CN109867770B - Conjugated microporous polymer based on porphyrin functional group and preparation method and application thereof - Google Patents
Conjugated microporous polymer based on porphyrin functional group and preparation method and application thereof Download PDFInfo
- Publication number
- CN109867770B CN109867770B CN201910178681.3A CN201910178681A CN109867770B CN 109867770 B CN109867770 B CN 109867770B CN 201910178681 A CN201910178681 A CN 201910178681A CN 109867770 B CN109867770 B CN 109867770B
- Authority
- CN
- China
- Prior art keywords
- porphyrin
- microporous polymer
- conjugated microporous
- functional group
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a conjugated microporous polymer based on porphyrin functional groups, a preparation method and application thereof, and belongs to the field of porous organic polymer materials. The microporous polymer is a conjugated microporous polymer material which takes porphyrin as a basic functional group and is connected through a 1, 3-diacetylene structure, and the preparation method comprises the following steps: weighing porphyrin monomer and Pd (PPh)3)2Cl2Adding CuI and the mixture into an ampoule, adding organic solvents of tetrahydrofuran and triethylamine, carrying out vacuum degassing circulation for three times, and heating and reacting in a nitrogen environment; stopping the reaction, standing to room temperature, filtering, and washing, extracting and vacuum-pumping a filter cake to obtain the conjugated microporous polymer based on the porphyrin functional group. The microporous polymer can be used for catalyzing the reduction reaction of nitrobenzene compounds. The material prepared by the invention has high specific surface area and excellent stability.
Description
Technical Field
The invention belongs to the field of porous organic polymer materials, and particularly relates to a porous organic polymer material with three porphyrins as basic functional groups and connected by 1,3 dialkynyl, a preparation method and application thereof in catalytic reaction.
Background art:
the organic porous material polymer includes various types such as a hypercrosslinked polymer (HCP), a covalent organic backbone (COF), a Conjugated Microporous Polymer (CMP), and the like. The material shows excellent performances in the aspects of gas adsorption and separation, clean energy storage, photoelectric materials, ion sensing and catalysis by virtue of various properties such as large specific surface area, porosity, assemblability, high adsorbability and the like. Compared with the traditional inorganic molecular sieve material, the organic porous polymer material is formed by polymerizing organic micromolecule monomers through various chemical reactions, and various properties of the material, such as specific surface area, pore diameter, energy level structure and the like, can be purposefully adjusted by changing the structure of the micromolecules. Most of the materials can keep stable to air, water and various organic solvents, so the materials have wide application prospects in various fields.
Nitrobenzene compounds are important chemical raw materials, the pollution of nitrobenzene compounds in the environment is mainly from waste water and waste gas of chemical plants and dye plants, and because the organic matters have strong toxicity, a method for effectively degrading the organic pollutants is urgently needed. The traditional reduction method needs hydrogen as a reactant, the reaction conditions are relatively harsh, and the hydrogen is a flammable and explosive gas and has certain danger. Therefore, the method has great significance for laboratories and even industries by degrading nitrobenzene substances under simple and mild conditions by using a simple catalyst.
The invention content is as follows:
the invention aims to provide a synthetic method of a Conjugated Microporous Polymer (CMP) with porphyrin as a basic functional group and application of the Conjugated Microporous Polymer (CMP) in heterogeneous catalysis of a nitrobenzene compound reduction reaction.
The technical scheme of the invention is as follows:
the conjugated microporous polymer based on porphyrin functional groups is characterized in that the conjugated microporous polymer material is a conjugated microporous polymer material which takes porphyrin as basic functional groups and is connected through a 1, 3-diacetylene structure, and has the following structural general formula:
a preparation method of a conjugated microporous polymer based on porphyrin functional groups comprises the following specific steps: weighing porphyrin monomer and Pd (PPh)3)2Cl2And CuI in an ampoule, in which the porphyrin monomer Pd (PPh) is added in molar ratio3)2Cl2CuI is 1:0.04:0.04, the porphyrin monomer is 5,10,15, 20-tetraynyl-porphyrin or 5,10,15, 20-tetraynyl-porphyrin zinc or 5,10,15, 20-tetraynyl-porphyrinAdding organic solvents of tetrahydrofuran and triethylamine into the nickel porphyrin, carrying out vacuum degassing circulation for three times, and heating and reacting in a nitrogen environment; stopping the reaction, standing to room temperature, filtering, and washing, extracting and vacuum-pumping a filter cake to obtain the conjugated microporous polymer based on the porphyrin functional group.
