CN108889291B - SnO2Modified fullerene composite material with micro-nano structure and preparation method and application thereof - Google Patents
SnO2Modified fullerene composite material with micro-nano structure and preparation method and application thereof Download PDFInfo
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910003472 fullerene Inorganic materials 0.000 claims abstract description 82
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
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- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000002071 nanotube Substances 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 24
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
- 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 claims description 4
- 229940043267 rhodamine b Drugs 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical group [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 2
- 229940012189 methyl orange Drugs 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 16
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- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 4
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 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 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
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- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
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- VSQYNPJPULBZKU-UHFFFAOYSA-N mercury xenon Chemical compound [Xe].[Hg] VSQYNPJPULBZKU-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229910002703 Al K Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Organic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention relates to the field of photocatalysis, and further relates to SnO2Modified fullerene composite material with micro-nano structure and preparation method and application thereof. The composite material comprises fullerene and SnO with micro-nano structure2Wherein: the micro-nano structure is used as a main body, and the SnO2Loaded on the surface of the fullerene with the micro-nano structure. The preparation method comprises the following steps: dispersing fullerene with a micro-nano structure in water to obtain a dispersion liquid; SnO2Adding a precursor, a complexing agent and a reducing agent into the dispersion liquid, reacting under the condition of heating, stirring and refluxing, cooling the solution, and separating to obtain the catalyst. The embodiment of the invention also provides application of the composite material in photocatalytic degradation of organic pollutants. The composite material has novel structure and excellent performance, and when the composite material is used as a photocatalyst, SnO is used2The fullerene has the advantages of high energy band structure matching degree with the fullerene with the micro-nano structure, low electron-hole recombination rate, good quantum efficiency, high light utilization rate and good photocatalytic activity.
Description
Technical Field
The invention relates to the field of photocatalysis, and further relates to SnO2Modified fullerene composite material with micro-nano structure and preparation method and application thereof.
Background
The semiconductor photocatalysis technology is a green environmental pollution treatment technology due to the characteristics of low energy consumption, low-temperature deep reaction, low cost, no secondary pollution, thorough purification, capability of directly utilizing solar energy as a light source to drive reaction and the like.
SnO2(tin dioxide) is a semiconductor with a wide band gap, has a forbidden band width and an exciton confinement energy of 3.6eV and 130meV at room temperature, and hardly absorbs in the visible region, so that the efficiency of light energy utilization is low. Fullerene is a carbon material with good optical characteristics and quantum characteristics, and has great application potential in the fields of semiconductors, photoelectricity, energy storage and the like. In previous researches, when a semiconductor and a fullerene molecule are compounded to be used as a photocatalyst, a semiconductor material is usually used as a main catalyst, and a small amount of fullerene molecules are loaded on the surface of the semiconductor in an amorphous mode to be used as a co-catalyst, but the binary catalyst in the form has still very little absorption to visible light, and other materials are often additionally loaded, such as: photosensitizers, and the like.
In addition, fullerene molecules can form different kinds of supramolecular assemblies through pi stacking, and besides self-assembly of fullerene molecules, fullerene can also form structures such as co-assemblies, donor/acceptor heterojunctions and the like with other host molecules. However, the understanding of ordered self-assembly of fullerene molecules at the nanoscale and the influence of self-assembled structures on the photoelectric properties are still limited, and need to be explored more.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Object of the Invention
In order to solve the above technical problems, the present invention provides a SnO2The composite material uses the fullerene with the micro-nano structure as a main body, and only needs to load trace SnO on the fullerene with the micro-nano structure2The material can realize high-efficiency photocatalytic reaction; when the composite material is used as a photocatalyst, SnO2The matching degree with the energy band structure of the fullerene with the micro-nano structure is high, and electrons on the composite materialLow hole recombination rate, good quantum efficiency, high light utilization rate and good photocatalytic activity.
Solution scheme
In order to achieve the purpose of the present invention, the embodiment of the present invention provides a SnO2The modified fullerene composite material with the micro-nano structure comprises fullerene with the micro-nano structure and SnO2Wherein: the fullerene with the micro-nano structure is taken as a main body, and the SnO2Loaded on the surface of the fullerene with the micro-nano structure.
SnO mentioned above2In a possible implementation mode of the modified fullerene composite material with the micro-nano structure, the fullerene and SnO with the micro-nano structure2The molar ratio of (A) to (B) is 1: 0.05-0.5; alternatively 1: 0.1-0.3; further optionally 1: 0.1-0.2; yet further alternatively 1: 0.16. Because the mol of fullerene micromolecules in 1mol of the fullerene with the micro-nano structure cannot be determined, the molar weight of the fullerene with the micro-nano structure in the invention is calculated by the following method: the molar weight of the fullerene with the micro-nano structure is divided by the mass of the fullerene with the micro-nano structure and the relative molecular weight of fullerene molecules. The invention relates to a method for calculating the molar ratio of fullerene with a micro-nano structure by adopting the molar quantity of fullerene with the micro-nano structure.
