CN112756014A - Preparation method of nitrogen-oxygen co-doped porous carbon loaded salen type monatomic catalyst - Google Patents
Preparation method of nitrogen-oxygen co-doped porous carbon loaded salen type monatomic catalyst Download PDFInfo
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- CN112756014A CN112756014A CN202110048554.9A CN202110048554A CN112756014A CN 112756014 A CN112756014 A CN 112756014A CN 202110048554 A CN202110048554 A CN 202110048554A CN 112756014 A CN112756014 A CN 112756014A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 8
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- BXYVBHVCQLBCID-UHFFFAOYSA-N 4-ethenyl-2-hydroxybenzaldehyde Chemical compound OC1=CC(C=C)=CC=C1C=O BXYVBHVCQLBCID-UHFFFAOYSA-N 0.000 claims description 4
- DZETWSGVBUVPMH-UHFFFAOYSA-N 4-formyl-3-hydroxybenzonitrile Chemical compound OC1=CC(C#N)=CC=C1C=O DZETWSGVBUVPMH-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon 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
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 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
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 159000000021 acetate salts Chemical class 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 13
- 229920002554 vinyl polymer Polymers 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- -1 cyano salen Chemical compound 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000000952 abberration-corrected high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/42—Tin
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Abstract
The invention relates to a preparation method of a nitrogen-oxygen co-doped porous carbon loaded salen type monatomic catalyst. A salen structure module and a polymerization functional group are reasonably designed, and the salen type monatomic catalyst is prepared through operations of polymerization-coordination-carbonization-acid washing and the like. Salen-type monatomic catalyst (M) of the present invention1the/NO-C) has the advantages of definite structure, convenient preparation, low cost and the like, enriches the research of related fields such as monatomic catalysts and the like, and has good research significance and value.
Description
Technical Field
The invention relates to a preparation method of a nitrogen-oxygen co-doped porous carbon loaded salen type monatomic catalyst, and belongs to the field of catalyst design and preparation.
Background
The monatomic catalyst has been one of the research hotspots in recent years due to its catalytic advantages of nearly 100% atomic utilization, high activity and high selectivity, and has received attention from a large number of researchers. Compared with the traditional nano particles, the monatomic catalyst has definite catalytic active sites and uniform structure, and is an ideal model for researching the intrinsic activity and catalytic reaction mechanism.
The carbon-based single-atom catalyst is a catalyst widely researched at present, and has great diversity in the fields of electrocatalysis, photocatalysis, thermal catalysis, concerted catalysis and the like. The conventional carbon-based single-atom catalyst usually takes a porous pure carbon carrier (C), a nitrogen-doped porous carbon carrier (N-C), a nitrogen-sulfur co-doped porous carbon carrier (NS-C) and a nitrogen-phosphorus co-doped porous carbon carrier (NP-C) as main materials, and effective synthesis and system research on the nitrogen-oxygen co-doped porous carbon (NO-C) are reduced; therefore, a preparation method of the adjustable and controllable nitrogen-oxygen co-doped porous carbon loaded monatomic catalyst with simple process and low cost is needed urgently.
The method for preparing the nitrogen-doped carbon-loaded monatomic catalyst by using the atomic layer deposition device is complex to operate and high in cost, and the technological conditions such as temperature, flow rate, time and the like need to be strictly controlled.
Korean patent KR 2020053323A, which prepares a carbon-supported monatomic catalyst by gas-phase dry-method arc discharge at a voltage of 10-100V and a current of 10-300A, has low safety, cumbersome process, and is inconvenient for general popularization.