The porphyrin monomer is preferably 5,10,15, 20-tetraethyl alkynyl-nickel porphyrin.
The organic solvents used are preferably tetrahydrofuran and triethylamine, 4.8-5.2 ml respectively, per 0.1mmol of porphyrin monomer.
The heating reaction is carried out in the nitrogen environment, the reaction temperature is preferably 80-100 ℃, and the reaction time is preferably 48-72 hours.
The cleaning is specifically that methanol, water, 1M HCl, water, chloroform and tetrahydrofuran are sequentially used for washing for three times, the extraction is specifically that tetrahydrofuran is used for extraction for 24 hours, and the vacuum pumping is specifically that the vacuum pumping is carried out for 6-8 hours under the vacuum condition of 80 ℃.
The application of conjugated microporous polymer based on porphyrin functional group in catalyzing the reduction reaction of nitrobenzene compounds includes the following steps: nitrobenzene and NaBH4Adding the mixture into a Schlenk bottle according to a molar ratio of 1:2.5, adding the conjugated microporous polymer as a catalyst, adding a mixed solvent consisting of ethanol and water according to a volume ratio of 6:1, sealing a bottle opening, performing ultrasonic treatment for 3 minutes, and stirring in a water bath kettle at 25 ℃ for 3-24 hours; 3mg of catalyst and 3.5ml of mixed solvent were used per 0.2mmol of nitrobenzene.
Has the advantages that:
1. the porphyrin-based conjugated microporous polymer obtained by the synthesis method provided by the invention has high specific surface area; very good thermal and chemical stability.
2. The porphyrin-based conjugated microporous polymer obtained by the method provided by the invention has excellent effect as a catalyst for nitrobenzene reduction, simple reaction conditions, high substrate conversion speed and high yield, and has potential for industrial production.
Description of the drawings:
FIG. 1 is an IR spectrum of H2-porphyrin-CMP prepared in example 1.
FIG. 2 is a nitrogen adsorption-desorption isotherm (77K) of H2-porphyrin-CMP prepared in example 1.
FIG. 3 is a thermogravimetric analysis of H2-porphyrin-CMP prepared in example 1.
FIG. 4 is an IR spectrum of Zn-porphyrin-CMP prepared in example 2.
Fig. 5 is a nitrogen adsorption-desorption isotherm (77K) of Zn-porphyrin-CMP prepared in example 2.
FIG. 6 is a thermogravimetric analysis chart of Zn-porphyrin-CMP prepared in example 2.
FIG. 7 is an IR spectrum of Ni-porphyrin-CMP prepared in example 3.
Fig. 8 is a nitrogen adsorption-desorption isotherm (77K) of Ni-porphyrin-CMP prepared in example 3.
FIG. 9 is a thermogravimetric analysis of Ni-porphyrin-CMP prepared in example 3.
FIG. 10 is a UV profile of Ni-porphyrin-CMP catalysis in example 4.
Detailed Description
Examples 1 to 3 below are specific examples of preparing three porphyrin-based conjugated microporous polymer materials of the present invention; examples 4 to 10 are specific applications of the three porphyrin-based conjugated microporous polymers in the reduction of the nitrobenzene compounds under heterogeneous catalysis.
The synthetic route of the conjugated microporous polymer is as follows:
example 1 preparation of H2-porphyrin-CMP
5,10,15, 20-tetraethyl-porphyrin (40.1mg 0.1mmol), Pd (PPh)3)2Cl2(2.8mg 0.004mmol) and CuI (0.76mg 0.004mmol) were added to an ampoule, 5ml each of tetrahydrofuran and triethylamine was added thereto, and vacuum degassing was repeated three times to react at 90 ℃ for 48 hours under a nitrogen atmosphere.
