CN110182784B - Pore-diameter-adjustable iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material and preparation method thereof - Google Patents

Pore-diameter-adjustable iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material and preparation method thereof Download PDF

Info

Publication number
CN110182784B
CN110182784B CN201910556424.9A CN201910556424A CN110182784B CN 110182784 B CN110182784 B CN 110182784B CN 201910556424 A CN201910556424 A CN 201910556424A CN 110182784 B CN110182784 B CN 110182784B
Authority
CN
China
Prior art keywords
urea
solution
ufc
iron
formaldehyde
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910556424.9A
Other languages
Chinese (zh)
Other versions
CN110182784A (en
Inventor
王芬
王雍慧
方园
戚霁
李腾飞
朱建锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201910556424.9A priority Critical patent/CN110182784B/en
Publication of CN110182784A publication Critical patent/CN110182784A/en
Application granted granted Critical
Publication of CN110182784B publication Critical patent/CN110182784B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention relates to an iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material with adjustable aperture and a preparation method thereof, which comprises the steps of adding a formaldehyde solution into a urea solution, uniformly stirring, adding an iron salt until the pH value of the solution is 2-4 to obtain a reaction solution, reacting the reaction solution to generate a precipitate, separating the precipitate, and performing post-treatment to obtain a Fe-UFC precursor; wherein the molar ratio of urea to formaldehyde is 1 (0.1-1.2); and calcining the Fe-UFC precursor for 2-3 h at the temperature of 700-1000 ℃ in a protective atmosphere to obtain the iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material with adjustable aperture. The method successfully synthesizes the Fe-UFC composite material by adopting a direct carbonization method under the condition of not adding any surfactant, and has the advantages of simple experimental process, low cost, controllable iron content, high nitrogen content, adjustable product aperture and controllable appearance.

