CN106140135A - The photocatalyst Li GaSn that a kind of high-efficient wide-frequency is visible light-responded2o6and preparation method thereof - Google Patents
The photocatalyst Li GaSn that a kind of high-efficient wide-frequency is visible light-responded2o6and preparation method thereof Download PDFInfo
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- CN106140135A CN106140135A CN201610559273.9A CN201610559273A CN106140135A CN 106140135 A CN106140135 A CN 106140135A CN 201610559273 A CN201610559273 A CN 201610559273A CN 106140135 A CN106140135 A CN 106140135A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910005538 GaSn Inorganic materials 0.000 title description 2
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000013064 chemical raw material Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000003595 spectral effect Effects 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 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 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910003334 KNbO3 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 206010051820 Sordes Diseases 0.000 description 1
- VEUKJXRCHYAIAW-UHFFFAOYSA-N [Nb].[K] Chemical compound [Nb].[K] VEUKJXRCHYAIAW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- -1 pottery Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000035922 thirst 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
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
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Abstract
The invention discloses the visible light responsive photocatalyst LiGaSn of a kind of high-efficient wide-frequency2O6And preparation method thereof.The chemical constitution formula of this photocatalyst is LiGaSn2O6.The invention also discloses the preparation method of above-mentioned material.The photocatalyst that the present invention obtains has the advantages such as spectral response range width, light conversion efficiency height and good stability, has decomposition harmful chemical, organic-biological matter and the effect of sterilization under visible light illumination；Additionally preparation method is simple, synthesis temperature is low, low cost, is suitable for commercial production and application.
Description
Technical field
The present invention relates to a kind of visible light-responded photocatalyst Li GaSn2O6And preparation method thereof, belong to inorganic photocatalysis
Material Field.
Background technology
Along with socioeconomic development, people increasingly pay close attention to for the energy and ecological environment, solve energy shortage and ring
Environment pollution problem be realize sustainable development, improve people's living standard and safeguard national security in the urgent need to.
From phase late 1970s, there has been proposed and utilize in photocatalyst decomposition water and the pesticide in air and evil
The Organic substances such as sordes matter, and the application example such as the self-cleaning scribbling the surface of solids of photocatalyst.Light-catalyzed reaction former
Reason be photocatalyst after absorbing higher than the photon of its band-gap energy, generate hole and electronics, these holes and electronics divide
Do not carry out oxidation reaction and reduction reaction, reach to decompose harmful chemical, organic-biological matter and the purpose of sterilization.Photocatalyst
Having many kinds, the most most representative is titanium dioxide (TiO2), utilize titanium dioxide to the agriculture in water and in air
The Organic substance such as medicine and odorant decomposes, but the band gap of titanium dioxide is 3.2eV, only in the ultraviolet shorter than 400nm
Just can show activity under the irradiation of line, can only be little to utilize visible ray at indoor or the local work having uviol lamp,
This greatly limits the use of titanium dioxide optical catalyst.
In view of photocatalyst practicality in decomposing harmful substances, it is indispensable for utilizing sunlight as light source
's.Irradiate sunlight medium wavelength maximum intensity of visible ray near 500nm to earth's surface, wavelength be 400nm～750nm can
The energy in Jian Guang district is about the 43% of sunlight gross energy, so in order to utilize efficiently, the exploitation of bismuth series photocatalyst and
Research has been achieved for a series of great achievement, bismuthous complex such as BiVO4、Bi2MoO6、Bi2Mo2O9、Bi2Mo3O12
And Bi2WO4It is in the news and there is good absorption under visible light.A series of niobiums (tantalum) hydrochlorate photocatalyst is higher owing to having
Photocatalytic activity and be widely studied.Such as, niobate photocatalyst Pb3Nb4O13、BiNbO4And Bi2MNbO7(M=Al, Ga,
In, Y, rare earth element and Fe) etc. and niobium potassium compound oxide photocatalyst such as KNbO3、KNb3O8、K4Nb6O17And K6Nb10.6O30Deng
All there is preferable photocatalysis performance, but its intrinsic photocatalytic effect is the most weak in visible-range or does not has activity.
