CN111715263A - Preparation method of nitrogen-doped carbon-supported monatomic catalyst - Google Patents
Preparation method of nitrogen-doped carbon-supported monatomic catalyst Download PDFInfo
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- CN111715263A CN111715263A CN202010638658.0A CN202010638658A CN111715263A CN 111715263 A CN111715263 A CN 111715263A CN 202010638658 A CN202010638658 A CN 202010638658A CN 111715263 A CN111715263 A CN 111715263A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 9
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 125000000168 pyrrolyl group Chemical group 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 18
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- CZSOUHCUPOPPRC-UHFFFAOYSA-N 3-phenylphthalaldehyde Chemical compound O=CC1=CC=CC(C=2C=CC=CC=2)=C1C=O CZSOUHCUPOPPRC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- JHTVIDPUSBGWLD-UHFFFAOYSA-N phenanthrene-2,7-dicarbaldehyde Chemical compound O=CC1=CC=C2C3=CC=C(C=O)C=C3C=CC2=C1 JHTVIDPUSBGWLD-UHFFFAOYSA-N 0.000 claims description 3
- YLMXAUXHLGWKOH-UHFFFAOYSA-N pyrene-2,7-dicarbaldehyde Chemical compound C1=C(C=O)C=C2C=CC3=CC(C=O)=CC4=CC=C1C2=C43 YLMXAUXHLGWKOH-UHFFFAOYSA-N 0.000 claims description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000005416 organic matter Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000002244 precipitate Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- B01J35/61—
Abstract
The invention relates to a nitrogen-doped carbon-supported monatomic catalyst (M)1A preparation method of/N-C). The pyrrole structure and dialdehyde organic matter structure monomer are reasonably designed, and the nitrogen-doped carbon-supported monatomic catalyst with high specific surface area and rich pore structure is prepared through operations such as polymerization-metal coordination-carbonization. The nitrogen-doped carbon-supported monatomic catalyst has the characteristics of novel structure, simplicity in preparation, low cost, industrial production and the like, enriches the research of monatomic catalysts and other related fields, and has good research significance and application value.
Description
Technical Field
The invention relates to a preparation method of a monatomic catalyst, in particular to a preparation method of a nitrogen-doped carbon-supported monatomic catalyst, belonging to the technical field of material science and engineering.
Background
Monatomic catalysts generally refer to catalyst materials in which the metal is in a single atom dispersed form, particularly transition metal catalysts. Compared with the traditional nano particles, the single-atom catalyst realizes the nearly 100 percent dispersion of metal in the catalyst, exposes more catalytic active sites and active centers with uniform structures, has better reaction selectivity and higher intrinsic activity, and is an ideal material for researching the utilization rate of metal atoms to the utmost extent.
Nitrogen doped carbon supported monatomic catalyst (M)1the/N-C) is the most studied catalyst at present, and is widely applied to catalyzing alkyne olefin ketone ether hydrogenation, electrocatalytic hydrogen evolution, electrocatalytic oxygen reduction, carbon dioxide reduction, water dissociation and the like. The conventional preparation method of the nitrogen-doped carbon-supported monatomic catalyst at present is a coprecipitation method, an atomic layer deposition method, an impregnation method, a photochemical method, a pyrolysis method, a ball milling method and the like, and has the defects of expensive preparation device, complex process, small catalyst scale and the like; therefore, a preparation method which has simple process and low cost and can be industrially produced is needed.
The chinese patent CN 108393092 a utilizes an expensive atomic layer deposition apparatus to prepare the nitrogen-doped carbon supported monatomic catalyst, and the preparation method requires strict control of the process conditions such as deposition temperature, carrier flow rate, deposition time, etc., and is complex to operate and too high in cost.
The method for preparing the nitrogen-doped carbon-supported monatomic catalyst has the advantages of complex operation process, low catalyst yield and unsuitability for large-scale industrial production.
The preparation method of the monatomic catalyst supported on the carbon carrier by arc discharge at a voltage of 10-100V and a current of 10-300A in a dry gas phase process of korean patent KR 2020053323A is cumbersome in operation process, low in safety, and inconvenient for general popularization.
Disclosure of Invention
Based on the great challenge of developing nitrogen-doped carbon-supported monatomic catalyst with the characteristics of novel structure, simple preparation, low cost, industrial production and the like. In order to realize the purpose of the invention, the adopted technical scheme is as follows:
nitrogen-doped carbon-supported monatomic catalyst (M)1The preparation method of the/N-C) adopts a pyrrole structure and a dialdehyde organic structure as monomers, and prepares the nitrogen-doped carbon-supported monatomic catalyst with high specific surface area and rich pore structure through operations such as polymerization-metal coordination-carbonization, and the structure is shown in a general formula (1):
in the general formula (1), M is a metal center and is selected from one of Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Mo, Ru, Rh, Ag, Cd, In, Sn, W, Re, Ir, Pt, Au, Bi and Er; r is a functional structure with a benzene ring and is selected from
The preparation method of the nitrogen-doped carbon-supported monatomic catalyst is characterized in that a polyporphyrin framework is synthesized by pyrrole structure and dialdehyde organic structure monomers under the action of propionic acid; then complexing and coordinating the polyporphyrin framework and metal salt to form a monoatomic precursor; and finally carbonizing the precursor at high temperature in an inert atmosphere to synthesize the nitrogen-doped carbon-supported monatomic catalyst.
