CN109616672B - ZIF-8@ FeMOF derived Fe-N co-doped carbon material and preparation method and application thereof - Google Patents
ZIF-8@ FeMOF derived Fe-N co-doped carbon material and preparation method and application thereof Download PDFInfo
- Publication number
- CN109616672B CN109616672B CN201811454105.9A CN201811454105A CN109616672B CN 109616672 B CN109616672 B CN 109616672B CN 201811454105 A CN201811454105 A CN 201811454105A CN 109616672 B CN109616672 B CN 109616672B
- Authority
- CN
- China
- Prior art keywords
- femof
- zif
- preparation
- derived
- solvent
- 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 34
- 239000002904 solvent Substances 0.000 claims abstract description 24
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000013110 organic ligand Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 13
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 6
- 239000010457 zeolite Substances 0.000 claims abstract description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 5
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 7
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 7
- 239000000446 fuel Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 238000012512 characterization method Methods 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 229910021397 glassy carbon Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 4
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229940075397 calomel Drugs 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910018089 Al Ka Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- -1 zeolite imidazole ester Chemical class 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- 239000013179 MIL-101(Fe) Substances 0.000 description 1
- 239000013206 MIL-53 Substances 0.000 description 1
- 239000013216 MIL-68 Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- SEQUALWBCFCDGP-UHFFFAOYSA-N [C].[N].[Fe] Chemical compound [C].[N].[Fe] SEQUALWBCFCDGP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000835 electrochemical detection Methods 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
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a ZIF-8@ FeMOF derived Fe-N co-doped carbon material and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) carrying out contact reaction on FeMOF, a zinc source, 2-methylimidazole and a surfactant in a solvent to prepare ZIF-8@ FeMOF; 2) calcining ZIF-8@ FeMOF to prepare a ZIF-8@ FeMOF derived Fe-N co-doped carbon material; wherein FeMOF is Fe3+A metal-organic framework material with a net structure and an organic ligand; ZIF-8 made of Zn2+And (3) reacting with 2-methylimidazole to obtain the zeolite imidazolate framework material. The Fe-N co-doped carbon material derived from the ZIF-8@ FeMOF has a loose and porous structure and multiple active sites, and can efficiently catalyze the cathode oxygen reduction reaction of a fuel cell; meanwhile, the preparation method has the advantages of greenness, cleanness, high efficiency, simplicity, low cost and the like.
Description
Technical Field
The invention relates to a doped material, and in particular relates to a ZIF-8@ FeMOF derived Fe-N co-doped carbon material and a preparation method and application thereof.
Background
With the consumption of energy resources and the aggravation of environmental pollution problems. Fuel cells are a hot spot in research today as a means of energy conversion and storage. Metal-organic frameworks (MOFs) are inorganic-organic hybrid functional materials assembled by Metal ions and organic ligands through coordination bonds, have the characteristics of large specific surface area, porosity, various structures and the like, and have good development prospects in the fields of gas storage, liquid phase separation, catalysis and the like. Zeolite imidazolate framework materials (ZIFs) are a branch of metal organic framework materials and have high chemical and thermal stability. ZIF-8 is made of Zn2+A zeolite imidazole ester framework material obtained by reacting with ligand 2-methylimidazole.
Metal-organic framework materials are compounds with a network structure composed of inorganic metals and organic ligands, which contain both inorganic and organic moieties connected by coordination bonds. By changing the metal ion center, designing and synthesizing ligand molecules and modifying the ligand molecules after synthesis, various MOFs materials and iron-based MOFs materials with different topological structures and different characteristics can be prepared. FeMOF alone does not preserve its morphology intact at high temperatures. The series of materials are formed by coordination of iron and organic ligands (terephthalic acid, 2-amino terephthalic acid) containing iron base, and the like, and mainly comprise MIL-53(Fe), MIL-l00Fe), MIL-101(Fe), MIL-88(Fe), MIL-68(Fe), and the like.
Disclosure of Invention
The invention aims to provide a ZIF-8@ FeMOF derived Fe-N co-doped carbon material, and a preparation method and application thereof, wherein the ZIF-8@ FeMOF derived Fe-N co-doped carbon material has a loose and porous structure and multiple active sites, and can efficiently catalyze the cathode oxygen reduction reaction of a fuel cell; meanwhile, the preparation method has the advantages of greenness, cleanness, high efficiency, simplicity, low cost and the like.
