (2 h), and the Faraday efficiency is 17%, which indicates that the Nb-based metal doping material prepared by the preparation method has better selectivity and yield (Faraday efficiency) in the production of hydrogen peroxide prepared by electrochemical oxygen reduction reaction and electrochemical ozone separation; meanwhile, the method has good stability, meets the high selectivity and high activity requirements of efficiently preparing hydrogen peroxide and ozone, and has development potential
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of Nb-based metal doping material (LanbOx) prepared in example 1 of the present invention;
FIG. 2 is an SEM image of Nb-based metal doping material (GdNbOx) prepared in example 2 of the present invention;
FIG. 3 is an SEM image of an Nb-based metal-doped material (PrNbOx) prepared in example 3 of the present invention;
FIG. 4 is an SEM image of Nb-based metal doping material (TmNbOx) obtained in example 4 of the present invention;
FIG. 5 is an SEM image of Nb-based metal doping material (EuNbOx) obtained in example 5 of the present invention;
FIG. 6 is an SEM image of an Nb-based metal doping material (YbNbOx) prepared in example 6 of the present invention;
FIG. 7 is an X-ray diffraction (XRD) pattern of Nb-based metal doping material (LanbOx) obtained in example 1 of the present invention;
FIG. 8 is an X-ray diffraction (XRD) pattern of a Nb-based metal dopant material (GdNbOx) prepared in example 2 of the present invention;
FIG. 9 is an X-ray diffraction (XRD) pattern of Nb-based metal doping material (PrNbOx) obtained in example 3 of the present invention;
FIG. 10 is a summary of the electrochemical hydrogen peroxide production selectivities of the Nb-based metal-doped materials of examples 1-9 and comparative examples 1-2 of the present invention;
FIG. 11 is a summary of electrochemical ozone precipitation performance of Nb-based metal-doped materials prepared in examples 1-9 and comparative examples 1-2 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, based on the embodiments of the invention, which are apparent to those of ordinary skill in the art without inventive faculty, are intended to be within the scope of the invention.
Example 1: nb-based metal doping material (LaNbOx)
240mg of urea was weighed into 30mL of deionized water and stirred to dissolve completely. 1mmol of Nb precursor (NbCl) was weighed out separately 5 270.17 mg) and 1mmol of doped metal precursor (La (NO 3 ) 3 ·6H 2 O,433 mg) was poured into the above solution, stirred until the metal precursor was completely dissolved, and the whole was transferred into a tetrafluoro-lined hydrothermal kettle, and placed in an oven with a rotary rod to rotate at a low speed of 10rpm, and the oven was kept at 200℃for 8 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. Calcining the powder after vacuum drying in a protective atmosphere (nitrogen) in a tube furnace at a temperature rising speed of 5 ℃ for 500 ℃ for 3 hours, cooling, taking out the powder, and grinding to obtain the corresponding Nb-based metal doped material (LaNbOx). The materials prepared in this example were subjected to scanning electron microscope characterization, and the results are shown in fig. 1. The X-ray diffraction technique test was performed simultaneously, and the results are shown in FIG. 7.
Example 2: nb-based metal doping material (GdNbOx)
240mg of urea was weighed into 30mL of deionized water and stirred to dissolve completely. 1mmol of Nb precursor (NbCl) was weighed out separately 5 270.17 mg) and 1mmol of doped metal precursor (Gd (NO) 3 ) 3 ·XH 2 O,343.24 mg) was poured into the above solution,stirring until the metal precursor is completely dissolved, transferring the whole into a tetrafluoro-lined hydrothermal kettle, placing the kettle into an oven with a rotary rod, rotating at a low speed of 10rpm, and keeping the oven at 200 ℃ for 8 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. And (3) calcining the powder after vacuum drying at a high temperature of 500 ℃ for 3 hours at a heating rate of 5 ℃/min under a protective atmosphere (nitrogen) in a tube furnace, cooling, taking out the powder, and grinding to obtain the corresponding Nb-based metal doping material (GdNbOx). The materials prepared in this example were subjected to scanning electron microscope characterization, and the results are shown in fig. 2. The X-ray diffraction technique test was performed simultaneously, and the results are shown in FIG. 8.
