CN114849785A - 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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CN114849785A
CN114849785A CN202210626628.7A CN202210626628A CN114849785A CN 114849785 A CN114849785 A CN 114849785A CN 202210626628 A CN202210626628 A CN 202210626628A CN 114849785 A CN114849785 A CN 114849785A
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thfb
cof
carbon dioxide
cobalt
photocatalyst
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CN114849785B (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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    • 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
    • B01J35/39—
    • 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

Abstract

A preparation method of a triazine ring covalent organic framework material doped with 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 and low in utilization rate of carbon dioxide in the atmosphere, so that the reduction efficiency is low, the sunlight utilization rate is low, and the reduction rate of the photocatalyst on the carbon dioxide is low. The method comprises the following steps: firstly, preparing THFB-COF-2-Zn by an organic solvothermal method; and secondly, uniformly mixing and dispersing the porphyrin cobalt and the THFB-COF-2-Zn material by an ultrasonic oscillation dispersion method and an organic solvothermal method to obtain the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst material. The THFB-COF-2-Zn doped porphyrin cobalt-containing carbon dioxide reduction photocatalyst material prepared by the invention is produced by carbon dioxide reduction under the irradiation of visible light of a 300W xenon lampThe highest carbon monoxide speed can reach 352.8 mu mol g ‑1 ～700μmol·g ‑1 . The invention can obtain the THFB-COF-2-Zn covalent organic framework material doped with the porphyrin cobalt 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, natural gas and the like is widely developed and utilized, resulting inSerious energy crisis and environmental crisis. Among them, the problem of greenhouse effect is getting more and more serious, and the content of carbon dioxide in the atmosphere is frequently innovative, which seriously harms the health and living environment of people. Therefore, conversion of carbon dioxide into energy to realize green recycling of energy is considered as the most ideal way to solve energy and environmental problems. The worldwide scholars dispute and 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, electrocatalysis and photocatalysis. The 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 supply of electrical energy. Photocatalysis takes solar energy as reaction power, reduces carbon dioxide under the action of a catalyst, and the process simulates photosynthesis of green plants, so that the photocatalysis is considered as an optimal carbon dioxide conversion and utilization way. The traditional photocatalysts such as titanium dioxide, cadmium sulfide, zinc oxide and other materials have small specific surface area, easy recombination of photoproduction electron-hole, easy photo-corrosion and low utilization rate of visible light, thereby causing the CO of the traditional photocatalysts 2 The reduction efficiency is low. The ideal photocatalyst should have 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 is widely researched. In particular, cobalt porphyrin has the effect of promoting electron transfer and carbon dioxide adsorption. Cobalt porphyrin tends to agglomerate, however, reducing surface area and high photoinduced electron and hole recombination rates. To solve these problems, we hope to limit the agglomeration of porphyrin cobalt particles, thereby increasing the photocatalytic activity of the porphyrin cobalt particles. Covalent Organic Frameworks (COFs) are a new class of zeolitic materials with a network-like structure formed by self-assembly with organic ligands. Currently, COFs are used in many different fields, such as gas separation and storage, catalysis, chemical sensing, and fluorescent materials. Covalent Organic Frameworks (covalence Organic Frameworks) are crystalline porous materials formed by C, B, O, N, Si and other light elements which are connected through strong Covalent bonds and polymerized through a thermodynamically controlled reversible reaction. The photocatalyst has the advantages of light weight, low density, high specific surface area, regular and uniform pore channels, relatively stable structure, strong pi-pi action in the lamella, strong light absorption and utilization capacity, easy functional modification, various building elements and the like, and is considered to be an ideal photocatalyst. THFB-COF-2-Zn is considered to be a composite carrier with very development potential. Therefore, the stirring method is provided for doping the cobalt porphyrin into the THFB-COF-2-Zn pore channel, and the limited space provided by the COFs pore channel is used as a microreactor to limit the agglomeration of the cobalt porphyrin particles, so that the photocatalytic activity of the cobalt porphyrin particles is improved.