Description

Pore-diameter-adjustable iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material and preparation method thereof
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to an iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material with adjustable aperture and a preparation method thereof.
Background
The rapid depletion of new fossil fuels and environmental pollution has prompted us to search for sustainable and clean energy resources. Direct Methanol Fuel Cells (DMFCs) can convert chemical energy directly into electrical energy, and have the advantages of high energy density, no pollution, low operating temperature, and the like, and are considered to be a promising portable and auxiliary power plant technology. In addition, the fuel of the DMFC is liquid methanol, the methanol is convenient and safe to transport and store, the fuel is rapidly supplemented, and the price is low. At present, DMFCs have great application potential, such as portable power supplies, electric vehicle power supplies, and the like. However, the slow kinetics of the Oxygen Reduction Reaction (ORR) of the cathode, the poor resistance to methanol poisoning, and the high cost of the commonly used Pt or Pt-based catalysts are major obstacles that have hindered the commercial development of DMFCs. Therefore, the preparation of the non-noble metal-based cathode catalyst with good ORR catalytic performance, methanol poisoning resistance and low cost is very urgent.
Non-noble metal catalysts, particularly transition metal oxides, have proven to be a good alternative to high performance metal oxides. However, due to the low conductivity and availability of transition metal oxides, their catalytic performance is lower than that of noble metal-based catalysts and limited in practical applications. In addition, the graphitized carbon-based catalyst containing heteroatoms (such as N, S) contains more free pi electrons, which is beneficial to the activation of oxygen molecules. Recent studies have shown that the transition metal M (such as Fe, Co, Ni) doped in the N-doped carbon-based material has high catalytic activity, and particularly, the iron-N-C composite catalyst has good methanol resistance, and has high conductivity and utilization rate. The traditional preparation method of the iron-N-C composite material has the defects of complexity, high cost, low nitrogen content, uncontrollable appearance, single aperture and the like.
Amino resins are one of the most important thermosetting synthetic resins, and urea-formaldehyde resins are produced in about 80% of the world's amino resins, being the most important and most widely used amino resins. The urea-formaldehyde resin is opaque thermosetting plastic or resin, and has the advantages of low preparation cost, mild curing temperature and the like. The urea resin can also be used as an organic precursor for preparing nitrogen-doped porous carbon. The urea resin is used as a precursor of the carbon material, and can be used as a carbon source and a nitrogen source. The traditional urea-formaldehyde resin is prepared by using urea and formaldehyde as raw materials and formic acid as a catalyst through the polymerization reaction of the formaldehyde and the urea at room temperature, and then the urea-formaldehyde resin-based carbon microspheres (UFC) are obtained through carbonization treatment.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides an iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material with adjustable aperture and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the method comprises the following steps:
(1) adding a formaldehyde solution into a urea solution, uniformly stirring, adding an iron salt until the pH value of the solution is 2-4 to obtain a reaction solution, reacting the reaction solution to generate a precipitate, separating the precipitate, and performing post-treatment to obtain a Fe-UFC precursor; wherein the molar ratio of urea to formaldehyde is 1 (0.1-1.2);
(2) and calcining the Fe-UFC precursor for 2-3 h at the temperature of 700-1000 ℃ in a protective atmosphere to obtain the iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material with adjustable aperture.
Further, in the step (1), the volume concentration of the adopted formaldehyde solution is 37%; the urea solution is prepared by adding 92.7mmol of urea into 120mL of water.
Further, the iron salt includes iron nitrate nonahydrate.
Further, in the step (1), the reaction solution is kept stand at room temperature for reaction for 1 to 6 hours.
Further, in the step (1), the separation is centrifugal separation; the post-treatment is to sequentially carry out cleaning and drying, curing and secondary cleaning and drying.
Further, the washing and drying and the secondary washing and drying are both carried out by washing the precipitate until the pH value of the supernatant is 6.5-7.5, and then drying for 12h at 60 ℃.
Further, the solidification is to solidify the dried precipitate in a 2mol/L hydrochloric acid solution for 48 h.
Further, the calcination was carried out in a tubular atmosphere furnace at a temperature rise rate of 1 ℃/min.
Further, the protective atmosphere was argon.
The iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material with adjustable pore size is prepared according to the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adds formaldehyde solution into urea solution, prepares Fe-UFC precursor under the coordination of iron salt, and takes urea resin in the Fe-UFC precursor as carbon source and nitrogen source, adopts direct carbonization method, and successfully synthesizes Fe-UFC composite material under the condition of not adding any surfactant. The method has the advantages of simple experimental process, low cost, controllable iron content, high nitrogen content, adjustable product aperture and controllable appearance, improves the performance of the oxygen reduction catalyst material, and has important significance for improving the oxygen reduction catalytic performance. Searching the literature, and finding that Fe (NO) has not been utilized so far3)3·9H2O is used as a catalyst, and the iron-containing nitrogen-doped urea-formaldehyde resin-based carbon microsphere (Fe-UFC) is prepared to improve the catalytic performance of oxygen reduction.
Further, the invention uses Fe (NO)3)3·9H2O is used as catalyst and iron source, and the raw material is simple.
Furthermore, the material keeps the original shape during high-temperature calcination through the curing process.