Example 3: nb-based metal doping materials (PrNbOx)
240mg of urea was weighed into 30mL of deionized water and stirred to dissolve completely. 1mmol of Nb precursor (NbCl) was weighed out separately 5 270.17 mg) and 1mmol of doped metal precursor (Pr (NO) 3 ) 3 ·6H 2 O,435 mg) was poured into the above solution, stirred until the metal precursor was completely dissolved, and the whole was transferred into a tetrafluoro-lined hydrothermal kettle, and placed in an oven with a rotating rod to rotate at a low speed of 10rpm, and the oven was kept at 200℃for 8 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. Calcining the powder after vacuum drying at 500 ℃ for 3 hours in a protective atmosphere (nitrogen) in a tube furnace at a heating rate of 5 ℃/min, cooling, taking out the powder, and grinding to obtain the corresponding Nb-based metal doped material (PrNbOx). The materials prepared in this example were subjected to scanning electron microscope characterization, and the results are shown in fig. 3. The X-ray diffraction technique test was performed simultaneously, and the results are shown in FIG. 9.
Example 4: nb-based metal doping material (TmNbOx)
240mg of urea was weighed into 30mL of deionized water and stirred to dissolve completely. 1mmol of Nb precursor (NbCl) was weighed out separately 5 270.17 mg) and 1mmol of the doped metal precursor (Tm (NO) 3 ) 3 ·nH 2 O,354.96 mg) is poured into the solution, stirred until the metal precursor is completely dissolved, and the whole is transferred into a hydrothermal kettle with a tetrafluoro lining and put into a rotary beltThe rod was rotated at a low speed in an oven at 10rpm and the oven was maintained at 200℃for 8 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. Calcining the powder after vacuum drying at 500 ℃ for 3 hours in a protective atmosphere (nitrogen) in a tube furnace at a heating rate of 5 ℃/min, cooling, taking out the powder, and grinding to obtain the corresponding Nb-based metal doped material (TmNbOx). The materials prepared in this example were subjected to scanning electron microscope characterization, and the results are shown in fig. 4.
Example 5: nb-based metal doping material (EuNbOx)
240mg of urea was weighed into 30mL of deionized water and stirred to dissolve completely. 1mmol of Nb precursor (NbCl) was weighed out separately 5 270.17 mg) and 1mmol of doped metal precursor (Eu (NO) 3 ) 3 6H2O,446.07 mg) was poured into the above solution, stirred until the metal precursor was completely dissolved, the whole was transferred into a tetrafluoro-lined hydrothermal kettle, placed in an oven with a rotating rod to rotate at a low speed of 10rpm, and the oven was kept at 200℃for 8 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. And (3) calcining the powder after vacuum drying at a high temperature of 500 ℃ for 3 hours at a heating rate of 5 ℃/min under a protective atmosphere (nitrogen) in a tube furnace, cooling, taking out the powder, and grinding to obtain the corresponding Nb-based metal doped material (EuNbOx). The materials prepared in this example were subjected to scanning electron microscope characterization, and the results are shown in fig. 5.
Example 6: nb-based metal doping material (YbNbOx)
240mg of urea was weighed into 30mL of deionized water and stirred to dissolve completely. 1mmol of Nb precursor (NbCl) was weighed out separately 5 270.17 mg) and 1mmol of doped metal precursor (Yb (NO) 3 ) 3 ·5H 2 O,449 mg) was poured into the above solution, stirred until the metal precursor was completely dissolved, and the whole was transferred into a tetrafluoro-lined hydrothermal kettle, and placed in an oven with a rotating rod to rotate at a low speed of 10rpm, and the oven was kept at 200 ℃ for 8 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. Placing the powder after vacuum drying into a tube furnace to protect the atmosphereNitrogen) calcining at 500 ℃ for 3 hours at a temperature rising speed of 5 ℃ min, cooling, taking out powder, and grinding to obtain the corresponding Nb-based metal doped material (YbNbOx). The materials prepared in this example were subjected to scanning electron microscope characterization, and the results are shown in fig. 6.