And (3) post-treatment: stopping the reaction, standing to room temperature, filtering, washing a filter cake with methanol, water, 1M HCl, water, chloroform and tetrahydrofuran for three times respectively, extracting with tetrahydrofuran for 24 hours, and vacuum-drying at 80 ℃ for 6 hours to obtain a black solid 39.5mg with the yield of 98 percent, thereby obtaining the product H2-porphyrin-CMP.
Example 2 preparation of Zn-porphyrin-CMP
5,10,15, 20-tetraethyl-zinc porphyrin (46.8mg 0.1mmol), Pd (PPh)3)2Cl2(2.8mg 0.004mmol) and CuI (0.76mg 0.004mmol) were added to an ampoule, 5ml each of tetrahydrofuran and triethylamine was added thereto, and vacuum degassing was repeated three times to react at 90 ℃ for 48 hours under a nitrogen atmosphere.
And (3) post-treatment: stopping the reaction, standing to room temperature, filtering, washing a filter cake with methanol, water, 1M HCl, water, chloroform and tetrahydrofuran for three times respectively, extracting with tetrahydrofuran for 24 hours, and vacuum-drying at 80 ℃ for 6 hours to obtain a black solid 46.3mg with a yield of 99%, thus obtaining the product Zn-porphyrin-CMP.
Example 3 preparation of Ni-porphyrin-CMP
5,10,15, 20-tetraethylalkynyl-nickel porphyrin (46.2mg 0.1mmol), Pd (PPh)3)2Cl2(2.8mg 0.004mmol) and CuI (0.76mg 0.004mmol) were added to an ampoule, 5ml each of tetrahydrofuran and triethylamine was added thereto, and vacuum degassing was repeated three times to react at 90 ℃ for 48 hours under a nitrogen atmosphere.
And (3) post-treatment: stopping the reaction, standing to room temperature, filtering, washing a filter cake with methanol, water, 1M HCl, water, chloroform and tetrahydrofuran for three times respectively, extracting with tetrahydrofuran for 24 hours, and vacuum-drying at 80 ℃ for 6 hours to obtain a black solid 45.9mg with a yield of 99%, thus obtaining the product Ni-porphyrin-CMP.
The solid products prepared in the above examples were subjected to infrared spectroscopic examination using a Fourier infrared spectrometer, and the results are shown in FIGS. 1, 4 and 7, respectively, which are 3100cm-1The peak of the terminal alkyne C-H bond basically disappears, which indicates that the coupling reaction is successful and verifies the structure.
The thermal stability analysis of the solid products prepared in the above examples by using a thermogravimetric analyzer showed that the materials were not decomposed by more than 70% even when the temperature was increased to 800 ℃, as shown in fig. 2, 5 and 8, respectively, which proves that the products have very good thermal stability.
Use ratio tableArea and pore size analyzer specific surface area measurements of the solid products prepared in the above examples, as shown in FIGS. 3, 6 and 9, were carried out, and the specific surface areas were 670m2g-1、692m2g-1And 513m2g-1。
Example 4: comparison of effects of three products in catalyzing p-nitrophenol reduction reaction
Weighing p-nitrophenol (27.8mg, 0.2mmol), NaBH4(19mg, 0.5mmol) is added into a Schlenk bottle, then 3mg of catalyst is added, 3.5ml (6: 1) of mixed solvent ethanol and water is added for sealing the bottle mouth, the mixture is placed into a water bath kettle at 25 ℃ for stirring after being subjected to ultrasonic treatment for 3min, and the reaction progress is monitored by gas phase by taking biphenyl as an internal standard. The three catalysts are respectively used for one time, and the 2H-porphyrin-CMP is detected to be completely catalyzed and reacted within 30 min; the Zn-porphyrin-CMP is catalyzed and reacted completely in 16 min; the Ni-porphyrin-CMP takes 5min to catalyze and react completely.
