CN115440992A - Preparation of hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber fuel cell cathode material - Google Patents
Preparation of hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber fuel cell cathode material Download PDFInfo
- Publication number
- CN115440992A CN115440992A CN202211117723.0A CN202211117723A CN115440992A CN 115440992 A CN115440992 A CN 115440992A CN 202211117723 A CN202211117723 A CN 202211117723A CN 115440992 A CN115440992 A CN 115440992A
- Authority
- CN
- China
- Prior art keywords
- mof
- temperature
- organic framework
- solution
- carbon nanofiber
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 102000008186 Collagen Human genes 0.000 title claims abstract description 24
- 108010035532 Collagen Proteins 0.000 title claims abstract description 24
- 229920001436 collagen Polymers 0.000 title claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 16
- 239000002184 metal Substances 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 12
- 239000000446 fuel Substances 0.000 title claims abstract description 11
- 239000013384 organic framework Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000010406 cathode material Substances 0.000 title claims description 5
- 239000000843 powder Substances 0.000 claims abstract description 22
- 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 claims abstract description 19
- 229940116852 myricetin Drugs 0.000 claims abstract description 18
- 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 claims abstract description 18
- 235000007743 myricetin Nutrition 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000835 fiber Substances 0.000 claims abstract description 13
- 235000001459 whitebark Nutrition 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000013118 MOF-74-type framework Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000010355 oscillation Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 2
- 235000008738 Clausena lansium Nutrition 0.000 claims 1
- 241000757020 Pontederia Species 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 47
- 239000003054 catalyst Substances 0.000 abstract description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229920001864 tannin Polymers 0.000 abstract description 12
- 239000001648 tannin Substances 0.000 abstract description 12
- 235000018553 tannin Nutrition 0.000 abstract description 12
- 238000006722 reduction reaction Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 239000002028 Biomass Substances 0.000 abstract description 2
- 208000021251 Methanol poisoning Diseases 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 20
- 238000001354 calcination Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 229920006395 saturated elastomer Polymers 0.000 description 13
- 239000012621 metal-organic framework Substances 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical class [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229920002770 condensed tannin Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002206 flavan-3-ols Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 240000005099 Cercis occidentalis Species 0.000 description 1
- 235000006228 Cercis occidentalis Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- CITFYDYEWQIEPX-UHFFFAOYSA-N Flavanol Natural products O1C2=CC(OCC=C(C)C)=CC(O)=C2C(=O)C(O)C1C1=CC=C(O)C=C1 CITFYDYEWQIEPX-UHFFFAOYSA-N 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 235000009134 Myrica cerifera Nutrition 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 244000061457 Solanum nigrum Species 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000005835 flavan-3,4-diols Chemical class 0.000 description 1
- 229930182497 flavan-3-ol Natural products 0.000 description 1
- 235000011987 flavanols Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012924 metal-organic framework composite Substances 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polyphenol compound Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 239000002699 waste material Substances 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
- H01M4/88—Processes of manufacture
-
- 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
-
- 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
- H01M4/9008—Organic or organo-metallic compounds
-
- 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
Abstract
The invention belongs to the field of oxygen reduction electrocatalysis, and particularly relates to a method for constructing a hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber MOF-74@ CCF-BT by using collagen fibers as main components of white bark powder as a base material and utilizing interface adhesion modification of myricetin. The synthesis method is simple, low in cost and short in reaction time, and the synthesized composite material is high in yield, uniform in appearance, large in specific surface area and easy to realize industrial production. The invention is used for solving the problems that the existing fuel cell catalyst generally faces single obstacle of a precursor, the synthesis cost is high, the reversibility of a cathode oxygen reduction reaction is low, and the exchange current density is small, and overcomes the defects that the traditional commercial Pt-based catalytic material is high in cost, toxic and the like, and the obtained oxygen reduction electrocatalyst has the advantages of high initial potential, half-slope potential, excellent limiting current, high stability, strong methanol poisoning resistance and the like, so that biomass peel powder is used as a good carrier and a carbon source, plant tannin is used as a bridge molecule for connecting gel fibrils and a nickel metal organic framework, and the developed MOF-74@ CCF-BT is used as a high-efficiency electrocatalyst capable of replacing the traditional commercial Pt/C, and has great potential application value and industrialization prospect.
Description
Technical Field
The invention belongs to the field of oxygen reduction electrocatalysis, and particularly relates to a preparation method of a hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber which takes collagen fiber as a main component of white bark powder as a base material and is modified by interface adhesion of myricetin.
