CN109267094B - Heteroatom-doped porous carbon/iron phosphide composite material - Google Patents

Heteroatom-doped porous carbon/iron phosphide composite material Download PDF

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CN109267094B
CN109267094B CN201811218318.1A CN201811218318A CN109267094B CN 109267094 B CN109267094 B CN 109267094B CN 201811218318 A CN201811218318 A CN 201811218318A CN 109267094 B CN109267094 B CN 109267094B
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porous carbon
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CN109267094A (en
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金辉乐
王舜
任倩
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Wenzhou University
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Abstract

The invention discloses a heteroatom-doped porous carbon/iron phosphide composite material, which comprises the following molar parts: iron source, in terms of iron atoms: 3-20 parts of hexachlorocyclotriphosphazene: 0.3-3 parts of aniline: 0.1-0.5 part, can be used for the coating of electrode, and it has following advantage: (1) compared with other coating materials, the carbon material has better electronic conductivity, so that electrons can enter and exit from the active particles more quickly and effectively and an electron transmission path can be shortened. (2) The carbon material has excellent chemical stability and electrochemical stability, and can effectively prevent the active substance from being oxidized, thereby prolonging the service life of the electrode. (3) The thin film layered matter is easy to form, the electrode surface is uniform, and the activity is kept. (4) Rich sources and low cost.

Description

Heteroatom-doped porous carbon/iron phosphide composite material
Technical Field
The invention relates to a composite material, in particular to a heteroatom-doped porous carbon/iron phosphide composite material.
Background
The energy sources commonly used at present, such as coal, petroleum and natural gas, are non-renewable energy sources, the amount of the energy sources on the earth is limited, and the greenhouse effect caused by the emission of a large amount of carbon dioxide is caused. Human survival and development are always in a constant distance, so that new energy sources must be searched to face the crisis that fossil fuel consumption increases and reserves decrease, and thus the dependence on the fossil fuels is eliminated. Under the background that the conventional energy is in a residual crisis and secondary energy needs to be developed urgently at present, the hydrogen energy is a new energy which is needed and expected by people.
Hydrogen is particularly attractive because of its advantages of cleanliness, renewability, zero carbon emission, and the like. Hydrogen is a clean and efficient fuel with various applications of electrochemical energy conversion, particularly for fuel cells for automobiles and power generation. The calorific value of hydrogen is as high as 142kJ/kg, which is about 3 times of gasoline and 4 times of ethanol. If the development and application of hydrogen energy sources go on the right way, the development and application of hydrogen energy sources will bring about great breakthrough and change to the energy source structure of the whole world.
In order to promote the industrialization of the hydrogen production by electrolyzing water, the key is to solve the most fundamental catalyst problem. Researchers focusing on the research of the water electrolysis hydrogen production catalyst find that the potential water electrolysis catalyst has a structure or properties similar to those of the known high-efficiency catalyst, and the phosphide catalyst just meets the conditions. Recent research make internal disorder or usurpIt was found that metal phosphides as a novel non-noble metal type catalyst exhibit higher catalytic activity in the HER reaction. Comprising Ni2P nanoparticles, CoP/CNT nanocomposites, CU3P nanowires, MoP particles, FeP nanoplatelets, and the like. For the VIII family, among many transition metals, iron has excellent affinity with people due to low cost and abundant materials, and meanwhile, the iron-based catalyst also has higher catalytic performance and meets various important conditions of the required transition metals. For example, the synthesized iron phosphide thin film catalyst in patent CN107999101A has good hydrogen evolution activity, but the stability is not good. The iron phosphide and carbon nanotube composite material prepared in the patent CN201610817477.8 has excellent hydrogen production performance and cycle stability, but the ionic liquid and the carbon nanotube are used as raw materials, so that the cost is high, and industrialization is difficult to realize. Whereas noble metal catalysts are relatively costly.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the heteroatom-doped porous carbon/iron phosphide composite material which is low in cost, easy to prepare and high in stability. .
In order to achieve the purpose, the invention provides the following technical scheme:
a heteroatom-doped porous carbon/iron phosphide composite material.
Comprises the following mol portions:
iron source, in terms of iron atoms: 3 to 20 portions of
Phosphonitrilic chloride trimer: 0.3 to 3 parts of
Aniline: 0.1 to 0.5 portion.
As a further improvement of the invention:
the iron source is iron powder or iron salt.
