CN112588323A - Preparation method of bulk porous PdCl/COFs material - Google Patents
Preparation method of bulk porous PdCl/COFs material Download PDFInfo
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- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 139
- 239000000463 material Substances 0.000 title claims abstract description 96
- 101150003085 Pdcl gene Proteins 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 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 16
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 35
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- -1 benzotriazole-1-yl-oxy tripyrrolidinyl phosphorus hexafluorophosphate Chemical compound 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 4
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- 238000005303 weighing Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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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
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- 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
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Abstract
The invention discloses a preparation method of bulk porous PdCl/COFs material, which takes azobenzene dicarboxylic acid and 4, 4' -2,4, 6-triamino-1, 3, 5-triazine as raw materials, prepares organic framework material COFs by a thermal polycondensation method, and adopts K2PdCl4And (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,the synthesis process is simple and easy to realize, 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 bandgap 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. The 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 easily available in raw materials, diversified and controllable in synthesized structure and wide in application prospect. 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 photostability of catalysts, low crystallinity, and slow multi-electron diffusion-controlled proton reduction process, 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 structure PdCl/COFs material specifically comprises the following steps:
Further, the preparation method of the organic framework materials COFs in the step 1 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 4, 4' -2,4, 6-triamino-1, 3, 5-triazine in N, N-dimethylformamide to obtain a solution B;
and 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 the organic framework material COFs.
Further, the azobenzene dicarboxylic acid, benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate and 4, 4' -2,4, 6-triamino-1, 3, 5-triazine are present in an amount ratio of 1:1:1.5 to 1:1: 2.0.
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 K2PdCl4The 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 K2PdCl4Taking methanol as a dispersing agent, and reacting at room temperature for 20-24 hours at the rotating speed of 1000r/min under the stirring condition;
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 K2PdCl4The mass ratio of (A) to (B) is 18:1 to 20: 1.
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 K2PdCl4The 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 shows an infrared spectrum of the bulk porous PdCl/COFs material prepared by the method of the present invention, the raw materials azobenzene dicarboxylic acid and 4, 4' -2,4, 6-triamino-1, 3, 5-triazine used in example 1, and the product COFs material;
FIG. 2 is an infrared spectrum of the COFs and PdCl/COFs materials prepared in example 1 of the preparation method of the bulk porous structure PdCl/COFs material of the present invention;
FIG. 3 shows the preparation method of PdCl/COFs materials with bulk porous structures of the invention, example 1 shows the preparation method of COFs1HNMR 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 used1HNMR spectrogram;
FIG. 5 is a UV diffuse reflection diagram of the bulk porous PdCl/COFs material and the raw materials azobenzene dicarboxylic acid and 4, 4' -2,4, 6-triamino-1, 3, 5-triazine used in example 1 of the preparation method of the bulk porous 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 structure PdCl/COFs material, which specifically 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 4, 4' -2,4, 6-triamino-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 ratio of the amounts of azobenzene dicarboxylic acid, benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate and 4, 4' -2,4, 6-triamino-1, 3, 5-triazine is 1:1:1.5 to 1:1: 2.0.
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 55-70 mL respectively.
The specific synthetic route is as follows:
taking synthetic COFs and K2PdCl4Taking methanol as a dispersing agent, and reacting at room temperature for 20-24 hours at the rotating speed of 1000r/min under the stirring condition;
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 K2PdCl4The mass ratio of (A) to (B) is 18:1 to 20: 1.
