CN113013428A - Preparation method and application of Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst - Google Patents
Preparation method and application of Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst Download PDFInfo
- Publication number
- CN113013428A CN113013428A CN202110222953.2A CN202110222953A CN113013428A CN 113013428 A CN113013428 A CN 113013428A CN 202110222953 A CN202110222953 A CN 202110222953A CN 113013428 A CN113013428 A CN 113013428A
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- oxygen reduction
- preparation
- zif
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- 230000009467 reduction Effects 0.000 title claims abstract description 42
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 114
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 54
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 33
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 18
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 92
- 238000003756 stirring Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 229910052573 porcelain Inorganic materials 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 14
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical group [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 claims description 13
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical group [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 6
- 239000012692 Fe precursor Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000012360 testing method Methods 0.000 abstract description 15
- 238000011068 loading method Methods 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 abstract description 2
- 238000000970 chrono-amperometry Methods 0.000 abstract 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 33
- 229910052760 oxygen Inorganic materials 0.000 description 32
- 239000001301 oxygen Substances 0.000 description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 230000010757 Reduction Activity Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种Fe,Co双金属掺杂介孔碳氧还原催化剂的制备方法及应用。该方法为将2‑甲基咪唑溶解在甲醇溶液中，得到的溶液命名为A溶液；将六水合硝酸锌溶解在甲醇溶液中，得到的溶液命名为B溶液；然后在搅拌的条件下将B溶液加到A溶液中，室温下搅拌得到白色的悬浊液ZIF‑8，再向其中加入乙酰丙酮铁和乙酰丙酮钴，再搅拌后转入聚四氟乙烯中水热反应，所得产物经离心、洗涤、干燥、热处理，即得。该方法制备成本低廉，过程简单，能够重复操作，克服了催化剂热解过程中团聚的问题；该催化剂载量高，具有良好的催化活性和稳定性，在酸性条件下半波电位达到了0.81V，经过40000s的计时电流测试后为88.6％。
The invention discloses a preparation method and application of a Fe, Co bimetallic doped mesoporous carbon-oxygen reduction catalyst. The method comprises the following steps: dissolving 2-methylimidazole in methanol solution, and the obtained solution is named A solution; dissolving zinc nitrate hexahydrate in methanol solution, the obtained solution is named B solution; The solution was added to the A solution, stirred at room temperature to obtain a white suspension ZIF-8, then added iron acetylacetonate and cobalt acetylacetonate to it, then stirred and then transferred to the polytetrafluoroethylene for hydrothermal reaction, and the obtained product was centrifuged. , washing, drying and heat treatment. The method has the advantages of low preparation cost, simple process, repeatable operation, and overcomes the problem of agglomeration in the process of catalyst pyrolysis; the catalyst has high loading, good catalytic activity and stability, and the half-wave potential reaches 0.81 V under acidic conditions , 88.6% after 40000s chronoamperometry test.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a preparation method of a Fe and Co bimetal doped ZIF-8 derived carbon-oxygen reduction catalyst and application of the catalyst in a cathode of a proton exchange membrane fuel cell.
Background
Energy shortage, environmental pollution and the like are two major problems to be solved urgently in human society, so that novel, clean and efficient sustainable development energy is urgently needed to be developed to replace traditional fossil energy. Among many new energy sources, fuel cells are considered to be the most promising form of energy production in the 21 st century because of their advantages such as high efficiency, environmental protection, and unlimited sources of reactants. However, the cathode oxygen reduction reaction rate of the fuel cell is very slow, and although the activity of the used Pt/C catalyst is good, the price of Pt is high, the reserves are limited, the durability is insufficient, and the methanol resistance is poor, so that the large-scale commercial development of the fuel cell is greatly limited. There is therefore a great need to develop and develop low-cost, highly active non-noble metal oxygen reduction catalysts to replace the expensive Pt/C catalysts.
In recent years, non-noble metal catalysts (M-N-C, M ═ Fe, Co) have attracted much attention because of their good catalytic activity, and at present, most of the non-noble metal catalysts are single metals, but the activity and stability of these catalysts are still very poor, and it is difficult to meet the commercialization demand of fuel cells. Recent researches show that the bimetal-doped carbon-based catalyst has better activity and stability, and a high-performance Fe and Co bimetal-doped mesoporous carbon-oxygen reduction catalyst taking ZIF-8 as a precursor is developed based on the patent. The catalyst has the advantages of simple preparation method, low cost, uniform metal dispersion, very wide application prospect and great significance for promoting the commercial application of fuel cells.
Disclosure of Invention
The invention provides a Fe and Co bimetal doped ZIF-8 derived carbon-oxygen reduction catalyst and a preparation method and application thereof, 2-methylimidazole and zinc nitrate hexahydrate are used as raw materials to synthesize a ZIF-8 carrier precursor, and a hydrothermal method is adopted to synthesize the Fe and Co bimetal Co-doped ZIF-8 derived carbon-oxygen reduction catalyst, so that the problems of large amount of agglomeration and low single metal catalyst loading capacity of the catalyst precursor in the pyrolysis process are solved; the catalyst prepared by the invention has uniform particle size, high catalyst loading, good catalytic activity and stability, and a half-wave potential of 0.81V (vs. RHE) under an acidic condition, and 88.6 percent (the mass activity is only reduced by 11.4 percent and is far lower than the activity reduction (65.6 percent) of commercial Pt/C after a timing current test of 40000 s.