In the material prepared by the invention, the microstructure is flower-shaped porous microspheres with the diameter of about 3 mu m, the aperture range of the spheres is 13 nm-99 nm, the porous microspheres are composed of bent nanosheets, the nanosheets are connected with one another, iron exists in a lamellar layer in a doped form, and a large amount of iron oxide grows on the surface of the lamellar layer of the Fe-UFC microspheres. The invention lays a foundation for further application in the fields of fuel cells, lithium oxygen batteries and the like. The Fe-UFC composite material obtained by the invention is used as a cathode catalyst of a direct methanol fuel cell, an anode catalyst is PtRu/C, and a fuel is a mixed solution of 4M KOH and 5M methanol. Testing the discharge performance of the battery by using a battery testing system at room temperature, wherein the maximum power density of the battery is 13.99-18.25 mW/cm at room temperature2。
Drawings
Figure 1 is an XRD pattern of Fe-UFC composite.
Fig. 2 is an SEM image of Fe-UFC composite, where fig. 2(a) is a 30000-fold SEM image of the next microsphere, and fig. 2(b) is an SEM image of the microsphere lamella of fig. 2(a) at 110000-fold.
FIG. 3 is an EDS elemental surface scan of an Fe-UFC composite, wherein FIG. 3(a) is a plurality of microsphere TEMs, and FIG. 3(b) is a carbon elemental map of the region of FIG. 3 (a); FIG. 3(c) is a nitrogen distribution diagram of the region of FIG. 3 (a); FIG. 3(d) is a graph showing the distribution of oxygen in the region of FIG. 3 (a); FIG. 3(e) is a distribution diagram of iron element in the region of FIG. 3 (a).
FIG. 4 is a diagram of cell performance at room temperature using Fe-UFC as cathode catalyst, PtRu/C as anode catalyst, and mixed solution of 4M KOH and 5M methanol as fuel.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
The preparation method comprises the following steps:
preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, then adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1 (0.1-1.2), uniformly stirring, and then adding a proper amount of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O), dissolving ferric nitrate in water to show acidity, adding more ferric nitrate to be more acidic until the pH value of the solution is 2-4, and stirring the solution properly to mix the solution uniformly. And then, standing the solution at room temperature for 1-6 h, carrying out centrifugal separation on the precipitate, carrying out centrifugal cleaning for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is 6.5-7.5, and drying at 60 ℃ for 12 h. Curing the dried sample in 2mol/L hydrochloric acid solution for 48h, wherein the original shape of the material can be kept during high-temperature calcination in the curing process; and then, centrifugally cleaning the precipitate for several times at 6500r/min by using ultrapure water, until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at 700-1000 ℃ under argon for 2-3 h, wherein the heating rate is 1 ℃/min, and taking out the product after cooling to room temperature to obtain the Fe-UFC composite material.
Example one
Preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:0.4, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) to adjust the pH of the solution to 2, and the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 1.5h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at the temperature of 800 ℃ under argon for 2h, wherein the heating rate is 1 ℃/min, and taking out the product after cooling to room temperature to obtain the Fe-UFC composite material.
Fig. 1 is an XRD pattern of Fe-UFC, which has a broad diffraction peak at 2 θ ═ 23 °, corresponding to the (002) crystal plane of graphitic carbon.
Fig. 2 is an SEM image of Fe-UFC composite, where fig. 2(a) is a 30000-fold SEM image of the next microsphere, and fig. 2(b) is an SEM image of the microsphere lamella of fig. 2(a) at 110000-fold. The Fe-UFC is a flower-shaped porous microsphere with the diameter of about 3 mu m, the pore diameter of the sphere is 13-99 nm, the porous microsphere is composed of bent nano sheets, the nano sheets are connected with each other, and a large number of small particles grow on the surface of the nano sheets.
FIG. 3 is an EDS elemental surface distribution plot of an Fe-UFC composite demonstrating C, N, O, Fe is uniformly distributed in the Fe-UFC composite.
Example two
Preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:0.4, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO) (NO is a non-ferrous nitrate salt and is a non-ferrous nitrate salt)3)3·9H2O), the pH value of the solution is adjusted to 3, and the solution is mixed uniformly by stirring. Then, the solution is kept stand at room temperature for 1.5h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at the temperature of 800 ℃ under argon for 2h, wherein the heating rate is 1 ℃/min, and taking out the product after cooling to room temperature to obtain the Fe-UFC composite material.
EXAMPLE III
The embodiment comprises the following steps:
preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:0.4, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO) (NO is a non-ferrous nitrate salt and is a non-ferrous nitrate salt)3)3·9H2O) to adjust the pH of the solution to 4, and the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 1.5h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; then, the precipitate was centrifuged and washed at 6500r/min with ultraCentrifugally cleaning with pure water for several times until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at the temperature of 800 ℃ under argon for 2h, wherein the heating rate is 1 ℃/min, and taking out the product after cooling to room temperature to obtain the Fe-UFC composite material.
Comparative example 1
The pH was set to 1 and the other conditions were the same as in example 1.
Referring to fig. 4, the Fe-UFC obtained in examples 1 to 3 and comparative example 1 at pH values of 1, 2, 3 and 4, respectively, was used as a cathode catalyst of a direct methanol fuel cell, an anode catalyst was PtRu/C, and a fuel was a mixed solution of 4M KOH and 5M methanol, and cell discharge performance was tested at room temperature using a novacar BTS400 type cell test system (shenzhen new technology ltd, china). The maximum power density at room temperature, as analyzed by the test, is shown in table 1 below.
Table 1 cell performance testing of Fe-UFC prepared in examples 1-3 as cathode catalyst for direct methanol fuel cell
Examples 1 2 3 Comparative example 1
Maximum power density (mW/cm)2) 18.25 17.09 13.99 12.15
As can be seen from Table 1, the Fe-UFC prepared by the method is used as a cathode catalyst of a direct methanol fuel cell, and the maximum power density of the assembled cell is 13.99-18.25 mW/cm2. The content of the added ferric nitrate is different, the appearance and the iron content of the obtained product are different, when the pH value is 2-4, the maximum power density of the assembled battery is gradually reduced along with the increase of the pH value, when the pH value is 2, the maximum power density value is maximum, and when the pH value is reduced, the maximum power density of the assembled battery is sharply reduced.