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 and 0.5mmol of azobenzene dicarboxylic acid, 0.5mmol of coupling agent PyBOP265.8mg and 0.5mmol of DIEA217.5 mu L into a round-bottomed flask, adding DMF55mL, and magnetically stirring at room temperature for 1.5 h;
step 1.2: weighing TTA265.8mg and 0.75mmol, adding into DMF55mL 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, K of COFs raw material synthesized in the step 12PdCl45mg, 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 infrared spectra of the raw materials azobenzene dicarboxylic acid and TTA, and the products COFs material and PdCl/COFs material, respectively, used in example 1 of the method for preparing a bulk porous PdCl/COFs material of the present invention. 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-1Is the characteristic out-of-plane bending vibration of the triazine ring, 3320.10cm-1、3430.35cm-1Is an upstream leaving amino-NH of TTA2The stretching vibration peak of (1). Azobenzene dicarboxylic acid 1630.10cm-l、1700cm-l2655cm as C ═ O peak of stretching vibration-1Is the stretching vibration peak of-OH. The amido bond is formed between the azobenzene dicarboxylic acid and the COFs material synthesized by TTA at 1635 and 1640cm-1Tensile vibration of C-N, which is 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 confirmed successful loading of azobenzene dicarboxylic acid onto TTA. In FIG. 2, synthetic COFs with K were found2PdCl4After 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 COFs1HNMR spectrogram. As shown in figure 1 of the drawings, in which,1HNMR (400MHz, DMSO), δ (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. Total 4 hydrogens, proton ratio (6:6:4: 4). 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 used1HNMR spectrogram. As shown in the figure, the first and second,1HNMR (400MHz, DMSO), δ (ppm): 8.36,8.34,8.34,8.19,8.17,8.04,8.01,6.70,6.68,2.5. A total of 5 hydrogens (1:1:1:2: 2). 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 proved2PdCl4/And (4) synthesizing COFs materials. FIG. 4 illustrates the COFs with K2PdCl4Reactions occurred to further confirm the successful synthesis of the material.
FIG. 5 shows a method for preparing PdCl/COFs material with bulk porous structure according to the present invention, wherein azobenzene dicarboxylic acid and 4, 4' -2,4, 6-triamino-1, 3, 5-triazine as raw materials and COFs and PdCl as products are used in example 1/Uv diffuse reflectance patterns 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 used2PdCl4After 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 the forbidden bandwidths of the PdCl/COFs and COFs materials prepared in example 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 K2PdCl4After 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 a method for preparing PdCl/COFs materials with bulk porous structures according to the present invention, COFs (7a) and PdCl prepared in example 1/SEM images of COFs (7b) materials. As can be seen from FIG. 7(a), COFs have a distinct bulk porous structure. However, via K2PdCl4After modification (fig. 7b), 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 (7a) and PdCl prepared in example 1/The effect graph of hydrogen production by photocatalytic water decomposition of COFs (7b) materials under the irradiation of visible light. As can be seen from FIG. 9, the resulting PdCl was compared to COFs/The COFs material has higher photocatalytic performance, and the hydrogen production amount of the COFs material 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 basically consistent with the result obtained by the ultraviolet diffuse reflection and forbidden band width diagram.
Example 2
Step 1: preparation of organic framework material COFs
Step 1.1: accurately weighing 135.1mg and 0.5mmol of azobenzene dicarboxylic acid, 0.8 mg and 0.5mmol of coupling agent PyBOP265.8mg and DIEA230.0 mu L into a round-bottomed flask, adding DMF65mL, and magnetically stirring at room temperature for 1.5 h;
step 1.2: weighing TTA265.8mg and 0.95mmol, adding the weighed TTA265.8mg and 0.95mmol into DMF55mL and a proper amount of container, and magnetically stirring the mixture 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.
Step 2: synthesizing PdCl/COFs material:
step 2.1: weighing 95mg, K of COFs raw material synthesized in the step 12PdCl45mg, 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 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 and 0.5mmol of azobenzene dicarboxylic acid, 0.5mmol of coupling agent PyBOP265.8mg and 0.5mmol of DIEA250.0 mu L into a round-bottomed flask, adding DMF70mL, and magnetically stirring at room temperature for 1.5 h;
step 1.2: weighing TTA354.4mg and 1.00mmol, adding into DMF55mL 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.
Step 2: synthesizing PdCl/COFs material:
step 2.1: weighing the COFs and K synthesized in the step 12PdCl4The mass ratio of (1) to (20) is 100mL 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 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, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
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 4, 4' -2,4, 6-triamino-1, 3, 5-triazine as raw materials through a thermal polycondensation method;
step 2, adopt K2PdCl4And (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 PdCl/COFs material with the bulk porous structure as claimed in claim 1, wherein the method for preparing the organic framework material COFs in step 1 specifically comprises:
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 4, 4' -2,4, 6-triamino-1, 3, 5-triazine in N, N-dimethylformamide to obtain a solution B;
and 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 the organic framework material COFs.