The catalyst of the invention is realized by the following technical scheme:
dissolving 2-methylimidazole in a methanol solution to obtain a solution named as A solution; dissolving zinc nitrate hexahydrate in a methanol solution to obtain a solution named as a solution B; adding the solution B into the solution A under the stirring condition, stirring at room temperature to obtain a white suspension ZIF-8, adding iron (III) acetylacetonate and cobalt (II) acetylacetonate into the suspension, stirring, transferring the mixture into polytetrafluoroethylene for hydrothermal reaction, centrifuging the obtained product, washing the product with ethanol for three times, and performing vacuum drying at 60 ℃; the precursor obtained is denoted as Fe1-x/Cox-ZIF-8(x ═ 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1). Transferring the product into a porcelain boat, and placing the porcelain boat into a tubular furnace for heat treatment to obtain Fe, Co bimetal doped ZIF-8 derived non-noble metal catalyst Fe1-x/Cox-NC(x＝0、0.1、0.3、0.5、0.7、0.9、1)。
Preferably, the mixed solution A is prepared by adding 1.314g of 2-methylimidazole into 15mL of methanol, and the mixed solution B is prepared by adding 1.19g of zinc nitrate hexahydrate into 30mL of methanol;
preferably, the stirring time at room temperature after the solution B is added to the solution A is 24 hours;
preferably, the molar ratio of the iron (III) acetylacetonate to the cobalt acetylacetonate is (1-x)/x, wherein the molar ratio of the total amount of iron and cobalt to the zinc in the zinc nitrate hexahydrate is 1/6, i.e., (Fe + Co)/Zn ═ 1/6;
preferably, the heat treatment conditions are as follows: the temperature was raised to 900 ℃ at a rate of 5 ℃ per minute under nitrogen atmosphere and held for 3 h.
The invention also discloses Fe, Co bimetal doped Fe and Co bimetal doped ZIF-8 derived Fe prepared by the preparation method1-x/Cox-NC bimetallic oxygen reduction catalyst Fe1-x/Cox-NC (x ═ 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1), preferably Fe0.1/Co0.9-NC。
The invention also discloses Fe and Co bimetal doped ZIF-8 derived Fe prepared by the preparation method1-x/Cox-NC bimetallic oxygen reduction catalyst Fe1-x/Cox-NC (x ═ 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) in proton exchange membrane fuel cells.
Compared with the prior art, the invention has the following advantages and effects:
the invention discloses a Fe and Co bimetal doped ZIF-8 derived carbon-oxygen reduction catalyst Fe1-x/Cox-NC and a process for its preparation. The method has low preparation cost and simple process, can be repeatedly operated, and overcomes the problem of agglomeration in the pyrolysis process of the catalyst; the influence of the doping amount of Fe and Co bimetal on the oxygen reduction activity of the catalyst is systematically researched, and the optimal catalyst Fe is obtained0.1/Co0.9the-NC has uniform particle size, high catalyst loading, good catalytic activity and stability, the half-wave potential reaches 0.81V (vs. RHE) under an acidic condition, and the half-wave potential is 88.6% after a timing current test of 40000 s.
Drawings
FIG. 1 is Fe1-x/Cox-schematic synthesis of NC bimetallic oxygen reduction catalyst.
FIG. 2 a) SEM picture of Fe-ZIF-8; b) SEM picture of Co-ZIF-8; c) fe0.1/Co0.9SEM picture of ZIF-8; d) SEM picture of Fe-NC; e) SEM image of Co-NC; f) fe0.1/Co0.9-SEM picture of NC; g. h) are each Fe0.1/Co0.9-TEM and high angular ring dark field images of the NC; i) fe0.1/Co0.9Distribution diagram of Fe, Co, C, N elements of NC.
FIG. 3a shows Fe-ZIF-8, Co-ZIF-8 and Fe0.1/Co0.9-XRD pattern of ZIF-8 precursor;
FIG. 3b shows Fe-NC, Co-NC and Fe0.1/Co0.9-XRD pattern of NC catalyst;
FIG. 4a shows Fe-NC, Co-NC and Fe0.1/Co0.9-a raman map of the NC;
FIG. 4b is Fe0.1/Co0.9-XPS plots of NC;
FIG. 5a is a graph of various bis-non-noble metal oxygen reduction catalysts prepared at 0.1M HClO4Oxygen reduction profile in solution;
FIG. 5b shows the best Fe0.1/Co0.9NC bimetallic oxygen reduction catalyst and commercial Pt/C at 0.1M HClO4Oxygen reduction profile in solution;
FIG. 6 shows the best Fe0.1/Co0.9NC bimetallic oxygen reduction catalyst and commercial Pt/C catalyst at 0.1M HClO4Hydrogen peroxide (H) in solution2O2) Yield and electron transfer number plots;
FIG. 7a is Fe0.1/Co0.9-oxygen reduction profiles before and after 5000 cycles for NC oxygen reduction catalysts and commercial Pt/C catalysts; FIG. 7b is Fe0.1/Co0.9Current-time (i-t) plots for NC oxygen reduction catalysts and commercial Pt/C catalysts.
Detailed Description
The present invention is described in further detail with reference to the following examples, which are only preferred embodiments of the present invention, but the present invention is not limited by the examples, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent substitutions and are included within the scope of the present invention.
