CN110038552A - With visible light-responded bismuth stannate photochemical catalyst and preparation method thereof - Google Patents
With visible light-responded bismuth stannate photochemical catalyst and preparation method thereof Download PDFInfo
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- CN110038552A CN110038552A CN201910450127.6A CN201910450127A CN110038552A CN 110038552 A CN110038552 A CN 110038552A CN 201910450127 A CN201910450127 A CN 201910450127A CN 110038552 A CN110038552 A CN 110038552A
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 42
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 229940071182 stannate Drugs 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005119 centrifugation Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000003643 water by type Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract 1
- 229920002472 Starch Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229960001229 ciprofloxacin hydrochloride Drugs 0.000 description 4
- DIOIOSKKIYDRIQ-UHFFFAOYSA-N ciprofloxacin hydrochloride Chemical compound Cl.C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 DIOIOSKKIYDRIQ-UHFFFAOYSA-N 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229910002902 BiFeO3 Inorganic materials 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- 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
- C02F2101/38—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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to catalysis material technical fields, disclose a kind of preparation method with visible light-responded bismuth stannate photochemical catalyst, include the following steps: SnCl4·5H2O is dissolved in 20 mL deionized waters, and is stirred to being completely dissolved；By Bi (NO3)3·5H2O is dissolved in the dilute nitric acid solution of 30 mL, 2 M；Above two solution is mixed in whipping process, continues stirring 30 minutes；The pH that the mixed solution is adjusted with certain density NaOH solution, after being adjusted to appropriate pH, the reaction was continued under stiring 60 min；Acquired solution is placed in 100 mL water heating kettles, 24 hours are reacted under the conditions of 180oC, are cooled down at room temperature, sediment centrifugation, washing are placed in drying box and are dried；Grinding obtains bismuth stannate photochemical catalyst in mortar；Also disclose has visible light-responded bismuth stannate photochemical catalyst as obtained by above-mentioned preparation method.The present invention is prepared with visible light-responded bismuth stannate material using pot hydro-thermal method, to the higher characteristic of organic pollutant degradation efficiency under simulated light irradiation.
Description
Technical field
It is specifically a kind of that there is visible light-responded bismuth stannate photochemical catalyst the present invention relates to catalysis material technical field
And preparation method thereof.
Background technique
Currently, energy crisis and environmental pollution have become the two large problems for attracting global researcher's concern.Semiconductor light
Catalysis is considered as one of the effective way for tapping a new source of energy and curbing environmental pollution.This method is simple with equipment, aoxidizes
The features such as performance is strong, energy-efficient, operating condition is easy to control, and secondary pollution will not be caused to environment.Work as photochemical catalyst
It absorbs an energy (h υ) and its band-gap energy (Eg) matches or the photon more than Eg, the electronics (e-) in valence band will be to conduction band
Transition, while positively charged hole (h+) is left in valence band, to form e--h+ pairs of photoproduction.H+ is a kind of strong oxidizer, is led
Band e- is a kind of strong reductant, they can be by most of organic and inorganic pollution non-selectivity direct, indirect oxidation
Or reduction, and do not need to add other chemical reagent, to realize the minimizing of pollutant and innoxious.Titanium dioxide is considered
One of most promising photochemical catalyst, under ultraviolet light have highlight catalytic active, excellent chemical stability, and
Low cost and nontoxicity.However, TiO2 does not respond to visible light since relatively large band gap (Eg) is about 3.2 eV,
Which has limited its uses in practical applications.Therefore, it is necessary to develop new visible light responsive photocatalyst.
