CN114715876A - Biomass tar-based dual-functional carbon-based electrocatalytic material and preparation method thereof - Google Patents
Biomass tar-based dual-functional carbon-based electrocatalytic material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 43
- 239000002028 Biomass Substances 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 25
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 19
- 238000000227 grinding Methods 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000000197 pyrolysis Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229920000877 Melamine resin Polymers 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 17
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- 230000000694 effects Effects 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
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- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- -1 monatomics Substances 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- 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
- H01M4/88—Processes of manufacture
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- 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
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Abstract
The invention discloses a biomass tar-based dual-function carbon-based electrocatalysis material and a preparation method thereof, belonging to the technical field of secondary resource utilization. According to the method, biomass tar is used as a carbon source, melamine is used as a nitrogen source, oxygen-containing functional groups are constructed on the surface of a pyrolyzed biomass tar-based carbon material through acid oxidation, and nitrogen heteroatoms are doped on the surface of the carbon material by utilizing an organic synthesis reaction mechanism. The preparation method comprises the following steps: (1) uniformly dispersing and mixing the biomass tar and the pore-forming agent; (2) pyrolyzing the mixture of step (1) in a tubular furnace; (3) taking out the product in the step (2), grinding, and oxidizing in a mixed acid solution; (4) and (4) mixing the carbon material in the step (3) with a nitrogen source. When the obtained product is used for energy conversion, the obtained product has high-efficiency bifunctional catalytic activity and excellent cycle stability. The invention solves the problems of high cost, poor circulation stability and the like of the bifunctional catalyst, realizes high-value utilization of biomass tar and has wide prospect.
Description
Technical Field
The invention belongs to the technical field of energy conversion, and discloses a biomass tar-based dual-function carbon-based electrocatalytic material and a preparation method thereof.
Background
With the increasing global energy demand, the development of energy storage technology is imperative. Among them, electrochemical energy storage has been widely regarded and applied due to its advantages of high energy density, long service life, low self-discharge, etc. However, slow oxygen reduction (ORR) kinetics have greatly limited the development of energy conversion technologies. Platinum (Pt) -based catalysts exhibit excellent performance and are critical for strengthening the cathode ORR. However, platinum has high cost, poor scarcity and poor methanol resistance, and it is difficult to achieve wide application in the field of energy conversion. Noble metal alloys, monatomics, core-shell structures, and nano-confinement structures have been developed to reduce the amount of noble metal used, however, achieving large-scale precision synthesis of nano-microstructures remains a significant challenge. Transition metals are expected to attract a wide range of attention as alternatives to noble metal catalysts due to their good stability. In particular, recently developed monatomic catalysts (SAC) having single Fe or Co monatomic sites, supported on N-doped carbon, have become one of the most promising alternatives due to their excellent ORR electrocatalytic properties and maximized atom utilization. However, the problems of leaching and agglomeration of transition metals in the use process still need to be solved. Therefore, it is of great importance to search for metal-free catalysts instead of metal catalysts.