Example 7: nb-based metal doping material (LaNbOx-2)
100mg of urea was weighed into 30mL of deionized water and stirred to dissolve completely. 1mmol of Nb precursor (NbCl) was weighed out separately 5 270.17 mg) and 1mmol of doped metal precursor (La (NO 3 ) 3 ·6H 2 O,433 mg) was poured into the above solution, stirred until the metal precursor was completely dissolved, and the whole was transferred into a tetrafluoro-lined hydrothermal kettle, and placed in an oven with a rotary rod to rotate at a low speed of 10rpm, and the oven was kept at 200℃for 8 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. And (3) calcining the powder after vacuum drying at a high temperature of 500 ℃ for 3 hours at a heating rate of 5 ℃/min under a protective atmosphere (nitrogen) in a tube furnace, cooling, taking out the powder, and grinding to obtain the corresponding Nb-based metal doped material (LaNbOx-2).
Example 8: nb-based metal doping material (LaNbOx-3)
240mg of urea was weighed into 30mL of deionized water and stirred to dissolve completely. 3mmol of Nb precursor (NbCl) was weighed out separately 5 810.51 mg) and 0.2mmol of doped metal precursor (La (NO 3 ) 3 ·6H 2 O,86.6 mg) was poured into the above solution, stirred until the metal precursor was completely dissolved, and the whole was transferred into a tetrafluoro-lined hydrothermal kettle, and placed in an oven with a rotating rod to rotate at a low speed of 10rpm, and the oven was kept at 200℃for 8 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. And (3) calcining the powder after vacuum drying at a high temperature of 500 ℃ for 3 hours at a heating rate of 5 ℃/min under a protective atmosphere (nitrogen) in a tube furnace, cooling, taking out the powder, and grinding to obtain the corresponding Nb-based metal doped material (LaNbOx-3).
Example 9: nb-based metal doping material (LaNbOx-4)
240mg of urea was weighed up and dissolved in 30mAnd (3) stirring in deionized water to completely dissolve the L-deionized water. 0.2mmol of Nb precursor (NbCl) was weighed out separately 5 54.03 mg) and 3mmol of doped metal precursor (La (NO 3 ) 3 ·6H 2 O,1299 mg) was poured into the above solution, stirred until the metal precursor was completely dissolved, and the whole was transferred into a tetrafluoro-lined hydrothermal kettle, and placed in an oven with a rotating rod to rotate at a low speed of 10rpm, and the oven was kept at 200 ℃ for 8 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. And (3) calcining the powder after vacuum drying at a high temperature of 500 ℃ for 3 hours at a heating rate of 5 ℃/min under a protective atmosphere (nitrogen) in a tube furnace, cooling, taking out the powder, and grinding to obtain the corresponding Nb-based metal doped material (LaNbOx-2).
As can be seen from SEM images of fig. 1-6, nb-based metal doped materials prepared by the present invention were all successfully prepared, six different doped metal precursors were all well combined with Nb, and the different doped metals had different morphology structures. The doped metal in example 1 is lanthanum La, which shows a multi-plate structure after being doped into Nb-based metal material, and the plate structure may be stacked with each other to cause stacked pores to appear, and the two-dimensional plate structure is beneficial to exposing more active sites, promoting adsorption and desorption of catalyst reaction, and the like. The doped metal liquid shown in other embodiments exhibits different morphologies, including spheroids, squares, etc. The Nb-based metal doped materials with different morphologies prepared by the preparation method provided by the invention are preliminarily proved to be successfully synthesized. Lays a solid foundation for the subsequent exploration of the application of the catalyst in the difunctional oxygen electrochemistry, and is favorable for further researching the structure-activity relationship and the like in the oxygen electrochemistry reaction.