It is well known that visible light responsive photocatalyst decomposes water or degradable organic pollutant because of it under visible light illumination
Potential application and cause more and more to pay close attention to.In recent years, many researchers are dedicated to the developmental research of the compound containing Bi, such as
BiFeO3, BiVO4 and Bi2WO6 etc..These Bi based compounds all show certain photo-catalysis capability in visible-range,
Due to the hydridization valence band of O 2p and Bi 6s make its band gap narrow.As a member of Bi base oxide, typical pyrochlore constitution
Bi2Sn2O7 is widely studied because of its special ionic conductivity, catalytic action and gas sensing capabilities.However, about
The research for improving the Photocatalytic Degradation Property of Bi2Sn2O7 under radiation of visible light is still seldom.Bi2Sn2O7 has as one kind can
The novel photocatalysis material of light-exposed response, it will open up a new approach for photocatalysis removal and degradable organic pollutant,
There is very good application prospect in terms of the depollution of environment and new energy development.Therefore, research and develop high activity, high stability and
The visible light catalyst of good circulation utility is the important front edge project of domestic and international water treatment field.
Summary of the invention
The purpose of the present invention is to provide a kind of with visible light-responded bismuth stannate photochemical catalyst and preparation method thereof, with
Solve the problems mentioned above in the background art.
To achieve the above object, the invention provides the following technical scheme:
It is a kind of with visible light-responded bismuth stannate photochemical catalyst and preparation method thereof, include the following steps:
(1) by SnCl4·5H2O is dissolved in 20 mL deionized waters, and is stirred to being completely dissolved；
(2) by Bi (NO3)3·5H2O is dissolved in the dilute nitric acid solution of 30 mL, 2 M；
(3) above two solution is mixed in whipping process, continues stirring 30 minutes；
(4) pH of the mixed solution is adjusted with certain density NaOH solution, after being adjusted to appropriate pH, the reaction was continued under stiring
60 min；
(5) acquired solution is placed in 100 mL water heating kettles, 24 hours is reacted under the conditions of 180oC, cools down, will precipitate at room temperature
Object centrifugation, washing are placed in drying box and dry；
(6) grinding obtains bismuth stannate photochemical catalyst in mortar.
As a further solution of the present invention: in step (1), SnCl4·5H2The molal weight of O is 0.01mol.
As a further solution of the present invention: in step (2), Bi (NO3)3·5H2The molal weight of O is 0.01mol.
As a further solution of the present invention: in step (3), the concentration of NaOH solution is 4 M.
As a further solution of the present invention: in step (3), adjusting pH to pH=7.
As a further solution of the present invention: in step (3), adjusting pH to pH=9.
As a further solution of the present invention: in step (3), adjusting pH to pH=11.
As further scheme of the invention: in step (3), adjusting pH to pH=13.
It is a kind of with visible light-responded bismuth stannate photochemical catalyst, by above-mentioned there is visible light-responded bismuth stannate light to urge
The preparation method of agent is prepared.
Compared with prior art, the beneficial effects of the present invention are:
Described a kind of with visible light-responded bismuth stannate photochemical catalyst and preparation method thereof, simple process and low in cost is adopted
It is prepared with pot hydro-thermal method with visible light-responded bismuth stannate material, to organic pollutant degradation efficiency under simulated light irradiation
Higher characteristic.
Detailed description of the invention
Fig. 1 is the XRD diagram with visible light-responded bismuth stannate photochemical catalyst.
Fig. 2 is the SEM figure with visible light-responded bismuth stannate photochemical catalyst.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
In the embodiment of the present invention 1, a kind of preparation method with visible light-responded bismuth stannate photochemical catalyst, including walk as follows
It is rapid: by 0.01mol SnCl4·5H2O is dissolved in 20 mL deionized waters, and is stirred to being completely dissolved, by 0.01mol Bi
(NO3)3·5H2O is dissolved in the dilute nitric acid solution of 30 mL, 2 M.Above two solution is mixed in whipping process, continues to stir
It mixes 30 minutes.The backward mixed solution in the NaOH solution of 4 M is added dropwise dropwise, adjust pH to pH=7, continue under stiring anti-
Answer 60 min.Acquired solution is placed in 100 mL water heating kettles, 24 hours are reacted under the conditions of 180oC, cools down, will sink at room temperature
Starch centrifugation, washing are placed in drying box and dry, and grinding obtains bismuth stannate photochemical catalyst in mortar.
The above-mentioned obtained bismuth stannate photochemical catalyst of preparation method irradiates 120 min by simulated light, to 10 mg/L's
The removal rate of Ciprofloxacin Hydrochloride waste water is 40.15%.
Embodiment 2
In the embodiment of the present invention 2, a kind of preparation method with visible light-responded bismuth stannate photochemical catalyst, including walk as follows
It is rapid: by 0.01mol SnCl4·5H2O is dissolved in 20 mL deionized waters, and is stirred to being completely dissolved, by 0.01mol Bi
(NO3)3·5H2O is dissolved in the dilute nitric acid solution of 30 mL, 2 M.Above two solution is mixed in whipping process, continues to stir
Mix 30 minutes, the backward mixed solution in the NaOH solution of 4 M is added dropwise dropwise, adjust pH to pH=9, continue under stiring anti-
Answer 60 min.Acquired solution is placed in 100 mL water heating kettles, 24 hours are reacted under the conditions of 180oC.It cools down, will sink at room temperature
Starch centrifugation, washing are placed in drying box and dry, and grinding obtains bismuth stannate photochemical catalyst in mortar.
The above-mentioned obtained bismuth stannate photochemical catalyst of preparation method irradiates 120 min by simulated light, to 10 mg/L's
The removal rate of Ciprofloxacin Hydrochloride waste water is 39.9%.
Embodiment 3
In the embodiment of the present invention 3, a kind of preparation method with visible light-responded bismuth stannate photochemical catalyst, including walk as follows
It is rapid: by 0.01mol SnCl4·5H2O is dissolved in 20 mL deionized waters, and is stirred to being completely dissolved, by 0.01mol Bi
(NO3)3·5H2O is dissolved in the dilute nitric acid solution of 30 mL, 2 M.Above two solution is mixed in whipping process, continues to stir
Mix 30 minutes, the backward mixed solution in the NaOH solution of 4 M is added dropwise dropwise, adjust pH to pH=11, continue under stiring anti-
Answer 60 min.Acquired solution is placed in 100 mL water heating kettles, 24 hours are reacted under the conditions of 180oC, cools down, will sink at room temperature
Starch centrifugation, washing are placed in drying box and dry, and grinding obtains bismuth stannate photochemical catalyst in mortar.
The above-mentioned obtained bismuth stannate photochemical catalyst of preparation method irradiates 120 min by simulated light, to 10 mg/L's
The removal rate of Ciprofloxacin Hydrochloride waste water is 68.5%.
Embodiment 4
In the embodiment of the present invention 4, a kind of preparation method with visible light-responded bismuth stannate photochemical catalyst, including walk as follows
It is rapid: by 0.01mol SnCl4·5H2O is dissolved in 20 mL deionized waters, and is stirred to being completely dissolved, by 0.01mol Bi
(NO3)3·5H2O is dissolved in the dilute nitric acid solution of 30 mL, 2 M.Above two solution is mixed in whipping process, continues to stir
It mixes 30 minutes.The backward mixed solution in the NaOH solution of 4 M is added dropwise dropwise, adjust pH to pH=13, continue under stiring anti-
60 min are answered, acquired solution is placed in 100 mL water heating kettles, 24 hours are reacted under the conditions of 180oC.It cools down, will sink at room temperature
Starch centrifugation, washing are placed in drying box and dry, and grinding obtains bismuth stannate photochemical catalyst in mortar.
The above-mentioned obtained bismuth stannate photochemical catalyst of preparation method irradiates 120 min by simulated light, to 10 mg/L's
The removal rate of Ciprofloxacin Hydrochloride waste water is 42.6%.
Refering to fig. 1 and Fig. 2, above embodiments are based on, the performance of the bismuth stannate photochemical catalyst prepared when choosing pH=11 compared with
Excellent, i.e. embodiment 3, by further characterizing research, the bismuth stannate photochemical catalyst prepared under this condition belongs to ball shaped nano piece,
Compared to traditional catalysis material, bismuth stannate photochemical catalyst produced by the present invention is able to respond simulated light, urges with visible light
Change activity, and preparation method is simple and quick, it is without secondary pollution.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (9)
1. a kind of preparation method with visible light-responded bismuth stannate photochemical catalyst, which comprises the steps of:
(1) by SnCl4·5H2O is dissolved in 20 mL deionized waters, and is stirred to being completely dissolved；
(2) by Bi (NO3)3·5H2O is dissolved in the dilute nitric acid solution of 30 mL, 2 M；
(3) above two solution is mixed in whipping process, continues stirring 30 minutes；
(4) pH of the mixed solution is adjusted with certain density NaOH solution, after being adjusted to appropriate pH, the reaction was continued under stiring
60 min；
(5) acquired solution is placed in 100 mL water heating kettles, 24 hours is reacted under the conditions of 180oC, cools down, will precipitate at room temperature
Object centrifugation, washing are placed in drying box and dry；
(6) grinding obtains bismuth stannate photochemical catalyst in mortar.
2. the preparation method according to claim 1 with visible light-responded bismuth stannate photochemical catalyst, which is characterized in that
In step (1), SnCl4·5H2The molal weight of O is 0.01mol.
3. the preparation method according to claim 1 with visible light-responded bismuth stannate photochemical catalyst, which is characterized in that
In step (2), Bi (NO3)3·5H2The molal weight of O is 0.01mol.
4. the preparation method according to claim 1 with visible light-responded bismuth stannate photochemical catalyst, which is characterized in that
In step (3), the concentration of NaOH solution is 4 M.
5. the preparation method according to claim 1 with visible light-responded bismuth stannate photochemical catalyst, which is characterized in that
In step (3), pH is adjusted to pH=7.
6. the preparation method according to claim 1 with visible light-responded bismuth stannate photochemical catalyst, which is characterized in that
In step (3), pH is adjusted to pH=9.
7. the preparation method according to claim 1 with visible light-responded bismuth stannate photochemical catalyst, which is characterized in that
In step (3), pH is adjusted to pH=11.
8. the preparation method according to claim 1 with visible light-responded bismuth stannate photochemical catalyst, which is characterized in that
In step (3), pH is adjusted to pH=13.
9. a kind of with visible light-responded bismuth stannate photochemical catalyst, which is characterized in that by any one of claim 1-8 institute
The preparation method with visible light-responded bismuth stannate photochemical catalyst stated is prepared.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111146407A (en) * | 2020-02-11 | 2020-05-12 | 河南创力新能源科技股份有限公司 | Preparation method of iron-nickel battery cathode additive |
| CN112293435A (en) * | 2020-11-02 | 2021-02-02 | 成都子之源绿能科技有限公司 | Spray and preparation method and application thereof |
| CN112340775A (en) * | 2020-10-26 | 2021-02-09 | 浙江工业大学 | Preparation method of flower cluster-shaped bismuth stannate nano powder |
| CN114515590A (en) * | 2022-03-11 | 2022-05-20 | 西安建筑科技大学 | Heterogeneous photocatalytic material and preparation and application thereof |
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| CN103332739A (en) * | 2013-07-03 | 2013-10-02 | 南京理工大学 | Bi2Sn2O7 composite oxide with unique morphology and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111146407A (en) * | 2020-02-11 | 2020-05-12 | 河南创力新能源科技股份有限公司 | Preparation method of iron-nickel battery cathode additive |
| CN111146407B (en) * | 2020-02-11 | 2022-11-29 | 河南创力新能源科技股份有限公司 | Preparation method of iron-nickel battery cathode additive |
| CN112340775A (en) * | 2020-10-26 | 2021-02-09 | 浙江工业大学 | Preparation method of flower cluster-shaped bismuth stannate nano powder |
| CN112340775B (en) * | 2020-10-26 | 2022-05-03 | 浙江工业大学 | Preparation method of flower cluster-shaped bismuth stannate nano powder |
| CN112293435A (en) * | 2020-11-02 | 2021-02-02 | 成都子之源绿能科技有限公司 | Spray and preparation method and application thereof |
| CN114515590A (en) * | 2022-03-11 | 2022-05-20 | 西安建筑科技大学 | Heterogeneous photocatalytic material and preparation and application thereof |
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