Disclosure of Invention
Based on the characteristics of novel structure, simple process, low cost, adjustability, controllability and the like, the nitrogen-oxygen co-doped porous carbon loaded salen type monatomic catalyst is developed. In order to realize the purpose of the invention, the adopted technical scheme is as follows:
a method for preparing a nitrogen-oxygen co-doped porous carbon loaded salen type monatomic catalyst comprises the steps of designing a salen structure module and a polymerization functional group, and preparing the nitrogen-oxygen co-doped carbon loaded salen type monatomic catalyst (M) with a high specific surface area and a rich pore structure through polymerization-coordination-carbonization-acid washing and other operations1The structure of the compound is shown in a general formula (1):
in the general formula (1), M is a metal center and is selected from one of Al, Cr, Mn, Fe, Co, Ni, Zn and Sn; r is a linking structure selected from
A preparation method of a nitrogen-oxygen co-doped porous carbon loaded salen type monatomic catalyst is characterized in that an organic monomer derived from o-phenylenediamine and salicylaldehyde synthesizes a salen structure module with a polymerization functional group in an organic solvent; then carrying out high-temperature auto-polymerization on the salen structure module to form a nitrogen-oxygen co-doped porous carbon poly-salen precursor; then complexing and coordinating the nitrogen-oxygen co-doped porous carbon polysalen precursor with metal to form a nitrogen-oxygen co-doped porous carbon loaded metal salen precursor; then carbonizing the nitrogen-oxygen co-doped porous carbon loaded metal salen precursor at high temperature in an inert atmosphere to synthesize a nitrogen-oxygen co-doped carbon loaded metal catalyst; and finally removing the nano particles from the nitrogen-oxygen co-doped carbon-supported metal catalyst through acid washing to obtain the nitrogen-oxygen co-doped carbon-supported monatomic catalyst.
Wherein the organic monomer derived from salicylaldehyde is selected from one of 4-formyl-3-hydroxybenzonitrile and 4-vinyl-2-hydroxybenzaldehyde. The Salen monomer adopts a high-temperature self-polymerization method, the polymerization temperature range is 100-600 ℃, and the time is 1-24 h. The metal precursor is selected from one of corresponding metal oxoacid, metal chloride, metal nitrate, metal acetate, metal acetylacetone salt, metal carbonyl salt and organic metal compound. The carbonization gas flow is selected from one of nitrogen and argon. The carbonization temperature range is 600-1100 ℃, and the time is 1-5 h. Hydrochloric acid (HCl) and sulfuric acid (H) are selected in the acid washing process2SO4) Perchloric acid (HClO)4) One kind of (1).
Compared with the prior art, the invention has the following advantages:
1. simple operation, high polymerization efficiency, high product yield and high preparation success rate.
2. The polymerization functional group, the polymerization mode, the metal concentration and the metal species can be adjusted and controlled.
3. The catalyst has stable physical and chemical properties, and the recyclability of the catalyst is improved.
4. Is non-toxic and harmless, is environment-friendly, and meets the requirements of economy, sustainability and green chemistry.
Description of the drawings:
FIG. 1 is M1The transmission electron microscope AC HAADF-STEM picture is corrected by the/NO-C monoatomic spherical aberration, and monoatomic metals are marked by yellow rings.
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
O-phenylenediamine (100mmol) and 4-formyl-3-hydroxybenzonitrile (200mmol) are added into a two-necked round-bottom flask (250mL) containing 125mL of absolute ethanol, and the mixture is refluxed for 12 hours at 80 ℃; and naturally cooling to room temperature after the reaction is finished, carrying out vacuum filtration, washing with absolute ethyl alcohol, and carrying out vacuum drying to obtain the cyano salen precursor. This cyano salen precursor (20mmol) and ZnCl were placed in a glove box2(2.0 g) is put into a 50mL quartz tube, then the tube is sealed, and the reaction is carried out for 20h at 400 ℃ and 20h at 600 ℃ in turn, after the reaction is finished, the reaction product is naturally cooled to room temperature, washed by 6mol/L HCl, and dried in vacuum to obtain the polycyanosalen precursor. Placing a polycyanosalen precursor (0.5g) in 100mL of chloroform under the atmosphere of nitrogen, slowly adding 10mL of diethyl aluminum chloride (0.9M toluene), carrying out reflux reaction at 60 ℃ for 3h, naturally cooling to room temperature after the reaction is finished, respectively washing with ethyl acetate and water, and carrying out vacuum drying to obtain the polycyanoAl-salen precursor. Placing the polycyano Al-salen precursor in a tube furnace under flowing nitrogen at 5 ℃ min-1Heating to 600 ℃, keeping for 3 hours, then naturally cooling to room temperature, then soaking and washing for 12 hours at 80 ℃ by using 6mol/L HCl, and finally drying in vacuum to obtain the nitrogen-oxygen co-doped carbon-supported aluminum monatomic catalyst (Al)1[ NO-C, FIG. 1A) ].
