CN113813975A - ZIF-8 derived hierarchical pore M-N-C catalyst and preparation method thereof - Google Patents
ZIF-8 derived hierarchical pore M-N-C catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 title claims abstract description 54
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 6
- 150000003624 transition metals Chemical class 0.000 claims abstract description 6
- 239000002091 nanocage Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 35
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000395 magnesium oxide Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- -1 transition metal salt Chemical class 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000010453 quartz Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 238000012546 transfer Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 230000010757 Reduction Activity Effects 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 57
- 239000002131 composite material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003091 WCl6 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HVENHVMWDAPFTH-UHFFFAOYSA-N iron(3+) trinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVENHVMWDAPFTH-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a ZIF-8 derived hierarchical pore M-N-C catalyst and a preparation method thereof, wherein the catalyst is of a concave structure, and the size of a dodecahedral carbon nanocage structure of the catalyst is 50-1 mu M; the diameter of the bamboo-shaped carbon nano tube is 20-30 nm, and the catalyst is provided with micropores with the aperture smaller than 2nm, mesopores with the aperture of 2-50 nm and macropores with the aperture larger than 50 nm; nanometer MgO is introduced as a mesoporous template in the process of ZIF-8 precursor crystal growth, transition metal is doped in situ at the same time, a microporous structure is derived from ZIF-8 after high-temperature carbonization, a product contains a large number of mesopores after MgO is removed by acid washing, and the two pores are mutually connected in carbon to form a macroporous network. The invention has higher mass transfer efficiency, higher oxygen reduction activity and stability in acid and alkaline media, and can be widely applied to the fields of proton exchange membrane fuel cells, metal-air cells and the like.
Description
Technical Field
The invention relates to a catalyst, in particular to a ZIF-8 derived hierarchical pore M-N-C catalyst and a preparation method thereof.
Background
Fuel cells and metal-air cells, which are based on Oxygen Reduction Reaction (ORR), can convert chemical energy into electrical energy using ORR catalysts. However, the existing precious metal ORR catalyst has scarce resources and poor durability, and is difficult to realize large-scale application. Non-noble metal M/N/C catalysts have attracted extensive attention due to the advantages of excellent activity, low cost and the like.
The ordered porous structure of the MOFs material enables the MOFs material to have various characteristics, wherein a large number of active sites are grown on the surface of a ZIF-8 derived carbon-based catalyst, and good ORR activity is shown. However, these catalysts are dominated by microporous structures, which are not conducive to the mass transfer process of the ORR reaction. However, the narrow characteristic of the microporous structure limits the transmission of oxygen, water molecules and the like, and the long-term stability of the catalyst is greatly influenced by the low efficiency of mass transfer, so that the mass transfer process of the oxygen reduction reaction can be effectively promoted by introducing mesopores and macropores into the M/N/C catalyst besides micropores, so that the activity and the stability of the catalyst are effectively improved, and the practical application of the M/N/C catalyst is expected to be promoted.
For example, patent CN109499620A discloses a method for preparing TiO2/ZIF-8 composite photocatalyst, which comprises performing solvothermal reaction on a mixed solution of soluble zinc salt, 2-methylimidazole and a first organic solvent, deprotonating 2-methylimidazole, self-assembling zinc ions to ZIF-8, filtering, washing, drying, and grinding to obtain ZIF-8Powder; hydrolyzing a hydrolyzable titanium source with water in a second organic solvent to obtain a first solution containing nano titanium dioxide; concentrating the first solution, and increasing the concentration of the nano titanium dioxide sol to obtain a second solution; and adding the ZIF-8 powder into the second solution, fully mixing by ultrasonic oscillation, filtering, washing and drying to obtain TiO2/ZIF-8 composite photocatalyst.
