CN111848932A - Preparation of porphyrin-based porous polymer and application of porphyrin-based porous polymer in styrene oxidation catalysis - Google Patents
Preparation of porphyrin-based porous polymer and application of porphyrin-based porous polymer in styrene oxidation catalysis Download PDFInfo
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- CN111848932A CN111848932A CN202010791940.2A CN202010791940A CN111848932A CN 111848932 A CN111848932 A CN 111848932A CN 202010791940 A CN202010791940 A CN 202010791940A CN 111848932 A CN111848932 A CN 111848932A
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- porous polymer
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 30
- 229920000642 polymer Polymers 0.000 title claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 230000003647 oxidation Effects 0.000 title abstract description 8
- 238000006555 catalytic reaction Methods 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002861 polymer material Substances 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006735 epoxidation reaction Methods 0.000 claims description 9
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 239000012043 crude product Substances 0.000 claims 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920000620 organic polymer Polymers 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004699 copper complex Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VZSXFJPZOCRDPW-UHFFFAOYSA-N carbanide;trioxorhenium Chemical compound [CH3-].O=[Re](=O)=O VZSXFJPZOCRDPW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
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Abstract
The invention relates to the technical field of material preparation and catalysis, in particular to a porphyrin-based porous polymer styrene oxidation catalyst and a preparation method and application thereof. The preparation method uses copper tetraphenylporphyrin containing 5,10,15, 20-as a monomer and dimethoxymethane as a connector to obtain a novel porous polymer material through a crosslinking reaction. The porous polymer material obtained by the preparation method has a multi-stage pore channel and an open Cu-N site, and shows good styrene oxidation catalytic capability.
Description
Technical Field
The invention relates to the technical field of inorganic and organic hybrid materials, in particular to a porphyrin-based porous polymer styrene oxidation catalyst, and a preparation method and application thereof.
Background
Epoxides are common intermediates for many chemical products (e.g., epoxy resins, pharmaceuticals, etc.), and for example, ring opening of epoxides can produce useful alpha-or beta-substituted alcohols. However, many toxic components in the olefin epoxidation reaction are still widely used in the traditional epoxidation industry, which not only has a great adverse effect on the environment and life, but also has complicated post-treatment steps and is not beneficial to development.Recently, homogeneous and heterogeneous epoxidation using transition metal complexes (e.g., methyltrioxorhenium, polyoxometallates, etc.) as catalysts has been extensively studied, but exhibits some disadvantages such as low utilization efficiency of the oxidizing agent, low selectivity of the epoxy, poor stability and difficulty in separation[143]. Due to the low nucleophilic activity resulting from p-pi conjugation to the benzene ring, styrene epoxidation requires highly efficient catalysts with higher conversion and excellent selectivity to styrene oxide.
The copper complex is one of the most effective and useful catalysts in industry as a transition metal complex/ion due to its high natural abundance and low cost, and can be used for catalyzing various oxidation reactions, such as epoxidation of aromatic olefin group, oxidation of organic alcohols and selective oxidation of methanol. Although copper complex supported heterogeneous catalysts have made great progress, it remains a challenge to develop new, superior catalyst supports with high catalytic activity and well-designed structures.
Porous organic polymers have excellent chemical stability, high surface area and adjustable pore size, which allow rapid diffusion of substrates and products throughout the catalytic process, and have become a particular type of amorphous porous material suitable for heterogeneous catalytic applications. 5,10,15, 20-tetraphenylporphyrin copper is a biological macromolecule, and is used as a monomer to synthesize a porous polymer, wherein active sites of copper metal on the monomer can be uniformly exposed in pore channels.
Disclosure of Invention
The invention aims to solve the technical problem of making up the defects of the original technology and provide a preparation method of a porphyrin-based porous polymer for styrene oxidation catalysis.
The functional porous organic polymer catalyst provided by the invention is characterized in that the skeleton of the porous organic polymer catalyst simultaneously contains porphyrin group, methylene and Cu-N sites.
The functional porous organic polymer catalyst provided by the invention takes styrene as a raw material, and styrene oxide is prepared in the presence of an oxidant, the reaction temperature is below 100 ℃, and the reaction time is 15-30 hours.
The preparation method of the catalyst is characterized in that dichloroethane is used as a solvent, anhydrous ferric trichloride is used as a catalyst, 5,10,15, 20-tetraphenylporphyrin and dimethyl methane react for 15-30 hours at 25-90 ℃, and the porphyrin-based porous polymer is obtained through filtration, washing and drying.
Has the advantages that:
1. the porphyrin-based porous polymer is used as a catalyst, and has the advantages of large specific surface area, easiness in performance regulation and control and the like.
2. The porphyrin-based porous polymer has amorphous hierarchical porous channels and good thermal stability, and is beneficial to rapid diffusion of substrates and products in the whole catalytic process.
3. Open Cu-N sites are uniformly distributed in the pore channels of the porphyrin-based porous polymer, so that substrate molecules
4. The catalyst is fully contacted with the active center, and has high selectivity to the epoxyphenylethane.
5. The catalyst of the invention can be recycled and has high catalytic activity.
Drawings
FIG. 1 shows structural units of a porphyrin-based porous polymer material according to an embodiment of the present invention;
FIG. 2 is an infrared spectrum of a porphyrin-based porous polymer material prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of a porphyrin-based porous polymer material prepared in example 1 of the present invention;
FIG. 4 is a thermogravimetric plot of the porphyrin-based porous polymer material prepared in example 1 of the present invention;
FIG. 577K, 0-101324 Pa, nitrogen adsorption isotherm of the porphyrin-based porous polymer material prepared in example 1 of the present invention;
FIG. 6 illustrates the use of the porphyrin-based porous polymer material prepared in example 1 of the present invention to catalyze the epoxidation of styrene;
FIG. 7 is a graph showing the stability of the catalytic activity of the catalyst of example 1 of the present invention;
Detailed Description
The invention will be described in further detail with reference to the following figures and examples, which are only intended to better understand the contents of the invention and are not intended to limit the scope of the invention.
Example 1:
synthesis of 5,10,15, 20-tetraphenylporphyrin copper monomer
4.5mmol of anhydrous cupric acetate was dissolved in 60mL of DMF, and 1.5mmol of 5,10,15, 20-tetraphenylporphyrin and 250mL of DMF were mixed in a flask and heated to 120 ℃ with slow stirring. Adding 20mL of prepared copper acetate solution every half hour, stirring under reflux for half hour after all the solution is added, cooling to room temperature, performing rotary evaporation on the mixture until 50-60mL of the solution remains, transferring the remaining mixture into 3M hydrochloric acid solution, and refrigerating in a refrigerator overnight. The precipitated solid was collected by filtration, washed with 1M hydrochloric acid and deionized water until a colorless transparent liquid leaked, and vacuum-dried for use to obtain purple 5,10,15, 20-tetraphenylporphyrin copper in 90% yield.
Example 2:
preparation of porphyrin-based porous polymers
Under nitrogen atmosphere, anhydrous FeCl is added3(8mmol), copper (2mmol) and 5,10,15, 20-tetraphenylporphyrin, dimethoxymethane (FDA) (8mmol), and 1, 2-dichloroethane (30mL) were added to a 50mL Schlenk flask and stirred at 25 ℃ for 2 hours, after which the mixture was warmed to 80 ℃ and stirring continued for 24 h. After the mixture was cooled to room temperature, the precipitate was collected by filtration and washed with water, methanol, dichloromethane, THF, DMF and acetone, respectively. After the collected precipitate was surface-dried, the obtained solid was subjected to soxhlet extraction with methanol, tetrahydrofuran, and chloroform, respectively, for 1 day. After final drying under vacuum at 60 ℃ for 24 hours, the black powder obtained was a porphyrin-based porous polymer with a yield of 92%. FIG. 1 shows the synthesis route of porphyrin-based porous polymer obtained in the example; FIG. 2 is an IR spectrum of the porphyrin-based porous polymer and the porphyrin-based porous polymer monomer obtained in the example, clearly showing that the prepared catalyst skeleton contains methylene and Cu-N bonds; FIG. 3 is an XRD pattern of a porphyrin-based porous polymer material prepared in the examples; FIG. 4 is a thermogravimetric plot of the porphyrin-based porous polymeric material prepared in the examples; FIG. 5 shows examples of the conditions of 77K and 0 to 101324PaThe nitrogen adsorption isotherm of the porphyrin-based porous polymer material prepared in (1);
example 3:
styrene epoxidation Performance test
0.5mmol of styrene and 0.75mmol of tert-butyl hydroperoxide are dissolved in 6ml of acetonitrile and transferred into a Schlenk bottle, 0.03mmol of polymer is slowly added, the reaction is carried out at 72 ℃, and after the product is cooled to room temperature, the corresponding product is extracted and the substance components are detected in GC-MS. For the recycle reaction, the mixture was centrifuged and the solid catalyst was washed with CH3CN was washed several times and the test was repeated.