Background
The slow redox reaction process of the cathode greatly hinders the development of Proton Exchange Membrane Fuel Cells (PEMFCs), and a high-efficiency catalyst is required for catalysis. The traditional method of preparing redox electrocatalysts is the templating method, involving the preparation and removal of the template. The template is typically removed by etching with hydrofluoric acid (HF), which is a highly corrosive acid and is associated with a high risk of handling during the synthesis process and environmental contamination. Currently, in order to increase the reaction kinetics of the oxidation-reduction reaction (ORR) at the cathode electrode, large amounts of expensive platinum-based electrocatalysts are required to improve this performance. However, the practical application prospect of fuel cell systems is hindered by the problems of very high price, scarcity, poor durability and toxicity resistance of platinum. The development of highly active non-noble metal redox catalysts is therefore one of the key steps in the commercialization of fuel cells.
Tannin is a secondary metabolite of plants, widely existing in roots, bark, leaves and fruits of plants, and is a natural polyphenol compound. Tannins in turn are classified into hydrolyzed tannins and condensed tannins. Hydrolyzed tannins refer to gallic acid (gallic acid) or tannins of waste acids, such as tannic acid and tala tannin, produced after hydrolysis under the action of acid, alkali or enzyme; whereas condensed tannins are generally derived from flavanols and are flavan-3-ols or polymers of flavan-3, 4-diols, such as cercis tannin, myricetin and larch tannin. The myricetin tannin has a plurality of ortho phenolic hydroxyl groups, so that the myricetin tannin can generate electrostatic binding and complexing reaction with a plurality of metal ions, wherein the former is a physical process, and the latter is a chemical process. Tannin mainly forms five-membered chelation with metal ions by the hydroxyl of ortho-diphenol, and other reactions such as oxidation reduction, hydrolytic complexation and the like can also occur simultaneously.
The metal and the organic compound are coordinated to form a specific framework structure, so that the metal activity is realized; meanwhile, the organic ligand has the characteristics of organic ligands, the selectivity of functional groups and other physical and chemical properties; and special space structure formed by coordination. The Metal Organic Frameworks (MOFs) material has the advantages of simple preparation, low production cost, large surface area, large pore volume, easiness in manufacturing and the like, and can load guest molecules and directly catalyze target objects, so that more active sites are provided, and the electrochemical detection sensitivity is improved. Therefore, different metal centers and organic linkers are selected to synthesize target molecules with specific structures, so that the generation of functional materials with both metal characteristics and organic characteristics has important significance for improving electrochemical performance.
The skin collagen fiber is derived from the skin of livestock animals, and is renewable animal biomass with the largest resource amount in nature. The tanning theory and practice of inorganic metal salt in the leather chemical field have proved that the leather collagen can generate cross linking effect with metal ions. Regularly distributing a large number of functional groups such as-COOH and-NH in the molecular structure of the collagen fibers 2 OH, etc., which can coordinate and combine with metal ions to carry the metal ions to the collagen fibers. The MOF-74 is a Metal Organic Framework (MOFs) material with open type, high-density unsaturation and metal sites and is made of Ni 2+ The metal ions are coordinated with the 2, 5-dihydroxy terephthalic acid to obtain the three-dimensional reticular framework material with one-dimensional pore canals. The MOF-74 and the myricetin are combined by utilizing the skin powder for modification, so that a composite material with large specific surface area and high activity is obtained to replace the traditional Pt/C catalyst.
Disclosure of Invention
The invention aims to solve the problems of the existing fuel cell catalyst, overcome the defects of the prior art, solve the problems of single precursor obstacle and synthesis cost of the existing fuel cell catalyst, and overcome the defects of high cost, toxicity and the like of a platinum-based catalytic material; the characteristics of many active sites and large specific surface area of a metal organic framework are utilized to develop a nano composite material which combines MOFs and myricetin and is modified by using peel powder, and the nano composite material has the advantages of high initial potential, half-slope potential, excellent limiting current, excellent stability, methanol tolerance and the like.
The invention provides a simple thermal decomposition preparation processForming a hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber MOF-74@ C taking collagen fiber as a main component of white bark powder as a base material and modified by interface adhesion of myricetin CF-BT The method comprises the following steps:
(1) Preparing a certain proportion of DMF-ethanol-ultrapure water solution;
(2) 0.1473gH 4 DOBDC and 0.7718gNi (NO) 3 ) 2 ·6H 2 Dissolving O in the solution, transferring the solution into a 100ml hydrothermal reaction kettle, keeping the solution at a certain temperature, cooling the solution to room temperature after a period of reaction is finished, washing the obtained solid with DMF and methanol for 3 times respectively, and finally performing vacuum drying under certain conditions to obtain Ni-MOF-74;
(3) Weighing 0.05g of hide powder, dissolving in 10ml of deionized water, adding 10% HCl solution to adjust the pH, and then oscillating for 2h at 40 ℃;
(4) Respectively weighing 0.05g of MOF-74 and 0.1g of myricetin, dissolving in the conical flask obtained in the step (3), stirring by using a magnetic stirrer, and then putting under an oscillator for oscillation;
(5) After full oscillation, washing the mixture for 2 to 3 times by using deionized water and absolute ethyl alcohol, filtering the mixture, and then putting the filtered mixture into an oven for drying;
(6) Placing the dried product in a tubular furnace in nitrogen atmosphere for heat treatment, and naturally cooling to room temperature to obtain a hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber MOF-74@ C taking collagen fiber as a main component of white bark powder as a substrate and modified by interface adhesion of myricetin CF-BT And (3) nano materials.