Calculating to obtain:
TOF 2.2 × 10 of 2H-porphyrin-CMP-3mmol/(mg*min)
TOF 4 × 10 of Zn-porphyrin-CMP-3mmol/(mg*min)
TOF of Ni-porphyrin-CMP 1.3 x 10-2mmol/(mg*min)
TOF is the amount of substrate converted per mass of catalyst per unit time.
The Ni-porphyrin-CMP is obtained to have the highest catalytic efficiency to the reaction, and the ultraviolet curve of the catalysis is shown in figure 10. The catalyst is recovered by filtration, washed by water and ethanol and then vacuum-pumped, and the catalytic efficiency is basically not reduced after 5 times of cyclic utilization.
Example 5: Ni-porphyrin-CMP catalysis nitrobenzene compound reduction
Nitrobenzene (20.4. mu.l, 0.2mmol) was weighed out and NaBH was weighed4(19mg, 0.5mmol) is added into a Schlenk bottle, 3mg of Ni-porphyrin-CMP is added, 3.5ml (6: 1) of mixed solvent ethanol and water is added for sealing the bottle mouth, the mixture is placed into a 25 ℃ water bath kettle for stirring for 3 hours after ultrasonic treatment for 3min, and biphenyl is used as biphenylInternal standard, gas phase yield 96%.
1H NMR(400MHz,CDCl3)δ7.19(t,J＝7.3Hz,2H),6.80(t,J＝7.9Hz,1H),6.71(d,J＝8.2Hz,2H),3.65(s,2H).
13C NMR(101MHz,CDCl3)δ146.70,129.61,118.85,115.41.
Example 6: Ni-porphyrin-CMP catalysis nitrobenzene compound reduction
Weighing p-chloronitrobenzene (31.5mg, 0.2mmol), and NaBH4(19mg, 0.5mmol) is added into a Schlenk bottle, 3mg of Ni-porphyrin-CMP is added, 3.5ml (6: 1) of mixed solvent ethanol and water is added for sealing the bottle mouth, the mixture is ultrasonically treated for 3min and then placed into a water bath kettle at 25 ℃ to be stirred for 12h, biphenyl is taken as an internal standard, and the gas phase yield is 91%.
1H NMR(400MHz,CDCl3)δ7.10(d,J＝8.7Hz,2H),6.61(d,J＝8.7Hz,2H),3.65(s,2H).
13C NMR(101MHz,CDCl3)δ145.30,129.48,123.51,116.58.
Example 7: Ni-porphyrin-CMP catalysis nitrobenzene compound reduction
P-nitrotoluene (27.4mg, 0.2mmol) was weighed and NaBH was weighed4(19mg, 0.5mmol) is added into a Schlenk bottle, 3mg of Ni-porphyrin-CMP is added, 3.5ml (6: 1) of mixed solvent ethanol and water is added for sealing the bottle mouth, the mixture is ultrasonically treated for 3min and then placed into a water bath kettle at 25 ℃ for stirring for 24h, biphenyl is taken as an internal standard, and the gas phase yield is 97%.
1H NMR(400MHz,CDCl3)δ7.00(d,J＝7.7Hz,2H),6.64(d,J＝8.0Hz,2H),3.55(s,2H).
13C NMR(101MHz,CDCl3)δ144.15,130.06,128.04,115.55,20.78.
Example 8: Ni-porphyrin-CMP catalysis nitrobenzene compound reduction
Weighing p-nitrobenzonitrile (29.6mg, 0.2mmol), weighing NaBH4(19mg, 0.5mmol) is added into a Schlenk bottle, 3mg of Ni-porphyrin-CMP is added, 3.5ml (6: 1) of mixed solvent ethanol and water is added for sealing the bottle mouth, the mixture is ultrasonically treated for 3min and then placed into a water bath kettle at 25 ℃ for stirring for 24h, biphenyl is taken as an internal standard, and the gas phase yield is 85 percent.
1H NMR(400MHz,CDCl3)δ7.37(d,J＝7.9Hz,2H),6.63(d,J＝7.9Hz,2H),4.29(s,2H).
