CN113318792B - Flaky CeO2/UIO-66-NH2Composite photocatalytic material and preparation method thereof - Google Patents
Flaky CeO2/UIO-66-NH2Composite photocatalytic material and preparation method thereof Download PDFInfo
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 91
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 65
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 72
- 239000002135 nanosheet Substances 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 18
- 239000002105 nanoparticle Substances 0.000 claims description 17
- 150000000703 Cerium Chemical class 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000002957 persistent organic pollutant Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002064 nanoplatelet Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 241000446313 Lamella Species 0.000 claims description 4
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000001308 synthesis method Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 14
- 238000000926 separation method Methods 0.000 abstract 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 13
- 229940043267 rhodamine b Drugs 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 10
- 230000006798 recombination Effects 0.000 description 8
- 238000005215 recombination Methods 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 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 description 4
- 230000000694 effects Effects 0.000 description 4
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- 238000013508 migration Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
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- 241000282414 Homo sapiens Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 230000004298 light response Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 239000013207 UiO-66 Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
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- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
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- 239000002351 wastewater Substances 0.000 description 2
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- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010039491 Sarcoma Diseases 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
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- 239000010436 fluorite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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- 230000002588 toxic effect Effects 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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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
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Abstract
The invention provides flaky CeO2/UIO‑66‑NH2A composite photocatalytic material and a preparation method thereof belong to the technical field of photocatalyst preparation. The preparation method comprises the following steps: s1 preparation of CeO by water bath synthesis2Nanosheet precursor, followed by calcination to obtain CeO2Nanosheets; s2, ultrasonically dispersing zirconium tetrachloride and 2-amino-1, 4 phthalic acid in a solvent, and then carrying out CeO2Adding the nano-sheets into a solvent, uniformly mixing, preserving the heat for 12-48h under the condition that the temperature is 100-180 ℃, then separating and drying to obtain the flaky CeO2/UIO‑66‑NH2A composite photocatalytic material. The invention utilizes the flaky CeO2And UIO-66-NH2The surface-to-surface composite structure forms a II-type heterojunction structure, the separation efficiency of photo-generated electrons can be improved, the specific surface area is increased, more active sites can be provided, and the photocatalytic performance can be improved.
Description
Technical Field
The invention relates to the technical field of photocatalyst preparation, in particular to flaky CeO2/UIO-66-NH2A composite photocatalytic material and a preparation method thereof.
Background
The pursuit of the human beings to the good life of the human beings leads to the infinite acquisition of the nature, so that the global environment is increasingly changedAnd is worsened. The waste water containing a large amount of organic substances with carcinogenic and teratogenic effects is the main cause of water pollution, for example, the synthetic waste water of Rhodamine B (RhB) can cause sarcoma of subcutaneous tissues. In order to reduce the harm of the organic matter to the environment and human beings, the organic matter is degraded into non-toxic and harmless micromolecular substances by utilizing a photocatalytic oxidation-reduction reaction, and the method is a green, energy-saving and sustainable technology. A semiconductor is used as a photocatalyst, sunlight is used as a light source, the semiconductor photocatalyst generates photoproduction electrons-holes with higher oxidation reduction capability under the irradiation of a specific light source, and organic matters in a water environment are catalytically degraded, so that the semiconductor photocatalyst is considered to be an ideal way for solving water pollution at present. The most studied semiconductor photocatalysts are currently, such as: TiO 22、 BiPO4When ultraviolet light response materials (ultraviolet light only accounts for about 5% of solar spectrum), the development of semiconductor photocatalysis technology is limited to a great extent due to low solar energy utilization efficiency, so that the development of novel and efficient visible light response semiconductor photocatalysts is a hotspot in the field of photocatalysis research.
Compared with the traditional semiconductor photocatalyst, Metal-organic frameworks (MOFs for short) have attracted extensive attention in the field of photocatalysis due to the high specific surface area, adjustable porous size and designable porous structure. Zirconium-based metal-metal organic framework material (UiO-66-NH)2) The MOFs has the capability of photolyzing water to produce hydrogen under visible light. As a photocatalytic reactant, UiO-66-NH2Additional pathways may be provided for the migration of photo-induced electrons, thereby facilitating the separation of charge carriers and thereby increasing photocatalytic efficiency. However, a single UiO-66-NH2The photocatalyst has poor conductivity, narrow photoresponse range, poor visible light absorption capacity, low stability, weak intrinsic catalytic activity and the like, so that the photocatalytic efficiency of the photocatalyst is severely limited, and the photocatalytic degradation effect on organic matters is not ideal.
