CN115939422B - Preparation method of biomass carbon composite material for modification of cerium-aluminum organic frame of fuel cell cathode - Google Patents
Preparation method of biomass carbon composite material for modification of cerium-aluminum organic frame of fuel cell cathode Download PDFInfo
- Publication number
- CN115939422B CN115939422B CN202211232269.3A CN202211232269A CN115939422B CN 115939422 B CN115939422 B CN 115939422B CN 202211232269 A CN202211232269 A CN 202211232269A CN 115939422 B CN115939422 B CN 115939422B
- Authority
- CN
- China
- Prior art keywords
- fuel cell
- cerium
- carbon composite
- biomass carbon
- drying
- 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.)
- Active
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002028 Biomass Substances 0.000 title claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 23
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000012986 modification Methods 0.000 title claims description 11
- 230000004048 modification Effects 0.000 title claims description 11
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 51
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 51
- 235000018262 Arachis monticola Nutrition 0.000 claims description 51
- 235000020232 peanut Nutrition 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 22
- 239000013384 organic framework Substances 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 15
- 235000013824 polyphenols Nutrition 0.000 claims description 15
- 241000196324 Embryophyta Species 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 10
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- 239000010411 electrocatalyst Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229920000557 Nafion® Polymers 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 2
- 241001553178 Arachis glabrata Species 0.000 claims 12
- 239000010406 cathode material Substances 0.000 claims 2
- 239000000758 substrate Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 61
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 11
- 150000002910 rare earth metals Chemical class 0.000 abstract description 8
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 abstract 1
- 244000105624 Arachis hypogaea Species 0.000 description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000012360 testing method Methods 0.000 description 19
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 238000002484 cyclic voltammetry Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000002994 raw material Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical class [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 238000000970 chrono-amperometry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- -1 rare earth ions Chemical class 0.000 description 3
- 239000001648 tannin Substances 0.000 description 3
- 235000018553 tannin Nutrition 0.000 description 3
- 229920001864 tannin Polymers 0.000 description 3
- 240000002470 Amphicarpaea bracteata Species 0.000 description 2
- 235000000073 Amphicarpaea bracteata Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- IKMDFBPHZNJCSN-UHFFFAOYSA-N Myricetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC(O)=C(O)C(O)=C1 IKMDFBPHZNJCSN-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940116852 myricetin Drugs 0.000 description 1
- PCOBUQBNVYZTBU-UHFFFAOYSA-N myricetin Natural products OC1=C(O)C(O)=CC(C=2OC3=CC(O)=C(O)C(O)=C3C(=O)C=2)=C1 PCOBUQBNVYZTBU-UHFFFAOYSA-N 0.000 description 1
- 235000007743 myricetin Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- Catalysts (AREA)
Abstract
The invention discloses a biomass carbon composite material for modifying a cerium-aluminum organic frame of a fuel cell cathode and a preparation method thereof, wherein the active substance of the nano material is Ce-Al@C PH‑BT. Fuel cell catalysts are currently commonly faced with the problems of single precursor and high synthesis cost, whereas commercial platinum carbon catalysts are not only costly but also poor in stability. To overcome these problems, the present invention developed a rare earth-based metal organic framework nano negative electrode material for proton fuel cell catalysts based on the unique structure of celi-MOF. The material exhibits a uniform laminated lamellar structure, has a high potential and good limiting current, and has excellent stability. The adopted synthesis method has the advantages of simple operation, low cost and short preparation time, and is favorable for realizing large-scale commercial production.
Description
Technical Field
The invention belongs to the technical field of fuel cell catalysts, and particularly relates to a rare earth-based organic framework nano electro-catalytic material prepared by taking peanut shells as a carrier, and a preparation method and application thereof.
Background
In the rapid development of economic globalization and the increasingly updated modern high-tech products, the consumption of fossil energy is gradually increased, a great deal of pollution is generated, and the environment is extremely unfavorable. Based on these problems, the creation and development of new green renewable energy and high-efficiency energy conversion and storage devices has become an indispensable task. As a new power generation device, fuel Cells (FCs) have the advantages of Fuel diversity, high Fuel energy density, cleanness, environmental protection, low noise and the like. Biomass is an energy source, generally refers to various plants and animal and plant derivatives, and biomass contacted in daily life of people mainly comes from forestry, agriculture and industrial wastes. Biomass contains a large amount of energy and has very large yield, and biomass can be produced in a global amount of 1.0 x 1011 tons each year, which shows that the biomass is an ideal renewable energy source. However, the utilization efficiency of biomass is not high, a large amount of agricultural and forestry waste is directly burnt or discarded, and meanwhile, the problems of resource waste, environmental pollution and the like are caused. The biomass activated carbon raw materials are low in price and wide in sources, and comprise peanut shells, coconut shells, rice hulls, corn stalks, bamboo, pine and the like.
