CN106865594A - A kind of preparation method and applications of water phase fluorination cerium particulate - Google Patents
A kind of preparation method and applications of water phase fluorination cerium particulate Download PDFInfo
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- CN106865594A CN106865594A CN201710093784.0A CN201710093784A CN106865594A CN 106865594 A CN106865594 A CN 106865594A CN 201710093784 A CN201710093784 A CN 201710093784A CN 106865594 A CN106865594 A CN 106865594A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/253—Halides
- C01F17/265—Fluorides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The present invention relates to a kind of preparation method and applications of water phase fluorination cerium particulate, belong to photocatalysis technology field, it is cerium source to use ammonium ceric nitrate or cerous nitrate, with ammonium hexa-fluorotitanate or ammonium fluoride as Fluorine source, the water phase fluorination cerium particulate of favorable dispersibility has been prepared with the preparation technology of relatively simple, mild condition, it has good photocatalysis performance under visible light conditions, has widened the application field of cerium fluoride.
Description
Technical field
The invention belongs to photocatalysis technology field, and in particular to a kind of preparation method of water phase fluorination cerium particulate and its should
With.
Background technology
Rare earth semiconductor material has chemism higher, chemical stability and heat endurance, in visible/ultraviolet
Degradable organic pollutant aspect is of great interest.Some rare earth compounds containing Ce elements, particularly cerium oxide,
Visible light catalytic field gets most of the attention.The compound containing cerium mischmetal reported out at present is with CeO2And the composite wood it based on
Expect to be a main class, its photocatalytic pollutant degradation efficiency is better than business oxide/titanium dioxide（P25）.Cerium fluoride（CeF3）As another
One class cerium-containing compound, it is at present to be applied to high-abrasive material, sensor, optical thin film, up-conversion luminescent material etc. more, in photocatalysis
The application in field slightly has report.
Jun Wana et al. are successfully prepared CeF using microwave-hydrothermal method3/TiO2Nanometer sheet tunic, due to CeF3Have
Upconversion mechanism, the nanometer sheet tunic both can have photocatalytic activity in ultraviolet light wave band, also have in visible light wave range same
Deng photocatalytic activity, and show excellent photocatalytic degradation methylene blue performance [Jun Wana, Lin Suna, Novel UV-
vis-driven photocatalysts of CeF3/TiO2 nano-sheet film with upconversion
properties for enhanced photocatalytic activity[J].Materials Letters,2016,
169:189~192]。
G-F Huang team uses cryogenic fluid combustion method, and by adjusting ammonium fluoride, the mol ratio of cerium chloride can obtain
Pure CeF3Nano particle, and its and Ce2O3Or Ce2O3The mixture of formation.The CeF of synthesis3Show excellent photocatalytic activity
With the good stability of the lower degradation of methylene blue of ultraviolet irradiation.By Density function theory, CeF3Unique electronics knot
Structure is that it has the major reason of good photocatalytic activity, can be as a kind of potential photochemical catalyst [Hui Miao, Gui-
Fang Huang,A novel photocatalyst CeF3:Facile fabrication and photocatalytic
performance[J],RSC Advances,2015,5(115):95171~95177]。
G-F Huang team uses Hydrothermal Synthesiss route with ethanol/water binary system as solvent again, is prepared for a kind of new
Photochemical catalyst.CeO2/CeF3Hexahedron structure there is outstanding photocatalysis effect, be mainly due to have in the structure high anti-
Should activity face can be more exposure, while heterojunction boundary produce photo-generate electron-hole to that can efficiently separate.
12min is irradiated under ultraviolet light, the degradation rate of methylene blue up to 87%, better than business P25 [Yao Xiang, Bai-Ran
Cheng,Facile one-step in-situ synthesis of type-II CeO2/CeF3 composite with
tunable morphology and photocatalytic activity[J].Ceramics International,
2016,42(14):16374~16381]。
Existing fluorination cerium material is still mainly used as anti-wear additive and semi-conducting material, and preparation method is complicated, part material
Expect that itself hydrophily is poor, generally require to carry out surface when being used in water phase to be modified to strengthen its dispersiveness in aqueous.