In order to improve the aforementioned problems, the catalytic performance of MOFs can be improved by constructing a heterojunction. For example, the MoS may be studied2Introduction of UiO-66-NH2Obtaining MoS2/UiO-66-NH2Composite photocatalystAgents, also investigated for the introduction of CdS into UiO-66 or UiO-66-NH2Obtaining CdS/UiO-66 and CdS/UiO-66-NH2Composite photocatalyst, however, in the above composite catalyst, MoS2The preparation conditions are harsh, and dangerous chemicals are usually used, so that certain pollution is caused to the environment; CdS has strong photo-corrosivity, S2+Is easily autoxidized by photoproduction holes during the photocatalytic reaction, which reduces the photostability and is easy to remove toxic heavy metal (Cd)2+) Released into the environment, causing secondary pollution. The composite catalyst has fast photon-generated carrier recombination rate, poor electron transport capacity and poor photocatalytic degradation performance.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a flaky CeO2/UIO-66-NH2Composite photocatalytic material, and further provides the flaky CeO2/UIO-66-NH2A preparation method of a composite photocatalytic material.
In order to achieve the purpose, the invention is specifically realized by the following technical scheme:
flaky CeO2/UIO-66-NH2The preparation method of the composite photocatalytic material comprises the following steps:
s1 preparation of CeO by water bath synthesis2Nanosheet precursor, followed by calcination of the CeO2Nanosheet precursor to give CeO2Nanosheets;
s2, ultrasonically dispersing zirconium tetrachloride and 2-amino-1, 4 phthalic acid in a solvent, and then carrying out CeO2Adding the nano-sheets into a solvent, uniformly mixing, preserving the heat for 12-48h under the condition that the temperature is 100-180 ℃, then separating and drying to obtain the flaky CeO2/UIO-66-NH2A composite photocatalytic material.
Further, in step S1, CeO is prepared by a water bath synthesis method2The specific operation of the nanosheet precursor is as follows: respectively dissolving cerium salt and alkali in deionized water, magnetically stirring until the cerium salt and the alkali are completely dissolved and the solution is uniformly mixed, then quickly pouring an alkali solution into the cerium salt solution for water bath reaction, and after the reaction is finished, pumping out the solutionFiltering the reaction solution to collect precipitate, washing and drying the precipitate to obtain CeO2And (4) a nanosheet precursor.
Further, the conditions of the water bath reaction are as follows: stirring and reacting for 10-60min at the temperature of 0-10 ℃.
Further, the cerium salt is one or more of cerium nitrate, cerium sulfate, cerium acetate and cerium trichloride, and the alkali is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or ammonium bicarbonate.
Further, in step S1, the temperature of the calcination is 300-600 ℃ and the time is 1-10 h.
Further, in step S2, the flaky CeO2/UIO-66-NH2CeO in composite photocatalytic material2With UIO-66-NH2In a mass ratio of 0.5-1.5: 1.
further, in step S2, the solvent is a mixed solution of dimethylformamide and acetic acid, and the volume ratio of dimethylformamide to acetic acid in the mixed solution is 8-9: 1.
further, in step S2, the specific operations of separating and drying are as follows: centrifuging the reaction solution, separating out a reaction product by centrifugation, repeatedly centrifuging and washing the reaction product by using dimethylformamide and methanol at the centrifugal rotation speed of 9000-10000r/min, and drying the reaction product at the temperature of 60-90 ℃ for 12-24h to obtain sheet CeO2/UIO-66-NH2A composite photocatalytic material.
In addition, the invention provides flaky CeO2/UIO-66-NH2Composite photocatalytic material comprising the above-mentioned flaky CeO2/UIO-66-NH2The flake CeO is prepared by the preparation method of the composite photocatalytic material2/UIO-66-NH2The composite photocatalytic material comprises CeO with three-dimensional flower shape2Nanosheets and dispersed deposited on the CeO2UIO-66-NH intermediate lamella interlayers of nanosheets2And (3) nanoparticles.