In order to achieve the aim, the invention provides a preparation method of a ZIF-8@ FeMOF derived Fe-N co-doped carbon material, which comprises the following steps:
1) carrying out contact reaction on FeMOF, a zinc source, 2-methylimidazole and a surfactant in a solvent to prepare ZIF-8@ FeMOF;
2) calcining ZIF-8@ FeMOF to prepare a ZIF-8@ FeMOF derived Fe-N co-doped carbon material;
wherein FeMOF is Fe3+A metal-organic framework material with a net structure and an organic ligand; ZIF-8 made of Zn2+And (3) reacting with 2-methylimidazole to obtain the zeolite imidazolate framework material.
The invention also provides a ZIF-8@ FeMOF derived Fe-N co-doped carbon material, and the ZIF-8@ FeMOF derived Fe-N co-doped carbon material is prepared by the preparation method.
The invention further provides an application of the ZIF-8@ FeMOF derived Fe-N co-doped carbon material in an oxygen reduction catalytic reaction.
In the technical scheme, ZIF-8 is used for providing a nitrogen source, FeMOF is used for providing an iron source, namely an active site is provided, a precursor of the Fe-N composite material containing iron-nitrogen-carbon is synthesized, and the precursor is calcined at high temperature to prepare the Fe-N co-doped carbon material derived from ZIF-8@ FeMOF; the composite material has excellent catalytic performance in an oxygen reduction catalytic reaction due to the large specific surface area and the doped iron and nitrogen elements; application of the catalyst to a fuel cell cathode catalyst exhibits better electrochemical catalytic activity than when each is present alone. And secondly, compared with Pt and Pt-based catalysts, the catalyst performance is equivalent, but the stability and methanol tolerance of the Fe-N co-doped carbon material derived from ZIF-8@ FeMOF are better than those of the Pt and Pt-based catalysts, and the cost is cheaper, so that the catalyst has wider application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph of the results of a scanning electron microscope characterization of B1;
FIG. 2 is a graph of the results of the characterization of the scanning electron microscope of C2;
FIG. 3 is a graph of the results of a scanning electron microscope characterization of C1;
FIG. 4 is a graph of the results of the characterization of the scanning electron microscope of C3;
FIG. 5 is a graph of the results of transmission electron microscopy characterization of B1;
fig. 6 is a graph of the characterization result of XPS of B1;
FIG. 7 is a graph of CV test results for B1;
FIG. 8 is a graph of LSV test results for B1, C2, C3, 20% Pt/C;
FIG. 9 is a graph of the results of the chronoamperometric (i-t) test at B1, 20% Pt/C.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a ZIF-8@ FeMOF derived Fe-N co-doped carbon material, which comprises the following steps:
1) carrying out contact reaction on FeMOF, a zinc source, 2-methylimidazole and a surfactant in a solvent to prepare ZIF-8@ FeMOF;
2) calcining ZIF-8@ FeMOF to prepare a ZIF-8@ FeMOF derived Fe-N co-doped carbon material;
wherein FeMOF is Fe3+A metal-organic framework material with a net structure and an organic ligand; ZIF-8 made of Zn2+And (3) reacting with 2-methylimidazole to obtain the zeolite imidazolate framework material.
In step 1) of the present invention, the amount of each material may be selected within a wide range, but in order to further improve the yield and catalytic performance of the Fe — N co-doped carbon material produced, it is preferable that in step 1), the ratio of the amounts of FeMOF, zinc source, 2-methylimidazole, and surfactant is 10 mg: 1-4 mmol: 7-16 mmol: 0.01-0.05 mmol.
In step 1) of the present invention, the amount of the solvent may be selected within a wide range, but in order to further improve the yield of the Fe — N co-doped carbon material produced, it is preferable that the ratio of the amount of the FeMOF to the amount of the solvent is 10 mg: 50-100 mL.
In step 1) of the present invention, the conditions of the contact reaction may be selected within a wide range, but in order to further improve the yield and catalytic performance of the produced Fe — N co-doped carbon material, it is preferable that in step 1), the contact reaction satisfies the following conditions: the reaction temperature is 20-30 ℃, and the reaction time is 3-5 h.
In step 1) of the present invention, the charging sequence can be selected within a wide range, but in order to further improve the yield and catalytic performance of the prepared Fe — N co-doped carbon material, preferably, the charging sequence of step 1) is: firstly, dispersing a zinc source in a solvent to form a first mixture, and dispersing 2-methylimidazole and a surfactant in the solvent to form a second mixture; and then mixing the mixture I, the mixture II and the FeMOF.
In step 1) of the present invention, the specific kind of the zinc source may be selected within a wide range, but in order to further improve the yield and catalytic performance of the Fe — N co-doped carbon material produced, it is preferable that in step 1), the zinc source is selected from at least one of zinc nitrate hexahydrate, zinc sulfate, and zinc chloride.
