CN113201147A - Synthesis and application of two-dimensional porphyrin MOFs material - Google Patents
Synthesis and application of two-dimensional porphyrin MOFs material Download PDFInfo
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- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 51
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- 230000001699 photocatalysis Effects 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
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- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 16
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 claims description 10
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000011160 research Methods 0.000 claims description 6
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- HJCNSOVRAZFJLK-UHFFFAOYSA-N C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC2=CC([N]3)=CC=C3C=C(C=C3)NC3=CC([N]3)=CC=C3C=C1N2 HJCNSOVRAZFJLK-UHFFFAOYSA-N 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
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- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
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- 239000011941 photocatalyst Substances 0.000 description 7
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- 150000002431 hydrogen Chemical class 0.000 description 3
- FEIOASZZURHTHB-UHFFFAOYSA-N methyl 4-formylbenzoate Chemical compound COC(=O)C1=CC=C(C=O)C=C1 FEIOASZZURHTHB-UHFFFAOYSA-N 0.000 description 3
- SEVSMVUOKAMPDO-UHFFFAOYSA-N para-Acetoxybenzaldehyde Natural products CC(=O)OC1=CC=C(C=O)C=C1 SEVSMVUOKAMPDO-UHFFFAOYSA-N 0.000 description 3
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- 239000013274 2D metal–organic framework Substances 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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Abstract
The invention relates to synthesis and application of two-dimensional porphyrin MOFs materials, wherein porphyrin has a symmetrical structure, so that the MOFs structure is diversified, and the MOFs has certain absorption capacity in a visible light region, and can expand the light absorbed by the MOFs to the visible light region. The porphyrin organic ligand adopted by the invention is 5,10,15, 20-tetra (4-carboxyphenyl) porphyrin, the preparation method is simple, the process is mature, the yield is high, and the method is suitable for batch production. A plurality of porphyrin MOFs materials with transition metal clusters as metal nodes are prepared by a simple solvothermal method, the appearance of the porphyrin MOFs materials is two-dimensional nanosheet-shaped, and active sites of the porphyrin MOFs materials can be fully exposed, so that a more excellent photocatalytic hydrogen evolution effect is realized. Therefore, the two-dimensional porphyrin MOFs material has good economic benefit and practical application prospect when being used for photocatalytic hydrogen evolution.
Description
Technical Field
The invention relates to the technical field of photocatalytic hydrogen evolution, in particular to synthesis and application of a two-dimensional porphyrin metal organic framework material.
Background
With the rapid development of human economy and civilization, the urgent need for energy, particularly fossil fuels, is increasing, accompanied by more and more serious environmental problems. Compared with fossil fuel, hydrogen has the advantage of high combustion value, which is about 3 times of petroleum equivalent, and especially, the combustion product is the only water without environmental pollution, which is the most ideal energy carrier. The hydrogen production technology by solar energy water decomposition is widely concerned by researchers due to the wide prospect of obtaining hydrogen energy. The key of the photocatalytic hydrogen evolution technology is to develop and utilize an inexhaustible solar photocatalyst for efficiently and stably decomposing water. The photocatalytic hydrogen evolution reaction generally has several key processes: light absorption of semiconductor photocatalysts, preparation of photocatalysts, separation and conversion of photogenerated electron-charge pairs, photogenerated electron-hole carriers, and H+Is introduced by active electrons to produce H2. Therefore, the design of high efficiency photocatalysts has been focused onImproving one or more aspects of these critical steps. In particular, researchers in this field have focused on facilitating the separation of the photogenerated electron-charge pair by different methods, probably because the high recombination rate of photogenerated electron-charge carriers is very common among various types of photocatalysts, and the band gap of the photocatalyst is strictly controlled, and the energy band structure is thermodynamically favorable for photocatalytic hydrogen evolution.
Metal Organic Frameworks (MOFs) are an emerging class of crystalline and porous materials with two-or three-dimensional structures assembled from metal ions (or metal clusters) and organic linkers. Although more and more MOF properties such as gas storage and separation, catalysis, proton conduction are now known. Until 2009, semiconductor-like photocatalytic hydrogen evolution activity of MOFs was not reported. Since then, research on the MOFs photocatalyst has been receiving increasing attention from researchers, and has been conducted on the hydrogen evolution activity of various stable MOFs, such as NH2-UIO-66,-NH2MIL-101 such as MIL-125(Ti), etc.