As a further improvement of the invention:
the preparation method comprises the following steps:
the method comprises the following steps: weighing an iron source, hexachlorocyclotriphosphazene and aniline, mixing, adding the mixture into a high-pressure kettle, and reacting for 5 hours at 200 ℃;
after the reaction is finished, taking out the solid in the kettle, centrifuging, washing and drying to obtain a primary product;
step two: calcining the primary product at 800-1000 ℃ and preserving heat for 2 hours to obtain the composite material. As a further improvement of the invention:
in the first step, the centrifugal speed is 10000rpm in the centrifugal process, and the centrifugal times are 3 times.
As a further improvement of the invention:
in the first step, absolute ethyl alcohol is adopted for washing in the washing process.
As a further improvement of the invention:
in the first step, in the drying process, the drying time is 8 hours, and the drying temperature is 100 ℃.
As a further improvement of the invention:
and in the second step, inert gas is introduced in the calcining process.
As a further improvement of the invention:
the inert gas is nitrogen.
As another object of the present invention, there is provided an electrode,
the electrode comprises an electrode, wherein the part of the electrode extending into the electrolyte is coated with a composite material.
As another object of the present invention, there is provided a method for preparing an electrode,
grinding the prepared conforming material to powder, adding water, ethanol and naphthol, putting the powder into an ultrasonic cleaner for timing and ultrasonic treatment, after the ultrasonic treatment is finished, sampling the mixed liquid and dripping the mixed liquid on an electrode, and finishing the volatilization of the solvent on the surface of the electrode to finish the preparation of the electrode.
The composite material prepared by the invention has a catalytic effect in the electrolytic process by doping the heteroatom in the iron-carbon composite material, so that the hydrogen production efficiency is improved, meanwhile, the iron material is rich and cheap, and the stability of the iron-based catalyst is higher than that of other metals. And can be used for a coating layer of an electrode, which has the following advantages:
(1) compared with other coating materials, the carbon material has better electronic conductivity, so that electrons can enter and exit from the active particles more quickly and effectively and an electron transmission path can be shortened.
(2) The carbon material has excellent chemical stability and electrochemical stability, and can effectively prevent the active substance from being oxidized, thereby prolonging the service life of the electrode.
(3) The thin film layered matter is easy to form, the electrode surface is uniform, and the activity is kept.
(4) Rich sources and low cost.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a first embodiment of the invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a second embodiment of the invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a third embodiment of the invention;
FIG. 4 is an X-ray spectrum (XRD) of example two of the present invention;
fig. 5 is a Raman spectrum (Raman) of the first, second, and third embodiments of the present invention;
FIG. 6 shows Raman spectra (Raman) of a second embodiment, a fourth embodiment and a fifth embodiment of the present invention;
FIG. 7 is an electrochemical impedance spectrum of a second example of the present invention;
FIG. 8 is a graph comparing L SV in the second embodiment of the present invention.
Detailed Description
The first embodiment is as follows:
weighing 10mmol of Fe powder and 1mmol of hexachlorocyclotriphosphazene, weighing 30m of L aniline, adding the mixture into a 50m L high-pressure kettle with a poly (tetrachloroethylene) lining, reacting for 5h at 200 ℃ in an oven, taking out the solid in the kettle after the reaction is finished, centrifuging for 3 times at 10000rpm, washing with absolute ethyl alcohol, transferring the solid into a small beaker, placing in the oven for 8h, and drying at 100 ℃ to obtain an initial product.
Step two: grinding the primary product into fine particles, placing a proper amount of the fine particles in a porcelain boat, and heating the porcelain boat by using a tube furnace in the whole process of N2Calcining in the atmosphere, setting the temperature to be 800 ℃, the heating rate to be 5 ℃/min and the heat preservation time to be 2 hours.
Example two:
weighing 10mmol of Fe powder and 1mmol of hexachlorocyclotriphosphazene, weighing 30m of L aniline, adding the mixture into a 50m L high-pressure kettle with a poly (tetrachloroethylene) lining, reacting for 5h at 200 ℃ in an oven, taking out the solid in the kettle after the reaction is finished, centrifuging for 3 times at 10000rpm, washing with absolute ethyl alcohol, transferring the solid into a small beaker, placing in the oven for 8h, and drying at 100 ℃ to obtain an initial product.
Step two: grinding the primary product into fine particles, placing a proper amount of the fine particles in a porcelain boat, and heating the porcelain boat by using a tube furnace in the whole process of N2Calcining in the atmosphere, setting the temperature to 900 ℃, the heating rate to 5 ℃/min and the heat preservation time to 2 hours.
Example three:
weighing 10mmol of Fe powder and 1mmol of hexachlorocyclotriphosphazene, weighing 30m of L aniline, adding the mixture into a 50m L high-pressure kettle with a poly (tetrachloroethylene) lining, reacting for 5h at 200 ℃ in an oven, taking out the solid in the kettle after the reaction is finished, centrifuging for 3 times at 10000rpm, washing with absolute ethyl alcohol, transferring the solid into a small beaker, placing in the oven for 8h, and drying at 100 ℃ to obtain an initial product.
