CN113600235A - Synthesis of 1DPDI/ZnFe by HCl mediated method2O4Method for preparing S-type heterojunction magnetic photocatalyst and application thereof - Google Patents
Synthesis of 1DPDI/ZnFe by HCl mediated method2O4Method for preparing S-type heterojunction magnetic photocatalyst and application thereof Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
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Abstract
The invention belongs to the technical field of synthesis of environmental materials, and particularly relates to 1D PDI/ZnFe2O4A preparation method and application of an S-type heterojunction magnetic photocatalyst; the method comprises the following steps: first, PDI and ZnFe are prepared2O4Then PDI and ZnFe are subjected to an acid induction method2O4Self-assembled S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4(ii) a S form prepared by the inventionThe heterojunction magnetic photocatalyst realizes the shape transformation due to the existence of HCl and PDI in the acid induction process, so that ZnFe is formed2O4Converted into dispersed small particles and dispersed on the surface of PDI, dispersed ZnFe2O4The small particles and the rod-shaped PDI increase the contact area with pollutants, and improve the photocatalytic degradation capability of the material; in addition, the construction of the S-type heterojunction eliminates meaningless photogenerated charge carriers through recombination and introduces strong redox to further enhance photodegradation.
Description
Technical Field
The invention belongs to the technical field of synthesis of environmental materials, and particularly relates to a method for synthesizing 1D PDI/ZnFe by an HCl-mediated method2O4A method for preparing S-type heterojunction magnetic photocatalyst and application thereof.
Background
Photocatalytic technology is receiving increasing attention due to its green advantages in water pollution. Conventional photocatalysts are susceptible to wide band gap, photo-corrosion, toxicity, and low utilization of visible light. Currently, due to the structural diversity of organic materials, more and more researchers have chosen organic materials as catalysts. As a typical n-type organic semiconductor, perylene imide (PDI) is a focus of attention due to its excellent electronic and optical properties. In addition, the PDI has not only a strong photoresponse under visible light irradiation, but also a suitable band gap and a relatively negative Conduction Band (CB), which allows photoexcited electrons to have a strong reduction capability. However, the applicability of semiconductor photocatalysts is limited by the recombination of photogenerated carriers. Among various methods for improving photocatalytic ability, constructing a suitable heterojunction system can ensure not only effective charge separation but also strong oxidation of holes and strong reduction of electrons, which is considered to be one of the most promising methods.
Currently, S-type heterojunctions have been proposed by the teaching of the rest of the national sciences. The S-type heterojunction catalyst mainly comprises an oxidation catalyst and a reduction catalyst. The oxidation catalyst has a higher work function and a lower fermi level. In contrast, reduction catalysts have a smaller work function and a higher fermi level. When the two catalysts are contacted, electrons of the reducing catalyst are transferred to the oxidizing catalyst through the interface, which creates an Internal Electric Field (IEF) at the interface. Finally, an S-type heterojunction with spatial separation and strong redox ability is formed. Among the synthesis methods for constructing the heterojunction, the HCl mediated method is beneficial to forming the composite material and can realize the controllability of the material appearance.
It is known that photocatalysts are difficult to separate and have low recovery rates. Therefore, the preparation of the composite catalyst by taking the magnetic material as the carrier is a good choice. The composite catalyst can be recovered by an external magnetic field to reduce the cost and ensure the recovery rate of the photocatalyst on the basis of improving the performance of the photocatalyst. As the magnetic material, ZnFe2O4Not only has wide visible light range and low cost, but also has excellent photochemical stability. At present, there is no 1D PDI/ZnFe2O4A report of heterojunction photocatalyst.