2D MOFs are a promising catalytic material that has recently emerged. Compared to bulk MOFs, metal nodes in 2D MOFs, due to their ultra-thin thickness, can expose more highly accessible active sites to contact other substrates as much as possible, thereby increasing the photocatalytic activity for hydrogen evolution. In addition, the porphyrin organic ligand has a tetrapyrrole macrocyclic conjugated structure with 18 pi electrons, has excellent light absorption capacity in a visible light region, and can expand the absorption spectrum of MOFs to the visible light region. Meanwhile, the structure of the porphyrin compound has higher symmetry, different topological structures can be formed by changing the node metal clusters or the connection number when the MOFs are constructed, the diversity of the structure of the porphyrin-metal framework material is greatly improved, and a novel topological structure can be further constructed by introducing a second ligand. The cavity of the porphyrin compound has obvious metal coordination capacity, metal can be introduced to serve as a catalytic active center, and a system of MOFs material can be constructed by changing the metal coordinated by the cavity, so that the regulation and control of the structure and the catalytic performance are realized.
Therefore, the synthesis of a class of two-dimensional porphyrin MOFs materials and the application of the two-dimensional porphyrin MOFs materials in photocatalytic hydrogen evolution research are the research directions of the technicians in the field.
Disclosure of Invention
The invention aims to synthesize porphyrin MOFs material with a two-dimensional structure, so that active sites of the porphyrin MOFs material are fully exposed, and an excellent photocatalytic hydrogen evolution effect is realized.
The technical scheme adopted by the invention is as follows:
a preparation method of two-dimensional porphyrin MOFs materials comprises the following steps:
(1) taking 4-formyl methyl benzoate and pyrrole as raw materials, and obtaining porphyrin organic ligand (TCPP) through reflux reaction in a propionic acid solvent;
(2) TCPP is used as an organic ligand, transition metal nitrate is used as a metal node raw material, and a two-dimensional nano-sheet MOFs material is obtained by a simple solvothermal method;
wherein, the reflux reaction temperature in the step (1) is 150 ℃, and the time is 12 hours.
In the step (2), the metal node raw material is nitrate hydrate of Cu, Cd and Zn.
The invention also provides the application of the two-dimensional porphyrin MOFs material, which is characterized in that the two-dimensional porphyrin MOFs material is prepared by the method of claim 1; the two-dimensional porphyrin MOFs material is suitable for photocatalytic hydrogen evolution research in an eosin system and shows a good effect.
Compared with the prior art, the invention has the following advantages:
1. the preparation method of the two-dimensional porphyrin MOFs material provided by the invention enables metal nodes in the two-dimensional porphyrin MOFs material to expose more highly accessible active sites due to the ultrathin thickness of the metal nodes so as to contact with other matrixes as much as possible, thereby improving the photocatalytic activity of hydrogen evolution.
2. The two-dimensional porphyrin MOFs material prepared by the invention is suitable for photocatalytic hydrogen evolution research in an eosin system and shows a better effect.
Drawings
FIG. 1 is an SEM picture of two-dimensional porphyrin MOFs prepared in example 1.
FIG. 2 is an AFM picture of two-dimensional porphyrin MOFs prepared in example 1.
FIG. 3 is an XPS plot of two-dimensional porphyrin MOFs prepared in example 1.
FIG. 4 is a graph of the photocatalytic hydrogen evolution rate of two-dimensional porphyrin MOFs prepared in example 1.
FIG. 5 is a diagram showing the stability of photocatalytic hydrogen evolution of two-dimensional porphyrin MOFs prepared in example 1.
FIG. 6 is an SEM picture of two-dimensional porphyrin MOFs prepared in example 2.
FIG. 7 is a graph of the photocatalytic hydrogen evolution rate of two-dimensional porphyrin MOFs prepared in example 2.
FIG. 8 is an SEM picture of two-dimensional porphyrin MOFs prepared in example 3.
FIG. 9 is a graph of the photocatalytic hydrogen evolution rate of the two-dimensional porphyrin MOFs prepared in example 3.
Detailed Description
The invention will be further explained with reference to the drawings and the embodiments.
Example 1:
the preparation method of the two-dimensional porphyrin MOFs material comprises the following steps:
(1) methyl 4-formylbenzoate (0.086mol, 14.41g) was first dissolved completely in propionic acid (250ml), then a solution of pyrrole (6.1ml pyrrole/20 ml propionic acid) was added slowly and the mixture was refluxed at 150 ℃ for 12 h. After the mixture was cooled, a precipitate was obtained by suction filtration and washed with a large amount of ethanol, ethyl acetate and a small amount of tetrahydrofuran, respectively. The precipitate was dried at 70 ℃ for 12 hours to give a purple product, which was recorded as TPPCOOMe.
(2) TPPCOOMe (3.0g) was stirred in a mixture of THF (60ml) and MeOH (60ml) and 60ml of aqueous KOH (10.5g) was added, followed by reflux at 90 ℃ for 12 hours. After cooling the mixture, the solution was filtered and the solvent was removed by rotary evaporation. Next, the filtrate was adjusted to pH 2 with 1M HCl to obtain a precipitate. The precipitate was filtered and washed several times with water and dried at 80 ℃ for 12 hours to give a violet product, recorded as TCPP.
