CN113881004B - Three-dimensional metal porphyrin-based covalent organic framework material with stp topological network structure, and preparation method and application thereof - Google Patents
Three-dimensional metal porphyrin-based covalent organic framework material with stp topological network structure, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a three-dimensional metal porphyrin-based covalent organic framework material with an stp topological network structure, and a preparation method and application thereof, the invention adopts triangular prism-shaped triplet-alkene framework molecules with six connecting nodes and square porphyrin-like framework molecules with four connecting nodes, orderly and expanded regular hexagonal prism-shaped double-interpenetrating three-dimensional stp topological network framework material is obtained through [6+4] imine condensation, and further through metal ion post-modification, the metallization of porphyrin units is realized, and the three-dimensional metal porphyrin-based covalent organic framework material is obtained; the novel three-dimensional covalent organic framework material has a unique highly-ordered stp topological network structure, a better specific surface area and good thermal stability, so that the novel three-dimensional covalent organic framework material has more excellent mass transfer efficiency and more accessible catalytic sites as a heterogeneous catalyst, and has a good catalytic effect in an electrocatalytic oxygen evolution reaction.
Description
Technical Field
The invention belongs to the field of Covalent Organic Frameworks (COFs) porous materials, and particularly relates to a novel three-dimensional metal porphyrin-based covalent organic framework material with an stp topological network structure, and a preparation method and application thereof.
Background
Covalent Organic Frameworks (COFs) are two-dimensional or three-dimensional porous framework compounds with periodic network structures formed by connecting Organic small molecular skeleton molecules through strong Covalent bonds, have highly ordered pore channel structures and high specific surface areas, and have wide application prospects in the fields of gas adsorption and storage, energy storage and conversion, heterogeneous catalysis and the like. At present, research on COFs materials is mainly focused on two-dimensional COFs materials, and the functionalized two-dimensional COFs materials realize ordered arrangement of active sites in one-dimensional channels by means of strong pi-pi stacking effect between two-dimensional layers. Unlike two-dimensional COFs, three-dimensional COFs are relatively less studied, but the unique three-dimensional pore structure of three-dimensional COFs is expected to bring higher mass transfer efficiency and more accessible catalytic sites in the heterogeneous catalytic process.
As a class of enzyme molecules and ideal metal ligands, porphyrin-based backbone molecules have been widely used in the construction of functionalized COFs. However, in two-dimensional porphyrin-based COFs materials, metalloporphyrin ring structure units with excellent catalytic active sites are spatially shielded by interlayer stacking, which limits application and development in the fields of heterogeneous catalysis and the like to a certain extent. The unique three-dimensional network structure of the three-dimensional porphyrin-based COFs material is expected to solve the problem, but because the types of three-dimensional skeleton molecules are limited, the development of the novel COFs material with the three-dimensional topological network structure is still a huge challenge. Until now, only a few reports of three-dimensional porphyrin-based COFs materials exist, and the types of topological networks involved are limited to pts, dia and tbo. The six-connection triptycene skeleton molecule has highly symmetrical triangular prisms and a well-defined three-dimensional space orientation, and is successfully applied to the construction of three-dimensional porous materials, so that the possibility is provided for developing three-dimensional porphyrin-based COFs with a new topological network structure.
Based on the topological structure design, the three-dimensional metal porphyrin-based COFs material with a novel stp topological network structure is synthesized by assembling regular hexagonal prism-shaped triplet-folded alkene skeleton molecules and tetraconnection end-based metal porphyrin skeleton molecules. The framework material has a specific highly-ordered three-dimensional stp topological network structure, a good specific surface area and good thermal stability, so that the novel three-dimensional covalent organic framework material has more excellent mass transfer efficiency and more accessible catalytic sites as a heterogeneous catalyst, has a good effect in the field of catalysis, and particularly has a good catalytic effect in electrocatalytic oxygen evolution reaction.