Example 2
O-phenylenediamine (100mmol) and 4-formyl-3-hydroxybenzonitrile (200mmol) are added into a two-necked round-bottom flask (250mL) containing 125mL of absolute ethanol, and the mixture is refluxed for 12 hours at 80 ℃; and naturally cooling to room temperature after the reaction is finished, carrying out vacuum filtration, washing with absolute ethyl alcohol, and carrying out vacuum drying to obtain the cyano salen precursor. This cyano salen precursor (20mmol) and ZnCl were placed in a glove box2(2.0 g) was put into a 50mL quartz tube, and then the tube was sealed and reacted at 400 ℃ for 20 hours and 600 ℃ in this orderAnd (5) naturally cooling to room temperature after the reaction is finished, washing with 6mol/L HCl, and drying in vacuum to obtain the polycyanosalen precursor. Placing polycyanosalen precursor (0.5g) in 100mL of anhydrous ethanol, and slowly adding 1mL of 0.1mol/L FeCl3And (3) refluxing and reacting the solution at 80 ℃ for 3h, naturally cooling to room temperature after the reaction is finished, washing with water, and drying in vacuum to obtain the polycyanoFe-salen precursor. Placing the polycyanoyl Fe-salen precursor in a tube furnace under flowing nitrogen at 10 ℃ min-1Heating to 800 ℃ for 3 hours, then naturally cooling to room temperature, and then adding 2mol/L of H2SO4Soaking and washing at 80 ℃ for 12h, and finally drying in vacuum to obtain the nitrogen-oxygen co-doped carbon-supported iron monoatomic catalyst (Fe)1[ NO-C, FIG. 1B) ].
Example 3
O-phenylenediamine (100mmol), 4-vinyl-2-hydroxybenzaldehyde (200mmol) were added to a two-necked round-bottomed flask (250mL) containing 125mL of anhydrous ethanol and refluxed at 80 ℃ for 12 h; and naturally cooling to room temperature after the reaction is finished, carrying out vacuum filtration, washing with absolute ethyl alcohol, and carrying out vacuum drying to obtain the vinyl salen precursor. The vinyl salen precursor (20mmol), azobisisobutyronitrile (0.2g) and N, N-dimethylformamide (100mL) were put into a 250mL Schlenk bottle in a glove box, reacted at 200 ℃ for 20 hours, naturally cooled to room temperature after the reaction was completed, and vacuum-dried to obtain a polyvinyl salen precursor. Putting a polyvinyl salen precursor (0.5g) into 100mL of absolute ethyl alcohol, slowly adding 1mL of 0.1mol/L cobalt acetate solution, carrying out reflux reaction at 80 ℃ for 3h, naturally cooling to room temperature after the reaction is finished, washing with water, and carrying out vacuum drying to obtain the polyvinyl Co-salen precursor. Placing the polyvinyl Co-salen precursor in a tube furnace under flowing nitrogen at 10 ℃ min-1Heating to 900 ℃, keeping for 3 hours, naturally cooling to room temperature, then soaking and washing with 6mol/L HCl at 80 ℃ for 12 hours, and finally drying in vacuum to obtain the nitrogen-oxygen Co-doped carbon-supported cobalt monatomic catalyst (Co)1[ NO-C, FIG. 1C) ].
Example 4
O-phenylenediamine (100mmol), 4-vinyl-2-hydroxybenzaldehyde (200mmol) were added to a two-necked round bottom flask containing 125mL of anhydrous ethanolRefluxing at 80 deg.C for 12h (250 mL); and naturally cooling to room temperature after the reaction is finished, carrying out vacuum filtration, washing with absolute ethyl alcohol, and carrying out vacuum drying to obtain the vinyl salen precursor. The vinyl salen precursor (20mmol), azobisisobutyronitrile (0.2g) and N, N-dimethylformamide (100mL) were put into a 250mL Schlenk bottle in a glove box, reacted at 200 ℃ for 20 hours, naturally cooled to room temperature after the reaction was completed, and vacuum-dried to obtain a polyvinyl salen precursor. Putting a polyvinyl salen precursor (0.5g) into 100mL of absolute ethyl alcohol, slowly adding 1mL of 0.1mol/L stannous chloride solution, carrying out reflux reaction at 80 ℃ for 3h, naturally cooling to room temperature after the reaction is finished, washing with water, and carrying out vacuum drying to obtain the polyvinyl Sn-salen precursor. Placing the polyethylene-based Sn-salen precursor in a tube furnace under flowing nitrogen at 10 ℃ min-1Heating to 1100 deg.C at a heating rate, maintaining for 3 hr, and naturally cooling to room temperature; followed by 6mol/L HClO4Soaking and washing at 80 ℃ for 12h, and finally drying in vacuum to obtain the nitrogen-oxygen co-doped carbon-loaded tin monoatomic catalyst (Sn)1[ NO-C, FIG. 1D) ].