(3) 12ml of a mixture of DMF and EtOH (V: V ═ 3:1) was added to a 25ml capped vial, followed by 3.6mg of Cu (NO)3)2·3H2O, 10ul TFA and 10.0mg PVP.
(4) To the mixture of (3) was added dropwise a solution of TCPP (4.0mg, 3ml DMF, 1ml EtOH) with stirring. The bottles were kept at 80 ℃ for centrifugation for 4h, cooled to room temperature, washed twice with EtOH and dried to give the product, designated NS-Cu.
As shown in fig. 1-3. From the SEM image of the material in FIG. 1, the morphology of the prepared two-dimensional porphyrin MOFs material presents a flower-like morphology similar to multilayer folds; the AFM results for the material of FIG. 2 show a lamellar thickness of around 15 nm; the XPS chart of figure 3 shows the successful attachment of porphyrin organic ligands to the metal node Cu, demonstrating the formation of MOFs materials.
The prepared two-dimensional porphyrin MOFs material is used for photocatalytic hydrogen evolution, and the specific steps are as follows:
(1) 5mg of material was dispersed in 12.5ml of deionized water, 15mg EY was added as photosensitizer, and 2.5ml Triethanolamine (TEOA) was added as sacrificial agent.
(2) Bubbling (N) into the reactor (1)2) For 20 minutes to exclude air.
(3) The reactor was irradiated with a 300w xenon lamp fitted with a 420nm cut-off filter. The temperature of the reactor was maintained at 10 ℃ using a thermostatically cooled circulating water pump. The hydrogen formation was detected on-line by gas chromatography (GC 7920, beijing eosin).
FIGS. 4-5 are graphs of the results of photocatalytic hydrogen evolution of the prepared two-dimensional porphyrin MOFs. As can be seen from FIG. 4, the prepared two-dimensional porphyrin MOFs material has excellent photocatalytic hydrogen evolution effect, and the hydrogen evolution rate can reach 15.39 mmol/g-1·h-1And as can be seen from fig. 5, it has better cycle stability.
Example 2:
the preparation method of the two-dimensional porphyrin MOFs material comprises the following steps:
(1) methyl 4-formylbenzoate (0.086mol, 14.41g) was first dissolved completely in propionic acid (250ml), then a solution of pyrrole (6.1ml pyrrole/20 ml propionic acid) was added slowly and the mixture was refluxed at 150 ℃ for 12 h. After the mixture was cooled, a precipitate was obtained by suction filtration and washed with a large amount of ethanol, ethyl acetate and a small amount of tetrahydrofuran, respectively. The precipitate was dried at 70 ℃ for 12 hours to give a purple product, which was recorded as TPPCOOMe.
(2) TPPCOOMe (3.0g) was stirred in a mixture of THF (60ml) and MeOH (60ml) and 60ml of aqueous KOH (10.5g) was added, followed by reflux at 90 ℃ for 12 hours. After cooling the mixture, the solution was filtered and the solvent was removed by rotary evaporation. Next, the filtrate was adjusted to pH 2 with 1M HCl to obtain a precipitate. The precipitate was filtered and washed several times with water and dried at 80 ℃ for 12 hours to give a violet product, recorded as TCPP.
(3) 12ml of a mixture of DMF and EtOH (V: V ═ 3:1) was added to a 25ml capped vial, followed by 4.6mg of Cd (NO)3)2·4H2O, 0.8mg pyrazine and 20.0mg PVP.
(4) To the mixture of (3) was added dropwise a solution of TCPP (4.0mg, 3ml DMF, 1ml EtOH) with stirring. These bottles were kept at 80 ℃ for centrifugation for 4h, cooled to room temperature, washed twice with EtOH and dried to give the product, denoted NS-Cd.
From the SEM image of the material in FIG. 6, the morphology of the prepared two-dimensional porphyrin MOFs material is two-dimensional sheet.
The prepared two-dimensional porphyrin MOFs material is used for photocatalytic hydrogen evolution, and the specific steps are as follows:
(1) 5mg of material was dispersed in 12.5ml of deionized water, 15mg EY was added as photosensitizer, and 2.5ml Triethanolamine (TEOA) was added as sacrificial agent.
(2) Bubbling (N) into the reactor (1)2) For 20 minutes to exclude air.
(3) The reactor was irradiated with a 300w xenon lamp fitted with a 420nm cut-off filter. The temperature of the reactor was maintained at 10 ℃ using a thermostatically cooled circulating water pump. The hydrogen formation was detected on-line by gas chromatography (GC 7920, beijing eosin).
