CN115160582B - Crystalline trimetallic pyridine porphyrin porous complex and preparation method and application thereof - Google Patents

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

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CN115160582B
CN115160582B CN202210799357.5A CN202210799357A CN115160582B CN 115160582 B CN115160582 B CN 115160582B CN 202210799357 A CN202210799357 A CN 202210799357A CN 115160582 B CN115160582 B CN 115160582B
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porous complex
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porphyrin
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CN115160582A (en
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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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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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    • 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
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
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    • 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
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper
    • 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
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten
    • 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 crystal material preparation, and particularly discloses a crystalline trimetallic pyridine porphyrin porous complex (TPyPZn-W-Cu) containing rich fluorine elements, and a preparation method and application thereof; under the guidance of top-down strategy, the inventor successfully prepares crystalline trimetallic pyridine porphyrin porous complex (TPyPZn-W-Cu) containing abundant fluorine elements, and the yield is up to more than 70 percent; in addition, the preparation method provided by the invention has less pollution and meets the green environment-friendly requirement; as the porous complex (TPyPZn-W-Cu) containing fluorine and containing the crystalline trimetallic pyridine porphyrin contains abundant fluorine, pore channels and active sites, the porous complex can be used for gas sensing and photocatalysis of CO 2 Reduction, electrocatalytic CO 2 Reduction of CO 2 Is used in the fields of cycloaddition catalytic reaction, photocatalytic pyrolysis of water to produce hydrogen, flame retardant and the like.

Description

Crystalline trimetallic pyridine porphyrin porous complex and preparation method and application thereof
Technical Field
The invention particularly relates to a crystalline trimetallic pyridine porphyrin porous complex and a preparation method and application thereof, belonging to the technical field of crystal material preparation.
Background
Porphyrin is a generic name of homologs and derivatives with substituent groups on the outer ring of porphine, is a special macrocyclic conjugated aromatic system, and can be applied to various fields such as organic reaction catalysts, solid adsorbents, optical storage devices, supermolecular chemistry and the like due to the specific pi conjugated system and coordination function.
Metalloporphyrins areConjugated organic molecules formed by porphyrin and metal ions are widely used in nature and organisms, for example, in human heme, the prosthetic group of hemoglobin is essentially a Fe-containing one 2+ Metalloporphyrin of (c); chlorophyll, which plays an important role in photosynthesis, is a substance containing Mg 2+ Metalloporphyrin of (c); because of its unique structural features, metalloporphyrin plays an important role in the fields of life activities, catalysis, bionics, medicine, luminescence, etc.
However, metalloporphyrin is a conjugated organic molecule, which is easy to agglomerate in practical application, thereby reducing efficiency. Therefore, in practical application, how to effectively reduce the agglomeration degree of metalloporphyrin and expose the active sites as much as possible has been paid attention to by the majority of scientific researchers.
Disclosure of Invention
In order to solve the technical problems, the invention provides the crystalline trimetallic pyridine porphyrin porous complex containing abundant fluorine elements, and the preparation method and the application thereof.
The technical scheme of the invention is as follows:
the invention aims to provide a crystalline trimetallic pyridine porphyrin porous complex which contains rich fluorine elements and is named as TPyPZn-W-Cu and has a structure shown as a formula (I):
the second object of the invention is to provide a preparation method of crystalline trimetallic pyridine porphyrin porous complex, which takes metallopyridine porphyrin, fluorine-containing substance, tungsten-containing substance and copper-containing substance as raw materials, and carries out solvothermal reaction at 10-180 ℃ for 18-480 h, and finally prepares the crystalline trimetallic pyridine porphyrin porous complex containing abundant fluorine elements.
Wherein the molar ratio of the metalloporphyrin to the fluorine-containing substance to the tungsten-containing substance to the copper-containing substance is (1:0.27:0.2:0.15) to (1:13:5:6).
Preferably, the molar ratio of the metalloporphyrin, the fluorine-containing substance, the tungsten-containing substance, and the copper-containing substance is further defined as (1:2:0.5:0.45) - (1:8:2:4).
Preferably, the metalloporphyrin is 5,10,15,20-tetrapyridylporphyrin-Zn, having a structure represented by formula (ii):
preferably, the fluorine-containing species is a fluorine-containing acid or a fluorine-containing salt.
Preferably, the tungsten-containing material is elemental tungsten, tungsten oxide or tungsten salt.