Comparative example 1: nb-based metal doping material (LaNbOx)
240mg of urea was weighed into 30mL of deionized water and stirred to dissolve completely. 1mmol of Nb precursor (NbCl) was weighed out separately 5 270.17 mg) and 1mmol of doped metal precursor (La (NO 3 ) 3 ·6H 2 O,433 mg) is poured into the solution, stirred until the metal precursor is completely dissolved, and the whole is transferred into a hydrothermal kettle with a tetrafluoro lining and placed into an oven with a rotary rodThe inner spin was at low speed, at 2rpm, and the oven was maintained at 150℃for 5 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. And (3) placing the powder after vacuum drying in a protective atmosphere (nitrogen) in a tube furnace, calcining at a temperature of 400 ℃ at a heating rate of 5 ℃/min for 1h, cooling, taking out the powder, and grinding to obtain the corresponding Nb-based metal doped material (LaNbOx).
Comparative example 2: nb-based metal doping material (LaNbOx)
240mg of urea was weighed into 30mL of deionized water and stirred to dissolve completely. 1mmol of Nb precursor (NbCl) was weighed out separately 5 270.17 mg) and 1mmol of doped metal precursor (La (NO 3 ) 3 ·6H 2 O,433 mg) was poured into the above solution, stirred until the metal precursor was completely dissolved, and the whole was transferred into a tetrafluoro-lined hydrothermal kettle, and placed in an oven with a rotating rod to rotate at a low speed of 20rpm, and the oven was kept at 220℃for 15 hours. And taking out the hydrothermal kettle after cooling, and carrying out suction filtration and water washing treatment on the product to obtain wet powder. Calcining the powder after vacuum drying in a protective atmosphere (nitrogen) in a tube furnace at a temperature rising speed of 5 ℃ for 700 ℃ for 5 hours, cooling, taking out the powder, and grinding to obtain the corresponding Nb-based metal doped material (LaNbOx).
Verification example 1
The electrochemical hydrogen peroxide generation selectivity performance of the Nb-based metal-doped materials prepared in examples 1-9 and comparative examples 1-2 was verified respectively:
catalyst slurries were prepared from Nb-based metal doping materials prepared in examples 1 to 9 and comparative examples 1 to 2, respectively: 4.0mg of powder material is taken and dispersed in a mixed solution consisting of 0.1mL of 5% Nafion solution of DuPont and 0.9mL of absolute ethyl alcohol, and the corresponding catalyst slurry is obtained by ultrasonic treatment for 30 min. Preparing a working electrode: and accurately transferring 5 microliters of catalyst slurry, dripping the catalyst slurry on the central glassy carbon region of the RRDE, and naturally airing. During testing, the alkaline electrolyte is selected to be a 0.1M NaOH solution, and oxygen is introduced in advance to saturate dissolved oxygen in the solution, so that oxygen is introduced directly during testing. After RRDE is assembled, hg/HgO is used as a reference electrode, a platinum wire is used as a counter electrode, and four-electrode test is performed. And testing by using a Cyclic Voltammetry (CV) and a Linear Sweep Voltammetry (LSV), and obtaining the selectivity of the hydrogen peroxide through formula conversion. The selectivity of hydrogen peroxide (at 0.4V) for examples 1-9 and comparative examples 1-2 is shown in fig. 10.
Verification example 2
Electrochemical ozone precipitation performance of Nb-based metal doped materials prepared in examples 1 to 9 and comparative examples 1 to 2, respectively, was verified:
catalyst slurries were prepared from Nb-based metal doping materials prepared in examples 1 to 9 and comparative examples 1 to 2, respectively: 8.0mg of the powder material is taken and dispersed in a mixed solution consisting of 0.2mL of 5% Nafion solution of DuPont and 0.8mL of absolute ethyl alcohol, and the corresponding catalyst slurry is obtained by ultrasonic treatment for 30 min. Preparing a working electrode: and (3) dripping all prepared catalyst slurry on a titanium fiber felt carrier in batches, and baking under a lamp to obtain the working electrode. During testing, the neutral electrolyte was selected to be 0.5M Na 2 SO 4 A solution. The selected electrolytic cell is a sealed single electrolytic cell, so that the produced ozone gas can be ensured to fully enter a 2B instrument for fine detection. And (3) carrying out three-electrode test by using the electrode clamp titanium fiber felt as a working electrode, ag/AgCl as a reference electrode and a platinum sheet as a counter electrode. The test was performed using Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV), and then a constant voltage mode was used for continuous ozone production reaction (typically 2 h). Recording the readings read by the instrument to obtain the ozone yield. The concentration of gaseous ozone for examples 1-9 and comparative examples 1-2 is shown in FIG. 11.