Carbon materials have the advantages of wide sources, easy regulation, good stability and the like, and thus are receiving wide attention. However, the intrinsic catalytic activity of the carbon material is not high because the charge distribution of the carbon material is uniform. The introduction of heteroatom (nitrogen, sulfur, boron, phosphorus and the like) doping in the carbon material can effectively improve the electronic property and chemical reactivity of the carbon-based material, thereby obviously improving the electrochemical performance of the material. Based on the difference of electronegativity between heteroatoms and carbon atoms, heteroatom-doped carbon interface atomic domains with modified electronic structures have the characteristics of large charge polarization, minimal change of conjugate length and the like, so that the atomic domains can transfer high electrochemical activity. Meanwhile, lone-pair electrons on some heteroatoms (such as N and S) are used as carriers to promote electron migration, and the space structure of a carbon material pi system can be changed, so that the van der Waals force of a carbon layer is changed, and the regulation and control of the adsorption capacity of the material on a precursor are facilitated. Generally speaking, the carbon material doped with foreign atoms/groups has higher surface activity, and can be used as an electrode material in electrochemical reaction to remarkably improve the catalytic performance of the material. Wherein, the nitrogen atom has the atom size close to that of carbon and larger electronegativity, and is the main flow direction of heteroatom doping of the carbon-based catalytic material. At present, most of the substrates of carbon materials doped with heteroatoms are carbon nanotubes, graphene, Covalent Organic Frameworks (COFs), and the like. These materials have excellent electrical conductivity, which helps to enhance electron transfer between the interface and the current collector. The preparation methods of the advanced carbon-based materials generally have long flow, harsh operating conditions and complex precursors required in the preparation process. The biomass tar is a byproduct generated in the biomass gasification process, is cheap and easily available, and has a main component of benzene derivatives. At high temperature, the biomass tar has the characteristics of a mobile phase, and the benzene derivative is easy to generate cross-linking reaction to generate thick ring carbon, so that a carbon substrate with high ordering degree is formed. The higher ordering degree is an important guarantee that the carbon-based catalytic material has excellent conductivity. Meanwhile, the biomass tar contains a small amount of heteroatoms such as N, S, the aromatic ring heteroatom content is increased (N, S, O) through modulation, a self-doped molecular structure is easily formed in the pyrolysis process, and the doping of the heteroatoms is beneficial to increasing the polarization of carbon charges, so that the electrocatalytic activity is improved. Therefore, biomass tar is an excellent raw material for carbon-based catalysts. The invention provides a biomass tar-based dual-functional carbon-based electro-catalytic material and a preparation method thereof, the preparation method is simple and green, large-scale preparation is easy, high-value utilization of cheap biomass tar is realized, the carbon neutralization process is promoted, and the prepared high-efficiency dual-functional carbon-based catalytic material can be widely applied to various energy conversion fields such as full-water electrolysis, fuel cells, metal-air cells and the like.
Disclosure of Invention
In order to solve the following two problems: (1) the preparation process of the carbon-based electro-catalytic material is long, the operation conditions are harsh, and a complex precursor is required; (2) the tar of the waste biomass is utilized in a high-value way. The invention provides a biomass tar-based bifunctional carbon-based electrocatalytic material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) uniformly dispersing and mixing the biomass tar and the pore-forming agent;
(2) pyrolyzing the mixture of step (1);
(3) taking out the product in the step (2), grinding, and oxidizing in a mixed acid solution;
(4) and (3) mixing the carbon material and the nitrogen source in the step (3), and forming heteroatom doping on the surface of the mixture through pyrolysis.
Further, the pore-forming agent in the step (1) is one or more of the following combinations: potassium hydroxide, ammonium carbonate, ammonium bicarbonate, ammonium chloride;
further, the mass ratio of the biomass tar to the pore-forming agent in the step (1) is 1: 1-1: 5, and the optimized mass ratio is 1: 3-1: 5.
Further, the solvent in the step (1) is one or more of deionized water, ethanol, ethylene glycol, methanol, glycerol, isopropanol and n-butanol;
further, the pyrolysis temperature in the step (2) is 700-1200 ℃, and the pyrolysis atmosphere is one or any two of the following gases: argon, nitrogen, carbon dioxide, water vapor and ammonia;
further, the mixed acid in the step (3) is one or any two or more of the following solutions: nitric acid, sulfuric acid, hypochlorous acid and hydrogen peroxide;
further, the oxidation time in the step (3) is 24-96 hours, and the optimized oxidation time is 36-48 hours;
further, the pyrolysis temperature in the step (4) is 400-900 ℃, and the pyrolysis atmosphere is one or any two of the following gases: argon, nitrogen and ammonia.
The invention has the beneficial effects that: on one hand, the process for preparing the carbon-based catalyst by using the biomass tar as the raw material is green and low in cost, and the characteristics of the biomass tar in a mobile phase at a high temperature are favorable for improving the graphitization degree, so that the problems of long preparation process, harsh operation conditions and complex precursor requirement of advanced carbon-based materials are solved; on the other hand, by utilizing organic synthesis reaction, hetero atoms are directionally introduced at the interface of the carbon material, so that the electrochemical activity of the catalytic material is remarkably improved; provides wide prospect for the preparation and the application of the high-efficiency bifunctional carbon-based catalyst.
