CN113134354A - Preparation method of high-efficiency oxygen reduction reaction catalyst - Google Patents
Preparation method of high-efficiency oxygen reduction reaction catalyst Download PDFInfo
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- CN113134354A CN113134354A CN202110254435.9A CN202110254435A CN113134354A CN 113134354 A CN113134354 A CN 113134354A CN 202110254435 A CN202110254435 A CN 202110254435A CN 113134354 A CN113134354 A CN 113134354A
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- oxygen reduction
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- coffee grounds
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000001301 oxygen Substances 0.000 title claims abstract description 64
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 64
- 238000006722 reduction reaction Methods 0.000 title claims abstract description 63
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 100
- 239000002243 precursor Substances 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000006229 carbon black Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000004140 cleaning Methods 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 43
- 239000003054 catalyst Substances 0.000 claims description 40
- 230000009467 reduction Effects 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229940099607 manganese chloride Drugs 0.000 claims description 6
- 235000002867 manganese chloride Nutrition 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000446 fuel Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 40
- 235000019241 carbon black Nutrition 0.000 description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910017112 Fe—C Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 241000533293 Sesbania emerus Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- 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
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Abstract
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a high-efficiency oxygen reduction reaction catalyst, which comprises the following steps of soaking coffee grounds in deionized water, cleaning until water turns clear, and drying; step two, adding Mn2+、Fe2+、Fe3+And Co2+Mixing one or two metal salts of the metal ions with the coffee grounds and the carbon black treated in the step one, adding ethanol, grinding into slurry, and drying to obtain a precursor; and step three, putting the precursor treated in the step two into a tubular furnace, and carrying out heat treatment in an ammonia atmosphere to obtain the high-efficiency oxygen reduction reaction catalyst. The invention adopts natural coffee grounds as basic raw materials and has the preparation functionThe high-efficiency oxygen reduction reaction catalyst prepared by the preparation method can be applied to the fields of fuel cells, metal-air cells and the like.
Description
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a preparation method of a high-efficiency oxygen reduction reaction catalyst.
Background
With the increasing shortage of conventional fossil fuels and the problem of environmental deterioration, efforts are being made to develop and utilize various energy conversion and storage systems. Fuel cells, which are capable of directly converting chemical energy into electrical energy and have high energy density and renewability, are considered to be the most promising candidates for automotive and portable electronic devices. The oxygen reduction reaction is a cathode reaction process when the fuel cell works, is a slow dynamic process, limits the performance of the fuel cell, and needs to use a catalyst to improve the discharge efficiency of the fuel cell.
The platinum-based catalyst has high-efficiency catalytic capability of oxygen reduction reaction and is widely applied to the oxygen reduction reaction. However, the platinum-based catalyst has the disadvantages of poor stability, low resistance to poisoning, high cost and the like, and the wide application of the platinum-based catalyst in fuel cells is limited. Therefore, the development of a non-noble metal catalyst with high catalytic activity for the oxygen reduction reaction, low cost and good stability is the key for the wide popularization and use of fuel cells.
Among the numerous non-noble metal catalysts, the electrocatalytic activity of nitrogen-doped carbon-based catalysts is comparable to or even superior to commercial Pt/C electrodes, and has good tolerance to methanol and CO; in addition, the carbon-based catalyst also has the advantages of low price and easy availability, so the nitrogen-doped carbon material has good application prospect in fuel cell application and is expected to replace the traditional platinum-based catalyst.
The typical preparation method of the nitrogen-doped carbon material catalyst is that transition metal ions, organic nitrogen-containing compounds and carbon black materials are mixed and then placed in a tubular furnace, and heat treatment is carried out at different temperatures and in different atmospheres, so that the doping of nitrogen atoms to carbon black is realized. The carbon black material used herein includes common carbon black, carbon nanotubes, graphene, and the like; the organic nitrogen-containing compound includes relatively inexpensive substances such as melamine and urea, and expensive substances such as phthalocyanine and porphyrin. These materials are all industrial products obtained after a plurality of processing steps, certain production cost is added, and the performance of the obtained catalyst is related to the combination of raw materials.