Step two: grinding the primary product into fine particles, placing a proper amount of the fine particles in a porcelain boat, and heating the porcelain boat by using a tube furnace in the whole process of N2Calcining in the atmosphere, setting the temperature to be 1000 ℃, the heating rate to be 5 ℃/min and the heat preservation time to be 2 hours.
Example four:
weighing 5mmol of Fe powder and 1mmol of hexachlorocyclotriphosphazene, weighing 30m of L aniline, adding the mixture into a 50m L high-pressure kettle with a poly (tetrachloroethylene) lining, reacting for 5h at 200 ℃ in an oven, taking out the solid in the kettle after the reaction is finished, centrifuging for 3 times at 10000rpm, washing with absolute ethyl alcohol, transferring the solid into a small beaker, placing in the oven for 8h, and drying at 100 ℃ to obtain an initial product.
Step two: grinding the primary product into fine particles, placing a proper amount of the fine particles in a porcelain boat, and heating the porcelain boat by using a tube furnace in the whole process of N2Calcining in the atmosphere, setting the temperature to 900 ℃, the heating rate to 5 ℃/min and the heat preservation time to 2 hours.
Example five:
weighing 15mmol of Fe powder and 1mmol of hexachlorocyclotriphosphazene, weighing 30m L aniline, adding the mixture into a 50m L high-pressure kettle with a poly (tetrachloroethylene) lining, reacting for 5h at 200 ℃ in an oven, taking out the solid in the kettle after the reaction is finished, centrifuging for 3 times at 10000rpm, washing with absolute ethyl alcohol, transferring the solid into a small beaker, placing in the oven for 8h, and drying at 100 ℃ to obtain an initial product.
Step two: grinding the primary product into fine particles, placing a proper amount of the fine particles in a porcelain boat, and heating the porcelain boat by using a tube furnace in the whole process of N2Calcining in the atmosphere, setting the temperature to 900 ℃, the heating rate to 5 ℃/min and the heat preservation time to 2 hours.
Example six:
weighing ferric chloride, taking 10mmol of ferric chloride and 1mmol of hexachlorocyclotriphosphazene in terms of Fe atom, taking 30m L aniline, adding the mixture into a 50m L high-pressure kettle with a poly-tetrachloroethylene lining, reacting for 5h at 200 ℃ in an oven, taking out the solid in the kettle after the reaction is finished, centrifuging for 3 times at 10000rpm, washing with absolute ethyl alcohol, transferring the solid into a small beaker, placing in the oven for 8h, and drying at 100 ℃ to obtain a primary product.
Step two: grinding the primary product into fine particles, placing a proper amount of the fine particles in a porcelain boat, and heating the porcelain boat by using a tube furnace in the whole process of N2Calcining in the atmosphere, setting the temperature to 900 ℃, the heating rate to 5 ℃/min and the heat preservation time to 2 hours.
Example seven:
weighing ferric sulfate, measuring 10mmol of ferric sulfate and 1mmol of hexachlorocyclotriphosphazene by Fe atom, measuring 30m of L aniline, adding the mixture into a 50m L high-pressure kettle with a poly (tetrachloroethylene) lining, reacting for 5h at 200 ℃ in an oven, taking out the solid in the kettle after the reaction is finished, centrifuging for 3 times at 10000rpm, washing with absolute ethyl alcohol, transferring the solid into a small beaker, placing in the oven for 8h, and drying at 100 ℃ to obtain a primary product.
Step two: grinding the primary product into fine particles, placing a proper amount of the fine particles in a porcelain boat, and heating the porcelain boat by using a tube furnace in the whole process of N2Calcining in the atmosphere, setting the temperature to 900 ℃, the heating rate to 5 ℃/min and the heat preservation time to 2 hours.
Example eight:
weighing ferrocene, taking 10mmol of ferrocene calculated by Fe atom and 1mmol of hexachlorocyclotriphosphazene, taking 30m of L aniline, adding the mixture into a 50m L high-pressure kettle with a poly (tetrachloroethylene) lining, reacting for 5h at 200 ℃ in an oven, taking out the solid in the kettle after the reaction is finished, centrifuging for 3 times at 10000rpm, washing with absolute ethyl alcohol, transferring the solid into a small beaker, placing in the oven for 8h, and drying at 100 ℃ to obtain a primary product.