Patent CN112517073A discloses a preparation method of a catalyst of WS2 supported on ZIF-8 material, which comprises the following steps: (1) dissolving zinc salt in a solvent to prepare a solution containing zinc; (2) dissolving dimethylimidazole in a solvent to prepare a ligand solution containing dimethylimidazole; (3) pouring the solution obtained in the step (1) into the solution obtained in the step (2), stirring at room temperature for a period of time, transferring to a 50ml reaction kettle, reacting at high temperature for a period of time, cooling, centrifuging, and drying to obtain a ZIF-8 hybrid material; (4) preparing a solution containing WCl6 to obtain a solution A; (5) 50mg of ZIF-8 is weighed and placed in 10ml of methanol solution, and stirring is carried out to obtain solution B; (6) adding a proper amount of the solution A into the solution B, stirring for 3 hours, centrifuging, and drying in a vacuum oven at 70 ℃; (7) introducing gas into a tubular furnace, carbonizing, and vulcanizing to obtain the catalyst of the ZIF-8 material loaded WS 2; (8) adding 0.5mol/L sulfuric acid into a constant-temperature container of a five-mouth bottle, and adding the ZIF-8 supported WS2 catalyst obtained in the step (7) onto a rotating disk electrode; (9) the progress of the catalytic reaction was recorded with nova2.1 software.
Patent CN110752380A discloses a ZIF-8 derived hollow Fe/Cu-N-C type oxygen reduction catalyst, a preparation method and application thereof, and specifically discloses the following technical contents: the method comprises the following steps:
(1) preparing a precursor ZIF-8 material:
respectively dissolving zinc nitrate hexahydrate and 2-methylimidazole in an organic solvent, and completely dissolving the zinc nitrate hexahydrate and the 2-methylimidazole by ultrasonic treatment to obtain a zinc nitrate hexahydrate solution and a 2-methylimidazole solution; mixing and stirring the two solutions at normal temperature to obtain a white precipitate, centrifuging the white precipitate, adding the white precipitate into an organic solution, performing reflux reaction to obtain a ZIF-8 solution, performing centrifugal washing, vacuum drying to obtain white solid powder ZIF-8, and performing vacuum activation to obtain pure ZIF-8;
(2) catalyst precursor Fe (OH)3-Cu(OH)2Preparation of @ ZIF-8 material:
ultrasonically dispersing pure ZIF-8 in an organic solution to obtain a ZIF-8 solution, and respectively adding CuCl2.2H2O and FeCl3.6H2Dissolving O in organic solution to obtain CuCl2.2H2O and FeCl3.6H2O mixing the solution with CuCl2.2H2O and FeCl3.6H2Slowly adding the O mixed solution into the ZIF-8 solution, and mixing and stirring the two solutions at normal temperature to obtain FeCl3-CuCl2@ ZIF-8 solution; FeCl obtained3-CuCl2@ ZIF-8 solution is centrifugally washed and dried in vacuum to obtain a catalyst precursor FeCl3-CuCl2@ ZIF-8 composite material; FeCl is added3-CuCl2Continuing to ultrasonically disperse the @ ZIF-8 composite material in an organic solution to obtain FeCl3-CuCl2@ ZIF-8 composite solution; dissolving KOH in an organic solution to obtain a KOH solution, slowly adding the KOH solution into a FeCl3-CuCl2@ ZIF-8 composite material solution, and stirring at normal temperature to obtain Fe (OH)3-Cu(OH)2@ ZIF-8 solution; the resulting Fe (OH)3-Cu(OH)2@ ZIF-8 solution is centrifugally washed, dried in vacuum and activated to obtain a precursor Fe (OH)3-Cu(OH)2@ ZIF-8 composite material;
(3) preparation of iron/copper and nitrogen co-doped carbon material oxygen reduction electrocatalyst from precursor Fe (OH) prepared in step (2)3-Cu (OH)2@ ZIF-8 composite material, pickling the carbon material obtained by carbonizing in inert gas with dilute sulfuric acid, and continuously carbonizing the carbon material obtained by pickling in inert gas for the second time to obtain a black solid powder Fe/Cu-N-C catalyst, namely the ZIF-8 derived hollow Fe/Cu-N-C type oxygen reduction catalyst.
According to the method, ZIF-8 is used as a precursor, low-cost CuCl2.2H2O and low-cost FeCl3.6H2O are used as metal sources, and a high-temperature calcination method is adopted to prepare the Fe/Cu-N-C hollow structure catalyst with high catalytic activity for oxygen reduction reaction.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a ZIF-8 derived hierarchical pore M-N-C catalyst and a preparation method thereof, the ZIF-8 has high specific surface area, adjustable structure, porosity and easy doping, and the M/N/C carbon-based catalyst derived by taking the ZIF-8 as a precursor can realize in-situ doping of transition metal and nitrogen element and provide high active area and a large number of active sites for ORR reaction.
