CN117510764A - Cobalt porphyrin-based porous organic polymer and preparation method and application thereof - Google Patents
Cobalt porphyrin-based porous organic polymer and preparation method and application thereof Download PDFInfo
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- 229920000620 organic polymer Polymers 0.000 title claims abstract description 62
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 claims abstract description 19
- -1 porphyrin macrocycle Chemical class 0.000 claims abstract description 15
- 238000007146 photocatalysis Methods 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 51
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- NPQXMTUQLRZKMK-UHFFFAOYSA-N 5-(6-formylpyridin-3-yl)pyridine-2-carbaldehyde Chemical compound C1=NC(C=O)=CC=C1C1=CC=C(C=O)N=C1 NPQXMTUQLRZKMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000013032 photocatalytic reaction Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 150000004032 porphyrins Chemical class 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- ICLZNGAELWYHKL-CAPFRKAQSA-N (E)-3-[5-[5-[4-(N-phenylanilino)phenyl]thiophen-2-yl]thiophen-2-yl]prop-2-enoic acid Chemical compound OC(=O)\C=C\c1ccc(s1)-c1ccc(s1)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 ICLZNGAELWYHKL-CAPFRKAQSA-N 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract 2
- 239000003446 ligand Substances 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 70
- 239000001569 carbon dioxide Substances 0.000 description 35
- 229910002092 carbon dioxide Inorganic materials 0.000 description 35
- 230000003197 catalytic effect Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 238000011056 performance test Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FEHLIYXNTWAEBQ-UHFFFAOYSA-N 4-(4-formylphenyl)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1C1=CC=C(C=O)C=C1 FEHLIYXNTWAEBQ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004577 artificial photosynthesis Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- KIQQAJNFBLKFPO-UHFFFAOYSA-N magnesium;porphyrin-22,23-diide Chemical compound [Mg+2].[N-]1C(C=C2[N-]C(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 KIQQAJNFBLKFPO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
- C08G12/08—Amines aromatic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a cobalt porphyrin-based porous organic polymer and a preparation method and application thereof, wherein the polymer takes a porphyrin-based material as a precursor, introduces a pyridine ligand rich in nitrogen, synthesizes a nano-sheet photocatalytic material through a one-pot method, and has the advantages that the porphyrin macrocycle of the material is complexed with cheap transition metal element Co, the whole length and width dimension is between 50 and 200nm, the thickness is less than 10nm, meanwhile, the material has a rich mesoporous structure, and the specific surface area is 400 to 500m 2 And/g. The material prepared by the invention has excellent photocatalysis CO 2 Performance, CO can be realized without adding any photosensitizer 2 The CO conversion rate can reach 413.08 mu mol g ‑1 ·h ‑1 。
Description
Technical Field
The invention belongs to the technical field of catalytic materials and nano materials, relates to a preparation method of a porous organic polymer nano sheet loaded by a transition metal catalyst, and in particular relates to a porous organic polymer based on cobalt porphyrin, a preparation method thereof and application thereof in preparing CO by photocatalysis.
Background
Carbon dioxide (CO) 2 ) The excessive emissions of (a) raise a serious global problem (e.g., energy shortage, global warming, etc.). CO is processed by 2 As a means of achieving sustainable development of energy and solving the global warming problem, direct conversion of abundant C1 resources into usable chemical fuels or value-added chemicals is one of the approaches.
Metalloporphyrin compounds are widely used in nature and play a vital role in photosynthesis of organisms, for example, chlorophyll used for photosynthesis in plants is a magnesium porphyrin complex. Based on the inspired that scientists simulate artificial photosynthesis, and utilize renewable sunlight to successfully realize CO by taking metalloporphyrin compounds as catalysts 2 Conversion to valuable chemicals or fuels (CO, CH 4 HCOOH, etc.), and exhibits relatively reliable efficiency and selectivity.
Porous organic polymers (Porous Organic Polymers, POPs) are an emerging class of organic semiconductor materials, possessing a large specific surface area, thus being able to carry high density of active sites, their highly crosslinked porous structure making it a distinct advantage in terms of trapping and conversion for gases; in addition, the catalyst also has good thermal stability and chemical stability, is insoluble in common organic solvents, and has the advantage of making separation and recycling after heterogeneous catalysis extremely simple.