The embodiment of the invention also provides SnO2The preparation method of the modified fullerene composite material with the micro-nano structure comprises the following steps: dispersing fullerene with a micro-nano structure in water to obtain a dispersion liquid; SnO2Adding a precursor, a complexing agent and a reducing agent into the dispersion liquid, reacting under the condition of heating, stirring and refluxing, cooling the solution, and separating to obtain SnO2Modified fullerene composite material with micro-nano structure.
SnO mentioned above2In one possible implementation manner, the modified fullerene composite material with the micro-nano structure or the preparation method comprises the following steps of: when the fullerene molecules in the fullerene with the micro-nano structure are hollow fullerene moleculesIt is called micro-nano structure hollow fullerene; when the fullerene molecules in the fullerene with the micro-nano structure are metal fullerene molecules, the fullerene molecules are called as metal fullerene with the micro-nano structure. Wherein:
the hollow fullerene with the micro-nano structure comprises a micro-nano structure C60Micro-nano structure C70Micro-nano structure C76Micro-nano structure C78Micro-nano structure C84At least one of;
the micro-nano structure metal fullerene is of a micro-nano structure A2C2@C2mOr a micro-nano structure B3N@C2mWherein A is at least one of Sc, La and Y, B is at least one of Sc, La, Y, Ho, Lu, Dy and Er, and m is 39-44;
optionally, the fullerene with the micro-nano structure is of a micro-nano structure C60Or micro-nano structure C70。
SnO mentioned above2In a possible implementation manner, the shape of the modified fullerene with the micro-nano structure comprises a tubular shape, a hexagonal prism shape, a micron needle shape, a micron rod shape, a sheet shape or a polyhedron.
SnO mentioned above2In a possible implementation manner, the modified fullerene composite material with the micro-nano structure or the preparation method thereof is characterized in that the size of the fullerene with the micro-nano structure is at least one of micrometer size and nanometer size.
SnO mentioned above2In one possible implementation manner, the modified fullerene composite material with the micro-nano structure or the preparation method comprises C60Nanosheets or C60A nanotube. C60The nano-sheet comprises a plurality of C60Molecular, sheet-like, nanoscale C60A self-assembly body; c60That is, the nanotube includes a plurality of C60Molecular, tubular, nanoscale C60A self-assembled body.
In one possible implementation mode of the preparation method, the SnO2The precursor comprises tin dichloride, tin tetrachloride or sodium stannateAt least one of; tin dichloride is optional.
In one possible implementation manner of the preparation method, the complexing agent comprises at least one of citric acid or Ethylene Diamine Tetraacetic Acid (EDTA); optionally citric acid.
In a possible implementation manner of the preparation method, the reducing agent comprises at least one of sodium borohydride or urea; optionally sodium borohydride.
In one possible implementation mode of the preparation method, the SnO2The molar ratio of the precursor to the fullerene with the micro-nano structure is 1-4: 1; alternatively 1-3: 1; further alternatively 1-2: 1.
In one possible implementation mode of the preparation method, the SnO2The molar ratio of the precursor to the complexing agent is 1:1-1: 10; the ratio of the raw materials to the raw materials can be 1: 1-2.
In one possible implementation mode of the preparation method, the SnO2The molar ratio of the precursor to the reducing agent is 1:10-1: 100; alternatively 1:55-65, further alternatively 1: 60.
In a possible implementation manner, the temperature of the heating, stirring and refluxing is 100-140 ℃; the stirring reflux time is 4-10 h.
SnO mentioned above2In one possible implementation manner, the preparation method of the modified fullerene composite material with the micro-nano structure is a liquid-liquid interface self-assembly method, and comprises the following steps: dissolving a fullerene raw material in a good solvent to obtain a fullerene good solution, then injecting the fullerene good solution into a poor solvent to obtain a mixed solution, then standing the mixed solution, and separating the precipitated precipitate to obtain the fullerene with the micro-nano structure.
SnO mentioned above2In one possible implementation manner, the fullerene raw material comprises a hollow fullerene raw material or a metal fullerene raw material, wherein: the hollow fullerene raw material comprises C60、C70、C76、C78、C84At leastThe metal fullerene raw material comprises A2C2@C2mOr is B3N@C2mWherein a ═ at least one of Sc, La, and Y; wherein B is at least one of Sc, La, Y, Ho, Lu, Dy and Er; m is 39-44; optionally, the fullerene raw material is C60Or C70。
SnO mentioned above2In one possible implementation manner, the good solvent comprises at least one of benzene, toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, o-xylene, p-xylene, m-xylene or mesitylene; the poor solvent comprises at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, n-hexanol or n-heptanol.