Although photocatalysis research has been carried out the several years, the exploration to visible light-responded photocatalyst is big with exploitation at present
Part is the summary of experience drawn by great many of experiments, the most also cannot be from the crystal structure of compound, composition, molecule
Predicting its photocatalysis performance in the physicochemical properties such as amount, that therefore reports at present has visible light-responded photocatalyst kind the most very
Limited, and also exist that light conversion efficiency is low, synthesis difficulty, poor stability and problem, the research and development such as spectral response range is narrow
New preparation method is simple and to have the visible light-responded high efficiency photocatalyst of wideband be that this area scientific and technical personnel thirst for solving always
Determine but be difficult to the difficult problem succeeded all the time, which greatly limits extensively application and the development of photocatalyst.We
To consisting of LiGaSn2O6、LiGaGe2O6And LiBSn2O6Sample carried out Photocatalytic Performance Study.Found that
LiGaSn2O6Band gap width is 2.62eV, has the visible light-responded photocatalysis performance of excellence；LiGaGe2O6And LiBSn2O6
For insulator, under ultraviolet irradiation, the most do not show activity.
Summary of the invention
It is an object of the invention to provide and a kind of there is visible light-responded photocatalyst Li GaSn2O6And preparation method thereof.
The chemical constitution formula with visible light-responded photocatalyst that the present invention relates to is: LiGaSn2O6。
The preparation method of above-mentioned visible light-responded photocatalyst concretely comprises the following steps:
(1) by 99.9% analytically pure chemical raw material Li2CO3、Ga2O3And SnO2Powder press LiGaSn2O6Composition claim
Amount dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and dehydrated alcohol, ball milling 8
Hour, it is mixed and finely ground, takes out and dry, cross 200 mesh sieves.
(3) by the powder of step (2) mix homogeneously 950～1000 DEG C of pre-burnings, and it is incubated 6 hours, naturally cools to room
Temperature, is then pulverized by ball mill and makes average diameter of particles diminish, less than 2 μm, i.e. obtain LiGaSn2O6Powder.
Advantages of the present invention: LiGaSn2O6The visible light-responded wide frequency range of photocatalyst, light conversion efficiency is high and steady
Qualitative good, there is decomposition harmful chemical, organic-biological matter and the effect of sterilization under visible light illumination；Additionally preparation method
Simply, synthesis temperature low, low cost, be suitable for commercial production and application.
Detailed description of the invention
Present invention will be described in detail below:
1, in order to obtain the composite oxides used in the present invention, prepare powder first by solid-phase synthesis, i.e.
Various oxides or carbonate as raw material mix according to target constitutional chemistry metering ratio, more at ambient pressure in air gas
Atmosphere synthesizes.
2 in order to effectively utilize light, and the size of the photocatalyst in the present invention, preferably in micron level, is even received
Rice corpuscles, and specific surface area is bigger.The oxide powder prepared with solid-phase synthesis, its particle is relatively big and surface area is less, but
Can be by ball mill pulverizing means makes particle diameter diminish.
3, the photocatalysis experiment of the present invention is using methyl orange as simulation organic pollution, and its concentration is 20mg/L；Photocatalysis
Agent LiGaSn2O6Addition be 1g/L；Light source uses the xenon lamp of 300W, and reactive tank uses the vessel that pyrex is made, logical
Wave filter obtains the wavelength light more than 420nm, then irradiates photocatalyst；Catalysis time is set as 60 minutes.
Embodiment 1:
(1) by analytical pure chemical raw material Li2CO3、Ga2O3And SnO2Powder press LiGaSn2O6Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and dehydrated alcohol, ball milling 8
Hour, it is mixed and finely ground, takes out and dry, cross 200 mesh sieves.
(3) by the powder of step (2) mix homogeneously 950 DEG C of pre-burnings, and it is incubated 6 hours, naturally cools to room temperature, then
Being pulverized by ball mill makes average diameter of particles diminish, and less than 2 μm, i.e. obtains LiGaSn2O6Powder.
Prepared photocatalyst, under the wavelength radiation of visible light more than 420nm, reaches for 60 minutes to methyl orange clearance
To 97.4%.
Embodiment 2:
(1) by analytical pure chemical raw material Li2CO3、Ga2O3And SnO2Powder press LiGaSn2O6Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and dehydrated alcohol, ball milling 8
Hour, it is mixed and finely ground, takes out and dry, cross 200 mesh sieves.
(3) by the powder of step (2) mix homogeneously 980 DEG C of pre-burnings, and it is incubated 6 hours, naturally cools to room temperature, then
Being pulverized by ball mill makes average diameter of particles diminish, and less than 2 μm, i.e. obtains LiGaSn2O6Powder.
Prepared photocatalyst, under the wavelength radiation of visible light more than 420nm, reaches for 60 minutes to methyl orange clearance
To 98.7%.
Embodiment 3:
(1) by analytical pure chemical raw material Li2CO3、Ga2O3And SnO2Powder press LiGaSn2O6Composition weigh dispensing.
(2) raw material mixing step (1) prepared, puts in ball grinder, adds zirconia ball and dehydrated alcohol, ball milling 8
Hour, it is mixed and finely ground, takes out and dry, cross 200 mesh sieves.
(3) by the powder of step (2) mix homogeneously 1000 DEG C of pre-burnings, and it is incubated 6 hours, naturally cools to room temperature, so
Being pulverized by ball mill afterwards makes average diameter of particles diminish, and less than 2 μm, i.e. obtains LiGaSn2O6Powder.
Prepared photocatalyst, under the wavelength radiation of visible light more than 420nm, methyl orange clearance is reached by 60min
To 98.1%.
The present invention is never limited to above example.The bound of each temperature, interval value can realize the present invention, at this not
Enumerate embodiment.
The made photocatalyst powder of above inventive embodiments can be carried on multiple matrix surface.Matrix can be glass
Glass, pottery, activated carbon or quartz sand etc., photocatalyst can be carried on matrix surface in the form of a film.
Claims (1)
1. the photocatalyst that a high-efficient wide-frequency is visible light-responded, it is characterised in that the chemical composition of described photocatalyst is
LiGaSn2O6；
The preparation method of described photocatalyst concretely comprises the following steps:
(1) by analytical pure chemical raw material Li2CO3、Ga2O3And SnO2Powder press photocatalyst Li GaSn2O6Composition weigh join
Material；
(2) raw material mixing step (1) prepared, puts in ball grinder, addition zirconia ball and dehydrated alcohol, ball milling 8 hours,
It is mixed and finely ground, takes out and dry, cross 200 mesh sieves；
(3) by the powder of step (2) mix homogeneously 950～1000 DEG C of pre-burnings, and it is incubated 6 hours, naturally cools to room temperature, so
Being pulverized by ball mill afterwards makes average diameter of particles be less than 2 μm, i.e. obtains photocatalyst Li GaSn2O6Powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610559273.9A CN106140135A (en) | 2016-07-17 | 2016-07-17 | The photocatalyst Li GaSn that a kind of high-efficient wide-frequency is visible light-responded2o6and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610559273.9A CN106140135A (en) | 2016-07-17 | 2016-07-17 | The photocatalyst Li GaSn that a kind of high-efficient wide-frequency is visible light-responded2o6and preparation method thereof |
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| CN106140135A true CN106140135A (en) | 2016-11-23 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105396595A (en) * | 2015-12-15 | 2016-03-16 | 桂林理工大学 | Visible light responsive photocatalyst Li3FeGe2O7 and preparation method thereof |
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2016
- 2016-07-17 CN CN201610559273.9A patent/CN106140135A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105396595A (en) * | 2015-12-15 | 2016-03-16 | 桂林理工大学 | Visible light responsive photocatalyst Li3FeGe2O7 and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LETICIA M. TORRES-MARTINEZ等: "Bi2MTaO7 (M = Al, Fe, Ga, In) PHOTOCATALYST FOR ORGANIC COMPOUNDS DEGRADATION UNDER UV AND VISIBLE LIGHT", 《WSEAS TRANSACTIONS ON ENVIRONMENT AND DEVELOPMENT》 * |
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