Example four
The embodiment comprises the following steps:
preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:0.1, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO) (NO is3)3·9H2O) to adjust the pH of the solution to 2, and the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 1.5h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at the temperature of 800 ℃ under argon for 2h, wherein the heating rate is 1 ℃/min, and taking out the product after cooling to room temperature to obtain the Fe-UFC composite material.
EXAMPLE five
The embodiment comprises the following steps:
preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:0.8, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO) (NO is a non-ferrous nitrate salt and is a non-ferrous nitrate salt)3)3·9H2O) to adjust the pH of the solution to 2, and the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 1.5h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at the temperature of 800 ℃ under argon for 2h, wherein the heating rate is 1 ℃/min, and taking out the product after cooling to room temperature to obtain the Fe-UFC composite material.
EXAMPLE six
The embodiment comprises the following steps:
preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:1.2, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO) (NO is a non-ferrous nitrate salt and is a non-ferrous nitrate salt)3)3·9H2O) to adjust the pH of the solution to 2, and the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 1.5h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Dissolving the dried sample in 2mol/L hydrochloric acidSolidifying in the liquid for 48 h; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at the temperature of 800 ℃ under argon for 2h, wherein the heating rate is 1 ℃/min, and taking out the product after cooling to room temperature to obtain the Fe-UFC composite material.
EXAMPLE seven
The embodiment comprises the following steps:
preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:0.4, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO) (NO is a non-ferrous nitrate salt and is a non-ferrous nitrate salt)3)3·9H2O) to adjust the pH of the solution to 2, and the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 4 hours, the precipitate is centrifugally separated, 6500r/min is centrifugally cleaned for a plurality of times by ultrapure water, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12 hours at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at the temperature of 800 ℃ under argon for 2h, wherein the heating rate is 1 ℃/min, and taking out the product after cooling to room temperature to obtain the Fe-UFC composite material.
Example eight
The embodiment comprises the following steps:
preparing a precursor of the iron-containing urea-formaldehyde resin;
92.7mmol of urea are weighed and fully dissolvedDissolving in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of urea to formaldehyde is 1:0.4, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) to adjust the pH of the solution to 2, and the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 6h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at the temperature of 800 ℃ under argon for 2h, wherein the heating rate is 1 ℃/min, and taking out the product after cooling to room temperature to obtain the Fe-UFC composite material.
Example nine
The embodiment comprises the following steps:
preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:0.4, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO) (NO is a non-ferrous nitrate salt and is a non-ferrous nitrate salt)3)3·9H2O) to adjust the pH of the solution to 2, and the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 1.5h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one for 2h in a tubular atmosphere furnace at 700 ℃ under argon, wherein the heating rate is 1 ℃/min, and taking out the product after cooling to room temperature to obtain the Fe-UFC composite material.
Example ten
The embodiment comprises the following steps:
preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:0.4, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O) to adjust the pH of the solution to 2, and the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 1.5h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at the temperature of 900 ℃ under argon for 2h, wherein the heating rate is 1 ℃/min, and taking out a product after cooling to room temperature to obtain the Fe-UFC composite material.
EXAMPLE eleven
The embodiment comprises the following steps:
preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:0.4, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO)3)3·9H2O), adjusting the pH value of the solutionTo 2, the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 1.5h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one for 2.5h in a tubular atmosphere furnace at the temperature of 1000 ℃ under argon, wherein the heating rate is 1 ℃/min, and taking out a product after cooling to room temperature to obtain the Fe-UFC composite material.
Example twelve
Preparing a precursor of the iron-containing urea-formaldehyde resin;
weighing 92.7mmol of urea, fully dissolving the urea in 120mL of ultrapure water, stirring to form a transparent solution, adding a proper amount of formaldehyde with the volume concentration of 37% so that the molar ratio of the urea to the formaldehyde is 1:0.4, uniformly stirring, and adding a proper amount of ferric nitrate nonahydrate (Fe (NO) (NO is a non-ferrous nitrate salt and is a non-ferrous nitrate salt)3)3·9H2O) to adjust the pH of the solution to 2, and the solution was mixed well with appropriate stirring. Then, the solution is kept stand at room temperature for 1.5h, the precipitate is centrifugally separated, and is centrifugally cleaned for several times by ultrapure water at 6500r/min, the pH value of the supernatant is 6.5-7.5, and the supernatant is dried for 12h at 60 ℃. Solidifying the dried sample in a 2mol/L hydrochloric acid solution for 48 hours; and then, centrifugally cleaning the precipitate for several times by using ultrapure water at 6500r/min until the pH value of the supernatant is about 6.5-7.5, and drying in an oven at 60 ℃ for 12h to obtain the Fe-UFC precursor.
Preparing iron-containing nitrogen-doped urea-formaldehyde resin-based carbon;
and (3) calcining the Fe-UFC precursor obtained in the step one in a tubular atmosphere furnace at the temperature of 800 ℃ under argon for 3h, wherein the heating rate is 1 ℃/min, and taking out a product after cooling to room temperature to obtain the Fe-UFC composite material.