The invention content is as follows:
the invention aims to solve the problem that the existing pure cobalt porphyrin photocatalyst is easy to agglomerate, so that the problems of surface area and high recombination rate of photo-generated electrons and holes are reduced, and provides a preparation method of a 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 a tetrahydrofuran solution, performing ultrasonic dispersion on a numerical control ultrasonic cleaner with the ultrasonic frequency of 30-50KHz for 30-60 min, transferring the solution to a magnetic stirrer with the stirring speed of 100-300 r/min, stirring the solution for 1-5 h, adding cobalt porphyrin solid powder, continuing stirring for 1-2 h, and heating the solution at 60 ℃ for continuously stirring for 10-12 h after the solution is uniformly mixed; carrying out suction filtration to obtain a precipitate, washing the precipitate for 2 to 3 times by tetrahydrofuran, then washing the precipitate for 2 to 3 times by absolute ethyl alcohol, and carrying out vacuum drying at the temperature of between 50 and 70 ℃ for 6 to 8 hours to obtain a THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst crude product; placing the crude product into a Schlenk tube, adding the crude product into mesitylene, keeping the temperature of the mesitylene at 100-120 ℃ for 18-24 h, and naturally cooling the mixture to room temperature; centrifuging to obtain a precipitate, washing the precipitate for 1 to 2 times by tetrahydrofuran, and then washing the precipitate for 1 to 2 times by absolute ethyl alcohol; and (3) drying the washed precipitate in vacuum at the temperature of 50-70 ℃ for 6-8 h to obtain the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst.
The ratio of the mass of the dried and activated THFB-COF-2-Zn to the volume of the tetrahydrofuran in the step one is 1mg:0.05 mL-1 mg:1.5 mL;
in the first step, the volume ratio of the dried and activated THFB-COF-2-Zn to the added cobalt porphyrin is 100mg:10 mg-100 mg:20 mg;
in the first step, the volume ratio of the mass of the crude product doped with the porphyrin cobalt to the mesitylene is 1mg:0.05 mL-1 mg:0.5 mL.
In order to investigate the effect of the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst material on catalyzing the reduction of carbon dioxide under visible light, the reduction performance of the visible light carbon dioxide is tested according to the following method, and the test process is as follows: placing the prepared composite catalyst film in a self-made photocatalytic gas-solid phase CO 2 And 0.2mL of distilled water is added into the reduction reactor, and the distilled water is ensured not to touch the composite catalyst film in the photocatalytic reaction process. Introducing steam and CO into the system 2 Air is removed, the system is closed after 30 minutes, sampling is carried out every 1 hour under the illumination condition after a light source is turned on, analysis is carried out by a gas chromatograph (GC112A), and the reaction time is 5 hours in total.
The invention has the beneficial effects that:
according to the invention, a tetrahydrofuran solution is used for doping porphyrin cobalt into a THFB-COF-2-Zn pore channel, the pore channel of a limited space provided by the THFB-COF-2-Zn pore channel is used as a microreactor to limit the agglomeration of porphyrin cobalt particles, and the light corrosion phenomenon of the porphyrin cobalt particles is relieved to a certain extent due to the wrapping effect of the THFB-COF-2-Zn, so that the light catalytic activity of the porphyrin cobalt 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 a carbon monoxide generation 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 pattern of THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst material;
FIG. 2 is a bar graph of the visible light photocatalytic carbon dioxide reduction rate of the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst material.
