CN114671820A - Aza-macrocyclic schiff base, metal complex thereof, micro-nano material and application - Google Patents
Aza-macrocyclic schiff base, metal complex thereof, micro-nano material and application Download PDFInfo
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- CN114671820A CN114671820A CN202210284615.6A CN202210284615A CN114671820A CN 114671820 A CN114671820 A CN 114671820A CN 202210284615 A CN202210284615 A CN 202210284615A CN 114671820 A CN114671820 A CN 114671820A
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- schiff base
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- macrocyclic
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- 239000002262 Schiff base Substances 0.000 title claims abstract description 51
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 50
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 26
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000033444 hydroxylation Effects 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000012530 fluid Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- -1 aza crown ether Chemical class 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical class OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
-
- 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
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- 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
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention discloses a aza-macrocyclic schiff base, a metal complex thereof, a micro-nano material and application, and relates to the technical field of aza-macrocyclic schiff bases16H34Cl2N4O8The structural formula is as follows:
the aza macrocyclic schiff base can be used as a ligand to prepare a metal complex, and the synthesis method is simple and convenient to operate; the metal complex is prepared into micro-nano particles, and is applied to catalyzing phenol hydroxylation reaction, so that the metal complex has good catalytic activityAnd the method has important significance for designing and exploring a novel azamacrocyclic complex catalyst.
Description
Technical Field
The invention relates to the technical field of aza-macrocyclic schiff bases, in particular to aza-macrocyclic schiff bases, metal complexes thereof, micro-nano materials and application.
Background
The aza crown ether is an electron-rich macrocyclic compound with a flexible skeleton structure, and is the first generation macrocyclic main molecule of supramolecular chemistry research. According to the size of a ring, the azacrown ether can selectively identify transition ions, lanthanide metal ions and electron-deficient neutral molecules.
Aza crown ether as phase transfer catalyst has been widely used in organic synthesis reaction, and its research in supermolecular catalysis has been reported.
In recent years, studies on metal complex catalysts in the field of selective catalysis have been attracting attention. At present, the metal complex catalyst mainly comprises porphyrin complexes, Salen complexes and other complexes, and the porphyrin complexes, the Salen complexes and the other complexes can catalyze olefin oxidation under relatively mild conditions to obtain higher conversion rate and selectivity. O-phenanthroline-CuCl synthesized by Li and the like2The complex can efficiently catalyze and oxidize cyclohexane under mild conditions, the conversion rate reaches 24.4%, and the selectivity of cyclohexanone is almost 100%. Binuclear Fe (III) complex synthesized by Esmelinhydro and the like is catalyzed by H2O2In the oxidation reaction of cyclohexane as oxygen source, the conversion rate reaches 19.2%, and the yield of alcohol ketone is 12.6% and 6.6% respectively.
Micro-nano technology and unique physics and chemistry of micro-nano particlesThe chemical characteristics attract wide attention, and the micro-nano catalyst can also bear more components due to a larger outer surface, more exposed unit cells, more active sites which are easy to approach and uniformly distributed and the like.
Research on Ag nano-loading on alpha-Al by the same people 2O3The carrier catalyzes molecular oxygen to oxidize styrene for epoxidation reaction, the conversion rate of styrene reaches 94.6 percent, the selectivity of styrene oxide is 55.6 percent, and the catalyst is passivated in a very small amount after reacting for 30 days.
With the reduction of material dimension and the reduction of characteristic dimension, a series of physical effects such as quantum effect, size effect, surface interface effect and the like of the nano structure become remarkable, and the physical effects are the key points for improving the catalytic performance of the organic-inorganic hybrid material.
In view of the above specific properties of metal complexes and nanoparticles, there have been studies in the prior art to combine the two, i.e. to prepare metal complexes as nanoscale particles, showing their surprising properties. The invention aims to provide a novel aza-macrocyclic Schiff base, which is applied to research on the action mechanism of a metal complex participating in catalytic reaction, and design and explore a novel aza-macrocyclic complex catalyst.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides aza macrocyclic schiff base, a metal complex thereof, a micro-nano material and application.
