CN113694917B - Rare earth metal Ce-doped petal-shaped ZnO photocatalyst and preparation method thereof - Google Patents

Rare earth metal Ce-doped petal-shaped ZnO photocatalyst and preparation method thereof Download PDF

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CN113694917B
CN113694917B CN202110869709.5A CN202110869709A CN113694917B CN 113694917 B CN113694917 B CN 113694917B CN 202110869709 A CN202110869709 A CN 202110869709A CN 113694917 B CN113694917 B CN 113694917B
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张瑶瑶
陈舒晗
朱磊
郭海峰
李楠
杨磊
李博解
何边阳
李维双
汪连生
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Abstract

The invention discloses a petal-shaped ZnO photocatalyst doped with rare earth metal Ce and a preparation method thereof. The invention takes cerium chloride as a doping agent and a temperature-sensitive material as a template, and rare earth metal Ce is doped into a petal-shaped ZnO catalyst to prepare the photocatalyst with high catalytic performance. The method comprises the following specific steps: (1) Polymerizing a temperature-sensitive material poly N-isopropylacrylamide-copolymer PN64 (IL) 4 containing polymerizable double-bond imidazole compounds; (2) Dissolving PN64 (IL) 4, zinc acetate, cerium chloride and citric acid in deionized water to form a transparent and uniform solution; (3) Adopting a microwave-assisted hydrothermal technology, firstly performing microwave dispersion on the mixed solution, transferring the mixed solution into a high-pressure reaction kettle, and performing hydrothermal reaction to obtain petal-shaped ZnO doped with Ce; the Ce-doped ZnO photocatalyst is prepared by taking the temperature-sensitive material PNx (IL) y as a template, and the catalyst has a controllable structure in the preparation process and has a good application prospect in the technical field of wastewater treatment.

Description

Rare earth metal Ce-doped petal-shaped ZnO photocatalyst and preparation method thereof
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a rare earth metal Ce doped petal-shaped ZnO photocatalyst with excellent appearance after an ionic liquid type temperature-sensitive material is added and a preparation method thereof.
Background
In recent years, semiconductor photocatalysts have attracted extensive attention as a "green technology" among various studies on the degradation of industrial wastewater by photocatalysts. Among them, the metallic oxide ZnO has the advantages of appropriate band gap energy of 3.37v, low cost, environmental protection and the like, and has important application in photocatalytic degradation. In view of the above problems, researchers have proposed many modification methods, such as doping with a metal, or forming a heterojunction with another metal, etc., all of which can significantly improve the degradation capability of ZnO as a photocatalyst.
The paper "preparation of two morphologies of nano ZnO and its photocatalytic performance test" discloses a method for preparing ZnO by hydrothermal reaction using citric acid and zinc acetate, when citric acid is not used, znO crystals are easy to form linear or rod-shaped materials, and after citric acid is added, the citric acid contains hydroxyl and carboxyl to make zinc ions and citrate radicals form complex chelate rings, so that the crystals can also grow along other directions to generate irregular flower-shaped nano/micron materials, the surface of the structure is relatively rough, mainly because ethanol is not added during the reaction, the precursor cannot be reduced and eroded, the formation of surface oxygen vacancies is promoted, the effect of citric acid is enhanced, so that ZnO uniformly grows beyond other directions, therefore, the surface of the obtained material is rough when oxygen vacancies are absent, and the efficiency of photocatalytic degradation of acid fuchsin the flower-shaped nano/micron materials is 86.8-87.6%.
The article "morphology of rare earth element cerium on zinc oxideAnd the influence of the photocatalytic performance indicates that when cerium is not doped, the used ZnO is recycled for carrying out photocatalytic degradation experiments by recycling, filtering, washing and drying, the photocatalytic degradation efficiency of the ZnO is reduced by 6 percent between 3 rd time and 4 th time, and the degradation efficiency is continuously reduced along with the increase of the cycle times. Therefore, the morphology of ZnO is changed by doping 2% of cerium, znO is round and irregular flake with uniform dispersion, the particle size is 100-200 nm when doping 1% of cerium, znO is disc-shaped with uniform dispersion when doping 2% of cerium, the particle size is 50-100 nm, the thickness is 10nm, the dispersion is uniform, znO is bulk flake accumulation when doping 3% of cerium, few microcrystals and a small amount of CeO2The ZnO crystal can be inhibited from being accumulated along a one-dimensional direction on the surface or the crystal lattice of ZnO, so that a two-dimensional structure is formed, the specific surface area of ZnO is improved, and the particle size is reduced.