In addition, the present invention provides the flaky CeO as described above2/UIO-66-NH2Composite photocatalytic material for degrading organic pollutantsThe use of (1).
Compared with the prior art, the invention has the following advantages:
1. the invention utilizes the flaky CeO with three-dimensional pattern morphology2And UIO-66-NH2The interface can promote the migration of photo-generated electrons and improve the electron-hole separation efficiency by forming a II-type heterojunction structure through surface-surface recombination, thereby reducing the recombination rate of photo-generated carriers, prolonging the service life of the photo-generated electrons and further improving the photocatalytic activity of the composite material. In addition, the specific surface area of the composite material is increased by forming the II-type heterojunction structure through surface-surface recombination, more heterojunction interfaces can be created at the contact position of the two materials and the light absorption efficiency is improved, more edge positions can be exposed, more active sites can be provided, and the photocatalytic performance can be improved.
2. The flake CeO prepared by the invention2/UIO-66-NH2The composite photocatalytic material takes 20mg/L rhodamine B as a target organic pollutant, the degradation rate of the composite photocatalytic material on the organic pollutant within 4h reaches 89%, the visible light utilization rate is high, the photocatalytic degradation performance is good, and the organic pollutant can be efficiently and quickly removed.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows CeO of an example of the present invention2And UIO-66-NH2An energy band relationship diagram;
FIG. 2 shows flaky CeO in example 1 of the present invention2/UIO-66-NH2XRD spectrogram of the composite photocatalytic material;
FIG. 3 is a flaky CeO according to example 1 of the present invention2/UIO-66-NH2Scanning electron microscope images of the composite photocatalytic material; wherein, the diagram (a) is CeO2Scanning electron microscope image of the nanosheet, image (b) being UIO-66-NH2Scanning electron micrograph of nanoparticles, wherein (c) shows flaky CeO2/UIO-66-NH2Scanning electron microscope images of the composite photocatalytic material;
FIG. 4 is a flaky CeO according to example 1 of the present invention2/UIO-66-NH2A degradation rate graph of the composite photocatalytic material on RhB;
FIG. 5 shows flaky CeO in example 2 of the present invention2/UIO-66-NH2Scanning electron microscope images of the composite photocatalytic material;
FIG. 6 shows CeO of example 4 of the present invention2Scanning electron microscope images of the nanosheets;
FIG. 7 shows CeO of example 5 of the present invention2Scanning electron microscopy of the nanoplatelets.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. In addition, the terms "comprising," "including," and "having" are intended to be non-limiting, i.e., other steps and other ingredients can be added that do not affect the results. Materials, equipment and reagents are commercially available unless otherwise specified.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, proportions and other numerical values used in the present invention are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
In order to solve the technical problem that the removal efficiency of the existing catalyst on organic pollutants is low, the embodiment of the invention provides flaky CeO2/UIO-66-NH2A process for preparing a composite photocatalytic material, which comprisesThe following steps:
s1 preparation of CeO by water bath synthesis2Nanosheet precursor, followed by calcination of the CeO2Nanosheet precursor to give CeO2Nanosheets;
s2, ultrasonically dispersing zirconium tetrachloride and 2-amino-1, 4 phthalic acid in a solvent, and then carrying out CeO2Adding the nano-sheets into a solvent, uniformly mixing, preserving the heat for 12-48h under the condition that the temperature is 100-180 ℃, then separating and drying to obtain the flaky CeO2/UIO-66-NH2A composite photocatalytic material.
One of the main problems of the existing catalyst is poor photocatalytic performance caused by high recombination rate of photon-generated carriers, and low organic pollutant removal efficiency. Firstly, synthesizing CeO with three-dimensional pattern morphology by a hydrothermal method2Nanosheets, which will then be synthesized as UiO-66-NH2Substrate of (2) and CeO2The nano-sheets are blended in a solvent, and the generated UiO-66-NH is subjected to a solvothermal method2The nano particles are deposited and dispersed in CeO in situ2The flaky CeO is obtained between the interlayer of the nanosheets2/UIO-66-NH2A composite photocatalytic material.
Due to the different energy bands and complex structures between the two semiconductors, how to select matched semiconductors for recombination to take maximum advantage becomes one of the key issues in preparing composite materials. The forbidden bandwidth is an important characteristic parameter influencing the photocatalytic performance of the semiconductor. CeO (CeO)2The valence and conduction band positions of (A) are both compared with UIO-66-NH2Such a band structure may form a type ii heterojunction structure, as shown in fig. 1. The invention utilizes the flaky CeO synthesized by a hydrothermal method2And UIO-66-NH2The interface can promote the migration of photo-generated electrons and improve the electron-hole separation efficiency, thereby reducing the recombination rate of photo-generated carriers, prolonging the service life of the photo-generated electrons and further improving the photocatalytic activity of the composite material. In addition, the surface-to-surface recombination to form a II-type heterojunction structure also increases the specific surface area of the composite material, and the increase of the specific surface area not only can create more heterojunction interfaces and heterojunction interfaces at the contact position of the twoThe light absorption efficiency is improved, more edge positions are exposed, more active sites are provided, and the photocatalytic performance is improved.
The CeO is selected and used in the invention2The nano-sheet is used as a carrier to construct a heterojunction structure, and the advantages of the nano-sheet are mainly considered. First, CeO2The structure of the tetragonal octahedral face-centered cubic fluorite is maintained in the temperature range from room temperature to the melting point, since Ce element has [ Xe]4f26s2The special outer electronic structure makes Ce show two different valence states, namely trivalent cerium (Ce)3+) And tetravalent cerium (Ce)4+) So that the reaction of Ce with O in stoichiometric ratio forms Ce2O3And CeO2In actual cases, CeO is often formed2-σ(σ ═ 0 to 0.5), and thus, CeO2The nano material is easy to store and release oxygen under the condition that the external conditions are changed, shows higher oxygen storage and release capacity, has excellent redox capacity and shows stronger advantage in degrading organic pollutants. Second, CeO2At Ce3+/Ce4+The circulation is easier to realize through oxidation reduction due to size effect and large amount of Ce3+And rich oxygen defect sites are formed. At the same time, CeO2The nanometer material has stable photochemistry and long-term service performance.
In step S1, CeO is prepared by a water bath synthesis method2The specific operation of the nanosheet precursor is as follows: respectively dissolving cerium salt and alkali in deionized water, magnetically stirring until the cerium salt and the alkali are completely dissolved and the solutions are uniformly mixed, then quickly pouring an alkali solution into the cerium salt solution to carry out water bath reaction, after the reaction is finished, carrying out suction filtration on the reaction solution to collect precipitates, washing and drying the precipitates to obtain CeO2And (3) a nanosheet precursor.
Wherein the conditions of the water bath reaction are as follows: stirring and reacting for 10-60min at the temperature of 0-10 ℃.
Wherein the concrete operations of washing and drying the precipitate are as follows: dissolving the precipitate in deionized water, and repeatedly centrifuging and washing at 9000-00r/min, the centrifugal washing times are 1-10 times, after cleaning, the precipitate is dried for 12-24h at the temperature of 60-90 ℃ to obtain CeO2And (3) a nanosheet precursor.
Optionally, in step S1, the temperature of the calcination is 300-600 ℃ and the time is 1-10 h. The calcination process is a key step affecting the flower type structure, the temperature is lower than the range, although the flower type structure can be formed, the formed CeO2If the thickness of the nanosheet is too thick and is higher than the range, the flower-shaped structure cannot be formed. Preferably, the calcination temperature is 400-450 ℃ and the calcination time is 3-5h, more preferably, the calcination temperature is 450 ℃ and the calcination time is 4h, and the CeO obtained under the conditions2The nanosheet has the best morphology. CeO in three-dimensional pattern shape2The nanosheet is used as a carrier, has larger specific surface area and better adsorption performance, can expose more edges, has more active sites and is beneficial to improving the photocatalytic activity.
The cerium salt and the alkali are not particularly limited in the present invention, and may be effective in forming Ce ions and an alkaline reaction environment, and in some embodiments, the cerium salt is preferably one or more of cerium nitrate, cerium sulfate, cerium acetate, and cerium trichloride. Preferably, the base is an inorganic base, and the base is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or ammonium bicarbonate. More preferably, the cerium salt is cerium nitrate hexahydrate (Ce (NO)3)3·6H2O), the alkali is ammonium bicarbonate (NH)4HCO3) Environment-friendly materials and can ensure the synthesis of CeO2The nano-sheets are uniformly dispersed.
Optionally, the solvent is a mixed solution of dimethylformamide and acetic acid, and the volume ratio of dimethylformamide to acetic acid in the mixed solution is 8-9: 1. the mixed solution of dimethylformamide and acetic acid is CeO2Nanosheets, zirconium tetrachloride and 2-amino-1, 4 benzenedicarboxylic acid, so that the aforementioned reaction substrates can be uniformly present in one system.
Optionally, in step S2, the flaky CeO2/UIO-66-NH2CeO in composite photocatalytic material2With UIO-66-NH2In a mass ratio of 0.5-1.5: 1. if compound CeO in the composite photocatalytic material2Too little to observe the composition of the material, and substantially pure UIO-66-NH2Morphology, and stacking between nanoparticles, and composite CeO2Too much will cause agglomeration and affect the photocatalytic performance. Therefore, the CeO is preferable2With said UIO-66-NH2The mass ratio of (1): 1, ensuring UiO-66-NH2The nano particles are uniformly dispersed in CeO2Firm heterojunction is formed on the interface of the surface of the nano sheet, so that the electron transfer on the interface is smoother and more effective.
In step S2, the specific operations of separating and drying are: centrifuging the reaction solution, separating out a reaction product by centrifugation, repeatedly centrifuging and washing the reaction product by using dimethylformamide and methanol at the centrifugal rotation speed of 9000-10000r/min, and drying the reaction product at the temperature of 60-90 ℃ for 12-24h to obtain sheet CeO2/UIO-66-NH2A composite photocatalytic material.
Another embodiment of the present invention provides a flaky CeO2/UIO-66-NH2Composite photocatalytic material comprising the above-mentioned flaky CeO2/UIO-66-NH2The flake CeO is prepared by the preparation method of the composite photocatalytic material2/UIO-66-NH2The composite photocatalytic material comprises CeO with three-dimensional flower shape2Nanosheets and dispersed deposited on the CeO2UIO-66-NH intermediate to the lamella interlayers of the nanoplatelets2And (3) nanoparticles. The invention relates to a method for preparing CeO with three-dimensional pattern morphology2Surface dispersed deposition of nano-sheets UIO-66-NH2Nano particles to obtain sheet CeO with binary heterostructure2/UIO-66-NH2The composite photocatalytic material prepared by the method has the characteristics of large specific surface area, good visible light response, high separation efficiency of photon-generated carriers and good stability, and can be applied to photocatalytic degradation of organic pollutants, especially rhodamine B.
In still another embodiment of the present invention, there is provided the above-mentioned flaky CeO2/UIO-66-NH2Composite photocatalytic material inApplication of flaky CeO in degradation of organic pollutants2/UIO-66-NH2Application of composite photocatalytic material and sheet CeO2/UIO-66-NH2The advantages of the composite photocatalytic material over the prior art are the same and will not be described herein.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are examples of experimental procedures not specified under specific conditions, generally according to the conditions recommended by the manufacturer.
In the following embodiments of the invention, cerium nitrate hexahydrate is selected as cerium salt, ammonium bicarbonate is selected as alkali, and the volume ratio of solvent is 25: 3 dimethylformamide and acetic acid.
Example 1
Flaky CeO2/UIO-66-NH2Composite photocatalytic material, said flaky CeO2/UIO-66-NH2The composite photocatalytic material comprises CeO with three-dimensional flower shape2Nanosheets and dispersed deposited on the CeO2UIO-66-NH intermediate to the lamella interlayers of the nanoplatelets2And (3) nanoparticles.
The flaky CeO2/UIO-66-NH2The preparation method of the composite photocatalytic material comprises the following steps:
s1, respectively dissolving 1.39g of cerium nitrate hexahydrate and 0.75g of ammonium bicarbonate in 200mL of deionized water, magnetically stirring until the cerium nitrate hexahydrate and the ammonium bicarbonate are completely dissolved and the solutions are uniformly mixed, then quickly pouring the ammonium bicarbonate solution into the cerium nitrate solution, stirring for 30min at 0 ℃ for water bath reaction, after the reaction is finished, filtering the reaction solution to collect precipitates, dissolving the precipitates in the deionized water, repeatedly centrifuging and washing, wherein the centrifuging speed is 9000r/min, the centrifuging and washing times are 3 times, after washing, drying the precipitates for 12h at 60 ℃ to obtain CeO2Nanosheet precursor, followed by CeO2Calcining the nanosheet precursor at the temperature of 450 ℃ for 4h to obtain CeO2Nanosheets;
s2, mixing 20.4mg of zirconium tetrachloride and 14.5mg of 2-amino-Ultrasonic dispersing 1, 4-phthalic acid in solvent of mixed solution of 10mL of dimethylformamide and 1.2mL of acetic acid, and adding 25mg of CeO2Adding the nanosheets into a solvent, stirring for 10min at room temperature, uniformly mixing, transferring the uniformly mixed reaction liquid into a reaction kettle with a polytetrafluoroethylene lining, preserving heat for 12h at 120 ℃, centrifuging the reaction liquid, centrifugally separating out a reaction product, repeatedly centrifuging and washing the reaction product by using dimethylformamide and methanol at a centrifugal rotation speed of 9000r/min, and drying the reaction product at 60 ℃ for 12h to obtain flaky CeO2/UIO-66-NH2A composite photocatalytic material.
Wherein the flaky CeO2/UIO-66-NH2CeO in composite photocatalytic material2With UIO-66-NH2The mass ratio of (1): 1.
for the flaky CeO of the present example2/UIO-66-NH2The X-ray diffraction (XRD) analysis of the composite photocatalytic material is shown in figure 2. As can be seen from FIG. 2, synthesized CeO2The nanosheets have distinct diffraction peaks at 28.55 °, 33.08 °, 47.49 °, 56.35 °, 59.09 °, 69.42 ° and 76.71 ° respectively corresponding to CeO2The (111), (200), (220), (311), (222), (400) and (331) crystal planes of (a). The diffraction peak intensity is highest at 28.55 ° 2 θ, which is consistent with standard PDF cards (JCPDS, 43-1002). Synthetic UiO-66-NH2The diffraction peak positions of the nanoparticles are consistent with those reported in the literature (DOI: S1872-2067(19) 63377-2). When the two materials are compounded, CeO can be clearly seen2Characteristic peak of (A) and UiO-66-NH2The characteristic peaks of the CeO composite material are simultaneously shown in an XRD (X-ray diffraction) pattern of the composite material, and no other miscellaneous peaks exist, which indicates that the CeO is synthesized by a hydrothermal method2/UIO-66-NH2A composite material.
The flaky CeO of the present example was observed by Scanning Electron Microscope (SEM)2/UIO-66-NH2The microscopic morphology of the composite photocatalytic material is shown in FIG. 3. As can be seen from FIG. 3(a), synthesized CeO2The three-dimensional pattern appearance mainly composed of sheet structures has larger specific surface area,more edge positions are exposed, so that more active sites can be provided for the photocatalytic reaction; as can be seen from FIG. 3(b), UiO-66-NH2The particle is in an octahedral shape, has no obvious agglomeration phenomenon, is uniformly dispersed, has uniform size and has the diameter of about 600 nm. As can be seen in FIG. 3(c), UiO-66-NH is present in the composite material2CeO uniformly dispersed and loaded in pattern morphology2The interlayer and the surface have no problems of stacking and insufficient combination, and show that UiO-66-NH2And CeO2A heterojunction structure is formed between the two layers, which is beneficial to the transmission of carriers.
The flake CeO of the example2/UIO-66-NH2The composite photocatalytic material is used for photocatalytic degradation of target pollutant rhodamine B (RhB) and is prepared from pure CeO in the step S12Nanosheets and no CeO added in step S22Pure UIO-66-NH prepared from nanosheets2Using the nano particles as a control group photocatalyst, adding 50mg of photocatalyst into 50mL of rhodamine B solution with the initial concentration of 20mg/L to ensure that the mass concentration of the photocatalyst is 1mg/mL, and adopting lambda<Visible light simulated by 420nm xenon lamp is used for photocatalytic experiment, the measurement result is shown in figure 4, the abscissa in the figure is Time, and the ordinate is C/C0(degradation rate of RhB, where C is the concentration of remaining rhodamine B, C0Is the initial concentration of rhodamine B). As can be seen from FIG. 4, pure CeO was present during 4h of visible light irradiation2The nano-sheet has almost no degradation effect on RhB, the 4h degradation rate is only 3.5%, and pure UiO-66-NH2Although the nano particles have a good adsorption effect, the photocatalytic degradation effect is not obvious. Under the same condition, after the two substances are compounded, the photocatalytic effect is obviously improved, and the degradation rate of the composite material on RhB reaches 89%, which shows that the composite photocatalytic material synthesized by the embodiment can have good photocatalytic degradation performance and high utilization rate of visible light. This is because of CeO2Nanosheets and UIO-66-NH2The nano particles are compounded to form an effective amount of heterojunction interface, so that migration of photo-generated electrons can be promoted, the electron-hole separation efficiency is improved, the compounding rate of photo-generated carriers is reduced, the service life of the photo-generated electrons is prolonged, and the photocatalysis performance of the composite material is improved.
Example 2
Example 2 is essentially the same as example 1, except that: the flaky CeO2/UIO-66-NH2CeO in composite photocatalytic material2With UIO-66-NH2The mass ratio of (A) to (B) is 1.5: 1.
the flaky CeO of the present example was observed by Scanning Electron Microscope (SEM)2/UIO-66-NH2The microscopic morphology of the composite photocatalytic material is shown in FIG. 5. As can be seen from FIG. 5, CeO2Agglomeration and accumulation of the nano-sheets occur, and part of UIO-66-NH2The nanoparticles have a problem of insufficient bonding.
Example 3
Example 3 is essentially the same as example 1, except that: the flaky CeO2/UIO-66-NH2CeO in composite photocatalytic material2With UIO-66-NH2Is 0.5: 1.
the flaky CeO of the present example was observed by Scanning Electron Microscope (SEM)2/UIO-66-NH2The microscopic morphology of the composite photocatalytic material was similar to that of FIG. 3(b), and the result was substantially pure UIO-66-NH2The image of the nanoparticles, not shown in this example.
As can be seen from examples 1 to 3, with CeO2Nanosheet with UIO-66-NH2The mass ratio of the nano particles is gradually increased, UIO-66-NH2The dispersibility of the nanoparticles shows a tendency of increasing first and then decreasing, in order to ensure UiO-66-NH2Can be well intercalated in CeO2Nano sheet is uniformly dispersed in CeO2On the nano-scale, the electron transport is enhanced and a large number of heterojunctions are formed, preferably the flaky CeO2/UIO-66-NH2CeO in composite photocatalytic material2With UIO-66-NH2The mass ratio of (1): 1, has better photocatalytic performance.
Example 4
Example 4 is essentially the same as example 1, except that: in step S1, CeO is added2Calcining the nanosheet precursor at the temperature of 400 ℃ for 4h to obtain CeO2Nanosheets.
Observation by Scanning Electron Microscope (SEM)This example step S1 preparation of the obtained CeO2The microscopic morphology of the nanoplatelets, the results are shown in figure 6. As is clear from FIG. 6, CeO2The nanosheets are in flower-shaped structure, but CeO2The thickness of the nanoplatelets was increased compared to example 1.
Example 5
Example 5 is essentially the same as example 1, except that: in step S1, CeO is added2Calcining the nanosheet precursor at 500 ℃ for 4h to obtain CeO2Nanosheets.
CeO prepared in step S1 of this example was observed by Scanning Electron Microscope (SEM)2The microscopic morphology of the nanoplatelets, the results are shown in figure 7. As can be seen from FIG. 7, CeO2The three-dimensional pattern structure of the nano-sheet is not obvious, CeO2The specific surface area of the nanoplatelets is greatly reduced compared to example 1.
As can be seen from example 1 and examples 6 to 7, with CeO2The calcination temperature of the nanosheet precursor is increased, CeO2The thickness of the nano-sheet is gradually reduced, and the specific area shows the trend of increasing firstly and then decreasing, because when the calcining temperature is overhigh, the crystal face becomes small, so that a three-dimensional flower type structure is not easy to form, and then UiO-66-NH2Can not be intercalated in CeO2In the nanosheets, this greatly reduces the number of heterojunctions and catalytically active sites. Therefore, the calcination temperature is preferably 400-450 ℃, the calcination time is 3-5h, more preferably 450 ℃, the calcination time is 4h, and the photocatalytic effect is best.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (8)
1. Flaky CeO2/UIO-66-NH2The preparation method of the composite photocatalytic material is characterized by comprising the following steps:
s1 preparation of CeO by water bath synthesis2Nanosheet precursor, followed by calcination of the CeO2Nano meterFlake precursor to obtain CeO2Nanosheets; the calcining temperature is 300-600 ℃, and the time is 1-10 h;
s2, ultrasonically dispersing zirconium tetrachloride and 2-amino-1, 4 phthalic acid in a solvent, and then carrying out CeO2Adding the nano-sheets into a solvent, uniformly mixing, keeping the temperature for 12-48h under the condition of 100-180 ℃, then separating and drying to obtain the flaky CeO2/UIO-66-NH2A composite photocatalytic material;
the flaky CeO2/UIO-66-NH2The composite photocatalytic material comprises CeO with three-dimensional flower shape2Nanosheets and dispersed deposited on the CeO2UIO-66-NH intermediate to the lamella interlayers of the nanoplatelets2A nanoparticle; the flaky CeO2/UIO-66-NH2CeO in composite photocatalytic material2With UIO-66-NH2In a mass ratio of 0.5-1.5: 1.
2. the method of claim 1, wherein the CeO is prepared by a water bath synthesis method in step S12The specific operation of the nanosheet precursor is as follows: respectively dissolving cerium salt and alkali in deionized water, magnetically stirring until the cerium salt and the alkali are completely dissolved and the solutions are uniformly mixed, then quickly pouring an alkali solution into the cerium salt solution to carry out water bath reaction, after the reaction is finished, carrying out suction filtration on the reaction solution to collect precipitates, washing and drying the precipitates to obtain CeO2And (3) a nanosheet precursor.
3. The method for preparing the compound of claim 2, wherein the conditions of the water bath reaction are as follows: stirring and reacting for 10-60min at the temperature of 0-10 ℃.
4. The method according to claim 2, wherein the cerium salt is one or more of cerium nitrate, cerium sulfate, cerium acetate, and cerium trichloride, and the base is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and ammonium bicarbonate.
5. The method according to claim 1, wherein in step S2, the solvent is a mixture of dimethylformamide and acetic acid, and the volume ratio of dimethylformamide to acetic acid in the mixture is 8 to 9: 1.
6. the method according to claim 1, wherein in step S2, the specific operations of separating and drying are as follows: centrifuging the reaction solution, separating out a reaction product by centrifugation, repeatedly centrifuging and washing the reaction product by using dimethylformamide and methanol at the centrifugal rotation speed of 9000-10000r/min, and drying the reaction product at the temperature of 60-90 ℃ for 12-24h to obtain sheet CeO2/UIO-66-NH2A composite photocatalytic material.
7. Flaky CeO2/UIO-66-NH2Composite photocatalytic material, characterized by being constituted by the flaky CeO according to any one of claims 1 to 62/UIO-66-NH2The composite photocatalytic material is prepared by the preparation method.
8. The flaky CeO according to claim 72/UIO-66-NH2The application of the composite photocatalytic material in degrading organic pollutants.
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| CN110128671A (en) * | 2019-05-27 | 2019-08-16 | 湘潭大学 | A kind of rodlike cerium dopping MIL-53(Fe) material preparation method |
| CN110270374A (en) * | 2019-06-04 | 2019-09-24 | 浙江和谐光催化科技有限公司 | A kind of preparation method of the Ce-MOF material with Photocatalytic Degradation of Methyl Orange function |
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