The rare earth ions ionize to a positive trivalent ion state, losing first 6s electrons, then 4f and 5d electrons. The energy level electrons of 4f, 5d and 6s have energy close to each other, so that the energy level relation of rare earth ions is particularly complex. Rare earth ions have changeable coordination numbers, show very rich optical, electric, magnetic and other properties, and are important elements in a plurality of novel materials. With the development of chemical research in recent years, rare earth metal organic frameworks Ce-MOFs are widely applied to the fields of gas adsorption, storage, separation, heterogeneous catalysis, electrochemistry, biomedicine, magnetism and fluorescence sensing as a porous material with novel structure and excellent performance, and more scientists are actively exploring and researching new rare earth complex materials and applications thereof.
In the invention, a series of rare earth-based organic frame-supported anode catalysts prepared by high-temperature heat treatment with different CeAl loadings are designed and synthesized by taking peanut shells as a carbon source. Electrochemical test research shows that when the CeAl-MOFs@BT/PH catalyst is in 0.1M KOH and the potential is equal to 0.1V, the limiting current density is close to that of a commercial Pt/C catalyst, meanwhile, the reaction process of ORR in an alkaline medium is mainly 4 electrons, and in addition, the catalyst has better stability than that of the commercial Pt/C catalyst.
Disclosure of Invention
The invention aims to solve the problems of the prior fuel cell catalyst, overcome the defects of the prior art, and the prior fuel cell catalyst generally faces the problems of single precursor and synthesis cost, and has the defects of high cost, toxicity and the like of a platinum-based catalytic material; the biomass carbon composite electrocatalyst material modified by the cerium-aluminum organic framework for the fuel cell cathode has high potential, good limiting current and good stability.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the preparation method of the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the fuel cell cathode comprises the following steps:
(1) Firstly, preparing a CeAl-MOF polymer substrate, weighing 1.6810g of trimesic acid to be dissolved in 30mL of absolute ethyl alcohol, dissolving 2.3158g of cerium nitrate hexahydrate and 1.0003g of aluminum nitrate nonahydrate in 30mL of deionized water for mixing, carrying out ultrasonic treatment at room temperature, pouring an ultrasonic trimesic acid solution into a mixed solution of cerium nitrate hexahydrate and aluminum nitrate nonahydrate for stirring, putting the solution into a constant-temperature oscillator for oscillation after stirring, washing the obtained product with deionized water and ethanol for several times respectively, and drying to obtain the CeAl-MOF;
(2) Washing peanut shells with deionized water for several times to remove ash attached to the surfaces of the peanut shells, placing the peanut shells in an oven at 80 ℃ for drying after the peanut shells are washed cleanly, and then crushing the peanut shells into powder and sieving the powder. Soaking the treated peanut shells in distilled water for 12 hours, performing suction filtration, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 80 ℃ to obtain the peanut shell;
(3) Dispersing the CeAl-MOF and plant polyphenol prepared in the step (1) in deionized water, and performing ultrasonic treatment at room temperature; the multiple ortho-phenolic hydroxyl groups in the plant polyphenol can be used as a multi-radical ligand to carry out complexation reaction with metal ions to form a stable five-membered ring chelate. The complex has multiple polyphenol coordination groups, strong complexing ability and stable complex, and most metal ions form precipitation after being complexed with polyphenol. Under alkaline conditions, polyphenols and metal ions tend to form multi-complex compounds. Polyphenols react with certain high valence metal ions such as Cr 6+、Fe3+, and the metal ions are reduced from a high valence state to a low valence state while complexing. The grabbing capacities of different plant polyphenols on different metal ions are different; the plant polyphenol used in the invention is myricetin, including but not limited to tannins (such as tannins, valonen tannins, larch and the like);
(4) Dispersing 1.0g of the peanut shells treated in the step (2) into the solution in the step (3);
(5) Washing the product obtained in the step (4) with deionized water and ethanol solution for 3 times respectively, centrifuging, and drying the product in an oven to obtain a precursor of CeAl-MOFs@BT/PH;
(6) And uniformly dispersing a proper amount of dried precursor at the bottom of a porcelain ark, placing the porcelain ark in a tube furnace for high-temperature pyrolysis under the argon or nitrogen atmosphere, and naturally cooling to room temperature to obtain the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material Ce-Al@C PH-BT for the fuel cell cathode.
The ultrasonic time of trimesic acid and absolute ethyl alcohol, cerium nitrate hexahydrate and aluminum nitrate nonahydrate and deionized water in the step (1) is 5-10 minutes, the stirring time on a magnetic stirrer is 30 minutes, the trimesic acid and absolute ethyl alcohol are vibrated for 1h at 60 ℃, and the trimesic acid and aluminum nitrate nonahydrate are dried for 15-20h at 60-80 ℃.