Preferably, the copper-containing species is elemental copper, copper oxide or copper salt.
Preferably, the solvent in the solvothermal 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 mixture of alcohols containing 1 to 40 carbon atoms.
Preferably, the preparation method of the crystalline trimetallic pyridine porphyrin porous complex further comprises the steps of purifying a product after solvothermal reaction; and (3) cleaning the reacted product by adopting an alcohol solvent, separating, and airing at room temperature.
The invention aims at providing a crystalline trimetallic pyridine porphyrin porous complex for gas sensing and photocatalysis of CO 2 Reduction, electrocatalytic CO 2 Reduction of CO 2 The application in the fields of cycloaddition catalytic reaction, photocatalytic pyrolysis of water to produce hydrogen and flame retardants.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the metallopyridine porphyrin TPyP-Zn synthesized by the inventor in the earlier stage is used as a raw material, so that the metallopyridine porphyrin TPyP-Zn not only has rich coordination sites, but also can introduce metal into porphyrin rings for regulating and controlling activity;
2. the crystalline trimetallic pyridine porphyrin porous complex is a novel metal organic porous material, and structural analysis shows that in the material, pyridine nitrogen and copper in metallopyridine porphyrin TPyP-Zn coordinate, and metal zinc and pyrrole nitrogen in porphyrin ring adopt a planar 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, electrocatalytic CO 2 Reduction of CO 2 Meanwhile, the crystalline trimetallic pyridine porphyrin porous complex (TPyPZn-W-Cu) prepared by the invention contains rich fluorine elements, so that the material can be used in the field of flame retardants, and the application range of the metal pyridine porphyrin porous material is greatly widened;
3. the preparation method provided by the invention has the advantages of simple requirements on raw material purity, easiness in raw material acquisition, low price and convenience in large-scale production; the post-treatment is simple and easy to implement, the pure-phase crystalline product can be obtained only by simple alcohol washing and separation and airing at room temperature, and the preparation pollution is less, so that the preparation meets the green environment-friendly requirement; in addition, the yield of the crystalline trimetallic pyridine porphyrin porous complex (TPyPZn-W-Cu) porous complex containing abundant fluorine elements obtained by the preparation method provided by the invention is as high as more than 70%, and the product can be used for gas sensing and photocatalysis of CO 2 Reduction, electrocatalytic CO 2 Reduction of CO 2 Is used in the fields of cycloaddition catalytic reaction, photocatalytic pyrolysis of water to produce hydrogen, flame retardant and the like.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of a crystalline trimetallic pyridine porphyrin porous complex TPyPZn-W-Cu in the invention;
FIG. 2 is an X-ray powder diffraction pattern of crystalline trimetallic pyridinium porphyrin porous complex TPyPZn-W-Cu according to the present invention;
FIG. 3 is a diagram showing the structure of ligand metalloporphyrin TPyP-Zn in example 1 of the present invention;
FIG. 4 is a graph showing the response of crystalline trimetallic pyridinium porphyrin porous complex TPyPZn-W-Cu to 100ppm of various gases (vapors) in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and the preferred embodiments, and the endpoints and any values of the ranges disclosed in the invention are not limited to the precise range or value, and the range or value should be understood to include the value near the range or value; for a range of values, one or more new ranges of values can be obtained in combination with each other between the endpoints of each range, between the endpoints of each range and the individual point values, and between the individual point values, and are to be considered as specifically disclosed herein;
the experimental methods used in the following examples are not specifically described, but the experimental methods in which specific conditions are not specified in the examples are generally carried out under conventional conditions, and the materials, reagents, etc. used in the following examples are commercially available unless otherwise specified;
the single crystal structure optimization used in the following examples was software Materials Studio 8.0; the source used for the X-ray powder diffraction test is Cu-K alpha rays.
