CN104689818A - ZnO/Ag@AgInO2 heterogeneous Z type photocatalytic material and preparation method thereof - Google Patents
ZnO/Ag@AgInO2 heterogeneous Z type photocatalytic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a ZnO/Ag@AgInO2 heterogeneous Z type photocatalytic material and a preparation method of the ZnO/Ag@AgInO2 heterogeneous Z type photocatalytic material. The method comprises the following steps: (1) preparing NaInO2 by an In-containing compound and a Na-containing compound through a solid phase sintering method; (2) preparing Ag@AgInO2 by taking the NaInO2 as a precursor with AgNO3 and KNO3 through an ion exchange method; and (3) preparing the ZnO/Ag@AgInO2 heterogeneous Z type photocatalytic material by Zn(NO3)2.6H2O and the Ag@AgInO2 through an impregnation method. The obtained photocatalytic material is used for carrying out surface modification and modification for a novel photocatalyst Ag@AgInO2 with a plasma effect through a transition metal oxide ZnO additive, so that the photocatalytic activity of the novel photocatalyst Ag@AgInO2 is improved, and the photoinduced stability of the novel photocatalyst Ag@AgInO2 is improved.
Description
Technical field
The present invention relates to a kind of ZnO/Ag@AgInO
2heterogeneous Z-type catalysis material and preparation method thereof, belongs to the preparations and applicatio field of inorganic functional material.
Background technology
Current, in order to improve photocatalytic water efficiency, various countries researcher have extensively studied the reaction principle of the photochemical catalyzing of the semi-conducting material possessing different level structure, and the wave-length coverage of response incident light is extended by methods such as noble metal loading, transition cations doping, dye sensitization, composite semiconductors, the compound of retardance Pair production improves the utilization rate to sunlight.
CN103480372A discloses a kind of AgAlO
2/ TiO
2the preparation method of catalysis material.It first adopts sol-gel process to prepare TiO
2, recycling sol-gel process prepares NaAlO
2, finally utilize ion-exchange to prepare AgAlO
2/ TiO
2heterogeneous catalysis material, this material is by p-type semiconductor AgAlO
2with n-type semiconductor TiO
2form p-n heterojunction structure catalysis material, improve photocatalytic activity to a certain extent, but in use find that its photoinduction stability needs to improve further.
Nature Z-type photosynthesis, be namely coupled by the level structure of two kinds of different photocatalytic semiconductor materials, the generation of the compound that retardance light induced electron one hole is right and back reaction, improves the utilization ratio to sunlight.The electron transfer process of Z-type catalysis material completes under two photosystems (PS I and PS II) series connection coordinates, and electron mediator, according to the arrangement of oxidation-reduction potential height, makes electron transport chain be " Z " font, so gain the name.
Summary of the invention
In order to improve the degradation property of catalysis material further, the invention provides a kind of preparation method based on the photosynthetic novel photocatalysis material of natural Z-type, gained catalysis material has the right yield of higher photo-generate electron-hole and quantum yield, shows better visible light catalysis activity and photoinduction stability.
To achieve these goals, the technical solution used in the present invention is as follows.
A kind of ZnO/Ag@AgInO
2the preparation method of heterogeneous Z-type catalysis material, comprises the steps:
1) NaInO is prepared containing In compound with containing Na compound by solid sintering technology
2;
2) with NaInO
2for presoma, with AgNO
3, KNO
3ag@AgInO is prepared by ion-exchange
2;
3) Zn (NO
3)
26H
2o and Ag@AgInO
2by infusion process making ZnO/Ag@AgInO
2heterogeneous Z-type catalysis material.
The present invention is in conjunction with solid sintering technology, ion-exchange and infusion process making ZnO/Ag@AgInO
2heterogeneous catalysis material, not only can widen the spectral response range of catalysis material, form the raising of multistep classification extinction system to the absorption of sunshine and conversion ratio, and the charge balance of light-catalyzed reaction system is realized by the band structure coupling of conduction band and valence band, improve the yield that photo-generate electron-hole is right, suppress the compound again of electron-hole pair, improve quantum yield, thus show better visible light catalysis activity and photoinduction stability; Adopt solid sintering technology to prepare presoma NaInO simultaneously
2, be more conducive to the suitability for industrialized production of material.
In the present invention, step 1) in, described is 1:(1 ~ 4 containing In compound and the mol ratio containing Na compound), preferred 1:2.
In the present invention, step 1) in, the described In compound that contains is selected from indium sesquioxide (In
2o
3), indium nitrate (In (NO
3)
3nH
2o), inidum chloride (InCl
3nH
2o) one or more in;
In the present invention, step 1) in, the described Na compound that contains is selected from sodium carbonate (Na
2cO
3), sodium acetate (CH
3cOONanH
2o), sodium peroxide (Na
2o
2) in one or more.
In the present invention, step 1) in, described solid sintering technology process conditions are: calcining heat is 700 ~ 900 DEG C, and temperature-time is 2 ~ 5h.
As the preferred embodiment of the present invention, step 1) described solid sintering technology prepares NaInO
2concrete steps are: will be 1:(1 ~ 4 according to mol ratio containing In compound with containing Na compound) ratio mix after, grinding, by mixture in 700 ~ 900 DEG C of calcining 2 ~ 5h, is cooled to room temperature, obtains NaInO
2.
In the present invention, step 2) in, described NaInO
2with AgNO
3, KNO
3mol ratio is 1:(1 ~ 5): (1 ~ 4), preferred 1:1.5:1.5.
In the present invention, step 2) in, described ion-exchange process condition is: prior to 200 ~ 280 DEG C of roasting 3 ~ 15h, then is warming up to 350 ~ 650 DEG C of insulation 2 ~ 5h.Preferably 250 DEG C of roasting 9 ~ 11h, then be warming up to 450 DEG C of insulation 2 ~ 5h.
As the preferred embodiment of the present invention, described ion-exchange prepares Ag@AgInO
2concrete steps are: by NaInO
2with AgNO
3, KNO
3be 1:(1 ~ 5 according to mol ratio): the ratio mixing of (1 ~ 4), after grinding, roasting 3 ~ 15h under 200 ~ 280 DEG C of temperature conditions, then be increased to 350 ~ 650 DEG C of insulation 2 ~ 5h, washing, centrifugation, dries, obtains Ag@AgInO
2.
In the present invention, step 3) in, described Ag@AgInO
2with Zn (NO
3)
26H
2the mass ratio of O is 1:0.01 ~ 1; Preferred 1:0.05 ~ 0.45.
As the preferred embodiment for the present invention, described infusion process making ZnO/Ag@AgInO
2concrete steps are: first by Zn (NO
3)
26H
2o dissolves, then adds Ag@AgInO
2, under 60 ~ 70 DEG C of water bath condition, be stirred to moisture and evaporate completely, in 300 ~ 600 DEG C of calcining 2 ~ 5h, be cooled to room temperature, obtain ZnO/Ag@AgInO
2heterogeneous Z-type catalysis material.
The ZnO/Ag@AgInO that the present invention also provides said method to prepare
2heterogeneous Z-type catalysis material, wherein, described Ag@AgInO
2be 1:(0.01 ~ 0.2 with the mass ratio of ZnO).
Compared with prior art, technical scheme of the present invention has following technique effect:
The present invention is in conjunction with solid sintering technology, ion-exchange and infusion process making ZnO/Ag@AgInO
2heterogeneous catalysis material, by ZnO and Ag@AgInO
2build Z-type catalysis material, not only can widen the spectral response range of catalysis material, form the raising of multistep classification extinction system to the absorption of sunshine and conversion ratio, and ZnO and Ag AgInO
2bi-material is coupled by the band structure of conduction band and valence band, the charge balance of light-catalyzed reaction system can be realized, while improving the right yield of its photo-generate electron-hole, again the compound of effective suppression electron-hole pair, improve its quantum yield, not only show better visible light catalysis activity, and effectively improve the photoinduction stability of material.Preparation method of the present invention is unique, has reaction condition gentleness, easily operates, be convenient to the features such as industrialization production, and prepared product photocatalysis performance is excellent.
Accompanying drawing explanation
Fig. 1 is ZnO/Ag@AgInO prepared by embodiment of the present invention 1-5
2heterogeneous Z-type catalysis material and two kinds of monomer ZnO and Ag@AgInO
2xRD figure.
Fig. 2 is 10wt%ZnO/Ag@AgInO prepared by the embodiment of the present invention 3
2the SEM figure of heterogeneous Z-type catalysis material.
Fig. 3 is AgAlO prepared by embodiment of the present invention 1-5
2/ TiO
2heterogeneous catalysis material and monomer A g@AgInO
2the photocatalysis performance figure of degradation of methylene blue solution.
Detailed description of the invention
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1 5%ZnO/Ag@AgInO
2heterogeneous catalysis material
(1) solid sintering technology prepares presoma NaInO
2
Respectively with In
2o
3and Na
2cO
3for containing In and containing Na compound, according to In
2o
3and Na
2cO
3mol ratio is, after the ratio of 1:1.5 mixes, in agate mortar, grind 10min, is transferred to by mixture in corundum crucible, and 850 DEG C of calcining 3h, are cooled to room temperature, obtain presoma NaInO
2;
(2) ion-exchange prepares Ag@AgInO
2
Presoma NaInO prepared by solid sintering technology
2powder, with AgNO
3, KNO
3according to ratio mixed grinding 5min in agate mortar that mol ratio is 1:1.5:1.5, mixture after grinding is transferred in corundum crucible, under 250 DEG C of temperature conditions, roasting 10h carries out ion-exchange reactions, again sintering temperature is increased to respectively 450 DEG C of insulation 3h, products obtained therefrom washs 2 times through deionized water, centrifugation, is placed in 80 DEG C, baking oven and dries 4h, obtain Ag@AgInO
2;
(3) infusion process making ZnO/Ag@AgInO
2
Take the Zn (NO of 0.193g
3)
26H
2o puts into crucible, adds 4ml distilled water and dissolves.Again by Ag/AgInO prepared by 1.0g ion-exchange
2join in above-mentioned solution, crucible is placed in the water-bath of 65 DEG C, be constantly stirred to moisture with glass bar and evaporate completely.Then biased sample is put into Muffle furnace, calcine 4h under 400 DEG C of temperature conditions, be cooled to room temperature, obtain 5wt%ZnO/Ag@AgInO
2heterogeneous Z-type catalysis material.
Embodiment 2 7wt%ZnO/Ag@AgInO
2heterogeneous catalysis material
(1) solid sintering technology prepares presoma NaInO
2
Respectively with indium nitrate and sodium acetate for containing In with containing Na compound, according to In
2o
3and Na
2cO
3mol ratio is, after the ratio of 1:2 mixes, in agate mortar, grind 10min, is transferred to by mixture in corundum crucible, and 800 DEG C of calcining 4h, are cooled to room temperature, obtain presoma NaInO
2;
(2) ion-exchange prepares Ag@AgInO
2
Presoma NaInO prepared by solid sintering technology
2powder, with AgNO
3, KNO
3according to ratio mixed grinding 5min in agate mortar that mol ratio is 1:2:1.05, mixture after grinding is transferred in corundum crucible, under 260 DEG C of temperature conditions, roasting 10h carries out ion-exchange reactions, again sintering temperature is increased to respectively 400 DEG C of insulation 3h, products obtained therefrom washs 2 times through deionized water, centrifugation, is placed in 80 DEG C, baking oven and dries 4h, obtain Ag@AgInO
2;
(3) infusion process making ZnO/Ag@AgInO
2
Take the Zn (NO of 0.276g
3)
26H
2o puts into crucible, adds 5ml distilled water and dissolves.The Ag@AgInO again prepared by 1.0g ion-exchange
2join in above-mentioned solution, crucible is placed in the water-bath of 65 DEG C, be constantly stirred to moisture with glass bar and evaporate completely.Then biased sample is put into Muffle furnace, calcine 4h under 450 DEG C of temperature conditions, be cooled to room temperature, obtain 7wt%ZnO/Ag@AgInO
2heterogeneous Z-type catalysis material.
Embodiment 3 10%ZnO/Ag@AgInO
2heterogeneous catalysis material
(1) solid sintering technology prepares presoma NaInO
2
Respectively with In
2o
3and Na
2cO
3for containing In and containing Na compound, according to In
2o
3and Na
2cO
3mol ratio is, after the ratio of 1:2 mixes, in agate mortar, grind 10min, is transferred to by mixture in corundum crucible, and 850 DEG C of calcining 3h, are cooled to room temperature, obtain presoma NaInO
2;
(2) ion-exchange prepares Ag@AgInO
2
Presoma NaInO prepared by solid sintering technology
2powder, with AgNO
3, KNO
3according to ratio mixed grinding 5min in agate mortar that mol ratio is 1:1.5:1.5, mixture after grinding is transferred in corundum crucible, under 250 DEG C of temperature conditions, roasting 10h carries out ion-exchange reactions, again sintering temperature is increased to respectively 450 DEG C of insulation 3h, products obtained therefrom washs 2 times through deionized water, centrifugation, is placed in 80 DEG C, baking oven and dries 4h, obtain Ag@AgInO
2;
(3) infusion process making ZnO/Ag@AgInO
2
Take the Zn (NO of 0.408g
3)
26H
2o puts into crucible, adds 4ml distilled water and dissolves.The Ag@AgInO again prepared by 1.0g ion-exchange
2join in above-mentioned solution, crucible is placed in the water-bath of 65 DEG C, be constantly stirred to moisture with glass bar and evaporate completely.Then biased sample is put into Muffle furnace, calcine 4h under 400 DEG C of temperature conditions, be cooled to room temperature, obtain 10wt%ZnO/Ag@AgInO
2heterogeneous Z-type catalysis material.
Embodiment 4 15%ZnO/Ag@AgInO
2heterogeneous catalysis material
(1) solid sintering technology prepares presoma NaInO
2
Respectively with indium nitrate and sodium peroxide for containing In with containing Na compound, according to In
2o
3and Na
2cO
3mol ratio is, after the ratio of 1:1 mixes, in agate mortar, grind 10min, is transferred to by mixture in corundum crucible, and 800 DEG C of calcining 4h, are cooled to room temperature, obtain presoma NaInO
2;
(2) ion-exchange prepares Ag@AgInO
2
Presoma NaInO prepared by solid sintering technology
2powder, with AgNO
3, KNO
3according to ratio mixed grinding 5min in agate mortar that mol ratio is 1:2:2, mixture after grinding is transferred in corundum crucible, under 270 DEG C of temperature conditions, roasting 10h carries out ion-exchange reactions, again sintering temperature is increased to respectively 400 DEG C of insulation 3h, products obtained therefrom washs 2 times through deionized water, centrifugation, is placed in 80 DEG C, baking oven and dries 4h, obtain Ag@AgInO
2;
(3) infusion process making ZnO/Ag@AgInO
2
Take the Zn (NO of 0.648g
3)
26H
2o puts into crucible, adds 5ml distilled water and dissolves.The Ag@AgInO again prepared by 1.0g ion-exchange
2join in above-mentioned solution, crucible is placed in the water-bath of 65 DEG C, be constantly stirred to moisture with glass bar and evaporate completely.Then biased sample is put into Muffle furnace, calcine 4h under 350 DEG C of temperature conditions, be cooled to room temperature, obtain 15wt%ZnO/Ag@AgInO
2heterogeneous Z-type catalysis material.
Embodiment 5 20%ZnO/Ag@AgInO
2heterogeneous catalysis material
(1) solid sintering technology prepares presoma NaInO
2
Respectively with inidum chloride and sodium carbonate for containing In with containing Na compound, according to In
2o
3and Na
2cO
3mol ratio is, after the ratio of 1:4 mixes, in agate mortar, grind 10min, is transferred to by mixture in corundum crucible, and 850 DEG C of calcining 4h, are cooled to room temperature, obtain presoma NaInO
2;
(2) ion-exchange prepares Ag@AgInO
2
Presoma NaInO prepared by solid sintering technology
2powder, with AgNO
3, KNO
3according to ratio mixed grinding 5min in agate mortar that mol ratio is 1:4:4, mixture after grinding is transferred in corundum crucible, under 270 DEG C of temperature conditions, roasting 8h carries out ion-exchange reactions, again sintering temperature is increased to respectively 400 DEG C of insulation 3h, products obtained therefrom washs 2 times through deionized water, centrifugation, is placed in 80 DEG C, baking oven and dries 4h, obtain Ag@AgInO
2;
(3) infusion process making ZnO/Ag@AgInO
2
Take the Zn (NO of 0.918g
3)
26H
2o puts into crucible, adds 5ml distilled water and dissolves.The Ag@AgInO again prepared by 1.0g ion-exchange
2join in above-mentioned solution, crucible is placed in the water-bath of 65 DEG C, be constantly stirred to moisture with glass bar and evaporate completely.Then biased sample is put into Muffle furnace, calcine 4h under 350 DEG C of temperature conditions, be cooled to room temperature, obtain 20wt%ZnO/Ag@AgInO
2heterogeneous Z-type catalysis material.
Effect experimental is verified
1, photocatalysis efficiency is investigated
By embodiment 1-5 gained ZnO/Ag@AgInO
2heterogeneous Z-type catalysis material and monomer A g@AgInO
2under visible light conditions, it is carried out to the photocatalysis experiment of photocatalytic degradation methylene blue solution.Concrete operation step is as follows:
Select methylene blue to be target degradation product, light source used is the high pressure xenon lamp of 300W, and filters out with the ultraviolet light that wavelength to be less than 400nm by specific optical filter.Detailed process for: it is in the methylene blue solution of 10mg/L that the photochemical catalyst taken prepared by 0.2g joins 200mL concentration, this solution is placed in dark condition lower magnetic force and stirs 30min, make between the methylene blue in reaction system and catalyst, to reach adsorption-desorption balance.Then open xenon lamp, sample about 10ml every 30min, after centrifugation 5min, utilize the absorbance of 722 type spectrophotometric determination methylene blue solutions, according to Lambert-Beer's law, within the specific limits, concentration and absorbance proportional, therefore its degradation rate can be expressed as:
Wherein D is the degradation rate of methylene blue t; C
0, C
tbe respectively the initial concentration of methylene blue and the concentration of t; A
0, A
tbe respectively the initial absorbance of methylene blue and the absorbance of t.
The photocatalysis efficiency of table 1 catalyst after illumination 210min
| Catalyst type | Catalytic efficiency |
| Embodiment 1:5wt%ZnO/Ag@AgInO 2 | 78.6％ |
| Embodiment 2:7wt%ZnO/Ag@AgInO 2 | 87.5％ |
| Embodiment 3:10wt%ZnO/Ag@AgInO 2 | 93.2％ |
| Embodiment 4:15wt%ZnO/Ag@AgInO 2 | 84.6％ |
| Embodiment 5:20wt%ZnO/Ag@AgInO 2 | 80.2％ |
| Ag@AgInO 2 | 61.16％ |
As seen from the above table, the ZnO/Ag@AgInO prepared by embodiment of the present invention 1-5
2, when after illumination 210min, its catalytic efficiency significantly improves, and demonstrates better photocatalytic activity.Wherein when ZnO content is Ag@AgInO
210wt% time, photocatalysis performance is better, reaches 93.2% to the degradation rate of methylene blue.
2, photoinduction study on the stability
The photoinduction stability of sample carries out measuring with the change of light application time by the generation of argent in mensuration catalysis material.In experimentation, light source used is the high pressure xenon lamp of 300W, and filters out with the ultraviolet light that wavelength to be less than 400nm by specific optical filter.To the ZnO/Ag@AgInO prepared by embodiment of the present invention 1-5
2and prepare AgAlO according to described in CN103480372A
2/ TiO
2sample irradiates under same light source, after 5 hours, sample is taken out and collects, utilizing XRD and XPS analysis, characterizes the changes of contents of argent in catalysis material after the different light time.
The content of the argent of table 2 catalyst before illumination and after illumination 300min
| Catalyst type | Before illumination | After illumination 300min |
| Embodiment 1:5wt%ZnO/Ag@AgInO 2 | 5.68％ | 5.65％ |
| Embodiment 2:7wt%ZnO/Ag@AgInO 2 | 6.32％ | 6.30％ |
| Embodiment 3:10wt%ZnO/Ag@AgInO 2 | 5.84％ | 5.80％ |
| Embodiment 4:15wt%ZnO/Ag@AgInO 2 | 4.85％ | 4.79％ |
| Embodiment 5:20wt%ZnO/Ag@AgInO 2 | 4.24％ | 4.11％ |
| 90/10AgAlO described in CN103480372A 2/TiO 2 | 0 | 4.85％ |
| 80/20AgAlO described in CN103480372A 2/TiO 2 | 0 | 3.64％ |
| 70/30AgAlO described in CN103480372A 2/TiO 2 | 0 | 2.76％ |
| 50/50AgAlO described in CN103480372A 2/TiO 2 | 0 | 2.13％ |
As seen from the above table, the ZnO/Ag@AgInO prepared by embodiment of the present invention 1-5
2sample, the content of its photoinduction stability test argent remains unchanged substantially; And argent content all has increase in various degree in the photoinduction stability test of sample described in CN103480372A; As can be seen here, the photoinduction good stability of the Z-type photochemical catalyst prepared by the present invention.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (10)
1. a ZnO/Ag AgInO
2the preparation method of heterogeneous Z-type catalysis material, is characterized in that, comprise the steps:
1) NaInO is prepared containing In compound with containing Na compound by solid sintering technology
2;
2) with NaInO
2for presoma, with AgNO
3, KNO
3ag@AgInO is prepared by ion-exchange
2;
3) Zn (NO
3)
26H
2o and Ag@AgInO
2by infusion process making ZnO/Ag@AgInO
2heterogeneous Z-type catalysis material.
2. preparation method according to claim 1, is characterized in that, step 1) in, described is 1:(1 ~ 4 containing In compound and the mol ratio containing Na compound).
3. preparation method according to claim 1, is characterized in that, step 1) in, described containing In compound be selected from indium sesquioxide, indium nitrate, inidum chloride one or more; Described containing Na compound be selected from sodium carbonate, sodium acetate, sodium peroxide one or more.
4. preparation method according to claim 1, is characterized in that, step 1) in, described solid sintering technology process conditions are: calcining heat is 700 ~ 900 DEG C, and temperature-time is 2 ~ 5h.
5. preparation method according to claim 1, is characterized in that, step 1) described solid sintering technology prepares NaInO
2concrete steps are: will be 1:(1 ~ 4 according to mol ratio containing In compound with containing Na compound) ratio mix after, grinding, by mixture in 700 ~ 900 DEG C of calcining 2 ~ 5h, is cooled to room temperature, obtains NaInO
2.
6., according to the arbitrary described preparation method of claim 1-4, it is characterized in that, step 2) in, described NaInO
2with AgNO
3, KNO
3mol ratio is 1:(1 ~ 5): (1 ~ 4).
7., according to the arbitrary described preparation method of claim 1-4, it is characterized in that, step 2) in, described ion-exchange process condition is: prior to 200 ~ 280 DEG C of roasting 3 ~ 15h, then is warming up to 350 ~ 650 DEG C of insulation 2 ~ 5h.
8., according to the arbitrary described preparation method of claim 1-4, it is characterized in that, described ion-exchange prepares Ag@AgInO
2concrete steps are: by NaInO
2with AgNO
3, KNO
3be 1:(1 ~ 5 according to mol ratio): the ratio mixing of (1 ~ 4), after grinding, roasting 3 ~ 15h under 200 ~ 280 DEG C of temperature conditions, then be increased to 350 ~ 650 DEG C of insulation 2 ~ 5h, washing, centrifugation, dries, obtains Ag@AgInO
2.
9., according to the arbitrary described preparation method of claim 1-4, it is characterized in that, step 3) in, described Ag@AgInO
2with Zn (NO
3)
26H
2the mass ratio of O is 1:0.01 ~ 1.
10. the ZnO/Ag@AgInO that obtains of the arbitrary described preparation method of claim 1-9
2heterogeneous Z-type catalysis material.
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| CN106000396A (en) * | 2016-06-23 | 2016-10-12 | 济南大学 | Visible-light responding photocatalytic material with Ag particles in different morphologies loaded on AgInO2 surface in situ and preparation method of visible-light responding photocatalytic material |
| WO2021072638A1 (en) * | 2019-10-15 | 2021-04-22 | 诸暨易联众创企业管理服务有限公司 | Mgo/au@aulno2 heterogeneous photocatalytic material and preparation method therefor |
| CN112517014A (en) * | 2020-11-11 | 2021-03-19 | 中国科学院长春应用化学研究所 | Ferroelectric semiconductor nano-particles with narrow band gap, preparation method and application thereof |
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