The soaking time of the peanut shells in the step (2) is 12 hours, and the peanut shells are dried at 80 ℃ for 12 hours.
The mass ratio of the plant polyphenol to the CeAl-MOF in the step (3) is 1:1, and the ultrasonic time is 30-40min;
the adding amount of the plant polyphenol in the step (3) is the same as that in the step (2), and the ultrasonic time is 30-40min;
the stirring time of the step (4) on a magnetic stirrer at normal temperature is 90min;
the drying temperature in the step (5) is 60-80 ℃ and the drying time is 48 hours;
and (3) pyrolysis, namely directly heating to 500 ℃ at a heating rate of 5 ℃/min under pure argon or nitrogen atmosphere, keeping the temperature for 30min, heating to 800 ℃ at the same heating rate, keeping for 2h, and naturally cooling to room temperature.
The invention has the technical advantages and beneficial effects that:
(1) The invention adopts a simple and convenient synthesis method and has the characteristics of economy, high efficiency and environmental protection. The synthesis steps are simple and convenient to operate, the reaction conditions are mild and easy to control, and the preparation cost is low. The prepared oxygen reduction catalyst not only shows high potential and good limiting current, but also has excellent stability.
(2) The prepared rare earth-based organic framework anode material catalyst taking peanut shells as a carbon source has an initial potential of 1.0V, a half-wave potential of 0.67V, a limiting current density of 7.83mA cm -2 which is slightly higher than that of a commercial platinum carbon catalyst, and has better electrocatalytic stability than that of the commercial Pt/C catalyst, and the catalyst is integrally better than the commercial platinum carbon catalyst.
Drawings
FIG. 1 is a scanning electron microscope image of a Ce-Al@C PH-BT nanocomposite;
FIG. 2 is a graph of specific surface area of Ce-Al@C PH-BT;
FIG. 3 is a pore size distribution plot of Ce-Al@C PH-BT;
FIG. 4 is a graph of cyclic voltammetry characteristics of a Ce-Al@C PH-BT catalyst (test voltage sweep range: -0.9-0.1V, sweep rate: 50 mV/s);
FIG. 5 is a linear cyclic voltammogram of different additives in 0.1M KOH saturated with O 2 (scan range-0.9-0.1V, scan rate 10 mv/s);
FIG. 6 is a linear cyclic voltammogram of varying ratios of Ce/Al in an organic framework in 0.1M KOH saturated with O 2 (scan range-0.9-0.1V, scan rate 10 mv/s).
FIG. 7 is a linear cyclic voltammogram (scan range-0.9-0.1V, scan rate 10 mv/s) of varying temperatures in O 2 saturated 0.1M KOH at a mass ratio of Ce/Al in CeAl-MOF of 2:1 for a peanut shell of 1.0 g;
FIG. 8 is a linear cyclic voltammogram (scan rate: 10 mV/s) of a Ce-Al@C PH-BT catalyst at various speeds (400, 625, 900, 1225, 1600, 2025 rmp);
FIG. 9 is a graph of methanol tolerance tests of a Ce-Al@C PH-BT catalyst and a commercial Pt/C (20wt% Pt) catalyst measured by a potentiostatic chronoamperometry;
FIG. 10 is a graph of stability tests of a Ce-Al@C PH-BT catalyst and a commercial Pt/C (20 wt% Pt) catalyst measured by a potentiostatic chronoamperometry.
Detailed Description
The invention provides a method for preparing a Ce-Al@C PH-BT catalyst, which comprises the following steps:
(1) Firstly, preparing a CeAl organic frame, weighing 1.6810g of trimesic acid to be dissolved in 30mL of absolute ethyl alcohol, dissolving 2.3158g of cerium nitrate hexahydrate and 1.0003g of aluminum nitrate nonahydrate in 30mL of deionized water for mixing, carrying out ultrasonic treatment at room temperature, pouring an ultrasonic trimesic acid solution into a mixed solution of cerium nitrate hexahydrate and aluminum nitrate nonahydrate for stirring, putting the solution into a constant-temperature oscillator for oscillation after stirring, washing the obtained product with deionized water and ethanol for a plurality of times respectively, and drying to obtain the CeAl-MOF;
(2) Preparing peanut shell precursor, namely washing peanut shells with deionized water for a plurality of times to remove ash attached to the surfaces of the peanut shells, placing the peanut shells in an oven at 80 ℃ after washing, and crushing the peanut shells into powder after drying for 72 hours. And then grinding the peanut shell powder, sieving the ground peanut shell powder by a 200-mesh sieve, taking the peanut shell powder with the particle size smaller than 200 meshes, drying the peanut shell powder at 80 ℃ for 24 hours, and cooling the dried peanut shell powder to room temperature after the drying is finished, thus obtaining the peanut shell powder. Soaking the raw materials in distilled water for 12 hours, filtering, washing the raw materials with deionized water and absolute ethyl alcohol for 3 times respectively, and drying the raw materials in an oven at 80 ℃ for 12 hours.