In nature, a plurality of natural substances containing carbon elements exist, and can be converted into carbon black with a specific structure after certain carbonization treatment processes. Coffee is a beverage that is used in large quantities worldwide. Coffee is extracted from coffee beans, and the residue coffee grounds after extraction are rich in elements such as carbon, nitrogen, etc., but are usually disposed of as waste. The invention provides a preparation method of a high-efficiency oxygen reduction reaction catalyst, which is characterized in that coffee grounds are used as basic raw materials, and the oxygen reduction reaction catalyst with simple preparation process, good catalytic performance and low cost is obtained after specific steps.
Disclosure of Invention
In order to solve the problems of high price, poor stability and the like of a fuel cell cathode oxygen reduction reaction catalyst, the invention provides a preparation method of a high-efficiency oxygen reduction reaction catalyst, and the catalyst obtained by the method has the remarkable advantages of simple preparation process, good catalytic performance, low cost and the like.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a preparation method of a high-efficiency oxygen reduction reaction catalyst comprises the following steps:
step one, pre-cleaning coffee grounds; soaking coffee grounds in deionized water, cleaning until water becomes clear, and drying for later use;
step two, preparing a precursor; mixing metal salt with the coffee grounds and the carbon black which are treated in the first step in proportion, adding ethanol, grinding into slurry, and drying to obtain a precursor;
step three, heat treatment; and (4) putting the precursor obtained in the step two into a tube furnace for heat treatment, and naturally cooling to room temperature after the heat treatment is finished to obtain the catalyst.
As a preferred embodiment of the present application, the metal salt in the second step is Mn-containing2+、Fe2+、Fe3+And Co2+A metal salt of either one or both of them.
In a preferred embodiment of the present invention, the mass ratio of the metal salt, coffee grounds and carbon black is 0.25 to 1.5: 1-8: 0.5 to 8; further preferably, the mass ratio of the metal salt, the coffee grounds and the carbon black is 8:2: 1.
As a preferred embodiment herein, the carbon black used is VXC 72R.
As a better embodiment in the application, ammonia gas is introduced in the whole process of the treatment, the heat treatment temperature is 600-1000 ℃, and the heat treatment time is 1-8 hours; more preferably, the heat treatment temperature is 850 ℃ and the time is 2 hours.
As a preferred embodiment in the present application, Mn is contained2+The metal salt of (a) is manganese chloride or manganese nitrate; containing Fe3+The metal salt is ferric trichloride or ferric nitrate containing Fe2+The metal salt of (a) is ferrous chloride or ferrous nitrate; containing Co2+The metal salt of (a) is cobalt chloride or cobalt nitrate.
The catalyst prepared by the method has higher current density and more corrected initial potential of oxygen reduction reaction.
Compared with the prior art, the invention has the beneficial effects that:
the waste coffee grounds are adopted as raw materials, are cheap and easy to obtain, and waste utilization is realized.
And (II) the preparation process of the catalyst is simple and convenient, and the operation and the control are easy.
And (III) the obtained catalyst has good catalytic activity of oxygen reduction reaction.
Drawings
FIG. 1 is a linear potential scanning curve of Pt/C and products obtained in examples 1 and 2, comparative examples 3 and 4, comparative examples 9 and 10
FIG. 2 is a linear potential scanning curve of the product obtained in example 3, comparative example 5 and comparative example 6 and Pt/C
FIG. 3 is a linear potential scanning curve of the products obtained in example 4, comparative example 7 and comparative example 8 and Pt/C
FIG. 4 is a linear potential sweep curve of the products obtained in examples 2, 3 and 4 and the catalysts obtained in Pt/C
FIG. 5 is an XRD scan of the product of example 2
FIG. 6 is a scanning electron micrograph of a raw material carbon black
FIG. 7 is a scanning electron micrograph of a product obtained in example 2
Detailed Description
A preparation method of a high-efficiency oxygen reduction reaction catalyst comprises the following steps:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until water becomes clear, and drying for later use.
Step two: and preparing a precursor. Will contain Mn2+、Fe2+、Fe3+And Co2+And (3) mixing one or two metal salts of the metal ions with the coffee grounds and the carbon black treated in the step one, wherein the mass of the metal salts is 0.25-1.5 g, the mass of the coffee grounds is 1-8 g, and the mass of the carbon black is 0.5-8 g, adding ethanol, grinding into slurry, and drying to obtain the precursor.