Step two: grinding the primary product into fine particles, placing a proper amount of the fine particles in a porcelain boat, and heating the porcelain boat by using a tube furnace in the whole process of N2Calcining in the atmosphere, setting the temperature to 900 ℃, the heating rate to 5 ℃/min and the heat preservation time to 2 hours.
Example nine:
weighing potassium ferricyanide, taking 10mmol of potassium ferricyanide and 1mmol of hexachlorocyclotriphosphazene in terms of Fe atom, taking 30m of L aniline, adding the mixture into a 50m L high-pressure kettle with a poly-tetrachloroethylene lining, reacting for 5h at 200 ℃ in an oven, taking out the solid in the kettle after the reaction is finished, centrifuging for 3 times at 10000rpm, washing with absolute ethyl alcohol, transferring the solid into a small beaker, placing in the oven for 8h, and drying at 100 ℃ to obtain a primary product.
Step two: grinding the primary product into fine particles, placing a proper amount of the fine particles in a porcelain boat, and heating the porcelain boat by using a tube furnace in the whole process of N2Calcining in the atmosphere, setting the temperature to 900 ℃, the heating rate to 5 ℃/min and the heat preservation time to 2 hours.
The first to ninth examples were all prepared into electrodes, and the preparation method of the electrodes was:
the method comprises the steps of adopting a glassy carbon electrode with the diameter of 5mm for testing, firstly adding water into alumina powder, then polishing and grinding the glassy carbon electrode, after grinding for 3-5min, washing dirt on the surface of the electrode with high-purity water, then sequentially carrying out ultrasonic washing with absolute ethyl alcohol and high-purity water, carrying out blow-drying with argon after one minute, grinding the composite material to fine powder for later use, weighing 6mg of a sample into a centrifugal tube, adding 0.8m L of water and 0.2m L of ethanol, then adding 20 mu L of naphthol, placing the centrifugal tube into a numerical control ultrasonic cleaner for ultrasonic treatment for one hour, after the ultrasonic treatment is finished, taking 12 mu L of the sample to be dropped on the cleaned and air-dried electrode, and after about 5 hours, completing the preparation of the electrode after the solvent on the surface of the electrode is volatilized.
Performing SEM scanning characterization on the first embodiment, the second embodiment and the third embodiment:
as shown in figure 1, (a) and (b) two composite materials are prepared by calcining iron powder, hexachlorocyclotriphosphazene and aniline in a 800 ℃ tubular furnace at high temperature through electron microscope scanning. The particle distribution is shown from the particle appearance in the figure.
As shown in FIG. 2, (a) and (b) are electron microscope scanning images of composite materials obtained by calcining iron powder, hexachlorocyclotriphosphazene and aniline at high temperature in a 900 ℃ tube furnace. The particle distribution is shown from the particle appearance in the figure.
As shown in FIG. 3, (a) and (b) two composite materials are prepared by calcining iron powder, hexachlorocyclotriphosphazene and aniline at high temperature in a 1000 ℃ tube furnace through electron microscope scanning. The particle distribution is shown from the particle appearance in the figure.
Comparing figures 1, 2 and 3,
in fig. 2, which is an example two, the particles calcined at a high temperature of 900 ℃ are moderate in size and uniform in distribution, and meanwhile, the particles have certain pores which are relatively loose, so that hydrophilic channels are provided, and the ion exchange rate is also accelerated. Thus, the catalyst is considered to be a composite catalyst material with relatively high efficiency and uniform distribution.
And (2) testing:
XRD test was performed on the second sample, and as shown in FIG. 4, there is a diffraction peak corresponding to the carbon material and Fe after characterization by XRD3P corresponding to the derived peak.
And (3) testing:
the raman spectroscopy test was performed on the first, second, third, fourth and fifth examples.
FIG. 5 shows Raman spectra of the first, second and third embodiments,
fe calcined at 800, 900 and 1000 ℃ and having a molar ratio of Fe to hexachlorocyclotriphosphazene of 10:13Raman spectrum of P/C. In the characteristic Raman spectrum peak shown in the figure, the D peak represents the defect of the crystal lattice, and the G peak represents the carbon atom sp2Hybrid in-plane stretching vibration (degree of graphitization of carbon material). First peak and second peakRelative intensity of the two peaks (I)D/IG) Proportional to the defect position in the composite material, and the temperature is I at 800 ℃ calculated by a graphD/IG0.951, I at 900 ℃D/IG0.979, I at 1000 ℃D/IG0.969. The composite material has more defect sites, is easier for electron conduction, and improves the catalytic performance.