The steps of this example are as follows:
dissolving 2-methylimidazole in a methanol solution to obtain a solution named as A solution; dissolving zinc nitrate hexahydrate in a methanol solution to obtain a solution named as a solution B; adding the solution B into the solution A under the stirring condition, stirring at room temperature to obtain a white suspension ZIF-8, adding an iron precursor and a cobalt precursor into the suspension, stirring, transferring the mixture into polytetrafluoroethylene for hydrothermal reaction, centrifuging the obtained product, washing the product with ethanol for three times, and performing vacuum drying at 60 ℃; the precursor obtained is denoted as Fe1-x/Cox-ZIF-8(x ═ 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1). Transferring the product into a porcelain boat, and placing the porcelain boat into a tubular furnace for heat treatment to obtain a non-noble metal catalyst derived from Fe and Co bimetal doped ZIF-8Agent Fe1-x/Cox-NC(x＝0、0.1、0.3、0.5、0.7、0.9、1)。
Further, the iron precursor is iron (III) acetylacetonate.
Further, the cobalt precursor is cobalt (II) acetylacetonate.
Further, the mixed solution A is prepared by adding 1.313-1.315 g of 2-methylimidazole into 14.5-15.5 mL of methanol; the mixed solution B is prepared by adding 1.18-1.20 g of zinc nitrate hexahydrate into 29.5-30.5mL of methanol.
Further, the stirring time of the solution B after being added to the solution A at room temperature is 24 hours.
Further, the molar ratio of the added iron (III) acetylacetonate and cobalt (II) acetylacetonate is (1-x)/x, wherein the molar ratio of the total amount of iron and cobalt to the zinc in the zinc nitrate hexahydrate is 1/6, i.e., (Fe + Co)/Zn 1/6.
Further, the heat treatment conditions are as follows: the temperature was raised to 900 ℃ at a rate of 5 ℃ per minute under nitrogen atmosphere and held for 3 h.
Further, the vacuum drying temperature was 60 ℃.
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
Preparation of Fe-NC catalyst:
dissolving 1.315g of 2-methylimidazole in 15.5mL of methanol solution to obtain a solution named as solution A; 1.18g of zinc nitrate hexahydrate is dissolved in 30.5mL of methanol solution, and the obtained solution is named as solution B; and then adding the solution B into the solution A under the stirring condition, stirring for 24 hours at room temperature to obtain a white suspension ZIF-8, adding 0.67mmol of iron (III) acetylacetonate and 0mmol of cobalt (II) acetylacetonate, stirring for 1 hour, transferring into polytetrafluoroethylene, carrying out hydrothermal reaction for 4 hours at 120 ℃, centrifuging and washing the obtained product with ethanol for three times, and carrying out vacuum drying at 60 ℃. And transferring the product into a porcelain boat, placing the porcelain boat into a tubular furnace, carrying out heat treatment for 3h at 900 ℃ in a nitrogen atmosphere, controlling the temperature rise rate of nitrogen to be 5 ℃/min, and recording the obtained product as Fe-NC.
Example 2
Fe0.9/Co0.1Preparation of NC catalyst:
1.315g of 2-methylimidazole is dissolved in 14.5mL of methanol solution, and the obtained solution is named as solution A; 1.20g of zinc nitrate hexahydrate is dissolved in 29.5mL of methanol solution, and the obtained solution is named as solution B; and then adding the solution B into the solution A under the stirring condition, stirring for 24h at room temperature to obtain a white suspension ZIF-8, adding 0.6mmol of iron (III) acetylacetonate and 0.07mmol of cobalt (II) acetylacetonate, stirring for 1h, transferring into polytetrafluoroethylene, carrying out hydrothermal reaction at 120 ℃ for 4h, centrifuging and washing the obtained product with ethanol for three times, and carrying out vacuum drying at 60 ℃. Transferring the product into a porcelain boat, placing the porcelain boat into a tubular furnace, carrying out heat treatment for 3h at 900 ℃ in nitrogen atmosphere, controlling the temperature rise rate of nitrogen to be 5 ℃/min, and recording the obtained product as Fe0.9/Co0.1-NC。
Example 3
Fe0.7/Co0.3Preparation of NC catalyst:
1.314g of 2-methylimidazole was dissolved in 15.0mL of a methanol solution, and the resulting solution was named solution A; 1.19g of zinc nitrate hexahydrate is dissolved in 30.0mL of methanol solution, and the obtained solution is named as solution B; and then adding the solution B into the solution A under the stirring condition, stirring for 24h at room temperature to obtain a white suspension ZIF-8, adding 0.47mmol of iron (III) acetylacetonate and 0.2mmol of cobalt (II) acetylacetonate, stirring for 1h, transferring into polytetrafluoroethylene, carrying out hydrothermal reaction at 120 ℃ for 4h, centrifuging and washing the obtained product with ethanol for three times, and carrying out vacuum drying at 60 ℃. Transferring the product into a porcelain boat, placing the porcelain boat into a tubular furnace, carrying out heat treatment for 3h at 900 ℃ in nitrogen atmosphere, controlling the temperature rise rate of nitrogen to be 5 ℃/min, and recording the obtained product as Fe0.7/Co0.3-NC。
Example 4
Fe0.5/Co0.5Preparation of NC catalyst:
1.313g of 2-methylimidazole was dissolvedIn 15.0mL of methanol solution, the obtained solution is named solution A; 1.20g of zinc nitrate hexahydrate is dissolved in 30.5mL of methanol solution, and the obtained solution is named as solution B; and then adding the solution B into the solution A under the stirring condition, stirring for 24h at room temperature to obtain a white suspension ZIF-8, adding 0.33mmol of iron (III) acetylacetonate and 0.33mmol of cobalt (II) acetylacetonate, stirring for 1h, transferring into polytetrafluoroethylene, carrying out hydrothermal reaction for 4h at 120 ℃, centrifuging and washing the obtained product with ethanol for three times, and carrying out vacuum drying at 60 ℃. Transferring the product into a porcelain boat, placing the porcelain boat into a tube furnace, carrying out heat treatment for 3h at 800 ℃ in a nitrogen atmosphere, controlling the temperature rise rate of nitrogen to be 6 ℃/min, and recording the obtained product as Fe0.5/Co0.5-NC。