Said Mn being contained2+The metal salt of (1) is manganese chloride or manganese nitrate; containing Fe3+The metal salt is selected from ferric chloride, ferric nitrate, and Fe2 +The metal salt of (A) is ferrous chloride or ferrous nitrate; containing Co2+The metal salt of (2) is cobalt chloride or cobalt nitrate.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole process of the heat treatment, wherein the heat treatment temperature is 600-1000 ℃, the heat treatment time is 1-8 hours, and naturally cooling to room temperature after the heat treatment is finished to obtain the high-efficiency oxygen reduction reaction catalyst.
Preferably, the heat treatment temperature is 850 ℃ and the heat treatment time is 2 hours. The mass ratio of the coffee grounds to the carbon black to the metal salt is 8:2: 1.
The present invention will be further illustrated below with reference to specific examples and comparative examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The carbon blacks used in the following cases are all VXC72R, a commercially available product.
Example 1:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. Adding 0.5g of ferric chloride, 4g of coffee grounds treated in the step one and 1g of carbon black into ethanol, grinding into slurry, and drying at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 800 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished to obtain the high-efficiency oxygen reduction reaction catalyst, wherein the mark is Fe-C-CG-800.
Example 2:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. Adding 0.5g of ferric chloride, 4g of coffee grounds treated in the step one and 1g of carbon black into ethanol, grinding into slurry, and drying at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished to obtain the high-efficiency oxygen reduction reaction catalyst which is marked as Fe-C-CG.
Example 3:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. Adding 0.5g of manganese chloride, 4g of coffee grounds treated in the first step and 1g of carbon black into ethanol, grinding into slurry, and drying at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished to obtain the high-efficiency oxygen reduction reaction catalyst, wherein the mark is Mn-C-CG.
Example 4:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. 0.5g of cobalt chloride, 4g of coffee grounds treated in the first step and 1g of carbon black are added into ethanol, ground into slurry and dried at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished to obtain the high-efficiency oxygen reduction reaction catalyst, wherein the mark is Co-C-CG. Comparative example 1:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. Adding ethanol into 4g of coffee grounds treated in the first step, grinding the mixture into pulp, and drying the pulp at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, naturally cooling to room temperature after the heat treatment is finished, and marking the obtained product as CG.
Comparative example 2:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. Adding ethanol into 4g of coffee grounds treated in the step one and 1g of carbon black, grinding into slurry, and drying at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished, wherein the obtained product is marked as C-CG.
Comparative example 3:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. Adding 0.5g of ferric chloride and 4g of coffee grounds treated in the first step into ethanol, grinding into slurry, and drying at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished, wherein the obtained product is marked as Fe-CG.
Comparative example 4:
the method comprises the following steps: and preparing a precursor. 0.5g of ferric chloride and 1g of carbon black are added into ethanol, ground into slurry and dried at 100 ℃ for 10 hours.
Step two: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished, wherein the obtained product is marked as Fe-C.
Comparative example 5:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. Adding 0.5g of manganese chloride and 4g of coffee grounds treated in the first step into ethanol, grinding into slurry, and drying at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished, wherein the obtained product is marked as Mn-CG.
Comparative example 6:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. 0.5g of manganese chloride and 1g of carbon black are added with ethanol and ground into slurry, and the slurry is dried for 10 hours at 100 ℃.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished, wherein the obtained product is marked as Mn-C.
Comparative example 7:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. 0.5g of cobalt chloride and 4g of coffee grounds treated in the first step were added with ethanol and ground into a slurry, which was dried at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. Putting the precursor treated in the second step into a tube furnace for heat treatment, introducing ammonia gas in the whole process of the heat treatment, heating to 850 ℃ at the speed of 5 ℃/min, carrying out the heat treatment for 2 hours, naturally cooling to room temperature after the heat treatment is finished, and marking the obtained product as Co-CG
Comparative example 8:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. 0.5g of cobalt chloride and 1g of carbon black were added to ethanol and ground into a slurry, which was dried at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. And (3) putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing ammonia gas in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished, wherein the obtained product is marked as Co-C.
Comparative example 9:
the method comprises the following steps: and pre-cleaning coffee grounds. Soaking coffee grounds in deionized water, cleaning until the water becomes clear, and drying at 120 ℃ for 12 hours.
Step two: and preparing a precursor. Adding 0.5g of ferric chloride, 4g of coffee grounds treated in the step one and 1g of carbon black into ethanol, grinding into slurry, and drying at 100 ℃ for 10 hours.
