CN106632454A - Boron-containing perovskite material serving as ray shielding material and preparation method thereof - Google Patents
Boron-containing perovskite material serving as ray shielding material and preparation method thereof Download PDFInfo
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- CN106632454A CN106632454A CN201611208445.4A CN201611208445A CN106632454A CN 106632454 A CN106632454 A CN 106632454A CN 201611208445 A CN201611208445 A CN 201611208445A CN 106632454 A CN106632454 A CN 106632454A
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- boracic
- perovskite material
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/24—Lead compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/10—Organic substances; Dispersions in organic carriers
Abstract
The invention discloses a boron-containing perovskite material serving as a ray shielding material. The chemical formula of the boron-containing perovskite material is (A1)x(A2)1-x(B1)y(B2)1-y(X1)z(X2)3-x, wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 3, A1 and A2 are organic or inorganic cations, B1 and B2 are divalent metal cations, X1 is a boron-free organic or inorganic anion, X2 is a boron-containing inorganic anion, and y is equal to 0 when x is equal to 0. The invention further provides a method for preparing the boron-containing perovskite material. The boron-containing perovskite material is used as an X/gamma ray shielding material, can significantly increase the carrier migration rate and the exciton diffusion length, and realizes effective shielding of X/gamma rays; meanwhile, the boron-containing perovskite material has the advantages of simple preparation process and low cost, so that the boron-containing perovskite material is suitable for popularization and application.
Description
Technical field
The present invention relates to radiation shield technical field, and in particular to be a kind of boracic calcium titanium as radiation shielding material
Pit wood material and preparation method thereof.
Background technology
Perovskite structural material is by its adjustable energy gap, high carrier mobility, good the two poles of the earth electric charge transmission
Characteristic, long exciton diffusion length and simple preparation technology so that it is in electronics devices such as solar cell, light shield devices
Part field is extensively studied and applies.And B element is due to absorption cross-section height, capture spectra width and aboundresources price is low, because
And nuclear industry is generally using iron containing B as high-energy ray shielding material.At present, preparation both at home and abroad to boron-containing steel and screen
Cover performance to conduct extensive research, it is ensured that excellent thermal neutron shielding simultaneously, takes into account good mechanical processability and low cost.
Therefore, how B element uniformly to be adulterated such as to enter in perovskite structural material with some form, using perovskite
Adjustable energy gap, high carrier mobility, long exciton diffusion length, design is prepared based on the perovskite structure of boracic
NEW TYPE OF COMPOSITE shielding material, it appears particularly important.
The content of the invention
The invention provides a kind of boracic perovskite material as radiation shielding material and preparation method thereof, can be effective
Raising MAPbX3To the gamma-ray radiation screening effects of X/.
For achieving the above object, the technical solution used in the present invention is as follows：
Boracic perovskite material as radiation shielding material, the chemical formula of the perovskite material is (A1)x(A2)1-x(B1)y
(B2)1-y(X1)z(X2)3-z, wherein 0≤x≤1,0≤y≤1,0≤z≤3, A1, A2 are organic or inorganic cation, B1, B2
Divalent metal is, X1 is the organic or inorganic anion of not boracic, and X2 is the inorganic anion of boracic, and during x=0,
y=0。
Preferably, the A1 and A2 be epoxy resin, methylamine, carbonamidine, lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium,
Any one in barium.
Preferably, the B1 and B2 are any one in lead, tin, copper, germanium.
Preferably, the X1 is I, Br, Cl, PF6, any one in SCN, X2 is BF4。
Based on above-mentioned material, present invention also offers the preparation method of the boracic perovskite material, comprises the following steps：
（1）Under an argon atmosphere, by the aqueous solution of the ethanol solution of methylamine and fluoboric acid by volume for 1: 1.6 ratio in 0
It is well mixed at temperature below DEG C, and the evaporation solvent at a temperature of more than 50 DEG C, obtain fluoboric acid methylamine powder；
（2）Organic solvent is dissolved in together with the ratio for being in mass ratio 0.012: 0.604 with lead iodide by good fortune boric acid methylamine powder
In, obtain the precursor solution of boracic calcium pit wood material；
（3）Precursor solution is dried into 2～15h at a temperature of 80～120 DEG C, perovskite material is obtained.
Preferably, the step（2）In, the oil machine solvent is methyl alcohol, ethanol, isopropanol, the tert-butyl alcohol, chloroform, second
Enediol, dimethyl acetamide, dimethyl sulfoxide, benzyl ether, 1-METHYLPYRROLIDONE, N- ethyl pyrrolidones, N, N- dimethyl
One or more in formamide.
Preferably, the step（3）In, precursor solution is done by the way of vacuum or nitrogen protection atmosphere
It is dry.