The technical scheme of the invention is as follows: a ZIF-8 derived hierarchical pore M-N-C catalyst is a dodecahedral carbon nanocage structure with a concave shape, a large number of pores and a small number of bamboo-shaped carbon nanotubes;
the size of the dodecahedral carbon nanocage structure is 50-1 mu m;
the diameter of a small amount of the bamboo-shaped carbon nano tubes is 20-30 nm;
the catalyst is provided with micropores with the aperture smaller than 2nm, mesopores with the aperture of 2-50 nm and macropores with the aperture larger than 50 nm;
the content of C in the catalyst is 80-86 at.%, the content of N is 5-10 at.%, and the content of transition metal is 0.2-1.5 at.%.
Preferably, the catalyst has a microporosity of 40% to 70%.
The invention also provides a preparation method of the ZIF-8 derived hierarchical pore M-N-C catalyst, which comprises the following steps:
s1) and preparation of M-MgO @ ZIF-8 precursor
S101), dissolving 2-methylimidazole in methanol, and fully stirring to obtain a solution A;
s102), dissolving zinc nitrate hexahydrate and transition metal salt in methanol, and fully performing ultrasonic treatment and stirring to obtain a solution B;
s103), dissolving nano magnesium oxide MgO in methanol, and fully performing ultrasonic treatment and stirring to obtain a solution C;
s104), pouring the solution A and the solution B into the solution C together, continuously stirring, standing for 24 hours after stirring is finished, then centrifugally collecting, centrifugally cleaning with ultrapure water and absolute ethyl alcohol, drying in vacuum at 60 ℃, and fully grinding to obtain M-MgO @ ZIF-8 precursor powder;
s2), preparation of M-N-C catalyst
Putting the M-MgO @ ZIF-8 precursor powder prepared in the step S1) into a quartz boat, carrying out high-temperature heat treatment at a certain heating rate in an inert gas atmosphere, cooling to room temperature to obtain carbon powder, grinding, acid washing, centrifugally cleaning to neutrality, and carrying out vacuum drying at 60 ℃ to obtain the ZIF-8 derived hierarchical pore M-N-C catalyst.
Further, in the step S1), the amount of the methanol is 20-200 mL; the ultrasonic time is 10-30 min; the stirring time is 0.5-12 h.
Further, in step S1), the transition metal salt is one or two of salts containing metal iron, nickel, cobalt or manganese, wherein the anion of the transition metal salt is chloride, nitrate, acetate or sulfate.
Further, in the step S1), the mass ratio of the transition metal salt to the zinc nitrate hexahydrate is 1: 1-10; the mass ratio of the 2-methylimidazole to the nano magnesium oxide is 1: 1-20.
Further, in the step S1), the size of the nano MgO is 10-50 nm.
Further, in the step S1) and the step S2), the centrifugal rotating speed is 8000-12000 rpm.
Further, in step S2), the inert gas atmosphere is one of nitrogen or argon.
Further, in the step S2), the temperature rise rate is 2-10 ℃/min; the temperature of the high-temperature heat treatment is 600-1050 ℃, and the heat preservation time is 1-4 h.
Further, in step S2), the acid washing condition is to pour the carbon powder obtained after the heat treatment into a beaker, add 200-400 ml0.5m sulfuric acid, stir at room temperature for 2 hours, then centrifugally collect with ultrapure water, and repeat the room temperature acid washing step again; then stirring the mixture for 6 to 12 hours at the constant temperature of 80 ℃ in a water bath by using 200mL0.5M sulfuric acid.
The invention has the beneficial effects that:
1. the ZIF-8 has high specific surface area, structure adjustability, porosity and easy doping, and the M/N/C carbon-based catalyst derived by taking the ZIF-8 as a precursor can realize in-situ doping of transition metal and nitrogen elements, thereby providing high active area and a large number of active sites for ORR reaction;
2. ZIF-8 porous Material of the present invention and Zn contained therein2+After the catalyst is volatilized at high temperature, the derived M/N/C catalyst has a microporous structure which is beneficial to the growth of active sites, but the narrow characteristic of the microporous structure limits the transmission of oxygen, water molecules and the like.
3. The improvement of the mass transfer performance of the M/N/C catalyst can overcome the serious polarization problem and the stability problem of the catalyst in battery application, and promote the practical application of the M/N/C catalyst.