Step three: and (6) heat treatment. Putting the precursor treated in the second step into a tubular furnace for heat treatment, introducing nitrogen in the whole heat treatment process, heating to 850 ℃ at the speed of 5 ℃/min, carrying out heat treatment for 2 hours, and naturally cooling to room temperature after the heat treatment is finished to obtain the high-efficiency oxygen reduction reaction catalyst marked as Fe-C-CG-N2。
Comparative example 10:
raw carbon black, noted AB.
The catalysts Fe-C-CG-800, Fe-C-CG, Mn-C-CG, Co-C-C and obtained in example 1, example 2, example 3 and example 4, the products CG, C-CG, Fe-C, Mn-CG, Mn-C, Co-CG, Co-C, Fe-C-CG-N and obtained in comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5, comparative example 6, comparative example 7, comparative example 8, comparative example 9 and comparative example 10 are mixed2AB to perform power supplyThe performance of the chemical catalytic oxygen reduction reaction is tested and compared with a commercial 20% Pt/C catalyst, and the specific test results are as follows:
FIG. 1 shows Pt/C and Fe-C-CG-800, Fe-C-CG, C-CG, Fe-C, Fe-C-CG-N, products obtained in example 1, example 2, comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 9, and comparative example 102AB linear potential scan curve; FIG. 2 is a graph showing the linear potential scanning curves of Pt/C and Mn-C-CG, Mn-CG and Mn-C of products obtained in example 3, comparative example 5 and comparative example 6; FIG. 3 is a linear potential scanning curve of Pt/C and Co-C-CG, Co-CG and Co-C products obtained in example 4, comparative example 7 and comparative example 8; FIG. 4 is a linear potential scanning curve of Pt/C and Fe-C-CG, Mn-C-CG and Co-C-CG of the products obtained in examples 2, 3 and 4. The electrochemical test conditions were: 0.1M KOH solution saturated with oxygen at 28 ℃ at a scanning rate of 5mV/s and an electrode rotation speed of 1600 rpm.
As can be seen from FIG. 1, the initial oxygen reduction potentials of the products CG, C-CG, Fe-C, Fe-C-CG-N2, AB and Pt/C catalysts obtained in comparative examples 1, 2, 3, 4, 9 and 10 were 0.74V, 0.76V, 0.86V, 0.81V, 0.87V and 1.04V (vs. RHE), respectively, and the initial oxygen reduction potentials of the products Fe-C-CG and Fe-C-CG obtained in inventive examples 1 and 2 were 1.06V and 1.04V, respectively. The products are CG, C-CG, Fe-C, Fe-C-CG-N2AB, Pt/C, Fe-C-CG-800 and Fe-C-CG are sequentially 2.98mA cm in oxygen reduction current density at 0.50V-2、3.89mA cm-2、2.71mA cm-2、4.19mA cm-2、4.51mA cm-2、3.51mA cm-2、4.52mA cm-2、6.82mA cm-2、5.49mA cm-2. The catalysts Fe-C-CG-800 and Fe-C-CG obtained by the preparation method of the high-efficiency oxygen reduction reaction catalyst have a positive initial oxygen reduction reaction potential and a large oxygen reduction reaction current density, which shows that the high-efficiency oxygen reduction reaction catalyst has good oxygen reduction catalytic activity.
As can be seen from FIG. 2, the initial oxygen reduction potentials of Mn-CG and Mn-C obtained in comparative examples 5 and 6 were 0.90V and 0.85V, respectively, and the initial oxygen of Mn-C-CG obtained in example 3 of the present inventionThe reduction potential was 0.96V. Mn-C-CG, Mn-C, oxygen reduction Current Density at 0.5V (vs. RHE) in this order, 4.67mA cm-2、3.26mA cm-2、5.34mA cm-2. The catalyst Mn-C-CG prepared by the preparation method of the high-efficiency oxygen reduction reaction catalyst has a positive initial oxygen reduction reaction potential and a large oxygen reduction reaction current density, which shows that the catalyst has good oxygen reduction catalytic activity.