FIG. 6 shows Raman spectra of the second, fourth and fifth embodiments,
raman spectra of high temperature calcination at 900 ℃ of Fe3P/C with Fe and hexachlorocyclotriphosphazene molar ratios of 5:1, 10:1 and 15: 1. Likewise, calculate ID/IGThe ratio of (A) to (B) is the relative intensity of the two peaks, i.e. the number of defect sites in the material can be represented. When the ratio of the iron powder to the hexachlorocyclotriphosphazene is 5:1, ID/IG0.952; is 10:1 hour ID/IG0.974; is 15:1 hour ID/IG0.928. Higher activity is also reflected by more defect sites compared to above.
And (4) testing:
the impedance test was performed on example two, referring to figure 7,
the electrochemical impedance spectrum shows that the electron transfer impedance of the composite material is very small, which shows that the electron transfer speed in the material is relatively high, and the electrochemical impedance spectrum is an ideal catalytic reaction.
And testing:
the current potential tests were carried out on example two, example six, example seven, example eight and example nine, and the overpotentials of iron powder, ferric chloride, ferric sulfate, ferrocene and potassium ferricyanide were-0.219V, -0.449V, -0.502V, -0.447V and-0.410V (vs Ag/AgCl), respectively, at a current of-0.0001A. The potential is low, especially when iron powder is used, the potential is lowest, and the current density can be maximum, so that the material has better hydrogen production activity by compounding with the iron powder.
And (6) testing:
the comparison graph of L SV after 500 CV cycles of sweep at 100mV/s is performed in example two, it can be seen from FIG. 8 that the curve traces before and after 500 CV cycles of sweep are substantially identical, the potential is approximately the same, and the current after 500 CV cycles is slightly reduced, so the composite material under the best condition can be said to have better stability.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims (8)

1. A heteroatom-doped porous carbon/iron phosphide composite material is characterized in that:
the raw materials comprise the following mole portions:
iron source, in terms of iron atoms: 3 to 20 portions of
Phosphonitrilic chloride trimer: 0.3 to 3 parts of
Aniline: 0.1-0.5 part;
the iron source is iron powder or iron salt;
the preparation method comprises the following steps:
the method comprises the following steps: weighing an iron source, hexachlorocyclotriphosphazene and aniline, mixing, adding the mixture into a high-pressure kettle, and reacting for 5 hours at 200 ℃;
after the reaction is finished, taking out the solid in the kettle, centrifuging, washing and drying to obtain a primary product;
step two: and calcining the primary product at 800-1000 ℃, and preserving heat for 2 hours to obtain the composite material.
2. The heteroatom-doped porous carbon/iron phosphide composite material of claim 1, wherein:
in the first step, the centrifugal speed is 10000rpm in the centrifugal process, and the centrifugal times are 3 times.
3. The heteroatom-doped porous carbon/iron phosphide composite material of claim 1, wherein:
in the first step, absolute ethyl alcohol is adopted for washing in the washing process.
4. A heteroatom-doped porous carbon/iron phosphide composite as claimed in claim 3 wherein:
in the first step, in the drying process, the drying time is 8 hours, and the drying temperature is 100 ℃.
5. The heteroatom-doped porous carbon/iron phosphide composite material of claim 4, wherein:
and in the second step, inert gas is introduced in the calcining process.
6. The heteroatom-doped porous carbon/iron phosphide composite material of claim 5, wherein:
the inert gas is nitrogen.
7. An electrode made of a composite material according to any one of claims 1 to 6, wherein:
the electrode comprises an electrode, wherein the part of the electrode extending into the electrolyte is coated with a composite material.
8. The method of preparing an electrode according to claim 7, wherein:
and grinding the prepared composite material to powder, adding water, ethanol and naphthol, putting the powder into an ultrasonic cleaner for timing and ultrasonic treatment, after the ultrasonic treatment is finished, sampling the mixed liquid, dripping the mixed liquid on an electrode, and finishing the volatilization of the solvent on the surface of the electrode to finish the preparation of the electrode.
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CN107362818B (en) * 2017-07-12 2020-08-25 武汉理工大学 Nitrogen-phosphorus double-doped carbon-coated transition metal diphosphide hydrogen evolution catalyst and preparation method thereof
CN107790164B (en) * 2017-10-12 2020-01-21 郑州大学 Nitrogen-phosphorus co-doped porous carbon-coated cuprous phosphide composite catalyst and preparation method thereof
CN107694581B (en) * 2017-10-12 2020-04-03 郑州大学 Application of heteroatom-doped porous carbon-coated cuprous phosphide composite catalyst
CN107999101A (en) * 2017-11-21 2018-05-08 上海理工大学 A kind of phosphatization iron thin film liberation of hydrogen catalyst and preparation method thereof

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