3. The method for preparing the bulk porous structure PdCl/COFs material according to claim 2, wherein the mass ratio of azobenzene dicarboxylic acid, benzotriazole-1-yl-oxytripyrrolidinophosphonium hexafluorophosphate and 4, 4', 4 "-2, 4, 6-triamino-1, 3, 5-triazine is 1:1: 1.5-1: 1: 2.0.
4. The method for preparing PdCl/COFs material with block-shaped porous structure according to claim 2, wherein the amount of N, N-diisopropylethylamine is 217.5-250.0 μ L.
5. The method for preparing the bulk porous structure PdCl/COFs material according to claim 2, wherein the amount of N, N-dimethylformamide used in the solutions A and B is 55-70 mL respectively.
6. The method for preparing PdCl/COFs material with bulk porous structure according to claim 1, wherein said step 2 employs noble metal compound K2PdCl4The 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 K2PdCl4Taking methanol as a dispersing agent, and reacting at room temperature for 20-24 hours at the rotating speed of 1000r/min under the stirring condition;
evaporating methanol to dryness, carrying out suction filtration, repeatedly washing with distilled water, and drying to obtain the complex PdCl/COFs of the COFs.
7. The method of any of claims 1 or 6, wherein the material of COFs is mixed with K2PdCl4The mass ratio of (A) to (B) is 18:1 to 20: 1.
8. The method for preparing the PdCl/COFs material with the bulk porous structure as claimed in claim 6, wherein the amount of the dispersant methanol is 50-100 mL.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018013682A1 (en) * | 2016-07-12 | 2018-01-18 | University Of Central Florida Research Foundation, Inc. | Mechanically shaped 2-dimensional covalent organic frameworks |
| CN110240708A (en) * | 2019-07-02 | 2019-09-17 | 吉林大学 | A kind of synthesis in water covalent organic frame material and preparation method thereof |
| CN110523354A (en) * | 2019-09-06 | 2019-12-03 | 浙江大学 | A kind of preparation method of the microreactor containing solid-carried catalyst |
| CN110982085A (en) * | 2019-12-11 | 2020-04-10 | 南开大学 | Preparation of azo bond-rich covalent organic framework material and application thereof in proton conduction and fuel cell |
| CN111205475A (en) * | 2020-02-24 | 2020-05-29 | 陕西师范大学 | Porous COFs block and application thereof in isomer separation |
| CN112111069A (en) * | 2020-09-30 | 2020-12-22 | 中国科学院生态环境研究中心 | Preparation method and application of palladium nanoparticle-supported benzothiazole-linked covalent organic framework material |
-
2020
- 2020-12-24 CN CN202011551503.XA patent/CN112588323B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018013682A1 (en) * | 2016-07-12 | 2018-01-18 | University Of Central Florida Research Foundation, Inc. | Mechanically shaped 2-dimensional covalent organic frameworks |
| CN110240708A (en) * | 2019-07-02 | 2019-09-17 | 吉林大学 | A kind of synthesis in water covalent organic frame material and preparation method thereof |
| CN110523354A (en) * | 2019-09-06 | 2019-12-03 | 浙江大学 | A kind of preparation method of the microreactor containing solid-carried catalyst |
| CN110982085A (en) * | 2019-12-11 | 2020-04-10 | 南开大学 | Preparation of azo bond-rich covalent organic framework material and application thereof in proton conduction and fuel cell |
| CN111205475A (en) * | 2020-02-24 | 2020-05-29 | 陕西师范大学 | Porous COFs block and application thereof in isomer separation |
| CN112111069A (en) * | 2020-09-30 | 2020-12-22 | 中国科学院生态环境研究中心 | Preparation method and application of palladium nanoparticle-supported benzothiazole-linked covalent organic framework material |
Non-Patent Citations (2)
| Title |
|---|
| YIN-JUAN CHEN等: "Triazine COF-supported single-atom catalyst (Pd1/trzn-COF) for CO oxidation", 《SCIENCE CHINA MATERIALS》 * |
| 李路路等: "共价有机框架材料研究进展", 《物理化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113117745A (en) * | 2021-04-13 | 2021-07-16 | 昆明理工大学 | Preparation method and application of metal-free catalyst |
| CN113117745B (en) * | 2021-04-13 | 2022-05-27 | 昆明理工大学 | Preparation method and application of metal-free catalyst |
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