However, the purposes of improving the photocatalytic degradation efficiency and increasing the cycle number of the catalyst are achieved, but the use amount of the rare earth element Ce is still high. The research of Hong et al and Labal et al shows that ZnO has a large specific surface area, which is beneficial to the adsorption of dye, and the regularly arranged ZnO can enable light rays to scatter for many times in the material, thereby improving the light capture efficiency and enhancing the photocatalytic activity of ZnO in the visible light range.
Disclosure of Invention
The invention aims to provide a rare earth metal Ce-doped petal-shaped ZnO photocatalyst which is used for carrying out photocatalytic degradation on wastewater and a preparation method thereof, in particular to a rare earth metal Ce-doped petal-shaped ZnO photocatalyst with excellent appearance after an ionic liquid type temperature-sensitive material is added and a preparation method thereof. The catalyst has small shape and size, large specific surface area and favorable dye adsorption, is regular in shape and highly dispersed, is not easy to agglomerate, and can ensure that light rays are scattered for many times in the material to improve the light capture efficiency, so that the catalyst has high photocatalytic degradation efficiency and can be recycled for many times, and the doping amount of rare earth is extremely low.
The invention has the conception that temperature-sensitive materials PNx (IL) y, zinc acetate, cerium salt and citric acid are dissolved in water together, the characteristic that the temperature-sensitive materials PNx (IL) y collapse to compact spheres above the critical temperature is utilized, the zinc acetate, the cerium salt and the citric acid are wrapped in the compact spheres, the compact spheres are uniformly dispersed, then a hydrothermal reaction is carried out to prepare a Ce-doped ZnO photocatalyst, after the temperature-sensitive materials PNx (IL) y are removed, the shape of the catalyst is regular, the size is small, the specific surface area is large, and the catalyst is not agglomerated.
An ionic liquid is a salt that is liquid at room temperature and is composed entirely of anions and cations, and is therefore called low temperature molten salt. The ionic liquid has designability, and the functionalized ionic liquid can be directionally designed according to the requirement. In the existing research, the ionic liquid has a wide application range, a wide operable temperature range and good thermal stability and chemical stability.
The temperature-sensitive material poly-N-isopropyl acrylamide is an amphiphilic polymer, the critical temperature (LCST) of the temperature-sensitive material poly-N-isopropyl acrylamide is 32 ℃, and a gelatinous aqueous solution can be formed in water, so that the dispersion performance of doped metal in metal oxide can be obviously improved. By utilizing the property, the ionic liquid temperature-sensitive polymer can be used as a template agent, metal salt and rare earth metal are dissolved in water to prepare rare earth metal doped metal oxide based on the template morphology, and the rare earth metal is uniformly dispersed on the surface of the metal oxide.
In order to achieve the purpose, the technical scheme of the invention is as follows: a rare earth metal Ce-doped petal-shaped ZnO photocatalyst comprises rare earth metal Ce-doped petal-shaped ZnO photocatalyst nanoparticles in a petal-shaped structure, wherein the nanoparticles are self-assembled into the petal-shaped structure by nanometer spindle blades with the average width of 0.3-0.8 mu m and the length of 1-1.5 mu m, the particle size of the nanoparticles is 3-8 mu m, and the chemical formula of the nanoparticles is Zn1-zCezO, wherein z =0.002 to 0.004.
Furthermore, the catalyst is obtained by dissolving a temperature-sensitive polymer PN64 (IL) 8, a soluble salt of zinc, a soluble salt of cerium and citric acid in deionized water, dispersing by microwave, performing hydrothermal reaction at 120 ℃ to obtain a precipitate, washing the precipitate with absolute ethyl alcohol and distilled water, removing the temperature-sensitive polymer PN64 (IL) 8, and drying, wherein the temperature-sensitive polymer PN64 (IL) 8 is a amphiphilic block copolymer containing an imidazole-based ionic liquid and a poly N-isopropyl acrylamide segment, which is synthesized by a polymerizable double-bond imidazole compound and an N-isopropyl acrylamide monomer by a reversible addition fragmentation chain transfer polymerization method, and 64 and 8 respectively represent the polymerization degrees of the poly N-isopropyl acrylamide segment monomer and the polymerizable double-bond imidazole compound in the temperature-sensitive polymer.