In current document report, cerium fluoride as a kind of new catalyst often and CeO2、TiO2It is compound, form CeF3/CeO2、CeF3/
TiO2Composite, can effectively improve the photocatalysis degradation organic contaminant efficiency under ultraviolet light, and pure cerium fluoride is visible
The application of photocatalysis field degradable organic pollutant is rarely reported.Therefore, develop a kind of process is simple, good hydrophilic property, efficiently
Visible light catalytic be fluorinated cerium material in terms of degradable organic pollutant have important application value.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of water phase fluorination cerium particulate, it is cerium to use ammonium ceric nitrate or cerous nitrate
Source, with ammonium hexa-fluorotitanate or ammonium fluoride as Fluorine source, favorable dispersibility has been prepared with the preparation technology of relatively simple, mild condition
Water phase fluorination cerium particulate, it has good photocatalysis performance under visible light, has widened the application field of cerium fluoride.
To achieve the above object, the present invention provides following technical scheme：
A kind of preparation method of water phase fluorination cerium particulate, comprises the following steps：
Step one：It is 1 according to mol ratio by cerium salt and fluorine-containing ammonium salt：（5~10）Ratio be dissolved in 50ml distilled water, room temperature is stirred
10 ~ 20min is mixed, transparent mixed solution is obtained；
Step 2：Under stirring condition, to it is slow in the transparent mixed solution of step one, be added dropwise over alkaline solution, it is white to being formed
Color colloidal sol stops being added dropwise；
Step 3：The leucosol of step 2 is transferred in hydrothermal reaction kettle, after 160 DEG C of reaction 300min, normal temperature is cooled to,
Centrifugation obtains micro- pink precipitate；
Step 4：By micro- pink precipitate distilled water, the absolute ethanol washing of step 3, drying to obtain fluorine under the conditions of 60 DEG C
Change cerium particulate；
Step 5：Cerium fluoride particulate obtained in step 4 is dispersed in water, that is, obtains water phase fluorination cerium particulate.
Further, the cerium salt is ammonium ceric nitrate, and the fluorine-containing ammonium salt is the one kind in ammonium hexa-fluorotitanate or ammonium fluoride.
Further, the cerium salt is cerous nitrate, and the fluorine-containing ammonium salt is ammonium hexa-fluorotitanate.
Further, the alkaline solution is the one kind in ammonium chloride solution or ammoniacal liquor.
Further, the concentration of the alkaline solution is 0.1mol/L.
Degraded under visible light conditions present invention also offers the water phase fluorination cerium particulate prepared using above-mentioned preparation method
The application of organic pollution.
Compared to existing technology, the beneficial effects of the present invention are：
1. 6 NO in ammonium ceric nitrate3 -Ion and Ce4+Coordination, 6 F in ammonium hexa-fluorotitanate-Ion and Ti4+Coordination, is respectively formed six
Angle double cone structure, the hexagonal crystallographic texture to cerium fluoride is similar.The reactive material selected in preparation method of the present invention be cerium salt and
Fluorine-containing ammonium salt, and define that the space structure of one of them, for double hexagonal pyramid structure, is so conducive in temperature in preparation method
Promote the growth quickly generated with crystal of cerium fluoride nucleus with the conditions of, the complete of crystal structure is then promoted by hydro-thermal reaction
Kind, by the generation of homogeneous co-precipitation process and hydro-thermal method control lattice defect, crystal growth is incomplete in coprecipitation reaction in addition
More lattice defects be result in as avtive spot, be conducive to cerium fluoride photochemical catalyst and substrate molecule electron transmission, improved
The light-catalyzed reaction activity of cerium fluoride；
2. the cerium salt and fluorine-containing ammonium salt that the present invention is used mix at room temperature, mild condition, overall preparation process is simple, it is easy to grasp
Make, it is easy to which technique is amplified, and have studied the application of cerium fluoride degradable organic pollutant under visible light conditions, widened cerium fluoride
Application field；
3. when the cerium fluoride particulate that prepared by the present invention is dissolved in water, it is not necessary to which adding surfactant carries out surface modification, in water
Favorable dispersibility, it is stable in properties when making it as catalysis material degradable organic pollutant.