FIG. 7 is a graph showing the effect of photocatalytic hydrogen evolution, with a hydrogen evolution rate of 2.38 mmol/g-1·h-1。
Example 3:
the preparation method of the two-dimensional porphyrin MOFs material comprises the following steps:
(1) methyl 4-formylbenzoate (0.086mol, 14.41g) was first dissolved completely in propionic acid (250ml), then a solution of pyrrole (6.1ml pyrrole/20 ml propionic acid) was added slowly and the mixture was refluxed at 150 ℃ for 12 h. After the mixture was cooled, a precipitate was obtained by suction filtration and washed with a large amount of ethanol, ethyl acetate and a small amount of tetrahydrofuran, respectively. The precipitate was dried at 70 ℃ for 12 hours to give a purple product, which was recorded as TPPCOOMe.
(2) TPPCOOMe (3.0g) was stirred in a mixture of THF (60ml) and MeOH (60ml) and 60ml of aqueous KOH (10.5g) was added, followed by reflux at 90 ℃ for 12 hours. After cooling the mixture, the solution was filtered and the solvent was removed by rotary evaporation. Next, the filtrate was adjusted to pH 2 with 1M HCl to obtain a precipitate. The precipitate was filtered and washed several times with water and dried at 80 ℃ for 12 hours to give a violet product, recorded as TCPP.
(3) 12ml of a mixture of DMF and EtOH (V: V ═ 3:1) was added to a 25ml capped vial, followed by 4.4mg of Zn (NO)3)2·3H2O, 0.8mg pyrazine and 10.0mg PVP.
(4) To the mixture of (3) was added dropwise a solution of TCPP (4.0mg, 3ml DMF, 1ml EtOH) with stirring. The bottles were kept at 80 ℃ for centrifugation for 4h, cooled to room temperature, washed twice with EtOH and dried to give the product, denoted NS-Zn.
From the SEM image of the material in FIG. 8, the morphology of the prepared two-dimensional porphyrin MOFs material is two-dimensional sheet.
The prepared two-dimensional porphyrin MOFs material is used for photocatalytic hydrogen evolution, and the specific steps are as follows:
(1) 5mg of material was dispersed in 12.5ml of deionized water, 15mg EY was added as photosensitizer, and 2.5ml Triethanolamine (TEOA) was added as sacrificial agent.
(2) Bubbling (N) into the reactor (1)2) For 20 minutes to exclude air.
(3) The reactor was irradiated with a 300w xenon lamp fitted with a 420nm cut-off filter. The temperature of the reactor was maintained at 10 ℃ using a thermostatically cooled circulating water pump. The hydrogen formation was detected on-line by gas chromatography (GC 7920, beijing eosin).
FIG. 9 is a graph showing the effect of photocatalytic hydrogen evolution, with a hydrogen evolution rate of 1.09 mmol/g-1·h-1。
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the technical solutions, and those skilled in the art should understand that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all that should be covered by the claims of the present invention.
Claims (4)
1. A preparation method of two-dimensional porphyrin MOFs materials is characterized by comprising the following steps:
(1) taking 4-formyl methyl benzoate and pyrrole as raw materials, and obtaining porphyrin organic ligand (TCPP) through reflux reaction in a propionic acid solvent;
(2) TCPP is used as an organic ligand, transition metal nitrate is used as a metal node raw material, and the two-dimensional nano-sheet MOFs material is obtained through a simple solvothermal method.
2. The method for preparing two-dimensional porphyrin MOFs according to claim 1, wherein the reflux reaction temperature in step (1) is 150 ℃ and the time is 12 hours.
3. The preparation method of the two-dimensional porphyrin metal organic framework material as claimed in claim 1, wherein in the step (2), the metal node material is nitrate hydrate of Cd.
4. The application of two-dimensional porphyrin MOFs materials is characterized in that the two-dimensional porphyrin MOFs materials are prepared by the method of claim 1; the two-dimensional porphyrin MOFs material is suitable for photocatalytic hydrogen evolution research in an eosin system and shows a good effect.
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| CN114130431A (en) * | 2021-11-23 | 2022-03-04 | 中国科学院大连化学物理研究所 | Preparation method and application of P-type pyrenyl metal organic framework single crystal material and nanobelt |
| CN115079480A (en) * | 2022-03-31 | 2022-09-20 | 中国人民解放军国防科技大学 | Porphyrin MOF-based electrochromic film material and preparation method thereof |
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| CN114130431A (en) * | 2021-11-23 | 2022-03-04 | 中国科学院大连化学物理研究所 | Preparation method and application of P-type pyrenyl metal organic framework single crystal material and nanobelt |
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