CN114713287A - Salen metal complex catalyst and preparation method thereof - Google Patents
Salen metal complex catalyst and preparation method thereof Download PDFInfo
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- CN114713287A CN114713287A CN202210423995.7A CN202210423995A CN114713287A CN 114713287 A CN114713287 A CN 114713287A CN 202210423995 A CN202210423995 A CN 202210423995A CN 114713287 A CN114713287 A CN 114713287A
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- diethylamino
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- -1 Salen metal complex Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002135 nanosheet Substances 0.000 claims abstract description 19
- 125000001725 pyrenyl group Chemical group 0.000 claims abstract description 11
- 230000021615 conjugation Effects 0.000 claims abstract description 10
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 229940011182 cobalt acetate Drugs 0.000 claims description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- QXYRRCOJHNZVDJ-UHFFFAOYSA-N 4-pyren-1-ylbutanoic acid Chemical compound C1=C2C(CCCC(=O)O)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 QXYRRCOJHNZVDJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- XFVZSRRZZNLWBW-UHFFFAOYSA-N 4-(Diethylamino)salicylaldehyde Chemical compound CCN(CC)C1=CC=C(C=O)C(O)=C1 XFVZSRRZZNLWBW-UHFFFAOYSA-N 0.000 claims description 6
- GDUDPOLSCZNKMK-UHFFFAOYSA-L cobalt(2+);diacetate;hydrate Chemical compound O.[Co+2].CC([O-])=O.CC([O-])=O GDUDPOLSCZNKMK-UHFFFAOYSA-L 0.000 claims description 6
- 150000004696 coordination complex Chemical class 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- BBEAQIROQSPTKN-UHFFFAOYSA-N antipyrene Natural products C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000004566 IR spectroscopy Methods 0.000 description 20
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 20
- 238000000921 elemental analysis Methods 0.000 description 10
- 238000002411 thermogravimetry Methods 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 8
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- 238000004627 transmission electron microscopy Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 125000005581 pyrene group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YXHVGMQJXJAUAR-UHFFFAOYSA-N 2-(diethylaminooxy)benzaldehyde Chemical compound CCN(CC)OC1=CC=CC=C1C=O YXHVGMQJXJAUAR-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- UGMXRPVWWWDPFC-UHFFFAOYSA-N 1-(bromomethyl)pyrene Chemical compound C1=C2C(CBr)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 UGMXRPVWWWDPFC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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
-
- 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
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of catalyst preparation, and discloses a Salen metal complex catalyst and a preparation method thereof. The invention synthesizes a Co (Salen) catalyst modified by pyrenyl groups, and then the Co (Salen) catalyst is respectively reacted with g-C through side chains or axial direction through pi-pi conjugation of pyrenyl groups3N4Non-covalent modification is carried out on the nano-sheet to obtain the Salen metal complex catalyst (g-C)3N4-Py-Co (salen) catalyst). Compared with the traditional Salen metal complex preparation process, the Salen metal complex catalyst provided by the invention is simple and easy to operate, safe and environment-friendly, and easy to realize industrial production.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a Salen metal complex catalyst and a preparation method thereof.
Background
The bis-schiff base metal complex is commonly referred to as a metal Salen catalyst. At present, the Salen ligand can be obtained by condensation reaction of different organic diamines and different aldehydes or ketones. Wherein the skeleton of the Salen ligand is very easy to modify, and different groups or functional groups are connected at the tail end of the skeleton, so that different Salen ligands can be formed, and different catalytic systems can be adopted. The Salen metal complex serving as a homogeneous catalyst has excellent catalytic activity, and the catalytic capability of the Salen metal complex is mainly influenced by three aspects: (1) a central metal atom or ion type; (2) synthesizing the type and the synthesis method of functional groups carried by the Salen ligand; (3) the interaction form of the Salen ligand with the central metal atom or ion. Therefore, the metal Salen catalyst is a catalyst which is easy to synthesize, widely applied and excellent in catalytic performance, and is widely applied to aspects such as pharmacology, catalysis, analytical reagents, chelation, biological regulators and the like.
