CN113663685A - Synthesis method and photocatalytic application of broadband composite photocatalyst - Google Patents
Synthesis method and photocatalytic application of broadband composite photocatalyst Download PDFInfo
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- CN113663685A CN113663685A CN202111052453.5A CN202111052453A CN113663685A CN 113663685 A CN113663685 A CN 113663685A CN 202111052453 A CN202111052453 A CN 202111052453A CN 113663685 A CN113663685 A CN 113663685A
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- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 67
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 58
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 69
- 229910019408 CoWO4 Inorganic materials 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002105 nanoparticle Substances 0.000 claims abstract description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
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- 239000000243 solution Substances 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 17
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- 238000002156 mixing Methods 0.000 claims description 10
- 238000000862 absorption spectrum Methods 0.000 claims description 7
- 238000002329 infrared spectrum Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000000295 emission spectrum Methods 0.000 claims description 2
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- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229910052691 Erbium Inorganic materials 0.000 description 27
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 19
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 17
- 238000003756 stirring Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 235000013024 sodium fluoride Nutrition 0.000 description 7
- 239000011775 sodium fluoride Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 229910001960 metal nitrate Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
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- 238000001228 spectrum Methods 0.000 description 4
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 description 4
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 238000013032 photocatalytic reaction Methods 0.000 description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000003911 water pollution Methods 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
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- 239000003054 catalyst Substances 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a synthesis method and a photocatalytic application of a broadband composite photocatalyst. The composite photocatalyst comprises NaYF which is prepared by passing through an up-conversion material4Uniformly adhering CoWO on the surface of Yb and Er4A heterostructure formed by photocatalytic semiconductor nanoparticles, in which the up-conversion material NaYF4Yb, Er can absorb near infrared spectrumLight, the visible light emitted being CoWO4Absorbed and enhanced CoWO4Light absorption of (2). The invention adopts a two-step hydrothermal method to compound the photocatalyst and the up-conversion material, and the synthesis process has certain universality; and the synthesis process is simple, the equipment cost is low, and the uniformity of the synthesized material is good. The invention obviously promotes the CoWO4The photocatalytic capability of the composite material has wide application prospect in the fields of preparation of high-performance photocatalytic materials and photocatalytic degradation of organic pollutants.
Description
Technical Field
The invention relates to the technical field of preparation of semiconductor photocatalytic materials, in particular to synthesis and application of a broadband composite photocatalytic material.
Background
With the rapid development of modern industrial technologies, serious environmental pollution problems become a great challenge to human society. In particular, the water pollution caused by organic pollutants seriously affects the survival and development of human beings. Photocatalytic materials and techniques based on photochemical redox reactions are considered to be an effective and environmentally friendly solution to the problem of water pollution. Titanium dioxide (TiO), a conventional photocatalytic material2) Due to its large forbidden band width (Eg)>3eV), only ultraviolet light occupying about 10% of the solar energy can be absorbed, and therefore, the solar energy utilization efficiency is low. Researchers in all countries around the world are working on developing new visible light photocatalytic materials and improving the solar light energy utilization efficiency of the photocatalytic materials, such as chinese patents CN107185565A and CN 111495396A. Wherein CN111495396A utilizes an upconverting material to increase available TiO2The absorbed ultraviolet light, CN107185565A, introduces Ag ions and utilizes the visible light formed by excitation of the upconverting material. These patents attempt to increase photocatalytic power by increasing the number of excited electrons and holes, but the photocatalytic efficiency increases only marginally as the absorption spectrum extends from ultraviolet to visible.
Since CoWO4The material has better chemical stability, and can absorb part of visible light (the forbidden band width Eg is 2.2-2.7 eV) compared with titanium dioxide, so that the material becomes one of research hotspots in the field of visible light photocatalytic materials. However, the pure cobalt tungstate material has low photocatalytic activity and cannot meet the requirements of practical application.And earlier studies focused primarily on the construction of CoWO4Heterojunction combined with narrow bandgap semiconductor, e.g. CdS/CoWO prepared by two-step hydrothermal method in Chinese patent CN106076367A4The heterojunction composite photocatalyst enhances the photocatalytic capacity by improving the quantum efficiency. In addition, Chinese patent CN108479811A utilizes hydrothermal method and precipitation method to synthesize composite Z-shaped acoustic catalyst SrTiO3/Ag2S/CoWO4The method has good acoustic catalytic degradation activity on the antibiotic wastewater by effectively inhibiting the recombination of photogenerated electrons and holes. However, heavy metal element cadmium (Cd) is introduced in the synthesis process of the CN106076367A composite photocatalyst, so that the risk of secondary water pollution exists, and the spectrum utilization range of the material is not expanded. The synthesis process of the CN108479811A composite acoustic catalyst is relatively complicated and is not beneficial to large-scale production; and moreover, noble metal Ag is introduced, so that the production cost is increased.