SnO mentioned above2In a possible implementation mode of the modified fullerene composite material with the micro-nano structure or the preparation method, the concentration of the good fullerene solution is 0.5-2 mg/mL; 20-80mL of poor solvent is needed for every 5-20mL of good fullerene solution.
SnO mentioned above2In a possible implementation manner, in the preparation method of the fullerene with the micro-nano structure, the standing time of the mixed solution is 18-36 hours, and optionally 24 hours.
On the other hand, the embodiment of the invention also provides the SnO2Modified fullerene composite material with micro-nano structure and SnO prepared by preparation method2Application of modified fullerene composite material with micro-nano structure in photocatalytic degradation of organic pollutants by using SnO2The method for carrying out photocatalytic degradation on organic pollutants by using the modified fullerene composite material with the micro-nano structure comprises the following steps: the above SnO2And dispersing the modified fullerene composite material with the micro-nano structure into a water sample containing organic pollutants, and irradiating the water sample containing the organic pollutants by adopting light containing visible light. In the laboratory research process, the adsorption step under the dark condition is adopted, so as to accurately detect the degradation rate and the degradation speed of the photocatalytic reaction after the startThe rate, when actual industrial application carries out degradation, need not to adsorb under the dark condition, can adsorb degradation simultaneously, can further improve the degradation rate.
In one possible implementation of the above method for photocatalytic degradation, the organic pollutant includes at least one of rhodamine B, methyl orange, methylene blue, tetracycline hydrochloride, or acid red.
In a possible implementation manner, the content of the organic pollutants in the water sample containing the organic pollutants is 5-50 mg/L.
In a possible implementation manner of the above method for photocatalytic degradation, the wavelength band of the visible light is 420-800 nm.
In one possible implementation manner, the energy of the light containing visible light irradiated to the sample can be 5-25 MW; the irradiation time with visible light may be 0.5-3h, optionally 2 h.
The embodiment of the invention has the beneficial effects that:
(1) in the embodiment of the invention, the fullerene with the micro-nano structure is used as a main body, and the extremely trace SnO is loaded on the main body2The material is prepared into the fullerene material with the characteristics of micro-nano structure and SnO2The composite material has characteristic absorption in a visible light region and a wide light response range, so that the utilization rate of a solar spectrum can be improved; the composite material has light stability and no light corrosion.
(2) Fullerene molecules and SnO in fullerene with micro-nano structure2The energy level structures of the light-emitting diode are matched, and efficient electronic excitation and electronic transfer can be realized between the light-emitting diode and the light-emitting diode under the excitation of light, so that efficient separation of electrons and holes is realized, the photocatalytic efficiency is improved, and efficient photocatalytic reaction is realized.
(3) Some intrinsic properties of fullerene molecules can be significantly enhanced or tuned by forming micro-nanostructured fullerenes of different geometries. The micro-nano structure fullerene obtained by self-assembly in the embodiment of the invention has adjustable and stable structure, wide photoresponse range, characteristic absorption in a visible light region, adjustable energy level structure and high chemical reaction activity, and the production process of the micro-nano structure fullerene is simple, mild in condition, various in available fullerene raw materials, low in required equipment investment, low in cost, high in yield, easy to operate and beneficial to industrial large-scale production and popularization.
(4) SnO prepared by embodiment of the invention2When the modified fullerene composite material with the micro-nano structure is used as a photocatalyst, various organic pollutants can be efficiently degraded under room temperature in a photocatalytic manner, the operation is simple and convenient, the reaction condition is mild, the method is simple and controllable, the practicability is high, the circulation stability is good, and the rate of catalytically degrading organic dyes is not obviously reduced after the fullerene composite material is repeatedly recycled for 3 times.
Drawings
One or more embodiments are illustrated by the corresponding figures in the drawings, which are not meant to be limiting. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
FIG. 1A is C prepared according to example 1 of the present invention60Surface Scanning Electron Microscope (SEM) images of nanotubes.
FIG. 1B is a SnO prepared in example 1 of the present invention2Modified C60Surface Scanning Electron Microscope (SEM) images of nanotube composites.
FIG. 2 is a SnO prepared according to example 1 of the present invention2Modified C60Transmission Electron Microscopy (TEM) images of nanotube composites.
FIG. 3 is C prepared in example 1 of the present invention60Nanotubes and SnO2Modified C60XRD patterns of nanotube composites.
FIG. 4A is C prepared in example 1 of the present invention60Nanotubes and SnO2Modified C60XPS full spectrum of nanotube composites.