Brief description of the drawings
Fig. 1 is the XRD spectrum of cerium fluoride particulate prepared by the present invention.
Fig. 2 is dispersiveness contrast of the cerium fluoride particulate of present invention preparation in water, paraffin oil, dichloromethane and acetone
Figure.
Fig. 3 is the blue standard working curve of the methylene of the embodiment of the present invention 7.
Fig. 4 be the methylene of the embodiment of the present invention 7 orchid under visible light conditions from degradation efficiency curve.
Fig. 5 is that P25 degrades the degradation efficiency curve of methylene blue under visible light conditions in the embodiment of the present invention 7.
Fig. 6 is the degradation efficiency curve of cerium fluoride particulate degradation of methylene blue under visible light conditions prepared by the present invention.
Specific embodiment
Make further statement to the present invention with reference to specific embodiment, but be not the limit to the scope of the present invention
Fixed, involved process in embodiment is unless otherwise instructed then conventional method or step, and medicine and reagent used is except special
Illustrate outer, be commercially available.
Room temperature in the present invention is 20 ~ 25 DEG C, and unless otherwise instructed, agents useful for same can be purchased from market in following examples
, wherein the molecular formula of ammonium ceric nitrate is Ce (NH4)2(NO3)6, the molecular formula of ammonium hexa-fluorotitanate is（NH4）2TiF6, cerous nitrate
Molecular formula is Ce (NO3)3·6H2O, the molecular formula of ammonium fluoride is NH4F。
In chemical field, water mutually refers generally to the phase of water or material composition compatible with water；Organic phase then refer generally to
The phase of the immiscible organic matter composition of water, such as chloroform, acetone etc..
Embodiment 1
Mol ratio according to cerium salt and fluorine-containing ammonium salt is 1：10, take 0.27g ammonium ceric nitrates, 1.0g ammonium hexa-fluorotitanates and be dissolved in 50mL steamings
Distilled water, stirs 10 ~ 20min at room temperature, obtains the clear solution containing cerium ion, fluorine ion；Stir and it is slow, dropwise to transparent
The ammonium chloride solution of 0.1moL/L is added in solution, stops being added dropwise to leucosol is formed；Take above-mentioned 30mL leucosols transfer
Into 50mL hydrothermal reaction kettles, 160 DEG C of reaction 300min are cooled to normal temperature, and centrifugation obtains micro- pink precipitate；With distilled water,
The above-mentioned micro- pink precipitate of absolute ethanol washing, 60 DEG C of dryings can obtain cerium fluoride particulate samples；By cerium fluoride obtained above
Particulate is dispersed in water, that is, obtain water phase fluorination cerium particulate.
As shown in figure 1, cerium fluoride particulate samples manufactured in the present embodiment are through XRD diffracting spectrums, 2 θ are located in figure
24.525°、25.021°、27.956°、44.112°、45.291°、51.091°、52.980°、56.954°、57.875°、
65.000 °, 68.924 °, 69.883 °, 71.293 °, 75.375 ° of diffraction maximum be attributed to CeF respectively3, with standard spectrum picture library
JCPDS 72-1436 are consistent, it was demonstrated that the sample is CeF3。
Embodiment 2
Mol ratio according to cerium salt and fluorine-containing ammonium salt is 1：5, take 0.27g ammonium ceric nitrates, 0.5g ammonium hexa-fluorotitanates and be dissolved in 50mL steamings
Distilled water, stirs 10 ~ 20min at room temperature, obtains the clear solution containing cerium ion, fluorine ion；Stir and it is slow, dropwise to transparent
The ammoniacal liquor of 0.1moL/L is added in solution, stops being added dropwise to leucosol is formed；Take above-mentioned 30mL leucosols and be transferred to 50mL
In hydrothermal reaction kettle, 160 DEG C of reaction 300min are cooled to normal temperature, and centrifugation obtains micro- pink precipitate；With distilled water, anhydrous second
Alcohol washs above-mentioned micro- pink precipitate, and 60 DEG C of dryings can obtain cerium fluoride particulate samples；By cerium fluoride particulate obtained above point
It is dispersed in water, that is, obtains water phase fluorination cerium particulate.