Claims (2)

1. A preparation method of an iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material with adjustable aperture is characterized by comprising the following steps: the method comprises the following steps:
(1) adding a formaldehyde solution into a urea solution, wherein the volume concentration of the adopted formaldehyde solution is 37%; adding 92.7mmol of urea into 120mL of water to prepare a urea solution, uniformly stirring, adding ferric nitrate nonahydrate until the pH value of the solution is 2-4 to obtain a reaction solution, standing the reaction solution at room temperature for 1-6 h to generate a precipitate, carrying out centrifugal separation on the precipitate, and then sequentially carrying out cleaning and drying, curing and secondary cleaning and drying to obtain a Fe-UFC precursor; wherein the molar ratio of urea to formaldehyde is 1 (0.1-1.2);
washing and drying the precipitate and secondary washing and drying, namely washing the precipitate until the pH value of the supernatant is 6.5-7.5, then drying the precipitate for 12 hours at the temperature of 60 ℃, and solidifying the dried precipitate for 48 hours in a 2mol/L hydrochloric acid solution;
(2) and calcining the Fe-UFC precursor in a tubular atmosphere furnace at 700-1000 ℃ for 2-3 h under argon at the heating rate of 1 ℃/min to obtain the iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material with adjustable pore diameter.
2. The iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material with adjustable pore size prepared by the preparation method of claim 1.
CN201910556424.9A 2019-06-25 2019-06-25 Pore-diameter-adjustable iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material and preparation method thereof Active CN110182784B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910556424.9A CN110182784B (en) 2019-06-25 2019-06-25 Pore-diameter-adjustable iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910556424.9A CN110182784B (en) 2019-06-25 2019-06-25 Pore-diameter-adjustable iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN110182784A CN110182784A (en) 2019-08-30
CN110182784B true CN110182784B (en) 2021-06-29

Family

ID=67723372

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910556424.9A Active CN110182784B (en) 2019-06-25 2019-06-25 Pore-diameter-adjustable iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN110182784B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113003557B (en) * 2019-12-19 2022-07-22 中国科学院化学研究所 Carbon microsphere and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1480476A (en) * 2003-07-21 2004-03-10 天津大学 Ferromagnetic microsphere medium made from urea-formaldehyde resin and its preparation method
TW200622050A (en) * 2004-12-31 2006-07-01 Yonyu Plastics Co Ltd Method producing vapor-grown carbon fibers having 3-D linkage structure
CN104812489A (en) * 2012-10-15 2015-07-29 Stc.Unm公司 Non-PGM catalyst for ORR based on pyrolysed poly-complexes
CN105253871A (en) * 2015-09-25 2016-01-20 深圳博磊达新能源科技有限公司 Nitrogen-containing carbon material for supercapacitosr, preparation method thereof, and supercapacitor electrode material
CN105576262A (en) * 2016-03-02 2016-05-11 中国石油大学(华东) Nitrogen ferride/carbide co-doped composite material used for increasing high oxygen reduction activation of fuel cell cathode
CN107482218A (en) * 2017-07-18 2017-12-15 中国科学院化学研究所 A kind of three-dimensional hollow material and preparation method thereof and the application in electrochemical energy storing device
CN107591250A (en) * 2017-09-12 2018-01-16 桂林电子科技大学 A kind of porous carbon composite of CoO N dopings and its preparation method and application

