CN111644170A - Rod-shaped cerium-doped zinc oxide and graphene composite photocatalyst with excellent photocatalytic performance under irradiation of visible light - Google Patents
Rod-shaped cerium-doped zinc oxide and graphene composite photocatalyst with excellent photocatalytic performance under irradiation of visible light Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 38
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- 239000002131 composite material Substances 0.000 title claims abstract description 16
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- 238000002360 preparation method Methods 0.000 claims abstract description 10
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- 229960000907 methylthioninium chloride Drugs 0.000 claims description 15
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000012018 catalyst precursor Substances 0.000 claims description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 2
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- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims 7
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
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- B01J35/39—
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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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—
Abstract
The invention discloses a preparation method and a flow of a rod-shaped cerium-doped zinc oxide and graphene composite material photocatalyst with excellent photocatalytic performance under the irradiation of visible light, and belongs to the technical field of material preparation. The invention is characterized in that: the photocatalyst has the advantages of simple preparation method, high catalytic efficiency, low cost, high yield and no pollution.
Description
Technical Field
The invention belongs to the field of material preparation, relates to preparation of a lanthanide cerium-doped N-type semiconductor zinc oxide and graphene composite material and research on photocatalytic performance of the lanthanide cerium-doped N-type semiconductor zinc oxide and graphene composite material, researches the difference of photocatalytic performance of the cerium-doped zinc oxide and graphene composite material and pure zinc oxide, and researches the influence of the doping concentration of cerium on the photocatalytic performance.
Background
As the most promising photocatalytic base material, zinc oxide (ZnO) has the advantages of no toxicity, no odor, low cost, simple preparation process and the like, and simultaneously has great potential in the fields of catalysts, gas sensitive elements, pressure sensitive devices, batteries, surface acoustic wave devices, quantum self-selection electronic devices, light emitting diodes and the like due to the wider band gap (3.37 eV) and the larger excitation binding energy (60 meV). However, the ZnO photo-generated electron-hole pair has the defects of high recombination rate, poor absorption capability in a visible light region and the like, so that the photocatalytic performance of the ZnO photo-generated electron-hole pair cannot achieve the expected effect, and the utilization rate in the field of photocatalysis is greatly reduced. Therefore, the photoresponse range of ZnO needs to be widened, and the improvement of the separation efficiency of photo-generated electron hole pairs is a way for improving the photocatalytic performance of zinc oxide. At present, in order to improve the photocatalytic activity of ZnO, there are mainly metal ion doping, noble metal compounding, semiconductor compounding, and the like. Doping may introduce new intermediate energy levels between the valence and conduction bands to reduce absorption energy. In addition, doping can also affect the grain size, crystallinity, and photoelectric properties of ZnO. Among the many doping elements, cerium is considered to be an ideal dopant to help increase the photocatalytic activity of zinc oxide. Cerium ion doped zinc oxide has been extensively studied and has made great progress. See Chemical Engineering Journal of high effective photocatalytic based on center ZnO nanoparticles, controlled synthetic and enhanced photocatalytic activity, No. 229, page 225, page 233, Powder Technology, Sonochemical genetic modified ZnO nanoparticles for high effective photocatalytic activity, No. 318, page 120, page 127. The composite material is an important means for making up the performance defect of a single material, enhancing the performance of the material and mixing the performance of various materials. Graphene is a two-dimensional honeycomb network composed of carbon atoms, which has a large specific surface area, high thermal and chemical stability, excellent electrical conductivity and mobility, and significant structural flexibility. Graphene provides a network with high electron conductivity in a photocatalytic process and serves as a support material as a carrier of a catalyst. The synergistic effect of the zinc oxide and the graphene is expected to improve the defect of the zinc oxide in photocatalysis, thereby improving the light absorption intensity, widening the light response range, inhibiting the carrier recombination, improving the surface activity and improving the photocatalytic activity. See SCIENCE, graphics _ Status and Prospectra, pp.1530-1534 at 324. See environmental science and Pollution Research of Synthesis and characterization of Ag/Bi2WO6GOcomposition for the fast definition of type in under visible light, 25 th 11754-11766 page. See The Journal of Physical Chemistry C: Controlled Synthesis CeO2Graphene Nanocomposites with high Enhanced Optical and catalytic Properties, phase 116, page 11741-11745.