Example 5
Fe0.3/Co0.7Preparation of NC catalyst:
1.314g of 2-methylimidazole was dissolved in 15.0mL of a methanol solution, and the resulting solution was named solution A; 1.19g of zinc nitrate hexahydrate is dissolved in 30.0mL of methanol solution, and the obtained solution is named as solution B; and then adding the solution B into the solution A under the stirring condition, stirring for 24h at room temperature to obtain a white suspension ZIF-8, adding 0.2mmol of iron (III) acetylacetonate and 0.47mmol of cobalt (II) acetylacetonate, stirring for 1h, transferring into polytetrafluoroethylene, carrying out hydrothermal reaction at 120 ℃ for 4h, centrifuging and washing the obtained product with ethanol for three times, and carrying out vacuum drying at 60 ℃. Transferring the product into a porcelain boat, placing the porcelain boat into a tubular furnace, carrying out heat treatment for 3h at 900 ℃ in nitrogen atmosphere, controlling the temperature rise rate of nitrogen to be 5 ℃/min, and recording the obtained product as Fe0.3/Co0.7-NC。
Example 6
Fe0.1/Co0.9Preparation of NC catalyst:
1.314g of 2-methylimidazole was dissolved in 15.0mL of a methanol solution, and the resulting solution was named solution A; 1.19g of zinc nitrate hexahydrate is dissolved in 30.0mL of methanol solution, and the obtained solution is named as solution B; adding the solution B into the solution A under stirring, stirring at room temperature for 24 hr to obtain white suspension ZIF-8, and adding 0.07mmol of iron (III) acetylacetonate and 0.6mmol of cobalt (II) acetylacetonate, stirring for 1h, hydrothermal reaction in polytetrafluoroethylene at 120 ℃ for 4h, centrifuging, washing with ethanol for three times, and vacuum drying at 60 ℃. Transferring the product into a porcelain boat, placing the porcelain boat into a tubular furnace, carrying out heat treatment for 3h at 900 ℃ in nitrogen atmosphere, controlling the temperature rise rate of nitrogen to be 5 ℃/min, and recording the obtained product as Fe0.1/Co0.9-NC。
Example 7
Preparation of Co-NC catalyst:
1.313g of 2-methylimidazole is dissolved in 14.5mL of methanol solution, and the obtained solution is named as solution A; 1.18g of zinc nitrate hexahydrate is dissolved in 30.0mL of methanol solution, and the obtained solution is named as solution B; and then adding the solution B into the solution A under the stirring condition, stirring for 24 hours at room temperature to obtain a white suspension ZIF-8, adding 0mmol of iron (III) acetylacetonate and 0.67mmol of cobalt (II) acetylacetonate, stirring for 1 hour, transferring into polytetrafluoroethylene, carrying out hydrothermal reaction for 4 hours at 120 ℃, centrifuging and washing the obtained product with ethanol for three times, and carrying out vacuum drying at 60 ℃. And transferring the product into a porcelain boat, placing the porcelain boat into a tubular furnace, carrying out heat treatment for 1h at 900 ℃ in a nitrogen atmosphere, controlling the temperature rise rate of nitrogen to be 5 ℃/min, and recording the obtained product as Co-NC.
Example 8
Characterization of the catalyst:
as can be seen from the SEM images of FIGS. 2(a-c), the synthesized precursors containing different metals, Fe-ZIF-8, Co-ZIF-8 and Fe0.1/Co0.9the-ZIF-8 has a complete rhombic dodecahedron structure, and after 3 hours of high-temperature 900 ℃ heat treatment in argon atmosphere, Fe-ZIF-8, Co-ZIF-8 and Fe0.1/Co0.9Conversion of-ZIF-8 to Fe-NC, Co-NC and Fe0.1/Co0.9NC while keeping Fe-ZIF-8, Co-ZIF-8, Fe intact0.1/Co0.9Morphology of ZIF-8 precursor, as shown in FIG. 2 (d-f). From FIG. 2g, Fe0.1/Co0.9The surface of the-NC catalyst is free from any agglomerated metal particles, clusters and the like, the morphology is very regular, and the four elements of Fe, Co, C and N in the catalyst are highly dispersed (as shown in figure 2i), and figure 2h also shows that Fe, C and N are dispersed in the catalyst,The distribution of two metals of Co is very uniform, and the metal content is high. According to Fe-ZIF-8, Co-ZIF-8 and Fe0.1/Co0.9XRD (FIG. 3a) of the precursor of ZIF-8 shows that the XRD peak shapes of the three are similar and the peak positions are basically the same, and comparing the XRD patterns of the ZIF-8 shows that Fe and Co metals are doped into the cavity of the ZIF-8 and the crystal structure of the ZIF-8 is not changed; according to Fe-NC, Co-NC and Fe0.1/Co0.9XRD (FIG. 3b) of NC catalyst shows that only two distinct carbon peaks, similar to NC after ZIF-8 carbonization, indicate that metal-doped carbon-oxygen reduction catalyst is successfully obtained, and no distinct metal particles and simple substances exist in the catalyst, which is consistent with TEM results. Fig. 4a is a Raman analysis of the catalyst, D for defect level and G for graphitization level, the ratio of which illustrates defect versus graphitization. According to the D/G value, the three catalysts Fe-NC, Co-NC and Fe0.1/Co0.9in-NC, Fe0.1/Co0.9Minimum D/G of-NC catalyst, thus indicating Fe0.1/Co0.9The NC catalyst has less defects and higher graphitization degree. The high graphitization degree can improve the oxidation corrosion resistance of the carbon carrier in the catalyst, so that Fe0.1/Co0.9The higher the stability of the NC catalyst. FIG. 4b is catalyst Fe0.1/Co0.9XPS analysis of NC, which indicates Fe0.1/Co0.9Five elements of C, N, O, Fe and Co exist in the NC catalyst, and the chemical states of the elements are different, wherein C, N, O is 1s, and the metals of Fe and Co are 2 p. Table 1 shows the analysis of the element content (ICP-MS) of the catalyst, and the higher the content of Fe and Co elements, the higher the metal loading of the catalyst is, and the better the catalytic activity is. According to the value, Fe0.1/Co0.9The total metal content of the-NC catalyst is 1.34%, and the metal content of the-NC catalyst is higher than that of the single metal catalysts Fe-NC (0.54%) and Co-NC (0.23%), which indicates that the metal loading of the catalyst is far larger than that of other single metals, and indicates that the catalyst prepared by the method is beneficial to improving the metal loading of the catalyst.