In the technical scheme, the volume ratio of DMF-ethanol-ultrapure water in the step (1) is 1:1:1, 60ml in total;
in the technical scheme, the temperature of the hydrothermal reaction in the step (2) is 100 ℃, the time is 24 hours, the temperature of vacuum drying is 80 ℃, and the time is 12 hours;
in the technical scheme, the pH value adjusting range in the step (3) is 1.5-2.0;
in the technical scheme, the magnetic stirring time in the step (4) is 30min, the temperature of an oscillator is 40 ℃, and the time is 2h;
in the technical scheme, the drying temperature in the step (5) is 80 ℃, and the time is 12 hours;
in the technical scheme, the heating rate of the heat treatment in the step (6) is 5 ℃/min, the temperature is 800 ℃, and the reaction time is 2h.
The MOF-74@ C CF-BT The oxygen reduction reaction catalyst has the following advantages compared with the commercial Pt/C catalyst:
(1) The preparation process of the catalyst adopts a thermal decomposition method with simple equipment, simple operation steps, environmental protection and easily controlled reaction conditions, and not only shows high initial potential, half-slope potential, excellent limiting current, excellent stability and good methanol tolerance, but also has the advantages of strong methanol poisoning resistance and the like.
(2) Prepared MOF-74@ C CF-BT The initial potential of the catalyst measured on an electrochemical workstation can reach 0.88V which is comparable with Pt/C relative to a standard hydrogen electrode, the material half slope potential is 0.78V which is slightly superior to Pt/C, and simultaneously the catalyst has a greater limiting current density of 5.54mAcm than Pt/C -2 。
Drawings
FIG. 1 is the composite carbon nanofiber MOF-74@ C prepared in example 1, and prepared by taking collagen fibers as main components of white bark powder as a base material and modifying the collagen fibers by utilizing interface adhesion of myricetin CF-BT Scanning electron microscope images of;
FIG. 2 is an XRD pattern of MOF-74@ BT material obtained at different calcination temperatures (600 deg.C, 700 deg.C, 800 deg.C) (scan interval: 5 deg. -80 deg., step size: 0.02 deg., scan rate: 1.5 deg./min);
FIG. 3 is the MOF-74@ C prepared at the calcination temperature of 800 ℃ in example 1 CF-BT Scanning electron micrographs and EDS spectra of the material;
FIG. 4 is a MOF-74@ C sample prepared at a calcination temperature of 800 ℃ in example 1 CF-BT Elemental and spectral spectra of the material;
FIG. 5 is a MOF-74@ C sample prepared at a calcination temperature of 800 ℃ in example 1 CF-BT Material at O 2 CV plot at 1600rmp in saturated 0.1MKOH (scan range-0.9-0.1V, scan rate 50 mV/s);
FIG. 6 shows different ratios of MOF-74 and myricetin at calcination temperature of 800 ℃ in O in example 1 2 CV plot at 1600rmp in saturated 0.1MKOH (scan range-0.9-0.1V, scan rate 50 mV/s);
FIG. 7 is a graph of control Pt/C and MOF-74@ C prepared at 800 ℃ calcination temperature in example 1 CF-BT In the presence of O 2 Comparison of LSV at 1600rmp in saturated 0.1 MKOH;
FIG. 8 is a graph of the preparation of MOF-74@ C at different calcination temperatures (700 deg.C, 800 deg.C, 900 deg.C) CF-BT The material is in O 2 Comparison plot of LSV at 1600rmp in saturated 0.1MKOH (scan range-0.9-0.1V, scan rate 10 mV/s);
FIG. 9 is a graph of different speeds of rotation MOF-74@ C CF-BT LSV profile of the material (rotation rate 400rmp,625rmp,900rmp,1225rmp,1600rmp,2025rmp, scan rate 10 mV/s);
FIG. 10 is the MOF-74@ C calcination temperature of 800 ℃ in example 1 CF-BT Materials and commercial Pt/C in O 2 I-t plot comparison of long run at 1600rmp in saturated 0.1M KOH;
FIG. 11 is the MOF-74@ C at calcination temperature of 800 ℃ in example 1 CF-BT Comparison of i-t curves for materials and commercial Pt/C runs after methanol addition.