FIG. 3 is a point line graph of the visible light photocatalytic carbon dioxide reduction rate of the THFB-COF-2-Zn doped porphyrin cobalt 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 porphyrin cobalt carbon dioxide reduction photocatalyst of the embodiment is completed according to the following steps:
step one, weighing 1,3, 5-triazine-2, 4, 6-tris (4 '-hydroxy-5' -formylphenyl) benzene (THFB) and adding the THFB into a Schlenk vacuum tube, then adding 2ml of mesitylene into the tube, sealing the tube and carrying out ultrasonic treatment until the THFB is uniformly mixed in a mesitylene system and has no large particles; weighing (1R,2R) - (-) -1, 2-cyclohexanediamine, placing in another beaker, adding 2mL ethanol, performing ultrasonic treatment to dissolve completely, and 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 Schlenk vacuum tube and sonication continued until the system was homogeneous. Adding acetic acid aqueous solution into a subsequent phase reaction system, shaking a vacuum tube to uniformly mix acid, performing freeze-degasification-melting circulation in a liquid nitrogen bath for three times, naturally cooling, placing in an oven naturally heated to 120 ℃, standing for reaction, closing the oven after 72 hours to naturally cool the oven to room temperature, and collecting the solid obtained by filtering.
And step two, extracting 0.25g of THFB-COF-2-Zn solid obtained in the step one by using an N, N dimethylformamide solvent until effluent is colorless, and finally extracting by using methanol for 8 hours and then carrying out vacuum drying treatment for 10 hours. Drying, soaking in ethanol for 12 hr while replacing ethanol for several times, and vacuum drying at 100 deg.C for 12 hr to obtain 100mg dried and activated THFB-COF-2-Zn yellow powder solid.
Step three, dispersing 100mg of dried and activated THFB-COF-2-Zn in the step two into a tetrahydrofuran solution, ultrasonically dispersing for 30-60 min, transferring to a magnetic stirrer, and stirring for 1-5 h at a stirring speed of 100-300 r/min; then adding porphyrin cobalt solid powder, continuously stirring for 1-2 h, heating at 60 ℃ and continuously stirring for 10-12 h when the solution is uniformly mixed; carrying out suction filtration to obtain a precipitate, washing the precipitate for 2 to 3 times by tetrahydrofuran, then washing the precipitate for 2 to 3 times by absolute ethyl alcohol, and carrying out vacuum drying at the temperature of between 50 and 70 ℃ for 6 to 8 hours to obtain a THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst crude product;
step four, placing the 80mg THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst crude product obtained in the step three into a Schlenk tube, adding the crude product, keeping the temperature at 100-120 ℃ for 18-24 h, and naturally cooling to room temperature; centrifuging to obtain a precipitate, washing the precipitate for 1 to 2 times by tetrahydrofuran, and then washing the precipitate for 1 to 2 times by absolute ethyl alcohol; drying the washed precipitate in vacuum at 50-70 ℃ for 6-8 h to obtain the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst;
characterization and performance detection of the THFB-COF-2-Zn/cobalt porphyrin composite material photocatalyst:
FIG. 1 is a graph showing the comparison of the carbon dioxide reduction rates of THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst materials with different contents obtained in example 1, and the comparison of the carbon dioxide reduction rates of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst materials shown in FIG. 1 is obtained. The maximum average carbon monoxide generation 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 shows the total yield data of THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst materials with different contents obtained in example 1 after visible light photocatalytic carbon dioxide reduction for 5h, and a carbon dioxide reduction rate comparison graph of the THFB-COF-2-Zn doped cobalt porphyrin carbon dioxide reduction photocatalyst materials shown in FIG. 2 is obtained. The maximum average carbon monoxide generation 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 in the specific example has good photocatalytic carbon dioxide reduction capability, can be used for photocatalytic carbon dioxide reduction, and can be used as a photocatalyst.

Claims (7)

1. A preparation method of a triazine ring covalent organic framework material doped porphyrin cobalt photocatalyst is characterized by comprising the following steps:
dispersing dried and activated THFB-COF-2-Zn into a tetrahydrofuran solution, performing ultrasonic dispersion on a numerical control ultrasonic cleaner with the ultrasonic frequency of 30-50KHz for 30-60 min, transferring the mixture to a magnetic stirrer with the stirring speed of 100-300 r/min, stirring the mixture for 1-5 h, adding cobalt phthalocyanine solid powder, continuing stirring for 1-2 h, and heating the mixture at 60 ℃ for continuously stirring for 10-12 h after the solution is uniformly mixed; carrying out suction filtration to obtain a precipitate, washing the precipitate for 2 to 3 times by tetrahydrofuran, then washing the precipitate for 2 to 3 times by absolute ethyl alcohol, and carrying out vacuum drying at the temperature of between 50 and 70 ℃ for 6 to 8 hours to obtain a THFB-COF-2-Zn supported cobalt phthalocyanine carbon dioxide reduction photocatalyst crude product; placing the crude product into a Schlenk tube, adding the crude product into mesitylene, keeping the temperature of the mixture at 100-120 ℃ for 18-24 h, and naturally cooling the mixture to room temperature; centrifuging to obtain a precipitate, washing the precipitate for 1 to 2 times by tetrahydrofuran, and then washing the precipitate for 1 to 2 times by absolute ethyl alcohol; and (3) drying the washed precipitate in vacuum at the temperature of 50-70 ℃ for 6-8 h to obtain the THFB-COF-2-Zn supported cobalt phthalocyanine carbon dioxide reduction photocatalyst.
The ratio of the mass of the dried and activated THFB-COF-2-Zn to the volume of the tetrahydrofuran in the step one is 1mg:0.05 mL-1 mg:1.5 mL;
in the first step, the volume ratio of the dried and activated THFB-COF-2-Zn to the added cobalt phthalocyanine is 100mg:10 mg-100 mg:20 mg;
the volume ratio of the mass of the crude product loaded with cobalt phthalocyanine to mesitylene in the first step is 1mg:0.05 mL-1 mg:0.5 mL.
2. The method for preparing THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst according to claim 1, wherein the reaction solvent in the step one is tetrahydrofuran solution.
3. The preparation method of the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst according to claim 1, wherein the volume ratio of the dried and activated THFB-COF-2-Zn to tetrahydrofuran is 1mg:0.05 mL-1 mg:1.5 mL.
4. The preparation method of the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst as claimed in claim 1, wherein the volume ratio of the dried and activated THFB-COF-2-Zn to the added porphyrin cobalt is 100mg:10 mg-100 mg:20 mg.
5. The preparation method of the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst as claimed in claim 1, wherein the heating temperature of the Schlenk tube is 100-120 ℃, and the reaction time is 18-24 h.
6. The method of claim 1, wherein the crude product of the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst is mesitylene as a reaction solvent in a Schlenk tube.
7. The preparation method of the THFB-COF-2-Zn doped porphyrin cobalt carbon dioxide reduction photocatalyst as claimed in claim 1, wherein the volume ratio of the mass of the crude product doped with porphyrin cobalt to mesitylene is 1mg:0.05 mL-1 mg:0.5 mL.
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CN115634717A (en) * 2022-10-31 2023-01-24 江南大学 Bimetallic COF-CdS composite photocatalyst for photocatalytic decomposition of water to produce hydrogen and preparation method thereof
CN115739170A (en) * 2022-09-08 2023-03-07 福州大学 Photocatalytic degradation purification material for organic pollutants and preparation method thereof

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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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CN106732796A (en) * 2016-12-05 2017-05-31 福州大学 A kind of efficiently reduction CO2Covalent organic polymer visible-light photocatalyst
US20200376475A1 (en) * 2019-06-03 2020-12-03 University Of New Hampshire Selective carbon dioxide reduction catalyzed by single metal sites on carbon nitride under visible light irradiation
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CN115739170A (en) * 2022-09-08 2023-03-07 福州大学 Photocatalytic degradation purification material for organic pollutants and preparation method thereof
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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CN115634717B (en) * 2022-10-31 2024-04-30 江南大学 Bimetallic COF-CdS composite photocatalyst for photocatalytic decomposition of aquatic hydrogen and preparation method thereof

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