Drawings
FIG. 1 is a flow chart of the present invention
FIG. 2 is an SEM image of a pyrolyzed carbon material as provided in example 1 of the present invention.
FIG. 3 is a BET plot of a pyrolyzed carbon material as provided in example 1 of the present invention.
Figure 4 is XPS peak separation results for carbon after interfacial modification as provided in embodiment 1 of the present invention.
FIG. 5 is the FT-IR results after interfacial oxidation as provided in example 1 of the present invention.
FIG. 6 is a graph of bifunctional electrochemical activities provided in example 1 of the present invention.
FIG. 7 shows the bifunctional electrochemical kinetics of carbon materials provided in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Dispersing biomass tar and a pore-forming agent in a solution of ethanol/deionized water (1:1) according to a mass ratio of 2:1, and stirring for 2 hours on a magnetic stirrer to form a mixed solution A; then pouring the solution A into a corundum crucible, heating to 800 ℃ under the argon atmosphere, keeping the temperature for 2 hours, taking out and grinding into powder B; then adding the powder B into 30mL of a mixed solution (1:1) of 30 wt% nitric acid and hydrogen peroxide, stirring for 24h, washing with water to be neutral, and drying to obtain powder C; and grinding and uniformly mixing the powder C and melamine (the mass ratio is 5:1), heating to 500 ℃ at the speed of 5 ℃/min under the argon atmosphere, and keeping the temperature for 3 hours. Finally, the carbon-based bifunctional electrocatalytic material is obtained, the material has a relatively rich mesoporous structure and surface functional groups, nitrogen heteroatoms are proved to be doped into a carbon interface to form a nitrogen-containing carbocycle, and the material shows excellent bifunctional catalytic activity in oxygen reduction (ORR) and Oxygen Evolution (OER) reactions.
Scanning electron microscopy (JSM-7800) was used to test the microstructure of the carbon-based catalytic material under the conditions described above. The test results are shown in fig. 1. The pore structure of the material is shown in fig. 2, and shows a uniform mesoporous structure. XPS was used to characterize the incorporation pattern of N, as shown in figure 3. FT-IR results As shown in FIG. 4, the carbonyl and aldehyde functional groups on the surface of powder C increased significantly after oxidation in the mixed acid.
The carbon-based bifunctional catalytic material prepared in example 1 was coated on a glassy carbon electrode of a rotating ring disk to perform ORR/OER bifunctional electrocatalytic reaction, a platinum sheet was used as a counter electrode, 0.1M KOH was used as an electrolyte, and Ag/AgCl was used as a reference electrode, and before the test, 10min of oxygen was introduced into the electrolyte to achieve oxygen saturation in the electrolyte. The electrochemical workstation was CHI 760e, the LSV scan speed was 50mV/s, and the rotation speeds were 400, 625, 900, 1225, 1600, and 2500rpm, respectively. The electrochemical reaction activity is shown in FIG. 4, and the kinetic activity is shown in FIG. 5.
Example 2
Dispersing biomass tar and a pore-forming agent in deionized water according to a mass ratio of 4:1, and stirring for 2 hours on a magnetic stirrer to form a mixed solution A1; then pouring the solution A1 into a corundum crucible, heating to 800 ℃ under the argon atmosphere, keeping the temperature for 2 hours, taking out and grinding into powder B1; then adding the powder B1 into 30mL of a mixed solution (1:1) of 30 wt% nitric acid and hydrogen peroxide, stirring for 24h, washing with water to be neutral, and drying to obtain powder C1; and grinding and uniformly mixing the powder C1 and melamine (the mass ratio is 4:1), heating to 500 ℃ at the speed of 5 ℃/min under the argon atmosphere, and keeping the temperature for 3 hours. Finally obtaining the carbon-based bifunctional electro-catalytic material.