Disclosure of Invention
The invention aims to provide a novel three-dimensional metal porphyrin-based covalent organic framework material with an stp topological network structure, a preparation method and application thereof.
The technical scheme of the invention is as follows:
a three-dimensional metal porphyrin-based covalent organic framework material is formed by connecting a triptycene six-site framework with six connecting end groups and a porphyrin four-site framework with four connecting end groups in a three-dimensional space; a linking group is selected from-C = N-, -C = N-N = C-, -C = N-NH-, -C = C or-C = C (CN) - (preferably-C = N-);
in at least one part of the three-dimensional metal porphyrin-based covalent organic framework material, each triptycene six-site skeleton is respectively connected with six adjacent porphyrin four-site skeletons, and each porphyrin four-site skeleton is respectively connected with four adjacent triptycene six-site skeletons to form a regular hexagonal prism-shaped three-dimensional stp topological network structure;
the triptycene six-site skeleton is shown as a formula (1), and the porphyrin four-site skeleton is shown as a formula (2);
in formula (1) or formula (2), the wavy line represents the attachment site;
formula (2) wherein M = a metal (metalloporphyrin) selected from one or more of iron (Fe), cobalt (Co), nickel (Ni), platinum (Pt), palladium (Pd), zinc (Zn), copper (Cu), or M =2H (no metalloporphyrin);
the specific surface area of the three-dimensional metal porphyrin group covalent organic framework material is 30-3000 m 2 The pore diameter is 0.6-6.0 nm.
Further, in the at least a part of the three-dimensional metalloporphyrin-based covalent organic framework material, the ratio of the number of moles of the triptycene six-site skeleton to the number of moles of the porphyrin four-site skeleton is (1.5-2.5): (2.5-3.5), preferably 2:3.
further, the three-dimensional metal porphyrin-based covalent organic framework material is a dual interpenetrating regular hexagonal prism-shaped three-dimensional stp topological network structure.
Further, the linking group comprises a dynamic covalent bond.
Further, the three-dimensional metal porphyrin-based covalent organic framework material comprises a framework unit represented by formula (3):
the preparation method of the three-dimensional metal porphyrin group covalent organic framework material comprises the following steps:
(A) Adding the triptycene compound shown in the formula (4), the porphyrin compound shown in the formula (5) and a reaction solvent into a reaction container, vacuumizing and sealing, heating to 80-180 ℃ (preferably 120 ℃) to react for 72-168 hours to generate solid precipitate, filtering and collecting the precipitate, washing and drying to obtain a product for later use;
the mole ratio of the triptycene compound shown in the formula (4) to the porphyrin compound shown in the formula (5) is 2:3;
the reaction solvent is mesitylene, N-dimethylacetamide and 6M acetic acid in a volume ratio of (5-15): (1-5): (1-3), preferably in a volume ratio of 9:3:2; wherein 6M acetic acid is simultaneously used as a catalyst;
the ratio of the volume of the reaction solvent to the total mass of the triptycene compound and the porphyrin compound is 1mL:15mg to 1mL:35mg, preferably 1mL:25mg;
the washing operation method comprises the following steps: soaking in N, N-dimethylacetamide for 12h, repeating twice, soaking in acetone for 12h, repeating twice, and performing Soxhlet extraction with tetrahydrofuran and acetone for 48h;
the drying is as follows: vacuumizing to 20mTorr at 80 ℃ in a vacuum drying oven, and drying for 24 hours;
in formula (4) or (5), R 1 、R 2 One of them is aldehyde group (-CHO), and the other is amino group (-NH) 2 ) (ii) a Preferably R 1 Is an aldehyde group (-CHO), R 2 Is amino (-NH) 2 )；M＝2H；
(B) Adding the product obtained in the step (A), metal salt and organic solvent into a reaction container, vacuumizing and sealing, heating to 90-150 ℃ (preferably 120 ℃) to react for 12-36 h (preferably 24 h), and then filtering, washing and drying to obtain the three-dimensional metal porphyrin-based covalent organic framework material;
the metal salt comprises Fe as metal ion 2+ 、Fe 3+ 、Co 2+ 、Co 3+ 、Ni 2+ 、Pt 2+ 、Pd 2+ 、Zn 2+ 、Cu 2+ One or more of (a); the mass ratio of the product obtained in the step (A) to the metal salt is 1: (1 to 3), preferably 1:2;
the organic solvent is N, N-dimethylformamide, N-dimethylacetamide, toluene or acetonitrile, preferably N, N-dimethylacetamide;
the volume of the organic solvent and the total mass ratio of the product obtained in the step (A) and the metal salt are 1mL:60mg to 1mL:120mg, preferably 1mL:90mg;
the washing operation method comprises the following steps: soaking in hot water at 80 deg.C for 12h, repeating for three times, soaking in N, N-dimethylacetamide for 12h, repeating for two times, soaking in acetone for 12h, repeating for two times, and performing Soxhlet extraction with tetrahydrofuran and acetone for 48h;
the drying comprises the following steps: in a vacuum drying oven, vacuum is pumped to 20mTorr at 80 ℃ and then drying is carried out for 24h.
Alternatively, the preparation method of the three-dimensional metal porphyrin-based covalent organic framework material can also comprise the following steps: directly using the porphyrin compound containing the metal M and shown in the formula (5) to obtain the target product through the step (A).
The three-dimensional metal porphyrin-based covalent organic framework material can be applied to electrocatalytic oxygen evolution reaction.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a design strategy of a three-dimensional metal porphyrin-based covalent organic framework material with a novel stp topological network structure, which adopts triangular prism-shaped triplet alkene framework molecules with six connecting nodes and square porphyrin framework molecules with four connecting nodes to obtain an ordered and expanded orthohexagonal prism-shaped double-interpenetrating three-dimensional stp topological network framework compound through [6+4] imine condensation. Further realizing the metallization of the porphyrin unit by metal ion post-modification to obtain the three-dimensional metal porphyrin group covalent organic framework material.
The three-dimensional covalent organic framework material has high crystallinity, better specific surface area and good thermal stability, so that the novel three-dimensional covalent organic framework material has more excellent mass transfer efficiency and more accessible catalytic sites as a heterogeneous catalyst, has better effect in the field of catalysis, and particularly has good catalytic effect in electrocatalytic oxygen evolution reaction.
Drawings
FIG. 1 is a diagram of a topological network structure of a three-dimensional covalent organic framework compound in accordance with an embodiment of the present invention.
FIG. 2 is a schematic diagram of the synthesis of a three-dimensional covalent organic framework compound according to one embodiment of the present invention.
FIG. 3 is a schematic diagram of synthesis of a three-dimensional metal porphyrin-based covalent organic framework compound by metal post-modification of the three-dimensional covalent organic framework compound according to an embodiment of the present invention.
FIG. 4 is a scanning electron micrograph of a three-dimensional covalent organic framework compound according to one embodiment of the present invention.
FIG. 5 is a three-dimensional space structure diagram of a three-dimensional covalent organic framework compound in the first embodiment of the present invention constructed by Materials studio software.
FIG. 6 shows a powder X-ray (PXRD) test spectrum of a three-dimensional covalent organic framework compound (a) and a metal porphyrin-based covalent organic framework compound (b) in accordance with one embodiment of the present invention.
FIG. 7 is an infrared absorption (FT-IR) spectrum (a) and a partial FT-IR spectrum (b) of a triplet-stacked skeleton molecule, a porphyrin skeleton molecule, a three-dimensional covalent organic framework compound and a metal-porphyrin-based covalent organic framework compound according to the first embodiment of the present invention.
FIG. 8 shows the nitrogen adsorption-desorption isotherms (a) and pore size distribution (b) for 77K of the three-dimensional covalent organic framework compound and the metalloporphyrin-based covalent organic framework compound in one example of the present invention.
FIG. 9 shows a three-dimensional covalent organic framework compound, a metal porphyrin-based covalent organic framework compound and a commercial RuO according to one embodiment of the present invention 2 Polarization plot of Linear Sweep Voltammetry (LSV).
Detailed Description
For a clearer understanding of the objects, aspects and advantages of the present invention. The present invention is described in further detail below with reference to specific embodiments and drawings, but it should be understood that the specific embodiments described in this section are merely for clarity of explanation of the features and advantages of the invention, and are not intended to limit the invention.
The embodiment of the invention provides a three-dimensional metal porphyrin-based covalent organic framework compound with a novel stp topological network structure, which is formed by connecting triptycene framework molecules with six connecting end groups and porphyrin framework molecules with four connecting end groups in a three-dimensional space; the triptycene six-site skeleton molecule is shown as a formula (1), and the porphyrin four-site skeleton molecule is shown as a formula (2); in at least one part of the three-dimensional covalent organic framework compound, each triptycene six-site skeleton molecule is respectively connected with adjacent six porphyrin four-site skeleton molecules, and each porphyrin four-site skeleton molecule is respectively connected with adjacent four triptycene six-site skeleton molecules to form a regular hexagonal prism-shaped three-dimensional stp topological network structure.
In the at least a part of the three-dimensional metal porphyrin-based covalent organic framework compound, a molar number ratio of the triptycene six-site framework molecules to the porphyrin four-site framework molecules is (1.5-2.5): (2.5-3.5), preferably 2:3. the three-dimensional covalent organic framework is a regular hexagonal prism-shaped three-dimensional organic framework structure and has a dual interpenetrating stp topological network structure.
Specifically, the triptycene six-site skeleton molecule has a three-dimensional rigid structure, three benzene rings are rotationally symmetrical relative to a central axis and extend outwards as planes with different three-dimensional space orientations, and an included angle between the planes is 120 degrees. The porphyrin four-site skeleton molecule has a two-dimensional quadrilateral structure, and the included angle between nodes is 90 degrees.
The arrangement positions and the connection relation among the units are shown in a reference figure 1, and each triptycene six-site skeleton molecule is used as a node of a regular hexagonal prism and is connected with six porphyrin four-site skeleton molecules. Each porphyrin four-site skeleton molecule is used as the side surface of a regular hexagonal prism and is connected with four triptycene six-site skeleton molecules. The adjacent four triptycene six-site skeleton molecules are connected through one porphyrin four-site skeleton molecule, and the adjacent two porphyrin four-site skeleton molecules are connected through the same flank of the triptycene six-site skeleton molecule, so that the three-dimensional covalent organic framework compound continuously extends in a three-dimensional space to form a dual interpenetrating three-dimensional stp topological network structure. The dual interpenetrating is formed by inserting two sets of identical stp topological network structures, the vertexes of three angles on the regular hexagon of each set of stp topological network structure are positioned at the center of the regular hexagon of another set of stp topological network structure, and the other three angles are coincided by the vertexes of one angle of the regular hexagon of another set of stp topological network structure.
It is understood that in the actually prepared compound structure, part of the groups may be dislocated to cause local structural deformation, but as long as at least one part of the compound has the above structure, the part can provide larger void ratio and specific surface area, thereby being within the protection scope of the present invention.
The linking group contains dynamic covalent bonds and is connected in a manner selected from the group consisting of-C = N-, -C = N-NH-, -C = C (CN) -.
In example one, the linking group is an imine group (-C = N-), and the three-dimensional covalent organic framework compound has a framework unit as shown in formula (3).
The specific surface area (BET) of the three-dimensional metal porphyrin-based covalent organic framework compound provided by the embodiment of the invention is 30-3000 m 2 The pore diameter is 0.6nm to 6.0nm.
The embodiment of the invention also provides application of the metalloporphyrin three-dimensional covalent organic framework compound in electrocatalytic oxygen evolution reaction.
The embodiment of the invention also provides a preparation method of the metalloporphyrin three-dimensional covalent organic framework compound, which comprises the following steps:
step one, preparing a covalent organic framework
S1-1, adding a triptycene compound shown as a formula (4), a porphyrin compound shown as a formula (5), an organic solvent and a catalyst into a reaction container, vacuumizing the container and sealing.
S1-2, heating the sealed container at the temperature of 80-180 ℃ for reaction to generate solid precipitate.
S1-3, filtering to obtain a precipitate, soaking and washing with an organic solvent, and drying to obtain the three-dimensional covalent organic framework compound.
R of formula (4) 1 And R of formula (5) 2 Reacting to form the linking group. For example, when the linking group is-C = N-, R 1 And R 2 One is aldehyde (-CHO) and the other is amino (-NH) 2 ). When the linking group is-C = N-NH-, R 1 And R 2 One is aldehyde group (-CHO) and the other is hydrazide group (-CONHNH) 2 ). When the linking group is-C = C (CN) -, R 1 And R 2 One is aldehyde (-CHO) and the other is-CH 2 And a CN group.
In the first embodiment, R 1 Is an aldehyde group (-CHO), R 2 Is amino (-NH) 2 ) The specific structures are respectively formula (6) and formula (7).
The organic solvent of step S1-1 is preferably a mixture of mesitylene, N-dimethylacetamide and acetic acid (6M). Wherein the volume ratio of mesitylene, N-dimethylacetamide and acetic acid is (5-15): (1-5): (1 to 3), preferably 9:3:2. the ratio of the volume of the organic solvent in the step S1-1 to the total mass of the triptycene compound and the porphyrin compound is 1mL:15mg to 1mL:35mg, preferably 1mL:25mg. In order to avoid the reaction between the triptycene compound and the porphyrin compound with oxygen, step S1-1 is preferably performed in a glove box filled with a protective gas (such as nitrogen), or performed by performing vacuum pumping at a low temperature, preferably a liquid nitrogen temperature, to remove oxygen in the organic solvent, and the cycle is performed three times. In the step S1-1, the triptycene compound and the porphyrin compound are added according to the stoichiometric ratio, and the preferred molar ratio is 2:3.
the heating temperature of the container in the step S1-2 is 80-180 ℃, and the crystallization degree and the specific surface area of the product are easily improved due to higher reaction temperature. However, too high a temperature may lead to decomposition of the reactants. Preferably, the heating temperature is from 100 ℃ to 130 ℃, more preferably 120 ℃. The reaction time is preferably 72h to 168h, and the material crystallinity can be improved by dynamic chemical regulation for a longer time. The step S1-2 is carried out in a closed container to avoid the entering of environmental oxygen, so that a positive pressure environment is formed inside, and the occurrence of a dynamic error correction process is promoted.
In step S1-3, since the synthesized three-dimensional covalent organic framework compound has a high porosity and a large specific surface area, a part of the monomer and the solvent which do not participate in the reaction remain in the nanopores of the material. Residues in the gaps can be better removed by adopting an organic solvent soaking mode. The organic solvent used for washing may be N, N-dimethylacetamide, anhydrous acetone, tetrahydrofuran, or the like. Preferably, the soaking in N, N-dimethylacetamide is repeated twice for 12h, and then the soaking in acetone is repeated twice for 12h to remove by-products in pores. Then, the high boiling point solvent in the voids was removed by Soxhlet extraction with tetrahydrofuran and acetone for 48h, respectively.
The drying treatment is carried out at 120 ℃ or lower, preferably 80 ℃ in a vacuum drying oven, and drying is carried out for 24h after vacuum pumping to 20 mTorr.
And step two, preparing the three-dimensional metal porphyrin group covalent organic framework material.
S2-1, adding the covalent organic framework material obtained in the step one, metal salt and organic solvent into a reaction container, and vacuumizing and sealing the container.
And S2-2, heating the sealed container at the temperature of 90-150 ℃ for reaction.
S2-3, filtering to obtain a precipitate, soaking and washing with water and an organic solvent, and drying to obtain the three-dimensional metal porphyrin-based covalent organic framework compound.
The metal ion contained in the metal salt in the step S2-1 is Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ 、Ni 2+ 、Pt 2+ 、Pd 2+ 、Zn 2 + 、Cu 2+ The mass ratio of the covalent organic framework material to the metal salt is 1: (1 to 3), preferably 1:2. the organic solvent is one of N, N-dimethylformamide, N-dimethylacetamide, toluene and acetonitrile, and preferably N, N-dimethylacetamide. The ratio between the volume of organic solvent and the total mass of the covalent organic framework material and the metal salt is 1mL:60mg to 1mL:120mg, preferably 1mL:90mg. In order to prevent the metal salt from being oxidized during the reaction in step S2-1, step S2-1 is preferably performed in a glove box filled with a protective gas (e.g., nitrogen gas), or vacuum pumping is performed at a low temperature, preferably a liquid nitrogen temperature, to remove oxygen in the organic solvent, and the cycle is performed three times.
The heating temperature of the container in the step S2-2 is 90 ℃ to 150 ℃, the higher temperature can promote the coordination reaction of the metal ions and the porphyrin, but the excessively high temperature can cause the damage of the crystallinity of the material, and the temperature is preferably 120 ℃. The reaction time is 12 to 36 hours, preferably 24 hours.
In the step S2-3, since the excessive metal ions participate in the reaction, the unreacted metal ions and part of by-products may remain in the pores of the material, and preferably, the material is first soaked in hot water at 80 ℃ for 12 hours to remove the remaining metal ions, which is repeated three times. Then soaking in N, N-dimethylacetamide for 12h to remove byproducts in the pores, repeating twice, and then soaking in acetone for 12h, repeating twice. Then, the high boiling point solvent in the voids was removed by Soxhlet extraction with tetrahydrofuran and acetone for 48h, respectively. The drying treatment is carried out by vacuumizing to 20mTorr in a vacuum drying oven at 120 deg.C or lower, preferably 80 deg.C for 24h.
Example one
(1) Synthesis of three-dimensional covalent organic framework Material (named ZJUT-1, ZJUT = Zhejiang university of industry)
Referring to FIG. 2, 2,3,6,7,14,15-hexa (4-formylphenyl) triene (HFTP) (17.6 mg, 0.02mmol) and 5,10,15,20-tetrakis (4-aminophenyl) porphyrin (TAPP) (20.2 mg, 0.03mmol) were weighed into glass ampoules together with mesitylene (0.9 mL) and N, N-dimethylacetamide (0.3 mL). The solution was sonicated for 5 minutes to give a dark purple cloudy solution. 6M acetic acid (0.2 mL) was added as a catalyst to a glass ampoule. The glass ampoules were snap frozen at 77K in a liquid nitrogen bath and degassed by freeze-pump-thaw, cycle three times and then sealed. The glass ampoule was placed in an oven at 120 ℃ for 5 days. The purple-red solid was separated by centrifugation and washed by immersion in N, N-dimethylacetamide (2X 10 mL) and acetone (2X 10 mL). The resulting precipitate was filtered and then washed thoroughly with tetrahydrofuran and acetone by soxhlet extraction for 48h. The sample was then transferred to a vacuum chamber, evacuated to 20mTorr at 80 ℃ and dried for 24h to give ZJUT-1 as a purple red powder (yield: 29.2mg, 81.9%).
(2) Three-dimensional metal porphyrin-based covalent organic framework material (named ZJUT-1@ Co)
Referring to FIG. 3, the three-dimensional covalent oil-valent framework material synthesized in the previous step (60 mg) and cobalt (II) acetate tetrahydrate (119.6 mg, 0.48mmol) were weighed into a glass ampoule along with N, N-dimethylacetamide (2.0 mL). The glass ampoules were snap frozen at 77K in a liquid nitrogen bath and degassed by freeze-pump-thaw, cycle three times and then sealed. The glass ampoule was placed in a 120 ℃ oven for 24h. The dark red solid was separated by centrifugation, washed with 80 ℃ hot water (3X 10 mL), and then immersed in N, N-dimethylacetamide, and the solvent was exchanged several times. The resulting precipitate was filtered and then washed thoroughly with tetrahydrofuran and acetone by soxhlet extraction for 48h. The sample was then transferred to a vacuum chamber and dried for 24h after evacuation to 20mTorr at 80 deg.C to give ZJUT-1@ Co as a dark red powder (yield: 53.4mg, 84.8%).
(3) Product characterization and Performance testing
Scanning Electron Microscope (SEM) pattern (FIG. 4 a) shows the ZJUT-1 is in the form of uniform particles of 100nm and further assembled into micron-sized spheres. The morphology of ZJUT-1@ Co obtained after metal post-repair was maintained in comparison with FIG. 4 b.
Referring to fig. 5, the crystal structure of the three-dimensional covalent organic framework was resolved by measurement and simulation of XRD, and geometric energy optimization was performed on the pre-set structure of the three-dimensional covalent organic framework using Materials Studio software based on the dual interpenetrating stp topological network structure. Referring to fig. 6a, the simulated XRD curves generated by the stp topology of dual interpenetration matched well with the experiment. The experimentally obtained peaks 1.82,3.50,4.02,4.63,4.95,5.14,5.36,6.26,6.57,6.91 and 7.82 correspond to the Bragg peaks (100), (110), (200), (101), (210), (111), (300), (121), (310), (301) and (230) of the P-3 (No. 147) space group. Referring to FIG. 6b, ZJUT-1@ Co crystallinity obtained by post-metal modification was maintained.
Referring to FIG. 7a, fourier transform Infrared (FT-IR) spectroscopy shows that ZJUT-1 has a new absorption peak for the comparison ligands HFPTP and TAPP, corresponding to 1622cm -1 Characteristic stretching vibration of C = N key at (C = O) and further C = O stretching vibration of HFPTP 1698cm -1 The conversion of aldehyde groups was confirmed by a significant reduction. Referring to FIG. 7b, a new Co-N peak at 1002cm was observed compared to ZJUT-1@ Co before the modification -1 Successful coordination of cobalt ions was demonstrated.
Referring to FIG. 8a, from N at 77K 2 The adsorption measurement shows that the three-dimensional covalent organic framework material has type IVAn isotherm, which is characteristic of a mesoporous material, with a specific surface area of ZJUT-1 (725 m) 2 /g)，ZJUT-1@Co(657m 2 In terms of/g). Referring to FIG. 8b, the pore size distribution of ZJUT-1, ZJUT-1@ Co calculated by non-local density functional theory (NLDFT) is mainly
And
consistent with the proposed dual interpenetrating stp structure.
(4) Electrocatalytic oxygen evolution activity test
ZJUT-1@ Co, ZJUT-1 and commercial noble metal catalyst RuO 2 Coating on carbon cloth to form electrode, comparing by Linear Sweep Voltammetry (LSV), FIG. 9 shows LSV polarization curve after current compensation, non-post-modified ZJUT-1 shows low anode current density and high overpotential, post-modified ZJUT-1@ Co anode current density after Co ion is greatly increased, and the electrode reaches 10mA/cm 2 With current density as a benchmark for comparative electrocatalytic performance, ZJUT-1@ co can achieve lower overpotential at 300mV, lower than most reported porphyrin-based covalent polymer catalysts, due to the three-dimensional framework structure promoting more excellent mass transfer efficiency and more exposure of catalytically active sites.
The technical features of the embodiments described above can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the technical features.
The above-mentioned examples only represent several embodiments of the present invention, and the description thereof is more specific and detailed, but should not be construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present invention should be subject to the appended claims.
Claims (9)
1. The three-dimensional metal porphyrin-based covalent organic framework material is characterized in that the three-dimensional metal porphyrin-based covalent organic framework material is formed by connecting a triptycene six-site framework with six connecting end groups and a porphyrin four-site framework with four connecting end groups in a three-dimensional space; the linking group is selected from-C = N-, -C = N-N = C-, -C = N-NH-, -C = C, or-C = C (CN) -;
in at least one part of the three-dimensional metal porphyrin-based covalent organic framework material, each triptycene six-site skeleton is respectively connected with six adjacent porphyrin four-site skeletons, and each porphyrin four-site skeleton is respectively connected with four adjacent triptycene six-site skeletons to form a three-dimensional stp topological network structure;
the triptycene six-site skeleton is shown as a formula (1), and the porphyrin four-site skeleton is shown as a formula (2);
in formula (1) or formula (2), the wavy line represents the attachment site;
in formula (2), M = metal selected from one or more of iron, cobalt, nickel, platinum, palladium, zinc, and copper.
2. The three-dimensional metalloporphyrin-based covalent organic framework material of claim 1, wherein in said at least one portion of said three-dimensional metalloporphyrin-based covalent organic framework material, the ratio of the number of moles of the triptycene six-site framework to the porphyrin four-site framework is (1.5-2.5): (2.5-3.5).
3. The three-dimensional metalloporphyrin-based covalent organic framework material of claim 1, wherein said three-dimensional metalloporphyrin-based covalent organic framework material is a dual interpenetrating three-dimensional stp topological network structure.
4. The three-dimensional metal porphyrin-based covalent organic framework material of claim 1, wherein said linking groups comprise dynamic covalent bonds.
5. The three-dimensional metalloporphyrin-based covalent organic framework material of claim 1, wherein said three-dimensional metalloporphyrin-based covalent organic framework material comprises a framework unit represented by formula (3):
6. the method for preparing the three-dimensional metal porphyrin-based covalent organic framework material of claim 1, wherein the method comprises the following steps:
(A) Adding a triptycene compound shown in a formula (4), a porphyrin compound shown in a formula (5) and a reaction solvent into a reaction container, vacuumizing and sealing, heating to 80-180 ℃, reacting for 72-168 hours to generate solid precipitates, filtering and collecting the precipitates, washing and drying to obtain a product for later use;
the mole ratio of the triptycene compound shown in the formula (4) to the porphyrin compound shown in the formula (5) is 2:3;
the reaction solvent is mesitylene, N-dimethylacetamide and 6M acetic acid according to the volume ratio of (5-15): (1-5): (1-3);
in formula (4) or (5), R 1 、R 2 One is aldehyde group and the other is amino group;
(B) Adding the product obtained in the step (A), metal salt and an organic solvent into a reaction container, vacuumizing and sealing, heating to 90-150 ℃, reacting for 12-36 h, filtering, washing and drying to obtain the three-dimensional metal porphyrin-based covalent organic framework material;
the metalThe salt comprising a metal ion of Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ 、Ni 2+ 、Pt 2+ 、Pd 2+ 、Zn 2+ 、Cu 2+ One or more of (a); the mass ratio of the product obtained in the step (A) to the metal salt is 1: (1-3);
the organic solvent is N, N-dimethylformamide, N-dimethylacetamide, toluene or acetonitrile.
7. The method according to claim 6, wherein in the step (A), the ratio of the volume of the reaction solvent to the total mass of the triptycene compound and the porphyrin compound is 1mL:15mg to 1mL:35mg.
8. The method of claim 6, wherein in step (B), the volume of the organic solvent and the combined mass ratio of the product of step (A) and the metal salt is 1mL:60mg to 1mL:120mg.
9. The use of the three-dimensional metal porphyrin-based covalent organic framework material of claim 1 in electrocatalytic oxygen evolution reactions.
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