The invention also provides a preparation method of the rare earth metal Ce doped petal-shaped ZnO photocatalyst, and the specific embodiment is as follows:
the method comprises the following steps:
1) AIBN is adopted as an initiator, an imidazole compound containing polymerizable double bonds and N-isopropylacrylamide are adopted as reaction monomers, mercaptoethylamine hydrochloride is adopted as an end-capping reagent, anhydrous methanol is adopted as a solvent, nitrogen is adopted as a protective gas, the reaction temperature is 60-80 ℃, the reaction time is 12-24 h, after the reaction is finished, diethyl ether is adopted as a precipitator, and the poly N-isopropylacrylamide-ionic liquid polymer PNIPAAm-co-IL is obtained, namely PNx (IL) y, x =64 and y =8 are respectively the polymerization degrees of the imidazole compound containing polymerizable double bonds and the N-isopropylacrylamide in the PNx (IL) y;
2) Dissolving a temperature-sensitive polymer PN64 (IL) 8, a soluble salt of zinc, a soluble salt of cerium and citric acid in deionized water, stirring and dissolving by adopting constant-temperature magnetic force until the solution is in a clear and transparent state, and then dispersing by using microwaves, wherein the molar ratio of the PN64 (IL) 8, the soluble salt of zinc and the citric acid is 4:4:3, the mol ratio of Zn to Ce in the soluble salt of zinc and the soluble salt of cerium is 1-z: z, z = 0.002-0.004;
3) Transferring the mixed solution into a reaction kettle, performing hydrothermal reaction at 120 ℃ to obtain a precipitate, washing the precipitate with absolute ethyl alcohol and distilled water, removing a temperature-sensitive polymer PN64 (IL) 8, and drying to obtain a rare metal Ce-doped ZnO photocatalyst Zn1- zCezO，z＝0.002～0.004。
In the scheme, the imidazole compound containing polymerizable double bonds is copolymerized with N-isopropyl acrylamide, so that the polymer can form micelles wrapping zinc ions, cerium ions and citric acid in water, each micelle is independently used as a micro-reaction space and can play a role of a template, crystals grow into petal shapes by taking the polymer as a center, and the effect of dispersing ZnO catalyst particles is achieved.
Preferably, the soluble salt of zinc comprises zinc acetate or zinc chloride.
Further, the imidazole compound containing polymerizable double bonds is 1-vinyl-3-methylimidazole.
Compared with the prior art, the invention has the following outstanding properties and remarkable advantages:
(1) The temperature sensitive material PN64 (IL) 8 can enhance the compatibility of each substance in the precursor and prevent each reaction precursor from aggregating in aqueous solution.
(2) In the invention, PN64 (IL) 8 is used as a template agent, and the shape of the template agent is controlled to form the metal Ce doped ZnO photocatalytic material with a controllable structure, so that the process flow is easy, the control is accurate, and the repeatability is high.
(3) The petal-shaped metal Ce doped ZnO photocatalyst prepared by the invention has better photodegradability than the prior art.
Drawings
FIG. 1 is a TEM (Transmission Electron microscope) representation of a micelle formed by a template agent PN64 (IL) 8;
FIG. 2 is a SEM representation of the photocatalyst of comparative example 1;
FIG. 3 is a SEM representation of the photocatalyst of comparative example 2;
FIG. 4 is a SEM representation of the photocatalyst of example 2;
FIG. 5 is a SEM representation of the photocatalyst of example 3;
FIG. 6 is a SEM representation of the photocatalyst of example 4;
FIG. 7 is a SEM representation of the photocatalyst of example 5;
FIG. 8 is a SEM representation of the photocatalyst of example 6;
FIG. 9 is an XRD characterization diagram of the petal-shaped metal Ce doped ZnO catalytic materials obtained in comparative example 1, example 2, example 4, example 5 and example 6;
FIG. 10 is a graph of the performance of the photocatalyst prepared in comparative example 1 for photocatalytic degradation of methyl orange;
FIG. 11 is a graph of the performance of the photocatalyst prepared in comparative example 2 for photocatalytic degradation of methyl orange;
FIG. 12 is a graph of the performance of the photocatalyst prepared in example 2 for photocatalytic degradation of methyl orange;
FIG. 13 is a graph of the performance of the photocatalysts prepared in examples 2, 4,5,6 and 7 in photocatalytic degradation of methyl orange;
FIG. 14 is a graph showing the photocatalytic degradation performance in reuse of the photocatalyst obtained in example 2. Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention, which is illustrated in the accompanying drawings and specific examples.
