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CN114849785B - Preparation of triazine ring covalent organic framework material doped cobalt porphyrin photocatalyst - Google Patents

Preparation of triazine ring covalent organic framework material doped cobalt porphyrin photocatalyst Download PDF

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CN114849785B
CN114849785B CN202210626628.7A CN202210626628A CN114849785B CN 114849785 B CN114849785 B CN 114849785B CN 202210626628 A CN202210626628 A CN 202210626628A CN 114849785 B CN114849785 B CN 114849785B
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carbon dioxide
thfb
cof
photocatalyst
cobalt porphyrin
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CN114849785A (en
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张凤鸣
刘颜生
吴迪
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Harbin University of Science and Technology
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Harbin University of Science and Technology
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    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

A preparation method of a triazine ring covalent organic framework material doped cobalt porphyrin photocatalyst relates to a preparation method of a photocatalyst for reducing carbon dioxide into carbon monoxide. The invention aims to solve the problems that the existing covalent organic framework material is low in light absorption capacity as a carbon dioxide catalyst, low in reduction efficiency and low in sunlight utilization rate due to low utilization rate of carbon dioxide in the atmosphere, so that the reduction rate of the carbon dioxide by the photocatalyst is low. The method comprises the following steps: 1. preparing THFB-COF-2-Zn by using an organic solvent thermal method; 2. and uniformly mixing and dispersing cobalt porphyrin and the THFB-COF-2-Zn material by an ultrasonic oscillation dispersion method and an organic solvent thermal method to obtain the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst material. The carbon dioxide reduction photocatalyst material containing THFB-COF-2-Zn doped porphyrin cobalt prepared by the invention has the carbon dioxide reduction rate of up to 352.8 mu mol.g under the irradiation of 300W xenon lamp visible light ‑1 ～700μmol·g ‑1 . The invention can obtain the THFB-COF-2-Zn covalent organic framework material doped cobalt porphyrin carbon dioxide reduction photocatalyst material.

