CN117384357A - Binuclear cobalt heterogeneous catalyst - Google Patents

Binuclear cobalt heterogeneous catalyst Download PDF

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CN117384357A
CN117384357A CN202311306486.7A CN202311306486A CN117384357A CN 117384357 A CN117384357 A CN 117384357A CN 202311306486 A CN202311306486 A CN 202311306486A CN 117384357 A CN117384357 A CN 117384357A
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dichloromethane
heterogeneous catalyst
anhydrous methanol
drying
cobalt
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龚云南
杨昊宇
吕思雅
钟地长
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Tianjin University of Technology
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Tianjin University of Technology
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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    • 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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
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Abstract

The invention provides a binuclear cobalt heterogeneous catalyst, co 2 L-Br and 4,4' -diacetylene biphenyl are used as precursors, and are obtained through Sonogashira Coupling reaction, so that the catalyst has excellent CO reduction effect 2 The capacity of CO is up to 1063mmol/g/h, and compared with the prior art, the binuclear cobalt heterogeneous catalyst has excellent photocatalytic performance, is favorable for recycling the catalyst and has commercial application value.

Description

Binuclear cobalt heterogeneous catalyst
Technical Field
The invention belongs to the field of photocatalysts, and particularly relates to a binuclear cobalt heterogeneous catalyst.
Background
Fossil fuels are used in large quantities, which not only causes global resource shortages, but also brings about difficult-to-estimate environmental pollution, for example due to CO 2 Global warming problems caused by excessive emissions. Therefore, renewable energy sources are greatly developed to convert CO 2 Is converted into fuel or chemicals with high added value, and can improve energy structure, relieve greenhouse effect and realize sustainable development of economy and societyHas important significance.
In recent years, chemical immobilization, thermal catalysis, photocatalysis, electrocatalysis, biochemical conversion, etc. have been used to convert CO 2 Converted into a variety of valuable fuels or chemicals such as carbon monoxide, methane, ethane, methanol, ethanol, formate, etc. Among them, the photocatalysis technology receives extensive attention from scientific researchers because of the advantages of mild reaction conditions, low cost and no pollution. Solar energy is radiant energy inside the sun, releasing huge nuclear energy mainly through "hydrogen helium nuclear fusion". It does not pollute the environment, has no regional limitation and is inexhaustible. As a renewable energy source, it becomes an important energy component for human beings and is continuously developed. Photocatalytic CO 2 The reduction is the process of converting solar energy into chemical energy, and the photosynthesis of plants is simulated by artificial natural photosynthesis to catalyze CO 2 Can be converted into chemical fuel to realize CO 2 Is recycled. Among them, the development of a high-efficiency photocatalyst is critical.
Photocatalysts generally fall into two categories: homogeneous catalysts and heterogeneous catalysts. Homogeneous phase catalyst has high activity and high selectivity, but the difficulty in recycling leads to high catalyst cost, is unfavorable for industrial application, and can bring about the pollution problem of heavy metal ions. While heterogeneous catalysts can just overcome the problem, heterogeneous catalysts face the problem of low activity and selectivity, so that researchers have made a great deal of research on the immobilization of homogeneous catalysts. The so-called homogeneous catalyst immobilization, i.e. the formation of a solid catalyst by physical or chemical means. The active components of the special catalyst have the same property and structure as those of the homogeneous catalyst, so that the selectivity and activity of the heterogeneous catalyst are greatly improved, the catalyst can be separated from a reaction system and used repeatedly, and the catalyst cost is greatly reduced.
Thus, a novel heterogeneous catalyst with a homogeneous catalyst as a catalytic active site is constructed for photocatalytic CO 2 Reduction is of great importance.
