CN112264065A - Iron/antimony-based heteroatom co-doped carbon nano material and preparation method and application thereof - Google Patents
Iron/antimony-based heteroatom co-doped carbon nano material and preparation method and application thereof Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 31
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 23
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 7
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 15
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 11
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000011161 development Methods 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 12
- 230000002378 acidificating effect Effects 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002082 metal nanoparticle Substances 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to the technical field of nano materials, in particular to an iron/antimony-based heteroatom co-doped carbon nano material and a preparation method and application thereof, wherein the preparation method comprises the steps of adding antimony sulfide, ferric chloride and sulfur powder into a butanediamine solution to form a uniform solution, and drying to obtain a precursor; placing the precursor in a porcelain boat, placing sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to the air inlet, coating the two porcelain boats together by tin foil under the atmosphere of argon, heating to 420-470 ℃ at the heating rate of 4-6 ℃/min, keeping for 1.5-3h, and cooling to obtain the material. According to the invention, iron and antimony metal nanoparticles are loaded on the nitrogen, phosphorus and sulfur co-doped carbon nanomaterial, the cost is low, the non-noble metal-based carbon nano electro-catalysis material with low overpotential and high stability in hydrogen evolution reaction under acidic and alkaline environments is prepared, and theoretical support and technical support are provided for industrial application of the non-noble metal electro-catalysis material.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to an iron/antimony-based heteroatom co-doped carbon nano material and a preparation method and application thereof.
Background
With the continuous consumption of fossil fuels and the increasing problem of environmental pollution, the development trend is to find clean and renewable energy sources that can replace fossil fuels. Among them, the production of hydrogen by electrocatalytic total hydrolysis technology is considered to be the most potential, environmentally friendly and sustainable technology. At present, a platinum noble metal catalyst shows higher catalytic performance in hydrogen evolution reaction, but the defects of low storage capacity, easy poisoning and the like limit the industrial application in the field of water electrolysis. Therefore, the selection of a proper non-noble metal catalyst to realize high-efficiency catalysis, so that the overpotential in the water electrolysis process is reduced, and the problem to be solved is urgently needed. Researches show that the catalytic activity of a pure metal-based nano material on hydrogen evolution reaction is far lower than that of a noble metal-based material, and the alkaline hydrogen evolution reaction rate is far slower than that of the noble metal-based material in an acidic medium, so that heteroatom doping is carried out on a non-noble metal (iron and antimony) based carbon nano material to reduce the overpotential in the hydrogen evolution reaction process, and the realization of efficient catalysis in acidic and alkaline environments is particularly important.
The problems of high cost and low reserve of noble metal catalysts and insufficient catalytic activity of pure metal-based carbon nano materials exist in metal-based carbon nano materials in the prior art, and the application of the carbon nano materials is seriously restricted, so that the development of a non-noble metal-based carbon nano electro-catalytic material which has low cost, low hydrogen evolution reaction overpotential in acidic and alkaline environments and high stability has good economic and social benefits.
Disclosure of Invention
The invention provides an iron/antimony-based heteroatom-doped carbon nanomaterial and a preparation method and application of the material, and aims to obtain a low-cost and high-performance non-noble metal catalyst capable of replacing a noble metal catalyst and realize a carbon nanomaterial with reduced overpotential of the non-noble metal catalyst.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of an iron/antimony-based heteroatom-codoped carbon nanomaterial comprises the following steps:
(1) adding antimony sulfide, ferric chloride and sulfur powder into a butanediamine solution, performing ultrasonic treatment to form a uniform solution, drying, cleaning and drying to obtain a precursor;
(2) placing the precursor obtained in the step (1) in a porcelain boat, placing another piece of sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to the air inlet, coating the two porcelain boats together by using tin foil, placing the porcelain boats in a tube furnace, heating to 420-470 ℃ at the heating rate of 4-6 ℃/min under the argon atmosphere, keeping the temperature for 1.5-3h, and cooling to obtain the carbon nano material doped with the iron/antimony-based heteroatom.
Preferably, the mass volume ratio of the antimony sulfide, the ferric chloride, the sulfur powder and the butanediamine in the step (1) is (3-5) g, (2-4) g, (0.5-1.5) g: 5 mL.