Wherein the dialdehyde organic matter structure monomer is selected from one of terephthalaldehyde, biphenyldicarbaldehyde, 2, 7-phenanthrene dicarbaldehyde and 2, 7-pyrenedicarbaldehyde. The metal salt monomer is selected from one of corresponding metal oxyacid, metal chloride salt, metal nitrate, metal acetate, metal acetylacetone salt and metal carbonyl salt. The carbonization gas flow is selected from one of nitrogen and argon. The carbonization temperature range is 100-1100 ℃, and the time is 1-5 h.
Compared with the prior art, the invention has the following beneficial effects:
1. high polymerization efficiency, high product yield, suitability for industrial production and the like.
2. The adjustable pore structure characteristics of the dialdehyde organic matter are controlled, and the selective enrichment and separation are enhanced.
3. The catalyst has good physical and chemical stability, and the stability and the recyclability of the catalyst are improved.
4. The reaction operation is simple, the metal universality is strong, the reproducibility is good, and the separation can be realized by filtering.
5. The method is nontoxic and harmless, environment-friendly, low in cost and high in economy, and meets the requirement of green chemistry.
Description of the drawings:
FIG. 1 is an electron micrograph of M1/N-C metal monoatomic spherical aberration.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the scope of the examples.
[ example 1 ]:
terephthalaldehyde (100mmol) was added to a two-necked round-bottom flask (1000mL) containing 500mL of propionic acid and heated to 140 ℃, then freshly distilled pyrrole (100mmol) was added slowly. After refluxing for 3 hours, the mixture was naturally cooled to room temperature, and 500mL of absolute ethanol was added. Subsequently, the resulting precipitate was suction-filtered under reduced pressure, washed with methanol to colorless and dried at 80 ℃ under vacuum to give a polyporphyrin framework. In N2The synthesized polyporphyrin framework (1g) was dispersed in 100mL of dry toluene under an atmosphere, and 5mL of an n-butyllithium solution (2.5M in n-hexane) was carefully injected and stirred at room temperature for 30 minutes. Then 0.1mL of titanium tetrachloride solution (TiCl) was added by syringe41.0M in toluene) was stirred at 100 ℃ for 3 h. Naturally cooling to room temperature, and then exposing the mixture to the air and stirring for 3 hours; and carrying out vacuum filtration on the obtained precipitate, washing the precipitate to be colorless by using methanol, and drying the precipitate at the temperature of 80 ℃ in vacuum to obtain the titanium monatomic precursor. Placing the titanium monatomic precursor in a tube furnace under flowing nitrogen at 5 ℃ for min-1Heating to 100 ℃ for 3 hours, and then naturally cooling to room temperature to obtain the nitrogen-doped carbon-supported titanium monatomic catalyst (Ti)1N-C, FIG. 1A).
[ example 2 ]:
biphenyldicarboxaldehyde (100mmol) was added to a two-necked round bottom flask (1000mL) containing 500mL propionic acid and heated to 140 deg.C, then freshly distilled pyrrole (100mmol) was added slowly. After refluxing for 3 hours, the mixture was naturally cooled to room temperature, and 500mL of absolute ethanol was added. Subsequently, the resulting precipitate was suction-filtered under reduced pressure, washed with methanol to colorless and dried at 80 ℃ under vacuum to give a polyporphyrin framework. In N2The synthesized polyporphyrin framework (1g) was dispersed in 100mL of N, N-dimethylformamide under an atmosphere, and 0.1mL of a copper nitrate solution (1M in N, N-dimethylformamide) was carefully injectedMethylformamide) was stirred at 150 ℃ for 3 h. Naturally cooling to room temperature, decompressing and filtering the obtained precipitate, washing the precipitate to be colorless by using methanol, and drying the precipitate in vacuum at 80 ℃ to obtain the copper monoatomic precursor. The copper monatomic precursor was placed in a tube furnace under flowing nitrogen at 5 ℃ for min-1Heating to 500 deg.C for 3 hours, and naturally cooling to room temperature to obtain nitrogen-doped carbon-supported copper monatomic catalyst (Cu)1N-C, FIG. 1B).