Disclosure of Invention
In view of this, the present invention aims to propose a binuclear cobalt heterogeneous catalyst to obtain heterogeneous catalyst materials with higher activity and selectivity.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a dinuclear cobalt heterogeneous catalyst comprising the steps of:
step A, preparing aza-hole ether ligand L-Br: adding an anhydrous methanol solution of tris (2-aminoethyl) amine into an anhydrous methanol solution containing 5-bromoisophthalaldehyde under inert atmosphere, stirring to obtain a pale yellow precipitate, centrifuging, washing, drying in vacuum, dissolving the dried pale yellow precipitate into a mixed solution of dichloromethane and the anhydrous methanol, stirring in an ice-water bath under inert atmosphere, adding sodium borohydride in batches, heating for reflux reaction, cooling the reaction solution to room temperature, injecting deionized water into a separating funnel, extracting with dichloromethane, drying an organic phase, filtering, and spin-evaporating the filtrate to obtain an aza-hole ether ligand L-Br;
step B, co 2 Preparation of L-Br: dissolving aza-hole ether ligand L-Br in mixed solution of dichloromethane and absolute ethyl alcohol under inert atmosphere to obtain ligand solution, and adding Co (ClO 4 ) 2 ·6H 2 O is dissolved in absolute ethanol to obtain ethanol solution containing cobalt metal salt, the ethanol solution containing cobalt metal salt is dripped into ligand solution, and Co is obtained through stirring, centrifugation, filtration, washing and drying 2 L-Br；
Step C, binuclear cobalt Polymer Co 2 Preparation of L-P: co is to be 2 Uniformly dispersing L-Br, 4' -diacetylene biphenyl, tetra (triphenylphosphine) palladium, N-dimethylformamide and triethylamine by ultrasonic, heating and refluxing to react under inert atmosphere, cooling the reaction mixture to room temperature, washing and drying to obtain the dinuclear cobalt polymer Co 2 L-P。
Further, in the step A, the molar ratio of the tri (2-amino ethyl) amine, the 5-bromoisophthalaldehyde and the sodium borohydride is 2:3:30.
Further, in the step A, the vacuum drying temperature is 50 ℃, the vacuum drying time is 12h, the volume ratio of the dichloromethane to the anhydrous methanol in the mixed solution of the dichloromethane and the anhydrous methanol is 1:1, the heating reflux reaction temperature is 50 ℃, the reaction time is 24h, and the rotary evaporation temperature is 35 ℃.
Further, the aza-hole ether ligands L-Br and Co (ClO) in step B 4 ) 2 ·6H 2 The mass ratio of O is 200:232.
further, in the step B, the volume ratio of the dichloromethane to the absolute ethyl alcohol in the mixed solution of the dichloromethane and the absolute ethyl alcohol is 18:80, the stirring time is 30min, the drying temperature is 60 ℃, and the drying time is 24h.
Further, co in step C 2 The dosage ratio of L-Br, 4' -diacetylene biphenyl, tetra (triphenylphosphine) palladium, N-dimethylformamide and triethylamine is 60mg:12.52mg:21.46mg:10mL:13.3mL.
Further, in the step C, the heating reflux reaction temperature is 120 ℃, the reaction time is 24 hours, the drying temperature is 40 ℃, and the drying time is 24 hours.
Further, the method comprises the following steps:
step A, 1g of tris (2-aminoethyl) amine was dissolved in 100mL of anhydrous methanol under argon atmosphere and slowly added to 200mL of an anhydrous methanol solution containing 2.22g of 5-bromoisophthalaldehyde over one hour. After stirring the mixed solution at room temperature for 24 hours, a pale yellow precipitate is obtained; centrifuging the pale yellow precipitate, washing with anhydrous methanol for three times in a centrifugal manner, and vacuum drying at 50deg.C for 12 hr; dissolving the pale yellow precipitate in a mixed solution of dichloromethane and anhydrous methanol in a ratio of 1:1, cooling to 0 ℃ in an ice-water bath, adding 114mmol of sodium borohydride in batches, stirring for 12 hours at room temperature under argon atmosphere, heating to 50 ℃ and refluxing for 24 hours at the temperature, cooling the reaction solution to room temperature, injecting into a separating funnel, adding 100mL of deionized water into the separating funnel, extracting three times with 100mL of dichloromethane, drying and filtering an organic phase by anhydrous magnesium sulfate, and removing the solution by rotary evaporation at 35 ℃ to obtain aza-hole ether ligand L-Br;
step B, under argon atmosphere, aza-hole ether ligandL-Br was dissolved in a mixed solution of 18mL of methylene chloride and 80mL of absolute ethanol to obtain a ligand solution, and an argon atmosphere was maintained for 15 minutes, and 200mg of Co (ClO) 4 ) 2 ·6H 2 O is dissolved in 3mL of absolute ethyl alcohol to obtain ethanol solution containing cobalt metal salt, the ethanol solution containing cobalt metal salt is slowly dripped into the ligand solution, the mixture is stirred for 30 minutes at room temperature, the green precipitate is centrifugally filtered, and is respectively washed three times with absolute ethyl alcohol and diethyl ether, and vacuum-dried for 24 hours at 60 ℃ to obtain Co 2 L-Br；
Step C, 60mg Co 2 L-Br, 12.52mg of 4,4' -diacetylene biphenyl and 21.46mg of tetra (triphenylphosphine) palladium are placed in a reaction vessel, 10mL of N, N-dimethylformamide and 13.3mL of triethylamine are sequentially added into the reaction vessel, and the solid powder is completely dissolved by ultrasonic treatment; repeatedly pumping air and backfilling argon gas for three times in a liquid nitrogen environment, completely replacing air in the reaction vessel, keeping the atmosphere of the argon gas, heating the mixture in the reaction vessel to 120 ℃ and refluxing for 24 hours, cooling the reaction mixture to room temperature, respectively washing the mixture with N, N-dimethylformamide and anhydrous methanol, and vacuum drying at 40 ℃ for 24 hours to obtain the binuclear cobalt polymer Co 2 L-P。
Use of a dinuclear cobalt heterogeneous catalyst according to any of the preceding claims in the field of photocatalysis.