At present, the adoption of 'CoWO' is not seen4With up-converting materials (e.g. NaYF)4Yb, Er) composite wide-band photocatalyst. And increasing CoWO in the context of broadband and even full spectrum applications4The photocatalytic efficiency of (a) is a technical problem in the art.
Disclosure of Invention
In order to promote CoWO4Decrease of the photocatalytic activity of CoWO4The invention provides a synthesis method of a broadband composite photocatalyst and photocatalytic application, and relates to the application cost of a base photocatalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
a broad-band composite photocatalyst is prepared from the photocatalytic semiconductor CoWO4Heterostructure compositions with up-converting materials having absorption spectra in combination with CoWO4Has a different absorption spectrum (the absorption spectrum is completely different or not completely the same), and the emission spectrum of the up-conversion material is the same as that of CoWO4The absorption spectra of the heterogeneous structures are matched (partially or completely matched), and the heterogeneous structure specifically comprises 1-2 layers of CoWO which are uniformly distributed and attached to different areas of the surface4The upconverting material microstructures of the nanoparticles.
Preferably, the composite photocatalyst further comprises CoWO dispersed around the heterostructure component4An aggregate of nanoparticles.
Preferably, the up-conversion material is selected from NaYF capable of absorbing light in a near infrared spectrum band (800-1100 nm)4Based on a fluorescent material.
Preferably, in the heterostructure components, the up-conversion material micron structure adopts NaYF with the length of 8-10 mu m and the diameter of 2.1-2.6 mu m4Yb, Er micron rod capable of absorbing near infrared light of 980 nm; CoWO (cobalt oxide)4The diameter of the nanoparticles is 30-55 nm.
Preferably, the composite photocatalyst is prepared by using CoWO4The precursor solution and the up-conversion material are used as raw materials and prepared by a hydrothermal method.
The preparation method of the broadband composite photocatalyst comprises the following steps:
mixing CoWO4And an upconverting material (e.g., NaYF)4Yb and Er powder are fully and uniformly mixed and then transferred into a high-pressure hydrothermal reaction kettle for hydrothermal reaction, cooling, centrifuging, washing and drying (at 60-80 ℃ for 10-12 hours) are carried out after the reaction process is finished, and the obtained powder is the broadband composite photocatalyst (such as CoWO)4-NaYF4Yb, Er composite photocatalyst) containing the above-described heterostructure component formed by in-situ synthesis.
Preferably, the CoWO4The mixing ratio of the precursor liquid and the upconversion material powder is according to CoWO4Upconverting materials (e.g., NaYF)4Yb, Er) is 30-90: 1.
Preferably, the reaction conditions are as follows: the temperature is 170-190 ℃ and the time is 10-12 hours.
Preferably, the preparation method of the up-conversion material specifically comprises the following steps: weighing a stoichiometric ratio of Y (NO)3)3·6H2O、Yb(NO3)3·5H2O and Er (NO)3)3·5H2O (molar ratio of elemental ions Y: Yb: Er: 88:10:2) and ethylenediaminetetraacetic acid (E)Mixing DTA with an aqueous solution with a molar ratio of 1:1 of the total of Y, Yb metal and Er cations to form a clear transparent solution, mixing the clear transparent solution with a NaF aqueous solution (the molar ratio of sodium ions to the total of Y, Yb metal and Er cations is 4-12: 1) to form a suspension, pouring the suspension into a high-pressure hydrothermal reaction kettle, carrying out hydrothermal reaction at 170-190 ℃ for 22-25 hours, naturally cooling the high-pressure hydrothermal reaction kettle to room temperature, and centrifuging, washing and drying (60-80 ℃ for 10-12 hours) to obtain NaYF4Yb, Er powder.
Preferably, the CoWO4The preparation method of the precursor solution specifically comprises the following steps: weighing Na in a certain stoichiometric ratio2WO4·2H2O and Co (NO)3)2·6H2O (molar ratio of element ions W: Co ═ 1:1), and each was prepared as Na2WO40.1-0.3 mol/L of aqueous solution and Co (NO)3)2An aqueous solution (0.1 to 0.3 mol/L); mixing solution B and solution A to form suspension, namely CoWO4The precursor solution of (1).
The application of the broadband composite photocatalyst in photocatalytic degradation of organic pollutants.
Preferably, the component of the organic contaminant comprises rhodamine-B.
Preferably, the degradation specifically comprises the following steps: adding the broadband composite photocatalyst into an organic pollutant solution, adsorbing for more than or equal to 30 minutes in a dark place, and irradiating by using a composite light source with the wavelength of 420-1100 nm.
The invention has the beneficial effects that:
the invention adopts CoWO4The broadband composite photocatalyst containing the heterostructure is constructed with the up-conversion material, so that the transmission and utilization efficiency of photons in the composite material is improved, and the CoWO is improved4The photocatalytic ability of the compound is expanded, and CoWO is expanded4The light absorption spectral range of (a).
Further, the broad band composite photocatalyst of the present invention is prepared by using an up-conversion material (such as NaYF)4Yb, Er) absorbs near infrared light and emits visible light to realize the composite photocatalyst from ultraviolet to nearThe solar energy of the infrared spectrum band is absorbed, and the solar energy utilization efficiency is improved.
Further, the upconversion material NaYF in the invention4The visible light emitted by Yb, Er can be treated by CoWO4Effective absorption is realized, and more electron-hole pairs are excited by enhancing the light absorption of the material, so that CoWO is promoted4The photocatalytic capability of the photocatalytic material.
The invention utilizes a hydrothermal method to prepare the broadband composite photocatalyst, and has the advantages of simple synthesis process, lower cost of raw materials and equipment and better uniformity of synthetic materials.
Drawings
FIG. 1 shows CoWO4-NaYF4X-ray diffraction pattern (XRD) of Yb, Er composite photocatalyst; in the figure: the top is NaYF4The XRD spectrum of Yb, Er, the bottom is CoWO4The middle is the XRD spectrum of 3 composite photocatalyst samples, and the dotted line marks NaYF4Characteristic diffraction peaks of Yb, Er.
FIG. 2 is 90CoWO4-1NaYF4Scanning electron microscope pictures of Yb, Er composite photocatalyst (CN-1).
FIG. 3 is 60CoWO4-1NaYF4A schematic structural diagram of a Yb, Er composite photocatalyst (CN-2); wherein, (a) is a scanning electron microscope picture of a CN-2 composite photocatalyst sample, and an inset in the lower right corner is a local high-definition enlarged view: shows CoWO4And NaYF4The composite state of Yb and Er; (b) is pure NaYF4Scanning electron microscope pictures of Yb, Er micron rods; (c) is pure CoWO4Scanning electron microscopy of nanoparticles.
FIG. 4 shows 30CoWO4-1NaYF4Scanning electron microscope pictures of Yb, Er composite photocatalyst (CN-3).
FIG. 5 shows CoWO4-NaYF4The photocatalytic test result of the Yb and Er composite photocatalyst; wherein, C0Is the initial absorbance of a standard rhodamine-B solution, C is the absorbance of the solution measured every 30 minutes, C/C0The rate or ability of the photocatalyst to catalyze degradation can be characterized.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples. The examples are given solely for the purpose of illustration and are not intended to limit the scope of the invention.
The invention adopts a two-step hydrothermal method to prepare an up-conversion material NaYF4On the basis of Yb and Er powder, CoWO is synthesized4With up-conversion material NaYF4Yb and Er composite structure material used as a composite photocatalyst absorbs near infrared light and emits visible light through an up-conversion material, so that solar energy absorption from ultraviolet to near infrared spectrum is realized, and CoWO is improved4The photocatalysis ability of the light source, and the utilization efficiency of the solar energy is enhanced. The crystal structure and the micro morphology of the composite photocatalyst are analyzed and characterized through X-ray diffraction and a scanning electron microscope, and the performance of typical organic pollutant (rhodamine-B) in photocatalytic decomposition is analyzed and characterized through a photocatalytic experiment, and the result shows that the broad band composite photocatalyst synthesized by the invention has CoWO synthesized through an in-situ hydrothermal method4-NaYF4Yb, Er heterostructure, in contrast to pure CoWO4The photocatalytic degradation efficiency of the broad band composite photocatalyst is improved by nearly 2 times (illumination for 2.5 hours).
(I) CoWO4Synthesis experiment of base broadband composite photocatalyst
Example 1 (preparation of sample No. CN-1):
(1) 2.338g of ethylenediaminetetraacetic acid (EDTA, C) were weighed10H16N2O8) Dissolved in 40mL of deionized water to form an aqueous solution of ethylenediaminetetraacetic acid, and then 1.348g of yttrium nitrate (Y (NO) was weighed3)3·6H2O), 0.179g ytterbium nitrate (Yb (NO)3)3·5H2O) and 0.035g erbium nitrate (Er (NO)3)3·5H2O), adding the mixture into an aqueous solution of ethylenediamine tetraacetic acid, and forming a clear and transparent solution (namely a mixed solution of EDTA and metal nitrate) after vigorously stirring for 1 hour. 2.183g of sodium fluoride (NaF) was dissolved in 20mL of deionized water with stirring to form an aqueous NaF solution. Then adding a NaF aqueous solution into the mixed solution of EDTA and metal nitrate, and continuously stirring for 30-60 minutes to obtain a uniformly mixed suspension, namely NaYF required in the hydrothermal method preparation4Precursor solution of Yb and Er.
(2) NaYF is added4Yb and Er precursor liquid is poured into a polytetrafluoroethylene-lined stainless steel autoclave with the volume of 100mL, the filling rate is set to be 80%, and the hydrothermal reaction is carried out for 24 hours at 180 ℃. Naturally cooling the autoclave to room temperature, centrifuging and washing for multiple times, collecting precipitate, and drying at 60 ℃ for 12 hours to obtain NaYF4Yb, Er powder. NaYF4Yb and Er powders absorb light in the near infrared spectrum (980 nm in wavelength) and emit visible light (650-675 nm, 520-535 nm and 540-560 nm in wavelength) of CoWO4And (4) absorbing. (references: Guo, Y., Wei, J., Liu, Y., Yang, T., Xu, Z. surface-engineered phase crystals and morphologies of NaYF4: Yb3+, Er3+ hexagonal microstructures and the same phosphor properties. journal of Materials Science: Materials in Electronics 2018,29(3),2463-
(3) 1.65g of sodium tungstate (Na) was weighed2WO4·2H2O) and 1.455g of cobalt nitrate Co (NO)3)2·6H2O, dissolved in two beakers with 30mL of deionized water to form clear and transparent A (Na)2WO4Aqueous solution) and B (Co (NO)3)2Aqueous solution), then slowly dripping the solution B into the solution A to generate purple precipitate, after dripping is finished, violently stirring for 20-30 minutes to form a uniformly mixed purple suspension system, and thus obtaining the CoWO required in hydrothermal preparation4The precursor solution of (1).
(4) According to mass ratio (CoWO)4And NaYF4Yb and Er in a mass ratio of 90:1), and mixing the NaYF obtained in the step (2)4Yb, Er powder (0.017g) added to CoWO4The precursor solution is stirred vigorously for 30-60 minutes to form a uniformly mixed suspension.
(5) The suspension obtained in step (4) was poured into a polytetrafluoroethylene-lined stainless steel autoclave having a capacity of 100mL, a filling rate was set to 80%, and the hydrothermal reaction was carried out at 180 ℃ for 12 hours. After the autoclave is naturally cooled to room temperature, through multiple times of centrifugation and washing, the precipitate is collected and dried for 12 hours at the temperature of 60 ℃, and finally 90CoWO is obtained4-1NaYF4Yb and Er composite photocatalyst powder is marked as sample CN-1.