Example 3
Dispersing biomass tar and a pore-forming agent in a solution of ethanol/deionized water (1:1) according to a mass ratio of 5:1, and stirring for 4 hours on a magnetic stirrer to form a mixed solution A2; then pouring the solution A2 into a corundum crucible, heating to 1000 ℃ under the argon atmosphere, keeping the temperature for 2 hours, taking out and grinding into powder B2; then adding the powder B2 into 30mL of a mixed solution (1:1) of 30 wt% nitric acid and hydrogen peroxide, stirring for 48h, washing with water to be neutral, and drying to obtain powder C2; and (3) grinding and uniformly mixing the powder C2 and melamine (the mass ratio is 5:1), heating to 500 ℃ at the speed of 5 ℃/min under the argon atmosphere, and keeping the temperature for 3 h. Finally obtaining the carbon-based bifunctional electro-catalytic material.
Example 4
Dispersing biomass tar and a pore-forming agent in a solution of ethanol/deionized water (1:1) according to a mass ratio of 5:1, and stirring for 2 hours on a magnetic stirrer to form a mixed solution A3; then pouring the solution A3 into a graphite crucible, heating to 800 ℃ in an ammonia atmosphere, keeping the temperature for 2 hours, taking out and grinding into powder B3; then adding the powder B3 into 30mL of 30% wt% nitric acid solution, stirring for 72h, washing with water to be neutral, and drying to obtain powder C3; and grinding and uniformly mixing the powder C3 and melamine (the mass ratio is 5:1), heating to 500 ℃ at the speed of 5 ℃/min under the argon atmosphere, and keeping the temperature for 3 hours. Finally obtaining the carbon-based bifunctional electro-catalytic material.
Example 5
Dispersing biomass tar and a pore-forming agent in a solution of ethanol/deionized water (1:1) according to a mass ratio of 5:1, and stirring for 4 hours on a magnetic stirrer to form a mixed solution A4; then pouring the solution A4 into a corundum crucible, heating to 900 ℃ under the argon atmosphere, keeping the temperature for 2 hours, taking out and grinding into powder B4; then adding the powder B4 into 30mL of a mixed solution (1:1) of 30 wt% nitric acid and hydrogen peroxide, stirring for 24h, washing with water to be neutral, and drying to obtain powder C4; and grinding and uniformly mixing the powder C4 and melamine (the mass ratio is 5:1), heating to 700 ℃ at the speed of 5 ℃/min under the argon atmosphere, and keeping the temperature for 3 h. Finally obtaining the carbon-based bifunctional electro-catalytic material.
Example 6
Dispersing biomass tar and a pore-forming agent in ethanol according to a mass ratio of 5:1, and stirring for 3 hours on a magnetic stirrer to form a mixed solution A5; then pouring the solution A5 into a corundum crucible, heating to 800 ℃ in a nitrogen atmosphere, keeping the temperature for 1h, taking out and grinding into powder B5; then adding the powder B5 into 30mL of 30 wt% hydrogen peroxide mixed solution (1:1), stirring for 48h, washing with water to neutrality, and drying to obtain powder C5; and grinding and uniformly mixing the powder C5 and melamine (the mass ratio is 5:1), heating to 500 ℃ at the speed of 5 ℃/min under the argon atmosphere, and keeping the temperature for 3 hours. Finally obtaining the carbon-based bifunctional electrocatalytic material.
Example 7
Dispersing biomass tar and a pore-forming agent in a solution of ethanol/deionized water (1:1) according to a mass ratio of 5:1, and stirring for 4 hours on a magnetic stirrer to form a mixed solution A6; then pouring the solution A6 into a graphite crucible, heating to 1200 ℃ under the argon atmosphere, keeping the temperature for 2 hours, taking out and grinding into powder B6; then adding the powder B6 into 30mL of a mixed solution (1:1) of 30 wt% nitric acid and hydrogen peroxide, stirring for 72h, washing with water to be neutral, and drying to obtain powder C6; and grinding and uniformly mixing the powder C6 and melamine (the mass ratio is 4:1), heating to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere, and keeping the temperature for 3 hours. Finally obtaining the carbon-based bifunctional electro-catalytic material.