Cerium fluoride particulate samples manufactured in the present embodiment prove CeF through XRD diffracting spectrums3。
Embodiment 3
Mol ratio according to cerium salt and fluorine-containing ammonium salt is 1：7, take 0.43g cerous nitrates, 1.39g ammonium hexa-fluorotitanates and be dissolved in 50mL distillations
Water, stirs 10 ~ 20min at room temperature, obtains the clear solution containing cerium ion, fluorine ion；Stir and it is slow, dropwise to transparent molten
The ammonium chloride solution of 0.1moL/L is added in liquid, stops being added dropwise to leucosol is formed；Above-mentioned 30mL leucosols are taken to be transferred to
In 50mL hydrothermal reaction kettles, 160 DEG C of reaction 300min are cooled to normal temperature, and centrifugation obtains micro- pink precipitate；With distilled water, nothing
Water-ethanol washs above-mentioned micro- pink precipitate, and 60 DEG C of dryings can obtain cerium fluoride particulate samples；Cerium fluoride obtained above is micro-
Grain is dispersed in water, that is, obtain water phase fluorination cerium particulate.
Cerium fluoride particulate samples manufactured in the present embodiment prove CeF through XRD diffracting spectrums3。
Embodiment 4
Mol ratio according to cerium salt and fluorine-containing ammonium salt is 1：8, take 0.27g ammonium ceric nitrates, 0.146g ammonium fluorides and be dissolved in 50mL distillations
Water, stirs 10 ~ 20min at room temperature, obtains the clear solution containing cerium ion, fluorine ion；Stir and it is slow, dropwise to transparent molten
The ammonium chloride solution of 0.1moL/L is added in liquid, stops being added dropwise to leucosol is formed；Above-mentioned 30mL leucosols are taken to be transferred to
In 50mL hydrothermal reaction kettles, 160 DEG C of reaction 300min are cooled to normal temperature, and centrifugation obtains micro- pink precipitate；With distilled water, nothing
Water-ethanol washs above-mentioned micro- pink precipitate, and 60 DEG C of dryings can obtain cerium fluoride particulate samples；Cerium fluoride obtained above is micro-
Grain is dispersed in water, that is, obtain water phase fluorination cerium particulate.
Cerium fluoride particulate samples manufactured in the present embodiment prove CeF through XRD diffracting spectrums3。
Embodiment 5
Mol ratio according to cerium salt and fluorine-containing ammonium salt is 1：9, take 0.27g ammonium ceric nitrates, 0.164g ammonium fluorides and be dissolved in 50mL distillations
Water, stirs 10 ~ 20min at room temperature, obtains the clear solution containing cerium ion, fluorine ion；Stir and it is slow, dropwise to transparent molten
The ammonia spirit of 0.1moL/L is added in liquid, stops being added dropwise to leucosol is formed；Above-mentioned 30mL leucosols are taken to be transferred to
In 50mL hydrothermal reaction kettles, 160 DEG C of reaction 300min are cooled to normal temperature, and centrifugation obtains micro- pink precipitate；With distilled water, nothing
Water-ethanol washs above-mentioned micro- pink precipitate, and 60 DEG C of dryings can obtain cerium fluoride particulate samples；Cerium fluoride obtained above is micro-
Grain is dispersed in water, that is, obtain water phase fluorination cerium particulate.
