CN115160582A - Crystalline trimetal pyridine porphyrin porous complex and preparation method and application thereof - Google Patents

Crystalline trimetal pyridine porphyrin porous complex and preparation method and application thereof Download PDF

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CN115160582A
CN115160582A CN202210799357.5A CN202210799357A CN115160582A CN 115160582 A CN115160582 A CN 115160582A CN 202210799357 A CN202210799357 A CN 202210799357A CN 115160582 A CN115160582 A CN 115160582A
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林启普
陈二霞
贺亮
黄山林
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Mindu Innovation Laboratory
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Abstract

The invention belongs to the technical field of crystal material preparation, and particularly discloses a crystalline trimetallic pyridylporphyrin porous complex (TPyPZn-W-Cu) containing rich fluorine elements, and a preparation method and application thereof; under the guidance of a top-down strategy, the inventor successfully prepares a crystalline trimetal pyridine porphyrin porous complex (TPyPZn-W-Cu) containing rich fluorine elements, and the yield of the crystalline trimetal pyridine porphyrin porous complex (TPyPZn-W-Cu) is up to more than 70%; in addition, the preparation method provided by the invention has less pollution and meets the requirements of environmental protection; the crystalline trimetallic pyridylporphyrin porous complex (TPy) rich in fluorine element prepared by the inventionPZn-W-Cu) structure contains rich fluorine elements, pore channels and active sites, and can be used for gas sensing and photocatalysis of CO 2 Reduction, electrocatalysis of CO 2 Reduction of CO 2 The cycloaddition catalytic reaction, the hydrogen production by photocatalytic splitting water, the flame retardant and the like.