Drawings
FIG. 1 is an XRD pattern of an M-N-C catalyst prepared in accordance with the present invention;
FIG. 2 is a plot of N2 adsorption-desorption for the M-N-C catalyst prepared in the present invention;
FIG. 3 is a Scanning Electron Micrograph (SEM) of an M-N-C catalyst prepared in the present invention;
FIG. 4 is a Transmission Electron Micrograph (TEM) of the M-N-C catalyst prepared in the present invention;
FIG. 5 is a plot of the linear voltammetric scan of the M-N-C catalyst prepared in the present invention in an oxygen-saturated acidic medium (0.1MHClO4) (electrode rotation speed 1600rmp, scan speed 10 mV/s);
FIG. 6 is a durability test (electrode potential 0.7Vvs. RHE, electrode speed 900rpm) of the M-N-C catalyst prepared in the present invention in an oxygen-saturated alkaline medium (0.1MKOH solution);
FIG. 7 is a graph showing the durability test (electrode potential 0.7Vvs. RHE, electrode speed 900rpm) of the M-N-C catalyst prepared in the present invention in an oxygen-saturated acidic medium (0.1MHClO4 solution).
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
example 1
This example provides a preparation method of a ZIF-8 derived hierarchical pore M-N-C catalyst, including the following steps:
s1) and preparation of M-MgO @ ZIF-8 precursor
Adding 4g of 2-methylimidazole into 60mL of methanol, and fully stirring to obtain a solution A;
dissolving 1.5g of zinc nitrate hexahydrate and 0.12g of ferric nitrate hexahydrate in 40mL of methanol, performing ultrasonic treatment for 10min, and fully stirring to obtain a solution B;
dissolving 800mg of nano magnesium oxide with the size of 20nm in 20mL of methanol, performing ultrasonic treatment for 10min, and fully stirring to obtain a solution C; then pouring the solution A and the solution B into the solution C together, continuously stirring for 6 hours, and standing for 24 hours after stirring is finished;
and then, centrifuging (8000rpm) to collect the precursor, centrifuging and cleaning ultrapure water and absolute ethyl alcohol, drying in vacuum at 60 ℃, and fully grinding to obtain M-MgO @ ZIF-8 precursor powder.
S2) preparation of M-N-C catalyst:
putting the M-MgO @ ZIF-8 precursor powder prepared in the step S1) into a quartz boat, heating to 950 ℃ at a heating rate of 5 ℃/min under the atmosphere of nitrogen inert gas for high-temperature heat treatment, preserving heat for 1h, cooling to room temperature after natural cooling to obtain carbon powder, fully grinding, pouring into a beaker, adding 300mL0.5M sulfuric acid, stirring for 2h at room temperature, centrifuging (10000rpm) with ultrapure water for collection, and repeating the room-temperature acid washing step again; then stirring the mixture for 8 hours in water bath at the constant temperature of 80 ℃ by using 300mL0.5M sulfuric acid;
and then repeatedly centrifuging and cleaning the catalyst by using deionized water to be neutral, and drying the catalyst in vacuum at 60 ℃ to obtain the ZIF-8 derived hierarchical pore M-N-C-1 catalyst.
Example 2
S1), preparation of an M-MgO @ ZIF-8 precursor:
adding 4g of 2-methylimidazole into 60mL of methanol, and fully stirring to obtain a solution A; dissolving 1.5g of zinc nitrate hexahydrate and 0.16g of cobalt nitrate hexahydrate in 20mL of methanol, performing ultrasonic treatment for 10min, and fully stirring to obtain a solution B; dissolving 400mg of nano magnesium oxide with the size of 20nm in 20mL of methanol, performing ultrasonic treatment for 10min, and fully stirring to obtain a solution C; then, the solution A and the solution B are poured into the solution C together, stirring is continued for 6 hours, and standing is carried out for 24 hours after the stirring is finished. And then, centrifuging (8000rpm) to collect the precursor, centrifuging and cleaning ultrapure water and absolute ethyl alcohol, drying in vacuum at 60 ℃, and fully grinding to obtain M-MgO @ ZIF-8 precursor powder.