(3) Dispersing 0.5g of the CeAl-MOF prepared in the step (1) and 0.5g of plant polyphenol in 50ml of deionized water respectively, carrying out ultrasonic treatment at room temperature for 5 minutes, and then pouring the plant polyphenol solution into the CeAl-MOF again for ultrasonic treatment for 30 minutes;
(4) Adding 1.0g of peanut shells into the solution in the step (2), and stirring for 90min at room temperature;
(5) Washing and centrifuging the product obtained in the step (3) by using deionized water and ethanol solution, and drying the product in an oven at 80 ℃ for 48 hours to obtain a CeAl-MOFs@BT/PH precursor;
(6) Uniformly dispersing a proper amount of dried precursor at the bottom of a porcelain ark, placing the porcelain ark in a tube furnace, carrying out high-temperature pyrolysis under an argon or nitrogen atmosphere, directly heating to 500 ℃ at a heating rate of 5 ℃/min under a pure nitrogen atmosphere, keeping the temperature for 30 minutes, heating to 800 ℃ at the same heating rate, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain Ce-Al@C PH-BT.
The invention provides a preparation method of a cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for a fuel cell cathode and application of the material as an oxygen reduction catalyst.
The active substance is abbreviated as Ce-Al@C PH-BT, and has a strip-shaped lamellar structure.
The invention uses carbon rod as counter electrode, saturated silver chloride electrode (Ag/AgCl) as reference electrode, and glassy carbon electrode as working electrode.
The concentration of Nafion added in the preparation process of the catalyst is 5 percent and the dosage is 15ul.
The catalyst preparation according to the invention was to prepare a catalyst ink (ink) by weighing 4mg of the mixture solution (deionized water 235uL, isopropanol 735uL and 5wt% Nafion solution 15 uL) dispersed in 1mL with a balance. Then 28uL of ink is gradually dripped on the surface of a glassy carbon electrode (catalyst loading capacity is 0.25mg cm -2), and after natural drying, the electrocatalytic performance test is carried out.
All electrocatalytic performance tests described herein were carried out in 0.1M KOH (ph=13.62) electrolyte, and the experimentally measured potential was converted to a potential relative to the reversible hydrogen electrode (Reversible Hydrogen Electrode, RHE) by the following equation:
E(RHE)＝E(Ag/AgCl)+0.059*pH+0.2224
the potential values referred to in the present invention are all potentials with respect to the reversible hydrogen electrode.
The catalyst of the present invention requires 3 CV activations before electrochemical tests are performed.
The catalyst disclosed by the invention is tested at normal temperature, so that the influence of large temperature variation difference on the performance of the catalyst is prevented.
The invention will be further illustrated with reference to specific examples. For a further understanding of the present invention, preferred embodiments of the invention are described in conjunction with the examples, but it is to be understood that these descriptions are merely intended to illustrate further features and advantages of the invention and are not limiting of the claims of the invention. Further, it is understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents are intended to fall within the scope of the present invention as defined by the appended claims.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Example 1:
This example shows a method for preparing a rare earth-based organic framework anode electrocatalyst material Ce-al@c PH-BT with peanut shells as a carbon source.
(1) Firstly, preparing a CeAl organic frame, weighing 1.6810g of trimesic acid to be dissolved in 30mL of absolute ethyl alcohol, dissolving 2.3158g of cerium nitrate hexahydrate and 1.0003g of aluminum nitrate nonahydrate in 30mL of deionized water for mixing, carrying out ultrasonic treatment at room temperature, pouring an ultrasonic trimesic acid solution into a mixed solution of cerium nitrate hexahydrate and aluminum nitrate nonahydrate for stirring, putting the solution into a constant-temperature oscillator for oscillation after stirring, washing the obtained product with deionized water and ethanol for a plurality of times respectively, and drying to obtain the CeAl-MOF;
(2) Preparing peanut shell precursor, namely washing peanut shells with deionized water for a plurality of times to remove ash attached to the surfaces of the peanut shells, placing the peanut shells in an oven at 80 ℃ after washing, and crushing the peanut shells into powder after drying for 72 hours. And then grinding the peanut shell powder, sieving the ground peanut shell powder by a 200-mesh sieve, taking the peanut shell powder with the particle size smaller than 200 meshes, drying the peanut shell powder at 80 ℃ for 24 hours, and cooling the dried peanut shell powder to room temperature after the drying is finished, thus obtaining the peanut shell powder. Soaking the raw materials in distilled water for 12 hours, filtering, washing the raw materials with deionized water and absolute ethyl alcohol for 3 times respectively, and drying the raw materials in an oven at 80 ℃ for 12 hours.