Description

Crystalline trimetal pyridine porphyrin porous complex and preparation method and application thereof
Technical Field
The invention particularly relates to a crystalline trimetal pyridine porphyrin porous complex, and a preparation method and application thereof, and belongs to the technical field of preparation of crystal materials.
Background
Porphyrin is a general name of homologs and derivatives of porphin with substituent at outer ring, is a special macrocyclic conjugated aromatic system, and can be applied to various fields such as organic reaction catalysts, solid adsorbents, optical storage devices, supramolecular chemistry and the like due to a specific pi conjugated system and coordination function.
Metalloporphyrins are conjugated organic molecules formed by porphyrin and metal ions, widely existing in nature and in organisms, such as human heme, the prosthetic group of hemoglobin is a Fe-containing substance 2+ The metalloporphyrin of (1); chlorophyll, which plays an important role in photosynthesis, is a substance containing Mg 2+ The metalloporphyrin of (1); because of its unique structural characteristics, metalloporphyrins play an important role in the fields of life activities, catalysis, bionics, medicine, luminescence, and the like.
However, metalloporphyrin is a kind of conjugated organic molecule, and is easy to agglomerate in practical application, thereby reducing efficiency. Therefore, in practical application, how to effectively reduce the aggregation degree of metalloporphyrin and expose active sites as much as possible is a concern of extensive scientific researchers.
Disclosure of Invention
In order to solve the technical problems, the invention provides a crystalline trimetallic pyridylporphyrin porous complex containing abundant fluorine elements, and a preparation method and application thereof.
The technical scheme of the invention is as follows:
one of the purposes of the invention is to provide a crystalline trimetal pyridine porphyrin porous complex which contains rich fluorine element and is named as TPyPZn-W-Cu, and the crystalline trimetal pyridine porphyrin porous complex has a structure shown in a formula (I):
Figure BDA0003736888600000021
the second purpose of the invention is to provide a preparation method of the crystalline trimetal pyridylporphyrin porous complex, which takes metal pyridylporphyrin, a fluorine-containing substance, a tungsten-containing substance and a copper-containing substance as raw materials, performs solvothermal reaction at the temperature of 10-180 ℃, and finally prepares the crystalline trimetal pyridylporphyrin porous complex containing abundant fluorine elements through full reaction for 18-480 hours.
Wherein the molar ratio of the metal pyridylporphyrin to the fluorine-containing substance to the tungsten-containing substance to the copper-containing substance is (1.
Preferably, the molar ratio of the metallopyridinoporphyrin, the fluorine-containing substance, the tungsten-containing substance, and the copper-containing substance is further defined as (1.
Preferably, the metal pyridine porphyrin is 5,10,15,20-tetrapyridylporphyrin-Zn, and has a structure shown as a formula (II):
Figure BDA0003736888600000031
preferably, the fluorine-containing substance is a fluorine-containing acid or a fluorine-containing salt.
Preferably, the tungsten-containing substance is elemental tungsten, tungsten oxide or a tungsten salt.
Preferably, the copper-containing substance is elemental copper, a copper oxide or a copper salt.
Preferably, the solvent in the solvent thermal reaction is an amide solvent or an alcohol solvent or a mixture of the amide solvent and the alcohol solvent.
Preferably, the alcoholic solvent is an alcohol or a mixture of alcohols containing 1 to 40 carbon atoms.
Preferably, the preparation method of the crystalline trimetallic pyridylporphyrin porous complex further comprises the step of purifying a product obtained after solvothermal reaction; and (3) cleaning the product after the reaction by using an alcohol solvent, separating, and airing at room temperature.
The invention also aims to provide a crystalline trimetallic pyridylporphyrin porous complex for gas sensing and photocatalysis of CO 2 Reduction and electrocatalysis of CO 2 Reduction, CO 2 Cycloaddition catalytic reaction, hydrogen production by water through photocatalytic cracking and application in the field of flame retardants.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the metallopyridylporphyrin TPyP-Zn synthesized by the inventor at the earlier stage is used as a raw material, and the metallopyridylporphyrin TPyP-Zn not only has rich coordination sites, but also can introduce metal into a porphyrin ring for regulating and controlling activity;
2. the crystalline trimetallic pyridylporphyrin porous complex is a novel metal organic porous material, and structural analysis shows that pyridine nitrogen in metal pyridylporphyrin TPyP-Zn is coordinated with copper in the material, and metal zinc and pyrrole nitrogen in a porphyrin ring adopt a plane four-coordination mode and can be used as active sites, so that the material can be used for gas sensing and photocatalysis of CO 2 Reduction, electrocatalysis of CO 2 Reduction of CO 2 The cycloaddition catalytic reaction and the photocatalytic water splitting hydrogen production field, and meanwhile, the crystalline trimetal pyridine porphyrin porous complex (TPyPZn-W-Cu) prepared by the invention contains rich fluorine elements, so that the material can also be used in the flame retardant field, and the application range of the metal pyridine porphyrin porous material is greatly expanded;