Example 1:
preparing a template agent:
AIBN is used as an initiator, an imidazole compound containing polymerizable double bonds and N-isopropyl acrylamide are used as reaction monomers, mercaptoethylamine hydrochloride is used as an end capping agent, and a reversible addition fragmentation chain transfer polymerization method is adopted, namely, anhydrous methanol is used as a solvent, nitrogen is used as protective gas, the reaction temperature is 60-80 ℃, and the reaction time is 12-24 hours. After the reaction was complete, diethyl ether was used as a precipitant to afford a white solid. The vacuum drying temperature is 30-60 ℃, and the drying time is 8-16 h. Obtaining the poly N-isopropyl acrylamide-ionic liquid polymer PNIPAAm-co-IL (PNx (IL) y), and characterizing the appearance of the poly N-isopropyl acrylamide-ionic liquid polymer PNIPAAm-co-IL. By controlling the ratio of adding two monomers of a poly N-isopropyl acrylamide sheet monomer and an imidazole compound containing a polymerizable double bond, a polymer PN64 (IL) 8 with a required morphology, x =64 and y =8 is obtained, and the TEM characterization of a transmission electron microscope is shown in FIG. 1.
Figure GDA0003315990740000071
In the embodiment, 1-vinyl-3-methylimidazole in imidazole compounds containing polymerizable double bonds is selected.
Comparative example 1:
when no template agent is added, the doping amount is 2 per mill rare element Ce doped ZnO photocatalysis preparation:
according to Zn1-zCezMolar ratio of Zn element and Ce element in O (z = 0.002) Zn (CH) was weighed out in a corresponding molar ratio3COO)2·2H2O and CeCl3·7H2Dissolving O in deionized water, and adding Zn (CH)3COO)2·2H2Amount of substance M of O1With citric acid (C)6H8O7) Mass M of2The ratio of M1：M2=4:3 accurately weighing citric acid and adding the citric acid into the solution. Dissolving the mixture by adopting constant-temperature magnetic stirring until the solution is in a clear and transparent state, then performing microwave dispersion on the mixed solution by using a microwave-assisted hydrothermal technology, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, filling the mixed solution into the polytetrafluoroethylene reaction kettle to be 3/4 of the total volume of the reaction kettle, screwing and sealing the reaction kettle, and adjusting the temperature to 120 ℃ for heating for 10 hours. After the reaction is finished, naturally cooling the reaction kettle to room temperature, taking out the solution, centrifuging to obtain white precipitate, washing with absolute ethyl alcohol and distilled water for 3 times respectively, and drying in vacuum for 4 hours to obtain a white powder product, namely the rare metal Ce doped ZnO photocatalyst Zn without the template agent0.998Ce0.002And O. The morphology is characterized as shown in figure 2, the catalyst particles are non-uniformly agglomerated into a whole, the diameter is 2-3 μm, and the surface is flat.
Comparative example 2:
after adding the template agent, preparing ZnO photocatalysis:
the template PN64 (IL) 8 prepared above was dissolved in 10mL of deionized water as Zn (CH)3COO)2·2H2The molar weight ratio of O to the template is 1:1 equal amount of Zn (CH)3COO)2·2H2O, according to Zn (CH)3COO)2·2H2Amount of substance M of O1With citric acid (C)6H8O7) Mass M of2The ratio of M1：M2=4:3 accurately weighing citric acid and adding the citric acid into the solution. Dissolving the mixture by constant-temperature magnetic stirring until the solution is in a clear and transparent state, then performing microwave dispersion on the mixed solution by using a microwave-assisted hydrothermal technology, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, filling the mixed solution into the reaction kettle by 3/4 of the total volume of the reaction kettle, screwing the reaction kettle, sealing, and adjusting the temperature to 120 ℃ for heating for 10 hours. After the reaction is finished, naturally cooling the reaction kettle to room temperature, taking out the solution, centrifuging to obtain white precipitate, washing with absolute ethyl alcohol and distilled water for 3 times respectively, removing the template agent PN64 (IL) 8, and drying in vacuum for 4 hours to obtain a white powder product, namely the photocatalyst ZnO. The morphology of the catalyst particles is represented as fig. 3, and the catalyst particles have rough surfaces and three-dimensional structures.
