CN114558561A - Preparation method and application of zinc titanate oxygen-containing defect photocatalyst - Google Patents
Preparation method and application of zinc titanate oxygen-containing defect photocatalyst Download PDFInfo
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- CN114558561A CN114558561A CN202210253453.XA CN202210253453A CN114558561A CN 114558561 A CN114558561 A CN 114558561A CN 202210253453 A CN202210253453 A CN 202210253453A CN 114558561 A CN114558561 A CN 114558561A
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- oxygen
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- zinc
- zinc titanate
- containing defect
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000001301 oxygen Substances 0.000 title claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 50
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000011701 zinc Substances 0.000 title claims abstract description 42
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 41
- 230000007547 defect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 6
- 150000003751 zinc Chemical class 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 230000002950 deficient Effects 0.000 claims description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 4
- 231100000719 pollutant Toxicity 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 230000000593 degrading effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910003080 TiO4 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- -1 and usually Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention belongs to the technical field of photocatalytic materials, and particularly discloses a preparation method and application of a zinc titanate oxygen-containing defect photocatalyst. Adding zinc salt into absolute ethyl alcohol, magnetically stirring, adding weak acid, adding an organic titanium compound into the solution, and stirring the obtained solution for 30 minutes; and drying overnight, calcining at high temperature in an inert gas environment, and naturally cooling to obtain the zinc titanate oxygen-containing defect photocatalyst. The zinc titanate material prepared by the method of the invention has oxygen defects which can not only activate lattice oxygen to participate in catalytic reaction, but also adsorb and degrade organic pollutants, thereby improving the photocatalytic activity.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a zinc titanate photocatalyst with oxygen defects, and a preparation method and application thereof.
Background
In recent years, the problem of environmental pollution has become one of the major problems of global concern, with gaseous pollution always being considered as one of the most serious environmental problems threatening human survival. Among the numerous environmental purification methods, various environmental catalysis techniques such as photocatalysis and electrocatalysis have attracted attention. The photocatalysis technology is an environment-friendly technology, realizes the degradation of gaseous pollutants by utilizing sunlight, and has the characteristics of no secondary pollution, recycling, regeneration and the like.
Zinc titanate (Zn)2TiO4) The magnetic material has a spinel crystal structure, is a soft magnetic material with excellent performance, has the outstanding advantages of extremely high resistivity and good magnetic spectrum characteristics, and is extremely suitable for application under high frequency and ultrahigh frequency. The characteristics determine the recyclability of the material, and in the aspect of catalysis, the prepared zinc titanate nano particles have the remarkable characteristic of fine and uniform particle size. And the narrow-band-gap semiconductor can absorb most visible light in sunlight. Relevant theoretical calculations and experiments also confirm that oxygen vacancies are likely to be surface reactive sites of the material. Therefore, the introduction of oxygen vacancy has important influence on the physicochemical properties of the material, including the electronic structure, the geometrical structure, the light absorption property and the surface adsorption property of the system. Oxygen defects may also enhance catalytic activity. The introduction of oxygen vacancies can also affect the light absorption characteristics and surface adsorption characteristics of the material, and usually, metal atoms of metal oxides have the characteristic of coordination saturation and cannot activate oxygen molecules through chemical adsorption. The construction of the oxygen vacancy defect overcomes the defect and promotes the efficient transfer of the photo-generated electrons from the oxide catalyst to oxygen molecules.
Disclosure of Invention
The invention aims to provide a zinc titanate oxygen-containing defect photocatalyst and a preparation method thereof, wherein the method is simple, convenient, low in cost, mild in condition and beneficial to large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that: the preparation method of the zinc titanate oxygen-containing defect photocatalyst comprises the following steps:
1) adding zinc salt into absolute ethyl alcohol, magnetically stirring for 30 minutes, dropwise adding acid, stirring again for 30 minutes, dropwise adding an organic titanium compound, and drying overnight to obtain a precursor;
2) grinding the precursor, calcining at high temperature in an inert gas environment, and naturally cooling to obtain the zinc titanate oxygen-containing defect photocatalyst.
Preferably, in the above method for preparing a zinc titanate oxygen-containing defect photocatalyst, in step 1), the zinc salt is zinc nitrate hexahydrate.
Preferably, in the above preparation method of the zinc titanate oxygen-containing defect photocatalyst, in step 1), the acid is glacial acetic acid.
Preferably, in the above preparation method of the zinc titanate oxygen-containing defect photocatalyst, in step 1), the organic titanium compound is tetra-n-butyl titanate.
Preferably, in the above method for preparing the oxygen-containing defect zinc titanate photocatalyst, in the step 1), the molar ratio of the zinc atom to the titanium atom is 1: 1.
Preferably, in the above preparation method of the zinc titanate oxygen-containing defect photocatalyst, in the step 2), the high-temperature calcination is performed at a calcination temperature of 450-650 ℃ for a calcination time of 2 h.
Preferably, in the above method for preparing the oxygen-containing defect zinc titanate photocatalyst, in step 2), the inert gas is nitrogen.