S2), preparation of M-N-C catalyst:
putting the M-MgO @ ZIF-8 precursor powder prepared in the step S1) into a quartz boat, heating to 950 ℃ at a heating rate of 2 ℃/min under the atmosphere of nitrogen inert gas for high-temperature heat treatment, preserving heat for 2h, cooling to room temperature after natural cooling to obtain carbon powder, fully grinding, pouring into a beaker, adding 300mL0.5M sulfuric acid, stirring for 2h at room temperature, centrifuging (10000rpm) with ultrapure water for collection, and repeating the room-temperature pickling step again; then stirred for 8 hours by 300mL0.5M sulfuric acid at the constant temperature of 80 ℃ in a water bath. And then repeatedly centrifuging and cleaning the mixture by using deionized water to be neutral, and drying the mixture in vacuum at 60 ℃ to obtain the ZIF-8 derived hierarchical pore M-N-C catalyst.
Example 3
Performance testing
In the embodiment, the research object of the ZIF-8 derived hierarchical porous M-N-C catalyst prepared in the embodiment 1 is used, wherein the structural representation of the prepared M-N-C catalyst is shown in fig. 1-4, and the ORR performance test result of the catalyst is shown in fig. 5-7, wherein the sample 1 is a control group catalyst prepared by adding no nano MgO in a ZIF-8 precursor under the same conditions, and the sample 2 is the M-N-C catalyst prepared in the embodiment two.
From fig. 1, it can be observed that two diffraction peaks with 2 θ located at about 26.5 ° and 43.5 ° belong to the (002) and (101) crystal faces of graphitized carbon, respectively, and it is proved that the transition metal in the precursor can effectively catalyze the precursor to form the carbon material.
FIG. 2 is N of M-N-C catalyst2Adsorption-desorption curve. As can be seen from the figure, N2Adsorption-desorption curve at P/P0The instantaneous adsorption capacity is increased at a lower valueIt is clear that the catalyst has a considerable degree of micropores, while the presence of a hysteresis loop in the middle and rear section of the curve implies that the catalyst has a large number of mesopores. The experimental result shows that the specific surface area of the catalyst is 890m2The introduction of nano-sized MgO causes the M-N-C catalyst to have a large number of mesoporous channels besides micropores generated by carbonization, and the microporosity is only 54 percent, which is far lower than that of a pure ZIF-8 derived carbon material.
It can be seen from fig. 3 that most of the prepared catalyst particles had a surface-depressed dodecahedral structure, the size of the dodecahedral particles was about 200nm, and significant depressions and holes were observed on a part of the particle surface, which were generated by removing MgO adhered to the catalyst surface during the acid washing process, and in addition, it was observed that the catalyst contained a small amount of carbon nanotubes.
As can be observed from fig. 4, a large number of micropores are uniformly distributed in the catalyst, and in addition, mesoporous pores with larger sizes exist in the catalyst, which strongly indicates that nano MgO particles are successfully introduced into the particles of ZIF-8 in the precursor preparation stage and are removed in the subsequent acid washing treatment, and the pores with larger sizes provide good diffusion channels for the transmission of oxygen and water molecules in the oxygen reduction reaction, so that the mass transfer capacity and the long-term use stability of the material can be greatly improved.
FIG. 5 shows the M-N-C catalyst prepared in example 1 in an oxygen-saturated acidic medium (0.1 MHClO)4) Linear voltammogram (electrode rotation speed 1600rmp, scan speed 10 mV/s). Wherein, the sample 1 is a control sample which is prepared by adding no nano MgO in the ZIF-8 precursor and has only micropores under the same other conditions. As can be seen from the graph, the initial potential, half-wave potential and limiting current density of the catalyst sample 2 prepared from the M-MgO @ ZIF-8 precursor in the acidic medium are 0.94V, 0.72V and 5.6mA/cm, respectively2Significantly higher than that of comparative sample 1. The M-N-C catalyst with the hierarchical pore structure derived from the ZIF-8 prepared by the invention has higher activity.
FIGS. 6 and 7 are the basic media (0.1MKOH solution) and acid, respectively, of the M-N-C catalyst prepared in example 1 in oxygen saturated basic mediumSex medium (0.1MHClO4Solution) was tested (electrode potential 0.7vvs. rhe, electrode rotation speed 900 rpm). It can be seen from the figure that the stability of the M-N-C catalyst sample 2 prepared from the M-MgO @ ZIF-8 precursor is higher than that of the catalyst sample 1 prepared without adding MgO in the precursor, both in alkaline and acidic media, indicating that the M-N-C catalyst with a hierarchical porous structure has more stable and longer-lasting output in the ORR process, which is benefited by the existence of a larger pore structure to provide a smooth diffusion channel for oxygen and reaction products, and improve the mass transfer performance of the catalyst.