In the drawings of the invention:
FIG. 1 is Fe1-x/Cox-NC bimetallic oxygen reductionSchematic synthesis of the catalyst.
FIG. 2 a) SEM picture of Fe-ZIF-8; b) SEM picture of Co-ZIF-8; c) fe0.1/Co0.9SEM picture of ZIF-8; d) SEM picture of Fe-NC; e) SEM image of Co-NC; f) fe0.1/Co0.9-SEM picture of NC; g. h) are each Fe0.1/Co0.9-TEM and high angular ring dark field images of the NC; i) fe0.1/Co0.9Distribution diagram of Fe, Co, C, N elements of NC.
FIG. 3a shows Fe-ZIF-8, Co-ZIF-8 and Fe0.1/Co0.9-XRD pattern of ZIF-8 precursor;
FIG. 3b shows Fe-NC, Co-NC and Fe0.1/Co0.9-XRD pattern of NC catalyst.
FIG. 4a shows Fe-NC, Co-NC and Fe0.1/Co0.9-a raman map of the NC;
FIG. 4b is Fe0.1/Co0.9XPS plots of NC.
TABLE 1Fe-NC, Co-NC, Fe0.1/Co0.9ICP-MS of-NC catalyst
Example 9
Electrochemical oxygen Reduction (RDE) test:
5mg of Fe are weighed1-x/CoxDispersing NC catalyst and 20% commercial Pt/C catalyst into 1mL mixed solution of ethanol and Nafion (2.5 wt%), ultrasonically dispersing uniformly, transferring 20 muL (5 ul Pt/C) onto the surface of a glassy carbon electrode, and airing at room temperature to obtain the catalyst electrode, wherein the loading capacity of the catalyst electrode is 0.510mg/cm2. Fe obtained by using the Pine electrochemical workstation of the United states1-x/CoxNC samples and Pt/C catalysts were tested for oxygen reduction activity. The oxygen reduction scanning rate is 10mV/s, and the electrolyte is O2And N2Saturated 0.1M HClO4An aqueous solution, the potential window is 1.0-0V (vs. RHE). With the resultant Fe1-x/Coxthe-NC catalyst and Pt/C catalyst electrodes are working electrodes, the Pt net is a counter electrode, the Ag/AgCl is a reference electrode,separate testing of different catalysts at O2And N2Saturated 0.1M HClO4Oxygen reduction activity of aqueous solution, wherein in N2The test in (1) was to subtract out the other background of the catalyst.
Example 10
Rotating Disk Electrode (RRDE) test:
5mg of Fe are weighed0.1/Co0.9Dispersing NC catalyst and 20% commercial Pt/C catalyst into 1mL mixed solution of ethanol and Nafion (2.5 wt%), ultrasonically dispersing uniformly, transferring 20 muL (5 ul Pt/C) onto the surface of a glassy carbon electrode, and airing at room temperature to obtain the catalyst electrode, wherein the loading capacity of the catalyst electrode is 0.510mg/cm2. Fe obtained by using the Pine electrochemical workstation of the United states0.1/Co0.9The NC samples and the Pt/C catalyst were subjected to the RRDE test. The oxygen reduction scanning rate is 10mV/s, and the electrolyte is O2And N2Saturated 0.1M HClO4An aqueous solution, a potential window of 1.0 to 0V (vs. RHE), and an applied ring voltage of 1.2V (vs. RHE). With the resultant Fe0.1/Co0.9The electrodes of the-NC catalyst and the Pt/C catalyst are working electrodes, the Pt net is a counter electrode, the Ag/AgCl is a reference electrode, and different catalysts are respectively tested in O2And N2Saturated 0.1M HClO4Oxygen reduction activity of aqueous solution, wherein in N2The test in (1) was to subtract out the other background of the catalyst.