As can be seen from fig. 10-11: the Nb-based metal-doped materials prepared in the embodiments 1-9 have good performances in the aspects of electrochemical hydrogen peroxide production and electrochemical ozone precipitation. Fig. 10 shows that the lowest hydrogen peroxide selectivity in examples 1-9 is 80.5% (example 6), indicating that the combination of the doping metal and Nb-based metal materials selected in this example does not have a good electrochemical hydrogen peroxide generation performance. But in general, the hydrogen peroxide selectivity of examples 1-9 is more than 80%, so that the method has application prospect and can efficiently reduce the raw material oxygen into hydrogen peroxide instead of water in a high selectivity manner. Fig. 11 shows that the lowest concentration of gaseous ozone is 2640ppb (example 9), and the faraday efficiency at this time is 11.5%. This set of data illustrates that changing the ratio of the two metal precursors of the LaNbOx material can change the performance of its electrochemical ozone precipitation reaction, where the data of example 1 is: 3350ppb and 16%. Although the embodiment with the best electrochemical hydrogen peroxide generation performance and the embodiment with the best electrochemical ozone precipitation performance are not the same embodiment, the Nb-based metal doping material prepared by the invention has the double-function oxygen electrochemical performance, and can be used for simultaneously and efficiently preparing hydrogen peroxide at a cathode and preparing ozone at an anode. On one hand, the novel material for producing hydrogen peroxide by high-selectivity electrochemistry is obtained, and on the other hand, the novel catalyst material for producing ozone by electrolysis of water in a non-lead system is obtained. Provides wide development prospect for environmental protection, especially water treatment.
The results of the electrochemical hydrogen peroxide production and electrochemical ozone precipitation performance of examples 7-9 and comparative examples 1-2 demonstrate that the Nb-based metal doped material prepared by changing the temperature and the rotation speed of the hydrothermal process and the high-temperature calcination temperature (comparative examples 1-comparative example 2) has a lower selectivity for hydrogen peroxide and a lower gaseous ozone concentration than the Nb-based metal doped material prepared under the conditions of example 1, which is mainly due to the adjustment of the preparation conditions. Other factors such as varying the urea content of the precursor (example 7), the ratio of the two metal precursors (examples 8-9), etc. also affect to some extent the selective performance of the electrocatalytic hydrogen peroxide production and the concentration of gaseous ozone. The versatility of the preparation method employed in the present invention is explained.
In conclusion, the conditions of changing the types and the proportions of Nb-based metal and doped metal precursors, the content of precursor urea, the hydrothermal rotation speed, the temperature time, the high-temperature calcination time temperature and the like have a certain influence on the final electrochemical hydrogen peroxide production and the electrochemical ozone precipitation, the optimal experimental conditions can be obtained through regulation and control, the cost is saved, the concentration of hydrogen peroxide selective gaseous ozone is improved, the catalyst has good overall mechanical property and no pollution, and the practical application of the electrochemical hydrogen peroxide production and the electrochemical ozone precipitation can be promoted.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and various modifications and variations may be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A preparation method of an Nb-based metal doping material is characterized in that an Nb precursor, a doped metal precursor, urea and water are mixed and stirred uniformly, after the metal precursor is completely dissolved, the mixture is transferred into a hydrothermal kettle with a tetrafluoro lining, the hydrothermal kettle is placed in an oven with a rotary rod and rotated at a low speed for a certain time at a high temperature, the hydrothermal kettle is taken out after the temperature is reduced, and a product is subjected to suction filtration and water washing treatment to obtain wet powder. And (3) drying the wet powder in a vacuum drying oven, taking out the dried powder, calcining the powder at a high temperature in a protective atmosphere in a tube furnace, cooling the powder, taking out the powder, and grinding the powder to obtain the corresponding Nb-based metal doping material.