Preferably, the mass ratio of the precursor to the sodium dihydrogen phosphate in the step (2) is 0.02-0.04: 1.
preferably, the ultrasonic power of the step (1) is 220W-270W, and the ultrasonic time is 10min-20 min.
Preferably, the first drying treatment in the step (1) is drying in a forced air drying oven at 120 ℃ for 6 days; the second drying in the step (1) is drying in a vacuum drying oven at 40 ℃ for 30 min; the cleaning in the step (1) is cleaning by using ethanol.
Preferably, the gas inlet speed of the argon in the step (2) is 140-160 mL/min.
An iron/antimony-based heteroatom-doped carbon nanomaterial prepared by the preparation method.
An application of the iron/antimony-based heteroatom-codoped carbon nanomaterial in the field of development or utilization of hydrogen energy.
Advantageous effects
According to the invention, iron and antimony metal nanoparticles are loaded on the nitrogen, phosphorus and sulfur co-doped carbon nanomaterial by using a simple hydrothermal synthesis method, so that the non-noble metal-based carbon nano electrocatalytic material with low cost, low hydrogen evolution reaction overpotential and high stability in acidic and alkaline environments is prepared, and theoretical support and technical support are provided for industrial application of the non-noble metal electrocatalyst.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is SEM and TEM images of example 3 of the present invention;
FIG. 2 is SEM and TEM images of comparative example 1 of the present invention;
FIG. 3 is SEM and TEM images of comparative example 2 of the present invention;
FIG. 4 is a graph showing the polarization of hydrogen evolution reaction under acidic and alkaline conditions for materials prepared in examples 1, 2 and 3 of the present invention;
FIG. 5 is a graph comparing the hydrogen evolution reaction performance under acidic and basic conditions for the materials prepared in comparative examples 1, 2 and example 3 of the present invention;
FIG. 6 is a graph comparing the hydrogen evolution reaction performance of the materials prepared in examples 3, 4 and 5 of the present invention under acidic and basic conditions.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings, in order that the present disclosure may be more fully understood and fully conveyed to those skilled in the art. While the exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the invention is not limited to the embodiments set forth herein.
Example 1
Adding 5g of antimony sulfide, 4g of ferric chloride and 1g of sulfur powder into 5mL of butanediamine solution, performing ultrasonic treatment for 20min to form a uniform solution, wherein the ultrasonic treatment power is 220W, transferring the solution into a 25mL reaction kettle with a stainless steel substrate, and keeping the reaction kettle in a blast drying oven at 120 ℃ for 6 days; naturally cooling, washing with ethanol, and drying in a vacuum drying oven at 40 deg.C for 30min to obtain precursor;
and (2) placing 0.03g of the precursor obtained in the step (1) in a porcelain boat, placing another 1g of sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to the air inlet, covering the two porcelain boats with tin foil, placing the porcelain boats in a tubular furnace, heating to 420 ℃ at the heating rate of 5 ℃/min in the argon atmosphere of 150mL/min, keeping the temperature for 3 hours, and cooling to room temperature to obtain the iron/antimony-based heteroatom-doped carbon nanomaterial.
Example 2
Adding 5g of antimony sulfide, 4g of ferric chloride and 1g of sulfur powder into 5mL of butanediamine solution, performing ultrasonic treatment for 10min to form a uniform solution, wherein the ultrasonic treatment power is 270W, transferring the solution into a 25mL reaction kettle with a stainless steel substrate, and keeping the reaction kettle in a blast drying oven at 120 ℃ for 6 days; naturally cooling, washing with ethanol, and drying in a vacuum drying oven at 40 deg.C for 30min to obtain precursor;
and (2) placing 0.02g of the precursor obtained in the step (1) in a porcelain boat, placing another 1g of sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to the air inlet, covering the two porcelain boats by using tin foil, placing the porcelain boats in a tubular furnace, heating to 470 ℃ at the heating rate of 4 ℃/min in the argon atmosphere of 140mL/min, keeping the temperature for 1.5h, and cooling to room temperature to obtain the iron/antimony-based heteroatom-doped carbon nano material.
Example 3
Adding 5g of antimony sulfide, 4g of ferric chloride and 1g of sulfur powder into 5mL of butanediamine solution, carrying out ultrasonic treatment for 15min to form a uniform solution, wherein the ultrasonic treatment power is 250W, the ultrasonic treatment time is 16min, transferring the solution into a 20mL reaction kettle with a stainless steel substrate, and keeping the reaction kettle in a blast drying oven at 120 ℃ for 6 days; naturally cooling, washing with ethanol, and drying in a vacuum drying oven at 40 deg.C for 30min to obtain precursor;
and (2) placing 0.04g of the precursor obtained in the step (1) in a porcelain boat, placing another 1g of sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to the air inlet, covering the two porcelain boats with tin foil, placing the porcelain boats in a tubular furnace, heating to 450 ℃ at the heating rate of 6 ℃/min in the argon atmosphere of 150mL/min, keeping the temperature for 2.2h, and cooling to room temperature to obtain the iron/antimony-based heteroatom-doped carbon nano material.
Example 4
Adding 3g of antimony sulfide, 2g of ferric chloride and 0.5g of sulfur powder into 5mL of butanediamine solution, and carrying out ultrasonic treatment for 15min until a uniform solution is formed; then the solution was transferred to a 25mL autoclave with a stainless steel substrate and kept in a forced air oven at 120 ℃ for 6 days; naturally cooling, washing with ethanol, and drying in a vacuum drying oven at 40 deg.C for 30min to obtain precursor;
and (2) placing 0.03g of the precursor obtained in the step (1) in a porcelain boat, placing another 1g of sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to the air inlet, covering the two porcelain boats with tin foil, placing the porcelain boats in a tubular furnace, heating to 450 ℃ at the heating rate of 5 ℃/min in the argon atmosphere of 150mL/min, keeping the temperature for 2 hours, and cooling to room temperature to obtain the iron/antimony-based heteroatom-doped carbon nanomaterial.
Example 5
Adding 5g of antimony sulfide, 4g of ferric chloride and 1.5g of sulfur powder into 5mL of butanediamine solution, and carrying out ultrasonic treatment for 15min until a uniform solution is formed; then the solution was transferred to a 25mL autoclave with a stainless steel substrate and kept in a forced air oven at 120 ℃ for 6 days; naturally cooling, washing with ethanol, and drying in a vacuum drying oven at 40 deg.C for 30min to obtain precursor;
and (2) placing 0.03g of the precursor obtained in the step (1) in a porcelain boat, placing another 1g of sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to the air inlet, covering the two porcelain boats with tin foil, placing the porcelain boats in a tubular furnace, heating to 450 ℃ at the heating rate of 5 ℃/min in the argon atmosphere of 150mL/min, keeping the temperature for 2 hours, and cooling to room temperature to obtain the iron/antimony-based heteroatom-doped carbon nanomaterial.
Comparative example 1
Adding 5g of antimony sulfide and 1g of sulfur powder into 5mL of butanediamine solution, and carrying out ultrasonic treatment for 15min until a uniform solution is formed, wherein the ultrasonic treatment power is 250W; then the solution was transferred to a 25mL autoclave with a stainless steel substrate and kept in a forced air oven at 120 ℃ for 6 days; naturally cooling, washing with ethanol, and drying in a vacuum drying oven at 40 deg.C for 30min to obtain precursor;
and (2) placing 0.03g of the precursor obtained in the step (1) in a porcelain boat, placing another 1g of sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to the air inlet, covering the two porcelain boats with tin foil, placing the porcelain boats in a tubular furnace, heating to 450 ℃ at the heating rate of 5 ℃/min in the argon atmosphere of 160mL/min, keeping the temperature for 1.5h, and cooling to room temperature to obtain the antimony-based heteroatom-doped carbon nanomaterial.
Comparative example 2
Adding 4g of ferric chloride and 1g of sulfur powder into 5mL of butanediamine solution, and carrying out ultrasonic treatment for 15min until a uniform solution is formed, wherein the ultrasonic power is 250W; then the solution was transferred to a 25mL autoclave with a stainless steel substrate and kept in a forced air oven at 120 ℃ for 6 days; naturally cooling, washing with ethanol, and drying in a vacuum drying oven at 40 deg.C for 30min to obtain precursor;
and (2) placing 0.03g of the precursor obtained in the step (1) in a porcelain boat, placing another 1g of sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to the air inlet, covering the two porcelain boats with tin foil, placing the porcelain boats in a tubular furnace, heating to 450 ℃ at the heating rate of 5 ℃/min in the argon atmosphere of 150mL/min, keeping the temperature for 2 hours, and cooling to room temperature to obtain the iron-based heteroatom-doped carbon nano material.
Effect test
Examples 1 to 5 and comparative examplesExamples 1-2 materials were prepared at 0.5MH2SO4And performing hydrogen evolution performance test in a 1MKOH solution, taking a glassy carbon electrode as a working electrode, and testing the hydrogen evolution performance on an electrochemical workstation by adopting a three-electrode method (a carbon rod is used as a counter electrode, and reversible hydrogen is used as a reference electrode). The results showed that the binding current density was 10 mA cm-2Corresponding overpotentials, the electrocatalytic materials prepared in examples 1-5 all showed lower overpotentials than comparative examples 1 and 2, and had excellent electrocatalytic hydrogen evolution performance. In summary, the invention utilizes a simple hydrothermal synthesis method to load iron and antimony metal nanoparticles on a nitrogen, phosphorus and sulfur co-doped carbon nanomaterial to prepare the non-noble metal-based carbon nano electro-catalytic material with low overpotential in hydrogen evolution reaction under acidic and alkaline environments.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described above with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the above detailed description of the embodiments of the invention presented in the drawings is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (8)
1. A preparation method of an iron/antimony-based heteroatom-codoped carbon nanomaterial is characterized by comprising the following steps:
(1) adding antimony sulfide, ferric chloride and sulfur powder into a butanediamine solution, performing ultrasonic treatment to form a uniform solution, drying, cleaning and drying to obtain a precursor;
(2) placing the precursor obtained in the step (1) in a porcelain boat, placing another piece of sodium dihydrogen hypophosphite in another porcelain boat, keeping the sodium dihydrogen hypophosphite close to the air inlet, coating the two porcelain boats together by using tin foil, placing the porcelain boats in a tube furnace, heating to 420-470 ℃ at the heating rate of 4-6 ℃/min under the argon atmosphere, keeping the temperature for 1.5-3h, and cooling to obtain the carbon nano material doped with the iron/antimony-based heteroatom.
2. The preparation method of claim 1, wherein the mass-to-volume ratio of the antimony sulfide, the ferric chloride, the sulfur powder and the butanediamine in the step (1) is (3-5) g, (2-4) g, (0.5-1.5) g: 5 mL.
3. The preparation method according to claim 1, wherein the mass ratio of the precursor in the step (2) to the sodium dihydrogen phosphate is 0.02-0.04: 1.
4. the preparation method according to claim 1, wherein the ultrasonic power of the step (1) is 220W-270W, and the ultrasonic time is 10min-20 min.
5. The method according to claim 1, wherein the first drying treatment in the step (1) is drying in a forced air drying oven at 120 ℃ for 6 days; the second drying in the step (1) is drying in a vacuum drying oven at 40 ℃ for 30 min; the cleaning in the step (1) is cleaning by using ethanol.
6. The method as claimed in claim 1, wherein the argon gas is introduced at a flow rate of 140-160mL/min in step (2).
7. An iron/antimony-based heteroatom-doped carbon nanomaterial prepared by the preparation method of any one of claims 1 to 6.
8. The application of the iron/antimony-based heteroatom-codoped carbon nanomaterial as claimed in claim 7 is characterized by application in the field of development or utilization of hydrogen energy.
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| CN116177531A (en) * | 2022-12-15 | 2023-05-30 | 青岛科技大学 | Phosphorus-sulfur co-doped antimony-based carbon nanomaterial and preparation method and application thereof |
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| WO2018205610A1 (en) * | 2017-05-12 | 2018-11-15 | 华南理工大学 | Porous biogold-doped zero-valent iron catalyst, preparation method therefor and use thereof |
| CN110252360A (en) * | 2019-06-28 | 2019-09-20 | 浙江理工大学 | A kind of cobalt manganese phosphorus sea urchin shape nano wire liberation of hydrogen catalysis material being grown on carbon cloth |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116177531A (en) * | 2022-12-15 | 2023-05-30 | 青岛科技大学 | Phosphorus-sulfur co-doped antimony-based carbon nanomaterial and preparation method and application thereof |
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