In step 1) of the present invention, the specific kind of the surfactant may be selected within a wide range, but in order to further improve the yield and catalytic performance of the Fe — N co-doped carbon material produced, preferably, the surfactant is selected from at least one of cetyltrimethylammonium bromide CTAB, polyvinylpyrrolidone PVP, sodium dodecylbenzenesulfonate, sodium dodecylsulfate.
In step 1) of the present invention, the specific kind of the solvent may be selected within a wide range, but in order to further improve the yield and catalytic performance of the produced Fe — N co-doped carbon material, it is preferable that the solvent is selected from at least one of anhydrous methanol, redistilled water, N-dimethylformamide DMF.
In step 2) of the present invention, the specific conditions of calcination may be selected within a wide range, but in order to further improve the catalytic performance of the resulting Fe — N co-doped carbon material, it is preferable that in step 2), the calcination satisfies the following conditions: in inert gas, the temperature is raised from 20-35 ℃ to 800-1000 ℃ at the speed of 3-5 ℃/min, the temperature is kept for 1-3h, and then the temperature is lowered to 20-40 ℃ at the speed of 5-10 ℃/min.
In the above embodiment, the specific kind of the inert gas may be selected within a wide range, but from the viewpoint of the protective effect and the cost, it is preferable that the inert gas is nitrogen and/or argon.
In step 1) of the present invention, in order to further improve the purity of the produced ZIF-8@ FeMOF, preferably, after the contacting reaction, the production method further comprises: the reaction was centrifuged to remove the solvent, followed by drying.
In the above embodiment, the conditions for drying may be selected within a wide range, but in order to improve the drying effect, it is preferable that the drying satisfies the following conditions: the drying temperature is 50-70 deg.C, and the drying time is 12-24 h.
In the present invention, the FeMOF may be a commercially available product or may be prepared by itself, but in order to further improve the purity of the FeMOF, preferably, the FeMOF is prepared by the following method: in a solvent, an iron source and an organic ligand are subjected to heat treatment.
In the above-described method for producing FeMOF, the specific conditions for the heat treatment may be selected within a wide range, but in order to further improve the yield of FeMOF, it is preferable that the heat treatment satisfies the following conditions: the temperature is 140-160 ℃, and the time is 12-26 h.
In the above method for producing FeMOF, the amount of each material may be selected within a wide range, but in order to further improve the yield of FeMOF, it is preferable that the ratio of the amount of iron source to the amount of organic ligand is 1.1 mmol: 0.5-1 mmol; more preferably, the ratio of the amount of the iron source to the amount of the solvent is 1.1 mmol: 10-20 mL.
In the above method for producing FeMOF, the specific kind of the iron source may be selected within a wide range, but in order to further improve the yield of FeMOF, preferably, the iron source is selected from at least one of iron sulfate, iron chloride hexahydrate, and iron nitrate.
In the above-described method for producing FeMOF, the specific kind of organic ligand may be selected within a wide range, but in order to further improve the yield of FeMOF, preferably, the organic ligand is selected from at least one of terephthalic acid, phthalic acid, 2-aminoterephthalic acid.
In the above method for producing FeMOF, the specific kind of the solvent may be selected within a wide range, but in order to further improve the yield of FeMOF, preferably, the solvent is selected from at least one of anhydrous methanol, redistilled water, N-dimethylformamide DMF.
The invention also provides a ZIF-8@ FeMOF derived Fe-N co-doped carbon material, and the ZIF-8@ FeMOF derived Fe-N co-doped carbon material is prepared by the preparation method.
The invention further provides an application of the ZIF-8@ FeMOF derived Fe-N co-doped carbon material in an oxygen reduction catalytic reaction.
The present invention will be described in detail below by way of examples.
Electrochemical detection is carried out on a chemical workstation of Shanghai Chenghua apparatus company with the model number of CHI 6211E; x-ray photoelectron spectroscopy characterization (XPS) obtained by Al Ka radiation from Thermo Fisher Scientific, USA, thermocouple ESCALB 250XI spectrometer; the transmission electron microscope characterization is carried out on a transmission electron microscope with a Japanese Hitachi company model number of JEOL-2010; the characterization of the scanning electron microscope is a JEOLJSM-6700F scanning electron microscope; the rotating disc electrode is a rotating disc electrode device of MSR model of Pine company in America.
Ferric chloride hexahydrate is a commercial product of chemical reagent company Limited of the national medicine group in hexahydrate; 2-methylimidazole is a commercially available product from Aladdin reagent company; the zinc nitrate hexahydrate is a commercial product of chemical reagent of national drug group, Inc.; cetyl trimethyl ammonium bromide was purchased from shanghai Linfeng Chemicals, ltd; the platinum carbon powder is Bailingwei CAS number 7440-06-4 platinum carbon powder.