13C NMR(101MHz,CDCl3)δ150.96,133.98,120.62,114.64,99.82.
Example 9: Ni-porphyrin-CMP catalysis nitrobenzene compound reduction
Weighing p-nitroanisole (30.6mg, 0.2mmol), and NaBH4(19mg, 0.5mmol) is added into a Schlenk bottle, 3mg of Ni-porphyrin-CMP is added, 3.5ml (6: 1) of mixed solvent ethanol and water is added for sealing the bottle mouth, the mixture is ultrasonically treated for 3min and then placed into a water bath kettle at 25 ℃ for stirring for 24h, biphenyl is taken as an internal standard, and the gas phase yield is 96%.
1H NMR(400MHz,CDCl3)δ6.76(d,J＝8.8Hz,2H),6.65(d,J＝8.8Hz,2H),3.75(s,3H),3.44(s,2H).
13C NMR(101MHz,CDCl3)δ152.98,140.28,116.65,115.04,55.97.
Example 10: Ni-porphyrin-CMP catalysis nitrobenzene compound reduction
1-nitronaphthalene (34.6mg, 0.2mmol) was weighed and NaBH was weighed4(19mg, 0.5mmol) is added into a Schlenk bottle, 3mg of Ni-porphyrin-CMP is added, 3.5ml (6: 1) of mixed solvent ethanol and water is added for sealing the bottle mouth, the mixture is ultrasonically treated for 3min and then placed into a water bath kettle at 25 ℃ for stirring for 24h, biphenyl is taken as an internal standard, and the gas phase yield is 94%.
1H NMR(400MHz,CDCl3)δ7.89–7.80(m,2H),7.55–7.44(m,2H),7.40–7.29(m,2H),6.80(dd,J＝6.9,1.4Hz,1H),4.15(s,2H).
13C NMR(101MHz,CDCl3)δ142.41,134.71,128.88,126.68,126.18,125.18,123.97,121.13,119.29,110.00.
Examples 4-10 demonstrate that the prepared material has a very good effect on catalyzing the reduction of nitrobenzene compounds, the required conditions are mild, and the yield can be more than 90% at normal temperature and normal pressure. Moreover, the material has wide applicability, and has high yield for the reaction substrate with substituent groups, namely electron-withdrawing substituent groups and electron-pushing substituent groups. The above examples will help to understand the present invention, but the scope of the present invention is not limited thereto.
Claims (7)
1. The conjugated microporous polymer based on porphyrin functional groups is characterized in that the conjugated microporous polymer material is a conjugated microporous polymer material which takes porphyrin as basic functional groups and is connected through a 1, 3-diacetylene structure, and has the following structural general formula:
2. the preparation method of the porphyrin functional group-based conjugated microporous polymer of claim 1, comprising the following steps: weighing porphyrin monomer and Pd (PPh)3)2Cl2And CuI in an ampoule, in which the porphyrin monomer Pd (PPh) is added in molar ratio3)2Cl2CuI is 1:0.04:0.04, the porphyrin monomer is 5,10,15, 20-tetraethyl-porphyrin or5,10,15, 20-tetraethyl alkynyl-zinc porphyrin or 5,10,15, 20-tetraethyl alkynyl-nickel porphyrin, then adding organic solvents of tetrahydrofuran and triethylamine, carrying out vacuum degassing circulation for three times, and heating and reacting in a nitrogen environment; stopping the reaction, standing to room temperature, filtering, and washing, extracting and vacuum-pumping a filter cake to obtain the conjugated microporous polymer based on the porphyrin functional group.
3. The method of claim 2, wherein the porphyrin monomer is nickel 5,10,15, 20-tetraacetylporphyrin.
4. The method of claim 2, wherein the organic solvents selected from tetrahydrofuran and triethylamine are used in an amount of 4.8-5.2 ml per 0.1mmol of porphyrin monomer.
5. The preparation method of the porphyrin functional group-based conjugated microporous polymer according to claim 2, wherein the heating reaction is carried out in a nitrogen environment, the reaction temperature is 80-100 ℃, and the reaction time is 48-72 hours.
