CN114985014A - Preparation method and application of Zn-atz @ COF-TD composite photocatalytic material - Google Patents
Preparation method and application of Zn-atz @ COF-TD composite photocatalytic material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 37
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- 238000000034 method Methods 0.000 claims abstract description 10
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- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
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- 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
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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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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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
- 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
- B01J35/396—Distribution of the active metal ingredient
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- 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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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the technical field of composite photocatalytic materials, and particularly relates to a preparation method and application of a Zn-atz @ COF-TD composite photocatalytic material. The catalytic material is a binary core-shell composite material, and is formed by wrapping a covalent organic framework COF-TD with a metal organic framework Zn-atz. The composite material is prepared by adopting a solvothermal method, wherein Zn-atz is subjected to aldehyde group formation, then is compounded with COF-TD through an imine bond, and is washed and dried to obtain a final material; the photocatalytic material prepared by the invention has better selectivity and visible light response capability, and still keeps stronger photocatalytic activity after multiple photocatalytic tests. The method has the advantages that no sacrificial agent is needed in the photocatalytic carbon dioxide reduction process, the method is green and environment-friendly, the problem of low photocatalytic carbon dioxide reduction efficiency caused by weak carbon dioxide adsorption capacity of the traditional photocatalyst is solved, and a new thought and a new method are provided for the research of the binary core-shell composite catalyst.
Description
Technical Field
The invention belongs to the technical field of composite photocatalytic materials, and particularly relates to a preparation method of a Zn-atz @ COF-TD composite photocatalytic material and application of the composite photocatalytic material in photocatalytic carbon dioxide reduction.
Background
Under the background of the strategic goals of carbon peak reaching and carbon neutralization, the method for efficiently converting carbon dioxide generated by the combustion of traditional fossil energy into a high-value-added chemical product which can be utilized becomes a problem to be solved urgently. Solar energy is a clean renewable energy source, and the main product carbon dioxide generated by combustion of fossil fuel is converted into hydrocarbon fuel with industrial value by using solar energy, so that the method not only accords with the environmental protection concept of green chemical industry, but also can further relieve the energy crisis caused by continuous exhaustion of the fossil fuel, and completely accords with the sustainable development strategy under the background of 'double carbon'.
Metal Organic Frameworks (MOFs) have great promise in gas adsorption and catalytic conversion due to their porous structure. The strategy for constructing porous structures is generally to select inorganic structural units as nodes, rigid organic bridging ligands as connectors, and various metal ions are usually chelated with organic structural units through coordination to form columnar or blocky framework structures. However, MOFs are generally accompanied by the disadvantage of poor stability, so it is very important to design a metal organic framework that can exist stably. Researches show that 3-amino-1, 2, 4-triazole (Atz) serving as a ligand can tend to form a robust network, and the interaction between a functionalized amino material and carbon dioxide molecules can improve the capture capacity of carbon dioxide gas. Zinc ions are widely used in photoelectrocatalysis due to their good conductivity and abundant storage capacity.
The triazine-based covalent organic backbone (COF-TD) is an organic semiconductor with a rigid structure and well-defined crystallinity. It has all the advantages of a covalent organic framework, such as: large specific surface area, easy structure adjustment, high chemical stability and the like. However, the limited light absorption range, the fast recombination rate of electron-hole pairs and the poor charge carrier transfer of the COFs materials limit the development of the COFs materials in the field of photocatalysis.
Disclosure of Invention
The invention aims to overcome the defects of low carbon dioxide capture capacity, narrow visible light absorption range and low charge carrier transfer rate of the existing photocatalytic material and prepare a core-shell type binary composite photocatalytic carbon dioxide reduction catalyst with high-efficiency catalytic capacity.
In order to solve the existing problems, the invention provides a preparation method of a Zn-atz @ COF-TD core-shell binary composite material. Through the covalently linked structural units, the composite material has good crystallinity and hierarchical porosity, and the synergistic effect of the MOFs and COFs composite material in heterogeneous catalysis is discussed. Divalent zinc ion salt, 3-amino-1, 2, 4-triazole and dicarboxylic acid compound are selected to synthesize a Zn-atz three-dimensional metal organic framework capable of stably existing in a polar solvent/deionized water mixed solution through solvent heat treatment; a COF-TD shell layer is constructed outside a Zn-atz core layer through an imine bond by a periodic organic building block 4,4 '-biphenyldicarboxaldehyde and 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine.
In order to achieve the technical purpose, the method comprises the following specific steps:
(1) preparing a metal organic framework Zn-atz;
mixing 3-amino-1, 2, 4-triazole, divalent zinc ion salt, dicarboxylic acid compound, polar solvent and water, adding into a hydrothermal kettle, ultrasonically dispersing uniformly, putting the hydrothermal kettle into an oven for hydrothermal reaction, centrifuging, washing and drying after the reaction to obtain white solid powder; is marked as Zn-atz material; the divalent zinc ion salt comprises basic zinc carbonate or zinc nitrate hexahydrate; the dicarboxylic acid compound comprises oxalic acid dihydrate, sodium bicarbonate or succinic acid; the polar solvent comprises methanol or N, N-dimethylformamide;
(2) preparing an aldehydized Zn-atz precursor;
firstly, mixing o-dichlorobenzene with ethanol to obtain an o-dichlorobenzene/ethanol mixed solution; then mixing the Zn-atz material prepared in the step (1) with a mixed solution of 4,4' -biphenyldicarboxaldehyde and o-dichlorobenzene/ethanol, adding acetic acid, marking the obtained solution as a mixed solution A, performing vacuum pumping treatment after the mixed solution A is uniformly dispersed by ultrasound, performing oil bath reaction under the stirring condition, naturally cooling to room temperature after the reaction, and then centrifuging, washing and drying to obtain an aldehyde Zn-atz precursor;
(3) preparation of Zn-atz @ COF-TD core-shell binary composite material (Zn-atz @ COF-TD is prepared by adopting a solvothermal method):
mixing the aldehydized Zn-atz precursor prepared in the step (2) with 4,4 '-biphenyldicarboxaldehyde, 4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine, mesitylene and 1, 4-dioxane, then adding acetic acid, ultrasonically dispersing uniformly, vacuumizing, placing in an oven for reaction for a period of time, centrifuging, washing and drying to obtain yellow powder, namely the Zn-atz @ COF-TD composite photocatalytic material.
Further, in the step (1), the mass ratio of the 3-amino-1, 2, 4-triazole, the divalent zinc ion salt and the dicarboxylic acid compound is (1-10): 1-5): 1; the volume ratio of the polar solvent to the deionized water is (0.1-10) to 1; the dosage ratio of the 3-amino-1, 2, 4-triazole to the polar solvent is 0.4g:20 mL; the hydrothermal kettle is a hydrothermal kettle with tetrafluoroethylene as a lining; the temperature of the hydrothermal reaction is 120-200 ℃, and the reaction time is 12-72 h.
Preferably, when the divalent zinc ion salt is basic zinc carbonate, the dicarboxylic acid compound is oxalic acid dihydrate, and the polar solvent is methanol, the mass ratio of the 3-amino-1, 2, 4-triazole to the basic zinc carbonate to the oxalic acid dihydrate is 4:1: 1; the volume ratio of the methanol to the deionized water is 8: 1;
preferably, when the divalent zinc ion salt is zinc nitrate hexahydrate, the dicarboxylic acid compound is sodium bicarbonate and the polar solvent is N, N-dimethylformamide, the mass ratio of the 3-amino-1, 2, 4-triazole to the zinc nitrate hexahydrate to the sodium bicarbonate is 2:7: 1; the volume ratio of the N, N-dimethylformamide to the deionized water is 0.4: 1;
preferably, when the divalent zinc ion salt is zinc nitrate hexahydrate, the dicarboxylic acid compound is succinic acid, and the polar solvent is N, N-dimethylformamide, the mass ratio of the 3-amino-1, 2, 4-triazole to the zinc nitrate hexahydrate to the succinic acid is 1.35:5: 1; the volume ratio of the N, N-dimethylformamide to the deionized water is 0.4: 1;
the hydrothermal reaction temperature is 180 ℃ and the time is 48 h.
Further, in the step (2), the mass ratio of the Zn-atz material to 4,4' -biphenyldicarboxaldehyde is (1-10): 1; the volume ratio of the o-dichlorobenzene to the ethanol to the acetic acid is (1-5) to (10) -5 ～5×10 -5 ) (ii) a The concentration of the acetic acid is (1-5) M; the 4,4' -biphenyldicarboxaldehyde: the dosage ratio of o-dichlorobenzene is 0.084g to 20 mL; the ultrasonic time is 5-15 min; the temperature of the oil bath reaction is 80-90 ℃, and the time is 8-15 h.
Further, in the step (2), the mass ratio of the Zn-atz material to 4,4' -biphenyldicarboxaldehyde is 3.6: 1; the volume ratio of the o-dichlorobenzene to the ethanol to the acetic acid is 1:1:10 -5 (ii) a The concentration of the acetic acid is 3M; the ultrasonic time is 10 min; the temperature of the oil bath reaction is 80 ℃, and the time is 12 h.
Further, in the step (3), the mass ratio of the aldehydized Zn-atz precursor, 4 '-biphenyldicarboxaldehyde and 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine is (1-5): 1; the volume ratio of the mesitylene to the 1, 4-dioxane is (1-10): 1; the dosage ratio of the 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine to the 1, 4-dioxane is 0.106g:2 mL; the dosage ratio of the 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine to the acetic acid is 0.106g:0.23 mL; the hydrothermal reaction temperature is 80-180 ℃, and the reaction time is 24-72 hours.
Further, in the step (3), the mass ratio of the aldehydized Zn-atz precursor, 4 '-biphenyldicarboxaldehyde and 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine is 2.4:0.9: 1; the volume ratio of the mesitylene to the 1, 4-dioxane is 6: 1; the temperature of the hydrothermal reaction is 120 ℃, and the reaction time is 72 h.
Further, in the step (3), the washing operation is to use tetrahydrofuran and ethanol to respectively carry out centrifugal washing three times.
The application is as follows: the Zn-atz @ COF-TD composite material prepared by the invention is applied to highly-selective reduction of carbon dioxide into carbon monoxide under the drive of visible light.
The invention has the following remarkable effects:
(1) the invention creatively adopts the aldehydized Zn-atz precursor, 4 '-biphenyldicarboxaldehyde, 4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine to carry out solvent thermal reaction, which is not reported in the prior literature, and the invention limits the mass ratio of the aldehydized Zn-atz precursor, 4 '-biphenyldicarboxaldehyde, 4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine to be (1-5): 1-5; the proportion of the double-component composite material is important, and is directly related to the construction of an external COF-TD shell layer of the double-component composite material, if the proportion of 4,4 '-biphenyldicarboxaldehyde and 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine is too low, a periodic long-range network wrapping Zn-atz core layer cannot be completely formed, and the stability of the Zn-atz @ COF-TD composite material is not good; if the ratio of 4,4 '-biphenyldicarboxaldehyde to 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine is too high, the optimum thickness of the external COF-TD shell layer is more than 200nm, which is not favorable for the Zn-atz core layer to CO 2 Trapping of gas molecules, thereby affecting photocatalytic performance. The present invention introduces this condition as a crucial improvement.
(2) The Zn-atz @ COF-TD core-shell binary composite material designed by the invention takes Zn-atz as a core, and an imine bond bridges COF-TD, and the compounded Zn-atz @ COF-TD keeps the high adsorption capacity of Zn-atz to carbon dioxide under low partial pressure, and with the introduction of COF-TD, a catalyst is endowed with a larger specific surface area and a proper band gap width, so that the composite material has good photocatalytic activity.
(3) According to the invention, the Zn-atz @ COF-TD core-shell binary composite material is prepared by a solvothermal method, a type I heterojunction is constructed, metal zinc ions serve as an active center, a Zn-atz core layer serves as an electron donor, a COF-TD shell layer serves as an electron transfer medium, and the photocurrent transfer efficiency of the composite material is increased, the charge transfer resistance is reduced and the catalytic activity in a photocatalytic reaction is further improved by a three-stage electron transfer mode of 'active center-donor-medium'.
(4) The Zn-atz @ COF-TD core-shell binary composite photocatalyst constructed by the invention can be used for reducing carbon dioxide in water under the irradiation of visible light, no sacrificial agent exists in the reaction process, carbon dioxide molecules are converted into fuel gas carbon monoxide with high added value, the selectivity is close to 100%, and the invention is a green technology which accords with the environment-friendly development strategy.
Description of the drawings:
FIG. 1 is an XRD pattern of catalytic materials Zn-atz, COF-TD, Zn-atz @ COF-TD obtained in example 1;
FIG. 2 is an SEM picture of Zn-atz, COF-TD, Zn-atz @ COF-TD catalytic materials prepared in example 1;
FIG. 3 is an electrochemical photo-amperometric graph of the catalytic materials Zn-atz, COF-TD and Zn-atz @ COF-TD prepared in example 1;
FIG. 4 is a carbon dioxide adsorption capacity diagram of the COF-TD, Zn-atz @ COF-TD catalytic material prepared in example 1;
FIG. 5 is a graph comparing the performance of the catalytic materials of Zn-atz, COF-TD and Zn-atz @ COF-TD prepared in example 1 in the reduction of carbon dioxide by light;
FIG. 6 is a graph of the photocatalytic carbon dioxide reduction stability test performance of the Zn-atz @ COF-TD catalytic material prepared in example 1.
Detailed Description
In order to make the related content of the present invention more comprehensible, the present invention is further described in conjunction with specific embodiments, but it should be noted that the scope of the present invention is not limited to the following embodiments.
Example 1:
(1) preparation of Metal organic framework Zn-atz
Weighing 0.400g of 3-amino-1, 2, 4-triazole, 0.100g of basic zinc carbonate and 0.100g of oxalic acid dihydrate in a 100mL tetrafluoroethylene lined hydrothermal kettle in sequence; then 20mL of methanol and 2.5mL of deionized water are respectively added, and the mixture is evenly dispersed by ultrasonic treatment for 20min in an ultrasonic instrument with the power of 1000W; carrying out hydrothermal reaction at 180 ℃ for 48h, centrifuging, washing with absolute ethanol for 3 times, and vacuum drying at 60 ℃ to obtain 0.516g of white solid powder which is recorded as Zn-atz material;
(2) preparation of aldehyde Zn-atz precursor
Weighing 0.300g of Zn-atz material and 0.084g of 4,4' -biphenyldicarboxaldehyde, adding the materials into a pressure-resistant bottle containing an o-dichlorobenzene/ethanol (1:1, 20mL:20mL) mixed solution, then adding 0.2 muL of 3M acetic acid as a catalyst, carrying out ultrasonic treatment for 10min, vacuumizing, carrying out oil bath reaction at 80 ℃ under the stirring condition for 12h, naturally cooling, washing for 3 times by using absolute ethyl alcohol after centrifuging, and drying in a vacuum drying oven at 60 ℃ for 8h to obtain 0.258g of an aldehyde-based Zn-atz precursor;
(3) preparation of Zn-atz @ COF-TD core-shell binary composite material
A method for preparing Zn-atz @ COF-TD by adopting a solvothermal method comprises the following steps: putting 0.25g of the aldehydized Zn-atz precursor prepared in the step (2) into a pressure-resistant bottle, weighing 0.095g of 4,4 '-biphenyldicarboxaldehyde and 0.106g of 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine, using 12mL of mesitylene and 2mL of 1, 4-dioxane as solvents, ultrasonically dispersing uniformly under the catalysis of 0.230mL of acetic acid, vacuumizing, putting the reaction system into a 120 ℃ oven for reaction for 72h, centrifuging, washing with tetrahydrofuran for 3 times, washing with absolute ethyl alcohol for 3 times, and drying at 60 ℃ for 8h in vacuum to obtain 0.327g of yellow powder which is recorded as Zn-atz @ COF-TD;
the preparation steps of COF-TD are as follows: the preparation steps are the same as the step (3) in the example 1, and only the aldehydized Zn-atz precursor is not added; 0.115g of a yellow powder is finally obtained, denoted COF-TD.
Example 2:
(1) preparation of carbonate modified Zn-atz
0.200g of 3-amino-1, 2, 4-triazole, 0.745g of zinc nitrate hexahydrate and 0.105g of sodium bicarbonate are sequentially weighed into a 100mL tetrafluoroethylene-lined hydrothermal kettle; then respectively adding 10mL of DMF and 25mL of deionized water, and carrying out ultrasonic treatment in an ultrasonic instrument with the power of 1000W for 20min to uniformly disperse; hydrothermal reaction at 180 deg.C for 48h, centrifuging, washing with DMF and deionized water (1:1) for 3 times, and vacuum drying at 80 deg.C to obtain 0.372g white solid powder, which is designated as Zn-atz (NaHCO) 3 )；
(2) Aldehyde Zn-atz (NaHCO) 3 ) Preparation of the precursor
0.300g of Zn-atz (NaHCO) was weighed 3 ) And 0.084g of 4,4' -biphenyldicarboxaldehyde in a pressure bottle, and then adding o-dichlorobenzene/ethanol (1:1, 20mL:20mL) for mixing and dissolvingPutting the solution in a pressure bottle, adding 0.2 μ L3M acetic acid as catalyst, performing ultrasonic treatment for 10min, vacuumizing, stirring, performing oil bath reaction at 80 deg.C for 12h, naturally cooling, centrifuging, washing with anhydrous ethanol for 3 times, and drying in a vacuum drying oven at 60 deg.C for 8h to obtain 0.224g aldehyde Zn-atz (NaHCO) 3 ) A precursor;
(3)Zn-atz(NaHCO 3 ) Preparation of @ COF-TD core-shell type binary composite material
Preparation of Zn-atz (NaHCO) by the Solvothermal method as in example 1 3 ) @ COF-TD: 0.20g of aldehyde Zn-atz (NaHCO) was reacted with 3 ) Putting the precursor into a pressure-resistant bottle, weighing 0.095g of 4,4 '-biphenyldicarboxaldehyde and 0.106g of 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine, using 12mL of mesitylene and 2mL of 1, 4-dioxane as solvents, adding 0.230mL of acetic acid for catalysis, ultrasonically dispersing uniformly, vacuumizing, putting into a 120 ℃ oven for reaction for 72h, centrifuging the obtained product, washing with tetrahydrofuran for 3 times, washing with anhydrous ethanol for 3 times, and drying at 60 ℃ for 8h in vacuum to obtain 0.283g of light yellow powder (marked as Zn-atz (NaHCO-C) 3 )@COF-TD。
Example 3:
(1) preparation of succinic acid modified Zn-atz
Weighing 0.200g of 3-amino-1, 2, 4-triazole, 0.745g of zinc nitrate hexahydrate and 0.148g of succinic acid in a tetrafluoroethylene lined hydrothermal kettle; then respectively adding 10mL of DMF and 25mL of deionized water, and carrying out ultrasonic treatment in an ultrasonic instrument with the power of 1000W for 20min to uniformly disperse; carrying out hydrothermal reaction at 180 ℃ for 48h, carrying out centrifugal separation on the obtained product, washing the product for 3 times by DMF (dimethyl formamide) and deionized water (1:1), and carrying out vacuum drying at 80 ℃ to obtain 0.582g of yellow white solid powder which is recorded as Zn-atz (succinic acid);
(2) preparation of aldehyde Zn-atz (succinic acid) precursor
Weighing 0.300g of Zn-atz (succinic acid) and 0.084g of 4,4' -biphenyldicarboxaldehyde, adding into a pressure-resistant bottle containing an o-dichlorobenzene/ethanol (1:1, 20mL:20mL) mixed solution, adding 0.2 muL of 3M acetic acid as a catalyst, carrying out ultrasonic treatment for 10min, vacuumizing, carrying out oil bath reaction for 12h under the stirring condition at 80 ℃, washing for 3 times by using absolute ethyl alcohol after natural cooling, centrifuging, and drying for 8h in a vacuum drying oven at 60 ℃ to obtain 0.265g of aldehyde Zn-atz (succinic acid) precursor;
(3) preparation of Zn-atz (succinic acid) @ COF-TD core-shell binary composite material
Preparation method of Zn-atz (succinic acid) @ COF-TD is the same as that of example 1, 0.25g of aldehyde-treated Zn-atz (succinic acid) precursor is weighed and put into a pressure-resistant bottle, 0.095g of 4,4 '-biphenylcarbaldehyde and 0.106g of 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine are weighed, 12mL of mesitylene and 2mL of 1, 4-dioxane are used as solvents, 0.230mL of acetic acid is introduced, ultrasonic dispersion is uniform, after vacuum pumping, the mixture is put into a 120 ℃ oven for reaction for 72h, centrifugation and washing is carried out for 3 times by tetrahydrofuran, washing is carried out for 3 times by absolute ethyl alcohol, vacuum drying is carried out for 8h at 60 ℃, 0.317g of dark yellow powder is obtained, and taken as Zn-atz (succinic acid) @ -COF-TD.
And (3) performance testing:
the invention respectively prepares Zn-atz @ COF-TD and Zn-atz (NaHCO) by a solvothermal method 3 ) The catalyst material is prepared from @ COF-TD and Zn-atz (succinic acid) @ COF-TD. In the method, Zn-atz @ COF-TD is taken as an example, and the following performance tests are carried out:
(1) photocatalytic carbon dioxide reduction performance test of Zn-atz @ COF-TD core-shell binary composite material
Weighing 0.020g of Zn-atz @ COF-TD sample into a top-illuminated quartz light reaction kettle, adding 100mL of deionized water, completely sealing the opening of the light reaction kettle by using a rubber plug, introducing carbon dioxide for 15min by using a needle, removing air in the light reaction kettle, maintaining the whole reaction system in a carbon dioxide atmosphere, taking a xenon lamp as a reaction light source, setting the current of the light source to be 20A, circulating condensed water at 20 ℃, reacting for 4h to obtain a carbon dioxide reduction product which is carbon monoxide, wherein the yield is 2.665 mu mol g -1 h -1 。
(2) Photocatalytic carbon dioxide reduction stability test of Zn-atz @ COF-TD core-shell binary composite material
After the performance of Zn-atz @ COF-TD is measured for 4 hours, introducing argon for 15min, completely discharging unreacted carbon dioxide and products in a reaction system, introducing the carbon dioxide for 15min, performing a cycle experiment under the same conditions of example 1 (4), and testing the stability of the Zn-atz @ COF-TD composite material; after each cycle was completed, the reaction system was thoroughly purged with argon to remove the influence of the product generated in the previous cycle(ii) a Then, continuously cleaning the reaction system with carbon dioxide for 15min to keep the system in the atmosphere of carbon dioxide, and then carrying out subsequent operation; the total 3 cycles of the experiment were carried out, and the carbon monoxide yields were 2.122. mu. mol g -1 h -1 、2.983μmol g -1 h -1 、0.832μmol g -1 h -1 。
Fig. 1 is an XRD pattern of the three materials prepared. As can be seen from the figure, Zn-atz has good crystallinity, while COF-TD has a large peak at about 20 ℃; the composite material Zn-atz @ COF-TD shows the same diffraction peak as the COF-TD at 2.2 degrees, and the same diffraction peak as the Zn-atz is reserved at 10.5 degrees, 12.6 degrees and 13.6 degrees, which indicates that the composite material has the diffraction peaks of two monomer materials, and the crystal form structure of the monomer is reserved. And no significant shift was found in the main peak, indicating that a higher long-range order was maintained.
Fig. 2 is an SEM image of the three materials prepared. As can be seen from the figure, Zn-atz (b) has a regular tetrahedron structure, each face being quite smooth; COF-TD (a) is a pellet having wrinkles on its surface; and the compounded Zn-atz @ COF-TD (c)/d is a polyhedron with wrinkled surfaces, wherein the main framework structure of Zn-atz is clearly visible, the wrapped COF-TD takes Zn-atz as a growth template, a uniformly coated cover grows vertically, and the shell layer thickness is about 200nm, which indicates that Zn-atz is successfully wrapped by the COF-TD to form a core-shell type binary structure.
FIG. 3 is an electrochemical photo-amperometric diagram of the prepared photocatalyst. The photocurrent intensity of Zn-atz @ COF-TD is obviously superior to that of Zn-atz and COF-TD, and the Zn-atz @ COF-TD is also verified to have good electron-hole separation efficiency; probably, Zn-atz and COF-TD construct a special heterojunction, in the structure, metal zinc ions serve as an active center, a Zn-atz nuclear layer serves as an electron donor, a COF-TD shell layer serves as an electron transfer medium, and a built-in electric field beneficial to carrier transmission is formed through a three-stage electron transfer mode of 'active center-donor-medium', so that the photocurrent characteristic of the composite material is improved.
FIG. 4 is a graph comparing the carbon dioxide adsorption capacity of the prepared COF-TD, Zn-atz @ COF-TD catalytic materials. COF-TD and Zn-atz @ COF-TD vs. bis when P/P0 ═ 1.0The absorption of carbon oxide was 4.3cm each 3 g -1 And 39.0cm 3 g -1 It is clear that this indicates that Zn-atz @ COF-TD has more excellent carbon dioxide adsorption capacity than COF-TD; the absorption capacity of carbon dioxide is improved by nearly 10 times, so that the number of carbon dioxide molecules on the surface of the catalyst is greatly improved, and more carbon dioxide molecules are combined with photo-generated electrons to participate in the reduction reaction; it is presumed that the catalyst can increase CO in the vicinity of the catalytic surface mainly by increasing the carbon dioxide molecular absorption ability of the catalyst 2 And further influences the surface reaction kinetics and improves the rate of catalytic reaction.
Fig. 5 is a graph comparing photocatalytic carbon dioxide reduction performance of the prepared catalysts. The yield of CO was calculated using the following formula: YCO ═ CO yield/(catalyst dosage × reaction time). As can be seen from the graph, the CO yields of Zn-atz, COF-TD and Zn-atz @ COF-TD were 0.673. mu. mol g, respectively -1 h -1 、1.314μmol g -1 h -1 、2.665μmol g -1 h -1 The yield of the composite material is 4 times higher than that of the monomer Zn-atz and 2 times higher than that of the COF-TD monomer, and the yield of the composite material is consistent with the result predicted by a carbon dioxide adsorption curve. In order to verify the reliability of the test result, 2 times of repeated experiments are carried out on the photocatalytic carbon dioxide reduction performance of Zn-atz @ COF-TD under the same conditions, and the test result shows that the CO yield of Zn-atz @ COF-TD1 is 2.660 mu mol g -1 h -1 CO yield of Zn-atz @ COF-TD2 was 2.510. mu. mol g -1 h -1 And the deviation value of the test result is within the tolerance of the experimental error, which shows that the obtained result is real and reliable.
FIG. 6 is a photocatalytic carbon dioxide reduction stability test performance graph of a Zn-atz @ COF-TD catalytic material. In order to confirm the stability of the composite catalyst prepared by the present invention, a cycle experiment was performed to obtain a yield of 2.665. mu. mol g -1 h -1 、2.122μmol g -1 h -1 、2.983μmol g -1 h -1 And 0.832. mu. mol g -1 h -1 After 3 times of operation, the catalytic activity of Zn-atz @ COF-TD is kept good, and the catalytic activity is obviously reduced only in the 4 th experiment, which shows that the catalyst can exist stably for more than ten hours.
The foregoing detailed description will provide those skilled in the art with a more complete understanding of the invention, and is not intended to limit the invention in any way. Thus, it will be appreciated by those skilled in the art that the invention may be modified and equivalents may be substituted; all technical solutions and modifications thereof which do not depart from the spirit and technical essence of the present invention should be covered by the scope of the present patent.
Claims (10)
1. A preparation method of a Zn-atz @ COF-TD composite photocatalytic material is characterized by comprising the following steps:
(1) mixing 3-amino-1, 2, 4-triazole, divalent zinc ion salt, dicarboxylic acid compound, polar solvent and water, adding into a hydrothermal kettle, ultrasonically dispersing uniformly, putting the hydrothermal kettle into an oven for hydrothermal reaction, centrifuging, washing and drying after the reaction to obtain white solid powder; is marked as Zn-atz material; the divalent zinc ion salt comprises basic zinc carbonate or zinc nitrate hexahydrate; the dicarboxylic acid compound comprises oxalic acid dihydrate, sodium bicarbonate or succinic acid; the polar solvent comprises methanol or N, N-dimethylformamide;
(2) firstly, mixing o-dichlorobenzene with ethanol to obtain an o-dichlorobenzene/ethanol mixed solution; then mixing the Zn-atz material prepared in the step (1) with a mixed solution of 4,4' -biphenyldicarboxaldehyde and o-dichlorobenzene/ethanol, adding acetic acid, marking the obtained solution as a mixed solution A, performing vacuum pumping treatment after the mixed solution A is uniformly dispersed by ultrasound, performing oil bath reaction under the stirring condition, naturally cooling to room temperature after the reaction, and then centrifuging, washing and drying to obtain an aldehyde Zn-atz precursor;
(3) mixing the aldehyde Zn-atz precursor prepared in the step (2) with 4,4 '-biphenyldicarboxaldehyde and 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine, mesitylene and 1, 4-dioxane, then adding acetic acid, ultrasonically dispersing uniformly, vacuumizing, placing in an oven for reacting for a period of time, and then centrifuging, washing and drying to obtain yellow powder, namely the Zn-atz @ COF-TD composite photocatalytic material.
2. The preparation method of the Zn-atz @ COF-TD composite photocatalytic material as claimed in claim 1, wherein in the step (1), the mass ratio of the 3-amino-1, 2, 4-triazole to the divalent zinc ion salt to the dicarboxylic acid compound is (1-10): 1-5): 1; the volume ratio of the polar solvent to the deionized water is (0.1-10) to 1; the dosage ratio of the 3-amino-1, 2, 4-triazole to the polar solvent is 0.4g:20 mL; the hydrothermal kettle is a hydrothermal kettle with tetrafluoroethylene as a lining; the temperature of the hydrothermal reaction is 120-200 ℃, and the reaction time is 12-72 h.
3. The preparation method of the Zn-atz @ COF-TD composite photocatalytic material, according to claim 2, is characterized in that when the divalent zinc ion salt is basic zinc carbonate, the dicarboxylic acid compound is oxalic acid dihydrate, and the polar solvent is methanol: the mass ratio of the 3-amino-1, 2, 4-triazole to the basic zinc carbonate to the oxalic acid dihydrate is 4:1: 1; the volume ratio of the methanol to the deionized water is 8: 1;
when the divalent zinc ion salt is zinc nitrate hexahydrate, the dicarboxylic acid compound is sodium bicarbonate, and the polar solvent is N, N-dimethylformamide: the mass ratio of the 3-amino-1, 2, 4-triazole to the zinc nitrate hexahydrate to the sodium bicarbonate is 2:7: 1; the volume ratio of the N, N-dimethylformamide to the deionized water is 0.4: 1;
when the divalent zinc ion salt is zinc nitrate hexahydrate, the dicarboxylic acid compound is succinic acid, and the polar solvent is N, N-dimethylformamide: the mass ratio of the 3-amino-1, 2, 4-triazole to the zinc nitrate hexahydrate to the succinic acid is 1.35:5: 1; the volume ratio of the N, N-dimethylformamide to the deionized water is 0.4: 1.
4. The preparation method of the Zn-atz @ COF-TD composite photocatalytic material as claimed in claim 2, wherein the hydrothermal reaction temperature is 180 ℃ and the time is 48 hours.
5. The preparation method of the Zn-atz @ COF-TD composite photocatalytic material as claimed in claim 1, wherein the preparation method is characterized in thatIn the step (2), the mass ratio of the Zn-atz material to 4,4' -biphenyldicarboxaldehyde is (1-10): 1; the volume ratio of the o-dichlorobenzene, the ethanol and the acetic acid is (1-5) to (10) -5 ～5×10 -5 ) (ii) a The concentration of the acetic acid is (1-5) M; the 4,4' -biphenyldicarboxaldehyde: the dosage ratio of o-dichlorobenzene is 0.084g to 20 mL; the ultrasonic time is (5-15) min; the temperature of the oil bath reaction is 80-90 ℃, and the time is (8-15) h.
6. The preparation method of the Zn-atz @ COF-TD composite photocatalytic material as claimed in claim 5, wherein in the step (2), the mass ratio of the Zn-atz material to the 4,4' -biphenyldicarboxaldehyde is 3.6: 1; the volume ratio of the o-dichlorobenzene to the ethanol to the acetic acid is 1:1:10 -5 (ii) a The acetic acid concentration is 3M; the ultrasonic time is 10 min; the temperature of the oil bath reaction is 80 ℃, and the time is 12 h.
7. The preparation method of the Zn-atz @ COF-TD composite photocatalytic material as claimed in claim 1, wherein in the step (3), the mass ratio of the aldehydized Zn-atz precursor, 4 '-biphenyldicarboxaldehyde, 4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine is (1-5): 1-5: 1; the volume ratio of the mesitylene to the 1, 4-dioxane is (1-10) to 1; the dosage ratio of the 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine to the 1, 4-dioxane is 0.106g:2 mL; the dosage ratio of the 4,4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine to the acetic acid is 0.106g:0.23 mL; the hydrothermal reaction temperature is 80-180 ℃, and the reaction time is 24-72 h.
8. The method for preparing the Zn-atz @ COF-TD composite photocatalytic material as claimed in claim 7, wherein in the step (3), the mass ratio of the aldehydized Zn-atz precursor, 4 '-biphenyldicarboxaldehyde, 4' - (1,3, 5-triazine-2, 4, 6-triyl) triphenylamine is 2.4:0.9: 1; the volume ratio of the mesitylene to the 1, 4-dioxane is 6: 1; the temperature of the hydrothermal reaction is 120 ℃, and the reaction time is 72 h.
9. The preparation method of Zn-atz @ COF-TD composite photocatalytic material as claimed in claim 1, wherein in the step (3), the washing operation is three times of centrifugal washing by using tetrahydrofuran and ethanol respectively.
10. Use of the Zn-atz @ COF-TD composite photocatalytic material prepared according to the method of any one of claims 1 to 9 in photocatalytic carbon dioxide reduction.
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