Preparation example 1
Adding 0.30g of ferric chloride hexahydrate (1.1mmol) and 0.10g of 2-amino terephthalic acid (0.55mmol) into 12mL of DMF (dimethyl formamide) serving as a solvent, stirring at 25 ℃ for 30min, transferring into a reaction kettle, carrying out heat treatment at 150 ℃ for 24h, cooling DMF, centrifuging, washing and drying to obtain FeMOF; designated as a 1.
Preparation example 2
FeMOF, designated A2, was prepared according to the procedure of preparation 1; except that ferric chloride hexahydrate was replaced by an equimolar amount of ferric nitrate and 2-aminoterephthalic acid was used in an amount of 1 mmol.
Preparation example 3
FeMOF, designated A3, was prepared according to the procedure of preparation 1; except that ferric chloride hexahydrate was replaced by an equimolar amount of ferric sulfate and 2-amino terephthalic acid was used in an amount of 0.5 mmol.
Preparation example 4
FeMOF, designated A4, was prepared according to the procedure of preparation 1; except that the heat treatment conditions were: heat treatment at 140 ℃ for 26 h.
Preparation example 5
FeMOF, designated A5, was prepared according to the procedure of preparation 1; except that the heat treatment conditions were: heat treatment is carried out for 12h at 160 ℃.
Example 1
1) 0.7930g of zinc nitrate hexahydrate (2.72mmol) is added into 41.7mL of methanol to obtain a first mixture;
2) 0.9240g of 2-methylimidazole (11.3mmol) and 0.0120g of CTAB (0.033mmol) were added to 33.3mL of methanol to give a second mixture.
3) Adding the first mixture into the second mixture, adding 10mg of A1, stirring at 20 deg.C for 5h, centrifuging with methanol, and drying at 50 deg.C for 24 h; finally, in nitrogen, the temperature is raised from 25 ℃ to 900 ℃ at the rate of 4 ℃/min and kept for 2h, and then the temperature is lowered to 30 ℃ at the rate of 8 ℃/min, so that the ZIF-8@ FeMOF derived Fe-N co-doped carbon composite material is obtained and is marked as B1.
Example 2
1) Adding zinc nitrate hexahydrate (4mmol) into 41.7mL of methanol to obtain a first mixture;
2) 2-methylimidazole (16mmol) and CTAB (0.05mmol) were added to 33.3mL of methanol to give mixture two.
3) Adding the first mixture into the second mixture, adding 10mg of A1, stirring at 20 deg.C for 5h, centrifuging with methanol, and drying at 50 deg.C for 24 h; finally, in nitrogen, the temperature is raised from 20 ℃ to 800 ℃ at the rate of 3 ℃/min and is kept for 3h, and then the temperature is lowered to 20 ℃ at the rate of 5 ℃/min, so that the ZIF-8@ FeMOF derived Fe-N co-doped carbon composite material is obtained and is marked as B2.
Example 3
1) Adding zinc nitrate hexahydrate (1mmol) into 41.7mL of methanol to obtain a first mixture;
2) 2-methylimidazole (7mmol) and CTAB (0.01mmol) were added to 33.3mL of methanol to give mixture two.
3) Adding the first mixture into the second mixture, adding 10mg of A1, stirring at 20 deg.C for 5h, centrifuging with methanol, and drying at 50 deg.C for 24 h; finally, in nitrogen, the temperature is raised from 20 ℃ to 1000 ℃ at the speed of 5 ℃/min and is kept for 1h, and then the temperature is lowered to 40 ℃ at the speed of 10 ℃/min, so that the ZIF-8@ FeMOF derived Fe-N co-doped carbon composite material is obtained and is marked as B3.
Example 4
The preparation of the Fe-N co-doped carbon composite material was performed in the same manner as in example 1, except that A1 was changed to any one of A2-A5.
Comparative example 1
1) 0.7930g of zinc nitrate hexahydrate (2.72mmol) is added into 41.7mL of methanol to obtain a first mixture;
2) 0.9240g of 2-methylimidazole (11.3mmol) and 0.0120g of CTAB (0.033mmol) were added to 33.3mL of methanol to give a second mixture.
3) Adding mixture one to mixture two, adding 10mg of A1, stirring at 20 deg.C for 5h, centrifuging with methanol, and drying at 50 deg.C for 24h to obtain ZIF-8 composite material, denoted as C1.
Comparative example 2
A1 was heated from 25 ℃ at 4 ℃/min to 900 ℃ under nitrogen and held for 2h, followed by cooling at 8 ℃/min to 30 ℃ to give the product designated C2.