6. The preparation method of the porphyrin functional group-based conjugated microporous polymer according to claim 2, wherein the washing is sequentially and respectively carried out three times with methanol, water, 1M HCl, water, chloroform and tetrahydrofuran, the extraction is carried out with tetrahydrofuran for 24 hours, and the vacuum drying is carried out under a vacuum condition of 80 ℃ for 6-8 hours.
7. Use of a porphyrin functional group-based conjugated microporous polymer according to claim 1 for catalyzing the reduction of nitrobenzene compounds, comprising the following steps: nitrobenzene and NaBH4Adding into Schlenk bottle at a molar ratio of 1:2.5, adding the conjugated microporous polymer as catalyst, and adding mixed solvent of ethanol and water at a volume ratio of 6:1Sealing the bottle mouth, performing ultrasonic treatment for 3 minutes, and then placing the bottle mouth in a water bath kettle at 25 ℃ to stir for 3-24 hours; 3mg of catalyst and 3.5ml of mixed solvent were used per 0.2mmol of nitrobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910178681.3A CN109867770B (en) | 2019-03-11 | 2019-03-11 | Conjugated microporous polymer based on porphyrin functional group and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910178681.3A CN109867770B (en) | 2019-03-11 | 2019-03-11 | Conjugated microporous polymer based on porphyrin functional group and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109867770A CN109867770A (en) | 2019-06-11 |
| CN109867770B true CN109867770B (en) | 2021-11-30 |
Family
ID=66920133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910178681.3A Active CN109867770B (en) | 2019-03-11 | 2019-03-11 | Conjugated microporous polymer based on porphyrin functional group and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109867770B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110294838B (en) * | 2019-07-03 | 2021-11-02 | 江南大学 | Polyhydroxy porphyrin polymer and preparation method thereof |
| CN110964179B (en) * | 2019-12-19 | 2022-06-21 | 湘潭大学 | Porphyrin polymer, preparation method thereof and application thereof in positive electrode material |
| CN111875795B (en) * | 2020-08-12 | 2022-04-12 | 台州学院 | Three-dimensional polyporphyrin and preparation method thereof |
| CN113698579B (en) * | 2021-07-23 | 2023-09-01 | 西北民族大学 | Porphyrin conjugated microporous polymer and its synthesis method and application |
| CN114369240B (en) * | 2021-11-10 | 2023-07-14 | 贵研铂业股份有限公司 | Porphyrin-based porous organic polymer, preparation method thereof and preparation method and application of supported palladium catalyst thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4242676A1 (en) * | 1992-12-17 | 1994-06-23 | Basf Ag | New polymeric porphyrin compounds useful in electrical and optical uses |
| WO1997027049A1 (en) * | 1996-01-26 | 1997-07-31 | The Trustees Of The University Of Pennsylvania | Hyperpolarizable compounds and devices fabricated therefrom |
| US5756723A (en) * | 1992-08-14 | 1998-05-26 | The Trustees Of The University Of Pennsylvania | Metal-mediated cross-coupling with ring-metalated porphyrins |
| CN105348303A (en) * | 2015-11-13 | 2016-02-24 | 中国科学院化学研究所 | Porphyrin two-dimension covalent organic framework conjugated polymer, and preparation method and application thereof |
| CN107126941A (en) * | 2017-06-07 | 2017-09-05 | 中山大学 | Solid-phase micro-extraction coating based on metalloporphyrin microporous polymer, preparation and application |
| CN109096456A (en) * | 2018-08-20 | 2018-12-28 | 吉林师范大学 | One kind is containing porphyryl conjugation microporous polymer and preparation method thereof |
-
2019
- 2019-03-11 CN CN201910178681.3A patent/CN109867770B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756723A (en) * | 1992-08-14 | 1998-05-26 | The Trustees Of The University Of Pennsylvania | Metal-mediated cross-coupling with ring-metalated porphyrins |
| DE4242676A1 (en) * | 1992-12-17 | 1994-06-23 | Basf Ag | New polymeric porphyrin compounds useful in electrical and optical uses |