FIG. 4B is SnO prepared according to example 1 of the present invention2Modified C60Fine spectrum of Sn3d for nanotube composites.
FIG. 5A is C prepared according to example 1 of the present invention60XPS fine spectrum of O1s for nanotubes.
FIG. 5B is a SnO prepared in example 1 of the present invention2Modified C60XPS fine spectrum of O1s for nanotube composites.
FIG. 6A is C prepared in example 1 of the present invention60Nanotubes and SnO2Modified C60Ultraviolet-visible diffuse reflectance patterns of nanotube composites.
FIG. 6B is a graph obtained using the Kubelka-Munk equation (ahv)0.5Graph of relationship with hv.
FIG. 7 shows a graph of C prepared in example 1 of the present invention60Nanotubes and SnO2Modified C60A photo-electric flow spectrum of the nanotube composite.
FIG. 8A is SnO in example 1 of the present invention2Modified C60A degradation curve of photocatalytic degradation of methylene blue by using a plurality of materials such as nanotube composite materials, wherein: the dotted line is preceded by a dark adsorption phase, C in FIG. 8A0Concentration of the initially prepared aqueous methylene blue solution (i.e., 30mg/L), CtThe concentration of methylene blue in the water sample at a certain time point during the whole experiment including the dark adsorption phase and the light source irradiation phase.
FIG. 8B is SnO in example 1 of the present invention2Modified C60Kinetic curves of several materials, such as nanotube composites, photocatalytic methylene blue, C in FIG. 8B0 lightConcentration of methylene blue in the water sample for the dark adsorption phase, i.e. for the period immediately before the light source irradiation phase, Ct lightIs the concentration of methylene blue in the water sample at a point in time after the start of the light source irradiation phase.
FIG. 9 is a SnO prepared in example 1 of the present invention2Modified C60And (3) testing the cycle performance of the photocatalytic degradation methylene blue of the nanotube composite material.
FIG. 10A is C prepared in example 4 of the present invention60Surface Scanning Electron Microscope (SEM) images of the nanoplatelets.
FIG. 10B is a graph of C prepared in example 4 of the present invention60Of nanosheetsHigh resolution Scanning Electron Microscope (SEM) images.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some instances, methods, means, elements well known to those skilled in the art have not been described in detail so as not to obscure the present invention.
EXAMPLE 1SnO2Modified C60Preparation of nanotube composites
(1)C60Preparing the nanotube:
selecting mesitylene as a good solvent and isopropanol as a poor solvent; 10mL of 0.5mg/mL of C60When the mesitylene solution is injected into 40mL of isopropanol rapidly by an injector, the mutual solubility of mesitylene and isopropanol is good, so that C in the mutual solution is dissolved60In a supersaturated state, C60The molecules begin to be separated out from the mesitylene molecules in an eutectic way. During this time, it was observed that the mixed solution became cloudy immediately, rose in color at the beginning, and quickly turned brown-yellow. After the mixed solution was allowed to stand for 24 hours, it was centrifuged at 11k in a high-speed centrifuge, and the supernatant was decanted to collect a solid precipitate at the bottom. Washing with isopropanol 3 times at 40 deg.CDrying in a vacuum drying oven overnight to obtain C60A solid powder of nanotubes.
(2)SnO2Modified C60Preparing the nanotube composite material:
taking C prepared in the step (1)600.014mmol of a solid powder of nanotubes was ultrasonically dispersed in a small amount of water to obtain a dispersion. Then, 20mL of SnCl solution containing 0.022mmol was added to the dispersion2And 0.026mmol of citric acid, the mixture was placed in a 250mL round bottom flask and heated to 120 ℃ on an oil bath and 20mL of NaBH containing 1.32mmol was gradually added4The solution was finally stirred under reflux for 6 h. Stopping heating after the reaction is finished, separating the liquid in the flask to obtain a solid on a high-speed centrifuge after the liquid is cooled to room temperature, washing the solid for 3 times by using deionized water, and drying the solid in vacuum at 40 ℃ to obtain SnO2Modified C60A solid powder of a nanotube composite.
The reaction mechanism is not necessarily limited to the above reaction, and may be C60A large amount of-OH functional groups, SnO, are introduced into the molecular surface through an alcohol poor solvent2After the tin ions of the precursor are bonded to the surface-OH functional groups, they are reduced first by a reducing agent and then by O2Under the oxidation of (C), reacting to form SnO2Thereby obtaining SnO2Modified fullerene composite material with micro-nano structure.