(3) Dispersing 0.5g of the CeAl-MOF prepared in the step (1) and 0.5g of plant polyphenol in 50ml of deionized water respectively, carrying out ultrasonic treatment at room temperature for 5 minutes, and then pouring the plant polyphenol solution into the CeAl-MOF again for ultrasonic treatment for 30 minutes;
(4) Adding 1.0g of peanut shells into the solution in the step (2), and stirring for 90min at room temperature;
(5) Washing and centrifuging the product obtained in the step (3) by using deionized water and ethanol solution, and drying the product in an oven at 80 ℃ for 48 hours to obtain a CeAl-MOFs@BT/PH precursor;
(6) Uniformly dispersing a proper amount of dried precursor at the bottom of a porcelain ark, placing the porcelain ark in a tube furnace, carrying out high-temperature pyrolysis under an argon or nitrogen atmosphere, directly heating to 500 ℃ at a heating rate of 5 ℃/min under a pure nitrogen atmosphere, keeping the temperature for 30min, heating to 800 ℃ at the same heating rate, keeping the temperature for 2h, and naturally cooling to room temperature to obtain Ce-Al@C PH-BT.
The Ce-Al@C PH-BT material obtained in the embodiment is subjected to phase identification and microscopic morphology and structure characterization, namely, a Raman spectrometer, a Fourier transform infrared spectrometer, a powder X-ray diffractometer and an X-ray photoelectron spectrometer are used for carrying out phase identification on the prepared material, and a scanning electron microscope is used for carrying out microscopic morphology and structure characterization on the obtained material.
FIG. 1 is a scanning electron microscope image of a Ce-Al@C PH-BT nanocomposite. As can be seen from the figure, the material exhibits an elongated sheet-like structure.
FIG. 2 is a graph of specific surface area of Ce-Al@C PH-BT nanocomposite. As can be seen from the graph, the specific surface area of the MOF material is 244.88m 2g-1, the specific surface area is larger, the characteristics of the MOF material are met, a typical hysteresis loop in the curve shows that the sample is a mesoporous carbon material, and the sample is represented as a type II isotherm.
FIG. 3 is a pore size distribution plot of Ce-Al@C PH-BT nanocomposite. From the graph, the catalyst has a pore diameter structure of a large amount of mesopores and a small amount of micropores, and the average pore diameter is 2.71nm
Example 2:
The present example shows the electrochemical performance study of rare earth-based organic framework anode electrocatalyst material Ce-al@c PH-BT as catalyst with peanut shell as carbon source.
The invention uses carbon rod as counter electrode, saturated silver chloride electrode (Ag/AgCl) as reference electrode, and glassy carbon electrode as working electrode.
The concentration of Nafion added in the preparation process of the catalyst is 5wt% and the dosage is 15ul.
The electrode pretreatment in the test process of the invention is to add alpha-Al 2O3 electrode polishing powder and a small amount of deionized water on a nylon polishing cloth base, polish the rotary disc electrode back and forth on the electrode in an 8 shape for 10 minutes, then clean the residual powder on the electrode with deionized water, and finally air-dry naturally to finish the treatment.
The preparation method of the catalyst comprises the steps of weighing 4mg of the catalyst, dispersing the catalyst in a 1mL centrifuge tube by using a balance, adding 235uL of deionized water, 735uL of isopropanol and 15uL of 5wt% Nafion solution, and performing ultrasonic treatment at room temperature for 50 minutes to obtain catalyst ink (ink). Then 28uL of ink is gradually dripped on the surface of a glassy carbon electrode (catalyst loading capacity is 0.25mg cm -2), and after natural drying, the electrocatalytic performance test is carried out.
All electrocatalytic performance tests described herein were carried out in 0.1M KOH (ph=13.62) electrolyte, and the experimentally measured potential was converted to a potential relative to the reversible hydrogen electrode (Reversible Hydrogen Electrode, RHE) by the following equation:
E(RHE)＝E(Ag/AgCl)+0.059*pH+0.2224
the potential values referred to in the present invention are all potentials with respect to the reversible hydrogen electrode.
The catalyst of the present invention requires 3 CV activations before electrochemical tests are performed.
The catalyst disclosed by the invention is tested at normal temperature, so that the influence of large temperature variation difference on the performance of the catalyst is prevented.
Nafion added in the preparation process of the catalyst is produced by ALDRICH SIGMA company, and the concentration is 5%.
And (3) sucking 7ul of catalyst by a pipetting gun, dripping the catalyst onto a working electrode, repeating the step for 3 times after waiting for natural airing, and then slowly immersing the working electrode into oxygen saturated 0.1M KOH electrolyte, wherein bubbles are prevented from being generated on the working electrode in the step, and oxygen is continuously introduced into the electrolyte in the whole testing process to ensure oxygen saturation.