| WO1997027049A1 (en) * | 1996-01-26 | 1997-07-31 | The Trustees Of The University Of Pennsylvania | Hyperpolarizable compounds and devices fabricated therefrom |
| CN105348303A (en) * | 2015-11-13 | 2016-02-24 | 中国科学院化学研究所 | Porphyrin two-dimension covalent organic framework conjugated polymer, and preparation method and application thereof |
| CN107126941A (en) * | 2017-06-07 | 2017-09-05 | 中山大学 | Solid-phase micro-extraction coating based on metalloporphyrin microporous polymer, preparation and application |
| CN109096456A (en) * | 2018-08-20 | 2018-12-28 | 吉林师范大学 | One kind is containing porphyryl conjugation microporous polymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109867770A (en) | 2019-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109867770B (en) | Conjugated microporous polymer based on porphyrin functional group and preparation method and application thereof | |
| Yang et al. | Construction of heterostructured MIL-125/Ag/g-C3N4 nanocomposite as an efficient bifunctional visible light photocatalyst for the organic oxidation and reduction reactions | |
| Jiang et al. | Metal–organic conjugated microporous polymers | |
| He et al. | Incorporation of Fe-phthalocyanines into a porous organic framework for highly efficient photocatalytic oxidation of arylalkanes | |
| CN106967216A (en) | A kind of covalent organic framework material of imines connection and preparation method and application | |
| CN111286010B (en) | Lipophilic super-hydrophobic porous aromatic skeleton material and preparation method and application thereof | |
| CN112159517B (en) | Dager base conjugated microporous polymer photocatalyst and preparation method and application thereof | |
| CN110560170B (en) | Pd @ MOF material, preparation method thereof and application thereof in biphenyl preparation | |
| CN110746601A (en) | Porphyrin-based polypyrrole conjugated microporous polymer and preparation method thereof | |
| WO2012103309A2 (en) | Polymeric systems containing chromophoric units for photo-driven catalysis and water splitting | |
| CN110433862B (en) | Preparation method and application of porous catalyst based on waste plastic | |
| Wang et al. | Catalytic transfer hydrogenation of ethyl levulinate to γ-valerolactone over zirconium (IV) Schiff base complexes on mesoporous silica with isopropanol as hydrogen source | |
| Tamami et al. | Synthesis and applications of poly (N-vinylimidazole) grafted silica-containing palladium nanoparticles as a new re-cyclable catalyst for Heck, Sonogashira and Suzuki coupling reactions | |
| CN115124655B (en) | Preparation and application of imidazolyl-containing organic polymer material | |
| Liu et al. | Highly hydrophilic covalent organic frameworks as efficient and reusable photocatalysts for oxidative coupling of amines in aqueous solution | |
| Hou et al. | Metal-free azo-bridged porphyrin porous organic polymers for visible-light-driven CO 2 reduction to CO with high selectivity | |
| Li et al. | A triformylphloroglucinol-based covalent organic polymer: Synthesis, characterization and its application in visible-light-driven oxidative coupling reactions of primary amines | |
| Zhao et al. | A BODIPY‐Based 1D Covalent Organic Framework for Photocatalytic Aerobic Oxidation | |
| Li et al. | Post‐synthetic Rhodium (III) Complexes in Covalent Organic Frameworks for Photothermal Heterogeneous C− H Activation | |
| Zhu et al. | Visible-light-driven carbonylation reaction over palladium supported on spherical-like graphitic carbon nitride | |
| CN111171331B (en) | Porphyrin-anthryl covalent organic framework material and preparation method and application thereof | |
| Xu et al. | Palladium catalyst imbedded in polymers of intrinsic microporosity for the Suzuki–Miyaura coupling reaction | |
| Wang et al. | Synthesis of ruthenium-based metallo-covalent organic frameworks for efficient photocatalytic ring opening of α-ketoepoxides under visible light | |
| Xu et al. | Upgrading of furfural by Knœvenagel condensation over functionalized carbonaceous basic catalysts | |
| CN111215149B (en) | MOF @ POP-n composite catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |