CN110048001A - A method of engineering being replaced by halogen to adjust bismuthino hybrid inorganic-organic materials pattern, band gap and stability - Google Patents
A method of engineering being replaced by halogen to adjust bismuthino hybrid inorganic-organic materials pattern, band gap and stability Download PDFInfo
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- CN110048001A CN110048001A CN201910258561.4A CN201910258561A CN110048001A CN 110048001 A CN110048001 A CN 110048001A CN 201910258561 A CN201910258561 A CN 201910258561A CN 110048001 A CN110048001 A CN 110048001A
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Abstract
The invention discloses a kind of methods for adjusting bismuthino hybrid inorganic-organic materials pattern, band gap and stability by halogen replacement engineering.It is an object of the invention to bismuthino hybrid material (NH3CH2CH2NH3)aBibXcThe position X carry out halogens replacement to adjust the pattern of material, optical band gap and the technique study of stability.The final low dimensional hybrid material for obtaining different-shape, band gap magnitude and stability, and then can be applicable to hybrid inorganic-organic perovskite solar battery and field of semiconductor materials.The present invention has many advantages, such as to be continuously adjusted in synthesis technology is simple, reaction condition is mild, low in cost, reproducible, optical band gap is wider range, stability is high, has preferable industrialization prospect.
Description
Technical field
The present invention relates to a kind of methods for adjusting hybrid inorganic-organic materials band gap by halogen replacement engineering.
Background technique
Organic and inorganic solar battery mainly includes lead base and tinbase hybrid inorganic-organic perovskite solar battery, is changed
Formula is ABX3, A is organic amine cation (mainly CH3NH3 +), B is metallic divalent cation (mainly Pb2+、Sn2+), X is
Halogen replaces anion (Cl-、Br-、I-).Hybrid inorganic-organic materials its show designability, the degree of controllability is
Remote super other materials, synthesize at it, properity and in terms of attracted numerous studies personnel.It is organic by adjusting A
The size of ion, the hybrid inorganic-organic materials of available different structure dimension；It, can by adjusting B metallic elements
To obtain different novel perovskite material systems；Replace elements by adjusting C halogens, available list halogen replace or
Mixed halogen replaces perovskite material system.
In order to develop and improve hybrid inorganic-organic perovskite solar battery, researcher by A, B with
And X be doped and replace to be modified battery obsorbing layer or the new perovskite absorbed layer of exploitation, finally all obtains certain
Scientific achievement.For different purposes, we can carry out the doping and replacement between component to material.These doping can be with
The photoelectric properties such as band gap, carrier concentration, the carrier lifetime of effective regulation ABX3 halogen replacement perovskite.This is also lead halogen
Compound perovskite can obtain the major reason developed very fast.Especially now, there is a energy deficiency exploitation transformation efficiency
High material is to solve one of energy deficiency method.It can use the cooperative interaction between dissimilar components, make material
Material generates or enhances performance of different nature, compared with single organic matter or inorganic matter, in mechanics, optics, electromagnetism, resistance to
Hot and functionalization etc. has many advantages, such as apparent performance advantage, and have both synthetic method simply, structurally variable.Therefore
Novel hybrid inorganic-organic materials are developed with huge application prospect.
Summary of the invention
In view of the application prospect and huge advantage of above-mentioned hybrid inorganic-organic materials, the object of the invention is to bismuthino
Hybrid material (NH3CH2CH2NH3)aBibXcThe replacement of X bit element is carried out to adjust its pattern, band gap and the technique study of stability.
The experimental method of use is simple and easy solvent evaporation method and hydrothermal synthesis method.
(the NH3CH2CH2NH3)aBibXcSynthetic method specific steps are as follows:
(1) 10.00~30.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) halogen acid solution of 25.00~60.00mL, magnetic agitation 2 is slowly added dropwise in the three-necked flask in step (1)
Obtain suspension within~5 hours；
(3) suspension of step (2) is poured into culture dish, forced air drying 20~30 hours, obtain under the conditions of 60~80 DEG C
To white crystal；
(4) white crystal that step (3) obtains is washed 2~4 times with 20.00~60.00mL ether, is put into culture dish,
It is dried in vacuo 20~30 hours under the conditions of subsequent 60~80 DEG C, obtains white powder A；
Its chemical equation: NH2CH2CH2NH2+2HX→X(NH3NH2CH2NH3)X
(5) Bi of 2.00~10mmol is weighed2O3It is added in sample bottle, the halogen acid solution that 10~45mL is then added obtains
To clear solution；
(6) 5.00~25.00mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) by the reaction solution of step (6) be put into sample bottle perhaps in hydrothermal reaction kettle volatilization at a certain temperature or
It is reacted in certain soaking time, finally can generate crystal, as (NH in sample bottle or reactor bottom3CH2CH2NH3)aBibXcCrystal；
Its chemical equation:
X(NH3NH2CH2NH3)X+Bi2O3+HX→(NH3CH2CH2NH3)aBibXc
The present invention is with synthesis technology is simple, reaction condition is mild, low in cost, reproducible, optical band gap continuously may be used
The advantages that tune, high stability, has preferable industrialization prospect.
Detailed description of the invention
Fig. 1 is the present invention (NH3CH2CHNH3)Bi2Cl8Crystal structure figure.(embodiment 1)
Fig. 2 is NH of the present invention3CH2CH2NH3BiBr5The FE-SEM (a) of crystal； NH3CH2CH2NH3BiBr5Crystal structure
Scheme (b)；(embodiment 5)
Fig. 3 is NH of the present invention3CH2CH2NH3Bi2I10The digital photograph (a) of crystal； NH3CH2CH2NH3Bi2I10Crystal knot
Composition (b)；(embodiment 9).
Fig. 4 is the present invention (NH3CH2CH2NH3)Bi2Cl8X-ray diffraction spectrogram and fit standard XRD spectrogram.
Fig. 5 is NH of the present invention3CH2CH2NH3BiBr5X-ray diffraction spectrogram and fitting standard x RD spectrogram (a)；
NH3CH2CH2NH3BiBr5EDS test map power spectrum test selected areas (b) of crystal；Energy spectrogram (c)；Element and its percentage
Than (d).
Fig. 6 is NH of the present invention3CH2CH2NH3Bi2I10X-ray diffraction spectrogram and fitting standard x RD spectrogram (a)；
NH3CH2CH2NH3Bi2I10The EDS of crystal tests map (b).
Fig. 7 is the present invention (NH3CH2CH2NH3)Bi2Cl8、NH3CH2CH2NH3BiBr5And NH3CH2CH2NH3Bi2I10Crystal
Ultraviolet-visible absorption spectroscopy and band gap diagram ((a), (b) and (c)) and hot weight curve ((d), (e) and (f)).
Specific embodiment
Embodiment 1:
(1) 10.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) hydrochloric acid solution of 25.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
Suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 20.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 2.00mmol is weighed2O3It is added in sample bottle, the hydrochloric acid solution that 15mL is then added obtains achromaticity and clarification
Solution；
(6) 5.00mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into sample bottle, is volatilized for 24 hours under the conditions of 60 DEG C；It can be given birth in sample bottle bottom
At the crystal of white, as (NH3CH2CH2NH3)Bi2Cl8Crystal；
Embodiment 2:
(1) 12.50mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) hydrochloric acid solution of 33.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
Suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 30.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 5.00mmol is weighed2O3It is added in sample bottle, the hydrochloric acid solution that 25mL is then added obtains achromaticity and clarification
Solution；
(6) 12.50mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into sample bottle, volatilize 20h under the conditions of 90 DEG C；It can be given birth in sample bottle bottom
At the crystal of white, as (NH3CH2CH2NH3)Bi2Cl8Crystal；
Embodiment 3:
(1) 18.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) hydrochloric acid solution of 45.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
Suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 35.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 8.00mmol is weighed2O3It is added in sample bottle, the hydrochloric acid solution that 35mL is then added obtains achromaticity and clarification
Solution；
(6) 14.00mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into sample bottle, volatilize 18h under the conditions of 110 DEG C；In the meeting of sample bottle bottom
Generate the crystal of white, as (NH3CH2CH2NH3)Bi2Cl8Crystal；
Embodiment 4:
(1) 25.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) hydrochloric acid solution of 60.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
Suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 50.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 10.00mmol is weighed2O3It is added in sample bottle, the hydrochloric acid solution that 43mL is then added obtains achromaticity and clarification
Solution；
(6) 15.00mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into sample bottle, volatilize 10h under the conditions of 150 DEG C；In the meeting of sample bottle bottom
Generate the crystal of white, as (NH3CH2CH2NH3)Bi2Cl8Crystal；
Embodiment 5:
(1) 13.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) hydrobromic acid solution of 26.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
To suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 33.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 5.00mmol is weighed2O3It is added in sample bottle, then the hydrobromic acid solution of addition 15mL obtains faint yellow
Clear solution；
(6) 13.80mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into hydrothermal reaction kettle, keeps the temperature 20h under the conditions of 90 DEG C；In reactor bottom
The crystal of glassy yellow, as (NH can be generated3CH2CH2NH3)BiBr5Crystal；
Embodiment 6:
(1) 16.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) hydrobromic acid solution of 32.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
To suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 40.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 6.50mmol is weighed2O3It is added in sample bottle, then the hydrobromic acid solution of addition 26mL obtains faint yellow
Clear solution；
(6) 14.50mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into hydrothermal reaction kettle, keeps the temperature 15h under the conditions of 110 DEG C；In reaction kettle bottom
Portion can generate the crystal of glassy yellow, as (NH3CH2CH2NH3)BiBr5Crystal；
Embodiment 7:
(1) 22.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) hydrobromic acid solution of 38.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
To suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 45.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 8.00mmol is weighed2O3It is added in sample bottle, then the hydrobromic acid solution of addition 33mL obtains faint yellow
Clear solution；
(6) 16.00mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into hydrothermal reaction kettle, volatilize 12h under the conditions of 130 DEG C；In reaction kettle bottom
Portion can generate the crystal of glassy yellow, as (NH3CH2CH2NH3)BiBr5Crystal；
Embodiment 8:
(1) 30.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) hydrobromic acid solution of 60.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
To suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 60.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 10.00mmol is weighed2O3It is added in sample bottle, then the hydrobromic acid solution of addition 40mL obtains faint yellow
Clear solution；
(6) 15.00mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into hydrothermal reaction kettle, volatilize 10h under the conditions of 180 DEG C；In reaction kettle bottom
Portion can generate the crystal of glassy yellow, as (NH3CH2CH2NH3)BiBr5Crystal；
Embodiment 9:
(1) 14.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) the hydroiodic acid solution of 26.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
To suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 25.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 3.00mmol is weighed2O3It is added in sample bottle, the hydroiodic acid solution that 18mL is then added obtains peony
Clear solution；
(6) 8.00mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into hydrothermal reaction kettle, keeps the temperature 36h under the conditions of 80 DEG C；In reactor bottom
Red crystal, as (NH can be generated3CH2CH2NH3)Bi2I10Crystal；
Embodiment 10:
(1) 23.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) the hydroiodic acid solution of 46.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
To suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 50.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 5.00mmol is weighed2O3It is added in sample bottle, the hydroiodic acid solution that 26mL is then added obtains peony
Clear solution；
(6) 13.00mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into hydrothermal reaction kettle, keeps the temperature 17h under the conditions of 110 DEG C；In reaction kettle bottom
Portion can generate red crystal, as (NH3CH2CH2NH3)Bi2I10Crystal；
Embodiment 11:
(1) 26.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) the hydroiodic acid solution of 43.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
To suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 50.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 8.00mmol is weighed2O3It is added in sample bottle, the hydroiodic acid solution that 36mL is then added obtains peony
Clear solution；
(6) 14.00mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into hydrothermal reaction kettle, keeps the temperature 14h under the conditions of 130 DEG C；In reaction kettle bottom
Portion can generate red crystal, as (NH3CH2CH2NH3)Bi2I10Crystal；
Embodiment 12:
(1) 30.00mL ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) the hydroiodic acid solution of 60.00mL is slowly added dropwise in the three-necked flask in step (1), obtains within magnetic agitation 2 hours
To suspension；
(3) suspension of step (2) is poured into culture dish, forced air drying 20 hours under the conditions of 60 DEG C, obtains white crystalline substance
Body；
(4) white crystal that step (3) obtains is washed 2 times with 60.00mL ether, is put into culture dish, subsequent 60 DEG C of items
It is dried in vacuo 20 hours under part, obtains white powder A；
(5) Bi of 10.00mmol is weighed2O3It is added in sample bottle, the hydroiodic acid solution that 45mL is then added obtains peony
Clear solution；
(6) 15.00mmol step (4) white powder A is weighed to be added in the clear solution of step (5)；
(7) reaction solution of step (6) is put into hydrothermal reaction kettle, keeps the temperature 10h under the conditions of 150 DEG C；In reaction kettle bottom
Portion can generate red crystal, as (NH3CH2CH2NH3)Bi2I10Crystal.
Claims (6)
1. a kind of method that bismuthino hybrid inorganic-organic materials pattern, band gap and stability are adjusted by halogen replacement engineering,
Its feature comprising the following specific steps
(1) a certain amount of ethylenediamine solution is measured with graduated cylinder to pour into three-necked flask, stir under the conditions of ice-water bath；
(2) halogen acid solution is slowly added dropwise in the three-necked flask in step (1), and magnetic agitation obtains suspension；
(3) suspension of step (2) is poured into culture dish, is dried, washs, recrystallization processing, finally obtains white powder
Last A；
(4) Bi of certain mol proportion is weighed respectively2O3With halogen ethylenediamine X (NH3NH2CH2NH3) X be added sample bottle in, then plus
Enter a certain amount of halogen acid solution and obtains clear solution；
(5) the white powder A for weighing a certain amount of step (3) is added in the clear solution of step (4)；
(6) reaction solution of step (5) is put into sample bottle perhaps volatilization at a certain temperature or one in hydrothermal reaction kettle
Reaction, finally can generate crystal, as (NH in sample bottle or reactor bottom in fixed soaking time3CH2CH2NH3)aBibXcCrystal.
2. it is according to claim 1 it is a kind of engineering replaced by halogen come adjust bismuthino hybrid inorganic-organic materials pattern,
The method of band gap and stability, it is characterised in that the bismuthino hybrid inorganic-organic materials chemical formula is (NH3CH2CH2NH3)aBibXc, and be the dotted material of zero dimension.
3. it is according to claim 1 it is a kind of engineering replaced by halogen come adjust bismuthino hybrid inorganic-organic materials pattern,
The method of band gap and stability, it is characterised in that the method is by hydrothermal synthesis and solvent volatilization two methods difference
Synthesize (NH3CH2CH2NH3)Bi2Cl8、(NH3CH2CH2NH3)BiBr5(NH3CH2CH2NH3)Bi2I10Three kinds of hybrid inorganic-organics
Material.
4. it is according to claim 1 it is a kind of engineering replaced by halogen come adjust bismuthino hybrid inorganic-organic materials pattern,
The method of band gap and stability, it is characterised in that the experiment is to prepare different-shape and optics by X halogen Shift Methods
The bismuthino hybrid inorganic-organic materials of band gap.Wherein presoma halogen ethylenediamine X (NH3NH2CH2NH3) X and Bi2O3Molar ratio
It is 1~2.And 10~36h is kept the temperature under the conditions of experimental temperature is 60~180 DEG C.
5. it is according to claim 1 it is a kind of engineering replaced by halogen come adjust bismuthino hybrid inorganic-organic materials pattern,
The method of band gap and stability, it is characterised in that the halogen acids be pure (A.R.) hydrochloric acid of analysis respectively, analyze pure
(A.R.) hydroiodic acid (wt:45%) of hydrobromic acid and analysis pure (A.R.).
6. it is according to claim 1 it is a kind of engineering replaced by halogen come adjust bismuthino hybrid inorganic-organic materials pattern,
The method of band gap and stability, it is characterised in that the zero dimension hybrid material (NH3CH2CH2NH3)aBibXcOptical band gap exist
It is continuously adjusted between 1.89eV~3.32eV, broader wave-length coverage in visible spectrum can be absorbed.Its stability is mentioned from 280 DEG C
Up to 350 DEG C, storage two weeks or so, high stability can be stablized in air.
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| CN112941613A (en) * | 2019-12-10 | 2021-06-11 | 桂林理工大学 | Bismuth-based 2-amino-4-methylpyridine organic-inorganic hybrid material and preparation method thereof |
| CN113239841A (en) * | 2021-05-24 | 2021-08-10 | 桂林理工大学博文管理学院 | Classroom concentration state detection method based on face recognition and related instrument |
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| US20170346024A1 (en) * | 2014-11-06 | 2017-11-30 | Postech Academy-Industry Foundation | Perovskite nanocrystal particle light emitting body with core-shell structure, method for fabricating same, and light emitting element using same |
| US20160155974A1 (en) * | 2014-12-01 | 2016-06-02 | The Regents Of The University Of California | Complex pnictide metal halides for optoelectronic applications |
| CN108780759A (en) * | 2016-03-09 | 2018-11-09 | 牛津大学科技创新有限公司 | The method for manufacturing A/M/X materials using alkylamine |
| CN109371470A (en) * | 2018-10-30 | 2019-02-22 | 桂林理工大学 | A kind of narrow band gap organic and inorganic low-dimensional hybrid material and its synthetic method |
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| CN112941613A (en) * | 2019-12-10 | 2021-06-11 | 桂林理工大学 | Bismuth-based 2-amino-4-methylpyridine organic-inorganic hybrid material and preparation method thereof |
| CN112941613B (en) * | 2019-12-10 | 2023-06-23 | 桂林理工大学 | Bismuth-based 2-amino-4-methylpyridine organic-inorganic hybrid material and preparation method thereof |
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