Disclosure of Invention
In order to efficiently solve the problem of antibiotic residue and realize high efficiency of wastewater treatment, PDI and ZnFe are subjected to acid induction2O4Self-assembled S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4And has good magnetic separation characteristic and stability. The presence of HCl during synthesis converts PDI from a random shape to a uniform rod shape. ZnFe in the coexistence of HCl and PDI2O4Converted into dispersed small particles and dispersed on the surface of the PDI. Dispersed ZnFe during photocatalytic degradation2O4The small particles and the rod-shaped PDI increase the contact area with pollutants, and are beneficial to improving the photocatalytic degradation capability of the material. In addition, the construction of the S-type heterojunction eliminates meaningless photogenerated charge carriers through recombination and introduces strong redox to further enhance photodegradation. The photocatalyst is used for the photocatalytic degradation of 100ml of 20mg/l tetracycline solution to obtain 1D PDI/ZnFe2O4The degradation rate under light was 66.67%, which was 9.18 times that of PDI (7.26%)Is ZnFe2O4(6.85%) 9.73 times. Overall, 1D PDI/ZnFe2O4The stability of (2) is better. The research comprehensively proves that the change of the material form and the S-shaped heterojunction form effectively improves the photocatalytic performance and stability, and provides a new prospect for the development of the S-shaped heterojunction.
The invention also provides an S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4The preparation method comprises the following steps:
step 1: preparation of PDI:
under the protection of nitrogen, 3,4,9, 10-perylene tetracarboxylic dianhydride, 3-aminopropionic acid and imidazole are mixed and reacted for a period of time; after the reaction is finished, cooling to room temperature, adding ethanol and HCl, stirring overnight, collecting the generated red solid, filtering by a filter membrane, washing by distilled water until the pH value is neutral, and finally drying the collected solid in vacuum to obtain PDI;
step 2: ZnFe2O4The preparation of (1):
FeCl is added3·6H2O and ZnCl2Dissolving in ethylene glycol, mixing to obtain mixed solution, adding CH3COOK and stirring for a period of time, then reacting in a reaction kettle, washing with deionized water and absolute ethyl alcohol after the reaction is finished, and drying to obtain a final product ZnFe2O4；
And step 3: 1D PDI/ZnFe2O4The preparation of (1):
dissolving PDI in triethylamine and distilled water, and adding ZnFe2O4Mechanically stirring the obtained mixed solution for a period of time under an ultrasonic state; then heating in water bath, adding HCl into the mixed solution for reaction, washing the product to be neutral after the reaction is finished, and drying in vacuum to obtain the final sample 1D PDI/ZnFe2O4。
Further, in the step 1, the using ratio of the 3,4,9, 10-perylenetetracarboxylic dianhydride to the 3-aminopropionic acid to the imidazole to the ethanol to the HCl is 1.177 g: 2.227 g: 16g of: 100mL of: 250 mL; the HCl concentration was 2M.
Further, in the step 1, the certain temperature condition is 100 ℃, and the reaction time is 4 hours.
Further, in step 2, the FeCl is3·6H2O、ZnCl2、CH3The dosage ratio of COOK to glycol is 4.325 g: 1.09 g: 2.453 g: 60 mL.
Further, in the step 2, stirring for a period of time of 20-30 min; the reaction temperature in the reaction kettle is 180 ℃, and the reaction time is 24 hours.
Further, in step 3, the PDI, triethylamine, distilled water and ZnFe are added2O4And HCl in a ratio of 0.5 g: 834 μ L of: 200mL of: 0.241 g: 30 mL; the HCl concentration was 4M.
Further, in the step 3, the time of mechanical stirring in the ultrasonic state is 45 min; the temperature of the water bath heating is 60 ℃, and the reaction time is 3 h.
Further, in the steps 1-3, the vacuum drying temperature is 60 ℃ and the drying time is 12 h.
The S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe of the invention2O4PDI and ZnFe2O4The structure is an S-shaped heterojunction, the form of the material and the electron transfer mode are improved, and the photocatalytic performance and stability are effectively improved.
The S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe prepared by the invention2O4The application of the compound in photocatalytic degradation of tetracycline.
The invention has the beneficial effects that:
(1) the S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe prepared by the invention2O4Due to the existence of HCl and PDI in the acid induction process, the shape transformation is realized, and ZnFe is ensured2O4Converted into dispersed small particles and dispersed on the surface of PDI, dispersed ZnFe2O4The small particles and the rod-shaped PDI increase the contact area with pollutants, and are beneficial to improving the photocatalytic degradation capability of the material.