The molecular formula of the aza-macrocyclic Schiff base provided by the invention is C16H34Cl2N4O8The structural formula is shown as the formula (I):
Preferably, the crystal of the azamacrocyclic schiff base is orthorhombic, Fbca; unit cell parameters:
β＝90°；
γ＝90°。
the invention also provides a preparation method of the aza-macrocyclic schiff base, which comprises the following steps: dispersing ethylenediamine into acetone, adding dropwise perchloric acid aqueous solution while stirring for reaction, filtering, standing, precipitating colorless square plate-shaped crystal, filtering, and washing.
In the above reaction process, acetone is used as solvent and reactant, and the methyl group on the macrocyclic ring of the product is derived from acetone. A perchloric acid aqueous solution was added dropwise to the reaction mixture, followed by reaction.
Preferably, the perchloric acid aqueous solution is added dropwise within 30 min; the molar ratio of ethylenediamine to perchloric acid is 1: 1.
the invention also provides a metal complex of the aza-macrocyclic Schiff base, which takes the aza-macrocyclic Schiff base as a ligand to react with Mn2+Carrying out coordination to obtain the manganese (II) complex of the aza-macrocyclic Schiff base.
The invention also provides a preparation method of the metal complex of the aza-macrocyclic schiff base, which comprises the following steps: dissolving azamacrocyclic schiff base in methanol, adding manganese acetate aqueous solution, transferring to a reaction kettle, reacting at 80 ℃ for 72h, and naturally cooling to room temperature to obtain yellow solid; wherein the molar ratio of the azamacrocyclic schiff base to the manganese acetate is 1: 1.
The invention also provides a metal complex micro-nano material of the aza-macrocyclic schiff base, which is prepared by grinding the metal complex of the aza-macrocyclic schiff base, dispersing the metal complex in methanol by ultrasonic, taking supernatant, centrifuging and drying.
The invention also provides application of the metal complex micro-nano material of the aza-macrocyclic schiff base in phenol hydroxylation catalysis.
Has the beneficial effects that: the invention provides a aza macrocyclic schiff base, and the aza macrocyclic schiff base is used as a ligand to prepare a metal complex, and the synthesis method is simple and convenient to operate; the metal complex is prepared into nano particles, and is applied to catalyzing phenol hydroxylation reaction, so that the metal complex has better catalytic activity and is of great significance for designing and exploring a novel aza-macrocyclic complex catalyst.
Drawings
FIG. 1 is a crystal structure diagram of an azamacrocyclic Schiff base prepared according to the present invention;
FIG. 2 is a diagram of the molecular unit cell packing arrangement of the azamacrocyclic Schiff bases prepared according to the present invention;
FIG. 3 is an SEM image of a manganese (II) complex micro-nano material of the aza-macrocyclic Schiff base prepared by the invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The synthesis method of the aza macrocyclic schiff base comprises the following steps: to 250mL of acetone was added 165mmol of ethylenediamine, and 170mmol of 70% perchloric acid was added dropwise over 30 minutes with stirring from a dropping funnel, followed by filtration and standing for 24 hours to precipitate colorless flaky crystals. Filtration, washing with acetone, yield 40%.
Characterization of the azamacrocyclic schiff base prepared as described above:
infrared analysis IR (KBr cm)-1)：ν(N-H)3190cm-1(s)，ν(C＝N)1666cm-1(s)，ν(C1O4 -),1076cm-1，629cm-1(vs)。
Elemental analysis: according to C16H32N4·2HClO4Calculation, theoretical value (%): c39.92, H7.07, N11.64; found (%): c40.10, H7.02, N11.57.
Structural characterization: the crystal data, and typical bond length and bond angle data of azamacrocyclic schiff bases are shown in tables 1-3, respectively, and the structures are analyzed, and the molecular structure diagram and the molecular unit cell stacking arrangement diagram are shown in fig. 1 and fig. 2, respectively.
TABLE 1 Crystal data for azamacrocyclic Schiff bases
TABLE 2 typical bond length data for azamacrocyclic Schiff bases
TABLE 3 bond Angle data for azamacrocyclic Schiff bases
Example 2
Preparation of metal complexes of azamacrocyclic schiff bases: 1mmol of the active ingredientThe azamacrocyclic schiff base prepared in example 1 was dissolved in 10mL of methanol solution, and then lmmol (CH) was added3COO)3Mn·2H2And (3) 10mL of water solution of O, placing the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into an oven, reacting at the temperature of 80 ℃ for 72 hours, and naturally cooling to room temperature to obtain a yellow solid A.