Detailed Description
The simple preparation process provided by the invention takes collagen fiber which is the main component of white bark powder as a base material, and utilizes interface adhesion modification of myricetin to modify the graded porous skin collagen-based metal nickel organic framework composite carbon nanofiber MOF-74@ C CF-BT The method is used as a cathode material of a fuel cell and comprises the following steps:
(1) Preparing a certain proportion of DMF-ethanol-ultrapure water solution;
(2) 0.1473gH 4 DOBDC and 0.7718gNi (NO) 3 ) 2 ·6H 2 Dissolving O in the above solution, transferring into 100ml hydrothermal reaction kettle, maintaining at certain temperature, reacting for a period of time, cooling to room temperature, washing the obtained solid with DMF and methanol for 3 times, and adding into a reactor under certain conditionsCarrying out vacuum drying to obtain Ni-MOF-74;
(3) Weighing 0.05g of hide powder, dissolving in 10ml of deionized water, adding 10% HCl solution to adjust pH, and then oscillating for 2h at 40 ℃;
(4) Respectively weighing 0.05g of MOF-74 and 0.1g of myricetin, dissolving in the conical flask obtained in the step (3), stirring by using a magnetic stirrer, and then putting under an oscillator for oscillation;
(5) After full oscillation, washing the mixture for 2 to 3 times by using deionized water and absolute ethyl alcohol, filtering the mixture, and then putting the filtered mixture into an oven for drying;
(6) Placing the dried product in a tubular furnace in nitrogen atmosphere for heat treatment, and then naturally cooling to room temperature to obtain the hierarchical porous carbon nano MOF-74@ C taking the peel powder as a good carrier and a carbon source CF-BT And (3) fibers.
In the technical scheme, the volume ratio of DMF-ethanol-ultrapure water in the step (1) is 1:1:1, 60ml in total;
in the technical scheme, the temperature of the hydrothermal reaction in the step (2) is 100 ℃, the time is 24 hours, the temperature of vacuum drying is 80 ℃, and the time is 12 hours;
in the technical scheme, the pH value adjusting range in the step (3) is 1.5-2.0;
in the technical scheme, the magnetic stirring time in the step (4) is 30min, the temperature of an oscillator is 40 ℃, and the time is 2h;
in the technical scheme, the drying temperature in the step (5) is 80 ℃, and the time is 12 hours;
in the technical scheme, the heating rate of the heat treatment in the step (6) is 5 ℃/min, the temperature is 800 ℃, and the reaction time is 2h.
The invention provides a nano composite material MOF-74@ C constructed by using skin powder for synthesis as a modification and using a metal organic framework polyphenol supramolecular network as a functional assembly CF-BT And the use of this material as an oxygen reduction catalyst.
The active substance is abbreviated as MOF-74@ C CF-BT 。
MOF-74@ C of the invention CF-BT The material is prepared from cortex Albizziae powder, collagen fiber as base material, and bayberry tanninThe surface is adhered with modified hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber.
The invention uses platinum electrode as counter electrode, saturated silver chloride electrode (Ag/AgCl) as reference electrode, MOF-74@ C CF-BT The platinum carbon electrode made of the composite material is used as a working electrode.
A catalyst ink (ink) was prepared by dispersing 4mg of the catalyst of the present invention in 1mL of a mixed solution (235. Mu.L deionized water, 750. Mu.L isopropyl alcohol and 5wt% Nafion solution, 15. Mu.L) by a balance. Then gradually dripping 28 mu L of ink on the surface of the glassy carbon electrode (the loading amount of the catalyst is 0.25 mgcm) -2 ) And carrying out an electrocatalysis performance test after naturally drying.
All electrocatalytic performance tests described in the present invention were performed in 0.1M KOH (pH = 13.62) electrolyte, and the experimentally measured potential was converted to a potential relative to a Reversible Hydrogen Electrode (RHE) by the following formula:
E(RHE)＝E(Ag/AgCl)+0.059*pH+0.2224
the potential values referred to in the present invention are all potentials relative to the reversible hydrogen electrode.
The catalyst of the present invention requires CV activation for 3 cycles before electrochemical testing.
The catalyst is tested at normal temperature, and the influence of large temperature change difference on the performance of the catalyst is prevented.