(2) The S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe prepared by the invention2O4PDI and ZnFe2O4S-type heterojunction is combined and constructed through self-assembly, nonsense photon-generated charge carriers are eliminated through recombination in the S-type heterojunction, and strong redox is introduced to further enhance the effect of photodegradation of tetracycline.
Drawings
FIG. 1 is a TEM spectrum of different samples; wherein (a) is PDI and (b) is ZnFe2O4(c) and (D) are S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4(e) PDI/ZnFe free of HCl2O4(f) is HCl-ZnFe2O4。
FIG. 2 shows FT-IR spectra of different samples; samples are S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4、ZnFe2O4And a PDI.
FIG. 3 is an XRD spectrum of different samples; the samples are PDI and ZnFe respectively2O4And S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4。
FIG. 4 is a graph of the UV-visible diffuse reflectance spectra of different samples; wherein a is S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4B is ZnFe2O4And c is PDI.
FIG. 5 is a graph of magnetization curves for different samples; wherein a is S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4B is ZnFe2O4The inset is S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe in the state of aqueous solution2O4(left) and S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe in aqueous solution state containing magnet2O4(Right).
FIG. 6 is a graph of an experimental photo-degradation experiment and a quasi-first order kinetic model of tetracycline by different samples; wherein a is a photodegradation experimental graph, and b is a quasi-first order kinetic model graph.
FIG. 7 shows an S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4Cyclic experimental picture for degradation of tetracycline.
Detailed Description
The invention is further illustrated by the following examples.
Evaluation of photocatalytic degradation Activity of tetracycline: (1) taking 0.02g S type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4Adding 100mL of 20mg/L tetracycline solution into a photocatalytic reaction bottle, putting the photocatalytic reaction bottle into a xenon light catalytic reactor, starting magnetic stirring, performing dark reaction for a period of time to reach adsorption balance, then starting a lamp, introducing air (the flow is 2mL/min), sampling every 10 minutes, taking the sample for 60 minutes, and sequentially marking as C1、C2、C3、C4、C5And C6The solution after adsorption is marked C0. Separating out solid catalyst by combining filtration and high speed centrifugation (about 8000 rpm/min), taking clear liquid to measure absorbance (concentration), and utilizing degradation rate formula for all degradation data. (C)0-Ci/C0) 100%, the degradation rate was calculated.
Example 1:
(1) preparation of PDI: preparation of PDI: under the protection of nitrogen, 1.177g of 3,4,9, 10-perylene tetracarboxylic dianhydride, 2.227g of 3-aminopropionic acid and 16g of imidazole are mixed and reacted for 4 hours at 100 ℃; after cooling, ethanol (100mL) and HCl (250mL, 2M) were added and stirred overnight; collecting the produced red solid, filtering through a 0.45 μm filter membrane and washing with distilled water until the pH value is neutral, and finally drying the collected solid at 60 ℃ for 12h to obtain PDI;
(2)ZnFe2O4the preparation of (1): 4.325g of FeCl3·6H2O and 1.09g ZnCl2Dissolved in 60mL of ethylene glycol, mixed well and added with 2.453g of CH3COOK, magnetic stirring for 20 min. Then reacting for 24 hours in a reaction kettle at 180 ℃, washing the reaction product by deionized water and absolute ethyl alcohol after the reaction is finished, and drying the reaction product for 12 hours at 60 ℃ to obtain a final product ZnFe2O4；
(3) S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4The preparation of (1): 0.5g PDI was dissolved in 834. mu.L triethylamine and 200mL distilled water, followed by the addition of 0.241g ZnFe2O4Mechanically stirring for 45min under ultrasonic condition; then theThe reaction mixture was heated in a water bath at 60 ℃ and reacted for 3h with 30mL of 4M HCl. Finally, washing the product to be neutral, and drying the product at 60 ℃ for 12h to obtain a final sample 1D PDI/ZnFe2O4。
Fig. 1 is a TEM image of different samples. As can be seen from the figure: the prepared PDI is in an irregular block shape, ZnFe2O4Is a large particle structure formed by the coalescence of small particles. The PDI is changed into a uniform rod shape after acid induction, and ZnFe2O4Become small particles and are dispersed on the surface of the PDI. ZnFe2O4The dispersed state of (A) shows ZnFe2O4The magnetic interaction between them is weakened. While PDI is still blocky under the condition of no HCl, ZnFe when PDI is not added in the synthesis process2O4Also did not change. Magnetic photocatalyst 1D PDI/ZnFe through S-type heterojunction2O4Further demonstrates that the presence of HCl changes PDI to rod-like and the co-presence of HCl and PDI changes ZnFe2O4Limited to small particles.