3. the preparation method provided by the invention has simple requirements, low requirements on the purity of the raw materials, easy obtainment of the raw materials, low price and convenience for large-scale production; the post-treatment is simple and easy to implement, a pure-phase crystalline product can be obtained only by simple alcohol washing separation and room-temperature air drying, the preparation pollution is less, and the preparation method meets the requirements of green environmental protection; in addition, the yield of the crystalline trimetallic pyridylporphyrin porous complex (TPyPZn-W-Cu) containing rich fluorine element obtained by the preparation method provided by the invention is up to more than 70%, and the product can be used for gas sensing and photocatalysis of CO 2 Reduction, electricityCatalysis of CO 2 Reduction of CO 2 The cyclic addition catalytic reaction, the hydrogen production by photocatalytic water splitting, the flame retardant and the like.
Drawings
FIG. 1 is a schematic diagram of a crystal structure of a crystalline trimetallic pyridylporphyrin porous complex TPyPZn-W-Cu in the invention;
FIG. 2 is an X-ray powder diffraction pattern of crystalline trimetal pyridylporphyrin porous complex TPyPZn-W-Cu in the present invention;
FIG. 3 is a structural diagram of ligand metalloporphyrin TPyP-Zn in example 1 of the present invention;
FIG. 4 is the response of crystalline trimetallic pyridylporphyrin porous complex TPyPZn-W-Cu of example 1 of the present invention to 100ppm of different gases (vapors).
Detailed Description
The invention is further described with reference to the drawings and the preferred embodiments, and the endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and should be understood to encompass values close to these ranges or values; for ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, which ranges of values are to be considered as specifically disclosed herein;
the experimental methods used in the following examples, unless otherwise specified, and experimental methods not specified in the examples, materials, reagents and the like used in the following examples, unless otherwise specified, are commercially available under usual conditions;
the single crystal structure optimization in the following examples used software Materials Studio 8.0; the X-ray powder diffraction test uses Cu-K alpha ray as the radiation source.
Example 1
A crystalline trimetal pyridylporphyrin porous complex TPyPZn-W-Cu contains rich fluorine elements and is named as TPyPZn-W-Cu, and has a structure shown in a formula (I):
Figure BDA0003736888600000051
example 2
Weighing sodium fluorotungstate Na 2 WO 2 F 4 (0.0080g, 0.0237mmol), copper nitrate Cu hexahydrate (NO) 3 ) 2 ·6H 2 O (0.0080g, 0.0270mmol), metal pyridine porphyrin TPyP-Zn (0.0100g, 0.0147mmol) are used as raw materials, a mixed solution of N-methyl pyrrolidone (5 mL) and ethylene glycol (2 mL) is used as a solvent, the raw materials are placed in a 20mL glass bottle, the mixture is uniformly mixed at room temperature, then the glass bottle is placed in a 70 ℃ oven for solvothermal reaction for 120 hours, the obtained product is naturally cooled to room temperature, a solid phase is separated, and the separated solid phase product is washed by methanol to obtain a purple crystalline product TPyPZn-W-Cu;
the yield of the crystalline product crystalline trimetallic pyridylporphyrin porous complex TPyPZn-W-Cu prepared in example 2 is over 70 percent through testing;
the crystal parameters of the crystalline trimetal pyridine porphyrin porous complex TPyPZn-W-Cu prepared in the embodiment 2 are shown in the table 1;
TABLE 1
Figure BDA0003736888600000061
Example 3
Measuring copper fluorotungstate CuWO 2 F 4 (0.0064g, 0.0180mmol), copper sulfate pentahydrate CuSO 4 ·5H 2 O (0.0069g, 0.0276 mmol) and TPyP-Zn (0.0100g, 0.0147mmol) are taken as raw materials, a mixed solution of N, N-dimethylformamide (5 ml) and N-butanol (2 ml) is taken as a solvent, the raw materials are placed in a 20ml glass bottle, the mixture is uniformly mixed at room temperature, then the mixture is placed in a drying oven at 40 ℃ for reaction for 240 hours, the mixture is naturally cooled to room temperature, a solid phase is separated, and the separated solid phase product is washed by methanol to obtain a purple crystalline product TPyPZn-W-Cu;
the crystalline product prepared in example 3 was tested to yield over 70% and the structure of the crystalline product prepared in example 3 was the same as that of example 1.
Example 4
Measuring ammonium fluosilicate (NH) 4 ) 2 SiF 6 (0.0481g, 0.2700mmol), elemental tungsten W (0.0366g, 0.2000mol), copper acetate monohydrate Cu (CH) 3 COO) 2 ·H 2 O (0.0299g, 0.1500mmol) and TPyP-Zn (0.6817g, 1.0000mmol) are taken as raw materials, a mixed solution of N-methylformamide (7 mL) and isopropanol (3 mL) is taken as a solvent, the raw materials are placed in a 20mL glass bottle, the mixture is uniformly mixed at room temperature, then the mixture is placed at room temperature (25 ℃) for reaction for 480 hours, a solid phase is separated, and the separated solid phase product is washed by methanol, so that a purple crystalline product TPyPZn-W-Cu can be obtained;
the crystalline product prepared in example 4 was tested to yield over 70% and the structure of the crystalline product prepared in example 4 was the same as that of example 1.
Example 5
Sodium fluoride NaF (0.0546g, 1.3000mmol) and tungsten dioxide WO are weighed 2 (0.1079g, 0.5000mmol), copper chloride CuCl 2 (0.0807g, 0.6000mmol), TPyP-Zn (0.0682g, 0.1000mmol) as raw materials, a mixed solution of N-methylformamide, a mixture of N-methylpyrrolidone (5 mL) and propylene glycol (2 mL) as a solvent, placing the mixture into a polytetrafluoroethylene pressure container with the volume of 20mL, uniformly mixing at room temperature, placing the mixture into an oven with the temperature of 120 ℃ for reaction for 100 hours, naturally cooling to the room temperature, separating a solid phase, and washing the separated solid phase product by using methanol to obtain a purple crystalline product TPyPZn-W-Cu;
the crystalline product prepared in example 5 was tested to have a yield of over 70% and the structure of the crystalline product prepared in example 5 was the same as that of example 1.
Example 6
Measuring sodium fluosilicate Na 2 SiF 6 (0.0150g, 0.0800 mmol), ammonium tungstate (NH) 4 ) 10 W 12 O 41 ·xH 2 O (0.0304g, 0.0100mmol), copper perchlorate Cu (ClO) 4 ) 2 (0.0236g, 0.0900mmol) and TPyP-Zn (0.1363g, 0.200mmol) are taken as raw materials, a mixed solution of N, N-dimethylacetamide (5 mL), methanol (1 mL) and ethanol (1 mL) is taken as a solvent, and the solvent is placed in a polytetrafluoroethylene pressure container with the volume of 20mLUniformly mixing at room temperature, placing the mixture in an oven at 100 ℃ for reaction for 110h, naturally cooling to room temperature, separating a solid phase, and washing the separated solid phase product by using methanol to obtain a purple crystalline product TPyPZn-W-Cu;
the crystalline product prepared in example 6 was tested to yield over 70% and the structure of the crystalline product prepared in example 6 was the same as that of example 1.
In addition to the selection of fluorine-containing species, tungsten-containing species, copper-containing species and solvents described in examples 2-6 above, the following alternatives may be made;
wherein, the fluorine-containing substance can be fluorine-containing acid or fluorine-containing salt; the fluorine-containing acid can be hydrofluoric acid or fluosilicic acid; the fluorine-containing salt may be one or a mixture of two or more of sodium fluoride, aluminum fluoride, calcium fluoride, sodium fluorosilicate, zinc fluorosilicate, copper fluorotungstate, sodium fluorovanadate, sodium fluorotungstate, sodium fluoromolybdate, sodium fluoroniobate, copper fluoroniobate, ammonium fluorotungstate, ammonium fluoromolybdate, ammonium fluorosilicate;
wherein, the tungsten-containing substance can be simple substance tungsten, tungsten oxide or tungsten salt; the simple substance tungsten can be tungsten wire; the tungsten oxide can be at least one of tungsten dioxide and tungsten trioxide; the tungsten salt can be at least one of sodium tungstate, potassium tungstate, ammonium tungstate, calcium tungstate, zinc tungstate, cobalt tungstate, ferrous tungstate, copper tungstate, cadmium tungstate and magnesium tungstate;
wherein, the copper-containing substance can be elementary copper, copper oxide or copper salt; the simple substance copper is a copper sheet; the copper oxide is one of cupric oxide or cuprous oxide; the copper salt can be at least one of cupric chloride, cuprous chloride, cupric bromide, cuprous bromide, cupric iodide, cupric sulfate, cupric nitrate, cupric acetate, basic cupric carbonate, basic cupric sulfate and cupric perchlorate;
wherein the solvent in the reaction heat process can be an amide solvent, an alcohol solvent or a mixture of the amide solvent and the alcohol; the amide solvent can be one or more of N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, N-methylformamide, N-methylacetamide and N-ethylformamide; the alcoholic solvent may be selected from an alcohol or a mixture of alcohols containing 1 to 40 carbon atoms (e.g. 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms), for example from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, neopentyl alcohol, n-hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol or a mixture of any two or more thereof;
in the case of cleaning and purifying the product with the solvent, the alcohol solvent used and the alcohol solvent added in the reaction stage may be the same or different and are independently selected from alcohols having 1 to 40 carbon atoms (e.g., 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms) or mixtures of alcohols.
Example 7
As the crystalline trimetal pyridylporphyrin porous complex (TPyPZn-W-Cu) prepared by the invention contains abundant fluorine elements, pore channels and active sites in the structure, the crystalline product can be used for gas sensing and photocatalysis of CO 2 Reduction, electrocatalysis of CO 2 Reduction of CO 2 The cyclic addition catalytic reaction, the hydrogen production by photocatalytic water splitting, the flame retardant and the like.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.

Claims (12)

1. A crystalline trimetallic pyridylporphyrin porous complex, which is characterized in that: contains rich fluorine elements, is named as TPyPZn-W-Cu and has a structure shown in a formula (I):
Figure FDA0003736888590000011
2. a preparation method of a crystalline trimetal pyridine porphyrin porous complex is characterized by comprising the following steps: the preparation method comprises the steps of taking metal pyridine porphyrin, a fluorine-containing substance, a tungsten-containing substance and a copper-containing substance as raw materials, carrying out solvothermal reaction at the temperature of 10-180 ℃, and fully reacting for 18-480 hours to finally prepare the crystalline trimetal pyridine porphyrin porous complex rich in fluorine elements.
3. The method of claim 2, wherein the method comprises the following steps: the molar ratio of the metal pyridylporphyrin to the fluorine-containing substance to the tungsten-containing substance to the copper-containing substance is (1.
4. The method of claim 3, wherein the method comprises the following steps: the preferable molar ratio of the metal pyridinoporphyrin, the fluorine-containing substance, the tungsten-containing substance, and the copper-containing substance is (1.
5. The method of claim 2, wherein the preparation method comprises the following steps: the metal pyridine porphyrin is 5,10,15,20-tetrapyridylporphyrin-Zn and has a structure shown in a formula (II):
Figure FDA0003736888590000021
6. the method of claim 2, wherein the preparation method comprises the following steps: the fluorine-containing substance is fluorine-containing acid or fluorine-containing salt.
7. The method of claim 2, wherein the method comprises the following steps: the tungsten-containing substance is simple substance tungsten, tungsten oxide or tungsten salt.
8. The method of claim 2, wherein the preparation method comprises the following steps: the copper-containing substance is elemental copper, copper oxide or copper salt.
9. The method of claim 2, wherein the preparation method comprises the following steps: the solvent in the solvent thermal reaction is an amide solvent or an alcohol solvent or a mixture of the amide solvent and the alcohol solvent.
10. The method of claim 2, wherein the preparation method comprises the following steps: the alcohol solvent is alcohol or alcohol mixture containing 1-40 carbon atoms.
11. The method of claim 2, wherein the preparation method comprises the following steps: the preparation method of the crystalline trimetal pyridine porphyrin porous complex also comprises the step of purifying a product after the solvothermal reaction; and cleaning and separating a product after reaction by using an alcohol solvent, and airing at room temperature.
12. The crystalline trimetallic pyridylporphyrin porous complex of claim 1 in gas sensing and photocatalysis 2 Reduction, electrocatalysis of CO 2 Reduction, CO 2 Cycloaddition catalytic reaction, hydrogen production by water through photocatalytic cracking and application in the field of flame retardants.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005255810A (en) * 2004-03-10 2005-09-22 Japan Science & Technology Agency Supramolecular complex of zinc porphyrin dendrimer and pyridylnaphthalenediimide having many artificial photosynthetic reaction centers
CN103779500A (en) * 2014-02-25 2014-05-07 吉林大学 Application of water or water/alcohol soluble porphyrin derivative in manufacturing organic and polymer solar photovoltaic device
CN108191550A (en) * 2018-03-06 2018-06-22 河北百禾丰化肥有限公司 A kind of multi-element biological organic soil modified form fertilizer and preparation method thereof
CN111607100A (en) * 2020-06-10 2020-09-01 苏州大学 Crystalline material based on iron-based porphyrin ligand, preparation and application thereof
CN112940278A (en) * 2021-02-21 2021-06-11 四川大学华西医院 Sound-sensitive active oxygen-generating metalloporphyrin coordination polymer and preparation and application thereof
CN113185701A (en) * 2021-04-28 2021-07-30 浙江理工大学 Metal porphyrin-based porous polymer, preparation thereof and application thereof in catalyzing addition reaction of carbon dioxide and epoxide ring
CN114126695A (en) * 2019-07-16 2022-03-01 巴西圣保罗大学 Method for obtaining functionalized polymer surfaces with photosensitizers, functionalized polymer materials and uses thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005255810A (en) * 2004-03-10 2005-09-22 Japan Science & Technology Agency Supramolecular complex of zinc porphyrin dendrimer and pyridylnaphthalenediimide having many artificial photosynthetic reaction centers
CN103779500A (en) * 2014-02-25 2014-05-07 吉林大学 Application of water or water/alcohol soluble porphyrin derivative in manufacturing organic and polymer solar photovoltaic device
CN108191550A (en) * 2018-03-06 2018-06-22 河北百禾丰化肥有限公司 A kind of multi-element biological organic soil modified form fertilizer and preparation method thereof
CN114126695A (en) * 2019-07-16 2022-03-01 巴西圣保罗大学 Method for obtaining functionalized polymer surfaces with photosensitizers, functionalized polymer materials and uses thereof
CN111607100A (en) * 2020-06-10 2020-09-01 苏州大学 Crystalline material based on iron-based porphyrin ligand, preparation and application thereof
CN112940278A (en) * 2021-02-21 2021-06-11 四川大学华西医院 Sound-sensitive active oxygen-generating metalloporphyrin coordination polymer and preparation and application thereof
CN113185701A (en) * 2021-04-28 2021-07-30 浙江理工大学 Metal porphyrin-based porous polymer, preparation thereof and application thereof in catalyzing addition reaction of carbon dioxide and epoxide ring

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KAZUKATA TOMITA,NOBUTAKA SHIOYA, TAKAFUMI SHIMOAKA,ET.AL: "Control of supramolecular organizations by coordination bonding in tetrapyridylporphyrin thin films" *
LI, DE-JING; LI, QIAO-HONG; WANG, ZI-RUI;ET.AL: "Interpenetrated Metal-Porphyrinic Framework for Enhanced Nonlinear Optical Limiting" *

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