The invention will be further illustrated with reference to the following specific examples. In order to further clarify the present invention, preferred embodiments of the present invention are described in connection with the examples which are intended to illustrate various features and advantages of the present invention, but not to limit the scope of the invention which is not defined by the claims. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1:
this example demonstrates a MOF-74@ C CF-BT The synthesis method of the nano composite carbon material comprises the following steps:
(1) Preparing 60ml of a DMF-ethanol-ultrapure water (ratio of 1;
(2) 0.1473gH 4 DOBDC and 0.7718gNi (NO) 3 ) 2 ·6H 2 Dissolving O in the solution, then transferring the solution into a 100ml hydrothermal reaction kettle, keeping the solution at 100 ℃ for 24 hours, cooling the solution to room temperature after the reaction is finished, washing the obtained solid with DMF and methanol for 3 times respectively, and finally performing vacuum drying at 80 ℃ for 12 hours to obtain Ni-MOF-74;
(3) Weighing 0.05g of hide powder, dissolving the hide powder in 10ml of deionized water, adding 10% HCl solution to adjust the pH value to be 1.5-2.0, and then oscillating the hide powder for 2 hours at the temperature of 40 ℃;
(4) Respectively weighing 0.05g of MOF-74 and 0.1g of myricetin, dissolving in the conical flask in the step (3), stirring by a magnetic stirrer at 40 ℃ for 30min, and then putting under an oscillator for oscillation;
(5) Washing the mixture for 2 to 3 times by using deionized water and absolute ethyl alcohol after full oscillation, filtering the mixture, and then putting the filtered mixture into an oven to dry the mixture for 12 hours at the temperature of 80 ℃;
(6) Placing the dried product in a tubular furnace in nitrogen atmosphere for heat treatment, and then naturally cooling to room temperature to obtain the nano MOF-74@ C constructed by using hide powder as a carrier CF-BT And (3) nano materials.
FIG. 1 is the MOF-74@ C prepared in example 1 CF-BT The scanning electron microscope image of the material shows that the nanometer material which is decorated by using the hide powder and is constructed by using the metal organic framework polyphenol supermolecule network as the functional assembly body is synthesized.
MOF-74@ C obtained in example 1 CF-BT Phase identification and microscopic morphology and structure characterization of the carbon material are carried out: performing phase identification on the prepared material by using a powder X-ray diffractometer and an X-ray photoelectron spectrometer, performing micro-morphology and structure characterization on the obtained material by using a scanning electron microscope, and synthesizing the MOF composite material taking a flower-shaped structure as the center according to a figureAnd (5) feeding.
FIG. 2 is an XRD pattern of MOF-74@ BT material obtained at different calcination temperatures (600 deg.C, 700 deg.C, 800 deg.C) in example 1.
As can be seen from the figure, the obtained sample has high purity, no obvious impurity is generated, the crystallization of the synthesized material is better when the diffraction peak is sharper, MOF-74@ C CF-BT The material has 3 obvious characteristic diffraction peaks appearing at 2 theta =44.5 degrees, 51.8 degrees and 76.3 degrees, which correspond to (111), (200) and (220) planes and are highly matched with Ni (PDF # 65-2865) cards.
FIG. 3 is the MOF-74@ C prepared at the calcination temperature of 800 ℃ in example 1 CF-BT Scanning electron micrographs and EDS spectra of the material. As can be seen from the figure, the synthesis of MOF-74 with flower-like structure as the central carrier, modification of other carbon sources, and a very high Ni content ratio was successful.
FIG. 4 is the MOF-74@ C prepared at the calcination temperature of 800 ℃ in example 1 CF-BT The elements and spectra of the material show that the main elements of the material comprise Ni, C, N, P and O.
Example 2:
this example shows a MOF-74@ C centered on a flower-like structure CF-BT Is the electrochemical performance research of the catalyst.
The invention uses platinum electrode as counter electrode, saturated silver chloride electrode (Ag/AgCl) as reference electrode, MOF-74@ C CF-BT The electrode made of the material is used as a working electrode.
The catalyst ink (ink) was prepared by dispersing 4mg of the catalyst of the present invention in 1mL of a mixed solution (235. Mu.L deionized water, 750. Mu.L isopropyl alcohol and 5wt% Nafion solution 15. Mu.L) by balance. Then gradually dripping 28 mu L of ink on the surface of the glassy carbon electrode (the loading amount of the catalyst is 0.25 mgcm) -2 ) And carrying out electrocatalysis performance test after natural drying.
All electrocatalytic performance tests described in the present invention were performed in 0.1M KOH (pH = 13.62) electrolyte, and the experimentally measured potential was converted to a potential relative to a Reversible Hydrogen Electrode (RHE) by the following formula:
E(RHE)＝E(Ag/AgCl)+0.059*pH+0.2224
the potential values referred to in the present invention are all potentials relative to the reversible hydrogen electrode.
The catalyst of the invention requires CV activation for 3 cycles before electrochemical testing.
The catalyst is tested at normal temperature, and the influence of large temperature change difference on the performance of the catalyst is prevented.
The Nafion added in the preparation process of the catalyst is produced by Aldrich sigma company, and the concentration is 5%.
The catalyst is absorbed by a pipette gun to be 7ul and dropped on a working electrode, the step is repeated for 3 times after the catalyst is naturally aired, then the working electrode slowly enters 0.1MKOH electrolyte saturated by oxygen, bubbles are prevented from being generated on the working electrode in the step, and the electrolyte is continuously introduced into oxygen in the whole testing process to ensure oxygen saturation.