In recent years, scientists have been on the use of visible light to induce reduction of CO 2 Porphyrin complex photocatalysts derived from porphyrins are increasingly known, as are increasingly interesting (Inorganic Chemistry,2020,59 (9): 6301-6307;Catalysis Science)&Technology,2022,12 (21): 6527-6539) also reports porphyrinic derived CO 2 The yield of the photocatalyst is low, but most of the photocatalysts have poor selectivity. Efficient photocatalysts in turn require expensive photosensitizers to assist in photon absorption by the catalyst. Thus, the preparation of a photocatalyst with high efficiency without the need for a photosensitizer is a highly desirable problem for researchers in this field.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing a preparation method of a cobalt porphyrin porous organic polymer, wherein the flaky metalloporphyrin porous organic polymer obtained by the method has strong visible light absorption capacity, rich mesoporous structure and large specific surface area, and meanwhile, the introduced Lewis basic site provides higher catalytic activity and higher selectivity for the material.
In order to achieve the above purpose, the present invention provides the following technical solutions:
in a first aspect, the present invention provides a cobalt porphyrin-based porous organic polymer prepared according to the following method:
dissolving 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin and 3,3 '-bipyridine-6, 6' -dicarboxaldehyde in an organic solvent, adding an aqueous solution of acetic acid and 3-aminopropyl triethoxysilane, uniformly dispersing, reacting the obtained mixed solution at 80-150 ℃ for 24-120 h (preferably at 120 ℃ for 72 h) under an anaerobic condition, and performing aftertreatment on the obtained reaction solution to obtain the cobalt porphyrin-based porous organic polymer; the molar ratio of acetic acid to 3-aminopropyl triethoxysilane in the aqueous solution of 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin, 3 '-bipyridine-6, 6' -dicarboxaldehyde is 1:0.3-3:25-100:0.3-3 (preferably 1:2:50:2).
The invention provides a high-performance metalloporphyrin porous organic polymer material, which has porphyrin macrocycle complex cheap transition metal element Co, sheet-shaped nano structure with the size between 50 and 200nm, rich mesoporous structure and specific surface area up to 400 to 500m 2 And/g. The polymers of the invention are repeating units of the following structure:
reaction monomer:
further, the organic solvent is one or more than two solvents selected from N-butanol, 1, 2-dichlorobenzene, N-dimethylacetamide, dioxane and mesitylene, and in one embodiment of the invention, the volume ratio is 1:0.3-3 of a mixed solvent of n-butanol and 1, 2-dichlorobenzene (preferably, a mixed solvent of n-butanol and 1, 2-dichlorobenzene in a ratio of 1:1).
Still further, the volume of the organic solvent is 0.045mL/mg to 0.135mL/mg (preferably 0.09 mL/mg) based on the mass of the 5,10,15, 20-tetrakis (4-aminophenyl) cobalt porphyrin.
In an embodiment of the invention, the anaerobic condition is obtained as follows: the mixed solution was subjected to deoxidation treatment in a schlenk tube, and then the reaction was carried out under sealed conditions. Further, the deoxidizing treatment is as follows: the procedure of liquid nitrogen flash freezing, degassing, thawing was repeated 2-5 times (3 times in the example of the present invention). Degassing under liquid nitrogen conditions is effective to remove oxygen while retaining solvent.
Further, the post-treatment is as follows: and (3) carrying out suction filtration on the reaction liquid, washing the filter cake in a Soxhlet extractor for 18-72 h by using a polymer impurity-removing organic solvent, and drying to obtain the cobalt porphyrin-based porous organic polymer.
Still further, the polymer impurity removing organic solvent is one of methanol, ethanol, dichloromethane, chloroform, acetone and tetrahydrofuran, and in one embodiment of the present invention is acetone, and the washing time is 24 hours.
Further, the concentration of the aqueous acetic acid solution is 3 to 12M, and preferably the concentration of the aqueous acetic acid solution is 6M.
The cobalt porphyrin-based porous organic polymer is particularly preferably prepared according to the following method:
dissolving 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin and 3,3 '-bipyridine-6, 6' -dicarboxaldehyde in an organic solvent, adding an aqueous solution of acetic acid and 3-aminopropyl triethoxysilane, uniformly dispersing, reacting the obtained mixed solution at 120 ℃ for 72 hours under an anaerobic condition, and performing post-treatment on the obtained reaction solution to obtain the cobalt porphyrin-based porous organic polymer; the molar ratio of acetic acid to 3-aminopropyl triethoxysilane in the aqueous solution of 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin, 3 '-bipyridine-6, 6' -dicarboxaldehyde is 1:2:50:2; the concentration of the acetic acid aqueous solution is 6M; the volume ratio of the organic solvent is 1:1 and 1, 2-dichlorobenzene.