Disclosure of Invention
The invention aims to prepare zinc oxide (ZnO), a zinc oxide graphene composite material (ZG), a cerium-doped zinc oxide and graphene composite material (ZGCeO 1, ZGCeO2, ZGCeO3 and ZGCeO 4) on the premise of the same experimental conditions, explore the optimal doping ratio concentration of cerium (the mass ratio of cerium doping is 2%) and explore the influence of doping and compounding on the photocatalytic performance of pure zinc oxide.
The method is realized by the following technical process that the graphene oxide used in the experiment is commercial graphene oxide, and the zinc source is zinc nitrate hexahydrate (Zn (NO)3)2•6H2O), the cerium source is cerium nitrate hexahydrate (Ce (NO)3)3•6H2O) and the alkali source is ammonia water (NH)3•H2O) and sodium hydroxide (NaOH), and the detergent is deionized water and absolute ethyl alcohol (C)2H5OH), all materials were analytically pure without further purification treatment. The catalyst precursor is prepared by adopting a one-step low-temperature hydrothermal method. First, 0.524g of Zn (NO) was added to a beaker containing 25ml of deionized water3)2•6H2And O. Stirring for 30 min, adding ammonia water dropwise to adjust pH to 11, stirring for 1 hr (solution A), loading into sealed stainless steel autoclave with polytetrafluoroethylene lining, reacting at 180 deg.C for 10 hr, washing the obtained product with deionized water and anhydrous ethanol several times, washing out impurities, and centrifuging to obtain white product, and vacuum drying at 70 deg.C for 10 hr. The obtained product is a ZnO sample. Repeating the preparation process of the solution A, adding 0.1125g of graphene oxide into another beaker filled with 25ml of deionized water, carrying out ultrasonic treatment for 30 minutes, then dropwise adding NaOH solution to adjust the pH value of the graphene oxide solution to 4, continuously stirring for 1 hour (solution B), mixing the solution A and the solution B after stirring for 30 minutes, then transferring the solution into a sealed stainless steel autoclave with a polytetrafluoroethylene lining, reacting for 10 hours at 180 ℃, and carrying out reverse reactionThe solution after reaction was washed with deionized water and absolute ethanol several times, and the resulting product was dried under vacuum at 70 ℃ for 10 hours. The resulting product was a ZG sample. 0.524g of Zn (NO) is weighed out3)2•6H2O into a beaker containing 25ml of deionized water, 0.0059g (1 wt%) of Ce (NO) was weighed3)3•6H2O was poured into the beaker and stirred for 30 minutes, then NaOH was added to both solutions to raise the pH to 11, stirring was carried out for 30 minutes, and ammonia was added dropwise to adjust the pH of the solution to 11 and stirring was carried out for 1 hour (solution C). During this period, 0.1125g of graphene oxide is weighed and poured into a beaker filled with 25ml of deionized water, ultrasonic treatment is carried out for 30 minutes, then NaOH solution is added dropwise to adjust the pH value of the graphene oxide solution to 4, stirring is carried out continuously for 1 hour (solution D), the stirred solutions C and D are mixed and stirred for 30 minutes, then the solution is transferred into a sealed stainless steel autoclave with a polytetrafluoroethylene lining, reaction is carried out for 10 hours at 180 ℃, the solution after the reaction is washed for a plurality of times by deionized water and absolute ethyl alcohol, and the obtained product is dried in vacuum for 10 hours at 70 ℃. The product obtained was a ZGCeO1 sample. Samples of ZGCeO2 (2 wt%), ZGCeO3 (3 wt%) and ZGCeO4 (4 wt%) were prepared using the same experimental procedure. Samples of 6 minutes including ZnO, ZG, ZGCeO1, ZGCeO2, ZGCeO3 and ZGCeO4 were co-produced and further characterized as described above.