Example 11
And (3) stability testing:
5mg of Fe are weighed0.1/Co0.9Dispersing NC catalyst and 20% commercial Pt/C catalyst into 1mL mixed solution of ethanol and Nafion (2.5 wt%), ultrasonically dispersing uniformly, transferring 20 muL (5 ul Pt/C) onto the surface of a glassy carbon electrode, and airing at room temperature to obtain the catalyst electrode, wherein the loading capacity of the catalyst electrode is 0.510mg/cm2. Fe obtained by using the Pine electrochemical workstation of the United states0.1/Co0.9NC samples and Pt/C catalysts were subjected to stability tests. Before and after 5000 circles of test, the oxygen reduction activity of the catalyst is respectively tested, wherein the oxygen reduction scanning rate is 10mV/s, and the electrolyte is O2And N2Saturated 0.1M HClO4An aqueous solution with a potential window of 1.0-0V (vs. RHE); the scanning speed of 5000-circle potential cycle test is 100mV/s, and the electrolyte is O20.1M HClO of4The potential window of the aqueous solution is 1.0-0.6V (vs. RHE). With the resultant Fe0.1/Co0.9the-NC catalyst and Pt/C catalyst electrodes are working electrodes, the Pt net is a counter electrode, and the Ag/AgCl is a reference electrode.
Example 12
Testing the timing current:
5mg of Fe are weighed0.1/Co0.9Dispersing NC catalyst and 20% commercial Pt/C catalyst into 1mL mixed solution of ethanol and Nafion (2.5 wt%), ultrasonically dispersing uniformly, transferring 20 muL (5 ul Pt/C) onto the surface of a glassy carbon electrode, and airing at room temperature to obtain the catalyst electrode, wherein the loading capacity of the catalyst electrode is 0.510mg/cm2. Fe obtained by using the Pine electrochemical workstation of the United states0.1/Co0.9The NC sample and the Pt/C catalyst were subjected to chronoamperometric test in which the test voltage was fixed at 0.7V (vs. RHE), the number of revolutions was 400rpm, the test time was 40000s, and the electrolyte was O2Saturated 0.1M HClO4Aqueous solution of Fe0.1/Co0.9the-NC catalyst and Pt/C catalyst electrodes are working electrodes, the Pt net is a counter electrode, and the Ag/AgCl is a reference electrode.
FIG. 5a is a graph of various bis-non-noble metal oxygen reduction catalysts prepared at 0.1M HClO4Oxygen reduction profile in solution; FIG. 5b shows the best Fe0.1/Co0.9NC bimetallic oxygen reduction catalyst and commercial Pt/C at 0.1M HClO4Oxygen reduction profile in solution.
FIG. 6 shows the best Fe0.1/Co0.9NC bimetallic oxygen reduction catalyst and commercial Pt/C catalyst at 0.1M HClO4Hydrogen peroxide (H) in solution2O2) Yield and electron transfer number.
FIG. 7a is Fe0.1/Co0.9-oxygen reduction profiles before and after 5000 cycles for NC oxygen reduction catalysts and commercial Pt/C catalysts; FIG. 7b is Fe0.1/Co0.9Current-time for NC oxygen reduction catalyst and for commercial Pt/C catalyst(i-t) diagram.
It should be understood that the above detailed description of the embodiments of the present invention with reference to the preferred embodiments is illustrative and not restrictive, and it should not be considered that the detailed description of the embodiments of the present invention is limited thereto, and it should be understood that those skilled in the art to which the present invention pertains that modifications may be made to the embodiments described in the embodiments or that equivalents may be substituted for some of the features thereof without departing from the spirit of the present invention and the scope of the patent protection is defined by the claims to be filed with the present invention.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst is characterized by comprising the following steps: dissolving 2-methylimidazole in a methanol solution to obtain a solution named as A solution; dissolving zinc nitrate hexahydrate in a methanol solution to obtain a solution named as a solution B; adding the solution B into the solution A under the stirring condition, stirring at room temperature to obtain a white suspension ZIF-8, adding an iron precursor and a cobalt precursor into the suspension, stirring, transferring the mixture into polytetrafluoroethylene for hydrothermal reaction, centrifuging the obtained product, washing the product with ethanol for three times, and drying the product in vacuum; the precursor obtained is denoted as Fe1-x/Cox-ZIF-8, x ═ 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1; transferring the product into a porcelain boat, and placing the porcelain boat into a tubular furnace for heat treatment to obtain Fe, Co bimetal doped ZIF-8 derived non-noble metal catalyst Fe1-x/Cox-NC, wherein x is 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1.
2. The preparation method of the Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst according to claim 1, which is characterized by comprising the following steps: the iron precursor is iron (III) acetylacetonate.
3. The preparation method of the Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst according to claim 1, which is characterized by comprising the following steps: the cobalt precursor is cobalt (II) acetylacetonate.
4. The preparation method of the Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst according to claim 1, which is characterized by comprising the following steps: the mixed solution A is prepared by adding 1.313-1.315 g of 2-methylimidazole into 14.5-15.5 mL of methanol; the mixed solution B is prepared by adding 1.18-1.20 g of zinc nitrate hexahydrate into 29.5-30.5mL of methanol.
5. The preparation method of the Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst according to claim 1, which is characterized by comprising the following steps: the stirring time of the solution B after being added to the solution A at room temperature is 24 hours.
6. The preparation method of the Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst according to claim 1, which is characterized by comprising the following steps: the molar ratio of the added iron (III) acetylacetonate to cobalt (II) acetylacetonate is (1-x)/x, wherein the molar ratio of the total amount of iron and cobalt to the zinc in the zinc nitrate hexahydrate is 1/6, i.e., (Fe + Co)/Zn is 1/6.