Example 2:
after adding the template agent, the rare element Ce doped ZnO photocatalysis preparation with the doping amount of 2 per mill:
the template PN64 (IL) 8 prepared above was dissolved in 10mL of deionized water as Zn (CH)3COO)2·2H2The molar weight ratio of O to the template is 1:1 equal amount of Zn (CH)3COO)2·2H2O, according to Zn1-zCezMolar ratio of Zn element and Ce element in O (z = 0.002) Zn (CH) was weighed out in a corresponding molar ratio3COO)2·2H2O and CeCl3·7H2Dissolving O in deionized water, according to Zn (CH)3COO)2·2H2Amount of substance M of O1With citric acid (C)6H8O7) Mass M of2The ratio of M1：M2=4:3 accurately weighing citric acid and adding the citric acid into the solution. Dissolving the mixture by constant-temperature magnetic stirring until the solution is in a clear and transparent state, then performing microwave dispersion on the mixed solution by using a microwave-assisted hydrothermal technology, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, filling the mixed solution into the reaction kettle by 3/4 of the total volume of the reaction kettle, screwing the reaction kettle, sealing, and adjusting the temperature to 120 ℃ for heating for 10 hours. After the reaction is finished, naturally cooling the reaction kettle to room temperature, taking out the solution, and centrifuging to obtain whitePrecipitating, washing with anhydrous ethanol and distilled water for 3 times respectively, removing template agent PN64 (IL) 8, vacuum drying for 4 hr to obtain white powder product, i.e. rare metal Ce doped ZnO photocatalyst Zn0.998Ce0.002And O. The morphology is characterized in fig. 4. The catalyst particles are self-assembled into a flower-shaped structure by a nano spindle piece with the average width of 0.3-0.8 mu m and the length of 1-1.5 mu m, the particle size of the nano particles is 3-8 mu m, and the catalyst particles are mutually dispersed.
Example 3:
after adding the template agent, preparing the rare element Ce doped ZnO photocatalysis with the doping amount of 3 per mill:
the template PN64 (IL) 8 prepared above was dissolved in 10mL of deionized water as Zn (CH)3COO)2·2H2The molar weight ratio of O to the template is 1:1 equal amount of Zn (CH)3COO)2·2H2O, according to Zn1-zCezMolar ratio of Zn element and Ce element in O (z = 0.003) Zn (CH) was weighed out in a corresponding molar ratio3COO)2·2H2O and CeCl3·7H2Dissolving O in deionized water, and adding Zn (CH)3COO)2·2H2Amount of substance M of O1With citric acid (C)6H8O7) Mass M of2The ratio of M1：M2=4:3 accurately weighing citric acid and adding the citric acid into the solution. Dissolving the mixture by constant-temperature magnetic stirring until the solution is in a clear and transparent state, then performing microwave dispersion on the mixed solution by using a microwave-assisted hydrothermal technology, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, filling the mixed solution into the reaction kettle by 3/4 of the total volume of the reaction kettle, screwing the reaction kettle, sealing, and adjusting the temperature to 120 ℃ for heating for 10 hours. After the reaction is finished, naturally cooling the reaction kettle to room temperature, taking out the solution, centrifuging to obtain white precipitate, washing with absolute ethyl alcohol and distilled water for 3 times respectively, removing the template agent PN64 (IL) 8, and drying in vacuum for 4h to obtain a white powder product, namely the rare metal Ce doped ZnO photocatalyst Zn0.997Ce0.003And O. The morphology is characterized as shown in fig. 5. The catalyst particles are self-assembled into flower shapes by nanometer spindle sheets with the average width of 0.3-0.5 mu m and the length of 1-1.5 mu mThe structure is that the grain diameter of the nano-particle is 3-6 μm, and the catalyst grains are mutually dispersed.
Example 4:
after adding the template agent, preparing the rare element Ce doped ZnO photocatalysis with doping amount of 6 per mill:
the template PN64 (IL) 8 prepared above was dissolved in 10mL deionized water as Zn (CH)3COO)2·2H2The molar weight ratio of O to the template is 1:1 equal amount of Zn (CH)3COO)2·2H2O, according to Zn1-zCezMolar ratio of Zn element and Ce element in O (z = 0.006) Zn (CH) was weighed in a corresponding molar ratio3COO)2·2H2O and CeCl3·7H2Dissolving O in deionized water, and adding Zn (CH)3COO)2·2H2Amount of substance M of O1With citric acid (C)6H8O7) Mass M of2The ratio of M1：M2=4:3 accurately weighing citric acid and adding the citric acid into the solution. Dissolving the mixture by constant-temperature magnetic stirring until the solution is in a clear and transparent state, then performing microwave dispersion on the mixed solution by using a microwave-assisted hydrothermal technology, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, filling the mixed solution into the reaction kettle by 3/4 of the total volume of the reaction kettle, screwing the reaction kettle, sealing, and adjusting the temperature to 120 ℃ for heating for 10 hours. After the reaction is finished, naturally cooling the reaction kettle to room temperature, taking out the solution, centrifuging to obtain white precipitate, washing with absolute ethyl alcohol and distilled water for 3 times respectively, removing the template agent PN64 (IL) 8, and drying in vacuum for 4 hours to obtain a white powder product, namely the rare metal Ce doped ZnO photocatalyst Zn0.994Ce0.006And O. The morphology is characterized as shown in FIG. 6, and the surface is rough and irregular.