The metal complexes of aza macrocyclic schiff bases prepared as described above were characterized:
infrared analysis: primary IR (KBr) data v (N-H)3440cm-1(s)，ν(C＝N)1641cm-1(s)，ν(C1O4 -)1099cm-1、633cm-1(vs)。
Elemental analysis: according to C16H32N4O8Cl2Mn (534.29) calculation, theoretical value (%): c35.97, H6.04, N10.49; found (%): c35.89, H6.98, N10.43.
Preparing a metal complex micro-nano material of aza-macrocyclic schiff base: grinding the yellow solid A prepared above for 1h, adding 20mL of methanol, performing ultrasonic treatment for 10 min, taking the supernatant, centrifuging, drying in air to obtain yellow powder B, and performing SEM characterization on the yellow powder B, wherein the result is shown in FIG. 3.
The metal complex micro-nano material of the aza-macrocyclic Schiff base is used for catalyzing phenol hydroxylation.
The reaction sequence for the oxidation of phenol is as follows:
the specific operation is as follows: weighing 10mg of yellow powder B, adding into a round-bottom flask, adding 0.1g of phenol, adding 15mL of mixed solvent of ethanol and water with the volume ratio of 1:1, heating to 50 ℃, and dropwise adding 3mmol of 30% H while stirring2O2The solution was stirred and refluxed at 50 ℃ for 5 hours, and then cooled. The yield of the benzenediol was measured by a liquid chromatograph, and an ultraviolet detector (λ 277nm), conversion rate: 46.1 percent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. The aza macrocyclic Schiff base is characterized in that the molecular formula is C16H34Cl2N4O8The structural formula is shown as the formula (I):
2. the azamacrocyclic schiff base of claim 1, wherein the crystal of the azamacrocyclic schiff base is orthorhombic, Fbca; unit cell parameters:
3. a process for the preparation of azamacrocyclic schiff bases as claimed in claim 1 or 2, comprising the steps of: dispersing ethylenediamine into acetone, adding dropwise perchloric acid aqueous solution while stirring for reaction, filtering, standing, precipitating colorless square plate-shaped crystal, filtering, and washing.
4. The process for preparing an azamacrocyclic schiff base according to claim 3, wherein the dropwise addition of the aqueous solution of perchloric acid is completed within 30 min; the molar ratio of ethylenediamine to perchloric acid is 1: 1.
5. a metal complex of aza macrocyclic schiff base, which is characterized in thatThus, using an azamacrocyclic schiff base as defined in claim 1 or 2 as a ligand with Mn2+Carrying out coordination to obtain the manganese (II) complex of the aza-macrocyclic Schiff base.
6. A process for preparing a metal complex of an azamacrocyclic Schiff base as claimed in claim 5, comprising the steps of: dissolving azamacrocyclic schiff base in methanol, adding manganese acetate aqueous solution, transferring to a reaction kettle, reacting at 80 ℃ for 72h, and naturally cooling to room temperature to obtain yellow solid; wherein the molar ratio of the azamacrocyclic schiff base to the manganese acetate is 1: 1.
7. A metal complex micro-nano material of aza-macrocyclic Schiff base, which is characterized in that the metal complex of aza-macrocyclic Schiff base of claim 5 is ground, ultrasonically dispersed in methanol, taken supernatant fluid is centrifuged, and dried to obtain the micro-nano material.
8. The use of the metal complex micro-nano material of aza-macrocyclic schiff bases as claimed in claim 7 in catalyzing the hydroxylation of phenol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117511527A (en) * | 2024-01-02 | 2024-02-06 | 东营煜煌能源技术有限公司 | Descaling blocking remover and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117511527A (en) * | 2024-01-02 | 2024-02-06 | 东营煜煌能源技术有限公司 | Descaling blocking remover and preparation method thereof |
| CN117511527B (en) * | 2024-01-02 | 2024-03-19 | 东营煜煌能源技术有限公司 | Descaling blocking remover and preparation method thereof |
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