The X-ray diffraction spectrograms (XRD) of the zinc oxide (ZnO), zinc oxide graphene composite material (ZG), cerium-doped zinc oxide and graphene composite material (ZGCeO 1, ZGCeO2, ZGCeO3, ZGCeO 4) prepared by the present invention are shown in fig. 1, the Scanning Electron Micrograph (SEM) of pure ZnO and ZGCeO2 samples are shown in fig. 2, the element Mapping (Mapping) of ZGCeO2 samples is shown in fig. 3, the ultraviolet-visible light absorption spectrum (UV-Vis) and the corresponding Tauc map of all samples are shown in fig. 4, the photoluminescence spectrogram (PL) of all samples is shown in fig. 5, the blank group, the absorbance maps of ZnO and ZGCeO2 light for 80 minutes of Methylene Blue (MB), and the photocatalytic activity tests of all samples are shown in fig. 6. The invention is characterized in that: 6 photocatalysts including zinc oxide (ZnO), zinc oxide graphene composite material (ZG), cerium-doped zinc oxide and graphene composite material (ZGCeO 1, ZGCeO2, ZGCeO3 and ZGCeO 4) are prepared by a simple one-step hydrothermal method, and grow in the same alkaline environment by adjusting the pH value, the grown morphology is hexagonal rod-shaped, the absorption of light of a target product (ZGCeO 2) is enhanced, the photoresponse range is widened, the separation efficiency of electron hole pairs is obviously enhanced, electrons jumping back to the ground state are reduced, photo-generated carriers are effectively separated, and the photocatalytic activity is greatly improved.
Drawings
Fig. 1 is an X-ray diffraction spectrum of zinc oxide (ZnO), zinc oxide graphene composite (ZG), cerium-doped zinc oxide and graphene composite (ZGCeO 1, ZGCeO2, ZGCeO3, ZGCeO 4), in which a is an XRD total spectrum with a diffraction angle of 20 ° to 80 °, and b is a diffraction peak spectrum of an enlarged (101) plane.
Fig. 2 is a Scanning Electron Micrograph (SEM) of pure ZnO and ZGCeO2 samples, wherein a and b correspond to micrographs of pure ZnO and ZGCeO2, respectively, and c is a schematic view of ZGCeO2 microstructure.
FIG. 3 is an element Mapping (Mapping) of the ZGCeO2 sample, wherein, the graphs a, b, C and d are Mapping graphs of C, O, Zn and Ce elements of the ZGCeO2 sample respectively.
Fig. 4 is an ultraviolet-visible absorption spectrum (UV-Vis) (panel a) and the corresponding Tauc plot (panel b) for all samples.
FIG. 5 is a photoluminescence spectrum (PL) of all samples.
FIG. 6 is a blank set, absorbance spectra of ZnO and ZGCeO2 illuminated for 80 minutes for Methylene Blue (MB) and photocatalytic activity test patterns of all samples, wherein panels a-c are the blank set, absorbance spectra of ZnO and ZGCeO2 illuminated for 80 minutes for Methylene Blue (MB), respectively; d is the photodegradation curve of the photocatalyst with different doping concentrations to MB; e is the MB photodegradation kinetics curve; f is a histogram of the rate constants of the photocatalysts with different doping concentrations.
Detailed Description
Example 1
First, 0.524g of Zn (NO) was added to a beaker containing 25ml of deionized water3)2•6H2And O. Continuously stirring for 30 minutesAfter dropping ammonia water to adjust the pH value of the solution to 11, stirring the solution continuously for 1 hour (solution A), putting the solution into a stainless steel autoclave with a sealed polytetrafluoroethylene lining, reacting the solution for 10 hours at 180 ℃, washing the obtained product with deionized water and absolute ethyl alcohol for a plurality of times, washing out impurities and centrifuging the product to obtain a white product, and drying the white product for 10 hours in vacuum at 70 ℃. The obtained product is a ZnO sample.
Example 2
Repeating the preparation process of the solution A, adding 0.1125g of graphene oxide into another beaker filled with 25ml of deionized water, carrying out ultrasonic treatment for 30 minutes, then dropwise adding NaOH solution to adjust the pH value of the graphene oxide solution to 4, continuously stirring for 1 hour (solution B), mixing the solution A and the solution B after stirring for 30 minutes, transferring the solution into a sealed stainless steel autoclave with a polytetrafluoroethylene lining, reacting for 10 hours at 180 ℃, washing the solution after reaction for multiple times with deionized water and absolute ethyl alcohol, and carrying out vacuum drying on the obtained product for 10 hours at 70 ℃. The resulting product was a ZG sample.
Example 3
0.524g of Zn (NO) is weighed out3)2•6H2O into a beaker containing 25ml of deionized water, 0.0059g (1 wt%) of Ce (NO) was weighed3)3•6H2O was poured into the beaker and stirred for 30 minutes, then NaOH was added to both solutions to raise the pH to 11, stirring was carried out for 30 minutes, and ammonia was added dropwise to adjust the pH of the solution to 11 and stirring was carried out for 1 hour (solution C). During this period, 0.1125g of graphene oxide is weighed and poured into a beaker filled with 25ml of deionized water, ultrasonic treatment is carried out for 30 minutes, then NaOH solution is added dropwise to adjust the pH value of the graphene oxide solution to 4, stirring is carried out continuously for 1 hour (solution D), the stirred solutions C and D are mixed and stirred for 30 minutes, then the solution is transferred into a sealed stainless steel autoclave with a polytetrafluoroethylene lining, reaction is carried out for 10 hours at 180 ℃, the solution after the reaction is washed for a plurality of times by deionized water and absolute ethyl alcohol, and the obtained product is dried in vacuum for 10 hours at 70 ℃. The product obtained was a ZGCeO1 sample. Samples of ZGCeO2 (2 wt%), ZGCeO3 (3 wt%) and ZGCeO4 (4 wt%) were prepared using the same experimental procedure.
Claims (4)
1. A rod-shaped cerium-doped zinc oxide and graphene composite photocatalyst with excellent photocatalytic performance under the irradiation of visible light is characterized by low cost, no pollution, high catalytic efficiency and simple preparation method; the graphene oxide used in the experiment was commercial graphene oxide, and the zinc source was zinc nitrate hexahydrate (Zn (NO)3)2•6H2O), the cerium source is cerium nitrate hexahydrate (Ce (NO)3)3•6H2O) and the alkali source is ammonia water (NH)3•H2O) and sodium hydroxide (NaOH), and the detergent is deionized water and absolute ethyl alcohol (C)2H5OH), all materials are analytically pure without further purification treatment; the catalyst precursor was prepared by a one-step low temperature hydrothermal method by first adding 0.524g Zn (NO) in a beaker containing 25ml deionized water3)2•6H2O; continuously stirring for 30 minutes, dropwise adding ammonia water to adjust the pH value of the solution to 11, continuously stirring for 1 hour (solution A), putting the solution into a sealed stainless steel autoclave with a polytetrafluoroethylene lining, reacting for 10 hours at 180 ℃, washing the obtained product for several times by using deionized water and absolute ethyl alcohol, washing out impurities and centrifuging to obtain a white product, and performing vacuum drying for 10 hours at 70 ℃, wherein the obtained product is a ZnO sample; repeating the preparation process of the solution A, adding 0.1125g of graphene oxide into another beaker filled with 25ml of deionized water, carrying out ultrasonic treatment for 30 minutes, then dropwise adding NaOH solution to adjust the pH value of the graphene oxide solution to 4, continuously stirring for 1 hour (solution B), mixing the solution A and the solution B after stirring, stirring for 30 minutes, transferring the solution into a sealed stainless steel autoclave with a polytetrafluoroethylene lining, reacting for 10 hours at 180 ℃, washing the solution after reaction with deionized water and absolute ethyl alcohol for multiple times, and carrying out vacuum drying on the obtained product for 10 hours at 70 ℃, wherein the obtained product is a ZG sample; 0.524g of Zn (NO) is weighed out3)2•6H2O into a beaker containing 25ml of deionized water, 0.0059g (1 wt%) of Ce (NO) was weighed3)3•6H2Pouring O into the beaker, continuously stirring for 30 minutes, then adding NaOH into the two solutions to increase the pH value to 11, stirring for 30 minutes, dropwise adding ammonia water to adjust the pH value of the solution to 11Stirring was continued for another 1 hour (solution C); weighing 0.1125g of graphene oxide in the period, pouring the graphene oxide into a beaker filled with 25ml of deionized water, carrying out ultrasonic treatment for 30 minutes, then dropwise adding NaOH solution to adjust the pH value of the graphene oxide solution to 4, continuously stirring for 1 hour (solution D), mixing the solution C and the solution D after stirring, stirring for 30 minutes, then transferring the solution into a sealed stainless steel autoclave with a polytetrafluoroethylene lining, reacting for 10 hours at 180 ℃, washing the solution after reaction for multiple times with deionized water and absolute ethyl alcohol, and carrying out vacuum drying on the obtained product for 10 hours at 70 ℃, wherein the obtained product is a ZGCeO1 sample; samples of ZGCeO2 (2 wt%), ZGCeO3 (3 wt%) and ZGCeO4 (4 wt%) were prepared using the same experimental procedure; co-producing a 6-clock sample including ZnO, ZG, ZGCeO1, ZGCeO2, ZGCeO3 and ZGCeO4 by the above method, analyzing the morphology, structure, composition and optical properties of the sample by a series of characterization means such as X-ray diffraction (XRD), Scanning Electron Microscope (SEM), element Mapping (Mapping), ultraviolet-visible light absorption spectrum (UV-Vis), fluorescence excitation spectrum (PL), photocatalytic performance test we used a 350w xenon lamp as the light source, and Methylene Blue (MB) as the degraded target dye; the concentration of the organic dye is 10mg/L, and the stirring is continued for 3 hours; weighing 30mg of sample, putting the sample into four test tubes filled with 50ml of organic dye, and stirring to ensure that the catalyst is fully contacted with the dye; after dark treatment for 30 minutes, the organic dye and the photocatalyst reach the balance of adsorption and desorption; then, turning on a xenon lamp, and taking out 3-4ml of solution every 30 minutes; the absorption peak of MB at 664nm was measured by UV-visible spectroscopy, based on the degradation rate a = ((C)0-C）/C0) 100% (initial absorbance value of MB as C)0Setting the absorbance value of degraded MB as C) calculating the degradation rate of MB, and evaluating the photocatalytic performance of the sample by using the change of the absorbance of methylene blue solution; based on the photocatalytic results, the ZGCeO2 (2 wt%) sample was found to exhibit the highest photocatalytic activity.
2. The method as claimed in claim 1, wherein the pH value of graphene oxide is adjusted to 4 during hydrothermal synthesis, the pH value of the metal salt solution is adjusted to 11, and the zinc oxide nanorod can be prepared by hydrothermal reaction at 180 ℃ for 10 hours.
3. The method according to claim 1, wherein the cerium is contained in the target product in an amount of 2% by mass.
4. The method according to claim 1, wherein the graphene is present in an amount of 23.8% by mass.
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