The catalyst obtained in this example was subjected to cyclic voltammetry and linear cyclic voltammetry tests using an electrochemical workstation manufactured by Pin, america, a test voltage scan range of-0.9 to 0.1V, a scan rate of 50mV/s, and the cyclic voltammetry test after activation for 3 cycles with a current density of 50mV/s. A linear cyclic voltammetric test was also performed using a Pin electrochemical workstation, with a test voltage sweep ranging from-0.9 to 0.1V and a sweep rate of 50mV/s. The current density of the catalyst material at different rotating speeds can be obtained by rotating speed test, the number of transferred electrons can be obtained by utilizing a K-L equation, the test current density is 10mV/s, and the rotating speeds are 400, 625, 900, 1225, 1600 and 2025rmp. Stability and methanol tolerance are also important indicators of catalyst performance, the test is also performed on an electrochemical workstation, the stability test voltage is-0.189V, and the test duration is 20 000s; the methanol tolerance test voltage was-0.189V for a test period of 1,000 s, and a 2M methanol solution was dropped at 300 s.
FIG. 4 is a graph of cyclic voltammetry characteristics (test voltage sweep range: -0.9-0.1V, sweep rate: 50 mV/s) of a Ce-Al@C PH-BT catalyst with a significant cathodic oxygen reduction peak at 0.66V in an O 2 saturated electrolyte, indicating that a catalytic oxygen reduction reaction has occurred and that the response to oxygen indicates that Ce-Al@C PH-BT has significant oxygen reduction catalytic activity in alkaline solution.
FIG. 5 is a linear cyclic voltammogram of a blank and Ce-Al@C PH-BT catalyst, respectively, (test voltage range: -0.9-0.1V, scan rate: 10 mV/s).
FIG. 6 is a linear cyclic voltammogram of varying proportions of Ce/Al in 0.1M KOH saturated with O 2 (scan range-0.9-0.1V, scan rate 10 mv/s) in an organic framework, from which it can be seen that the limiting current density increases from 4.9mA cm 2 to 7.83mA cm 2 when the Ce/Al addition is 2:1 when the Ce/Al addition is at a heat treatment temperature of 500℃to 800 ℃.
FIG. 7 is a linear cyclic voltammogram of a blank and Ce-Al@C PH-BT catalyst, respectively, (test voltage range: -0.9-0.1V, scan rate: 10 mV/s), with Ce-Al@C PH-BT catalyst performance being optimal when the calcination temperature is raised to 800 ℃.
FIG. 8 is a linear cyclic voltammogram (scan rate: 10 mV/s) of a Ce-Al@C PH-BT catalyst at various speeds (400, 625, 900, 1225, 1600, 2025 rmp) showing that the limiting diffusion current density of the catalyst increases gradually with increasing speed, as the diffusion rate of oxygen is also faster with faster speed, indicating that the oxygen reduction catalytic process is mass transfer controlled, conforming to the first order kinetic reaction.
FIG. 9 is a graph of the methanol tolerance of the best samples Ce-Al@C PH-BT and commercial 20% Pt/C catalyst measured using the i-t technique with 2mL of methanol added to 0.1M KOH electrolyte at 1600rmp at 300 s. From the graph, only a slight change in the limiting current density of Ce-al@c PH-BT can be observed, while the Pt/C catalyst showed a significant change in current density due to methanol oxidation, and after 700 seconds of continued operation, the Ce-al@c PH-BT current density remained stable, while the Pt/C retention decayed to below 50%. The Ce-Al@C PH-BT was demonstrated to be superior to Pt/C in terms of methanol tolerance.