Example 8
Dispersing biomass tar and a pore-forming agent in a solution of ethanol/deionized water (1:1) according to a mass ratio of 5:1, and stirring for 2 hours on a magnetic stirrer to form a mixed solution A7; then pouring the solution A7 into a corundum crucible, heating to 1200 ℃ under the argon atmosphere, keeping the temperature for 2 hours, taking out and grinding into powder B7; then adding the powder B7 into 30mL of a mixed solution (2:1) of 30 wt% nitric acid and hydrogen peroxide, stirring for 36h, washing with water to be neutral, and drying to obtain powder C7; and grinding and uniformly mixing the powder C7 and melamine (the mass ratio is 3:1), heating to 900 ℃ at the speed of 5 ℃/min in a nitrogen atmosphere, and keeping the temperature for 2 hours. Finally obtaining the carbon-based bifunctional electro-catalytic material.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is a more detailed description of the present invention that is presented in conjunction with specific embodiments, and the practice of the invention is not to be considered limited to those descriptions. It will be apparent to those skilled in the art that a number of simple derivations or substitutions can be made without departing from the inventive concept.
Claims (9)
1. A high-efficiency double-function water-decomposition carbon-based catalytic material and a preparation method thereof are characterized by comprising the following steps:
(1) uniformly dispersing and mixing the biomass tar and the pore-forming agent;
(2) pyrolyzing the mixture of step (1);
(3) taking out the product in the step (2), grinding, and oxidizing in a mixed acid solution;
(4) and (3) mixing the carbon material and the nitrogen source in the step (3), and forming heteroatom doping on the surface of the mixture through pyrolysis.
2. The biomass tar-based bifunctional carbon-based electrocatalytic material and the preparation method thereof as claimed in claim 1, wherein: the biomass tar used in the step (1) is a byproduct generated in a biomass gasification process, and the main component of the biomass tar is a benzene derivative;
3. the biomass tar-based bifunctional carbon-based electrocatalytic material and the preparation method thereof as claimed in claim 1, wherein: the pore-forming agent in the step (1) is one or more of the following combinations: potassium hydroxide, ammonium carbonate, ammonium bicarbonate, ammonium chloride;
4. the biomass tar-based bifunctional carbon-based electrocatalytic material and the preparation method thereof as claimed in claim 1, wherein: the mass ratio of the biomass tar to the pore-forming agent in the step (1) is 1: 1-1: 5, and the optimized mass ratio is 1: 3-1: 5.
5. The biomass tar-based bifunctional carbon-based electrocatalytic material as claimed in claim 1, and the preparation method thereof, wherein the electrocatalytic material comprises: the solvent in the step (1) is one or more of deionized water, ethanol, glycol, methanol, glycerol, isopropanol and n-butanol;
6. the biomass tar-based bifunctional carbon-based electrocatalytic material and the preparation method thereof as claimed in claim 1, wherein: the pyrolysis temperature in the step (2) is 700-1200 ℃, and the pyrolysis atmosphere is one or any combination of two of the following gases: argon, nitrogen, carbon dioxide, water vapor and ammonia;
7. the biomass tar-based bifunctional carbon-based electrocatalytic material and the preparation method thereof as claimed in claim 1, wherein: the mixed acid in the step (3) is one or the combination of any two or more of the following solutions: nitric acid, sulfuric acid, hypochlorous acid and hydrogen peroxide.
8. The biomass tar-based bifunctional carbon-based electrocatalytic material and the preparation method thereof as claimed in claim 1, wherein: the oxidation time in the step (3) is 24-96 hours, and the optimized oxidation time is 36-48 hours.
9. The biomass tar-based bifunctional carbon-based electrocatalytic material and the preparation method thereof as claimed in claim 1, wherein: the pyrolysis temperature in the step (4) is 400-900 ℃, and the pyrolysis atmosphere is one or any combination of two of the following gases: argon, nitrogen and ammonia.
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