The binuclear cobalt heterogeneous catalyst of the invention mainly has a block structure. The catalyst mainly consists of Co 2 L-Br and 4,4 '-diacetylene biphenyl are synthesized through Sonogashira Coupling reaction, and the L-Br and the 4,4' -diacetylene biphenyl are linked through a covalent bond.
The binuclear cobalt heterogeneous catalyst of the invention can be used as a photocatalyst, especially as a catalyst for photocatalytic carbon dioxide reduction, such as in CH 3 CN/H 2 The main reduction products of O systems are CO and H 2 。
Compared with the prior art, the binuclear cobalt heterogeneous catalyst has the following advantages:
the binuclear cobalt heterogeneous catalyst uses Co 2 L-Br and 4,4' -diacetylene biphenyl are used as precursors, and are obtained through Sonogashira Coupling reaction, and the catalyst has excellent propertiesRaw CO 2 The capacity of CO is up to 1063mmol/g/h, and compared with the prior art, the binuclear cobalt heterogeneous catalyst has excellent photocatalytic performance and is favorable for recycling the catalyst, has commercial application value and is expected to become a universal and convenient method for solidifying the homogeneous catalyst.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is a schematic diagram of Co according to an embodiment of the present invention 2 A synthetic route schematic of the L-P catalyst;
FIG. 2 is a graph of Co according to an embodiment of the present invention 2 Powder X-ray diffraction pattern of L-P catalyst;
FIG. 3 is a graph of Co according to an embodiment of the present invention 2 Fourier transform infrared spectrum schematic of L-P catalyst;
FIG. 4 is a graph of Co according to an embodiment of the present invention 2 A schematic of the raman spectrum of the L-P catalyst;
FIG. 5 is a graph of Co according to an embodiment of the present invention 2 Ultra-high resolution field emission scanning electron microscope (FETS) schematic diagram of L-P catalyst, wherein (a) is catalyst Co 2 L-P high resolution scanning electron microscope schematic diagram, (b-e) is Co 2 An energy dispersive X-ray spectroscopy schematic of L-P;
FIG. 6 is a graph of Co according to an embodiment of the present invention 2 L-P catalyst photo-reduction of CO 2 The product is schematically shown as a function of time.
Detailed Description
It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be described in detail below with reference to the drawings in connection with embodiments.