Cyclic voltammetry and linear cyclic voltammetry tests were performed on the catalyst obtained in this example: the cyclic voltammetry test was carried out using an electrochemical workstation manufactured by Pine of the United states, the test voltage sweep range was-0.9-0.1V, the sweep rate was 50mV/s, and during the test, the cyclic voltammetry test was carried out after 3 cycles of activation with a current density of 50mV/s. Linear cyclic voltammetry tests were also performed using the Pine electrochemical workstation, with a test voltage sweep range of-0.9-0.1V and a sweep rate of 50mV/s. The current density of the catalyst material under different rotating speeds can be obtained through 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 400rmp,625rmp,900rmp,1225rmp,1600rmp and 2025rmp. The stability and the methanol tolerance are also important indexes of the catalyst performance, the test is also completed on an electrochemical workstation, the stability test voltage is-0.189V, and the test time length is 20000s; the methanol tolerance test voltage was-0.189V, the test duration was 1000s, and 2mL of the methanol solution was dropped at 300 s.
FIG. 5 is a graph of the preparation of MOF-74@ C at a calcination temperature of 800 ℃ in example 1 CF-BT The material is in O 2 Cyclic voltammogram at 1600rmp in saturated 0.1MKOH (test voltage sweep range: -0.9-0.1V)The scanning speed: 50 mV/s). As can be seen from the figure, the CV curve under oxygen saturation conditions exhibited a distinct peak of oxygen reduction at a potential of 0.71V (vs. RHE) when in the oxygen saturated test environment, indicating that the sample MOF-74@ C CF-BT The material has obvious catalytic activity for oxygen reduction.
FIG. 6 is the MOF-74@ C mixture of example 1 with different ratios of MOF-74 and myricetin added at 800 deg.C calcination temperature CF-BT Of a material in O 2 Comparison of LSV at 1600rmp in saturated 0.1MKOH (scan range-0.9-0.1V, scan rate 10 mV/s), it can be seen that when MOF-74 is added 0.05 @C CF-BT0.1 The catalytic performance of the sample was best.
FIG. 7 is Pt/C and MOF-74@ C prepared at 800 ℃ calcination temperature in example 1 CF-BT In the presence of O 2 Comparison of LSV at 1600rmp in saturated 0.1MKOH (scan range-0.9-0.1V, scan rate 10 mV/s) shows that the initial potential of the material is 1.10V, which is better than that of the Pt/C electrode, and the half-slope potential of 0.76V is slightly lower than that of the Pt/C electrode, but the material has a greater limiting current density than that of Pt/C, 6.3mAcm -2 。
FIG. 8 is a graph of MOF-74@ C prepared at different calcination temperatures (700 deg.C, 750 deg.C, 800 deg.C) in example 1 CF-BT Material at O 2 Comparison of LSV at 1600rmp in saturated 0.1MKOH (test voltage range: -0.9-0.1V, scanning speed: 50 mV/s), it can be seen that MOF-74@ C when the calcination temperature was 800 deg.C CF-BT The material performance is optimal.
FIG. 9 is the best sample MOF-74@ C prepared at 800 ℃ in example 1 CF-BT At O 2 Catalysts MOF-74@ C in saturated 0.1MKOH under different rotation speed conditions (400rmp, 625rmp,900rmp,1225rmp,1600rmp, 2025rmp) CF-BT The LSV curve (scanning speed: 10 mV/s) shows that the limiting current density tends to increase uniformly with the increase in the number of revolutions. The electron transfer number was 3.7 as shown by the ring-disk electrode test, indicating that the reaction process followed a 4-electron mechanism.
FIG. 10 is the best sample MOF-74@ C prepared at 800 ℃ in example 1 CF-BT And commercial Pt/C in O 2 Saturated 0.1MKComparative plot of i-t curves run for prolonged periods at 1600rmp in OH. As can be seen, the initial current density of the commercial Pt/C catalyst was significantly lost 23% after 20000s of chronoamperometry, whereas MOF-74@ C CF-BT The material loss was 18%, indicating that the catalyst has better stability than the commercial Pt/C catalyst.
The best sample prepared at 800 ℃ in example 1, MOF-74@ C, was determined by adding 2mL of methanol to 0.1MKOH electrolyte at 1600rmp at 300s using the i-t technique CF-BT And commercial 20% methanol tolerance of the pt/C catalyst, the results are shown in fig. 11. From the figure, MOF-74@ C can be observed CF-BT Has only a slight change in the limiting current density, while the Pt/C catalyst shows a significant change in the current density due to the oxidation of methanol, after running for 700s, MOF-74@ C CF-BT The current density still keeps a stable trend, and the Pt/C retention rate decays to below 50%. Explanation of MOF-74@C CF-BT Is superior to Pt/C in methanol tolerance.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (8)
1. The preparation method of the hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber fuel cell cathode material is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) Preparing a certain proportion of DMF-ethanol-ultrapure water solution;
(2) Dissolving H4DOBDC and Ni (NO 3) 2.6H 2O in the solution, then transferring the solution into a 100ml hydrothermal reaction kettle, keeping the solution at a certain temperature, cooling the solution to room temperature after a period of reaction is finished, washing the obtained solid with DMF and methanol for 3 times respectively, and finally carrying out vacuum drying under certain conditions to obtain Ni-MOF-74;
(3) Weighing and dissolving the Chinese wampee powder in 10ml of deionized water, adding 10% HCl solution to adjust the pH, and then oscillating for 2 hours at 40 ℃;
(4) Respectively weighing a certain amount of MOF-74 and myricetin (BT) and dissolving in the conical flask in the step (3), stirring by a magnetic stirrer, and then putting under an oscillator for oscillation;
(5) Washing the mixture for 2 to 3 times by using deionized water and absolute ethyl alcohol after full oscillation, filtering the mixture, and then putting the filtered mixture into an oven for drying;
(6) And (3) putting the dried product into a tubular furnace in a nitrogen atmosphere for heat treatment, and then naturally cooling to room temperature to obtain the hierarchical porous collagen-based metal-nickel organic framework composite carbon nanofiber MOF-74@ CCF-BT nano material which takes the collagen fiber as the main component of the white bark powder as a substrate and is modified by the interface adhesion of myricetin.
2. The method of claim 1, wherein: in the step (1), the volume ratio of DMF-ethanol-ultrapure water is 1:1:1, 60ml in total.
3. The method of claim 1, wherein: the temperature of the hydrothermal reaction in the step (2) is 100 ℃, the time is 24 hours, the temperature of the vacuum drying is 80 ℃, and the time is 12 hours.
4. The production method according to claim 1, characterized in that: the pH value is adjusted to be 1.5-2.0 in the step (3).
5. The method of claim 1, wherein: in the step (4), the magnetic stirring time is 30min, the oscillator temperature is 40 ℃, and the time is 2h.
6. The production method according to claim 1, characterized in that: in the step (5), the drying temperature is 80 ℃ and the time is 12h.
7. The method of claim 1, wherein: the heat treatment in the step (6) comprises the following steps: heating to 800 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and then naturally cooling to room temperature.
8. A novel cathode material of a hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber MOF-74@ CCF-BT fuel cell prepared by the preparation method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211117723.0A CN115440992A (en) | 2022-09-14 | 2022-09-14 | Preparation of hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber fuel cell cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211117723.0A CN115440992A (en) | 2022-09-14 | 2022-09-14 | Preparation of hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber fuel cell cathode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115440992A true CN115440992A (en) | 2022-12-06 |
Family
ID=84247493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211117723.0A Pending CN115440992A (en) | 2022-09-14 | 2022-09-14 | Preparation of hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber fuel cell cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115440992A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104289249A (en) * | 2014-11-03 | 2015-01-21 | 中国科学技术大学 | Preparation method of Fe and N-doped porous carbon nanofiber applicable to cathode catalyst for polymer fuel cell |
| WO2015040638A1 (en) * | 2013-09-19 | 2015-03-26 | Council Of Scientific & Industrial Research | N-doped porous carbon electrocatalyst and process for preparation thereof |
| US20150180045A1 (en) * | 2010-09-27 | 2015-06-25 | Uchicago Argonne, Llc | Non-platinum group metal electrocatalysts using metal organic framework materials and method of preparation |
| CN110265669A (en) * | 2019-05-30 | 2019-09-20 | 南京源恒能源科技有限公司 | N doping carbonization bacteria cellulose-base graded porous carbon composite material and preparation method |
| WO2020010750A1 (en) * | 2018-07-09 | 2020-01-16 | 华南理工大学 | Nitrogen-doped 3d porous carbon material, preparation method therefor and use thereof |
| CN110783577A (en) * | 2019-10-08 | 2020-02-11 | 华中科技大学 | Platinum nickel cobalt alloy @ carbon nanotube composite material, and preparation and application thereof |
| CN112886024A (en) * | 2021-03-05 | 2021-06-01 | 福州大学 | Preparation method of myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst |
| CN113422069A (en) * | 2021-06-18 | 2021-09-21 | 福州大学 | Carbon-based inverse spinel type copper ferrite fuel cell cathode material constructed by taking collagen fiber/nanofiber composite aerogel as template |
| KR20220110906A (en) * | 2021-02-01 | 2022-08-09 | 숭실대학교산학협력단 | Method of producing platinum alloy catalyst for fuel cell, and fuel cell using same |
-
2022
- 2022-09-14 CN CN202211117723.0A patent/CN115440992A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150180045A1 (en) * | 2010-09-27 | 2015-06-25 | Uchicago Argonne, Llc | Non-platinum group metal electrocatalysts using metal organic framework materials and method of preparation |
| WO2015040638A1 (en) * | 2013-09-19 | 2015-03-26 | Council Of Scientific & Industrial Research | N-doped porous carbon electrocatalyst and process for preparation thereof |
| CN104289249A (en) * | 2014-11-03 | 2015-01-21 | 中国科学技术大学 | Preparation method of Fe and N-doped porous carbon nanofiber applicable to cathode catalyst for polymer fuel cell |
| WO2020010750A1 (en) * | 2018-07-09 | 2020-01-16 | 华南理工大学 | Nitrogen-doped 3d porous carbon material, preparation method therefor and use thereof |
| CN110265669A (en) * | 2019-05-30 | 2019-09-20 | 南京源恒能源科技有限公司 | N doping carbonization bacteria cellulose-base graded porous carbon composite material and preparation method |
| CN110783577A (en) * | 2019-10-08 | 2020-02-11 | 华中科技大学 | Platinum nickel cobalt alloy @ carbon nanotube composite material, and preparation and application thereof |
| KR20220110906A (en) * | 2021-02-01 | 2022-08-09 | 숭실대학교산학협력단 | Method of producing platinum alloy catalyst for fuel cell, and fuel cell using same |
| CN112886024A (en) * | 2021-03-05 | 2021-06-01 | 福州大学 | Preparation method of myrica cobalt nickel boron composite carbon material proton membrane fuel cell catalyst |
| CN113422069A (en) * | 2021-06-18 | 2021-09-21 | 福州大学 | Carbon-based inverse spinel type copper ferrite fuel cell cathode material constructed by taking collagen fiber/nanofiber composite aerogel as template |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107394215B (en) | Preparation and application of heteroatom-doped functional carbon material | |
| CN106955725A (en) | The preparation and the application as electrochemical catalyst of a kind of N, S codope graphitized carbon material | |
| CN112968185A (en) | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure | |
| CN112133929B (en) | Preparation method of ZIF-8-derived Au-N-C oxygen reduction electrocatalyst | |
| CN110560117A (en) | Bimetallic cobalt ruthenium-nitrogen phosphorus doped porous carbon electrocatalyst and preparation method and application thereof | |
| CN114920228B (en) | Transition metal phosphate nano enzyme material and preparation method and application thereof | |
| CN114108004A (en) | Ruthenium-based alloy catalyst and preparation method and application thereof | |
| CN110862548A (en) | Preparation method and new application of metal organogel catalyst based on MIL-53 | |
| CN113394414B (en) | Construction of flower-core type S-doped manganese-copper electrocatalyst based on metal polyphenol modified sodium alginate/nano-cellulose composite aerogel | |
| CN113410480B (en) | Nickel polyphenol network modified composite triazine-based copolymer carbon nano electro-catalyst material and preparation method and application thereof | |
| CN113394413B (en) | Preparation method of catalyst for cathode oxygen reduction reaction based on two-dimensional graphite phase carbon nitride cobalt doped porous carbon material | |
| CN114316510A (en) | Method for preparing sulfonic group-containing bimetallic composite polymer nano material | |
| CN113497237B (en) | Synthesis method and application of copper polyphenol-triazine supermolecular network structure nano composite material | |
| CN112592484B (en) | MOF material constructed by taking 5-mercapto-1-phenyl-1H-tetrazole as ligand and preparation method and application of derivative thereof | |
| CN115440992A (en) | Preparation of hierarchical porous collagen-based metal nickel organic framework composite carbon nanofiber fuel cell cathode material | |
| CN108842165B (en) | Solvothermal preparation of sulfur doped NiFe (CN)5NO electrolysis water oxygen evolution catalyst and application thereof | |
| CN114784303B (en) | Preparation and application of rare earth-based organic framework anode material modified by copper polyphenol supermolecular network interface | |
| CN111193039A (en) | Method for preparing oxygen reduction catalyst from biomass and product | |
| CN109926095A (en) | Cobalt-based oxygen-separating catalyst, preparation method and its electro-catalysis based on eutectic solvent analyse oxygen application | |
| CN113422069B (en) | Carbon-based inverse spinel type copper ferrite fuel cell cathode material constructed by taking collagen fiber/nanofiber composite aerogel as template | |
| CN108270017A (en) | A kind of nickel-nitrogen-doped carbon composite material and its preparation method and application | |
| CN115084558A (en) | Preparation of lanthanum-based organic framework composite modified waste chromium chip derived porous carbon nano anode material | |
| CN109301261B (en) | Phosphorus-nickel-palladium co-doped carbon-based composite catalyst and preparation method and application thereof | |
| CN110975922A (en) | Co @ FePx-NCs material for hydrogen evolution of alkaline solution and preparation method and application thereof | |
| CN114420957B (en) | Method for constructing porous iron nanocomposite carbon material based on saccharomycete carbon template |
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 |