FIG. 10 is a graph showing that the initial current density of the Pt/C catalyst was significantly lost by 23% after 20000s by chronoamperometry test Ce-Al@C PH-BT and Pt/C, while the Ce-Al@C PH-BT catalyst was reduced by 13%, indicating that the catalyst had slightly better stability than the commercial Pt/C catalyst.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a biomass carbon composite material for modifying a cerium-aluminum organic framework of a fuel cell cathode is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) Preparation of CeAl-MOF polymeric substrates: weighing a certain amount of trimesic acid white powder and dissolving the powder in a certain amount of absolute ethyl alcohol; weighing a certain amount of cerium nitrate hexahydrate and aluminum nitrate nonahydrate, dissolving in a certain amount of deionized water, mixing, pouring trimesic acid solution into the mixed solution of cerium nitrate hexahydrate and aluminum nitrate nonahydrate, stirring on a magnetic stirrer, putting the solution into a constant-temperature oscillator for oscillation at a certain temperature after stirring, washing the obtained product with deionized water and ethanol for a plurality of times respectively, and drying at a certain temperature to obtain white powder CeAl-MOF;
(2) Preparing a peanut shell precursor: washing peanut shells with deionized water for several times to remove ash attached to the surfaces of the peanut shells, drying the peanut shells in an oven after the peanut shells are washed cleanly, crushing the peanut shells into powder, sieving the powder, drying the sieved peanut shells in the oven, cooling the dried peanut shells to room temperature, soaking the treated peanut shells in distilled water for 12 hours, carrying out suction filtration, washing the treated peanut shells with deionized water and absolute ethyl alcohol for several times, and drying the treated peanut shells in the oven;
(3) Dispersing the CeAl-MOF prepared in the step (1) and plant polyphenol in deionized water according to a mass ratio of 1:1, and carrying out ultrasonic treatment for 30-40 minutes at room temperature;
(4) Pouring the peanut shells treated in the step (2) into the solution which is subjected to ultrasonic treatment in the step (3), and stirring at room temperature;
(5) Washing and centrifuging the product obtained in the step (4) by using deionized water and ethanol solution, and drying the product in an oven to obtain CeAl-MOFs@BT/PH;
(6) Uniformly dispersing a proper amount of dried precursor at the bottom of a porcelain ark, and placing the porcelain ark in a tube furnace for pyrolysis under argon or nitrogen atmosphere, wherein the pyrolysis process comprises the following steps: directly heating to 500 ℃ at a heating rate of 5 ℃/min under pure argon or nitrogen atmosphere, keeping the temperature for 30 minutes, heating to 800 ℃ at the same heating rate, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the fuel cell cathode.
2. The method for preparing the biomass carbon composite material for modification of the cerium-aluminum organic framework of the fuel cell cathode according to claim 1, which is characterized in that: in the step (1), stirring is carried out on a magnetic stirrer for 30 minutes, shaking is carried out for 1 hour at 60 ℃, and drying is carried out for 15-20 hours at 60-80 ℃.
3. The method for preparing the biomass carbon composite material for modification of the cerium-aluminum organic framework of the fuel cell cathode according to claim 1, which is characterized in that: the drying temperature of the oven in the step (2) is 80 ℃ and the drying time is 12 hours.
4. The method for preparing the biomass carbon composite material for modification of the cerium-aluminum organic framework of the fuel cell cathode according to claim 1, which is characterized in that: the stirring in the step (4) is carried out on a magnetic stirrer at room temperature, and the stirring time is 90 minutes.
5. The method for preparing the biomass carbon composite material for modification of the cerium-aluminum organic framework of the fuel cell cathode according to claim 1, which is characterized in that: in the step (5), the drying temperature is 60-80 ℃ and the drying time is 48 hours.
6. A biomass carbon composite material for modification of a cerium-aluminum organic framework of a fuel cell anode, which is prepared by the preparation method of any one of claims 1 to 5.
7. Use of a cerium-aluminum organic framework modified biomass carbon composite material for a fuel cell anode according to claim 6 in a fuel cell, characterized in that: the biomass carbon composite material for the cerium-aluminum organic framework modification of the fuel cell cathode is used as a part of a cathode material of the fuel cell, and the cathode material is prepared by uniformly mixing the biomass carbon composite material for the cerium-aluminum organic framework modification of the fuel cell cathode with isopropanol, deionized water and Nafion solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211232269.3A CN115939422B (en) | 2022-10-10 | 2022-10-10 | Preparation method of biomass carbon composite material for modification of cerium-aluminum organic frame of fuel cell cathode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211232269.3A CN115939422B (en) | 2022-10-10 | 2022-10-10 | Preparation method of biomass carbon composite material for modification of cerium-aluminum organic frame of fuel cell cathode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115939422A CN115939422A (en) | 2023-04-07 |
| CN115939422B true CN115939422B (en) | 2024-09-17 |
Family
ID=86549552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211232269.3A Active CN115939422B (en) | 2022-10-10 | 2022-10-10 | Preparation method of biomass carbon composite material for modification of cerium-aluminum organic frame of fuel cell cathode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115939422B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109494381A (en) * | 2017-09-12 | 2019-03-19 | 中国科学院大连化学物理研究所 | The monatomic iron-based carbon material of one kind and preparation method and electro-catalysis application |