The foregoing embodiments and description have been presented only to illustrate the principles and preferred embodiments of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as hereinafter claimed.
Claims (10)
1. A ZIF-8 derived hierarchical pore M-N-C catalyst is characterized in that the catalyst is a dodecahedral carbon nanocage structure with a concave shape, a large number of pores and a small number of bamboo-shaped carbon nanotubes;
the size of the dodecahedral carbon nanocage structure is 50-1 mu m;
the diameter of a small amount of the bamboo-shaped carbon nano tubes is 20-30 nm;
the catalyst is provided with micropores with the aperture smaller than 2nm, mesopores with the aperture of 2-50 nm and macropores with the aperture larger than 50 nm;
the content of C in the catalyst is 80-86 at.%, the content of N is 5-10 at.%, and the content of transition metal is 0.2-1.5 at.%.
2. A ZIF-8 derived hierarchical pore M-N-C catalyst as claimed in claim 1 wherein: the catalyst has a microporosity of 40-70%.
3. A process for preparing the ZIF-8 derived hierarchical pore M-N-C catalyst of any of claims 1-2, comprising the steps of:
s1) and preparation of M-MgO @ ZIF-8 precursor
S101), dissolving 2-methylimidazole in methanol, and fully stirring to obtain a solution A;
s102), dissolving zinc nitrate hexahydrate and transition metal salt in methanol, and fully performing ultrasonic treatment and stirring to obtain a solution B;
s103), dissolving nano magnesium oxide MgO in methanol, and fully performing ultrasonic treatment and stirring to obtain a solution C;
s104), pouring the solution A and the solution B into the solution C together, continuously stirring, standing for 24 hours after stirring is finished, then centrifugally collecting, centrifugally cleaning with ultrapure water and absolute ethyl alcohol, drying in vacuum at 60 ℃, and fully grinding to obtain M-MgO @ ZIF-8 precursor powder;
s2), preparation of M-N-C catalyst
Putting the M-MgO @ ZIF-8 precursor powder prepared in the step S1) into a quartz boat, carrying out high-temperature heat treatment at a certain heating rate in an inert gas atmosphere, cooling to room temperature to obtain carbon powder, grinding, acid washing, centrifugally cleaning to neutrality, and carrying out vacuum drying at 60 ℃ to obtain the ZIF-8 derived hierarchical pore M-N-C catalyst;
pouring carbon powder obtained after heat treatment into a beaker, adding 200-400 mL0.5M sulfuric acid, stirring for 2h at room temperature, then centrifugally collecting with ultrapure water, and repeating the room-temperature acid washing step again; then stirring the mixture for 6 to 12 hours at the constant temperature of 80 ℃ in a water bath by using 200mL0.5M sulfuric acid.
4. The preparation method of the ZIF-8 derived hierarchical pore M-N-C catalyst as claimed in claim 3, wherein in the step S1), the amount of the methanol is 20-200 mL; the ultrasonic time is 10-30 min; the stirring time is 0.5-12 h.
5. The method of claim 3, wherein in step S1), the transition metal salt is one or two of salts containing iron, nickel, cobalt or manganese, and wherein an anion of the transition metal salt is chloride, nitrate, acetate or sulfate.
6. The preparation method of the ZIF-8 derived hierarchical pore M-N-C catalyst as claimed in claim 3, wherein in the step S1), the mass ratio of the transition metal salt to the zinc nitrate hexahydrate is 1: 1-10; the mass ratio of the 2-methylimidazole to the nano magnesium oxide is 1: 1-20.
7. The method of preparing the ZIF-8 derived hierarchical pore M-N-C catalyst as claimed in claim 3, wherein the nano MgO has a size of 10 to 50nm in the step S1).
8. The method of preparing a ZIF-8 derived hierarchical pore M-N-C catalyst of claim 3, wherein the centrifugation speed is 8000-12000 rpm in step S1) and step S2).
9. The method of preparing a ZIF-8 derived hierarchical pore M-N-C catalyst according to claim 3, wherein the inert gas atmosphere is one of nitrogen or argon in the step S2).
10. The preparation method of the ZIF-8 derived hierarchical pore M-N-C catalyst as claimed in claim 3, wherein in the step S2), the temperature rise rate is 2-10 ℃/min; the temperature of the high-temperature heat treatment is 600-1050 ℃, and the heat preservation time is 1-4 h.
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