Cerium fluoride particulate samples manufactured in the present embodiment prove CeF through XRD diffracting spectrums3。
Embodiment 6
As shown in Fig. 2 obtained cerium fluoride particulate samples 10mg is dissolved in water, atoleine, dichloromethane and third in Example 1
In ketone, the AR that the atoleine, dichloromethane and acetone are bought for market.
Show that dispersion stabilization sequence of the cerium fluoride particulate in above-mentioned four kinds of solvents is in Fig. 2：Water ＞ liquid stones
Wax ＞ dichloromethane ＞ acetone, cerium fluoride particulate can be uniformly dispersed in water and atoleine and stability is preferable, can keep 72h
More than；And cerium fluoride particulate is deposited in bottom substantially after standing three minutes in dichloromethane and acetone, it is seen that its stably dispersing
Property is poor, while also indicate that cerium fluoride microparticle surfaces group polarity is larger, the favorable dispersibility in the larger solvent of polarity.
Embodiment 7
The standard working curve of methylene blue as shown in Figure 3, shows with the increase of methylene blue solution concentration, extinction in figure
Degree is linearly increased, and linearly dependent coefficient is 0.9963.
In order to investigate the visible light catalytic performance of cerium fluoride, first the degraded energy certainly to methylene blue in itself under visible light
Power is tested, as shown in Figure 4.The degradation rate of methylene blue only reaches 0.09 after reacting 3h in Fig. 4, shows methylene blue can
See under light that there is excellent stability, it is not easy to from degraded.
Titanium dioxide has been widely used as a kind of catalysis material, but the light source master that its photocatalysis is utilized
If ultraviolet light, in order to investigate its utilization to visible ray, with iodine-tungsten lamp as light source, filtered off with optical filter ultraviolet under 420nm
Light, tests its photocatalysis, as shown in Figure 5.The degradation rate of methylene blue is 16% after illumination 3h in Fig. 5, far smaller than
Catalytic degradation efficiency under ultraviolet source.
Obtained cerium fluoride particulate 10mg in Example 1, is dispersed in the 50ml methylene blue solutions that concentration is 20mg/L
In, favorable dispersibility of the cerium fluoride particulate in methylene blue solution.Using 50w iodine-tungsten lamps, apart from liquid level 20cm, use
420nm optical filter filtering ultraviolet light, it is seen that after light irradiation 3h, its disposal efficiency can reach 97%, and solution colour is by blueness
It is changed into light red, methylene blue solution basically reaches degraded completely, as shown in fig. 6, showing that the cerium fluoride that the present invention is prepared is micro-
Grain has good photocatalysis performance under visible light illumination, can be used for the organic pollutions such as degradation of methylene blue.
Contrasted from Fig. 5 and Fig. 6, under visible light illumination, the cerium fluoride particle phase that the present invention is prepared is than business P25
For, with good photocatalysis performance.In the practical application of photocatalysis degradation organic contaminant, if prepared by the present invention
Cerium fluoride particulate and business P25 are combined, then organic pollution can be degraded under visible ray and ultraviolet light, degradation rate
Also can greatly promote, application prospect is good.
The embodiment of the above, simply presently preferred embodiments of the present invention, is only used to explain the present invention, not limits
The scope of the present invention processed, to those of ordinary skill in the art, certainly can be according to skill disclosed in this specification
Art content, other implementation methods are made by way of replacing or changing easily, therefore all in principle of the invention and technique bar
Changes and improvements that part is done etc., all should be included in scope of the present invention patent.
Claims (6)
1. a kind of preparation method of water phase fluorination cerium particulate, it is characterised in that comprise the following steps：
Step one：It is 1 according to mol ratio by cerium salt and fluorine-containing ammonium salt：（5~10）Ratio be dissolved in 50ml distilled water, room temperature is stirred
10 ~ 20min is mixed, transparent mixed solution is obtained；
Step 2：Under stirring condition, to it is slow in the transparent mixed solution of step one, be added dropwise over alkaline solution, it is white to being formed
Color colloidal sol stops being added dropwise；
Step 3：The leucosol of step 2 is transferred in hydrothermal reaction kettle, after 160 DEG C of reaction 300min, normal temperature is cooled to,
Centrifugation obtains micro- pink precipitate；
Step 4：By micro- pink precipitate distilled water, the absolute ethanol washing of step 3, drying to obtain fluorine under the conditions of 60 DEG C
Change cerium particulate；
Step 5：Cerium fluoride particulate obtained in step 4 is dispersed in water, that is, obtains water phase fluorination cerium particulate.
2. the preparation method of a kind of water phase fluorination cerium particulate according to claim 1, it is characterised in that the cerium salt is nitre
Sour cerium ammonium, the fluorine-containing ammonium salt is the one kind in ammonium hexa-fluorotitanate or ammonium fluoride.
3. the preparation method of a kind of water phase fluorination cerium particulate according to claim 1, it is characterised in that the cerium salt is nitre
Sour cerium, the fluorine-containing ammonium salt is ammonium hexa-fluorotitanate.
4. a kind of preparation method of water phase fluorination cerium particulate according to claim 1, it is characterised in that the alkaline solution
It is the one kind in ammonium chloride solution or ammoniacal liquor.
5. a kind of preparation method of water phase fluorination cerium particulate according to claim 1, it is characterised in that the alkaline solution
Concentration be 0.1mol/L.
6. the water phase fluorination cerium particulate that prepared by the preparation method as described in any one of claim 1 ~ 5 is degraded under visible light conditions
The application of organic pollution.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479859A (en) * | 2018-04-17 | 2018-09-04 | 常州大学 | Composite photocatalyst material and the preparation method and application thereof is converted on praseodymium doped cerium fluoride/attapulgite |
| CN108543540A (en) * | 2018-04-17 | 2018-09-18 | 常州大学 | Conversion composite photocatalyst material and the preparation method and application thereof on a kind of cerium fluoride/attapulgite |
| CN113413907A (en) * | 2021-07-19 | 2021-09-21 | 浙江省科创新材料研究院 | Compound near-infrared photocatalyst and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177568A (en) * | 1997-09-18 | 1998-04-01 | 吉林大学 | Water-heating preparation method for fluoride and composite fluoride material under mild condition |
| CN102284292A (en) * | 2010-06-18 | 2011-12-21 | 上海牛翼新能源科技有限公司 | Ceria load-type high-efficient cold catalyst for purifying formaldehyde in air |
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2017
- 2017-02-21 CN CN201710093784.0A patent/CN106865594A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1177568A (en) * | 1997-09-18 | 1998-04-01 | 吉林大学 | Water-heating preparation method for fluoride and composite fluoride material under mild condition |
| CN102284292A (en) * | 2010-06-18 | 2011-12-21 | 上海牛翼新能源科技有限公司 | Ceria load-type high-efficient cold catalyst for purifying formaldehyde in air |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108479859A (en) * | 2018-04-17 | 2018-09-04 | 常州大学 | Composite photocatalyst material and the preparation method and application thereof is converted on praseodymium doped cerium fluoride/attapulgite |
| CN108543540A (en) * | 2018-04-17 | 2018-09-18 | 常州大学 | Conversion composite photocatalyst material and the preparation method and application thereof on a kind of cerium fluoride/attapulgite |
| CN108543540B (en) * | 2018-04-17 | 2020-02-14 | 常州大学 | Cerium fluoride/attapulgite up-conversion composite photocatalytic material and preparation method and application thereof |
| CN113413907A (en) * | 2021-07-19 | 2021-09-21 | 浙江省科创新材料研究院 | Compound near-infrared photocatalyst and preparation method and application thereof |
| CN113413907B (en) * | 2021-07-19 | 2022-05-03 | 浙江省科创新材料研究院 | Compound near-infrared photocatalyst and preparation method and application thereof |
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