FIG. 2 is a FT-IR spectrum of various samples, from which it can be seen that: at 1692cm-1The stretching vibration peak at (A) is attributed to C ═ O in the carboxylic acid moiety, and is located at 1656cm-1The tensile vibration peaks at (a) correspond to the ketone functional groups in the PDI. 1588cm-1The absorption band at (a) is due to the C ═ C group in the aromatic carbon skeleton. Magnetic photocatalyst 1D PDI/ZnFe in S-type heterojunction2O4These characteristic peaks of PDI were also found, and these results indicate that S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4The successful preparation.
FIG. 3 is the XRD spectra of different samples, from which ZnFe can be seen2O4The diffraction peak of (2) corresponds to the standard card number JCPDS No. 22-1012. Typical diffraction peaks of PDI ranged from 5 to 30, consistent with the characteristic peaks of PDI in the figure, indicating successful production of PDI. Introduction of ZnFe2O4Then, S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe can be observed2O4Can detect PDI and ZnFe2O4Thereby indicating the S-type heterojunction magnetic propertyPhotocatalyst 1D PDI/ZnFe2O4The successful preparation.
FIG. 4 shows the UV-visible diffuse reflectance spectra of different samples, from which it can be seen that PDI has strong light absorption property in the range of 200nm to 700nm, while ZnFe2O4And S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4Having light absorbing capabilities over the entire spectral range. Furthermore, with ZnFe2O4Compared with the S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4Exhibit better visible response capability.
FIG. 5 is the magnetization curves of different samples, from which it can be seen that the S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4The magnetic saturation intensity value of the magnetic core is 22.63emu/g and is slightly lower than ZnFe2O4(39.89emu/g) due to ZnFe in the composite2O4In an amount less than ZnFe alone2O4A material. And the S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe can be clearly seen according to the insets2O4Yet still be easily separated by the magnet. These results demonstrate that the S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4Has good magnetic separation characteristics.
FIG. 6 is a graph of the experimental photo-degradation and quasi-first order kinetic model of tetracycline by different samples, and it can be seen from the graph that: PDI and ZnFe2O4Shows relatively poor activity in degrading tetracycline, but the S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4Compared with the prior art, the degradation rate of the composite material is greatly improved, and the degradation rate of the composite material reaches 66.67 percent, which is 9.18 times of PDI (7.26 percent) and ZnFe2O4(6.85%) 9.73 times. This indicates that PDI and ZnFe are synthesized by acid induction2O4The combination is an effective means of enhancing photocatalytic activity. S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4Has a maximum k of 1.10min-1PDI and ZnFe respectively2O46.88 and 5.79 times. This is probably due to ZnFe2O4The particles become small and the electron transfer is promoted, and in additionPDI and ZnFe2O4A heterojunction may be formed which further facilitates electron transfer and improves photocatalytic performance. This further illustrates the prepared S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4Has excellent photocatalytic performance.