Without addition of C60Under the condition of the powder of the nanotube, SnO was also used in this example2Precursor SnCl2Complexing agent citric acid and reducing agent NaBH4Preparation of SnO2For use in subsequent studies. The specific method comprises the following steps:
20mL of a solution containing 0.022mmol of SnCl2And 0.026mmol of citric acid, the mixture was placed in a 250mL round bottom flask and heated to 120 ℃ on an oil bath and 20mL of NaBH containing 1.32mmol was gradually added4The solution was finally stirred under reflux for 6 h. Stopping heating after the reaction is finished, separating the liquid in the flask to obtain a solid on a high-speed centrifuge after the liquid is cooled to room temperature, washing the solid for 3 times by using deionized water, and drying the solid in vacuum at 40 ℃ to obtain the productTo SnO2The solid powder of (4).
Inventive example 1 step (1) prepared C60The surface Scanning Electron Microscope (SEM) image of the nanotube is shown in FIG. 1A, and the morphology of the nanotube is observed and analyzed by using a HITACHI S-4800 scanning electron microscope of Japan at a high voltage of 10 kV. As can be seen, C was prepared60The nanotubes are hollow tubular structures with regular hexagonal cross-sections, the diameter of the tube being 0.8 μm and the length of the tube being 7 μm.
SnO prepared in step (2) of example 1 of the present invention2Modified C60A surface Scanning Electron Microscope (SEM) view of the nanotube composite is shown in FIG. 1B, and it can be seen that the composite structure retains C60The original tubular structure of the nanotube.
SnO prepared in step (2) of example 1 of the present invention2Modified C60A Transmission Electron Microscope (TEM) image of the nanotube composite material is shown in FIG. 2, and a field emission transmission electron microscope JEOL JEM-2100F is used to test the microstructure of a sample, with a working voltage of 160kV, and SnO can be observed2Are uniformly dispersed in C60Inner and outer surfaces of the nanotubes, C is also observed in HR-TEM60A clear lattice line of nanotubes.
C prepared in inventive example 160Nanotubes and SnO2Modified C60The XRD pattern of the nanotube composite is shown in fig. 3, and the sample crystal structure was measured using an X-ray diffractometer, where the wavelength of X-rays was 0.154nm, the operating voltage was 40kV, the operating current was 20mA, the scanning speed was 10 °/min, the step width was 0.02 °, and the 2 θ scanning range was 10 to 80 °. As can be seen from FIG. 3, C was prepared60The nanotube structure has an hcp I crystal form. This shows that C60The nanotube retains C60Characteristic diffraction peak of crystal structure and modified SnO2Then, the relative intensity of the diffraction peak was slightly changed, but C was60The diffraction peak position of the nanotube is not changed, indicating that SnO2Introduction of (2) without destroying C60The original crystal structure of the nanotube. Due to SnO2Is small in the amount of and C60Nano-structured XRD peak and SnO2There is a large overlap of the two,thus, no significant SnO was shown in the composite2Characteristic diffraction peaks.
C prepared in inventive example 160Nanotubes and SnO2Modified C60The X-ray photoelectron spectra of the nanotube composite material are shown in fig. 4A and 4B, and analyzed by ESCALab250Xi multifunctional photoelectron spectrometer. The excitation source is monochromatized Al K alpha X-ray with the power of about 200W. The analysis area was 500. mu.m. The base vacuum during analysis was 3X 10-9mbar. As can be seen in FIG. 4A, C60The nano-tube only contains carbon and oxygen elements, while SnO2After the semiconductor is modified, a spectrum shows obvious signals of tin elements. Meanwhile, FIG. 4B shows SnO2Modified C60The energy spectrum of the Sn3d nanotube composite material shows that the binding energy peaks are respectively located at 487.3eV and 495.8eV, and respectively correspond to the 3d of positive tetravalent tin3/2And 3d5/2Orbitals, indicating that the tin is present in the composite as a positive four valence. From the XPS fine spectra of FIGS. 5A and 5B O1s, it can be seen that the lattice oxygen content at the 531eV position is increased, indicating that SnO is generated on the surface of the micro-nano fullerene structure2。
Calculation of SnO according to ICP-MS2Modified C60Nanotube composite material C60Nanotubes and SnO2In a molar ratio of 1: 0.16. because the mol of fullerene micromolecules in 1mol of the fullerene with the micro-nano structure cannot be determined, the molar weight of the fullerene with the micro-nano structure in the invention is calculated by the following method: the molar weight of the fullerene with the micro-nano structure is divided by the mass of the fullerene with the micro-nano structure and the relative molecular weight of fullerene molecules. The invention relates to a method for calculating the molar ratio of fullerene with a micro-nano structure by adopting the molar quantity of fullerene with the micro-nano structure.