The preparation method of the binuclear cobalt heterogeneous catalyst comprises the following steps:
step A, 1g of tris (2-aminoethyl) amine was dissolved in 100mL of anhydrous methanol under argon atmosphere and slowly added to 200mL of an anhydrous methanol solution containing 2.22g of 5-bromoisophthalaldehyde over one hour. After stirring the mixed solution at room temperature for 24 hours, a pale yellow precipitate is obtained; centrifuging the pale yellow precipitate, washing with anhydrous methanol for three times in a centrifugal manner, and vacuum drying at 50deg.C for 12 hr; dissolving the pale yellow precipitate in a mixed solution of dichloromethane and anhydrous methanol in a ratio of 1:1, cooling to 0 ℃ in an ice-water bath, adding 114mmol of sodium borohydride in batches, stirring for 12 hours at room temperature under argon atmosphere, heating to 50 ℃ and refluxing for 24 hours at the temperature, cooling the reaction solution to room temperature, injecting into a separating funnel, adding 100mL of deionized water into the separating funnel, extracting three times with 100mL of dichloromethane, drying and filtering an organic phase by anhydrous magnesium sulfate, removing the solution by rotary evaporation at 35 ℃ to obtain aza-hole ether ligand L-Br, and obtaining the yield: 83%;
step B, dissolving aza-hole ether ligand L-Br in a mixed solution of 18mL of dichloromethane and 80mL of absolute ethyl alcohol under argon atmosphere to obtain ligand solution, maintaining the argon atmosphere for 15 minutes, and weighing 200mg of Co (ClO) 4 ) 2 ·6H 2 O is dissolved in 3mL of absolute ethyl alcohol to obtain ethanol solution containing cobalt metal salt, the ethanol solution containing cobalt metal salt is slowly dripped into the ligand solution, the mixture is stirred for 30 minutes at room temperature, the green precipitate is centrifugally filtered, and is respectively washed three times with absolute ethyl alcohol and diethyl ether, and vacuum-dried for 24 hours at 60 ℃ to obtain Co 2 L-Br, yield: 97%;
step C, 60mg Co 2 L-Br, 12.52mg of 4,4' -diacetylene biphenyl and 21.46mg of tetra (triphenylphosphine) palladium are placed in a reaction vessel, 10mL of N, N-dimethylformamide and 13.3mL of triethylamine are sequentially added into the reaction vessel, and the solid powder is completely dissolved by ultrasonic treatment; repeatedly pumping air and backfilling argon gas for three times in a liquid nitrogen environment, completely replacing air in the reaction vessel, keeping the atmosphere of the argon gas, heating the mixture in the reaction vessel to 120 ℃ and refluxing for 24 hours, cooling the reaction mixture to room temperature, respectively washing the mixture with N, N-dimethylformamide and anhydrous methanol, and vacuum drying at 40 ℃ for 24 hours to obtain the binuclear cobalt polymer Co 2 L-P was produced in a yield of 95%.
Co prepared in the above example 2 Structural analysis is carried out on the L-P catalytic material, and the results shown in the figures 2-4 are obtained; co prepared in the above example 2 The L-P catalytic material was subjected to morphology analysis, resulting in the results shown in FIG. 5.
FIG. 2 is Co prepared in the above example 2 The powder X-ray diffraction pattern of the L-P catalyst is shown in FIG. 2: catalyst Co 2 L-P has no sharp diffraction peak, and only has one unobvious wrap peak, which indicates that the catalyst Co 2 L-P is an amorphous polymer.
FIG. 3 is Co prepared in the above example 2 The Fourier transform infrared spectrum of the L-P catalyst is shown in FIG. 3: reactant 4,4' -diacetylenyl biphenyl at 2106cm -1 Where there is a pronounced mono-substituted alkyne-C.ident.CH at 3273cm -1 There is a stretching vibration of ≡C-H, and the above two characteristic peaks are characteristic absorption peaks of terminal alkyne. And polymer Co 2 L-P has no characteristic absorption peak of terminal alkyne, and is only 2208cm -1 Shows a characteristic absorption peak of binary substituted alkyne-C≡C-at the position of (C), thus proving that the polymeric material Co 2 Successful synthesis of L-P.
FIG. 4 is Co prepared in the above example 2 The raman spectrum of the L-P catalyst is shown in fig. 4: catalyst Co 2 L-P at 2207cm -1 There is a more pronounced absorption peak, which corresponds to-C.ident.C-acetylenes in the polymer, providing further evidence for the successful preparation of the polymer Co 2L-P.
FIG. 5 is Co prepared in the above example 2 The ultra-high resolution field emission scanning electron microscope image of the L-P catalyst is shown in FIG. 5: FIG. (a) is a catalyst Co 2 L-P high resolution scanning electron microscope image, from which it can be seen that the polymer exhibits a blocky morphology. In addition, in order to explore the corresponding distribution of each element, the catalyst Co is prepared by 2 L-P was subjected to energy dispersive X-ray spectroscopy to determine the elemental distribution, as shown in figures (b-e). The results show that C, N, O and Co elements are in polymer Co 2 Evenly distributed in the L-P.