The Salen metal complex is a compound with adjustable metal, adjustable structure and unique property, and the research on the design and the catalytic organic reaction of the Salen metal complex is rapidly developing. However, the existing Salen metal complex has significant disadvantages such as not easy separation and high price, and cannot satisfy the industrial production process from the viewpoint of environmental protection and economic efficiency.
Disclosure of Invention
In view of the above, the invention provides a Salen metal complex catalyst and a preparation method thereof, which solve the problems that Salen metal complexes are not easy to separate and expensive and cannot meet the requirement of industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a Salen metal complex catalyst, which is prepared by mixing Py-Co and g-C3N4Conjugation is carried out to obtain g-C3N4-Py-CoSalen metal complex catalyst;
the g to C3N4The structure of the-Py-CoSalen metal complex catalyst comprises:
an axial immobilization mode:
or side chain immobilization mode:
preferably, the conjugation comprises axial pi-pi conjugation or side chain pi-pi conjugation.
Preferably, the Py-Co structure comprises
Preferably, said g-C3N4Graphite phase carbon nitride nanosheets.
Another object of the present invention is to disclose a method for preparing a Salen metal complex catalyst, comprising the steps of:
1) reacting p-diethylamino salicylaldehyde with ethylenediamine to generate diethylamino Salen;
2) adding cobalt acetate or cobalt acetate hydrate into the system reacted in the step 1) to obtain diethylamino SalencO;
3) mixing and oxidizing diethylamino SalenCo and acetic acid to obtain diethylamino SalenCoOAc, and then reacting pyrenyl group modified bromobenzyl with diethylamino SalenCoOAc in toluene to obtain pyrenyl group side chain modified Py-Co or mixing and oxidizing diethylamino SalenCo and pyrenebutyric acid to obtain pyrenyl group axially modified Py-Co;
4) preparation of g-C3N4A nanosheet solution;
5) Py-Co with g-C3N4Carrying out immobilization to obtain the Salen metal complex catalyst.
Preferably, the molar ratio of the p-diethylamino salicylaldehyde to the ethylenediamine in the step 1) is 1.8-2.2: 1; the reaction is carried out in ethanol solution, the reaction temperature is 60-80 ℃, and the reaction time is 8-12 h.
Preferably, the molar ratio of cobalt acetate or cobalt acetate hydrate to diethylamino Salen in step 2) is independently 1: 1-1.2; the reaction temperature is 60-80 ℃, and the reaction time is 8-12 h.
Preferably, the reaction temperature of the pyrenyl group modified bromobenzyl and diethylamino SalenCoOAc in the step 3) is 70-80 ℃, and the reaction time is 24-30 h; the oxidation time of the mixture of the diethylamino Salenco and the pyrenebutyric acid is 22-26 h.
Preferably, said g-C3N4The specific preparation steps of the nanosheet solution are as follows:
a) heating the nitrogenous organic matter at the temperature of 500-600 ℃ for 3-5h to obtain a bulk phase g-C3N4；
b) The bulk phase g to C3N4Grinding into powder, dispersing in solvent to obtain suspension, and collecting g-C3N4A nanosheet solution;
wherein the nitrogen-containing organic matter is one or more of urea, dicyandiamide or melamine; the particle size of the powder in the step b) is 300-500 nm.
Preferably, Py-Co and g-C in said step 5)3N4In a molar ratio of 0.8 to 1.2: 0.8-1.2.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
g-C of the invention3N4The nano sheet film has larger specific surface area, the synthesis method is simple and efficient, and the nano sheet film can be produced in large scale and has wide application prospect;
firstly, synthesizing Co (Salen) catalyst modified by pyrenyl group and g-C3N4The Py-Co (Salen) catalyst is respectively supported to g-C in a side chain and axial mode3N4The whole preparation process of the catalyst is simple and easy to implement, safe and environment-friendly, and the prepared Salen metal complex is easy to separate.
Detailed Description
A Salen metal complex catalyst, which is prepared by mixing Py-Co and g-C3N4Conjugation is carried out to obtain g-C3N4-Py-CoSalen metal complex catalyst;
the g to C3N4The structure of the-Py-CoSalen metal complex catalyst comprises:
axial load-fixing squareFormula (II):
or side chain immobilization mode:
in the present invention, the conjugation includes axial pi-pi conjugation or side chain pi-pi conjugation.
In the present invention, the Py-Co structure comprises
In the present invention, the g-C3N4Graphite phase carbon nitride nanosheets.
The invention also discloses a preparation method of the Salen metal complex catalyst, which comprises the following steps:
1) reacting p-diethylamino salicylaldehyde with ethylenediamine to generate diethylamino Salen;
2) adding cobalt acetate or cobalt acetate hydrate into the system reacted in the step 1) to obtain diethylamino SalencO; wherein, cobalt in the diethylamino SalenCo is divalent;
3) mixing and oxidizing diethylamino SalenCo and acetic acid to obtain diethylamino SalenCoOAc, and then reacting pyrenyl group modified bromobenzyl with diethylamino SalenCoOAc in toluene to obtain pyrenyl group side chain modified Py-Co or mixing and oxidizing diethylamino SalenCo and pyrenebutyric acid to obtain pyrenyl group axially modified Py-Co; wherein, cobalt in the diethylamino SalenCoOAc is trivalent;
4) preparation of g-C3N4A nanosheet solution;
5) Py-Co with g-C3N4Carrying out solid support to obtain the Salen metal complex catalyst.
In the invention, the molar ratio of the p-diethylamino salicylaldehyde to the ethylenediamine in the step 1) is 1.8-2.2: 1, preferably 2: 1; the reaction is carried out in an ethanol solution, and the reaction temperature is 60-80 ℃, preferably 72-78 ℃, and further preferably 75 ℃; the reaction time is 8 to 12 hours, more preferably 10 hours.
In the invention, the molar ratio of the cobalt acetate or the cobalt acetate hydrate to the diethylamino Salen in the step 2) is independently 1: 1-1.2, preferably 1: 1.1; the reaction temperature is 60-80 ℃, preferably 72-78 ℃, and more preferably 75 ℃; the reaction time is 8 to 12 hours, more preferably 10 hours.
In the invention, the reaction temperature of the pyrenyl group modified bromobenzyl and diethylamino SalenCoOAc in the step 3) is 70-80 ℃, preferably 72-78 ℃, and further preferably 75 ℃; the reaction time is 24-30h, preferably 25-28h, and further preferably 26 h; the oxidation time of the mixture of the diethylamino Salenco and pyrenebutyric acid is 22-26h, preferably 23-25h, and more preferably 24 h.
In the present invention, the g-C3N4The specific preparation steps of the nanosheet solution are as follows:
a) heating the nitrogenous organic matter at the temperature of 500-600 ℃ for 3-5h to obtain a bulk phase g-C3N4The heating temperature is preferably 530 ℃ to 570 ℃, and is more preferably 550 ℃; the heating time is preferably 4 h.
b) The bulk phase g to C3N4Grinding into powder, dispersing in solvent to obtain suspension to obtain g-C3N4A nanosheet solution;
wherein the nitrogen-containing organic matter is one or more of urea, dicyandiamide or melamine; the particle size of the powder in the step b) is 300-500 nm.
In the present invention, Py-Co and g-C in the step 5) are used3N4In a molar ratio of 0.8 to 1.2: 0.8-1.2, preferably 1:1.
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Synthesizing diethylamino Salenco:
a) reacting diethylamino salicylaldehyde and ethylenediamine in ethanol according to a molar ratio of 2:1 to generate diethylamino Salen (the reaction temperature is 70 ℃, the reaction time is 8 hours), and adding cobalt acetate with the same molar ratio as that of the diethylamino Salen to obtain diethylamino SalenCo (II);
b) the characterization is carried out by means of Mass Spectrometry (MS), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG-DSC), elemental analysis and the like.
(2) Synthesis of diethylamino SalencO (III) OAc:
a) oxidizing the diethylamine SalenCo (II) with acetic acid in oxygen to obtain diethylamine SalenCo (III) OAc;
b) the characterization is carried out by means of Mass Spectrometry (MS), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG-DSC), elemental analysis and the like.
(3) Synthesizing a pyrene group side chain-modified SalenCo (III) OAc:
a) reacting bromomethylpyrene and diethylamino SalenCo (III) OAc in toluene to obtain a SalenCo (III) OAc modified by a pyrenyl group side chain (the reaction temperature is 75 ℃, and the reaction time is 24 h);
b) the characterization is carried out by means of infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), thermogravimetric analysis (TG-DSC), elemental analysis and the like.
(4) The g to C3N4The nanosheet solution is specifically prepared by the following method:
a) placing 20.0g of dicyandiamide in a 50mL crucible, placing the crucible in a muffle furnace, carrying out high-temperature reaction in the air atmosphere, controlling the heating rate to be 2.5 ℃/min, raising the temperature from room temperature to 550 ℃, keeping the temperature for 4h, after the reaction is finished, naturally cooling to room temperature, taking out the crucible, and obtaining a bulk phase g-C3N4；
b) The bulk phase g to C3N4Grinding into powder with particle size of 300nm, dispersing in solvent to form suspension, stirring, ultrasonic treating, standing, centrifuging, collecting supernatant to obtain g-C3N4And (5) nanosheet solution for later use.
c) Subjecting the synthesized g-C to infrared spectroscopy (IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), thermogravimetric analysis (TG-DSC), elemental analysis, etc3N4And (6) performing characterization.
(5) Py-Co with g-C3N4Carrying out immobilization:
side chain immobilization mode:
equimolar ratio of Co (Salen) catalyst modified by pyrene group side chain and g-C3N4Non-covalent loading is carried out to obtain heterogeneous catalyst g-C3N4-Py-Co(Salen)；
The synthesized catalysts are characterized by means of infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), thermogravimetric analysis (TG-DSC), elemental analysis and the like.
Example 2
(1) Synthesizing diethylamino Salenco:
a) reacting diethylamino salicylaldehyde and ethylenediamine in ethanol according to a molar ratio of 2:1 to generate diethylamino Salen (the reaction temperature is 70 ℃, the reaction time is 12 hours), and adding cobalt acetate with the same molar ratio as that of the diethylamino Salen to obtain diethylamino SalenCo (II);
b) the characterization is carried out by means of Mass Spectrometry (MS), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG-DSC), elemental analysis and the like.
(2) Synthesis of diethylamino SalencO (III) OAc:
a) oxidizing the diethylamine SalenCo (II) with acetic acid in oxygen to obtain diethylamine SalenCo (III) OAc;
b) the characterization is carried out by means of Mass Spectrometry (MS), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG-DSC), elemental analysis and the like.
(3) Synthesis of pyrene group axially modified SalenCo (III) OOC- (CH)2)3Py：
a) The diethylamino SalenCo (II) and pyrenebutyric acid are oxidized in oxygen to obtain SalenCo (III) OOC- (CH) with pyrenyl group modified axially2)3Py；
b) The characterization is carried out by means of nuclear magnetic resonance spectroscopy (NMR), Mass Spectrometry (MS), infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), thermogravimetric analysis (TG-DSC), elemental analysis and the like.
(4) The graphite phase carbon nitride nanosheet is prepared by the following method:
a) placing 20.0g of melamine into a 50mL crucible, placing the crucible into a muffle furnace, carrying out high-temperature reaction in the air atmosphere, controlling the heating rate to be 2.5 ℃/min, raising the temperature to 550 ℃ from the room temperature, keeping the temperature for 4h, naturally cooling to the room temperature after the reaction is finished, taking out the crucible, and obtaining a bulk phase g-C3N4；
b) The bulk phase g to C3N4Grinding into powder with the particle size of 500nm,dispersing in solvent to form suspension, stirring, ultrasonic treating, standing, centrifuging, collecting supernatant to obtain g-C3N4And (5) nanosheet solution for later use.
c) Subjecting the synthesized g-C to infrared spectroscopy (IR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), thermogravimetric analysis (TG-DSC), elemental analysis, etc3N4And (6) performing characterization.
(5) Py-Co with g-C3N4Carrying out immobilization:
an axial immobilization mode:
axially modifying Co (Salen) catalyst with pyrene group in equal molar ratio with g-C3N4Non-covalent loading is carried out to obtain heterogeneous catalyst g-C3N4-Py-Co(Salen)；
The synthesized catalysts are characterized by means of infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), thermogravimetric analysis (TG-DSC), elemental analysis and the like.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. Salen metal complexA hybrid catalyst characterized by: Py-Co with g-C3N4Conjugation is carried out to obtain g-C3N4-Py-Co Salen metal complex catalyst;
the g to C3N4The structure of the-Py-CoSalen metal complex catalyst comprises:
an axial immobilization mode:
or side chain immobilization mode:
2. the Salen metal complex catalyst set forth in claim 1, wherein said conjugation comprises axial pi-pi conjugation or side chain pi-pi conjugation.
3. The Salen metal complex catalyst according to claim 2, wherein said Py-Co structure comprises
4. The Salen metal complex catalyst set forth in claim 2 or claim 3, wherein said g-C is3N4Graphite phase carbon nitride nanosheets.
5. The process of any one of claims 1 to 4, comprising the steps of:
1) reacting p-diethylamino salicylaldehyde with ethylenediamine to generate diethylamino Salen;
2) adding cobalt acetate or cobalt acetate hydrate into the system reacted in the step 1) to obtain diethylamino SalencO;
3) mixing and oxidizing diethylamino SalenCo and acetic acid to obtain diethylamino SalenCoOAc, and then reacting pyrenyl group modified bromobenzyl with diethylamino SalenCoOAc in toluene to obtain pyrenyl group side chain modified Py-Co or mixing and oxidizing diethylamino SalenCo and pyrenebutyric acid to obtain pyrenyl group axially modified Py-Co;
4) preparation of g-C3N4A nanosheet solution;
5) Py-Co with g-C3N4Carrying out immobilization to obtain the Salen metal complex catalyst.
6. The method of claim 5, wherein the molar ratio of p-diethylamino salicylaldehyde to ethylenediamine in step 1) is 1.8-2.2: 1; the reaction is carried out in ethanol solution, the reaction temperature is 60-80 ℃, and the reaction time is 8-12 h.
7. The method of claim 6, wherein the molar ratio of cobalt acetate or cobalt acetate hydrate to diethylamino Salen in step 2) is independently 1: 1-1.2; the reaction temperature is 60-80 ℃, and the reaction time is 8-12 h.
8. The method for preparing the Salen metal complex catalyst according to claim 7, wherein the reaction temperature of the pyrene group-modified bromobenzyl with diethylamino SalenCoOAc in step 3) is 70-80 ℃, and the reaction time is 24-30 h; the oxidation time of the mixture of the diethylamino Salenco and the pyrenebutyric acid is 22-26 h.
9. The method of any of claims 5-8, wherein g-C is the product of the Salen metal complex catalyst3N4The specific preparation steps of the nanosheet solution are as follows:
a) heating the nitrogen-containing organic substance at 500-600 deg.C for 3-5h to obtain a bulk phase g-C3N4；
b) The bulk phase g to C3N4Grinding into powder, dispersing in solvent to obtain suspension to obtain g-C3N4A nanosheet solution;
wherein the nitrogen-containing organic matter is one or more of urea, dicyandiamide or melamine; the particle size of the powder in the step b) is 300-500 nm.
10. The method of claim 9, wherein the step 5) of preparing the Salen metal complex catalyst comprises Py-Co and g-C3N4In a molar ratio of 0.8 to 1.2: 0.8-1.2.
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| CN111359669A (en) * | 2020-04-29 | 2020-07-03 | 河北工程大学 | Non-covalent supported GOx-Py-Co (Salen) catalyst and synthesis method thereof |
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| CN111359669A (en) * | 2020-04-29 | 2020-07-03 | 河北工程大学 | Non-covalent supported GOx-Py-Co (Salen) catalyst and synthesis method thereof |
| CN111790432A (en) * | 2020-08-10 | 2020-10-20 | 泰州市海创新能源研究院有限公司 | Nickel carbide/carbon nitride nanosheet photocatalytic material and preparation method and application thereof |
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