Comparative example 3
C1 was heated from 25 ℃ at 4 ℃/min to 900 ℃ in nitrogen and held for 2h, followed by cooling at 8 ℃/min to 30 ℃ to give the product designated C3.
Detection example 1
Performing morphology characterization on B1 through a JEOLJSM-6700F scanning electron microscope, wherein the specific result is shown in figure 1; carrying out morphology characterization on the C2, wherein the specific result is shown in a figure 2; carrying out morphology characterization on the C1, wherein the specific result is shown in a figure 3; the morphology of C3 was characterized, and the specific results are shown in FIG. 4.
The morphology of B1 was characterized by a transmission electron microscope of JEOL-2010, Hitachi, Japan, and the specific results are shown in FIG. 5.
X-ray photoelectron spectroscopy (XPS) characterization of B1 was obtained by Al Ka radiation from Thermo Fisher Scientific, USA, thermocouple ESCALAB250XI spectrometer, as shown in FIG. 6.
Compare fig. 1 pure FeMOF before calcination; FIG. 2 shows that the collapse color of the calcined FeMOF is yellow brown, and the main component is iron oxide; comparing the pure ZIF-8 before calcination in FIG. 3 with the pure ZIF-8 after calcination in FIG. 4, the dispersibility is poor, but the Zn compound is volatilized at the temperature of above 900 ℃, so that a plurality of small holes are formed on the surface of the calcined ZIF-8, the surface area is increased, and the calcined ZIF-8 is a loose and porous carbon material; FIG. 5 shows that FeMOF is surrounded by many ZIF-8 with small size, during the reaction, ZIF-8 wraps FeMOF, and the two are compounded to form a porous Fe-N co-doped carbon composite material with exposed multi-active sites through high-temperature calcination.
And the XPS analysis and characterization of figure 6 are combined, so that the prepared composite material contains elements Fe, N, C and O, and the successful preparation of the Fe-N co-doped carbon composite material derived from ZIF-8@ FeMOF is further proved.
The products of examples 2-4 were characterized according to the same method, with results substantially identical to those of example 1; the products of preparation examples 2 to 5 were characterized in the same manner, and the results were substantially identical to those of preparation example 1.
Application example 1
The glassy carbon modified electrodes modified by B1, C2 and C3 are correspondingly marked as B1 ', C2 ' and C3 '; in addition, a glassy carbon modified electrode made from commercial platinum carbon powder (containing 20 wt% platinum) was also recorded as 20% Pt/C;
preparing a modified electrode:
the glassy carbon electrode and the disc electrode are carefully cleaned before use, are polished on wet polishing cloth by using alumina powder, and are sequentially subjected to ultrasonic treatment in acetone and deionized water to achieve thorough cleaning.
5mg of the final sample was added to the mixture (naphthol: isopropanol in a volume ratio of 5: 200: 800) to prepare a catalyst suspension at a concentration of 5 mg/mL. Respectively taking 5 microliter (dripping twice, 2.5 microliter each time) to a glassy carbon electrode with the diameter of 3mm to prepare the glassy carbon modified electrode.
A disk modified electrode was prepared separately from 10. mu.l (two drops, 5. mu.l each) to a 5mm disk electrode for future use.
A0.1 mol/L KOH solution is used as an electrolyte, a platinum electrode is selected as a counter electrode, a calomel electrode is selected as a reference electrode, B1 'is used as a working electrode, and CV test is carried out on B1' in a three-electrode test system. Introducing nitrogen into the electrolyte for 30-40min, and performing CV test; then, oxygen is introduced into the electrolyte for 30-40min, and then CV test is carried out. In the CV test, the potential was selected to be-0.9-0.1V and the scanning rate was 0.01V/s. The CV curve obtained from the test is shown in FIG. 7; in FIG. 7, the abscissa E/V represents the voltage in volts V; ordinate Current Density (mA.cm)-2) Expressed is the current density in mA.cm-2。
Selecting 0.1mol/L KOH as electrolyte, selecting a platinum electrode as a counter electrode and a calomel electrode as a reference electrode, introducing oxygen into the electrolyte for 30-40min in a rotating disc three-electrode test system, and then sequentially selecting a platinum carbon powder modified electrode, B1 ', C2 ' and C3 ' as working electrodes to carry out LSV test; wherein, the potential of LSV test is selected to be-0.9-0.1V, the scanning speed is 0.01V/s, and the electrode rotating speed is 1600 rpm; finally, overlapping the obtained LSV test curves to obtain a graph 8; in FIG. 8, the abscissa E/V represents the voltage in volts V; ordinate Current Density (mA.cm)-2) Expressed is the current density in mA.cm-2。
Respectively taking B1' and 20% Pt/C modified electrodes as working electrodes, taking 0.1mol/L KOH solution as electrolyte, selecting a platinum electrode as a counter electrode and a calomel electrode as a reference electrode, and carrying out timing current (i-t) test in a three-electrode test system; firstly, introducing oxygen into the electrolyte for 30-40min, maintaining the oxygen introduction state, and then performing a timing current (i-t) test; finally, the test curves of the two are superposed to obtain the result shown in the figure 9; the test result shows that the composite material prepared by the experiment has stability superior to platinum carbon powder. In FIG. 9, the abscissa E/V represents the voltage in volts V; the ordinate Current (mA) indicates the current density in mA.