Example 4
Similar to example 2, 5,10,15, 20-tetraphenylporphyrin is used as a monomer, dimethoxymethane is used as a linking agent, and the reaction conditions such as reaction time, temperature, catalyst and the like are changed, so that the reaction results are shown in the attached figures 1-5.
Example 5
Similar to example 3, the conditions such as time and the like were changed by using a porphyrin-based porous organic polymer as a catalyst, and the reaction results are shown in FIG. 6. FIG. 6 is a graph showing the conversion of styrene to ethylene oxide in the porphyrin-based porous organic polymer obtained in the example.
Example 6
Similar to example 3, the catalyst obtained from the porphyrin-based porous organic polymer was recycled for 4 times, and the conversion rate still reached 97% of the first reaction (fig. 7), indicating that the catalyst has excellent recycling performance.
The above description is only exemplary of the present invention, and all modifications and variations that fall within the scope of the claims should be considered as falling within the scope of the present invention.
Claims (3)
1. A porous polymeric material for the epoxidation of styrene having the formula:
the material is characterized by simultaneously containing methylene and porphyrin groups.
2. The method for preparing a porous polymer material for styrene epoxidation according to claim 1, characterized in that 5,10,15, 20-tetraphenylporphyrin copper and dimethoxymethane are dissolved in 1, 2-dichloroethane under nitrogen atmosphere, anhydrous ferric chloride catalyst is added and stirred at room temperature for 1-4 hours, and then the mixture is heated to 60-100 ℃ and stirred for 24-48 hours to obtain a crude product; after filtration, washing, vacuum drying at 60 ℃ for 24 hours gave a brown powder.
3. The porous polymer catalyst as claimed in claim 1 is used in the catalytic oxidation reaction of styrene, and is characterized in that styrene is oxidized into ethylene oxide and benzaldehyde in acetonitrile solution by using tert-butyl hydroperoxide as an oxidant, the conversion rate of styrene is 70-100%, the selectivity of ethylene oxide is 70-100%, the catalyst can be recycled, the reaction temperature is 60-80 ℃, and the reaction time is 15-30 hours.
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| CN115449073A (en) * | 2022-10-25 | 2022-12-09 | 广东工业大学 | Metal porphyrin-based super-crosslinked ionic polymer, and preparation method and application thereof |
| CN115838470A (en) * | 2022-12-02 | 2023-03-24 | 山东大学 | Hollow porphyrin-based porous organic polymer, preparation method thereof and application thereof in colorimetric detection of Cr (VI) |
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| CN105251535A (en) * | 2015-11-18 | 2016-01-20 | 吉林大学 | Porous organic polymer material and preparation method thereof |
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| CN105251535A (en) * | 2015-11-18 | 2016-01-20 | 吉林大学 | Porous organic polymer material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449073A (en) * | 2022-10-25 | 2022-12-09 | 广东工业大学 | Metal porphyrin-based super-crosslinked ionic polymer, and preparation method and application thereof |
| CN115449073B (en) * | 2022-10-25 | 2024-01-12 | 广东工业大学 | Metalloporphyrin-based super-crosslinked ionic polymer, preparation method and application thereof |
| CN115838470A (en) * | 2022-12-02 | 2023-03-24 | 山东大学 | Hollow porphyrin-based porous organic polymer, preparation method thereof and application thereof in colorimetric detection of Cr (VI) |
| CN115838470B (en) * | 2022-12-02 | 2024-06-07 | 山东大学 | Hollow porphyrin-based porous organic polymer, preparation method thereof and application thereof in colorimetric detection of Cr (VI) |
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