In a second aspect, the present invention provides a porous organic polymer based on cobalt porphyrin as described above for photocatalytic CO 2 Use in the preparation of CO by reduction.
Specifically, the application is: placing the cobalt porphyrin-based porous organic polymer, triethylamine and acetonitrile in a quartz-top photocatalytic device, and using CO 2 Replacing gas in the quartz top photocatalysis device to saturation, and carrying out photocatalysis reaction under sunlight to obtain CO; the volume of triethylamine was 2mL/mg based on the mass of the cobalt porphyrin-based porous organic polymer.
In one embodiment of the invention, the mass of the cobalt porphyrin-based porous organic polymer is 10mg/L based on the volume of the reaction chamber of the quartz-top photocatalytic device.
Further, the volume of acetonitrile is 10mL/mg based on the mass of the porous organic polymer of cobalt porphyrin.
The invention recommends that the photocatalytic reaction be carried out in acetonitrile solvent, otherwise the conversion effect is poor.
The invention recommends that the light intensity of the photocatalysis reaction is AM1.5G, and meanwhile, the reaction device is cooled by condensed water at 25 ℃.
Compared with the prior art, the invention has the beneficial effects that:
starting from porphyrin, introducing Lewis basic sites, and obtaining the cobalt-porphyrin-based porous organic nano lamellar polymer through one-step coupling reaction, wherein the Lewis basic sites can enhance the material pair CO 2 The adsorption and activation performance of the catalyst can improve the selectivity of target products and reduce the generation of byproducts while improving the catalytic performance, so that the material has excellent CO 2 Catalytic performance in performing photocatalytic CO 2 During reduction, CO can be realized without any photosensitizer 2 High-efficiency and high-selectivity conversion of (a) with a conversion rate of up to 413.08 mu mol g -1 ·h -1 And has a selectivity of greater than 98%.
Drawings
FIG. 1 is a thermogravimetric analysis of a cobalt porphyrin porous organic polymer;
FIG. 2 is an infrared spectrum of CoTAPP (a), bpy (b) and CoPPOP-1 (c);
FIG. 3 is an SEM image of a CoPPOP-1 material;
FIG. 4 is a PXRD diffraction pattern for a CoPPOP-1 material;
FIG. 5 is a graph of the adsorption and desorption of nitrogen from the CoPPOP-1 material;
FIG. 6 is a solid UV visible diffuse reflectance spectrum of CoTAPP (a), bpy (b) and CoPPOP-1 (c).
Detailed Description
The invention will be further described with reference to specific examples to provide a better understanding of the invention.
Example 1
A method for preparing cobalt porphyrin porous organic polymer (CoPPOP-1), which comprises the following steps:
44mg (0.06 mmol) of 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin and 25mg (0.12 mmol) of 3,3 '-bipyridine-6, 6' -dicarboxaldehyde are put in a schlenk tube, 2mL of n-butanol, 2mL of 1, 2-dichlorobenzene are added for dissolution, then 0.5mL of 6M aqueous acetic acid solution and 30 μl (0.12 mmol) of 3-aminopropyl triethoxysilane are added, and the mixture is sonicated until a homogeneous solution is formed. And (3) putting the schlenk tube into liquid nitrogen for quick freezing, then degassing the schlenk tube by using a vacuum pump, then thawing, sealing the schlenk tube, putting the schlenk tube into an oven for heating reaction at 120 ℃ for 72 hours after repeating the steps for three times, putting the reaction product into a Soxhlet extractor after suction filtration and collection by using a suction filtration bottle, washing the reaction product with acetone for 24 hours, and then putting the reaction product into a vacuum oven for drying at 80 ℃ for 20 hours to obtain CoPPOP-1.
Thermogravimetric analysis, infrared analysis, electron microscope analysis and X-ray diffraction analysis were performed on the CoPPOP-1 photocatalytic material prepared in example 1, and the results were as follows:
the thermogravimetric graph of copop-1, as shown in figure 1, shows that the total weight loss rate of the material heated to 800 ℃ is not more than 30%, indicating that the material has good thermal stability.
From the infrared plot of FIG. 2, it can be observed that 3350cm of CoTAPP (a) -1 at-NH 2 Peak disappeared, 1699cm of Bpy (b) -1 -c=o-peak cancellation1622cm of CoPPOP-1 (c) -1 The generation of-c=n-peak can prove that the amine-aldehyde condensation reaction between two monomers generates a new product, and meanwhile, no obvious diffraction peak exists in the PXRD diffractogram of copop-1, so that the amorphous structure of the material can be proved.
The specific morphology of the copop-1 appears as a regular nanoplatelet structure as shown in fig. 3, and it shows broadband light absorption capacity within 800nm (fig. 6).
Catalytic performance test: CO 2 The photocatalytic conversion experiments of (2) were performed in a 500mL quartz-top photocatalytic device, test steps: 5mg CoPPOP-1 is put into a photocatalysis device, 50mL acetonitrile and 10mL triethylamine are added, a top cover is sealed, and the gas in the device is treated by CO 2 Half an hour of displacement to CO 2 Saturation; the system is placed under a xenon lamp, a sunlight filter is installed, the light intensity is AM1.5G, and meanwhile, the reaction device is cooled by condensed water at 25 ℃. After two hours of reaction, a sample was taken with a 1mL sampling needle, and then the gaseous product was detected by gas chromatography equipped with thermal conductivity detectors (FID), (TCD), and the liquid product was detected by liquid Nuclear Magnetism (NMR).
Experimental results show that a large amount of CO can be generated by gas chromatography detection, and the conversion rate reaches 413.08 mu mol.g -1 ·h -1 Trace of NH 4 Generating, less than 2%; liquid nuclear magnetic resonance detection shows that no products such as formic acid, methanol and the like are generated. In addition, N under the same conditions 2 Saturation was tested and no CO was produced, indicating that the CO produced was derived from CO 2 Rather than other organics.
Example 2
A preparation method of cobalt porphyrin porous organic polymer is different from example 1 in that the concentration of acetic acid aqueous solution is 3M, and the reaction time is 120h;
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has the CO generation rate of 295.37 mu mol.g -1 ·h -1 。
Example 3
A preparation method of cobalt porphyrin porous organic polymer is different from example 1 in that the concentration of acetic acid aqueous solution is 12M, and the reaction time is 24 hours;
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has CO generation rate of 318 mu mol g -1 ·h -1 。
Example 4
A preparation method of cobalt porphyrin porous organic polymer is different from example 1 in that the reaction temperature is 80 ℃ and the reaction time is 120 hours;
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has the CO generation rate of 315.13 mu mol.g -1 ·h -1 。
Example 5
A preparation method of cobalt porphyrin porous organic polymer is different from example 1 in that the reaction temperature is 150 ℃ and the reaction time is 24 hours;
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has the CO generation rate of 297.09 mu mol.g -1 ·h -1 。
Example 6
A preparation method of cobalt porphyrin porous organic polymer is different from example 1 in that the solvent system is dioxane 2mL and mesitylene 2mL;
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that cobalt chlorin prepared in this comparative examplePorous organic polymer of the line, CO generation rate of 310.79 mu mol g -1 ·h -1 。
Example 7
A method for preparing cobalt porphyrin porous organic polymer is different from example 1 in 73mg (0.1 mmol) of 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin, 6.25mg (0.03 mmol) of 3,3 '-bipyridine-6, 6' -dicarboxaldehyde, 3mL of n-butanol, and 1mL of 1, 2-dichlorobenzene;
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has the CO generation rate of 316.55 mu mol.g -1 ·h -1 。
Example 8
A method for preparing cobalt porphyrin porous organic polymer is different from example 1 in that 44mg (0.06 mmol) of 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin, 37.5mg (0.18 mmol) of 3,3 '-bipyridine-6, 6' -dicarboxaldehyde, 1mL of n-butanol and 3mL of 1, 2-dichlorobenzene;
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has the CO generation rate of 288.69 mu mol.g -1 ·h -1 。
Comparative example 1
A method for preparing cobalt porphyrin porous organic polymer, which is different from example 1 in that the reaction time is 24 hours;
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has the CO generation rate of 147.24 mu mol.g -1 ·h -1 。
Comparative example 2
A preparation method of cobalt porphyrin porous organic polymer, which is different from example 1 in that the reaction temperature is 80 ℃; the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has the CO generation rate of 207.35 mu mol.g -1 ·h -1 。
Comparative example 3
A method for preparing cobalt porphyrin porous organic polymer, which is different from example 1 in that 3-aminopropyl triethoxysilane is not added;
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has the CO generation rate of 126.05 1 μmol·g -1 ·h -1 。
Comparative example 4
A method for preparing cobalt porphyrin porous organic polymer, which is different from example 1 in that the concentration of acetic acid aqueous solution is 3M;
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has the CO generation rate of 137.15 mu mol.g -1 ·h -1 。
Comparative example 5
A preparation method of cobalt porphyrin porous organic polymer is different from example 1 in that 3,3' -bipyridine-6, 6' -dicarboxaldehyde in the raw material is changed into 4,4' -biphenyl dicarboxaldehyde, and the feeding amount is 25mg (0.12 mmol);
the rest of the procedure is the same as in example 1.