Example 1
A crystalline trimetallic pyridine porphyrin porous complex TPyPZn-W-Cu contains abundant fluorine elements, is named as TPyPZn-W-Cu, and has a structure shown in a formula (I):
example 2
Weighing sodium fluotungstate Na 2 WO 2 F 4 (0.0080 g,0.0237 mmol), copper nitrate hexahydrate Cu (NO) 3 ) 2 ·6H 2 O (0.0080 g,0.0270 mmol), metalloporphyrin TPyP-Zn (0.0100 g,0.0147 mmol) as raw material, mixed solution of N-methylpyrrolidone (5 mL) and ethylene glycol (2 mL) as solvent, placing in a 20mL glass bottle, mixing uniformly at room temperature, placing in a 70 ℃ oven for solvothermal reaction for 120h, naturally cooling to room temperature, separating solid phase, and bisecting with methanolWashing the separated solid phase product to obtain a purple crystalline product TPyPZn-W-Cu;
the crystalline product prepared in example 2 was tested to yield more than 70% of crystalline trimetallic pyridine porphyrin porous complex TPyPZn-W-Cu;
the crystal parameters of the crystalline trimetallic pyridine porphyrin porous complex TPyPZn-W-Cu prepared in the example 2 are shown in the table 1;
TABLE 1
Example 3
Copper fluotungstate CuWO 2 F 4 (0.0064 g,0.0180 mmol), copper sulphate pentahydrate CuSO 4 ·5H 2 O (0.0069 g,0.0276 mmol), TPyP-Zn (0.0100 g,0.0147 mmol) is taken as a raw material, a mixed solution of N, N-dimethylformamide (5 ml) and N-butanol (2 ml) is taken as a solvent, the raw material is placed in a 20ml glass bottle, the raw material is uniformly mixed at room temperature, the raw material is placed in a baking oven at 40 ℃ for reaction for 240 hours, the raw material is naturally cooled to room temperature, a solid phase is separated, and the separated solid phase product is washed by methanol, so that a purple crystalline product TPyPZn-W-Cu is obtained;
the crystalline product prepared in example 3 was tested to have a yield of over 70% and the crystalline product prepared in example 3 had the same structure as example 1.
Example 4
Measuring ammonium fluorosilicate (NH) 4 ) 2 SiF 6 (0.0481 g,0.2700 mmol), elemental tungsten W (0.0366 g,0.2000 mol), copper acetate monohydrate Cu (CH) 3 COO) 2 ·H 2 O (0.0299 g,0.1500 mmol), TPyP-Zn (0.6817 g,1.0000 mmol) is taken as a raw material, a mixed solution of N-methyl formamide (7 mL) and isopropanol (3 mL) is taken as a solvent, the raw material is placed in a 20mL glass bottle, the raw material is uniformly mixed at room temperature, the raw material is placed at room temperature (25 ℃) for reaction for 480 hours, a solid phase is separated, and methanol is utilized to wash the separated solid phase product, so that a purple crystalline product TPyPZn-W-Cu can be obtained;
the crystalline product prepared in example 4 was tested to have a yield of over 70% and the crystalline product prepared in example 4 had the same structure as example 1.
Example 5
Sodium fluoride NaF (0.0546 g,1.3000 mmol), tungsten dioxide WO 2 (0.1079 g,0.5000 mmol) copper chloride CuCl 2 (0.0807 g,0.6000 mmol) of TPyP-Zn (0.0682 g,0.1000 mmol) is taken as a raw material, a mixed solution of N-methyl formamide, N-methyl pyrrolidone mixture (5 mL) and propylene glycol (2 mL) is taken as a solvent, the mixture is placed in a 20mL polytetrafluoroethylene pressure container, uniformly mixed at room temperature, then placed in a baking oven at 120 ℃ for reaction for 100 hours, naturally cooled to room temperature, 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 5 was tested to have a yield of over 70% and the crystalline product prepared in example 5 had the same structure as example 1.
Example 6
Measuring sodium fluosilicate Na 2 SiF 6 (0.0150 g,0.0800 mmol), ammonium tungstate (NH) 4 ) 10 W 12 O 41 ·xH 2 O (0.0304 g,0.0100 mmol), copper perchlorate Cu (ClO) 4 ) 2 (0.0236 g,0.0900 mmol) TPyP-Zn (0.1363 g,0.200 mmol) is taken as a raw material, a mixed solution of N, N-dimethylacetamide (5 mL), methanol (1 mL) and ethanol (1 mL) is taken as a solvent, the mixed solution is placed in a 20mL polytetrafluoroethylene pressure container, the mixed solution is uniformly mixed at room temperature, then the mixed solution is placed in a 100 ℃ oven for reaction for 110 hours, the mixed solution is naturally cooled to room temperature, a solid phase is separated, and then methanol is utilized to wash the separated solid phase product, thus obtaining a purple crystalline product TPyPZn-W-Cu;
the crystalline product prepared in example 6 was tested to have a yield of over 70% and the crystalline product prepared in example 6 had the same structure as example 1.
In addition to the above examples 2-6 regarding the selection of fluorine-containing species, tungsten-containing species, copper-containing species and solvents, the following substitutions may be made;
wherein the fluorine-containing substance may be a fluorine-containing acid or a fluorine-containing salt; the fluorine-containing acid may 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 fluorosilicate, sodium fluorovanadate, sodium fluorotungstate, sodium fluoromolybdate, sodium fluoroniobate, copper fluoroniobate, ammonium fluorotungstate, ammonium fluoromolybdate, ammonium fluorosilicate;
wherein the tungsten-containing substance can be elemental tungsten, tungsten oxide or tungsten salt; the elemental tungsten can be tungsten wire; the tungsten oxide may 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 material can be elemental copper, copper oxide or copper salt; the simple substance copper is a copper sheet; the copper oxide is one of copper oxide or cuprous oxide; the copper salt can be at least one of copper 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 amide solvents, alcohol solvents or a mixture of the amide solvents and alcohols; 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 alcohols or mixtures 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 selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, isoamyl alcohol, neopentyl alcohol, n-hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol or mixtures of any two or more thereof;
in the case of the purification of the product by washing with a 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 or mixtures of alcohols having 1 to 40 carbon atoms (for example, 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms).
Example 7
As the porous complex (TPyPZn-W-Cu) containing the crystalline trimetallic pyridine porphyrin rich in fluorine elements has rich fluorine elements, pore channels and active sites, the crystalline product can be used for gas sensing and photocatalysis of CO 2 Reduction, electrocatalytic CO 2 Reduction of CO 2 Is used in the fields of cycloaddition catalytic reaction, photocatalytic pyrolysis of water to produce hydrogen, flame retardant and the like.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related arts are included in the scope of the present invention.

Claims (7)

1. A preparation method of a crystalline trimetallic pyridine porphyrin porous complex is characterized by comprising the following steps: taking metalloporphyrin, fluorine-containing substances, tungsten-containing substances and copper-containing substances as raw materials, performing solvothermal reaction at the temperature of 10-180 ℃, and fully reacting for 18-480 hours to finally prepare the crystalline trimetallic porphyrin porous complex containing abundant fluorine elements; wherein the fluorine-containing substance is a fluorine-containing acid or a fluorine-containing salt; the tungsten-containing substance is simple substance tungsten, tungsten oxide or tungsten salt; the copper-containing substance is elemental copper, copper oxide or copper salt; the metalloporphyrin is 5,10,15,20-tetrapyridyl porphyrin-Zn, and has a structure shown in a formula (II): the molar ratio of the metalloporphyrin to the fluorine-containing substance to the tungsten-containing substance to the copper-containing substance is (1:0.27:0.2:0.15) - (1:13:5:6);
2. the method for preparing the crystalline trimetallic pyridinylporphyrin porous complex according to claim 1, wherein: the preferable molar ratio of the metalloporphyrin, the fluorine-containing substance, the tungsten-containing substance, and the copper-containing substance is (1:2:0.5:0.45) to (1:8:2:4).
3. The method for preparing the crystalline trimetallic pyridinylporphyrin porous complex according to claim 1, wherein: the solvent in the solvothermal reaction is an amide solvent or an alcohol solvent or a mixture of the amide solvent and the alcohol solvent.
4. The method for preparing the crystalline trimetallic pyridinylporphyrin porous complex according to claim 1, wherein: the alcohol solvent is alcohol or mixture of alcohols containing 1-40 carbon atoms.
5. The method for preparing the crystalline trimetallic pyridinylporphyrin porous complex according to claim 1, wherein: the preparation method of the crystalline trimetallic pyridine porphyrin porous complex also comprises the steps of purifying a product after solvothermal reaction; and (3) cleaning the reacted product by adopting an alcohol solvent, separating, and airing at room temperature.
6. A crystalline trimetallic pyridinium porphyrin porous complex according to the method of any one of claims 1-5, characterized in that: contains abundant fluorine elements, is named as TPyPZn-W-Cu, and has a structure shown in a formula (I):
7. a crystalline trimetallic pyridine porphyrin porous complex as defined in claim 6 for gas sensing and photocatalysis of CO 2 Reduction, electrocatalytic CO 2 Reduction of CO 2 The application in the fields of cycloaddition catalytic reaction, photocatalytic pyrolysis of water to produce hydrogen and flame retardants.
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