7. The preparation method of the Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst according to claim 1, which is characterized by comprising the following steps: the heat treatment conditions are as follows: the temperature was raised to 900 ℃ at a rate of 5 ℃ per minute under nitrogen atmosphere and held for 3 h.
8. The preparation method of the Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst according to claim 1, which is characterized by comprising the following steps: the vacuum drying temperature was 60 ℃.
9. The process of any one of claims 1 to 8Fe and Co bimetal doped ZIF-8 derived Fe/Co-NC non-noble metal catalyst Fe prepared by the preparation method1-x/Cox-NC, wherein x is 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1.
10. Fe, Co bimetal doped ZIF-8 derived Fe as claimed in claim 71-x/Cox-NC non-noble metal catalyst is applied to the cathode of the proton exchange membrane fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110222953.2A CN113013428A (en) | 2021-02-26 | 2021-02-26 | Preparation method and application of Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110222953.2A CN113013428A (en) | 2021-02-26 | 2021-02-26 | Preparation method and application of Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113013428A true CN113013428A (en) | 2021-06-22 |
Family
ID=76386763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110222953.2A Pending CN113013428A (en) | 2021-02-26 | 2021-02-26 | Preparation method and application of Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113013428A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113745532A (en) * | 2021-07-01 | 2021-12-03 | 深圳大学 | Oxygen reduction electrocatalyst and preparation method and application thereof |
| CN114188558A (en) * | 2021-11-29 | 2022-03-15 | 西安理工大学 | A kind of preparation method of using oxygen vacancy to modify Fe-NC catalyst |
| CN114267847A (en) * | 2021-12-15 | 2022-04-01 | 常州大学 | A Novel Bimetallic Oxygen Reduction Electrocatalyst |
| CN114361483A (en) * | 2022-01-06 | 2022-04-15 | 北京化工大学 | An iron-based bimetallic porous oxygen reduction catalyst with strong acid tolerance |
| CN114497576A (en) * | 2022-01-19 | 2022-05-13 | 佛山仙湖实验室 | Low-cost ordered porous oxygen reduction catalyst and preparation method thereof |
| CN114614032A (en) * | 2022-03-18 | 2022-06-10 | 江苏索普化工股份有限公司 | Anode composite nano catalyst material of methanol fuel cell and preparation method and application thereof |
| CN114678543A (en) * | 2022-03-28 | 2022-06-28 | 江苏大学 | Low-temperature liquid phase preparation method of high-activity metal-nitrogen-carbon electrocatalyst |
| CN115216790A (en) * | 2022-08-08 | 2022-10-21 | 郑州轻工业大学 | A kind of preparation method and application of Zn-MOF@Co2+ derivative material |
| CN115337964A (en) * | 2022-08-24 | 2022-11-15 | 浙江工业大学 | Cobalt-iron modified ZIF-8 composite material and preparation method and application thereof |
| CN116435527A (en) * | 2023-05-30 | 2023-07-14 | 四川轻化工大学 | Oxygen-enriched vacancy carbon-oxygen reduction catalyst and preparation method and application thereof |
| CN118016915A (en) * | 2024-02-07 | 2024-05-10 | 深圳大学 | Preparation method of single-atom catalyst for regulating the size of carbon particles with three-dimensional ordered pore structure |
| WO2024222337A1 (en) * | 2023-04-27 | 2024-10-31 | 安徽理工大学 | Ferrocenyl-doped mof-derived metal carbide electrocatalyst, preparation method therefor and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953135A (en) * | 2015-04-30 | 2015-09-30 | 北京化工大学 | N-doped carbon nano tube loaded cobalt-based electro-catalytic material and preparation method thereof |
| EP3524574A1 (en) * | 2018-02-13 | 2019-08-14 | Gaznat SA, Société pour l'pprovisionnement et le transport du gaz naturel en Suisse Romande | Fe-n-c catalyst, method of preparation and uses thereof |
| CN111952610A (en) * | 2020-08-24 | 2020-11-17 | 兰州大学 | FeCo-doped ZIF8 self-derived cnts@FeCo-NC bifunctional catalyst |
-
2021
- 2021-02-26 CN CN202110222953.2A patent/CN113013428A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104953135A (en) * | 2015-04-30 | 2015-09-30 | 北京化工大学 | N-doped carbon nano tube loaded cobalt-based electro-catalytic material and preparation method thereof |
| EP3524574A1 (en) * | 2018-02-13 | 2019-08-14 | Gaznat SA, Société pour l'pprovisionnement et le transport du gaz naturel en Suisse Romande | Fe-n-c catalyst, method of preparation and uses thereof |
| CN111952610A (en) * | 2020-08-24 | 2020-11-17 | 兰州大学 | FeCo-doped ZIF8 self-derived cnts@FeCo-NC bifunctional catalyst |
Non-Patent Citations (1)
| Title |
|---|
| KE FAN等: "Ultrafine iron-cobalt nanoparticles embedded in nitrogen-doped porous carbon matrix for oxygen reduction reaction and zinc-air batteries", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113745532A (en) * | 2021-07-01 | 2021-12-03 | 深圳大学 | Oxygen reduction electrocatalyst and preparation method and application thereof |
| CN114188558A (en) * | 2021-11-29 | 2022-03-15 | 西安理工大学 | A kind of preparation method of using oxygen vacancy to modify Fe-NC catalyst |
| CN114267847B (en) * | 2021-12-15 | 2024-01-23 | 常州大学 | Bimetallic oxygen reduction electrocatalyst |
| CN114267847A (en) * | 2021-12-15 | 2022-04-01 | 常州大学 | A Novel Bimetallic Oxygen Reduction Electrocatalyst |