FIG. 7 shows an S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4Cyclic experimental picture for degradation of tetracycline. From the figure, it can be seen that the S-type heterojunction magnetic photocatalyst 1D PDI/ZnFe2O4Has good stability and keeps higher photocatalytic performance in the process of five-cycle tetracycline degradation. After five cycles of experiment, PDI/ZnFe2O4The degradation rate of (a) was slightly reduced to 58.20%, which was probably due to the mass loss of the photocatalyst during the subsequent cycling experiments.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
- Synthesis of 1D PDI/ZnFe by HCl-mediated method2O4The method for preparing the S-type heterojunction magnetic photocatalyst is characterized by comprising the following steps:step 1: preparation of PDI:under the protection of nitrogen, 3,4,9, 10-perylene tetracarboxylic dianhydride, 3-aminopropionic acid and imidazole are mixed to obtain a mixture, and the mixture is reacted for a period of time under a certain temperature condition; after the reaction is finished, cooling to room temperature, adding ethanol and HCl, stirring overnight, collecting generated red solid, filtering by a filter membrane, washing by distilled water until the pH value is neutral, and finally drying the collected solid in vacuum to obtain PDI;step 2: ZnFe2O4The preparation of (1):FeCl is added3·6H2O and ZnCl2Dissolving in ethylene glycol, mixing to obtain mixed solution, adding CH3COOK and stirring for a period of time, then reacting in a reaction kettle, washing with deionized water and absolute ethyl alcohol after the reaction is finished, and drying in vacuum to obtain a final product ZnFe2O4；And step 3: 1D PDI/ZnFe2O4The preparation of (1):dissolving PDI prepared in the step 1 in triethylamine and distilled water, and then adding ZnFe prepared in the step 22O4Mechanically stirring the obtained mixed solution for a period of time under an ultrasonic state; then heating in water bath, adding HCl into the mixed solution for reaction, washing the product to be neutral after the reaction is finished, and drying in vacuum to obtain the final sample 1D PDI/ZnFe2O4。
- 2. The HCl-mediated synthesis of 1D PDI/ZnFe as claimed in claim 12O4The method for preparing the S-type heterojunction magnetic photocatalyst is characterized in that in the step 1, the using amount ratio of the 3,4,9, 10-perylene tetracarboxylic dianhydride to the 3-aminopropionic acid to the imidazole to the ethanol to the HCl is 1.177 g: 2.227 g: 16g of: 100mL of: 250 mL; the HCl concentration was 2M.
- 3. The HCl-mediated synthesis of 1D PDI/ZnFe as claimed in claim 12O4The method for preparing the S-type heterojunction magnetic photocatalyst is characterized in that in the step 1, the certain temperature condition is 100 ℃, and the reaction time is 4 hours.
- 4. The HCl-mediated synthesis of 1D PDI/ZnFe as claimed in claim 12O4The method of the S-type heterojunction magnetic photocatalyst is characterized in that in the step 2, FeCl is adopted3·6H2O、ZnCl2、CH3The dosage ratio of COOK to glycol is 4.325 g: 1.09 g: 2.453 g: 60 mL.
- 5. The HCl-mediated process of claim 1Method for synthesizing 1D PDI/ZnFe2O4The method for preparing the S-type heterojunction magnetic photocatalyst is characterized in that in the step 2, the stirring is carried out for 20-30 min; the reaction temperature in the reaction kettle is 180 ℃, and the reaction time is 24 hours.
- 6. The HCl-mediated synthesis of 1D PDI/ZnFe as claimed in claim 12O4The method for preparing the S-type heterojunction magnetic photocatalyst is characterized in that in the step 3, the PDI, the triethylamine, the distilled water and the ZnFe are obtained2O4And HCl in a ratio of 0.5 g: 834 μ L of: 200mL of: 0.241 g: 30 mL; the HCl concentration was 4M.
- 7. The HCl-mediated synthesis of 1D PDI/ZnFe as claimed in claim 12O4The method for preparing the S-type heterojunction magnetic photocatalyst is characterized in that in the step 3, the mechanical stirring time in the ultrasonic state is 45 min; the temperature of the water bath heating is 60 ℃, and the reaction time is 3 h.
- 8. The HCl-mediated synthesis of 1D PDI/ZnFe as claimed in claim 12O4The method for preparing the S-type heterojunction magnetic photocatalyst is characterized in that in the step 1-3, the vacuum drying temperature is 60 ℃ and the drying time is 12 hours.
- 9. PDI/ZnFe prepared according to the method of any one of claims 1-92O4The S-type heterojunction magnetic photocatalyst is characterized in that the PDI is uniform rod-shaped, and ZnFe2O4Are dispersed small particles; the ZnFe2O4Dispersed on the surface of the PDI.
- 10. The 1D PDI/ZnFe of claim 92O4The S-type heterojunction magnetic photocatalyst is applied to the application of photocatalytic degradation of tetracycline.
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