Compared with prior art, the invention has the advantages that：
（1）The present invention is with ABX3Based on perovskite structure, using the organic or inorganic doping agent of boracic preparation is doped
Obtain boracic perovskite material（Chemical formula is：(A1)x(A2)1-x(B1)y(B2)1-y(X1)z(X2)3-z）, the present invention is by reasonable
Preparation technology design, by using boride as absorber mix perovskite structure MAPbI3In molecule, using boride
Less ionic radius, improves stability in its environment, suppresses MAPbI3Decomposition in aqueous oxygen atmosphere, while can be effective
Improve MAPbX3To the gamma-ray radiation screening effects of X/.Also, the present invention can also utilize the absorption characteristic of boride, carry
The comprehensive shielded performance of high composite.
（2）Raw material of the present invention and equipment cost is cheap, raw material sources extensively, it is convenient to prepare, can with whole soln working process,
Therefore, the present invention is with a wide range of applications.
Specific embodiment
With reference to embodiment, the invention will be further described, and the mode of the present invention includes but are not limited to following enforcement
Example.
The invention provides a kind of boracic perovskite material, can be used as X/ gamma ray shielding materials, its chemical formula is (A1)x
(A2)1-x(B1)y(B2)1-y(X1)z(X2)3-z, wherein 0≤x≤1,0≤y≤1,0≤z≤3, A1, A2 are organic or inorganic sun
Ion（Such as epoxy resin, methylamine, carbonamidine, lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium or barium）, B1, B2 are divalent metal
Cation（Such as lead, tin, copper or germanium）, X1 is the organic or inorganic anion of not boracic（For example, I, Br, Cl, PF6Or
SCN）, X2 is the inorganic anion of boracic（Such as BF4）, and during x=0, y=0.The system of boracic perovskite material of the present invention
Standby process is as follows：
（1）Under an argon atmosphere, the ethanol solution of methylamine is mixed with the aqueous solution of fluoboric acid at less than 0 DEG C of temperature
It is even, and the evaporation solvent at a temperature of more than 50 DEG C, obtain fluoboric acid methylamine powder；
（2）Fluoboric acid methylamine powder is dissolved in organic solvent together with lead iodide, the presoma for obtaining perovskite material is molten
Liquid；
（3）Precursor solution is dried into 2～15h at a temperature of 80～120 DEG C, perovskite material is obtained.
With arranging the present invention is illustrated as one example below.
In the perovskite-based material of boracic, A is CH3NH3 +, B1 is Pb2+, X1 is I-, X2 is BF4 -, and x=1, y=1, z=2.9,
The chemical formula of the perovskite-based material of corresponding boracic is CH3NH3PbI2.9(BF4)0.1, specific implementation step prepared by the material is such as
Under：
（1）Under an argon atmosphere, the ethanol solution (8wt%) of 10ml methylamines is taken, the aqueous solution with 16ml fluoboric acid is allowed to
(48wt%) it is well mixed at 0 DEG C, the evaporation solvent at 50 DEG C, obtains fluoboric acid methylamine powder；
（2）Take the PbI of 0.461g2, the CH of 0.143g3NH3The CH of I and 0.012g3NH3BF4, DMF is dissolved in together（Dimethyl methyl
Acid amides）In, obtain the precursor solution of boracic perovskite material；
（3）Take step（2）The precursor solution of gained, 80 DEG C are dried 2h, obtain boracic perovskite material.
The method of testing of material shielding performance：Using the boracic perovskite material for preparing as main body, with epoxy resin
Be respectively adopted normal pressure open type pouring technology with polyimides macromolecule matrix and die press technology for forming prepare 5mm it is thick containing boron rock
Thing/polymer composite.It is tested to medical 60～250 kVp medical X-rays and the gamma-ray shielding in 125I sources
Energy.
Change presoma composition, on the premise of other conditions are constant, (A1) for obtainingx(A2)1-x(B1)y(B2)1-y(X1)z
(X2)3-zShielding properties is as shown in table 1 below.
(A1) that the different presoma compositions of table 1 are obtainedx(A2)1-x(B1)y(B2)1-y(X1)z(X2)3-zResult of detection
As it can be seen from table 1 changing (A1)x(A2)1-x(B1)y(B2)1-y(X1)z(X2)3-zComposition, it can be directly affected to X/
Gamma-ray shield effectiveness.Especially with respect to the perovskite material CH of not boracic3NH3PbI3, after being doped into boron-containing compound,
Composite will be obviously improved to the gamma-ray shield effectivenesses of X/, and the absorption cross-section that this is likely due to B is high, capture spectra width
The reason for.Particularly, when with part Sn substitute Pb after, material keep shield effectiveness higher to X/ gamma-rays while, its
The stability of itself also improves.