Example 2 (preparation of sample No. CN-2):
(1) 2.338g of ethylenediaminetetraacetic acid (EDTA, C) were weighed10H16N2O8) Dissolved in 40mL of deionized water to form a solution of ethylenediaminetetraacetic acid, and then 1.348g of yttrium nitrate (Y (NO) was weighed3)3·6H2O), 0.179g ytterbium nitrate (Yb (NO)3)3·5H2O) and 0.035g erbium nitrate (Er (NO)3)3·5H2O), adding the mixture into an aqueous solution of ethylenediamine tetraacetic acid, and forming a clear and transparent solution (namely a mixed solution of EDTA and metal nitrate) after vigorously stirring for 1 hour. 2.183g of sodium fluoride (NaF) was dissolved in 20mL of deionized water with stirring to form an aqueous NaF solution. Then adding a NaF aqueous solution into the mixed solution of EDTA and metal nitrate, and continuously stirring for 30-60 minutes to obtain a uniformly mixed suspension, namely NaYF required in the hydrothermal method preparation4Precursor solution of Yb and Er.
(2) NaYF is added4The precursor solution of Yb and Er is poured into a stainless steel autoclave with a polytetrafluoroethylene liner and a volume of 100mL, the filling rate is set to be 80 percent, and the hydrothermal reaction is carried out for 24 hours at 180 ℃. Naturally cooling the autoclave to room temperature, centrifuging and washing for multiple times, collecting precipitate, and drying at 60 ℃ for 12 hours to obtain NaYF4Yb, Er powder.
(3) 1.65g of sodium tungstate (Na) was weighed2WO4·2H2O) and 1.455g of cobalt nitrate Co (NO)3)2·6H2O, dissolved in two beakers with 30mL of deionized water to form clear and transparent A (Na)2WO4Aqueous solution) and B (Co (NO)3)2Aqueous solution), then slowly dripping the solution B into the solution A to generate purple precipitate, after dripping is finished, violently stirring for 20-30 minutes to form a uniformly mixed purple suspension system, and thus obtaining the CoWO required in hydrothermal preparation4The precursor solution of (1).
(4) According to mass ratio (CoWO)4And NaYF4Yb and Er in a mass ratio of 60:1), and mixing the NaYF obtained in the step (2)4:Yb,ErPowder (0.026g) was added to CoWO4The precursor solution is stirred vigorously for 30-60 minutes to form a uniformly mixed suspension.
(5) The suspension obtained in step (4) was poured into a polytetrafluoroethylene-lined stainless steel autoclave having a capacity of 100mL, a filling rate was set to 80%, and the hydrothermal reaction was carried out at 180 ℃ for 12 hours. After the autoclave is naturally cooled to room temperature, through multiple times of centrifugation and washing, the precipitate is collected and dried for 12 hours at the temperature of 60 ℃, and finally 60CoWO is obtained4-1NaYF4Yb and Er composite photocatalyst powder is marked as sample CN-2.
Example 3 (preparation of sample No. CN-3):
(1) 2.338g of ethylenediaminetetraacetic acid (EDTA, C) were weighed10H16N2O8) Dissolved in 40mL of deionized water to form a solution of ethylenediaminetetraacetic acid, and then 1.348g of yttrium nitrate (Y (NO) was weighed3)3·6H2O), 0.179g ytterbium nitrate (Yb (NO)3)3·5H2O) and 0.035g erbium nitrate (Er (NO)3)3·5H2O), adding the mixture into an aqueous solution of ethylenediamine tetraacetic acid, and forming a clear and transparent solution (namely a mixed solution of EDTA and metal nitrate) after vigorously stirring for 1 hour. 2.183g of sodium fluoride (NaF) was dissolved in 20mL of deionized water with stirring to form an aqueous NaF solution. Then adding a NaF aqueous solution into the mixed solution of EDTA and metal nitrate, and continuously stirring for 30-60 minutes to obtain a uniformly mixed suspension, namely NaYF required in the hydrothermal method preparation4Precursor solution of Yb and Er.
(2) NaYF is added4The precursor solution of Yb and Er is poured into a stainless steel autoclave with a polytetrafluoroethylene liner and a volume of 100mL, the filling rate is set to be 80 percent, and the hydrothermal reaction is carried out for 24 hours at 180 ℃. Naturally cooling the autoclave to room temperature, centrifuging and washing for multiple times, collecting precipitate, and drying at 60 ℃ for 12 hours to obtain NaYF4Yb, Er powder.
(3) 1.65g of sodium tungstate (Na) was weighed2WO4·2H2O) and 1.455g of cobalt nitrate Co (NO)3)2·6H2O, dissolved in two beakers with 30mL of deionized water to form clear and transparent A (Na)2WO4Aqueous solution) and B (Co (NO)3)2Aqueous solution), then slowly dripping the solution B into the solution A to generate purple precipitate, after dripping is finished, violently stirring for 20-30 minutes to form a uniformly mixed purple suspension system, and thus obtaining the CoWO required in hydrothermal preparation4The precursor solution of (1).