| CN115084558A (en) * | 2022-07-21 | 2022-09-20 | 福州大学 | Preparation of lanthanum-based organic framework composite modified waste chromium chip derived porous carbon nano anode material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004087264A (en) * | 2002-08-26 | 2004-03-18 | Mitsui Mining & Smelting Co Ltd | Negative electrode material for non-water electrolysis liquid secondary battery, and its manufacturing method |
| KR101341550B1 (en) * | 2012-06-20 | 2013-12-13 | 한국에너지기술연구원 | Preparation method of catalyst for fuel cell electrode using covaporization and preparation method of fuel cell electrode including catalyst prepared by and fuel cell including the same |
| CN105895884B (en) * | 2016-06-13 | 2018-05-15 | 吉林大学 | A kind of method and its application for carrying out surface modification to hydrogen bearing alloy using molybdenum disulfide |
| CN106328960A (en) * | 2016-10-08 | 2017-01-11 | 华南理工大学 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
| WO2019031766A2 (en) * | 2017-08-10 | 2019-02-14 | 주식회사 엘지화학 | Method for forming lithium metal and inorganic material composite thin film and method for pre-lithiation of negative electrode for lithium secondary battery by using same |
| CN108428904B (en) * | 2018-04-04 | 2020-05-08 | 北京航空航天大学 | Cerium-silver-containing hydrotalcite oxygen reduction catalyst and preparation method and application thereof |
| CN112397732A (en) * | 2020-11-13 | 2021-02-23 | 上海海事大学 | ORR catalyst material and preparation method and application thereof |
| CN112952118A (en) * | 2020-12-22 | 2021-06-11 | 华南理工大学 | high-Pt-content high-performance catalyst with high stability and reverse polarity resistance and preparation method thereof |
| CN114784303B (en) * | 2022-04-19 | 2023-10-20 | 福州大学 | Preparation and application of rare earth-based organic framework anode material modified by copper polyphenol supermolecular network interface |
-
2022
- 2022-10-10 CN CN202211232269.3A patent/CN115939422B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109494381A (en) * | 2017-09-12 | 2019-03-19 | 中国科学院大连化学物理研究所 | The monatomic iron-based carbon material of one kind and preparation method and electro-catalysis application |
| CN115084558A (en) * | 2022-07-21 | 2022-09-20 | 福州大学 | Preparation of lanthanum-based organic framework composite modified waste chromium chip derived porous carbon nano anode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115939422A (en) | 2023-04-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108736031B (en) | Self-supporting PtCo alloy nanoparticle catalyst and preparation method and application thereof | |
| GB2603717A (en) | Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof | |
| CN103143378B (en) | Preparation method of non-noble metal oxygen reduction electrocatalyst for cathode of fuel cell | |
| CN107887613A (en) | Oxygen reduction electrode and preparation method and application based on three-dimensional netted nitrogen phosphorus sulphur codope porous carbon materials | |
| CN109908938A (en) | A kind of preparation method of Novel electrolytic water Oxygen anodic evolution catalyst Co@NC/CNT | |
| CN113881965B (en) | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof | |
| CN110048134A (en) | A kind of universality method preparing porous nitrogen fluorine codope carbon oxygen reduction catalyst | |
| CN109950566A (en) | A kind of high-performance oxygen reduction catalyst and its preparation method based on function of surface enhancing | |
| CN109694071A (en) | A kind of method and application preparing nitrogen-doped porous carbon material using coconut husk as raw material | |
| CN114784303B (en) | Preparation and application of rare earth-based organic framework anode material modified by copper polyphenol supermolecular network interface | |
| CN109301260A (en) | A kind of biomass derived complex carbon material and its preparation method and application | |
| CN109467068A (en) | A kind of preparation method of biological material Ba Danmu base porous carbon materials and its application in terms of anode of microbial fuel cell | |
| CN113497237B (en) | Synthesis method and application of copper polyphenol-triazine supermolecular network structure nano composite material | |
| CN109659572B (en) | NiMoW nano material and preparation method thereof, hydrogen electrocatalytic oxidation catalyst electrode material and preparation method thereof | |
| CN113410480B (en) | Nickel polyphenol network modified composite triazine-based copolymer carbon nano electro-catalyst material and preparation method and application thereof | |
| CN113174053A (en) | Mn-MOF based on urotropine and preparation method and application thereof | |
| CN115084558B (en) | Preparation of lanthanum-based organic framework composite modified waste chromium scrap-derived porous carbon nano negative electrode material | |
| CN111193039B (en) | Method for preparing oxygen reduction catalyst from biomass and product | |
| CN115939422B (en) | Preparation method of biomass carbon composite material for modification of cerium-aluminum organic frame of fuel cell cathode | |
| CN103594718A (en) | Preparation and usage of nanoribbon-shaped Cucurbit[6]uril carried cubic palladium nanoparticles | |
| CN113948718B (en) | Covalent organic polymer cerium-based nano carbon sphere coated by rare earth polyphenol supermolecule | |
| CN114210315B (en) | Preparation and application of rare earth erbium modified pollen carbon composite photocatalyst | |
| CN113113618A (en) | Preparation method of cobalt-based nitrogen-doped MOF (metal organic framework) derived porous carbon material | |
| CN110055555B (en) | Oxygen evolution reaction catalyst and preparation method and application thereof | |
| CN112421057A (en) | Preparation method of P-doped CuMnCoO4/N-CNs composite material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |