CN112588323B - Preparation method of bulk porous PdCl/COFs material - Google Patents
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 136
- 239000000463 material Substances 0.000 title claims abstract description 96
- 101150003085 Pdcl gene Proteins 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 22
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013384 organic framework Substances 0.000 claims abstract description 14
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims abstract description 13
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 23
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
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- 238000001035 drying Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
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- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 13
- 239000001257 hydrogen Substances 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 12
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- 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
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/28—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
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- 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
- B01J2531/02—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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- 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 discloses a preparation method of a bulk porous PdCl/COFs material, which takes azobenzene dicarboxylic acid and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine as raw materials, prepares an organic framework material COFs by a thermal polycondensation method, and adopts K 2 PdCl 4 And (3) matching with COFs to obtain the bulk porous PdCl/COFs material. The PdCl/COFs material prepared by the preparation method can effectively improve the response capability and the electron transmission capability of the COFs material to visible light, so that the photocatalytic performance of the COFs material is improved, and the PdCl/COFs material has higher hydrogen production performance under the catalysis of visible light. In addition, the preparation method has mild reaction conditions, and the synthesis process is simple and easy to implement, and can provide reference basis for preparing other COFs materials.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, and particularly relates to a preparation method of a bulk porous PdCl/COFs material.
Background
Environmental deterioration and energy depletion are serious challenges in the development of human society, and the problems of replacement, no pollution and low cost are urgently needed to be solved at present by searching and developing. The preparation of hydrogen by utilizing solar photocatalytic water decomposition is an important technology for providing clean energy, and the key for solving the problem is to find a material with a photocatalytic hydrogen production effect. Of the many known materials, semiconductor materials have been widely used for photocatalytic reactions, and many semiconductor photocatalytic materials affect their photocatalytic activity due to their wide band gap or photo-induced corrosion. Therefore, the research and design of the high-efficiency photocatalytic material are the key points for the development of the photolytic hydrogen production technology. Covalent Organic Frameworks (COFs) are similar to semiconductor nitrogen carbide and are composed of light elements, so that the Covalent Organic Frameworks are heterogeneous photocatalysts which are cheap and easy to obtain as raw materials, have diversified and controllable synthesized structures and have wide application prospects. Due to the pi electrons in the conjugated plane and the axial charge transmission performance, the COFs material has high carrier mobility, potential high-efficiency light-capturing performance and electron transmission capability. Therefore, in recent years, COFs have become one of the hot research spots in the field of photocatalytic water splitting hydrogen production, and later scientists find that the effect of hydrogen production can be improved by adding a metal complex as a catalyst. However, due to the limited photo-stability, low crystallinity and slow multi-electron diffusion-controlled proton reduction process of the catalyst, the synthesis of an efficient photocatalytic COFs tends to be challenging.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a bulk porous structure PdCl/COFs material which has a simple synthesis process and has stronger visible light response performance and photocatalytic hydrogen production capacity.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a bulk porous PdCl/COFs material specifically comprises the following steps:
dissolving azobenzene dicarboxylic acid, benzotriazole-1-yl-oxy tripyrrolidinyl phosphorus hexafluorophosphate and N, N-diisopropylethylamine in N, N-dimethylformamide to obtain a solution A;
dissolving 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine in N, N-dimethylformamide to obtain a solution B;
then mixing the solution A and the solution B, reacting for 6-8 h at 60 ℃, washing with water, filtering, and drying after the reaction is finished to obtain organic framework materials COFs;
Further, the mass ratio of azobenzene dicarboxylic acid, benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine is 1.
Furthermore, the dosage of the N, N-diisopropylethylamine is 217.5-250.0 mu L.
Furthermore, the dosage of the N, N-dimethylformamide in the solution A and the solution B is 55-70 mL respectively.
Further, the step 2 adopts a noble metal compound K 2 PdCl 4 The complex PdCl/COFs is coordinated with organic framework material COFs to form a complex PdCl/COFs, and the specific method comprises the following steps:
taking synthetic COFs and K 2 PdCl 4 Taking methanol as a dispersing agent, and reacting for 20-24 h at room temperature under the condition of stirring at the rotating speed of 1000 r/min;
evaporating methanol to dryness, carrying out suction filtration, repeatedly washing with distilled water, and drying to obtain the complex PdCl/COFs of the COFs.
Further, the COFs material and K 2 PdCl 4 The mass ratio of (1) to (20) is 18.
Furthermore, the dosage of the dispersant methanol is 50-100 mL.
Compared with the prior art, the invention can obtain the following technical effects:
1) The preparation method successfully synthesizes organic framework materials COFs by using a simple thermal polycondensation method, the reaction condition is mild, and the synthesis process is simple and easy to realize;
2) The preparation method of the invention uses the noble metal compound K 2 PdCl 4 The functional modification is carried out on the COFs, so that the response capability and the electron transmission capability of the COFs to visible light are effectively improved, and the photocatalytic performance of the COFs is improved;
3) The PdCl/COFs material with the blocky porous structure prepared by the preparation method has higher hydrogen production performance under the catalysis of visible light;
4) The method provides reference for preparing other COFs materials.
Drawings
FIG. 1 is an infrared spectrum of the bulk porous PdCl/COFs material and the materials azobenzene dicarboxylic acid and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine used in example 1 of the preparation method of the invention and the products COFs;
FIG. 2 is an infrared spectrum of the CoFs and PdCl/COFs material prepared in example 1 of the preparation method of a bulk porous structure PdCl/COFs material of the present invention;
FIG. 3 shows the preparation method of PdCl/COFs Material with bulk porous Structure according to the present invention, example 1 shows that the COFs 1 HNMR spectrogram;
FIG. 4 shows a method for preparing PdCl/COFs materials with bulk porous structures according to the present invention, in which the PdCl/COFs materials prepared in example 1 are used 1 H NMR spectrum;
FIG. 5 is a diagram showing the diffuse reflection of ultraviolet light of the bulk porous PdCl/COFs material and the materials azobenzene dicarboxylic acid and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine used in example 1 of the preparation method of the PdCl/COFs material of the present invention;
FIG. 6 is a spectrum of forbidden band widths of products COFs and PdCl/COFs obtained in example 1 of the preparation method of the PdCl/COFs material with the bulk porous structure of the present invention;
FIG. 7 is a scanning electron microscope image of the products of the invention COFs and PdCl/COFs in example 1 of the method for preparing a bulk porous PdCl/COFs material of the invention;
FIG. 8 is a spatial structure diagram of the products COFs of the invention in example 1 of the preparation method of a bulk porous PdCl/COFs material of the invention;
FIG. 9 is a diagram showing the hydrogen production effect of the products of the invention COFs and PdCl/COFs under visible light irradiation in example 1 of the preparation method of the bulk porous PdCl/COFs material of the invention.
Detailed Description
The following embodiments are described in detail with reference to the accompanying drawings, so that how to implement the technical features of the present invention to solve the technical problems and achieve the technical effects can be fully understood and implemented.
The invention discloses a preparation method of a bulk porous PdCl/COFs material, which comprises the following steps:
dissolving azobenzene dicarboxylic acid, benzotriazole-1-yl-oxy tripyrrolidinyl phosphorus hexafluorophosphate (PyBOP) and N, N-Diisopropylethylamine (DIEA) in N, N-Dimethylformamide (DMF) to obtain a solution A;
dissolving 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (TTA) in N, N-Dimethylformamide (DMF) to obtain a solution B;
and mixing the solution A and the solution B, reacting for 6-8 h at 60 ℃, washing with water, filtering, and drying after the reaction is finished to obtain the organic framework material COFs.
Wherein the mass ratio of azobenzene dicarboxylic acid, benzotriazol-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine is 1.
Wherein the dosage of the N, N-diisopropylethylamine is 217.5-250.0 mu L.
Wherein the dosage of the N, N-dimethylformamide in the solution A and the solution B is 55 to 70mL respectively.
The specific synthetic route is as follows:
taking synthetic COFs and K 2 PdCl 4 Taking methanol as a dispersing agent, and reacting for 20-24 h at room temperature under the condition of stirring at the rotating speed of 1000 r/min;
then, evaporating methanol to dryness, carrying out suction filtration, repeatedly washing with distilled water, and drying to obtain the complex PdCl/COFs of the COFs.
Wherein, COFs material and K 2 PdCl 4 Of (2)The ratio of 18.
Wherein the dosage of the dispersant methanol is 50-100 mL.
The specific synthetic route is as follows:
example 1
Step 1: preparation of organic framework material COFs
Step 1.1: accurately weighing 135.1mg of azobenzene dicarboxylic acid, 0.5mmol, 0.5mmol of coupling agent PyBOP265.8mg,0.5mmol and 217.5 mu L of DIEA in a round bottom flask, adding 55mL of DMF, and magnetically stirring at room temperature for 1.5h;
step 1.2: weighing 265.8mg of TTA and 0.75mmol of TTA, adding the TTA and the 0.75mmol of TTA into 55mL of DMF and a proper amount of container, and magnetically stirring for 0.5h at room temperature;
step 1.3: mixing the solutions obtained in the steps 1.1 and 1.2, and reacting for 6.5 hours at 60 ℃ by using a magnetic stirrer at a speed of 500 r/min;
step 1.4: after the reaction in the step 1.3 is determined to be finished, evaporating DMF by using a rotary evaporator and an oil bath until the DMF is viscous or solid;
step 1.5: and (3) washing and filtering the product obtained in the step (1.4) to obtain solid powder, wherein the solid powder is the COFs material as the synthetic product.
Step 2: synthesizing PdCl/COFs material:
step 2.1: weighing 90mg of COFs raw material synthesized in the step 1 2 PdCl 4 5mg of 50ml of methanol in a round bottom flask;
step 2.2: adding a magnetic stirrer into the solution obtained in the step 2.1, and reacting at 20 ℃ for 20h at 1000 r/min;
step 2.3: evaporating the methanol in step 2.2 by using a rotary evaporator;
step 2.4: washing the product obtained in the step 2.3 by using distilled water for many times, and drying the product in an oven to obtain a brown product.
FIGS. 1 and 2 show the materials azobenzene dicarboxylic acid and TTA used in example 1 of the preparation method of PdCl/COFs material with bulk porous structure, and the products COFs material,An infrared spectrum of the PdCl/COFs material. The information of the groups contained in the molecular structure of the sample can be illustrated by FT-IR spectroscopy, as shown in FIG. 1: TTA is a triazine ring derivative having a characteristic peak peculiar to a triazine ring, 809cm -1 Is the out-of-plane bending vibration of the characteristics of the triazine ring, 3320.10cm -1 、3430.35cm -1 Is an upstream leaving amino-NH of TTA 2 The stretching vibration peak of (2). The concentration of azobenzene dicarboxylic acid is 1630.10cm -l 、1700cm -l Expansion vibration peak of C = O, 2655cm -1 Is the stretching vibration peak of-OH. The azobenzene dicarboxylic acid and the COFs material synthesized by TTA form an amido bond at 1635 and 1640cm -1 C = N tensile vibrations are formed, which are characteristic of amides in COFs, the amino band present in TTA and azobenzene dicarboxylic acid (3213-3435 cm) -1 ) And carboxyl tape (1360 cm) -1 ) Disappearance of the reaction proves that the azobenzene dicarboxylic acid is successfully loaded on TTA. In FIG. 2, synthetic COFs with K were found 2 PdCl 4 After the reaction, the amido bond is retained and is not changed, which indicates that the molecular structure of the COFs material is not changed by the existence of the ligand.
FIG. 3 shows the preparation method of PdCl/COFs materials with bulk porous structures of the invention, example 1 shows the preparation method of COFs 1 HNMR spectrogram. As shown in figure 1 of the drawings, in which, 1 HNMR (400MHz, DMSO), delta (ppm): 8.38,8.37,8.35,8.19,8.17,8.04.2.5ppm is the solvent peak deuterated DMSO and 3.36ppm is the water peak. In total of 4 hydrogen, the proton ratio (6. FIG. 3 shows that TTA successfully reacts with azobenzene dicarboxylic acid, thus confirming the structural correctness.
FIG. 4 shows a method for preparing PdCl/COFs materials with bulk porous structures according to the present invention, in which the PdCl/COFs materials prepared in example 1 are used 1 H NMR spectrum. As shown in the figure, the first and second, 1 HNMR (400MHz, DMSO), delta (ppm): 8.36,8.34,8.34,8.19,8.17,8.04,8.01,6.70,6.68,2.5. Total 5 hydrogen (1. 8.17ppm to (a), 6.68ppm to (b), 8.36ppm to (c), 8.04ppm to (d), 5.92ppm to (e). The structure of the material can be determined by nuclear magnetic diagram, and COFs material and K are proved 2 PdCl 4/ And (4) synthesizing COFs materials. The COFs materials and K can be illustrated by FIG. 4 2 PdCl 4 Reactions occurred, further confirming successful synthesis of the material.
FIG. 5 shows a method for preparing PdCl/COFs material with bulk porous structure according to the present invention, in example 1, the raw materials azobenzene dicarboxylic acid and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, and the products COFs and PdCl / Uv diffuse reflectance of COFs materials. As can be seen in FIG. 5, the response performance of COFs materials in the visible light region is remarkably improved, and K is used 2 PdCl 4 After modification, pdCl / The COFs material has stronger light capturing performance than COFs in the visible light region, and contributes to further improvement of the photocatalytic performance.
FIG. 6 is a spectrum of forbidden bandwidths of PdCl/COFs and COFs materials prepared in embodiment 1 of the preparation method of the PdCl/COFs material with the bulk porous structure. As can be seen from fig. 6 (b), the obtained COFs material has a smaller forbidden bandwidth and a stronger response performance to sunlight. However, via K 2 PdCl 4 After modification, as shown in fig. 6 (a), the forbidden band width is further reduced from 2.56eV to 2.40eV, and electrons and vacancies are more easily separated under the irradiation of visible light.
FIG. 7 shows the preparation method of PdCl/COFs Material with bulk porous Structure according to the present invention, COFs (7 a) and PdCl prepared in example 1 / SEM images of COFs (7 b) materials. As can be seen from FIG. 7 (a), COFs have a distinct bulk porous structure. However, via K 2 PdCl 4 After modification (fig. 7 b), it can be seen that the COFs structure is preserved, and the bulk porous morphology is not significantly changed.
FIG. 8 is a spatial structure diagram of the products COFs of the invention in example 1 of the preparation method of the bulk porous PdCl/COFs material of the invention.
FIG. 9 shows a method for preparing PdCl/COFs materials with bulk porous structures according to the present invention, COFs (7 a) and PdCl prepared in example 1 / The effect graph of the COFs (7 b) material on hydrogen production by photocatalytic water decomposition under the condition of irradiation of visible light. As can be seen from FIG. 9, the resulting PdCl is compared to COFs / The COFs material has higher photocatalytic performance, and the hydrogen production amount in 5h is 1593.33 mu mol/g, which is 2 times (764.84 mu mol/g) that of the COFs material. The experimental result is compared with the ultraviolet diffuse reflection and forbidden band width diagramsThe results were substantially consistent.
Example 2
Step 1: preparation of organic framework material COFs
Step 1.1: accurately weighing 135.1mg of azobenzene dicarboxylic acid, 0.5mmol, pyBOP265.8mg of coupling agent, 0.5mmol and 230.0 mu L of DIEA in a round-bottom flask, adding 65mL of DMF, and magnetically stirring at room temperature for 1.5h;
step 1.2: weighing 265.8mg and 0.95mmol of TTA, adding the TTA into 55mL of DMF and a proper amount of container, and magnetically stirring for 0.5h at room temperature;
step 1.3: mixing the solutions obtained in the steps 1.1 and 1.2, and reacting for 6 hours at 60 ℃ by using a magnetic stirrer at a speed of 500 r/min;
step 1.4: after the reaction in the step 1.3 is determined to be finished, evaporating DMF by using a rotary evaporator and an oil bath until the DMF is viscous or solid;
step 1.5: and (3) washing and filtering the product obtained in the step (1.4) to obtain solid powder, wherein the solid powder is the COFs material as the synthetic product.
And 2, step: synthesizing PdCl/COFs material:
step 2.1: 95mg of COFs raw material synthesized in the step 1 is weighed 2 PdCl 4 5mg of 75ml of methanol in a round bottom flask;
step 2.2: adding a magnetic stirrer into the solution in the step 2.1, and reacting at 20 ℃ for 22h at 1000 r/min;
step 2.3: evaporating the methanol in the step 2.2 by using a rotary evaporator;
step 2.4: washing the product obtained in the step 2.3 by using distilled water for many times, and drying the product in an oven to obtain a brown product.
Example 3
Step 1: preparation of organic framework material COFs
Step 1.1: accurately weighing 135.1mg of azobenzene dicarboxylic acid, 0.5mmol, 265.8mg of coupling agent PyBOP, 0.5mmol and 250.0 mu L of DIEA into a round bottom flask, adding 70mL of DMF, and magnetically stirring at room temperature for 1.5h;
step 1.2: weighing 354.4mg of TTA and 1.00mmol of TTA, adding the TTA and the 1.00mmol of TTA into 55mL of DMF and a proper amount of container, and magnetically stirring for 0.5h at room temperature;
step 1.3: mixing the solutions obtained in the steps 1.1 and 1.2, and reacting for 8 hours at 60 ℃ by using a magnetic stirrer at a speed of 500 r/min;
step 1.4: after the reaction in the step 1.3 is determined to be finished, evaporating DMF by using a rotary evaporator and an oil bath until the DMF is viscous or solid;
step 1.5: and (3) washing and filtering the product obtained in the step (1.4) to obtain solid powder, wherein the solid powder is the COFs material as the synthetic product.
And 2, step: synthesizing PdCl/COFs material:
step 2.1: weighing the COFs and K synthesized in the step 1 2 PdCl 4 The mass ratio of (1) to (2) is 20, and 100mL of methanol is placed in a round-bottom flask;
step 2.2: adding a magnetic stirrer into the solution obtained in the step 2.1, and reacting at 20 ℃ for 24 hours at 1000 r/min;
step 2.3: evaporating the methanol in the step 2.2 by using a rotary evaporator;
step 2.4: washing the product obtained in the step 2.3 by using distilled water for many times, and drying the product in an oven to obtain a brown product.
The above-mentioned embodiments only express the specific embodiments of the present invention, and the description thereof is specific and detailed, but not construed as limiting the scope of the 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 patent shall be subject to the appended claims.
Claims (7)
1. A preparation method of a bulk porous PdCl/COFs material is characterized by comprising the following steps:
step 1, preparing organic framework materials COFs by using azobenzene dicarboxylic acid and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine as raw materials through a thermal polycondensation method, wherein the method specifically comprises the following steps:
dissolving azobenzene dicarboxylic acid, benzotriazole-1-yl-oxy tripyrrolidinyl phosphorus hexafluorophosphate and N, N-diisopropylethylamine in N, N-dimethylformamide to obtain a solution A;
dissolving 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine in N, N-dimethylformamide to obtain a solution B;
then mixing the solution A and the solution B, reacting for 6-8 h at 60 ℃, washing with water, filtering, and drying after the reaction is finished to obtain organic framework materials COFs;
step 2, adopt K 2 PdCl 4 And (3) matching with the COFs prepared in the step (1) to obtain the bulk PdCl/COFs material with the porous structure.
2. The method for preparing the bulk porous structure PdCl/COFs material according to claim 1, wherein the mass ratio of azobenzene dicarboxylic acid, benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine is 1.
3. The method for preparing the bulk porous structure PdCl/COFs material according to claim 1, wherein the dosage of said N, N-diisopropylethylamine is 217.5-250.0 μ L.
4. The method for preparing the bulk porous structure PdCl/COFs material according to claim 1, wherein the amount of N, N-dimethylformamide used in the solutions A and B is 55-70 mL respectively.
5. The method for preparing PdCl/COFs material with bulk porous structure according to claim 1, wherein said step 2 employs noble metal compound K 2 PdCl 4 The complex PdCl/COFs is coordinated with organic framework materials COFs to form a complex PdCl/COFs, and the specific method comprises the following steps:
taking synthetic COFs and K 2 PdCl 4 Taking methanol as a dispersing agent, and reacting for 20-24 h at room temperature under the condition of stirring at the rotating speed of 1000 r/min;
evaporating methanol to dryness, carrying out suction filtration, repeatedly washing with distilled water, and drying to obtain the complex PdCl/COFs of the COFs.
6. A porous block according to any one of claims 1 or 5The preparation method of the structural PdCl/COFs material is characterized in that the COFs material and K are mixed 2 PdCl 4 The mass ratio of (1) to (20) is 18.
7. The method for preparing the bulk porous structure PdCl/COFs material according to claim 5, wherein the amount of the dispersant methanol is 50-100 mL.
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