Application examples
Catalyst Co was placed in a 16mL quartz tube 2 L-P (1 mg/L) was treated with BIH (0.025M) as a sacrificial agent, [ Ru (phen) )3 ](P F6 ) 2 (0.4 mM) as photosensitizer in 5mL CH 3 CN/H 2 O (v/v=4:1) mixed solvent was used as a system solution, and 300 mW.cm was used for light intensity -2 The intensity xenon lamp (lambda is more than or equal to 420 nm) is used as an irradiation light source, and the temperature of the space where the quartz tube is positioned is kept at about 25 ℃ in the catalysis process, and the illumination is carried out for 2 hours. Introducing high-purity CO into the quartz tube for 30 minutes before the catalytic reaction starts 2 The purpose of the gas or Ar gas was to purge the air in the reaction tube, and after the reaction was completed, the gas produced by the experiment was analyzed by GC to detect a gas phase product, as shown in FIG. 6.
As can be seen from fig. 6: when the catalyst Co 2 The content of L-P is 1 mg.L -1 At the time, photocatalytic CO after 2 hours 2 The rate of CO reduction is 1063 mmol.g -1 ·h -1 The selectivity to CO was 94.9%. Meanwhile, the liquid phase product was not detected by ion chromatography, and the yield of CO did not substantially rise after 2 hours.
At present, a heterogeneous catalyst (CO-ZIF-8) is used for photocatalytic reduction of CO 2 The highest production rate of CO is 748 mmol.g -1 ·h -1 The CO selectivity is 74%, co under the conditions of laboratory light source and natural sunlight 2 L-P has higher CO 2 Photo-reduction catalytic performance. Co (Co) 2 This high photocatalytic performance of L-P is attributed to its large pore size, which facilitates encapsulation of the photosensitizer to accelerate the transfer of electrons from the photosensitizer to the catalytic center. The method has the advantages of simple process, convenient operation and higher yield, can obtain heterogeneous catalyst materials with higher activity and selectivity, and is hopeful to become a universal and convenient method for solidifying homogeneous catalyst.

Claims (9)

1. The preparation method of the binuclear cobalt heterogeneous catalyst is characterized by comprising the following steps of:
step A, preparing aza-hole ether ligand L-Br: adding an anhydrous methanol solution of tris (2-aminoethyl) amine into an anhydrous methanol solution containing 5-bromoisophthalaldehyde under inert atmosphere, stirring to obtain a pale yellow precipitate, centrifuging, washing, drying in vacuum, dissolving the dried pale yellow precipitate into a mixed solution of dichloromethane and the anhydrous methanol, stirring in an ice-water bath under inert atmosphere, adding sodium borohydride in batches, heating for reflux reaction, cooling the reaction solution to room temperature, injecting deionized water into a separating funnel, extracting with dichloromethane, drying an organic phase, filtering, and spin-evaporating the filtrate to obtain an aza-hole ether ligand L-Br;
step B, co 2 Preparation of L-Br: dissolving aza-hole ether ligand L-Br in mixed solution of dichloromethane and absolute ethyl alcohol under inert atmosphere to obtain ligand solution, and adding Co (ClO 4 ) 2 ·6H 2 O is dissolved in absolute ethanol to obtain ethanol solution containing cobalt metal salt, the ethanol solution containing cobalt metal salt is dripped into ligand solution, and Co is obtained through stirring, centrifugation, filtration, washing and drying 2 L-Br；
Step C, binuclear cobalt Polymer Co 2 Preparation of L-P: co is to be 2 Uniformly dispersing L-Br, 4' -diacetylene biphenyl, tetra (triphenylphosphine) palladium, N-dimethylformamide and triethylamine by ultrasonic, heating and refluxing to react under inert atmosphere, cooling the reaction mixture to room temperature, washing and drying to obtain the dinuclear cobalt polymer Co 2 L-P。
2. The dinuclear cobalt heterogeneous catalyst according to claim 1, characterized in that: in the step A, the molar ratio of the tri (2-aminoethyl) amine to the 5-bromoisophthalaldehyde to the sodium borohydride is 2:3:30.
3. The dinuclear cobalt heterogeneous catalyst according to claim 1, characterized in that: in the step A, the vacuum drying temperature is 50 ℃, the vacuum drying time is 12h, the volume ratio of the dichloromethane to the anhydrous methanol in the mixed solution of the dichloromethane and the anhydrous methanol is 1:1, the heating reflux reaction temperature is 50 ℃, the reaction time is 24h, and the rotary steaming temperature is 35 ℃.