C prepared in inventive example 160Nanotubes and SnO2Modified C60The diffuse reflectance spectrogram of nanotube composite material is shown in FIG. 6A, and the light absorption capacity of the sample is measured by Shimadzu UV-2550 UV spectrophotometer at room temperatureIs carried out with BaSO4For reference, the wavelength range was measured at 220-800 nm. As can be seen in FIG. 6A, C60Nanotubes and SnO2Modified C60The nanotube composite material has strong absorption in the whole ultraviolet visible light area, which shows that the prepared material has potential high-efficiency light utilization rate. As shown in FIG. 6B, using the Kubelka-Munk equation, one obtains (ahv)1/2Do (ahv) as B (hv-Eg)1/2For the straight line of hv, the intercept with the horizontal axis is Eg, giving C60The band gap Eg of the nanotubes is 1.57eV, while SnO2Modified C60The band gap of the nanotube composite material is 1.37eV, and it is obvious that SnO2The introduction of the photocatalyst reduces the energy band gap of the material, further widens the absorption range of the material and provides possibility for improving the photodynamics of the photocatalyst.
Example 2SnO2Modified C60Research on photocurrent properties of nanotube composite material
Testing photocurrent with a three-electrode system, taking a Pt sheet as a counter electrode, calomel as a reference electrode, a prepared sample electrode as a working electrode, and 0.5mol/L Na electrolyte2SO4Solution, (300W, lambda)>420nm) xenon-mercury lamp as the visible light source, with an applied bias of 0.3V.
C prepared in inventive example 160Nanotubes and SnO2Modified C60Nanotube composite and C60The photocurrent of the powder was measured as shown in FIG. 7 using (300W,. lambda.)>420nm), the electrons in the valence band of the material are excited to a conduction band to generate photo-generated electron-hole pairs, under the action of an external bias voltage of 0.3V, the photo-generated electrons are transferred from the working electrode to the Pt sheet electrode to generate current signals, and the more the photo-generated electrons, the stronger the generated current signals; when the light source is turned off, the electron-hole recombination and the current signal disappear. As is clear from FIG. 7, under visible light excitation, C60The photocurrent signal generated by the nanotube is obviously higher than that of C60The photocurrent signal generated by the powder shows that the formation of the self-assembled micro-nano structure effectively improves C60Photoelectric properties of, SnO2Modified C60Nanotube and method of manufacturing the sameThe photocurrent signal generated by the composite material can reach 25nA/cm when the current is stable2With pure C60Nanotubes (15 nA/cm)2) In contrast, it has a stronger photocurrent signal, indicating SnO2The introduction of (2) promotes the separation of electron-hole in the composite material, thereby generating more photo-generated electrons, and meanwhile, as can be observed from fig. 7, under the repeated light excitation, SnO2Modified C60The photoresponse current signal of the nanotube composite material can still be kept at 20nA/cm2The above shows that the composite material has good photochemical stability.
Example 3SnO2Modified C60Research on photocatalytic performance of nanotube composite material
SnO prepared in example 12Modified C60The nanotube composite material has excellent photocatalytic performance on the degradation of methylene blue, rhodamine B, tetracycline hydrochloride and other various organic pollutants, and the degradation reaches more than 70% within 2 hours. SnO is shown by taking photocatalytic degradation of methylene blue as an example in combination with the attached drawing2Modified C60The effect of the nanotube composite material in degrading organic pollutants.
The experimental procedure was as follows: 4mL of a 30mg/L methylene blue solution was taken and placed in a vial, and 3mg of SnO prepared in example 1 was added2Modified C60Nanotube composite material, C60Nanotubes or SnO2And dispersing into the methylene blue solution. Standing the vial in dark for 1 hr to adsorb organic pollutants, sampling every 30min, detecting absorbance of water sample with Shimadzu UV-2550 ultraviolet-visible spectrophotometer, and after adsorption balance is reached, using (300W, lambda)>420nm) xenon-mercury lamp as visible light source for 2h, sampling every 30min to detect the absorbance of the water sample.
The photocatalytic degradation efficiency E is calculated by the formula (1).
E＝(C0-Ct)/C0×100％ (1)
In the formula: c0Is the initial absorbance of a water sample containing organic pollutants before degradation; ctIs the absorbance of a water sample containing organic contaminants after degradation.
Calculation of SnO prepared in example 1 from the results of UV-Vis Spectrophotometer2、C60Nanotubes and SnO2Modified C60The degradation capability of the nanotube composite material in photocatalysis of methylene blue, the degradation curve and kinetic curve results are shown in fig. 8A and 8B, and the prepared C is irradiated by visible light60The nanotube material has certain catalytic activity on photocatalytic degradation of methylene blue, and the degradation can reach more than 45% within 2 h; SnO2Modified C60The activity of the nanotube composite material for photocatalytic degradation of methylene blue is improved, the degradation can reach more than 75% within 2h, and the activity is similar to that of pure SnO2And C60Compared with the nanotube, the reaction kinetic rate is respectively improved by about 3 times and 2 times.
SnO prepared according to inventive example 12Modified C60The photocatalytic degradation methylene blue cycle test of the nanotube composite material is shown in fig. 9, and it can be obviously seen that the prepared SnO2Modified C60The nanotube composite material has good stability, more than 60% of methylene blue can be still catalytically degraded within 2 hours after the nanotube composite material is recycled for 3 times, and the catalytic degradation effect is only slightly changed, which may have a certain relation with the loss in the recovery and washing process.
Example 4SnO2Modified C60Preparation of nanosheet composite
(1)C60Preparing a nano sheet:
selecting carbon tetrachloride as a good solvent and isopropanol as a poor solvent; 10mL of 0.5mg/mL of C60When the mesitylene solution is quickly injected into 40mL of isopropanol by an injector, the mixed solution is subjected to ultrasonic dispersion for 10min and then is kept stand for 12 h. The precipitate was centrifuged at 11k in a high speed centrifuge, the supernatant was decanted, and the bottom solid precipitate was collected. Washing with isopropanol for 3 times, and drying in vacuum oven at 40 deg.C overnight to obtain C60A solid powder of nanoplatelets.
(2)SnO2Modified C60Preparing the nano-sheet composite material:
taking C prepared in the step (1)600.014mmol of a solid powder of nanotubes was ultrasonically dispersed in a small amount of water to obtain a dispersion. Then, 20mL of SnCl solution containing 0.022mmol was added to the dispersion2And 0.026mmol of citric acid, the mixture was placed in a 250mL round bottom flask and heated to 120 ℃ on an oil bath and 20mL of NaBH containing 1.32mmol was gradually added4The solution was finally stirred under reflux for 6 h. Stopping heating after the reaction is finished, separating the liquid in the flask to obtain a solid on a high-speed centrifuge after the liquid is cooled to room temperature, washing the solid for 3 times by using deionized water, and drying the solid in vacuum at 40 ℃ to obtain SnO2Modified C60A solid powder of a nanoplatelet composite.
Inventive example 4 step (1) prepared C60The surface Scanning Electron Microscope (SEM) image of the nanosheet is shown in FIG. 9, and the morphology thereof was observed and analyzed under a high pressure of 10kV using a HITACHI S-4800 scanning electron microscope of Japan. As can be seen, C was prepared60The nano-sheet has controllable structure and uniform size, and the side length is about 1 mu m. SnO prepared by the step (2)2Modified C60The nanosheet composite, as shown in FIG. 10, still maintained a lamellar structure and the stacking of C was also observed by projection electron microscopy60A small amount of SnO is uniformly distributed on the surface of the nanosheet2And (3) nanoparticles.
(3)SnO2Modified C60Research on photocatalytic performance of the nanosheet composite material:
SnO prepared in example 42Modified C60The nano-sheet composite material has photocatalytic performance for degrading methylene blue, rhodamine B, tetracycline hydrochloride and other various organic pollutants. And C60Nanotube composite phase, C60The lamellar structures of the nano-sheets are mutually staggered to form nano-microspheres, so that the prepared C60The specific surface area of the nano-sheet is smaller, so that the adsorption quantity of organic pollutants on the surface is reduced, and C60The catalytic activity of the sheet material is reduced compared to the nanotube composite material. Within 2h, C60The degradation rate of the nano-sheets to methylene blue is about 35 percent and is less than C60A nanotube structure.
At the same time, becauseAggregation of the flakes results in C60On the nano-sheet with SnO2Reduction of binding sites, SnO2The amount of the supported compound is reduced, and the migration of electrons is influenced. Thus, with SnO2Modified C60Comparison of nanotubes to SnO2Modified C60The electron-hole separation efficiency of the nanosheets is low, so that the photocatalytic degradation efficiency is reduced, namely SnO2Modified C60The nano-sheet composite material only degrades about 50% of methylene blue within 2 h.
As can be seen from the above, C produced by the liquid-liquid interface self-assembly method60Nanotubes and C60The nano-sheet has certain photocatalysis capability. In the presence of SnO2After the composite material is compounded, the photoproduction electron-hole recombination rate of the composite material is reduced, the photocatalytic performance of the composite material is greatly improved, the photocatalytic reaction rate is accelerated, and the composite material has good chemical stability and has important significance for the practical application of the photocatalytic material.
In addition, through the selection of a liquid-liquid interface self-assembly method reaction system, such as: selection of good solvent and poor solvent in reaction System, C60The concentration in the good solvent can be controlled by C60And (4) self-assembling. Such as: using p-xylene as good solvent, n-propanol as poor solvent, C60The concentration of the solution in a good solvent is 0.5mg/mL, and hexagonal prism-shaped C can be obtained60A micro-nano structure; while p-xylene is used as a good solvent, n-heptanol is used as a poor solvent, C60The concentration of the resulting mixture in a good solvent was 0.5mg/mL, and polyhedral C was obtained60And (4) a micro-nano structure. SnO can be obtained by the micro-nano fullerene structures according to the method2Modified fullerene composite material with micro-nano structure.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (3)
1. SnO (stannic oxide)2The preparation method of the modified fullerene composite material with the micro-nano structure is characterized by comprising the following steps of: dispersing fullerene with a micro-nano structure in water to obtain a dispersion liquid; SnO2Adding a precursor, a complexing agent and a reducing agent into the dispersion liquid, reacting under the condition of heating, stirring and refluxing, cooling the solution, and separating to obtain SnO2A modified fullerene composite material with a micro-nano structure;
the fullerene with the micro-nano structure is C60A nanotube;
said SnO2Precursors and C60The molar ratio of the nanotubes is 1-2: 1;
said C60The preparation method of the nanotube comprises the following steps: firstly, dissolving a fullerene raw material in a good solvent to obtain a fullerene good solution, then injecting the fullerene good solution into a poor solvent to obtain a mixed solution, then standing the mixed solution, and separating precipitated precipitates to obtain the fullerene with a micro-nano structure; the good solvent is mesitylene; the poor solvent is isopropanol; the concentration of the good fullerene solution is 0.5mg/mL, and 20mL of poor solvent is needed for every 5mL of good fullerene solution; the mixed solution is kept still for 18-36 h;
said SnO2The precursor is tin dichloride;
the complexing agent is citric acid;
the reducing agent is sodium borohydride;
said SnO2The molar ratio of the precursor to the complexing agent is 1: 1-2;
said SnO2The molar ratio of the precursor to the reducing agent is 1: 55-65;
the heating temperature is 100-140 ℃; the stirring reflux time is 4-10 h;
SnO prepared by the preparation method2The modified fullerene composite material with the micro-nano structure is used for photocatalytic degradation of organic pollutants: the SnO2And dispersing the modified fullerene composite material with the micro-nano structure into a water sample containing organic pollutants, and irradiating the water sample containing the organic pollutants by adopting light containing visible light.
2. The method of claim 1, wherein the organic contaminant comprises at least one of rhodamine B, methyl orange, methylene blue, tetracycline hydrochloride, or acid red.
3. The method according to claim 1, wherein the content of the organic contaminant in the water sample containing the organic contaminant is 5 to 50 mg/L;
and/or the wave band of the visible light is 420-800 nm;
and/or the energy of the light containing visible light irradiating the sample is 5-25 MW;
and/or the irradiation time containing visible light is 0.5-3 h.
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| CN109980126B (en) * | 2017-12-27 | 2020-07-31 | Tcl科技集团股份有限公司 | Carrier transmission material, carrier transmission film, and preparation method and application thereof |
| CN111111428A (en) * | 2019-10-21 | 2020-05-08 | 中国科学院化学研究所 | Application of fullerene and semiconductor composite material loaded by fullerene derivative in photocatalytic degradation of indoor VOCs (volatile organic compounds) |
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| JP2006101031A (en) * | 2004-09-28 | 2006-04-13 | Matsushita Electric Ind Co Ltd | Speaker instrument |
| CN102953150A (en) * | 2012-11-14 | 2013-03-06 | 青岛科技大学 | Preparation of fullerene micro-nano fiber in volatilization and diffusion ways |
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| CN105435771A (en) * | 2015-12-18 | 2016-03-30 | 清华大学 | Preparation methods of tin-based composite catalyst and cathode material containing tin-based composite catalyst |
| CN108114754A (en) * | 2017-12-04 | 2018-06-05 | 中国科学院化学研究所 | Composite material, preparation method and the application of carboxylated metal fullerene modified titanic oxide |
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| JP2006101031A (en) * | 2004-09-28 | 2006-04-13 | Matsushita Electric Ind Co Ltd | Speaker instrument |
| CN102953150A (en) * | 2012-11-14 | 2013-03-06 | 青岛科技大学 | Preparation of fullerene micro-nano fiber in volatilization and diffusion ways |
| CN104549281A (en) * | 2015-02-04 | 2015-04-29 | 中国科学技术大学 | Active graphene-metal oxide composite photocatalyst and preparation method and application thereof |
| CN105435771A (en) * | 2015-12-18 | 2016-03-30 | 清华大学 | Preparation methods of tin-based composite catalyst and cathode material containing tin-based composite catalyst |
| CN108114754A (en) * | 2017-12-04 | 2018-06-05 | 中国科学院化学研究所 | Composite material, preparation method and the application of carboxylated metal fullerene modified titanic oxide |
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