| CN114361483A (en) * | 2022-01-06 | 2022-04-15 | 北京化工大学 | An iron-based bimetallic porous oxygen reduction catalyst with strong acid tolerance |
| CN114497576A (en) * | 2022-01-19 | 2022-05-13 | 佛山仙湖实验室 | Low-cost ordered porous oxygen reduction catalyst and preparation method thereof |
| CN114497576B (en) * | 2022-01-19 | 2024-05-14 | 佛山仙湖实验室 | Low-cost ordered porous oxygen reduction catalyst and preparation method thereof |
| CN114614032A (en) * | 2022-03-18 | 2022-06-10 | 江苏索普化工股份有限公司 | Anode composite nano catalyst material of methanol fuel cell and preparation method and application thereof |
| CN114678543A (en) * | 2022-03-28 | 2022-06-28 | 江苏大学 | Low-temperature liquid phase preparation method of high-activity metal-nitrogen-carbon electrocatalyst |
| CN115216790A (en) * | 2022-08-08 | 2022-10-21 | 郑州轻工业大学 | A kind of preparation method and application of Zn-MOF@Co2+ derivative material |
| CN115337964A (en) * | 2022-08-24 | 2022-11-15 | 浙江工业大学 | Cobalt-iron modified ZIF-8 composite material and preparation method and application thereof |
| CN115337964B (en) * | 2022-08-24 | 2024-03-26 | 浙江工业大学 | A cobalt-iron modified ZIF-8 composite material and its preparation method and application |
| WO2024222337A1 (en) * | 2023-04-27 | 2024-10-31 | 安徽理工大学 | Ferrocenyl-doped mof-derived metal carbide electrocatalyst, preparation method therefor and use thereof |
| CN116435527B (en) * | 2023-05-30 | 2024-04-16 | 四川轻化工大学 | Oxygen-enriched vacancy carbon-oxygen reduction catalyst and preparation method and application thereof |
| CN116435527A (en) * | 2023-05-30 | 2023-07-14 | 四川轻化工大学 | Oxygen-enriched vacancy carbon-oxygen reduction catalyst and preparation method and application thereof |
| CN118016915A (en) * | 2024-02-07 | 2024-05-10 | 深圳大学 | Preparation method of single-atom catalyst for regulating the size of carbon particles with three-dimensional ordered pore structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113013428A (en) | Preparation method and application of Fe and Co bimetal doped mesoporous carbon-oxygen reduction catalyst | |
| CN105107536B (en) | A kind of preparation method of polyhedron shape phosphatization cobalt water electrolysis hydrogen production catalyst | |
| CN113437314B (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| CN112647095B (en) | Atomically dispersed bimetallic site anchored nitrogen-doped carbon material and preparation and application thereof | |
| CN113235104B (en) | ZIF-67-based lanthanum-doped cobalt oxide catalyst and preparation method and application thereof | |
| CN107321368B (en) | A kind of Au atom-modified CoSe2 nanobelt and its preparation method and application | |
| CN110127655B (en) | Method for preparing biomass carbon-supported cobalt phosphide electrode material by one-step calcination method | |
| CN106111177A (en) | The nitrogen functional carbon material of a kind of carrying transition metal chalcogenide and preparation thereof and application | |
| CN110215928A (en) | A kind of preparation method of sulfur doping phosphatization Ni nanopowders and its application in electrolysis water | |
| CN113737200B (en) | Water splitting catalyst and its prepn and application | |
| CN113663712A (en) | Efficient bimetallic OER catalyst derived based on double-template method and preparation method thereof | |
| CN110699701B (en) | Foam nickel loaded with metal nickel and vanadium trioxide compound and preparation method and application thereof | |
| CN108682873B (en) | A kind of Ru-MoO3-x/ rGO composite material and preparation method and application | |
| CN108579785A (en) | Efficient visible light decomposes aquatic products H2Sulfur doping carbonitride preparation method | |
| CN113463128B (en) | Water splitting catalyst and its preparation method and application | |
| CN109616670B (en) | Cobalt sulfide with controllable morphology and preparation method thereof, and cobalt sulfide/nitrogen-doped carbon nanotube catalyst and application thereof | |
| CN111215056A (en) | Preparation method and application of low-load Pd/hollow carbon sphere oxygen reduction electrocatalyst | |
| CN109004239A (en) | A kind of Co of P doping3S4Nanometer sheet and its preparation method and application | |
| CN112058297B (en) | Nickel-based electro-catalytic material and preparation method and application thereof | |
| CN113136591B (en) | Ruthenium and nitrogen co-doped porous carbon catalyst, preparation method thereof and application thereof in hydrogen electrolysis | |
| CN113201759B (en) | A three-dimensional porous carbon-supported bismuth sulfide/bismuth oxide composite catalyst and its preparation method and application | |
| CN112002909B (en) | A kind of preparation method based on Zn-Cu-N co-doped carbon composites | |
| CN109012683B (en) | A kind of preparation method of cobalt molybdate hollow microsphere electrocatalyst | |
| CN114592210B (en) | Preparation method and application of Co3O4-RuO2 composite material | |
| CN113174612B (en) | Carbon tube composite material loaded with Ni nano-particles and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210622 |
|
| RJ01 | Rejection of invention patent application after publication |