4. According to claim 1The binuclear cobalt heterogeneous catalyst is characterized in that: aza-hole ether ligands L-Br and Co (ClO) in step B 4 ) 2 ·6H 2 The mass ratio of O is 200:232.
5. the dinuclear cobalt heterogeneous catalyst according to claim 1, characterized in that: and B, mixing the mixed solution of the dichloromethane and the absolute ethyl alcohol in the volume ratio of the dichloromethane to the absolute ethyl alcohol in the step 18:80, stirring for 30min, and drying at 60 ℃ for 24h.
6. The dinuclear cobalt heterogeneous catalyst according to claim 1, characterized in that: co in step C 2 The dosage ratio of L-Br, 4' -diacetylene biphenyl, tetra (triphenylphosphine) palladium, N-dimethylformamide and triethylamine is 60mg:12.52mg:21.46mg:10mL:13.3mL.
7. The dinuclear cobalt heterogeneous catalyst according to claim 1, characterized in that: in the step C, the heating reflux reaction temperature is 120 ℃, the reaction time is 24 hours, the drying temperature is 40 ℃, and the drying time is 24 hours.
8. The dinuclear cobalt heterogeneous catalyst according to claim 1, comprising the steps of: step A, 1g of tris (2-aminoethyl) amine was dissolved in 100mL of anhydrous methanol under argon atmosphere and slowly added to 200mL of an anhydrous methanol solution containing 2.22g of 5-bromoisophthalaldehyde over one hour. After stirring the mixed solution at room temperature for 24 hours, a pale yellow precipitate is obtained; centrifuging the pale yellow precipitate, washing with anhydrous methanol for three times in a centrifugal manner, and vacuum drying at 50deg.C for 12 hr; dissolving the pale yellow precipitate in a mixed solution of dichloromethane and anhydrous methanol in a ratio of 1:1, cooling to 0 ℃ in an ice-water bath, adding 114mmol of sodium borohydride in batches, stirring for 12 hours at room temperature under argon atmosphere, heating to 50 ℃ and refluxing for 24 hours at the temperature, cooling the reaction solution to room temperature, injecting into a separating funnel, adding 100mL of deionized water into the separating funnel, extracting three times with 100mL of dichloromethane, drying and filtering an organic phase by anhydrous magnesium sulfate, and removing the solution by rotary evaporation at 35 ℃ to obtain aza-hole ether ligand L-Br;
step B, dissolving aza-hole ether ligand L-Br in a mixed solution of 18mL of dichloromethane and 80mL of absolute ethyl alcohol under argon atmosphere to obtain ligand solution, maintaining the argon atmosphere for 15 minutes, and weighing 200mg of Co (ClO) 4 ) 2 ·6H 2 O is dissolved in 3mL of absolute ethyl alcohol to obtain ethanol solution containing cobalt metal salt, the ethanol solution containing cobalt metal salt is slowly dripped into the ligand solution, the mixture is stirred for 30 minutes at room temperature, the green precipitate is centrifugally filtered, and is respectively washed three times with absolute ethyl alcohol and diethyl ether, and vacuum-dried for 24 hours at 60 ℃ to obtain Co 2 L-Br；
Step C, 60mg Co 2 L-Br, 12.52mg of 4,4' -diacetylene biphenyl and 21.46mg of tetra (triphenylphosphine) palladium are placed in a reaction vessel, 10mL of N, N-dimethylformamide and 13.3mL of triethylamine are sequentially added into the reaction vessel, and the solid powder is completely dissolved by ultrasonic treatment; repeatedly pumping air and backfilling argon gas for three times in a liquid nitrogen environment, completely replacing air in the reaction vessel, keeping the atmosphere of the argon gas, heating the mixture in the reaction vessel to 120 ℃ and refluxing for 24 hours, cooling the reaction mixture to room temperature, respectively washing the mixture with N, N-dimethylformamide and anhydrous methanol, and vacuum drying at 40 ℃ for 24 hours to obtain the binuclear cobalt polymer Co 2 L-P。
9. Use of a dinuclear cobalt heterogeneous catalyst according to any of claims 1 to 8 in the field of photocatalysis.
CN202311306486.7A 2023-10-10 2023-10-10 Binuclear cobalt heterogeneous catalyst Pending CN117384357A (en)

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