Example 5:
after adding the template agent, the preparation of the rare element Ce doped ZnO photocatalysis with the doping amount of 10 per mill:
the template PN64 (IL) 8 prepared above was dissolved in 10mL of deionized water as Zn (CH)3COO)2·2H2The molar weight ratio of O to the template is 1:1 equal amount of Zn (CH)3COO)2·2H2O, according to Zn1-zCezMolar ratio of Zn element and Ce element in O (z = 0.010) Zn (CH) was weighed out in a corresponding molar ratio3COO)2·2H2O and CeCl3·7H2Dissolving O in deionized water, and adding Zn (CH)3COO)2·2H2Amount of substance M of O1With citric acid (C)6H8O7) Mass M of2The ratio of M1：M2=4:3 accurately weighing citric acid and adding the citric acid into the solution. Dissolving the mixture by constant-temperature magnetic stirring until the solution is in a clear and transparent state, then performing microwave dispersion on the mixed solution by using a microwave-assisted hydrothermal technology, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, filling the mixed solution into the reaction kettle by 3/4 of the total volume of the reaction kettle, screwing the reaction kettle, sealing, and adjusting the temperature to 120 ℃ for heating for 10 hours. After the reaction is finished, naturally cooling the reaction kettle to room temperature, taking out the solution, centrifuging to obtain white precipitate, washing with absolute ethyl alcohol and distilled water for 3 times respectively, removing the template agent PN64 (IL) 8, and drying in vacuum for 4 hours to obtain a white powder product, namely the rare metal Ce doped ZnO photocatalyst Zn0.990Ce0.010And O. The morphology is shown in FIG. 7, and the specific surface area is reduced compared with the catalysts obtained in examples 2-4.
Example 6:
after adding the template agent, the preparation of the rare element Ce doped ZnO photocatalysis with the doping amount of 14 per mill:
the template PN64 (IL) 8 prepared above was dissolved in 10mL of deionized water as Zn (CH)3COO)2·2H2The molar weight ratio of O to the template is 1:1 equal amount of Zn (CH)3COO)2·2H2O, according to Zn1-zCezMolar ratio of Zn element and Ce element in O (z = 0.014) Zn (CH) was weighed out in a corresponding molar ratio3COO)2·2H2O and CeCl3·7H2Dissolving O in deionized water, and adding Zn (CH)3COO)2·2H2Amount of substance M of O1With citric acid (C)6H8O7) Mass M of2The ratio of M1：M2=4:3 accurately weighing citric acid and adding to the upper partIn the solution. Dissolving the mixture by constant-temperature magnetic stirring until the solution is clear and transparent, then performing microwave dispersion on the mixed solution by using a microwave-assisted hydrothermal technology, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, filling the mixed solution to 3/4 of the total volume, screwing and sealing the reaction kettle, and adjusting the temperature to 120 ℃ for heating for 10 hours. After the reaction is finished, naturally cooling the reaction kettle to room temperature, taking out the solution, centrifuging to obtain white precipitate, washing with absolute ethyl alcohol and distilled water for 3 times respectively, and drying in vacuum for 4 hours to obtain a white powder product, namely the rare metal Ce doped ZnO photocatalyst Zn0.986Ce0.014And O. The morphology is shown in FIG. 8, and the specific surface area is reduced compared with the catalysts obtained in examples 2-4.
Example 7
After adding the template agent, the doping amount is 4 per mill rare element Ce doped ZnO photocatalysis preparation:
the template PN64 (IL) 8 prepared above was dissolved in 10mL of deionized water as Zn (CH)3COO)2·2H2The molar weight ratio of O to the template is 1:1 equal amount of Zn (CH)3COO)2·2H2O, according to Zn1-zCezMolar ratio of Zn element and Ce element in O (z = 0.004) Zn (CH) was weighed out in a corresponding molar ratio3COO)2·2H2O and CeCl3·7H2Dissolving O in deionized water, and adding Zn (CH)3COO)2·2H2Amount of substance M of O1With citric acid (C)6H8O7) Mass M of2The ratio of M1：M2=4:3 accurately weighing citric acid and adding the citric acid into the solution. Dissolving the mixture by constant-temperature magnetic stirring until the solution is clear and transparent, then performing microwave dispersion on the mixed solution by using a microwave-assisted hydrothermal technology, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, filling the mixed solution to 3/4 of the total volume, screwing and sealing the reaction kettle, and adjusting the temperature to 120 ℃ for heating for 10 hours. After the reaction is finished, naturally cooling the reaction kettle to room temperature, taking out the solution, centrifuging to obtain white precipitate, washing with absolute ethyl alcohol and distilled water for 3 times respectively, and drying in vacuum for 4 hours to obtain a white powder product, namely the rare metal Ce-doped ZnOPhotocatalyst Zn0.996Ce0.004O。
The rare metal Ce doped ZnO photocatalyst synthesized by the template hydrothermal method obtained in this example 2-example 7 by controlling different experimental factors was compared, and the results are shown in the following table 1:
TABLE 1 template hydrothermal method synthesized rare metal Ce doped ZnO photocatalyst
Figure GDA0003315990740000141
Hydrothermal method conditions: water-30 ml, temperature =120 ℃, time =10h, nZn2+:nC6H8O7＝4：3
Example 6
And (3) testing the performance of the sample on degrading methyl orange: the photocatalysts prepared in examples 2, 7, 4 and 5 were applied to methyl orange degradation experiments, respectively. Accurately preparing a methyl orange solution with the concentration of 20mg/L, weighing 0.01g of the prepared photocatalyst, adding the photocatalyst into 100mL of the methyl orange solution with the concentration of 20mg/L, and stirring and dispersing for 30min in a dark place to ensure that the methyl orange is completely pre-adsorbed on the surface of the catalyst. Placing the solution in a photocatalytic reactor, starting circulating water, performing parallel test on the multiple groups of solutions by adopting a multi-channel photoreaction system, illuminating under an ultraviolet lamp, observing the color change of the solution, centrifuging the catalyst at a high speed after the reaction is finished, and taking out the supernatant. Performing full-waveband scanning on 20mg/L methyl orange at 200-900nm by using an ultraviolet-visible spectrophotometer, selecting the optimal detection wavelength, and recording the initial absorbance A0. Testing the absorbance A of the multiple groups of parallel solutions at the optimal detection wavelength, and calculating the photodegradation efficiency = [ (A)0-A)÷A0]×100％。
The experimental result shown in fig. 10 shows that when the temperature-sensitive polymer is not added to the material as a template, the obtained material (comparative example 1) reacts for 1.0 hour when being used in an experiment for photocatalytic degradation of methyl orange, and the degradation efficiency can only reach 36.4%. The reason may be that the photodegradation efficiency is low due to the uneven morphology of the resulting material.
As can be seen from the experimental graph 11, in comparative example 2, when the rare metal Ce is not added, the polymer is used as the template, and the obtained material ZnO is used as the photocatalyst for the methyl orange degradation experiment, the illumination time is 1.0h, the degradation rate reaches 40.2%, and when the rare metal Ce is not doped, the forbidden bandwidth of ZnO is wide, so that the electron holes generated by the ZnO under illumination are slow.
From the experimental results shown in fig. 12, it can be seen that when the doping amount of the metal Ce in the material is 2 ‰, the illumination time is 1.0h, and the degradation rate reaches 94.5% at most, i.e., the photocatalytic effect in example 2 is the best. In example 2, the Ce-doped ZnO can obtain a petal-shaped material with regular morphology, and the material regularity and morphology are the most excellent.
As shown in fig. 13, compared with example 2 with excellent morphology, when the doping amount of the rare metal Ce is increased to 4 ‰, the morphology of the material still maintains good, and the photodegradation efficiency thereof can be maintained at 94%. In other examples 4,5,6, the obtained morphology has no regular structure, and when the photocatalytic materials in other examples are also used in the photocatalytic degradation experiment of methyl orange, the catalytic effects are found to be lower than those in example 2.
Example 7
And (3) testing the material recovery performance: the photocatalysts prepared in examples 2, 3, 4 and 5 were respectively subjected to a recovery performance test. The specific operation is as follows: and centrifuging, filtering, drying and collecting the catalyst from the reaction solution after the reaction is finished. The dried catalyst was reused in the above example 6 to perform repeated experimental tests, and the photodegradation efficiency = [ (a) was calculated from the uv test results0-A)÷A0]X 100%. The cycle experiment result of fig. 14 proves that the Ce-doped ZnO catalyst has good stability and repeatability, and is an industrial photocatalyst with good application prospect.
Comprehensive analysis shows that the Ce doped ZnO prepared by taking the temperature-sensitive polymer PN64 (IL) 8 as the template has good photocatalytic performance. The material has such excellent photocatalytic performance, which is mainly attributed to the template effect of the temperature-sensitive polymer PN64 (IL) 8, and meanwhile, the temperature-sensitive polymer PN64 (IL) 8 has good solubility in an aqueous solution, so that the dispersion condition of zinc salt and cerium nitrate in water can be effectively improved, and the petal-shaped Ce-doped ZnO material with uniform appearance can be prepared.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution ways, so long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention as long as the technical principle and inventive concept of the method for preparing the temperature-sensitive Ce doped ZnO material and the application thereof are not departed from the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (5)

1. A rare earth metal Ce doped petal-shaped ZnO photocatalyst is characterized by comprising rare earth metal Ce doped petal-shaped ZnO photocatalyst nanoparticles in a petal-shaped structure, wherein the nanoparticles are self-assembled into the petal-shaped structure through nanometer spindle blades with the average width of 0.3-0.8 mu m and the length of 1-1.5 mu m, the particle size of the nanoparticles is 3~8 mu m, and the chemical formula of the nanoparticles is Zn1-zCezO, wherein z =0.002 to 0.004.
2. The photocatalyst of claim 1, wherein the catalyst is obtained by dissolving a temperature sensitive polymer PNx (IL) y, a soluble salt of zinc, a soluble salt of cerium, and citric acid in deionized water, dispersing the mixture in a microwave, subjecting the mixture to hydrothermal reaction at 120 ℃ to obtain a precipitate, washing the precipitate with absolute ethanol and distilled water, removing the temperature sensitive polymer PNx (IL) y, and drying the precipitate, wherein the temperature sensitive polymer PN64 (IL) 8 is a amphiphilic block copolymer of an imidazole-containing ionic liquid and a poly N-isopropylacrylamide fragment synthesized from a polymerizable double-bond imidazole compound and an N-isopropylacrylamide monomer by a reversible fragmentation chain transfer polymerization method, and 64 and 8 respectively represent the polymerization degrees of the poly N-isopropylacrylamide fragment monomer and the polymerizable double-bond imidazole compound in the temperature sensitive polymer.
3. The method of preparing the photocatalyst according to claim 1, comprising the steps of:
1) Using AIBN as initiator, imidazole compounds containing polymerizable double bonds andN-isopropylacrylamide is used as a reaction monomer, mercaptoethylamine hydrochloride is used as an end capping agent, anhydrous methanol is used as a solvent, nitrogen is used as a protective gas, the reaction temperature is 60 to 80 ℃, the reaction time is 12 to 24 hours, and after the reaction is finished, diethyl ether is used as a precipitator to obtain the poly (acrylamide-co-hydroxyethylamine) copolymerN-isopropylacrylamide-ionic liquid polymer PNIPAAm-co-IL, i.e. PNx (IL) y, x =64, y =8 for the degree of polymerization of the poly N-isopropylacrylamide platelet monomer and polymerizable double bond-containing imidazole compound, respectively, in PNx (IL) y;
2) Dissolving temperature-sensitive polymers PNx (IL) y, soluble salt of zinc, soluble salt of cerium and citric acid in deionized water, stirring and dissolving by adopting constant-temperature magnetic force until the solution is in a clear and transparent state, and then dispersing by using microwaves, wherein the molar ratio of PNx (IL) y to zinc acetate to citric acid is 4:4:3, the mol ratio of Zn to Ce in the soluble salt of zinc and the soluble salt of cerium is 1-z: z, z =0.002 to 0.004; 3) Transferring the mixed solution into a reaction kettle, performing hydrothermal reaction at 120 ℃ to obtain a precipitate, washing the precipitate with absolute ethyl alcohol and distilled water, removing a temperature-sensitive polymer PN64 (IL) 8, and drying to obtain a rare metal Ce-doped ZnO photocatalyst Zn1- zCezO，z=0.002~0.004。
4. A method of preparation according to claim 3 wherein the soluble salt of zinc comprises zinc acetate or zinc chloride.
5. The method according to claim 3, wherein the imidazole compound having a polymerizable double bond is 1-vinyl-3-methylimidazole.
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