Claims (7)
1. A preparation method of a nitrogen-oxygen co-doped porous carbon loaded salen type monatomic catalyst is characterized in that a salen structure module and a polymerization functional group are designed, and the nitrogen-oxygen co-doped carbon loaded salen type monatomic catalyst (M) with a high specific surface area and a rich pore structure is prepared through polymerization-coordination-carbonization-acid washing and other operations1The structure of the compound is shown in a general formula (1):
in the general formula (1), M is a metal center and is selected from one of Al, Cr, Mn, Fe, Co, Ni, Zn and Sn; r is a linking structure selected from
2. The preparation method of the nitrogen-oxygen co-doped porous carbon supported salen type monatomic catalyst according to claim 1, wherein an organic monomer derived from o-phenylenediamine and salicylaldehyde is synthesized into a salen structure module with a polymerization functional group in an organic solvent; then carrying out high-temperature auto-polymerization on the salen structure module to form a nitrogen-oxygen co-doped porous carbon poly-salen precursor; then complexing and coordinating the nitrogen-oxygen co-doped porous carbon poly-salen precursor with metal to form a nitrogen-oxygen co-doped porous carbon loaded metal salen precursor; then carbonizing the nitrogen-oxygen co-doped porous carbon loaded metal salen precursor at high temperature in an inert atmosphere to synthesize a nitrogen-oxygen co-doped carbon loaded metal catalyst; and finally removing the nano particles from the nitrogen-oxygen co-doped carbon-supported metal catalyst through acid washing to obtain the nitrogen-oxygen co-doped carbon-supported monatomic catalyst.
3. The preparation method of the nitrogen-oxygen co-doped porous carbon supported salen-type monatomic catalyst according to claim 1, wherein the salicylaldehyde-derived organic monomer is one selected from 4-formyl-3-hydroxybenzonitrile and 4-vinyl-2-hydroxybenzaldehyde.
4. The preparation method of the nitrogen-oxygen co-doped porous carbon supported salen type monatomic catalyst as claimed in claim 1, wherein the salen monomer is prepared by a high-temperature self-polymerization method, and the polymerization temperature range is 100-600 ℃ and the time is 1-24 h.
5. The preparation method of the nitrogen-oxygen co-doped porous carbon supported salen type monatomic catalyst according to claim 1, wherein the metal precursor is one selected from corresponding metal oxyacids, metal chloride salts, metal nitrate salts, metal acetate salts, metal acetylacetone salts, metal carbonyl salts and organometallic compounds.
6. The preparation method of the nitrogen-oxygen co-doped porous carbon supported salen type monatomic catalyst according to claim 1, wherein the carbonization gas flow is selected from one of nitrogen and argon. The carbonization temperature range is 600-1100 ℃, and the time is 1-5 h.
7. The preparation method of the nitrogen-oxygen co-doped porous carbon-supported salen type monatomic catalyst according to claim 1, wherein hydrochloric acid (HCl) and sulfuric acid (H) are selected during acid washing2SO4) Perchloric acid (HClO)4) One kind of (1).
Priority Applications (1)
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| CN106824281A (en) * | 2017-02-16 | 2017-06-13 | 辽宁大学 | Salen Co catalyst based on molecular level and its preparation method and application |
| CN111715263A (en) * | 2020-07-03 | 2020-09-29 | 广州志成新材料有限公司 | Preparation method of nitrogen-doped carbon-supported monatomic catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106824281A (en) * | 2017-02-16 | 2017-06-13 | 辽宁大学 | Salen Co catalyst based on molecular level and its preparation method and application |
| CN111715263A (en) * | 2020-07-03 | 2020-09-29 | 广州志成新材料有限公司 | Preparation method of nitrogen-doped carbon-supported monatomic catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113624821A (en) * | 2021-08-11 | 2021-11-09 | 山东大学 | Containing MN2O2Carbon material of unit, preparation method and application for detecting NO |
| CN113624821B (en) * | 2021-08-11 | 2022-11-01 | 山东大学 | Containing MN2O2Carbon material of unit, preparation method and application for detecting NO |
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