2. The method of claim 1, wherein the Nb precursor is NbCl 5 、Nb 2 O 5 、NbF 5 Or NbC, the doped metal precursor is lanthanum nitrate (La (NO 3 ) 3 ·6H 2 O), gadolinium nitrate (Gd (NO) 3 ) 3 ·XH 2 O), praseodymium nitrate (prN) 3 O 9 ·6H 2 O), thulium nitrate (Tm (NO) 3 ) 3 ·nH 2 O), europium nitrate (Eu (NO) 3 ) 3 ·6H 2 O) or ytterbium nitrate (Yb (NO) 3 ) 3 ·5H 2 O)。
3. The method for producing Nb-based metal doped material according to claim 1, wherein urea: water=10 to 30:3mg/mL, the amount of Nb precursor is 0.2 to 3mmol/L, and the amount of doped metal precursor is 0.2 to 3mmol/L.
4. The method for producing an Nb-based metal-doped material according to claim 1, wherein the temperature is set to 150 to 220 ℃ and the high-temperature maintenance time is set to 5 to 15 hours in an oven with a rotary rod, the rotary rod is set to 2 to 20rpm, the temperature time of a tube furnace is set to 400 to 700 ℃ and 1 to 5 hours, and the protective atmosphere of the tube furnace is nitrogen or argon.
5. The method of producing Nb-based metal doping material according to claim 4, wherein the temperature is set to 200 ℃ in an oven with a rotating rod; the high temperature maintaining time is 8 hours; the rotational speed of the rotating rod was set to 10rpm; the temperature time of the tube furnace was set at 500℃and 3 hours.
6. The use of Nb-based metal doping material obtained by the method according to any one of claims 1 to 5 in electrochemical oxygen reduction reactions, wherein the selectivity of hydrogen peroxide produced by electrochemical oxygen reduction is tested using a Rotating Ring Disk Electrode (RRDE), wherein a slurry prepared from Nb-based metal doping material is dripped on the RRDE as a working electrode, hg/HgO or Ag/AgCl as a reference electrode, a platinum wire as a counter electrode, a platinum area on the RRDE as a ring electrode, and a four electrode test is performed, wherein the selectivity of hydrogen peroxide is obtained by means of Cyclic Voltammetry (CV) and Linear Sweep Voltammetry (LSV), and the electrolyte is an acidic, neutral or alkaline electrolyte.
7. The method according to claim 6, wherein the Nb-based metal-doped materials are prepared into a slurry with a proportion of 1-8mg of catalyst powder, the slurry is dispersed in 0.5-0.9mL of solvent dispersant, 0.1-0.5mL of Nafion solution is added as an adhesive, and the catalyst slurry is obtained by ultrasonic dispersion for 10-60 min.
8. The use according to claim 6, wherein the concentration of the Nafion solution is 5wt%.
9. The use according to claim 6, wherein the electrolyte is 0.1-1.0M H 2 SO 4 Aqueous solution, na 0.1-1.0M 2 SO 4 Aqueous solution or 0.01-0.5M NaOH aqueous solution.
10. Use of Nb-based metal doped material obtained according to any of claims 1 to 5 in a reaction for electrochemical ozone precipitation, wherein a sealed single electrolytic cell is used for testing the yield of electrochemical ozone precipitation, wherein a slurry prepared from Nb-based metal doped material is dripped on a carrier as a working electrode, ag/AgCl as a reference electrode, a platinum sheet as a counter electrode, and a three-electrode test is performed, wherein ozone yield is obtained using a 2B detection instrument, and the electrolyte is a neutral electrolyte.
11. The use according to claim 10, wherein the carrier is one of a titanium fiber felt, a carbon cloth and a carbon paper.
12. The use according to claim 10, wherein the Nb-based metal doped material is prepared in a slurry ratio of 5-20mg of the catalyst powder, dispersed in 0.5-0.9mL of the solvent dispersant, and then added with 0.1-0.5mL of Nafion solution as an adhesive, and subjected to ultrasonic dispersion for 10-60min to obtain the catalyst slurry.
13. The use according to claim 12, wherein the concentration of the Nafion solution is 5wt%.
14. The use according to claim 10, wherein the electrolyte is Na 0.1-1.0M 2 SO 4 An aqueous solution.
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