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1480476A (en) * 2003-07-21 2004-03-10 天津大学 Ferromagnetic microsphere medium made from urea-formaldehyde resin and its preparation method
TW200622050A (en) * 2004-12-31 2006-07-01 Yonyu Plastics Co Ltd Method producing vapor-grown carbon fibers having 3-D linkage structure
CN104812489A (en) * 2012-10-15 2015-07-29 Stc.Unm公司 Non-PGM catalyst for ORR based on pyrolysed poly-complexes
CN105253871A (en) * 2015-09-25 2016-01-20 深圳博磊达新能源科技有限公司 Nitrogen-containing carbon material for supercapacitosr, preparation method thereof, and supercapacitor electrode material
CN105576262A (en) * 2016-03-02 2016-05-11 中国石油大学(华东) Nitrogen ferride/carbide co-doped composite material used for increasing high oxygen reduction activation of fuel cell cathode
CN107482218A (en) * 2017-07-18 2017-12-15 中国科学院化学研究所 A kind of three-dimensional hollow material and preparation method thereof and the application in electrochemical energy storing device
CN107591250A (en) * 2017-09-12 2018-01-16 桂林电子科技大学 A kind of porous carbon composite of CoO N dopings and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Polymerization-Induced Colloid Assembly Route to Iron Oxide-Based Mesoporous Microspheres for Gas Sensing and Fenton Catalysis;Wan, Li et al;《ACS APPLIED MATERIALS & INTERFACES》;20180321;第10卷(第15期);全文 *
碳基氧气电催化剂的制备及其性能和应用研究;孟凡陆;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20180315(第3期);第67~69页 *

Also Published As

Publication number Publication date
CN110182784A (en) 2019-08-30

Similar Documents

Publication Publication Date Title
CN108767260B (en) Carbon-coated FeP hollow nano-electrode material and preparation method and application thereof
CN105854918B (en) Composite material of nano-scale cobalt-based particles and nitrogen-doped carbon, synthetic method and application
CN104289242B (en) Preparation method for the high graphitization degree carbon base catalyst of fuel battery negative pole
CN102476058B (en) Carbon gel catalyst, its preparation and its application
CN108923050B (en) Core-shell carbon nanostructure electrocatalyst with high catalytic performance and preparation method thereof
WO2021232751A1 (en) Porous coo/cop nanotubes, preparation method therefor and use thereof
CN108091871A (en) A kind of porous spherical ternary cathode material of lithium ion battery and preparation method thereof
CN104218250A (en) PtM/C electrocatalyst for fuel cell and preparation method of PtM/C electrocatalyst for fuel cell
CN107464938B (en) Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery
CN107871876B (en) Preparation method of bifunctional catalytic carbon material for zinc-air battery
CN109665525B (en) Preparation method of dumbbell-shaped iron-nitrogen double-doped porous carbon
CN112259751B (en) ORR and OER bifunctional catalyst, and preparation method and application thereof
CN109037718A (en) A kind of biomass carbon carried transition metal oxide composite and the preparation method and application thereof
CN111477887A (en) Co3O4Composite oxygen reduction catalyst loaded with hollow carbon microspheres and preparation method thereof
CN112142037A (en) Cobalt and nitrogen doped carbon nano tube and preparation method and application thereof
CN111634954A (en) Iron-modified cobalt-iron oxide with self-assembled flower ball structure and preparation and application thereof
CN114628696B (en) Preparation method of porous carbon-supported cobalt-based bifunctional oxygen catalyst
CN114477163B (en) Iron/nitrogen co-doped single-atom carbon catalyst and preparation method thereof
CN113976122B (en) NiO/Ni dual-function electrolytic water catalyst and preparation method thereof
CN109873172B (en) Preparation method of methanol fuel cell catalyst
CN110182784B (en) Pore-diameter-adjustable iron-containing nitrogen-doped urea-formaldehyde resin-based carbon material and preparation method thereof
CN110474059B (en) Method for solid-phase macro synthesis of non-noble metal oxygen reduction catalyst, catalyst and application thereof
CN113410480A (en) Nickel polyphenol network modified composite triazine-based copolymer carbon nano electro-catalyst material and preparation method and application thereof
CN108232212B (en) Hollow carbon nanosphere-loaded nano Ag particle fuel cell oxygen reduction catalyst and preparation method and application thereof
CN113629258B (en) Platinum-cobalt alloy catalyst with platinum-rich surface and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant