CN114653402B - Preparation method of transition metal complex @ covalent organic framework photocatalyst - Google Patents
Preparation method of transition metal complex @ covalent organic framework photocatalyst Download PDFInfo
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- CN114653402B CN114653402B CN202210244153.5A CN202210244153A CN114653402B CN 114653402 B CN114653402 B CN 114653402B CN 202210244153 A CN202210244153 A CN 202210244153A CN 114653402 B CN114653402 B CN 114653402B
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Abstract
The invention relates to the technical field of photocatalytic degradation of organic pollutants, in particular to a preparation method of a transition metal complex @ covalent organic framework photocatalyst, which is characterized in that a transition metal complex @ covalent organic framework composite photocatalytic material is synthesized through solvothermal and self-assembly methodsλNot less than 600 nm), has excellent photocatalytic degradation performance on organic pollutants in water body, and can be recycled for multiple times.
Description
Technical Field
The invention belongs to the technical field of synthesis of composite photocatalytic materials, in particular to the technical field of photocatalytic materials for widening the absorption spectrum range of visible light, and particularly relates to a preparation method of a transition metal complex @ covalent organic framework photocatalyst.
Background
Visible light photocatalysis is used as a sustainable solar energy conversion technology, and attractive application prospects are shown in the related fields of energy and environment. A typical photocatalytic process includes four steps: photo-trapping, separation of photogenerated electrons and holes, and migration of carriers to the photocatalyst surface and reaction with chemicals. Among them, light trapping is the first and most important step, which determines the photocatalytic performance of the photocatalyst. In the last decades, efficient semiconductor photocatalysts with photoactivity under visible light irradiation have been widely studied, and these photocatalysts can be applied to water decomposition, carbon dioxide reduction and organic pollutant degradation. Wherein graphite carbonitride (g-C) 3 N 4 ) There is great interest as a novel polymeric photocatalyst. However, g-C 3 N 4 There are two difficult drawbacks to overcome, namely low utilization efficiency of visible light and rapid electron-hole pair recombination, which hinders efficient photocatalysis.
Triazinyl covalent organic frameworks possess the same meaning as g-C 3 N 4 Similar conjugated units act as catalytic active sites for visible light photocatalysis. The energy band structure and the electronic properties of the covalent organic framework can be reasonably improved by adjusting the structure of the covalent organic framework, so that the covalent organic framework breaks through and solves a plurality of g-C 3 N 4 The short plate on photocatalysis becomes a kind of photocatalyst with attractive prospect. However, triazinyl covalent organic frameworks have not been successful in practical applications because the light absorption edge of triazinyl covalent organic frameworks is generally below 550 nm, which isλAnd less than or equal to 550 nm is only a very small part of the visible spectrum. Based on the low light absorption and utilization rate of visible light, a method for breaking the limited light absorption range of the triazinyl covalent organic framework is urgently needed.
In recent years, many composite photocatalytic systems containing transition metal (e.g., iron, cobalt, nickel, copper, zinc) complexes and photocatalysts have been studied. The composite photocatalytic system utilizes d-d transition between iron-based transition metal complexes, and can expand the light absorption range to a long wavelength spectrum range. However, most and transition metal complexes constitute the complex photocatalytic system as inorganic, and organic systems have little involvement, especially in covalent organic frameworks. Since the covalent organic frameworks have no reactive groups with the transition metal, it is necessary to develop a method to realize a complex photocatalytic system of the transition metal and the covalent organic frameworks.
Disclosure of Invention
The invention aims to provide a preparation method and application of a transition metal complex@covalent organic framework photocatalyst, wherein the catalyst has excellent visible light response, widens the visible light absorption range, can efficiently treat organic pollutants in a water body, has a simple synthesis method and high yield, has good stability, can be recycled for multiple times, and solves the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the transition metal complex @ covalent organic framework photocatalyst comprises the steps of synthesizing a transition metal complex @ covalent organic framework composite photocatalytic material by a solvothermal and self-assembly one-step method, wherein the solvothermal is obtained by monomer synthesis; the covalent organic framework material is mixed and stirred with metal salt and tannic acid or phytic acid, and the metal salt and tannic acid or phytic acid coordinate to generate coordination compound during stirring and are coated on the covalent organic framework.
Further, the preparation of the covalent organic framework precursor comprises forming a mixed solution by adding 2,4, 6-tris (4-aldehydylphenyl) -1,3, 5-triazine and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine to 1,3, 5-trimethylbenzene, 1, 4-dioxane and acetic acid.
Further, the mixed solution precursor is subjected to ultrasonic treatment to obtain a uniform mixed solution, and then nitrogen is filled into the uniform mixed solution to carry out degassing treatment.
Further, the mixed solution precursor is subjected to solvothermal reaction, the reaction temperature is 110-130 ℃, and the reaction time is 72 hours.
Further, the synthesized covalent organic frameworks are washed by tetrahydrofuran and acetone and dried in vacuum, wherein the drying temperature is 100-120 ℃ and the drying time is 12 h.
Further, 80-100 mg of the covalent organic framework is added into 160-200 mL of absolute ethyl alcohol, and the cell grinder is subjected to 80-120W ultrasonic treatment for 1 hour to obtain a uniform mixed solution.
Further, the mixed solution is firstly mixed and stirred with corresponding metal (Fe/Co/Ni/Cu/Zn) salt solution in vigorous stirring, and then tannic acid or phytic acid is added for coordination reaction.
Further, the mixed solution is stirred for 8-h, then is washed by absolute ethyl alcohol and is dried in vacuum at 60-80 ℃ for 12-h.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method is simple and the preparation method is simpleThe covalent organic framework is obtained by agent heating, and the transition metal complex @ covalent organic framework composite photocatalytic material is obtained by further coordination treatment, and the material is prepared in the long wavelength spectrum range @λNot less than 600 nm), has excellent photocatalytic degradation performance on organic pollutants in water body, and can be recycled for multiple times.
Drawings
FIG. 1 is a diagram of Fe prepared in example 2 of the present invention Ⅲ Solid-state nuclear magnetism of-TA@TTB-TTA composite material and TTB-TTA material prepared in example 1 13 C spectrum;
FIG. 2 Fe prepared in example 2 of the present invention Ⅲ -a (a) fourier transform infrared spectrogram, (b) X-ray powder diffraction pattern of ta@ttb-TTA composite material and TTB-TTA material prepared in example 1;
FIG. 3 (a) is a transmission electron micrograph of a TTB-TTA material prepared in example 1 of the present invention, and (b) and (c) are Fe prepared in example 2 of the present invention Ⅲ -transmission electron microscopy and X-ray photoelectron spectroscopy of ta@ttb-TTA composites;
FIG. 4 Fe prepared in example 2 of the present invention Ⅲ -a thermogravimetric analysis of (a) a ta@ttb-TTA composite material and (b) a nitrogen adsorption desorption isotherm of the TTB-TTA material prepared in example 1;
FIG. 5 is a diagram of Fe prepared in example 2 Ⅲ -a (a) uv-vis diffuse reflectance spectrum, (b) Tauc pattern of ta@ttb-TTA composite material with TTB-TTA material prepared in example 1;
FIG. 6 (a) shows Fe prepared in example 3 Ⅲ The photo-catalytic methyl orange degradation curve corresponding to the TA@TTB-TTA composite material and the TTB-TTA material prepared in example 1λMore than or equal to 420 nm and (b) is Fe prepared in example 2 Ⅲ Dynamics curve of photocatalytic degradation methyl orange corresponding to TA@TTB-TTA composite material and TTB-TTA material prepared in example 1λ ≥ 600 nm）；
FIG. 7 is a diagram of Fe prepared in example 2 Ⅲ -electrochemical impedance spectroscopy of ta@ttb-TTA composite material and TTB-TTA material prepared in example 1;
FIG. 8 is a diagram of Fe prepared in example 2 Ⅲ Photocurrent response of ta@ttb-TTA composite material with TTB-TTA material prepared in example 1;
FIG. 9 is a diagram of Fe prepared in example 2 Ⅲ Visible light of-TA@TTB-TTA composite materialλAnd (3) photocatalytic cycle test under the conditions of more than or equal to 420 nm.
Detailed Description
The following describes the technical solution in the embodiment of the present invention with reference to fig. 1 to 9 in the embodiment of the present invention.
1. Example 1: preparation of TTB-TTA materials
Step (1): 0.25 mmol of 2,4, 6-tris (4-aldehydephenyl) -1,3, 5-triazine and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine were weighed separately into the reactor liner, and 5 mL of 1,3, 5-trimethylbenzene, 5 mL of 1, 4-dioxane and 1 mL of 3M acetic acid were added to form a mixed solution.
Step (2): placing the reaction kettle containing the mixed solution in an ultrasonic cleaner for ultrasonic treatment for 15min to uniformly mix, further filling nitrogen for 15min to remove gas, and finally filling the reaction kettle.
Step (3) solvothermal reaction: the reaction vessel was placed in an oven and incubated at 120℃for 72 hours. After natural cooling, the product was washed with a large amount of tetrahydrofuran and acetone and then dried in vacuum at 120 degrees celsius to produce TTB-TTA.
2. Example 2: preparation of Fe III -TA@TTB-TTA composite photocatalytic material
Step (1): 0.25 mmol of 2,4, 6-tris (4-aldehydephenyl) -1,3, 5-triazine and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine were weighed separately into the reactor liner, and 5 mL of 1,3, 5-trimethylbenzene, 5 mL of 1, 4-dioxane and 1 mL of 3M acetic acid were added to form a mixed solution.
Step (2): placing the reaction kettle containing the mixed solution in an ultrasonic cleaner for ultrasonic treatment for 15min to uniformly mix, further filling nitrogen for 15min to remove gas, and finally filling the reaction kettle.
Step (3) solvothermal reaction: the reaction vessel was placed in an oven and incubated at 120℃for 72 hours. After natural cooling, the product was washed with a large amount of tetrahydrofuran and acetone and then dried in vacuum at 120 degrees celsius to produce TTB-TTA.
Step (4) adding Fe III -TA: weighing 90 mg TTB-TTA, adding 180 mL absolute ethanol, mixing into uniform solution with cell pulverizer 100W ultrasonic 1h, stirring, adding 12.50 mg/L anhydrous FeCl 3 50.00 mg/L tannic acid is added after being stirred evenly, and 8 h of tannic acid is stirred vigorously.
Step (5): washing the product with a large amount of absolute ethanol after vigorously stirring, and vacuum drying at 60 ℃ for 12 h to obtain Fe III -ta@ttb-TTA composite photocatalytic material.
3. Example 3: preparation of different Fe III Additive amount of Fe III -TA@TTB-TTA composite photocatalytic material
Based on examples 1 and 2, fe was prepared by a one-step method III The TA@TTB-TTA composite photocatalytic material has the optimal effect, and Fe III The addition amount of Fe is the main influencing factor of the target catalyst III When the amount of Fe to be added is low, fe is produced III The amount of TA complex is too small and the absorption capacity for increasing the long wavelength light in the spectrum is limited; and Fe (Fe) III When the addition amount of (B) is too high, the TTB-TTA material itself is deteriorated, thereby causing Fe III The performance of the TA@TTB-TTA composite photocatalytic material for photocatalytic degradation of organic pollutants is reduced. This example is achieved by adjusting Fe III To regulate and control Fe III -optimal ratio of TA@TTB-TTA.
Step (1): 0.25 mmol of 2,4, 6-tris (4-aldehydephenyl) -1,3, 5-triazine and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine were weighed separately into the reactor liner, and 5 mL of 1,3, 5-trimethylbenzene, 5 mL of 1, 4-dioxane and 1 mL of 3M acetic acid were added to form a mixed solution.
Step (2): placing the reaction kettle containing the mixed solution in an ultrasonic cleaner for ultrasonic treatment for 15min to uniformly mix, further filling nitrogen for 15min to remove gas, and finally filling the reaction kettle.
Step (3) solvothermal reaction: the reaction vessel was placed in an oven and incubated at 120℃for 72 hours. After natural cooling, the product was washed with a large amount of tetrahydrofuran and acetone and then dried in vacuum at 120 degrees celsius to produce TTB-TTA.
Step (4) adding Fe III -TA: weighing 90 mg TTB-TTA, adding 180 mL anhydrous alcohol, mixing with cell pulverizer 100W ultrasonic 1h to obtain uniform solution, and stirring strongly, adding anhydrous FeCl at 6.25 mg/L, 12.50 mg/L, 25.00mg/L 3 After being stirred evenly, 25.00mg/L, 50.00 mg/L and 100.00 mg/L tannic acid are added respectively, and 8 h parts are stirred vigorously.
Step (5): washing the product with a large amount of absolute ethanol after vigorously stirring, and drying 12 h at 60 ℃ under vacuum to obtain different Fe III Content of Fe III -ta@ttb-TTA composite photocatalytic material.
4. Application example 1: photocatalytic degradation of organic pollutant methyl orange
TTB-TTA and Fe prepared in examples 1 and 3 of 20 mg are weighed respectively III TA@TTB-TTA, homogeneously dispersed in 100 mL methyl orange. The light source was a CEL-HXF300F3 300W xenon lamp (CEAULIGHT) equipped with 420 nm cut-off filter and 600 nm cut-off filter, respectively, corresponding to 10 mg/L and 5 mg/L methyl orange. The suspension was stirred in the dark using a magnetic stirrer for 1h to reach adsorption-desorption equilibrium before starting the illumination. During photocatalytic degradation, the reaction mixture is stirred with a magnetic stirrer and cooled with circulating water to maintain ambient temperature. At given time intervals, the extracted 3 mL solution was centrifuged and filtered with a filter membrane. Methyl orange concentration was analyzed by uv-vis spectrophotometer at 464 nm. Methyl orange degradation (%) was calculated according to the following equation: methyl orange degradation rate (%) = (C) 0 -C）/C 0 X 100%, where C 0 The initial concentration of methyl orange is indicated, and C is the actual concentration of methyl orange.
5. Photoelectrochemical test
Photoelectrochemical test: photoelectrochemical response testing of photocatalysts the test was performed on an electrochemical workstation (Chenhua CHI 660E) using a three electrode system. TTB-TTA and Fe prepared in examples 1 and 2 III The TA@TTB-TTA composite photocatalytic material is coated onFluorine doped tin oxide (FTO) is used as a working electrode, platinum foil is used as a counter electrode, ag/AgCl is used as a reference electrode, and 0.1 mol/L sodium sulfate solution is used as electrolyte. The preparation of the working electrode specifically comprises the following steps: dip coating containing 5 mg photocatalyst, 0.5 mL ethanol and 20 μl of 5% nafion was applied to FTO glass and dried in a vacuum oven at 60 ℃ to improve adhesion. Visible light illumination was provided by CEL-HXF300F3 300W xenon lamp (CEAULIGHT) and 420 nm cutoff filter. Electrochemical Impedance Spectroscopy (EIS) is measured by applying an ac voltage with an amplitude of 10 mV in the frequency range of 1000 kHz to 10 Hz.
6. Test results
FIG. 1 shows a solid state nuclear magnetic resonance 13 C spectrum, characteristic resonance signal at 152 ppm indicates successful synthesis of imine bond, and characteristic peak of triazine carbon atom appears at 170 ppm, indicating successful synthesis of target catalyst and Fe III The presence of TA does not alter the framework structure of TTB-TTA.
Fig. 2 (a) shows a fourier transform infrared spectrum, and the occurrence of a c=n characteristic absorption peak indicates successful synthesis of a material; as shown in fig. 2 (b) which shows an X-ray powder diffraction pattern, it can be seen that crystals are formed during synthesis and are unchanged after coordinate coating.
FIGS. 3 (a) and (b) show transmission electron microscopy images, showing that the catalyst is in a coral cluster shape before and after coordination; fig. 3 (c) shows an X-ray photoelectron spectrum showing that the elements (C, N, fe) are uniformly distributed in the composite material, i.e., the target composite catalyst was successfully synthesized.
FIG. 4 (a) is a thermogravimetric analysis, showing that the catalyst has a thermal stability of up to 500 degrees Celsius under nitrogen; as shown in fig. 4 (b), which shows the nitrogen adsorption and desorption isotherms, the two catalysts have similar specific surfaces, indicating that the specific surface area is not changed by the coordinate coating.
FIG. 5 (a) is a UV-visible diffuse reflectance spectrum showing Fe III -TA@TTB-TTA composite materialλThe light absorption is strong at 600 nm, which indicates that the composite photocatalyst can obviously increase the light absorption range of visible spectrum; FIG. 5 (b) is a Tauc plot showing Fe III -TA@TThe TB-TTA composite photocatalyst has a narrower band gap.
FIG. 6 (a) shows the photocatalytic methyl orange degradation curves of examples 1 and 3λMore than or equal to 420 nm, inλFe under the irradiation of visible light of more than or equal to 420 nm III 12.50 The photocatalysis effect of the-TA@TTB-TTA composite photocatalyst is the best, when Fe III When the addition amount of (2) is 12.50 mg/L, the catalyst has the optimal photocatalytic performance; FIG. 6 (b) shows the kinetics curves of degradation of methyl orange of examples 1 and 2λNot less than 600 nmλFe under the irradiation of visible light of more than or equal to 600 nm III The photocatalysis effect of the TA@TTB-TTA composite photocatalyst is 372 times of that of TTB-TTA, which shows that Fe III The presence of TA enhances the long wavelength [ ]λNot less than 600 nm), the photocatalytic efficiency is improved;
FIG. 7 shows electrochemical impedance spectra, fe III TA@TTB-TTA has a smaller Nyquist semicircle, indicating Fe III TA@TTB-TTA possesses faster interfacial charge transfer.
The photocurrent response diagram shown in fig. 8 shows that Fe III The photocurrent density of-TA@TTB-TTA was three times that of TTB-TTA, indicating Fe III TA@TTB-TTA can generate more photo-generated electrons and has a faster photocurrent response.
FIG. 9 shows the visible lightλPhotocatalytic cycle test for degrading methyl orange at 420 nm or more, the degradation efficiency can still reach 80.5% or more after four times of cycle, no obvious effect reduction is shown, and Fe is shown III The TA@TTB-TTA can be recycled and has cyclic stability.
Comparative examples 1 and 2, example 1 was conducted with solvothermal reaction alone to give TTB-TTA, and example 2 was conducted with Fe incorporated in TTB-TTA III -TA-complex. As shown in FIG. 5, example 2 has a significant light absorption in a long wavelength range of more than 600 nm and a narrower band gap, compared to example 1, indicating Fe III The TA@TTB-TTA can effectively perform light capturing, and high-efficiency photocatalysis is realized. As shown in fig. 6, example 1, which performs photocatalytic degradation of methyl orange under the same conditions, exhibited inferior photocatalytic performance compared to example 2.
In conclusion, the preparation method is simple, the transition metal complex @ covalent organic framework composite photocatalytic material is obtained through solvothermal and simple coordination treatment in the polytetrafluoroethylene reaction kettle, has excellent photocatalytic activity under the condition of visible light, can efficiently degrade organic pollutants, widens the visible light spectrum absorption range, expands to absorb near infrared light for effective photocatalysis, has higher yield, and has good stability and can be recycled for multiple times.
The foregoing description of the preferred embodiments of the invention is merely illustrative of the invention, and it is not intended to limit the scope of the invention to the specific embodiments described, but to rely on the doctrine of equivalents to which the invention pertains.
Claims (4)
1. The catalyst for photocatalytic degradation of organic pollutants in water is characterized in that a transition metal complex @ covalent organic framework composite photocatalytic material is synthesized through solvothermal and coordination reaction, and covalent organic framework precursors are obtained through monomer synthesis by solvothermal; then mixing and stirring the covalent organic framework precursor, metal salt and tannic acid or phytic acid, and carrying out the coordination reaction on the metal salt and the tannic acid or the phytic acid in stirring to generate a coordination compound and coating the coordination compound on the covalent organic framework; the preparation of the covalent organic framework precursor comprises the steps of adding 2,4, 6-tris (4-aldehyde phenyl) -1,3, 5-triazine and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine into 1,3, 5-trimethylbenzene, 1, 4-dioxane and acetic acid to form a mixed solution; the metal salt is iron metal salt.
2. The catalyst according to claim 1, wherein the mixed solution is subjected to ultrasonic treatment to obtain a uniform mixed solution, and then nitrogen is introduced to carry out degassing treatment.
3. The catalyst of claim 2, wherein the mixed solution is subjected to solvothermal reaction at a temperature of 110-130 ℃ for 72 hours.
4. The catalyst according to claim 3, wherein the amount of the metal salt added in the coordination reaction is 6.25 to 25.00mg/L.
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