Catalytic performance test: the test conditions were the same as in example 1.
Experimental results show that the cobalt porphyrin porous organic polymer prepared in the comparative example has CO generation rate of 26.08 mu mol.g -1 ·h -1 。
Claims (10)
1. A cobalt porphyrin-based porous organic polymer, characterized in that the cobalt porphyrin-based porous organic polymer is prepared according to the following method:
dissolving 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin and 3,3 '-bipyridine-6, 6' -dicarboxaldehyde in an organic solvent, adding an aqueous solution of acetic acid and 3-aminopropyl triethoxysilane, uniformly dispersing, reacting the obtained mixed solution for 24-120 h under the anaerobic condition at 80-150 ℃, and carrying out post-treatment on the obtained reaction solution to obtain the cobalt porphyrin-based porous organic polymer; the molar ratio of acetic acid to 3-aminopropyl triethoxysilane in the aqueous solution of 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin, 3 '-bipyridine-6, 6' -dicarboxaldehyde is 1:0.3-3:25-100:0.3-3.
2. The cobalt porphyrin-based porous organic polymer of claim 1, wherein: the organic solvent is one or more than two of N-butanol, 1, 2-dichlorobenzene, N-dimethylacetamide, dioxane and mesitylene; the volume of the organic solvent is 0.045 mL/mg-0.135 mL/mg based on the mass of the 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin.
3. The cobalt porphyrin-based porous organic polymer according to claim 1, characterized in that said post-treatment is: and (3) carrying out suction filtration on the reaction liquid, washing the filter cake in a Soxhlet extractor for 18-72 h by using a polymer impurity-removing organic solvent, and drying to obtain the cobalt porphyrin-based porous organic polymer.
4. A cobalt porphyrin-based porous organic polymer according to claim 3, wherein: the polymer impurity removing organic solvent is one of methanol, ethanol, methylene dichloride, chloroform, acetone and tetrahydrofuran.
5. The cobalt porphyrin-based porous organic polymer of claim 1, wherein: the concentration of the acetic acid aqueous solution is 3-12M.
6. The cobalt porphyrin-based porous organic polymer according to claim 1, characterized in that said cobalt porphyrin-based porous organic polymer is prepared according to the following method:
dissolving 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin and 3,3 '-bipyridine-6, 6' -dicarboxaldehyde in an organic solvent, adding an aqueous solution of acetic acid and 3-aminopropyl triethoxysilane, uniformly dispersing, reacting the obtained mixed solution at 120 ℃ for 72 hours under the anaerobic condition, and performing post-treatment on the obtained reaction solution to obtain the cobalt porphyrin-based porous organic polymer; the molar ratio of acetic acid to 3-aminopropyl triethoxysilane in the aqueous solution of 5,10,15, 20-tetra (4-aminophenyl) cobalt porphyrin, 3 '-bipyridine-6, 6' -dicarboxaldehyde is 1:2:50:2; the concentration of the acetic acid aqueous solution is 6M; the volume ratio of the organic solvent is 1:1 and 1, 2-dichlorobenzene.
7. The cobalt porphyrin-based porous organic polymer of any of claims 1-6 for photocatalytic CO 2 Use in the preparation of CO by reduction.
8. The application according to claim 7, characterized in that the application is: placing the cobalt porphyrin-based porous organic polymer, triethylamine and acetonitrile in a quartz-top photocatalytic device, and using CO 2 Replacing gas in the quartz top photocatalysis device to saturation, and carrying out photocatalysis reaction under sunlight to obtain CO; the volume of triethylamine was 2mL/mg based on the mass of the cobalt porphyrin-based porous organic polymer.
9. The use according to claim 8, wherein: the mass of the cobalt porphyrin-based porous organic polymer is 10mg/L based on the volume of the reaction chamber of the quartz-top photocatalysis device;
the volume of acetonitrile was 10mL/mg based on the mass of the porous organic polymer of cobalt porphyrin.
10. The use according to claim 8, wherein: the light intensity of the photocatalytic reaction is AM1.5G.
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