The zinc titanate oxygen-containing defect photocatalyst provided by the invention is applied to the low-temperature catalytic degradation of gas pollutants.
Preferably, the gaseous contaminant is isopropanol.
Preferably, the method is as follows: adding zinc titanate oxygen-containing defect photocatalyst into a sealed reaction container, adding isopropanol, and carrying out catalytic degradation under a xenon lamp.
The invention has the beneficial effects that: the zinc titanate catalyst is prepared by using the zinc salt and the organic titanium compound, a large number of oxygen defect structures are constructed, and the oxygen defects can activate lattice oxygen and adsorb organic pollutants, so that the photocatalytic activity is improved. The preparation method provided by the invention has the advantages of cheap raw materials, simple operation, no pollution to the environment, realization of green chemistry and effective degradation of gas pollutants, and greatly reduces the cost.
Drawings
FIG. 1 is an XRD pattern of oxygen deficient zinc titanate photocatalysts prepared in examples 1-4 of the present invention.
FIG. 2 is a graph comparing the activity of oxygen deficient zinc titanate photocatalysts prepared in examples 1-4 of the present invention to degrade isopropanol gas.
Detailed Description
EXAMPLE 1 Zinc titanate oxygen-deficient photocatalyst
The preparation method comprises the following steps:
1) 0.874g of zinc nitrate hexahydrate is dissolved in 10ml of absolute ethyl alcohol, after magnetic stirring is carried out for 30 minutes, 2ml of glacial acetic acid is dripped, after stirring is carried out for 30 minutes at room temperature, 1ml of tetra-n-butyl titanate is dripped dropwise and slowly, after stirring is carried out for 30 minutes, the obtained mixed solution is aged for 24 hours, and is dried overnight at 80 ℃, so as to obtain the precursor.
2) Grinding the precursor, calcining for 2h at 450 ℃ in a nitrogen environment at the heating rate of 5 ℃/min, and then naturally cooling to obtain the zinc titanate oxygen-containing defect photocatalyst which is marked as OVs-ZTO-450.
EXAMPLE 2 Zinc titanate oxygen deficient photocatalyst
The preparation method comprises the following steps:
1) 0.874g of zinc nitrate hexahydrate is dissolved in 10ml of absolute ethyl alcohol, after magnetic stirring is carried out for 30 minutes, 2ml of glacial acetic acid is dripped, after stirring is carried out for 30 minutes at room temperature, 1ml of tetra-n-butyl titanate is dripped dropwise and slowly, after stirring is carried out for 30 minutes, the obtained mixed solution is aged for 24 hours, and is dried overnight at 80 ℃, so as to obtain the precursor.
2) Grinding the precursor, calcining at 550 ℃ for 2h in a nitrogen environment at the heating rate of 5 ℃/min, and then naturally cooling to obtain the zinc titanate oxygen-containing defect photocatalyst which is marked as OVs-ZTO-550.
EXAMPLE 3 Zinc titanate oxygen deficient photocatalyst
The preparation method comprises the following steps:
1) 0.874g of zinc nitrate hexahydrate is dissolved in 10ml of absolute ethyl alcohol, after magnetic stirring is carried out for 30 minutes, 2ml of glacial acetic acid is dripped, after stirring is carried out for 30 minutes at room temperature, 1ml of tetra-n-butyl titanate is dripped dropwise and slowly, after stirring is carried out for 30 minutes, the obtained mixed solution is aged for 24 hours, and is dried overnight at 80 ℃, so as to obtain the precursor.
2) Grinding the precursor, calcining at 650 ℃ for 2h in a nitrogen environment at the heating rate of 5 ℃/min, and then naturally cooling to obtain the zinc titanate oxygen-containing defect photocatalyst which is marked as OVs-ZTO-650.
EXAMPLE 4 Zinc titanate oxygen deficient photocatalyst
The preparation method comprises the following steps:
1) 0.874g of zinc nitrate hexahydrate is dissolved in 10ml of absolute ethyl alcohol, after magnetic stirring is carried out for 30 minutes, 2ml of glacial acetic acid is dripped, after stirring is carried out for 30 minutes at room temperature, 1ml of tetra-n-butyl titanate is dripped dropwise and slowly, after stirring is carried out for 30 minutes, the obtained mixed solution is aged for 24 hours, and is dried overnight at 80 ℃, so as to obtain the precursor.
2) Grinding the precursor, calcining at 550 ℃ for 2h in an air environment at the heating rate of 5 ℃/min, and then naturally cooling to obtain the oxygen-containing defect zinc titanate photocatalyst, which is marked as ZTO-550.
FIG. 1 is an XRD test pattern of the oxygen defect-containing zinc titanate photocatalysts prepared in examples 1-4. As can be seen from FIG. 1, comparison of this with a standard card demonstrates the successful synthesis of Zn2TiO4A material.
Example 5 application
The photocatalysts prepared in examples 1 to 4 were placed at 4cm in length, respectively2In the glass groove, the glass groove loaded with the photocatalyst is respectively placed into 224ml reactors containing atmospheric pressure air, 5ul of isopropanol liquid is finally injected into the reactors, the reactors are heated by illumination of a 300W xenon lamp, timing is started after 10min, and a needle is drawn out of the samples every 20 min for testing. The acetone produced was subjected to gas chromatography using a FID detector (GC1690, Jiedo technologies, Ltd.). After the reaction was completed, the reactor was cooled to room temperature, and the catalyst was collected for further characterization.
FIG. 2 is a graph comparing the activities of the photocatalysts prepared in examples 1 to 4 for degrading isopropanol gas, and it can be seen that all the photocatalysts prepared in example 2 can effectively degrade isopropanol, and it is obvious that the photocatalyst OVs-ZTO-550 prepared in example 2 has the highest photocatalytic activity, which is about 2.16 times of the rate of degrading isopropanol of the photocatalyst OVs-ZTO-450 prepared in example 1, the photocatalyst OVs-ZTO-550 prepared in example 2 is about 3.39 times of the rate of degrading isopropanol of the photocatalyst OVs-ZTO-650 prepared in example 3, and the photocatalyst OVs-ZTO-550 prepared in example 2 is about 3.6 times of the rate of degrading isopropanol of the photocatalyst ZTO-550 prepared in example 4, because the photocatalyst prepared in this application contains a large amount of oxygen defects, which can not only activate lattice oxygen, participate in catalytic reaction and can adsorb and degrade organic pollutants, thereby improving the photocatalytic activity.
Claims (10)
1. The preparation method of the zinc titanate oxygen-containing defect photocatalyst is characterized by comprising the following steps:
1) adding zinc salt into absolute ethyl alcohol, magnetically stirring for 30 minutes, dropwise adding acid, stirring again for 30 minutes, dropwise adding an organic titanium compound, and drying overnight to obtain a precursor;
2) grinding the precursor, calcining at high temperature in an inert gas environment or an air environment, and naturally cooling to obtain the oxygen-containing defect photocatalyst of zinc titanate.
2. The method of preparing the zinc titanate oxygen-containing defect photocatalyst of claim 1, wherein in step 1), the zinc salt is zinc nitrate hexahydrate.
3. The method of preparing the zinc titanate oxygen-containing defect photocatalyst of claim 1, wherein in step 1), the acid is glacial acetic acid.
4. The method of preparing the zinc titanate oxygen-containing defect photocatalyst of claim 1, wherein in step 1), the organic titanium compound is tetra-n-butyl titanate.
5. The method of preparing the oxygen-deficient zinc titanate photocatalyst according to claim 1, wherein in step 1), the molar ratio of zinc atoms to titanium atoms is 1: 1.
6. The method for preparing the oxygen-containing defect zinc titanate photocatalyst as claimed in claim 1, wherein in the step 2), the high-temperature calcination is carried out at a calcination temperature of 450-650 ℃ for a calcination time of 2 h.
7. The method of claim 1, wherein in step 2), the inert gas is nitrogen.
8. Use of the oxygen-containing defect zinc titanate photocatalyst prepared according to the process of any one of claims 1 to 7 for the low temperature catalytic degradation of gaseous pollutants.
9. The use of claim 8, wherein the gaseous contaminant is isopropanol.
10. Use according to claim 9, characterized in that the method is as follows: adding zinc titanate oxygen-containing defect photocatalyst into a sealed reaction container, adding isopropanol, and carrying out catalytic degradation under a xenon lamp.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786780A (en) * | 2018-06-03 | 2018-11-13 | 常州德维勒新材料科技有限公司 | A kind of nano combined Zn2TiO4The preparation method of functional material and its dispersion liquid |
| CN111468096A (en) * | 2020-04-09 | 2020-07-31 | 浙江工业大学 | Zn2TiO4/TiO2Composite material and preparation method and application thereof |
| CN112958093A (en) * | 2021-02-05 | 2021-06-15 | 辽宁大学 | Cobalt ferrite photocatalyst with oxygen-containing defect and preparation method and application thereof |
| CN114042471A (en) * | 2021-12-03 | 2022-02-15 | 辽宁大学 | Visible light response type Zn2TiO4/g-C3N4Heterojunction material and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786780A (en) * | 2018-06-03 | 2018-11-13 | 常州德维勒新材料科技有限公司 | A kind of nano combined Zn2TiO4The preparation method of functional material and its dispersion liquid |
| CN111468096A (en) * | 2020-04-09 | 2020-07-31 | 浙江工业大学 | Zn2TiO4/TiO2Composite material and preparation method and application thereof |
| CN112958093A (en) * | 2021-02-05 | 2021-06-15 | 辽宁大学 | Cobalt ferrite photocatalyst with oxygen-containing defect and preparation method and application thereof |
| CN114042471A (en) * | 2021-12-03 | 2022-02-15 | 辽宁大学 | Visible light response type Zn2TiO4/g-C3N4Heterojunction material and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ALIMA MEBREK ET AL.: "Preparation and characterization of spinel type Zn2TiO4 nanocomposite" * |
| 万利远等: "Zn2TiO4纳米线的合成及其应用于丙酮的光催化降解" * |
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