As can be seen from FIG. 3, the initial oxygen reduction potentials of Co-CG and Co-C obtained in comparative examples 7 and 8 were 1.06V and 1.02V; the initial oxygen reduction current density of the product Co-C-CG obtained in the embodiment 4 of the invention is 1.09V. The oxygen reduction current densities of Co-C-CG, Co-CG and Co-C at 0.50V are 5.15mA cm in sequence-2、4.83mA cm-2、4.77mA cm-2. The catalyst Co-C-CG prepared by the preparation method of the high-efficiency oxygen reduction reaction catalyst has a positive initial oxygen reduction reaction potential and a large oxygen reduction reaction current density, which shows that the catalyst has good oxygen reduction catalytic activity.
As can be seen from FIG. 4, the products Fe-C-CG-800, Fe-C-CG, Mn-C-CG and Co-C-CG obtained in examples 1, 2, 3 and 4 all have a positive initial oxygen reduction reaction potential and a larger oxygen reduction reaction current density, and the catalytic performance of the products is close to that of a Pt/C catalyst, which shows that the catalyst prepared by the preparation method of the high efficiency oxygen reduction reaction catalyst has good oxygen reduction reaction catalytic activity.
As can be seen from FIG. 5, in the high efficiency oxygen reduction catalyst prepared in example 2, Fe is the main component of Fe in Fe-C-CG2The N (PDF 50-0958) form exists.
As can be seen from FIG. 6, the morphology of the carbon black under the scanning electron microscope is spherical nanoparticles, and the particle size of the carbon black is about 30-50 nm.
As can be seen from fig. 7, in addition to the raw material carbon black in the form of spherical nanoparticles, smaller-sized particles were filled in the raw material carbon black, and this portion of the particles was converted from coffee grounds. The structure can increase the specific surface area of the catalyst, enrich the pore structure, provide more active sites for oxygen reduction reaction and enable the catalyst to have good performance.
The above embodiments are only used for illustrating the technical solutions of the present patent, and not for limiting the same; although the present patent is described in detail with reference to the foregoing embodiments, those of ordinary skill in the art will understand that: the technical solutions described in the foregoing embodiments can be modified, or some technical features can be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the spirit and scope of the technical solutions of the embodiments of the present patent.
Claims (9)
1. A preparation method of a high-efficiency oxygen reduction reaction catalyst is characterized by comprising the following steps:
step one, pre-cleaning coffee grounds; soaking coffee grounds in deionized water, cleaning until water becomes clear, and drying for later use;
step two, preparing a precursor; mixing metal salt with the coffee grounds and the carbon black which are treated in the first step in proportion, adding ethanol, grinding into slurry, and drying to obtain a precursor;
step three, heat treatment; and (4) putting the precursor obtained in the step two into a tube furnace for heat treatment, and naturally cooling to room temperature after the heat treatment is finished to obtain the catalyst.
2. The method of preparing a catalyst for high efficiency oxygen reduction according to claim 1, wherein: the metal salt in the second step is Mn-containing2+、Fe2+、Fe3+And Co2+A metal salt of either one or both of them.
3. The method of preparing a catalyst for high efficiency oxygen reduction according to claim 1, wherein: the mass ratio of the metal salt to the coffee grounds to the carbon black is 0.25-1.5: 1-8: 0.5 to 8.
4. The method of preparing a catalyst for high efficiency oxygen reduction according to claim 1, wherein: the carbon black used was VXC 72R.
5. The method of preparing a catalyst for high efficiency oxygen reduction according to claim 1, wherein: ammonia gas is introduced in the whole process of the treatment process, the heat treatment temperature is 600-1000 ℃, and the heat treatment time is 1-8 hours.
6. The method of preparing a catalyst for high efficiency oxygen reduction according to claim 2, wherein: containing Mn2+The metal salt of (a) is manganese chloride or manganese nitrate; containing Fe3+The metal salt is ferric trichloride or ferric nitrate containing Fe2+The metal salt of (a) is ferrous chloride or ferrous nitrate; containing Co2+The metal salt of (a) is cobalt chloride or cobalt nitrate.
7. The method of preparing a catalyst for high efficiency oxygen reduction reaction according to claim 3, wherein: the mass ratio of the metal salt, the coffee grounds and the carbon black is 8:2: 1.
8. The method of claim 5, wherein the catalyst for high efficiency oxygen reduction reaction comprises: the heat treatment was carried out in an ammonia atmosphere at 850 ℃ for 2 hours.
9. The method for preparing a high efficiency oxygen reduction catalyst according to any one of claims 1 to 8, wherein: the catalyst has a large current density and a more positive initial potential for oxygen reduction.
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