Description

Preparation of triazine ring covalent organic framework material doped cobalt porphyrin photocatalyst
Technical Field
The invention relates to a preparation method of a photocatalytic carbon dioxide reduction catalyst and a photocatalytic performance test.
Background
With the progress of human society and the development of industry, fossil energy such as coal, oil, and natural gas is widely developed and utilized, resulting in serious energy crisis and environmental crisis. The greenhouse effect problem is more and more serious, the carbon dioxide content in the atmosphere is newly created and high, and the physical health and living environment of people are seriously endangered. Converting carbon dioxide into energy to achieve green recycling of the energy is therefore considered to be the most desirable way to solve energy and environmental problems. Worldwide scholars report that the current method for converting carbon dioxide into energy mainly reduces the carbon dioxide into low-carbon energy through the action of a catalyst, and the conversion method is divided into three types of traditional catalysis, electrocatalytic and photocatalytic. Traditional catalytic reaction conditions are harsh, and a large amount of heat energy needs to be provided; the electrocatalytic reaction conditions are mild but still require the provision of electrical energy. The photocatalysis, namely, the solar energy is taken as reaction power, carbon dioxide is reduced under the action of a catalyst, and the process simulates photosynthesis of green plants, so that the photocatalysis is considered to be the most ideal carbon dioxide conversion and utilization way. Traditional photocatalysts such as titanium dioxide, cadmium sulfide, zinc oxide and other materials, and have small specific surface area and lightElectron-hole generation is easy to be combined, is easy to be corroded by light and has low utilization rate of visible light, thereby leading to CO thereof 2 The reduction efficiency is low. The ideal photocatalyst has the requirements of large specific surface area, difficult recombination of photo-generated electrons and holes, high utilization rate of visible light, difficult photo-corrosion and the like.
The phthalocyanine series is a powerful candidate material and has been widely studied. In particular, cobalt porphyrin has an effect of promoting electron transfer and carbon dioxide adsorption because of its effect. Cobalt porphyrin, however, tends to agglomerate, thereby reducing surface area and high photoinduced electron, hole recombination rates. To solve these problems, it is desirable to limit agglomeration of cobalt porphyrin particles, thereby increasing the photocatalytic activity of the cobalt porphyrin particles. Covalent Organic Frameworks (COFs) are a novel network-like structure of zeolite-like materials formed by self-assembly with organic ligands. COFs have been used in a number of different fields such as gas separation and storage, catalysis, chemical sensing and fluorescent materials. The covalent organic framework material (Covalent Organic Frameworks) is a crystalline porous material formed by carrying out reversible reaction polymerization through thermodynamic control by connecting light elements such as C, B, O, N and Si through strong covalent bonds. The photocatalyst has the advantages of light weight, low density, high specific surface area, regular and uniform pore canal, relatively stable structure, strong pi-pi effect in the lamellar layer, strong light absorption and utilization capability, easiness in functional modification, various construction primitives and the like, and is considered to be an ideal photocatalyst. THFB-COF-2-Zn is considered as a very potential complex carrier. Therefore, we propose to dope cobalt porphyrin into THFB-COF-2-Zn pore canal by stirring method, and utilize limited space provided by COFs pore canal as a microreactor to limit agglomeration of cobalt porphyrin particles, thereby improving photocatalytic activity of cobalt porphyrin particles.
The invention comprises the following steps:
the invention aims to solve the problem that the existing pure cobalt porphyrin photocatalyst is easy to agglomerate, so as to reduce the problems of surface area and high photo-generated electron and hole recombination rate, and provides a preparation method of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst.
The preparation method of the triazine ring covalent organic framework material doped porphyrin cobalt carbon dioxide reduction photocatalyst is completed according to the following steps:
dispersing dried and activated THFB-COF-2-Zn into tetrahydrofuran solution, ultrasonically dispersing on a numerical control ultrasonic cleaner with ultrasonic frequency of 30-50KHz for 30-60 min, transferring to a magnetic stirrer with stirring speed of 100-300 r/min for 1-5 h, adding cobalt porphyrin solid powder, continuously stirring for 1-2 h, uniformly mixing the solution, and heating at 60 ℃ for 10-12 h; filtering to obtain a precipitate, washing the precipitate with tetrahydrofuran for 2-3 times, washing the precipitate with absolute ethyl alcohol for 2-3 times, and vacuum drying at 50-70 ℃ for 6-8 hours to obtain a crude product of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst; placing the crude product into a Shi Langke pipe, adding the crude product into mesitylene, keeping the temperature at 100-120 ℃ for 18-24 h, and naturally cooling to room temperature; centrifuging to obtain a precipitate, washing the precipitate with tetrahydrofuran for 1-2 times, and washing the precipitate with absolute ethyl alcohol for 1-2 times; and (3) vacuum drying the washed precipitate for 6-8 hours at the temperature of 50-70 ℃ to obtain the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst.
The volume ratio of the dry and activated THFB-COF-2-Zn to tetrahydrofuran in the first step is 1mg:0.05 mL-1 mg:1.5mL;
the mass ratio of the dried and activated THFB-COF-2-Zn to the added cobalt porphyrin is 100mg:10 mg-100 mg:20mg;
in the first step, the volume ratio of the mass of the crude product doped with cobalt porphyrin to mesitylene is 1mg:0.05 mL-1 mg:0.5mL.
In order to examine the catalytic carbon dioxide reduction effect of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst material under visible light, the visible light carbon dioxide reduction performance of the material is tested according to the following method, and the test process is as follows: placing the prepared composite catalyst film in self-made photocatalytic gas-solid phase CO 2 And adding 0.2mL of distilled water into the reduction reactor, and ensuring that the distilled water does not touch the composite catalyst film in the photocatalytic reaction process. Introducing steam and CO into the system 2 The system was turned off after 30 minutes to remove air, the light source was turned on, and samples were taken at 1 hour intervals under light conditions, and analyzed by a gas chromatograph (GC 112A) for a total of 5 hours.
The invention has the beneficial effects that:
according to the invention, the tetrahydrofuran solution is used for doping cobalt porphyrin into the THFB-COF-2-Zn pore canal, the pore canal with limited space provided by the THFB-COF-2-Zn pore canal is used as a microreactor for limiting the agglomeration of cobalt porphyrin particles, and the photo-corrosion phenomenon of the cobalt porphyrin particles is lightened to a certain extent due to the wrapping effect of the THFB-COF-2-Zn, so that the photo-catalytic activity of the cobalt porphyrin particles is comprehensively improved. The THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst prepared by the invention performs photocatalytic carbon dioxide reduction reaction under the irradiation of a 300W xenon lamp. The THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst prepared by the invention can reach the carbon monoxide production rate of 352.8 mu mol g < -1 > -700 mu mol g under the irradiation of a 300W xenon lamp -1 。
Drawings
FIG. 1 is an X-ray powder diffraction diagram of a THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst material;
FIG. 2 is a bar graph of the visible light photocatalytic carbon dioxide reduction rate of a THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst material.
FIG. 3 is a plot of the visible light photocatalytic carbon dioxide reduction rate for a THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst material.
Detailed Description
The present invention will be described in more detail with reference to specific examples.
Example 1: the preparation method of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst in the embodiment is completed according to the following steps:
step one, 1,3, 5-triazine-2, 4, 6-tris (4 '-hydroxy-5' -formylphenyl) benzene (THFB) is weighed and added into a Shi Langke vacuum tube, then 2ml of mesitylene is added into the tube, the tube is closed and then ultrasonic treatment is carried out until the THFB is uniformly mixed in the mesitylene systemNo large particles; weighing (1R, 2R) - (-) -1, 2-cyclohexanediamine, placing in another beaker, adding 2mL ethanol, dissolving completely by ultrasound, adding Zn (ClO) 4 ) 2 ·6H 2 O, the white flocculent precipitate produced is a complex of cyclohexanediamine and zinc perchlorate. The white precipitate was added to a Shi Langke vacuum tube and ultrasound continued until the system was homogeneous. Then adding aqueous acetic acid solution into the phase reaction system, shaking a vacuum tube to uniformly mix the acid, naturally cooling the mixture through three times of cooling, degassing and melting in a liquid nitrogen bath, placing the mixture in an oven which naturally heats to 120 ℃ for standing reaction, closing the oven after 72 hours to naturally cool the mixture to room temperature, and collecting solid obtained by filtration.
And step two, carrying out rope extraction on 0.25g of THFB-COF-2-Zn solid obtained in the step one by using an N, N-dimethylformamide solvent until effluent liquid is colorless, and finally carrying out rope extraction by using methanol for 8 hours and then carrying out vacuum drying treatment for 10 hours. And (3) soaking the dried solid in ethanol for 12 hours, replacing the ethanol for multiple times, and finally placing the obtained solid in a vacuum drying oven at 100 ℃ for 12 hours to obtain 100mg of dried and activated THFB-COF-2-Zn yellow powder solid.
Dispersing 100mg of the dried and activated THFB-COF-2-Zn in the step two into tetrahydrofuran solution, ultrasonically dispersing for 30-60 min, and then transferring to a magnetic stirrer to stir for 1-5 h at a stirring speed of 100-300 r/min; adding cobalt porphyrin solid powder, continuously stirring for 1-2 h, and heating at 60 ℃ for continuously stirring for 10-12 h when the solution is uniformly mixed; filtering to obtain a precipitate, washing the precipitate with tetrahydrofuran for 2-3 times, washing the precipitate with absolute ethyl alcohol for 2-3 times, and vacuum drying at 50-70 ℃ for 6-8 hours to obtain a crude product of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst;
step four, placing 80mg of the crude product of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst obtained in the step three into a Shi Langke pipe, adding the crude product to the raw product, keeping the temperature at 100-120 ℃ for 18-24 h, and naturally cooling the raw product to room temperature; centrifuging to obtain a precipitate, washing the precipitate with tetrahydrofuran for 1-2 times, and washing the precipitate with absolute ethyl alcohol for 1-2 times; vacuum drying the washed precipitate at 50-70 deg.c for 6-8 hr to obtain THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reducing photocatalyst;
characterization and performance detection of THFB-COF-2-Zn/cobalt porphyrin composite photocatalyst:
FIG. 1 is a graph showing comparison of reduction rates of visible light photocatalytic carbon dioxide for THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst materials with different contents obtained in example 1, and is obtained as shown in FIG. 1. The maximum average carbon monoxide production rate of the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst material prepared by the invention can reach 692.2 mu mol.g -1 。
FIG. 2 is a graph showing the comparison of the carbon dioxide reduction rate of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst material shown in FIG. 2, wherein the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst material obtained in example 1 is subjected to visible light photocatalytic carbon dioxide reduction for 5 hours. The maximum average carbon monoxide production rate of the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst material prepared by the invention can reach 692.2 mu mol.g -1 。
The THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst material obtained by the embodiment has good photocatalytic carbon dioxide reduction capability, can reduce carbon dioxide by photocatalysis, and can be used as a photocatalyst.

Claims (1)

1. A preparation method of a THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst is characterized by comprising the following steps:
dispersing the dried and activated THFB-COF-2-Zn into tetrahydrofuran solution, ultrasonically dispersing for 30-60 min on a numerical control ultrasonic cleaner with ultrasonic frequency of 30-50kHz, transferring to a magnetic stirrer with stirring speed of 100-300 r/min for stirring for 1-5 h, adding cobalt porphyrin solid powder, continuously stirring for 1-2 h, heating at 60 ℃ for continuously stirring for 10-12 h after the solution is uniformly mixed; filtering to obtain a precipitate, washing the precipitate with tetrahydrofuran for 2-3 times, washing the precipitate with absolute ethyl alcohol for 2-3 times, and vacuum drying at 50-70 ℃ for 6-8 hours to obtain a crude product of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst; placing the crude product into a Shi Langke pipe, adding the crude product into mesitylene, keeping the temperature at 100-120 ℃ for 18-24 h, and naturally cooling to room temperature; centrifuging to obtain a precipitate, washing the precipitate with tetrahydrofuran for 1-2 times, and washing the precipitate with absolute ethyl alcohol for 1-2 times; vacuum drying the washed precipitate at 50-70 deg.c for 6-8 hr to obtain THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reducing photocatalyst;
the volume ratio of the dry and activated THFB-COF-2-Zn to tetrahydrofuran is 1mg:0.05 mL-1 mg:1.5mL;
the mass ratio of the dried and activated THFB-COF-2-Zn to the cobalt porphyrin is 100mg:10 mg-100 mg:20mg;
the volume ratio of the mass of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst crude product to the volume of mesitylene is 1mg:0.05 mL-1 mg:0.5mL.
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CN115739170B (en) * 2022-09-08 2024-04-26 福州大学 Photocatalytic degradation purifying material for organic pollutants and preparation method thereof
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106732796A (en) * 2016-12-05 2017-05-31 福州大学 A kind of efficiently reduction CO2Covalent organic polymer visible-light photocatalyst
CN107433205A (en) * 2016-05-25 2017-12-05 中国科学院大连化学物理研究所 Covalent organic frame load cobalt catalyst and its preparation and application
CN112480132A (en) * 2020-12-02 2021-03-12 哈尔滨理工大学 Preparation and application of covalent organic framework material based on Salen structure
CN112920357A (en) * 2021-01-27 2021-06-08 吉林大学 Porphyrin-based covalent organic framework material based on metal ion doping and preparation method and application thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020247466A1 (en) * 2019-06-03 2020-12-10 Steve Burkholder Plate valve four stroke head

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107433205A (en) * 2016-05-25 2017-12-05 中国科学院大连化学物理研究所 Covalent organic frame load cobalt catalyst and its preparation and application
CN106732796A (en) * 2016-12-05 2017-05-31 福州大学 A kind of efficiently reduction CO2Covalent organic polymer visible-light photocatalyst
CN112480132A (en) * 2020-12-02 2021-03-12 哈尔滨理工大学 Preparation and application of covalent organic framework material based on Salen structure
CN112920357A (en) * 2021-01-27 2021-06-08 吉林大学 Porphyrin-based covalent organic framework material based on metal ion doping and preparation method and application thereof

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