As can be seen from fig. 7-9: in the oxygen reduction catalytic performances of B1, C2 and C3, the Fe-N co-doped carbon composite material derived from ZIF-8@ FeMOF is obviously shown to have optimal catalytic activity and lower catalytic potential; and has better stability compared with the current commercial platinum carbon powder with the best oxygen reduction catalytic activity.
The products of examples 2-4 were characterized in the same manner and were substantially identical to the product of example 1.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (21)
1. A preparation method of a ZIF-8@ FeMOF derived Fe-N co-doped carbon material is characterized by comprising the following steps:
1) carrying out contact reaction on FeMOF, a zinc source, 2-methylimidazole and a surfactant in a solvent to prepare ZIF-8@ FeMOF;
2) calcining the ZIF-8@ FeMOF to produce the ZIF-8@ FeMOF derived Fe-N co-doped carbon material;
wherein the FeMOF is Fe3+A metal-organic framework material with a net structure and an organic ligand; the ZIF-8 is Zn2+And (3) reacting with 2-methylimidazole to obtain the zeolite imidazolate framework material.
2. The preparation method according to claim 1, wherein in step 1), the FeMOF, the zinc source, the 2-methylimidazole and the surfactant are used in a ratio of 10 mg: 1-4 mmol: 7-16 mmol: 0.01-0.05 mmol.
3. The preparation method according to claim 1, wherein in step 1), the FeMOF and the solvent are used in a ratio of 10 mg: 50-100 mL.
4. The production method according to claim 1, wherein, in step 1), the contact reaction satisfies the following condition: the reaction temperature is 20-30 ℃, and the reaction time is 3-5 h.
5. The preparation method according to claim 1, wherein the charging sequence of step 1) is: firstly, dispersing a zinc source in a solvent to form a first mixture, and dispersing 2-methylimidazole and a surfactant in the solvent to form a second mixture; and then mixing the mixture I, the mixture II and the FeMOF.
6. The preparation method according to claim 1, wherein, in step 1), the zinc source is selected from at least one of zinc nitrate hexahydrate, zinc sulfate, and zinc chloride.
7. The production method according to claim 1, wherein, in step 1), the surfactant is selected from at least one of cetyltrimethylammonium bromide CTAB, polyvinylpyrrolidone PVP, sodium dodecylbenzenesulfonate, sodium dodecylsulfate.
8. The preparation method according to claim 1, wherein, in step 1), the solvent is at least one selected from the group consisting of anhydrous methanol, redistilled water, and N, N-dimethylformamide DMF.
9. The production method according to claim 1, wherein, in step 2), the calcination satisfies the following condition: in nitrogen or inert gas, raising the temperature from 20-35 ℃ to 800-1000 ℃ at the rate of 3-5 ℃/min, preserving the temperature for 1-3h, and then lowering the temperature to 20-40 ℃ at the rate of 5-10 ℃/min.
10. The production method according to claim 9, wherein the inert gas is argon.
11. The production method according to claim 1, wherein, after the contact reaction, the production method further comprises: the reaction was centrifuged to remove the solvent, followed by drying.
12. The production method according to claim 11, wherein the drying satisfies the following condition: the drying temperature is 50-70 deg.C, and the drying time is 12-24 h.
13. The method of claim 1, wherein the FeMOF is prepared by: in a solvent, an iron source and an organic ligand are subjected to heat treatment.
14. The production method according to claim 13, wherein the heat treatment satisfies the following condition: the temperature is 140-160 ℃, and the time is 12-26 h.
15. The preparation method according to claim 13, wherein the iron source and the organic ligand are used in a ratio of 1.1 mmol: 0.5-1 mmol.
16. The preparation method of claim 13, wherein during the preparation of the FeMOF, the ratio of the iron source to the solvent is 1.1 mmol: 10-20 mL.
17. The production method according to claim 13, wherein the iron source is selected from at least one of iron sulfate, iron chloride hexahydrate, and iron nitrate.
18. The production method according to claim 13, wherein the organic ligand is selected from at least one of terephthalic acid, phthalic acid, 2-aminoterephthalic acid.
19. A process according to claim 13, wherein the solvent used in the preparation of the FeMOF is at least one selected from the group consisting of absolute methanol, redistilled water, N-dimethylformamide DMF.
20. A ZIF-8@ FeMOF derived Fe-N co-doped carbon material, wherein the ZIF-8@ FeMOF derived Fe-N co-doped carbon material is prepared by the preparation method of any one of claims 1 to 19.
21. Use of the ZIF-8@ FeMOF-derived Fe-N co-doped carbon material of claim 20 in catalytic reactions for oxygen reduction.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811454105.9A CN109616672B (en) | 2018-11-30 | 2018-11-30 | ZIF-8@ FeMOF derived Fe-N co-doped carbon material and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811454105.9A CN109616672B (en) | 2018-11-30 | 2018-11-30 | ZIF-8@ FeMOF derived Fe-N co-doped carbon material and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109616672A CN109616672A (en) | 2019-04-12 |
CN109616672B true CN109616672B (en) | 2021-08-27 |
Family
ID=66005568
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811454105.9A Active CN109616672B (en) | 2018-11-30 | 2018-11-30 | ZIF-8@ FeMOF derived Fe-N co-doped carbon material and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109616672B (en) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112005413B (en) * | 2019-07-01 | 2022-05-17 | 青岛科技大学 | ZIF-8-based nickel-iron-nitrogen-doped carbon material three-function electrocatalyst and preparation method and application thereof |
CN110571440B (en) * | 2019-08-14 | 2022-01-25 | 电子科技大学 | FeN4-CNT oxygen reduction catalyst preparation method |
CN110380067A (en) * | 2019-08-15 | 2019-10-25 | 中国科学技术大学 | A kind of fuel cell membrane electrode catalyst, preparation method and application |
CN110624584B (en) * | 2019-09-09 | 2022-09-13 | 浙江工业大学 | Fe-Zn-based nitrogen-doped nano catalyst and application thereof in preparation of fluoroalcohol compound |
CN111697239B (en) * | 2020-06-28 | 2022-03-04 | 全球能源互联网研究院有限公司 | Cobalt-iron alloy and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof |
CN112394095B (en) * | 2020-11-30 | 2021-10-12 | 江西农业大学 | Electrochemical sensor for selectively detecting nitrite ions and preparation method and application thereof |
CN112730323B (en) * | 2020-12-18 | 2022-04-29 | 上海交通大学 | Novel hybrid metal nano material, preparation method thereof and application thereof in matrix-assisted laser desorption ionization mass spectrometry |
CN112827495B (en) * | 2021-01-05 | 2023-03-31 | 北京科技大学 | Preparation method of heat storage/catalysis integrated material |
CN112979983B (en) * | 2021-03-03 | 2022-08-05 | 太原理工大学 | Surface-doped porous ZIF-8 flexible MOFs material, preparation method and application |
CN113314721A (en) * | 2021-06-10 | 2021-08-27 | 广东省武理工氢能产业技术研究院 | Doping type oxygen reduction catalyst with graded ventilation structure and preparation method thereof |
CN113699553B (en) * | 2021-08-31 | 2022-09-02 | 常州工学院 | Supported porous N-doped carbon nanomaterial and preparation method and application thereof |
CN114409914B (en) * | 2022-01-12 | 2023-04-18 | 中山大学肿瘤防治中心(中山大学附属肿瘤医院、中山大学肿瘤研究所) | Preparation method of iron-based metal organic framework composite material with MOF-On-MOF framework, obtained product and application |
CN115301268B (en) * | 2022-07-08 | 2023-11-24 | 华南理工大学 | Activation of peroxodisulfates to selectively produce singlet oxygen Fe-N 4 Active site monoatomic catalyst and preparation method and application thereof |
CN116177692A (en) * | 2023-02-09 | 2023-05-30 | 四川大学 | MOFs derived carbon electrode material for CDI dephosphorization and electrode |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106495128A (en) * | 2016-11-09 | 2017-03-15 | 江苏理工学院 | A kind of single dispersing N doping hollow carbon nanometer polyhedral and preparation method thereof |
CN107949941A (en) * | 2015-09-08 | 2018-04-20 | 庄信万丰燃料电池有限公司 | Redox reactions catalyst |
CN107974734A (en) * | 2017-11-24 | 2018-05-01 | 合肥工业大学 | A kind of preparation method of the porous carbon fiber of Fe/N doping |
CN108682872A (en) * | 2018-05-22 | 2018-10-19 | 江苏理工学院 | A kind of preparation method of the nitrogen co-doped grading-hole carbon nanosheet oxygen reduction catalyst of iron cobalt |
CN108808018A (en) * | 2018-06-26 | 2018-11-13 | 西北师范大学 | A kind of preparation and application of octahedron nitrating carbon skeleton material |
-
2018
- 2018-11-30 CN CN201811454105.9A patent/CN109616672B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107949941A (en) * | 2015-09-08 | 2018-04-20 | 庄信万丰燃料电池有限公司 | Redox reactions catalyst |
CN106495128A (en) * | 2016-11-09 | 2017-03-15 | 江苏理工学院 | A kind of single dispersing N doping hollow carbon nanometer polyhedral and preparation method thereof |
CN107974734A (en) * | 2017-11-24 | 2018-05-01 | 合肥工业大学 | A kind of preparation method of the porous carbon fiber of Fe/N doping |
CN108682872A (en) * | 2018-05-22 | 2018-10-19 | 江苏理工学院 | A kind of preparation method of the nitrogen co-doped grading-hole carbon nanosheet oxygen reduction catalyst of iron cobalt |
CN108808018A (en) * | 2018-06-26 | 2018-11-13 | 西北师范大学 | A kind of preparation and application of octahedron nitrating carbon skeleton material |
Non-Patent Citations (1)
Title |
---|
"A Fe-N-C hybrid electrocatalyst derived from bimetal-organic framework for efficient oxygen reduction";Teng Liu等;《Journal of Materials Chemistry A》;20161231;第4卷(第29期);第11357-11364页 * |
Also Published As
Publication number | Publication date |
---|---|
CN109616672A (en) | 2019-04-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109616672B (en) | ZIF-8@ FeMOF derived Fe-N co-doped carbon material and preparation method and application thereof | |
CN109841854B (en) | Nitrogen-doped carbon-supported monatomic oxygen reduction catalyst and preparation method thereof | |
CN108365230B (en) | Universal preparation method for active site and air electrode structure combination and application | |
CN109103468B (en) | Iron and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof | |
CN111146457B (en) | Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound | |
CN112447986B (en) | Rare earth metal organic framework derived bifunctional catalyst and application thereof | |
CN111883792B (en) | Transition metal manganese and nitrogen-doped carbon oxygen reduction electrocatalyst and preparation method and application thereof | |
CN114293223B (en) | Method for preparing superfine cerium dioxide supported metal monoatomic catalyst from cluster-based framework material | |
CN110137516B (en) | Iron-tin alloy loaded sulfur-nitrogen co-doped carbon electrocatalyst and preparation method thereof | |
CN110961162B (en) | Catalyst carrier, precious metal catalyst, and preparation method and application thereof | |
CN110534755A (en) | A kind of preparation method and application of zinc-base metal-organic framework material and its nitrogen co-doped carbon-based oxygen reduction electro-catalyst of iron | |
CN109192996B (en) | Spherical nitrogen-doped carbon-supported cobalt-based oxygen reduction catalyst and preparation method and application thereof | |
CN111359608A (en) | Nano Ag-MnO2Modified graphene composite oxygen reduction catalyst and preparation method thereof | |
Huang et al. | Fe–N–C nanostick derived from 1D Fe-ZIFs for electrocatalytic oxygen reduction | |
CN110061251A (en) | A kind of pyridine based triazine derivative polymer matrix nitrogen-doped carbon catalyst and its preparation method and application | |
CN107123816B (en) | A kind of on-vehicle fuel novel PtM octahedron cathode alloy catalyst and preparation method thereof | |
CN104241664B (en) | A kind of PtM/M '-PPy-C eelctro-catalyst for fuel cell oxygen reduction reaction and preparation method thereof | |
CN113451592A (en) | Carbon-based catalyst with hierarchical pore structure and preparation method and application thereof | |
CN102806106A (en) | Preparation method of carbon-supported metal polypyrrole oxygen reduction catalyst | |
CN116093348A (en) | Preparation method of cobalt-nitrogen-carbon material with high electrocatalytic performance | |
CN111193042A (en) | Nitrogen-doped graphene @ copper-iron ball composite material and preparation method and application thereof | |
CN110137518B (en) | Self-loading Fe-N-C oxygen reduction catalyst and preparation method thereof | |
CN110064436B (en) | Catalyst based on pyridyl tetrazine ring based metal coordination polymer and preparation method and application thereof | |
CN115161695B (en) | Non-noble metal catalyst and preparation method and application thereof | |
CN116463663B (en) | Nanoparticle material and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |