CN113582156A - Preparation method of nitrogen and sulfur double-doped carbon catalyst with full pH range - Google Patents
Preparation method of nitrogen and sulfur double-doped carbon catalyst with full pH range Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 42
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000011593 sulfur Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 17
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000011592 zinc chloride Substances 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 7
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 7
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 7
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 7
- 241001661970 Icterus nigrogularis Species 0.000 claims abstract description 5
- 239000007833 carbon precursor Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 239000012498 ultrapure water Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000003929 acidic solution Substances 0.000 claims abstract description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 36
- 239000003792 electrolyte Substances 0.000 description 13
- 239000011148 porous material Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 229910021397 glassy carbon Inorganic materials 0.000 description 5
- 230000009977 dual effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Classifications
-
- 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
-
- 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
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- 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
-
- 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
Abstract
The invention discloses a preparation method of a nitrogen and sulfur double-doped carbon catalyst with a full pH range, which comprises the steps of uniformly mixing a carbon precursor yellow oriole plant, double-template zinc chloride and zinc hydroxide to obtain a material A; carrying out high-temperature pyrolysis on the material A to obtain a material B; and transferring the material B into a container, adding an acidic solution, soaking for 24 h, washing with high-purity water until the filtrate is neutral, and drying to obtain the target product, namely the nitrogen and sulfur double-doped hierarchical pore carbon catalyst with the full pH range, wherein the total content of N, S in the nitrogen and sulfur double-doped hierarchical pore carbon catalyst is 2.25 at.%. The method is simple to operate, low in cost and environment-friendly, and the prepared nitrogen and sulfur double-doped hierarchical porous carbon catalyst has excellent ORR catalytic activity in the full pH range, stability and methanol resistance.
Description
Technical Field
The invention belongs to the technical field of preparation of cathode catalysts of zinc-air batteries or fuel cells, and particularly relates to a preparation method of a nitrogen and sulfur double-doped carbon catalyst with a full pH range.
Background
A series ofSuch as accelerated depletion of fossil fuels, compel us to seek renewable energy storage and conversion devices. As a new energy conversion device in sustainable development and carbon neutral and background, fuel cells and zinc-air cells play a very important role in the future energy conversion stage. However, their widespread use is hampered by a number of technical problems, one of which is the lack of bifunctional cathode catalysts suitable for ORR. Currently, Pt-based and IrO2Catalysts are still considered to be the best ORR electrocatalysts because of their excellent activity and high selectivity of the four electron reduction pathway. Notably, their low reserves and high cost have somewhat hindered the widespread use of fuel cells and zinc-air cells. Therefore, the search for stable, inexpensive and efficient ORR non-noble metal catalysts is crucial to facilitate the implementation of these clean energy plants.
The key to the high efficiency of a fuel cell is the availability of a suitable catalyst for the Oxygen Reduction Reaction (ORR). With the low cost, high environmental protection and large-scale requirements of China on energy conversion and energy storage devices, and the defects of high price, rare reserves, poor stability, poor toxicity resistance and the like of commercialized catalysts, namely Pt-based, Ir, Ru and metal oxide catalysts are still considered as commercial ORR and OER electrocatalysts at present due to excellent activity and higher four-electron reduction pathway selectivity of the Pt-based, Ir, Ru and metal oxide catalysts. However, their widespread use in fuel cells and zinc-air cells is greatly hindered by high cost. Therefore, the search for stable, inexpensive and efficient ORR and OER non-Pt and non-Ir, Ru and its metal oxides and other noble metals and oxide catalysts is crucial to facilitating the realization of large-scale applications of these clean energy facilities.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of a nitrogen and sulfur double-doped carbon catalyst with a full pH range, which has simple synthesis process and lower cost.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the nitrogen and sulfur double-doped carbon catalyst with the full pH range is characterized by comprising the following specific steps of:
step S1: fully and uniformly mixing carbon precursor yellow oriole plant powder with a double-template agent zinc chloride and zinc hydroxide to obtain a material A;
step S2: transferring the material A into a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat from 25 ℃ for 60 min to 300 ℃ under the protection of inert gas, keeping the porcelain boat at 300 ℃ for 60 min, heating the porcelain boat to 900 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat at 900 ℃ for 120min, and naturally cooling the porcelain boat to room temperature to obtain a material B;
step S3: transferring the material B into a container, adding an acid solution, soaking for 24 h, washing with high-purity water until the filtrate is neutral, and then placing the filtrate in a 110 ℃ forced air drying oven for drying for 12 h to obtain a nitrogen and sulfur double-doped hierarchical porous carbon catalyst with a target product having a full pH range;
the total content of N, S in the nitrogen and sulfur double-doped hierarchical pore carbon catalyst with the full pH range is 2.25 at.%, and the catalyst has excellent ORR catalytic activity, stability and methanol resistance in the full pH range.
Further preferably, the feeding mass ratio of the carbon precursor yellow oriole plant powder to the double templates of zinc chloride and zinc hydroxide in step S1 is 1:0.682: 0.497.
Further preferably, the inert gas in step S2 is one or more of nitrogen or argon.
More preferably, the acidic solution in step S3 is a 2M hydrochloric acid solution.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, rich trace element N, S in biomass is induced to be in situ in the carbon skeleton by a high-temperature pyrolysis process to promote the formation of more active sites, so that the electrochemical performance of the prepared doped carbon material is enhanced.
2. The pore-forming mechanism of the double-template agent zinc chloride and zinc hydroxide used in the invention is as follows: when the temperature rises to about 125 ℃, Zn (OH)2Decomposing into ZnO; secondly, the temperature is continuedContinuously rising to about 283 ℃, and obtaining molten ZnCl2Molecules enter the carbon to act as a backbone. After carbonization, the carbon polymer is deposited on the framework and then converted into ZnO; above 600 ℃, ZnO is reduced by carbon to obtain Zn element and CO/CO2(ii) a Zn reaches the boiling point at about 900 ℃ and is in a gaseous state. CO, CO2、H2Gas molecules such as O and the like are regarded as soft templates, and after the gas molecules escape, residual Zn, ZnO and ZnCl2And the like, which cannot be gasified, as a hard template. Due to the different sizes of the "placeholder" molecules, they will lay down the synthesis of the layered porous carbon material upon exit. The finally formed hierarchical pore structure is beneficial to the mass transfer process of the electrocatalyst in the electrochemical ORR reaction, and simultaneously, the specific surface area of the carbon catalyst is increased.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) Electron micrograph of a nitrogen and sulfur double-doped hierarchical porous carbon catalyst E1 with a full pH range prepared in example 1;
FIG. 2 is N of the nitrogen, sulfur double-doped hierarchical porous carbon catalyst E1 with full pH range prepared in example 12Adsorption and desorption isotherm (N)2adsorption/desorption isochrorm) and aperture Distribution (PSD) maps;
FIG. 3 is a Water Contact Angle (Water Contact Angle) graph of the N-S double-doped hierarchical porous carbon catalyst E1 with an Angle of 2.5 for example 1 with a full pH rangeo（<5.0oIs a super hydrophilic material);
FIG. 4 is an X-ray Photoelectron Spectroscopy (XPS) plot of a nitrogen, sulfur double-doped graded pore carbon catalyst E1 with a full pH range prepared in example 1;
FIG. 5 is a plot of the X-ray Photoelectron Spectroscopy (XPS) nitrogen element of the nitrogen, sulfur double-doped graded pore carbon catalyst E1 with the full pH range prepared in example 1;
FIG. 6 is an X-ray Photoelectron Spectroscopy (XPS) sulfur element plot of the nitrogen, sulfur double-doped graded pore carbon catalyst E1 with the full pH range prepared in example 1;
fig. 7 is an X-ray diffraction (XRD) pattern of the nitrogen, sulfur double-doped graded pore carbon catalyst E1 with a full pH range prepared in example 1;
fig. 8 is a Raman spectroscopy (Raman) plot of a nitrogen, sulfur double-doped graded pore carbon catalyst E1 with a full pH range prepared in example 1;
FIG. 9 is a plot of the polarization curves/ORR activity of the rotating disk-ring electrode (RRDE) of the nitrogen, sulfur double-doped graded-pore carbon catalyst E1 in 0.1M KOH electrolyte prepared in example 1 and a commercial reference Pt/C;
FIG. 10 is a chart showing the results of example 1 at 0.5M H2SO4Polarization curve/ORR activity plot of nitrogen, sulfur double doped graded pore carbon catalyst E1 in electrolyte and commercial reference Pt/C rotating disk-disk electrode (RRDE);
FIG. 11 is a plot of the polarization curves/ORR activity of the rotating disk-ring electrode (RRDE) of the nitrogen, sulfur double-doped graded-pore carbon catalyst E1 in 0.1M PBS electrolyte prepared in example 1 and a commercial reference Pt/C;
FIG. 12 is a plot of Cyclic Voltammetry (CV) curves/stability performance of nitrogen, sulfur double doped graded pore carbon catalyst E1 and a commercial reference Pt/C in 0.1M KOH electrolyte prepared in example 1;
FIG. 13 is a plot of Cyclic Voltammetry (CV) curves/methanol resistance for nitrogen, sulfur double doped graded pore carbon catalyst E1 and a commercial reference Pt/C in 0.1M KOH electrolyte prepared in example 1;
FIG. 14 is a graph of the dual capacitive performance of the nitrogen, sulfur dual doped graded pore carbon catalyst E1 and a commercial reference Pt/C in 0.1M KOH electrolyte prepared in example 1;
FIG. 15 is a chart showing the results of example 1 preparation at 0.5M H2SO4Cyclic Voltammetry (CV) curves/stability performance graphs of a nitrogen and sulfur double-doped hierarchical pore carbon catalyst E1 and a commercial reference Pt/C in electrolyte;
FIG. 16 is a chart showing the results of example 1 preparation at 0.5M H2SO4Nitrogen and sulfur double doping in electrolyteCyclic Voltammetry (CV) profile/methanol resistance profile for the heterograded pore carbon catalyst E1 and a commercial reference Pt/C;
FIG. 17 is a plot of Cyclic Voltammetry (CV) versus catalytic performance for nitrogen, sulfur double doped graded pore carbon catalyst E1 and a commercial reference Pt/C in 0.1M PBS electrolyte prepared in example 1.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
Step S1: mixing 1 g of yellow oriole plant powder, 0.682 g of zinc chloride and 0.497 g of zinc hydroxide completely to obtain material A1;
step S2: transferring the material A1 to a porcelain boat, placing the porcelain boat in a tube furnace, under the protection of inert gas nitrogen, heating the porcelain boat from 25 ℃ to 300 ℃ within 60 min, keeping the porcelain boat at 300 ℃ for 60 min, heating the porcelain boat to 900 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat at 900 ℃ for 120min, and naturally cooling the porcelain boat to room temperature to obtain a material B1;
step S3: and transferring the material B1 to a beaker, adding hydrochloric acid with the concentration of 2M, soaking for 24 h, washing with high-purity water until the filtrate is neutral, and then placing the filtrate in a 110 ℃ forced air drying oven for drying for 12 h to obtain the target product, namely the nitrogen and sulfur double-doped hierarchical porous carbon catalyst with the full pH range.
Example 2
Full pH range ORR test procedure: weighing a certain amount of nitrogen and sulfur double-doped hierarchical pore carbon catalyst (N, S) doped carbon catalyst E1 sample which is ground into powder in a full pH range by using an electronic balance, uniformly mixing the sample with Nafion with the mass fraction of 5wt% and high-purity water, and performing ultrasonic treatment for several minutes to finally obtain a uniform ink-shaped solution; in the ultrasonic process, the surface of the glassy carbon electrode is polished to be bright without any stain or scratch by using aluminum oxide polishing powder, then the glassy carbon electrode is placed in an ultrasonic instrument for ultrasonic treatment for several minutes, and finally the surface of the electrode is dried by air for standby; by usingAnd transferring a proper amount of the ultrasonically-treated ink-like active substance to the glassy carbon electrode by using a liquid transfer gun, and then airing at room temperature to finish the preparation of the working electrode. All electrochemical tests used a three-electrode system. During the test of the rotating disk-ring disk electrode (RRDE), the working electrode is a 5 mm-diameter glassy carbon electrode with a platinum ring coated with active substances (the prepared ink-shaped active substances) with certain volume and certain concentration, the reference electrodes are respectively Hg/HgO and calomel electrodes, the counter electrode is a platinum sheet electrode, and the electrolyte is 0.1M KOH and 0.5H2SO40.1 aqueous PBS was used for the ORR activity test, saturated with oxygen/nitrogen in advance, and the scan rate was 10 mV s-1The rotation speed was 1600 rpm, and the scanning range was 0.07-1.27V (vs. RHE). In the Cyclic Voltammetry (CV) test, the working electrode is a glassy carbon electrode with a diameter of 3 mm coated with a certain volume of active material (the prepared ink-like active material) at a certain concentration, the reference electrode is still a Hg/HgO electrode, the counter electrode is still a platinum sheet electrode, the electrolyte is 0.1M KOH aqueous solution and is saturated with oxygen or nitrogen in advance, and the scanning speed is still 10 mVs in the test-1The scan range is 0.07-1.27V (vs. RHE). When the ORR activity is tested, the current of the disc and the current of the ring are simultaneously measured by the disc.
The ORR catalytic performance of the samples in example 1 in a 0.1M KOH electrolyte was as follows: as shown in fig. 9, the half-wave potentials of the example E1 sample and the commercial reference Pt/C under the rotating disk-ring electrode test obtained at 1600 rpm were 0.87V and 0.85V (vs. RHE), respectively, indicating that the half-wave potential of the E1 sample is more positive than the commercial reference Pt/C20 mV, fully demonstrating the excellent ORR activity of the E1 sample; the limiting current densities of the example E1 sample and the commercial reference Pt/C were 7.5 mA cm-2And 6.0 mA cm-2Indicating that the E1 sample had good conductivity. As shown in FIG. 10, with the stability plots for the example E1 sample and the commercial reference Pt/C in 0.1M KOH solution, it can be seen that the performance of the E1 sample is more stable after 9000 cycles of cycling; as shown in FIG. 11, with the methanol resistance plots of the example E1 sample and the commercial reference Pt/C, it can be seen that the performance of the E1 sample was barely disturbed after the addition of the methanol solution. As shown in figure 12 of the drawings,using the dual capacitance plots of the example E1 sample and the commercial reference Pt/C, it can be seen that the dual capacitance at E1 sample and the commercial reference Pt/C is 44990 μ F cm-2And 15270. mu.F cm-2The electrochemical active area is proportional to the double capacitance, so that the electrochemical area of the E1 sample can be obtained to be higher than that of the commercial reference Pt/C, and the stability and methanol resistance of the E1 sample in an alkaline environment can be obtained to be better than that of the commercial reference Pt/C.
The sample in example 1 was 0.5M H2SO4The ORR catalytic performance in the electrolyte was as follows: as shown in FIG. 13, the half-wave potentials of the example E1 sample and the commercial reference Pt/C under the test of the rotating disk ring electrode obtained at 1600 rpm were 1.25V and 1.28V (vs. RHE), respectively, indicating that the half-wave potential of the E1 sample is comparable to the commercial reference Pt/C, while the limiting current densities of the example E1 sample and the commercial reference Pt/C are 10.98 mA cm, respectively-2And 8.30 mA cm-2The excellent ORR activity of the E1 sample was well demonstrated, indicating that the E1 sample had good conductivity. As shown in FIG. 14, with the stability plots for the example E1 sample and the commercial reference Pt/C, it can be seen that the performance of the E1 sample is more stable after 4000 cycles; as shown in FIG. 15, with the graphs of methanol resistance of the example E1 sample and the commercial reference Pt/C, it can be seen that the performance of the E1 sample is hardly disturbed after the addition of the methanol solution, and thus the stability and methanol resistance of the E1 sample can be obtained to be superior to the commercial reference Pt/C.
The ORR catalytic performance of sample E1 in 0.1M PBS electrolyte in example 1 is as follows: as shown in fig. 16, the half-wave potentials of the example E1 sample and the commercial reference Pt/C under the rotating disk-ring electrode test obtained at 1600 rpm were 0.81V and 0.82V (vs. RHE), respectively; as shown in fig. 17, the CV peak potentials of the example E1 sample and the commercial reference Pt/C were 0.86V and 0.90V (vs. RHE), respectively, indicating that the half-wave potential of the E1 sample is comparable to the commercial reference Pt/C, and, taken together, indicating that the synthetic nitrogen and sulfur hierarchical porous carbon material of the present invention (E1) has excellent ORR catalytic activity over the full pH range.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (4)
1. A preparation method of a nitrogen and sulfur double-doped carbon catalyst with a full pH range is characterized by comprising the following specific steps:
step S1: fully and uniformly mixing carbon precursor yellow oriole plant powder with a double-template agent zinc chloride and zinc hydroxide to obtain a material A;
step S2: transferring the material A into a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat from 25 ℃ for 60 min to 300 ℃ under the protection of inert gas, keeping the porcelain boat at 300 ℃ for 60 min, heating the porcelain boat to 900 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat at 900 ℃ for 120min, and naturally cooling the porcelain boat to room temperature to obtain a material B;
step S3: transferring the material B into a container, adding an acid solution, soaking for 24 h, washing with high-purity water until the filtrate is neutral, and then placing the filtrate in a 110 ℃ forced air drying oven for drying for 12 h to obtain a nitrogen and sulfur double-doped hierarchical porous carbon catalyst with a target product having a full pH range;
the total content of N, S in the nitrogen and sulfur double-doped hierarchical pore carbon catalyst with the full pH range is 2.25 at.%, and the catalyst has excellent ORR catalytic activity, stability and methanol resistance in the full pH range.
2. The method of preparing a nitrogen, sulfur double doped carbon catalyst with full pH range according to claim 1, characterized in that: in step S1, the feeding mass ratio of the carbon precursor oriole plant powder to the double templates zinc chloride and zinc hydroxide is 1:0.682: 0.497.
3. The method of preparing a nitrogen, sulfur double doped carbon catalyst with full pH range according to claim 1, characterized in that: in step S2, the inert gas is one or more of nitrogen or argon.
4. The method of preparing a nitrogen, sulfur double doped carbon catalyst with full pH range according to claim 1, characterized in that: the acidic solution in step S3 is a hydrochloric acid solution with a concentration of 2M.
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