(4) According to mass ratio (CoWO)4And NaYF4Yb and Er with the mass ratio of 30:1), and mixing the NaYF obtained in the step (2)4Yb, Er powder (0.051g) added to CoWO4The precursor solution is stirred vigorously for 30-60 minutes to form a uniformly mixed suspension.
(5) The suspension obtained in step (4) was poured into a polytetrafluoroethylene-lined stainless steel autoclave having a capacity of 100mL, a filling rate was set to 80%, and the hydrothermal reaction was carried out at 180 ℃ for 12 hours. After the autoclave is naturally cooled to room temperature, the precipitate is collected by centrifuging and washing for a plurality of times, and is dried for 12 hours at the temperature of 60 ℃, and finally the 30CoWO is obtained4-1NaYF4Yb and Er composite photocatalyst powder is marked as sample CN-3.
For CoWO prepared by the invention4-NaYF4The Yb, Er composite photocatalysts (CN-1, CN-2 and CN-3 samples) were subjected to X-ray diffraction analysis (XRD) and Scanning Electron Microscope (SEM) observation, and the results are shown in FIGS. 1, 2, 3 and 4.
As shown in fig. 1: CoWO (cobalt oxide)4And NaYF4The XRD diffraction peaks of Yb and Er correspond to the JCPDS card (No.15-0867) and the JCPDS card (No.28-1192) of the standard powder diffraction card of the substance one by one respectively, and the CoWO adopted by the invention is illustrated4And NaYF4Yb and Er are pure phase materials, and no impurity phase exists. For the synthetic CoWO4-NaYF4Yb, Er composite photocatalyst sample due to CoWO4As main component, the diffraction peak of the composite photocatalyst is represented by CoWO4Mainly comprises the following steps. Particularly for CN-1 and CN-2 samples (CoWO)4And NaYF4Yb and Er in the mass ratio of 90:1 to 60:1), NaYF4The diffraction peaks of Yb, Er are not resolved (this is due to the limited sensitivity of the XRD measurements). However, for the CN-3 sample (CoWO)4And NaYF4Substances of Yb, ErRatio of 30:1) in the range of 2 θ to 17.2°、30.1°、43.6°Can still clearly see the NaYF4Diffraction peaks of Yb, Er (as shown by the dotted line in FIG. 1), which indicates that the composite photocatalyst prepared by the present invention is indeed CoWO4-NaYF4Yb and Er composite structure.
CoWO obtained by Scanning Electron Microscope (SEM)4-NaYF4The microscopic morphology of the Yb, Er composite photocatalyst sample CN-2 is shown in figure 3. According to the CN-2 sample (CoWO) shown in FIG. 3a4And NaYF4Yb, Er mass ratio 60:1), the bulk morphology of the CN-2 sample was composed of many irregular aggregates of varying sizes, and these aggregates were combined with the CoWO shown in fig. 3c4The morphology is consistent, and the nano particles are formed by a large number of nano particles with the diameters of 30-55 nm, which shows that the main component of the CN-2 sample is CoWO4Nanoparticles, which is also consistent with XRD results. While in the central region of the CN-2 sample was a hexagonal prism micron rod about 9 μm in length and about 2.3 μm in diameter, which is shown in FIG. 3b as the NaYF4The microscopic morphology of Yb, Er was consistent, which also confirmed that the CN-2 sample did contain the upconversion material NaYF4Yb, Er. It should be particularly noted that according to the partial high-definition SEM picture of the micro-rods shown in the inset in the lower right corner of fig. 3a, it can be clearly observed that: NaYF4Yb, Er micron rod with CoWO attached4Nanoparticles, which fully illustrate NaYF4Yb, Er and CoWO4Better combined together, rather than simply physically mixed, i.e. CoWO is realized4Nanoparticles in NaYF4In-situ composite growth on Yb, Er micron rods and formation of heterostructures. This heterostructure is characterized in that: in the same matrix (specifically NaYF)4Yb, Er micron rod) surface with a layer of uniformly distributed CoWO4Nanoparticles, this heterostructure, may be an important reason for exciting more electrons and holes and enabling the composite photocatalyst to exhibit better photocatalytic capability.
As can be seen from FIGS. 2 and 4, the heterostructures of samples CN-1 and CN-3 are shown in CoWO4The distribution of nanoparticles varies in number and uniformity. CN-3 in the sample (as shown in FIG. 4), NaYF4CoWO attached to Yb, Er micron rod4The nano-particles are obviously less than CN-2 samples, which shows that the heterogeneous structure is formed less, and the visible light excited by the up-conversion material cannot be excited by CoWO4Complete absorption and thus reduced photocatalytic ability. In contrast, in the CN-1 sample (as shown in FIG. 2), NaYF4The surface of the Yb, Er micron rod is completely coated with CoWO4The light absorption of the up-conversion material is seriously influenced due to the close wrapping and covering of the nano particles, the excited visible light is reduced, and the photocatalytic capacity of the composite structure is also reduced.
(II) CoWO4Photocatalytic experiment (photocatalytic performance evaluation) of base broadband composite photocatalyst
Adding 25mg of photocatalyst sample into 50mL of rhodamine-B solution (the concentration is 5mg/L), and under the irradiation of visible light and infrared light (by superposing wavelengths in front of a 500W xenon lamp light source)>A 420nm filter). Before the light irradiation, dark room adsorption was performed for 1 hour in order to exclude the effect of nanoparticle adsorption on the rate of photocatalytic reaction. During the photocatalytic degradation reaction, about 6mL of the solution was withdrawn every 30 minutes for absorbance measurement. The absorbance of a standard rhodamine-B solution was used as the initial concentration C0And the absorbance of the solution measured at each interval is recorded as C, C/C0The rate of the photocatalytic reaction or the photocatalytic ability of the photocatalytic material can be reflected, and a photocatalytic experiment test curve (fig. 5) is drawn.
The photocatalytic performance of the composite photocatalyst samples CN-1, CN-2 and CN-3 is characterized and analyzed by using the graph of FIG. 5. Dark room adsorption (adsorption in Dark) was performed for 1 hour before the light irradiation in order to eliminate the effect of nanoparticle adsorption effect (adsorption of organic contaminant molecules on the surface of nanoparticles) on the rate of photocatalytic reaction, and it can be seen that: different samples have different abilities of adsorbing the organic pollutant rhodamine-B, wherein the CN-3 sample has the strongest adsorption ability. For pure CoWO4The nano-particles have the weakest photocatalytic capability, and after 2.5 hours of illumination, only about 11 percent of organic pollutants are catalytically decomposed (wherein the influence of the adsorption part of a dark room is removed), which further proves that pure CoWO4The photocatalytic activity of the material is low. And the composite photocatalyst samples CN-1, CN-2 and CN-3 all show more excellent photocatalytic capability. Among them, CN-2 samples (CoWO)4And NaYF4Yb, Er mass ratio of 60:1) is the most excellent photocatalytic ability: after 2.5 hours of light irradiation, about 20% of the organic pollutants were catalytically decomposed (in which the influence of the adsorption part in the dark room was removed). Relative to pure CoWO4The photocatalytic capability of the nano-particle, CN-2 sample, is improved by nearly 2 times, which fully illustrates that the CoWO prepared by the invention4-NaYF4The Yb and Er composite photocatalyst has excellent photocatalytic performance.
Other experimental results show that under the irradiation of visible light, the photocatalytic capacity of the composite photocatalyst samples CN-1, CN-2 and CN-3 is also superior to that of pure CoWO4And (3) nanoparticles.
(III) comparative example
Comparative example 1
Except CoWO4And NaYF4Yb, Er mass ratio 20:1, otherwise the same procedure was followed as for the sample preparation of example 3.
Comparative example 2
Except CoWO4And NaYF4Yb, Er mass ratio 10:1, otherwise the same procedure was followed as for the sample preparation of example 3.
Referring to table 1, the photocatalytic performance characterization analysis results show: comparative examples 1, 2 samples prepared with CN-3 (CoWO)4And NaYF4Yb, Er mass ratio of 30:1) is much poorer than that of pure CoWO4The photocatalytic ability of the nanoparticles. This is because: in the composite photocatalytic material prepared by the invention, CoWO4The up-conversion material NaYF is an effective photocatalysis main body4Yb and Er have no photocatalytic ability. When CoWO is used4And NaYF4Yb, Er mass ratio is too low (e.g., CoWO)4And NaYF4Mass ratio of Yb to Er<30:1), efficient photocatalytic host CoWO4The content is lower, which causes the overall photocatalytic performance of the composite photocatalytic material to be reduced and even lower than that of pure CoWO4The photocatalytic capacity of the material.
TABLE 1 comparison of photocatalytic Capacity
| CN-3 | Comparative example 1 | Comparative example 2 | |
| C/C0(2.5 hours) | 11％ | 9％ | 7％ |
| C/C0(2.0 hours) | 10％ | 7％ | 6％ |
In conclusion, the composite photocatalyst synthesized by the experiment of the invention is a photocatalyst containing a photocatalytic semiconductor CoWO4With up-conversion material NaYF4A heterostructure broad-band composite photocatalytic material consisting of Yb, Er, which not only utilizes the contained up-conversion material NaYF4Yb, Er absorbs light in the near infrared spectrum and emits as CoWO4Absorbed visible light, thereby enhancing CoWO4And significantly improves CoWO4The photocatalytic ability of (c). The synthetic process of the present invention is equally applicable to the construction of CoWO4The composite structure with other up-conversion materials has certain universality; and the synthesis process is simple, the equipment cost is low, and the uniformity of the synthesized material is good. Thus, the present inventionHas wide application prospect in the preparation field of high-performance photocatalytic materials and the field of photocatalytic degradation of organic pollutants.
Claims (10)
1. A broadband composite photocatalyst is characterized in that: the composite photocatalyst comprises a photocatalytic semiconductor CoWO4Heterostructure compositions with upconverting materials with CoWO4Has a different absorption spectrum from that of CoWO, and the emission spectrum of the up-conversion material is different from that of CoWO4The absorption spectra of the materials are matched, and the heterostructure specifically comprises 1-2 layers of CoWO uniformly distributed on different areas of the surface4The upconverting material microstructures of the nanoparticles.
2. The broadband composite photocatalyst of claim 1, wherein: the composite photocatalyst further comprises CoWO dispersed around the heterostructure component4An aggregate of nanoparticles.
3. The broadband composite photocatalyst of claim 1, wherein: the up-conversion material is selected from NaYF capable of absorbing light in a near infrared spectrum band4Based on a fluorescent material.
4. The broadband composite photocatalyst of claim 1, wherein: in the heterostructure components, the up-conversion material micron structure adopts NaYF with the length of 8-10 mu m and the diameter of 2.1-2.6 mu m4Yb, Er micron rods; CoWO (cobalt oxide)4The diameter of the nanoparticles is 30-55 nm.
5. The broadband composite photocatalyst of claim 1, wherein: the composite photocatalyst is prepared by using CoWO4The precursor solution and the up-conversion material are used as raw materials and prepared by a hydrothermal method.
6. A preparation method of a broadband composite photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
mixing CoWO4The precursor solution and the up-conversion material powder are uniformly mixed and then subjected to hydrothermal reaction, and after the reaction process is finished, the mixture is cooled, centrifuged, washed and dried to obtain the broad band composite photocatalyst, wherein the composite photocatalyst contains heterostructure components formed by in-situ synthesis, and the heterostructure components specifically comprise 1-2 layers of CoWO (cobalt oxide) which are uniformly distributed and attached to different areas of the surface4The upconverting material microstructures of the nanoparticles.
7. The method for preparing a broadband composite photocatalyst as claimed in claim 6, wherein: the CoWO4The mixing ratio of the precursor liquid and the upconversion material powder is according to CoWO4The mass ratio of the up-conversion material is 30-90: 1.
8. The method for preparing a broadband composite photocatalyst as claimed in claim 6, wherein: the reaction conditions are as follows: the temperature is 170-190 ℃ and the time is 10-12 hours.
9. The method for preparing a broadband composite photocatalyst as claimed in claim 6, wherein: the CoWO4The preparation method of the precursor solution specifically comprises the following steps: separately preparing Na2WO4Aqueous solution and Co (NO)3)2Aqueous solution of Co (NO)3)2Aqueous solution with Na2WO4The aqueous solution being mixed to form a suspension, i.e. CoWO4The precursor solution of (1).
10. Use of a broad band composite photocatalyst as claimed in claim 1 in the degradation of organic contaminants.
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