[ example 3 ]:
2, 7-phenanthrene dicarboxaldehyde (100mmol) was added to a two-necked round bottom flask (1000mL) containing 500mL of propionic acid and heated to 140 deg.C, then freshly distilled pyrrole (100mmol) was added slowly. After refluxing for 3 hours, the mixture was naturally cooled to room temperature, and 500mL of absolute ethanol was added. Subsequently, the resulting precipitate was suction-filtered under reduced pressure, washed with methanol to colorless and dried at 80 ℃ under vacuum to give a polyporphyrin framework. In N2The synthesized polyporphyrin framework (1g) was dispersed in 100mL of N, N-dimethylformamide under an atmosphere, 0.1mL of palladium acetylacetonate solution (1M in N, N-dimethylformamide) was carefully injected, and stirred at 150 ℃ for 3 h. Naturally cooling to room temperature, decompressing and filtering the obtained precipitate, washing the precipitate to be colorless by using methanol, and drying the precipitate in vacuum at 80 ℃ to obtain the palladium monoatomic precursor. The palladium monatomic precursor was placed in a tube furnace under flowing nitrogen at 5 ℃ for min-1Is heated to 800 ℃ for 3 hours and then naturally cooled to room temperature to obtain the nitrogen-doped carbon-supported palladium monatomic catalyst (Pd)1N-C, FIG. 1C).
Example 4:
2, 7-pyrene dicarboxaldehyde (100mmol) was added to a two-necked round bottom flask (1000mL) containing 500mL of propionic acid and heated to 140 deg.C, then freshly distilled pyrrole (100mmol) was added slowly. After refluxing for 3 hours, the mixture was naturally cooled to room temperature, and 500mL of absolute ethanol was added. Subsequently, the resulting precipitate was suction-filtered under reduced pressure, washed with methanol to colorless and dried at 80 ℃ under vacuum to give a polyporphyrin framework. In N2The synthesized polyporphyrin framework (1g) was dispersed in 100mL of diphenyl ether under an atmosphere, 0.005g of platinum chloride was carefully added, and stirred at 200 ℃ for 3 h. Naturally cooling to room temperature, and vacuum filtering to obtain precipitateThe material was washed with methanol to colorless and dried under vacuum at 80 ℃ to obtain a platinum monoatomic precursor. The platinum monatomic precursor was placed in a tube furnace, heated to 1100 ℃ under flowing argon at a heating rate of 5 ℃ min1, held for 3 hours, and then naturally cooled to room temperature to obtain a nitrogen-doped carbon-supported palladium monatomic catalyst (Pt1/N-C, fig. 1D).
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. Nitrogen-doped carbon-supported monatomic catalyst (M)1The preparation method of the/N-C) is characterized in that a pyrrole structure and a dialdehyde organic structure are used as monomers, and the nitrogen-doped carbon-supported monatomic catalyst with high specific surface area and rich pore structure is prepared through operations such as polymerization-metal coordination-carbonization, and the structure is shown in a general formula (1):
in the general formula (1), M is a metal center and is selected from one of Al, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Mo, Ru, Rh, Ag, Cd, In, Sn, W, Re, Ir, Pt, Au, Bi and Er; r is a functional structure with a benzene ring and is selected from
2. The preparation method of the nitrogen-doped carbon-supported monatomic catalyst according to claim 1, characterized in that a polyporphyrin framework is synthesized from pyrrole structural and dialdehyde organic structural monomers under the action of propionic acid; then complexing and coordinating the polyporphyrin framework and metal salt to form a monoatomic precursor; and finally carbonizing the precursor at high temperature in an inert atmosphere to synthesize the nitrogen-doped carbon-supported monatomic catalyst.
3. The method for preparing the nitrogen-doped carbon-supported monatomic catalyst according to claim 1, wherein the dialdehyde organic structural monomer is one selected from terephthalaldehyde, biphenyldicarbaldehyde, 2, 7-phenanthrene dicarbaldehyde and 2, 7-pyrenedicarbaldehyde.
4. The method for preparing the nitrogen-doped carbon-supported monatomic catalyst according to claim 1, wherein the metal salt monomer is one selected from the group consisting of a corresponding metal oxyacid, a metal chloride salt, a metal nitrate, a metal acetate, a metal acetylacetonate salt and a metal carbonyl salt.
5. The method of claim 1, wherein the carbonization gas flow is selected from nitrogen and argon.
6. The method as claimed in claim 1, wherein the carbonization temperature is 100-1100 ℃ for 1-5 h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112756014A (en) * | 2021-01-14 | 2021-05-07 | 武汉绿知行环保科技有限公司 | Preparation method of nitrogen-oxygen co-doped porous carbon loaded salen type monatomic catalyst |
| CN113871632A (en) * | 2021-08-23 | 2021-12-31 | 温州大学 | Nitrogen-doped carbon-loaded Mo/Pd alloy catalyst and application thereof |
| CN114438547A (en) * | 2022-01-28 | 2022-05-06 | 四川大学 | Electrocatalytic conjugated polymer composite material for hydrogen evolution reaction |
| CN114702023A (en) * | 2022-03-29 | 2022-07-05 | 河南师范大学 | Preparation method of carbon material with high monatomic metal loading capacity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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