The present invention is selected and Proportionality design by rational raw material, and organic using boracic or inorganic doping agent is mixed
It is miscellaneous, boracic perovskite material has been prepared, this kind of boracic perovskite material can carry out high-efficiency shielding, have again to X/ gamma-rays
Good stability.Therefore, compared with prior art, the technology of the present invention progress is fairly obvious, and it has prominent substance special
Point and significant progress.
Above-described embodiment is only one of the preferred embodiment of the present invention, should not be taken to limit the protection model of the present invention
Enclose, all body design thought and the change or polishing of having no essential meaning mentally made in the present invention, what it was solved
Technical problem is still consistent with the present invention, should be included within protection scope of the present invention.
Claims (7)
1. the boracic perovskite material as radiation shielding material, it is characterised in that the chemical formula of described perovskite material is
(A1)x(A2)1-x(B1)y(B2)1-y(X1)z(X2)3-z, wherein 0≤x≤1,0≤y≤1,0≤z≤3, A1, A2 be it is organic or
Inorganic cation, B1, B2 are divalent metal, and X1 is the organic or inorganic anion of not boracic, and X2 is the nothing of boracic
Machine anion, and during x=0, y=0.
2. the boracic perovskite material as radiation shielding material according to claim 1, it is characterised in that the A1 and
A2 is any one in epoxy resin, methylamine, carbonamidine, lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium.
3. the boracic perovskite material as radiation shielding material according to claim 2, it is characterised in that the B1 and
B2 is any one in lead, tin, copper, germanium.
4. the boracic perovskite material as radiation shielding material according to claim 3, it is characterised in that the X1 is
I、Br、Cl、PF6, any one in SCN, X2 is BF4。
5. the preparation method of the boracic perovskite material described in Claims 1 to 4 any one, it is characterised in that including following
Step：
（1）Under an argon atmosphere, by the aqueous solution of the ethanol solution of methylamine and fluoboric acid by volume for 1: 1.6 ratio in 0
It is well mixed at temperature below DEG C, and the evaporation solvent at a temperature of more than 50 DEG C, obtain fluoboric acid methylamine powder；
（2）Organic solvent is dissolved in together with the ratio for being in mass ratio 0.012: 0.604 with lead iodide by good fortune boric acid methylamine powder
In, obtain the precursor solution of boracic calcium pit wood material；
（3）Precursor solution is dried into 2～15h at a temperature of 80～120 DEG C, perovskite material is obtained.
6. preparation method according to claim 5, it is characterised in that the step（2）In, the oil machine solvent is first
Alcohol, ethanol, isopropanol, the tert-butyl alcohol, chloroform, ethylene glycol, dimethyl acetamide, dimethyl sulfoxide, benzyl ether, N- crassitudes
One or more in ketone, N- ethyl pyrrolidones, DMF.
7. preparation method according to claim 6, it is characterised in that the step（3）In, to precursor solution using true
The mode of empty or nitrogen protection atmosphere is dried.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611208445.4A CN106632454A (en) | 2016-12-23 | 2016-12-23 | Boron-containing perovskite material serving as ray shielding material and preparation method thereof |
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| CN201611208445.4A CN106632454A (en) | 2016-12-23 | 2016-12-23 | Boron-containing perovskite material serving as ray shielding material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107316668A (en) * | 2017-08-02 | 2017-11-03 | 北京大学 | A kind of X-ray protection structure based on perovskite material and preparation method thereof |
| CN109206449A (en) * | 2018-08-01 | 2019-01-15 | 南京航空航天大学 | A kind of organic and inorganic perovskite crystal material and the preparation method and application thereof |
| CN109921043A (en) * | 2019-02-26 | 2019-06-21 | 五邑大学 | A kind of elctro-catalyst and preparation method thereof of B adulterated with Ca and Ti ore type oxide |
| WO2020249927A1 (en) * | 2019-06-11 | 2020-12-17 | Oxford University Innovation Limited | Optoelectronic device |
| CN115286513A (en) * | 2022-08-11 | 2022-11-04 | 哈尔滨工业大学 | Methylamine lead iodide perovskite powder and preparation method and application thereof |
| CN115304982A (en) * | 2022-08-11 | 2022-11-08 | 哈尔滨工业大学 | Shielding coating for satellite-borne integrated circuit packaging and preparation method thereof |
-
2016
- 2016-12-23 CN CN201611208445.4A patent/CN106632454A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| JIANGZHAO CHEN等: ""Hole-Conductor-Free Fully Printable Mesoscopic Solar Cell with Mixed-Anion Perovskite CH3NH3PbI(3-x)(BF4)x"", 《ADVANCED ENERGY MATERIALS》 * |
| SATYAWAN NAGANE等: ""CH3NH3Pb(BF4)3 and (C4H9NH3)2Pb(BF4)4 Family of 3D and 2D Perovskites without and with Iodide and Bromide Ions Substitution"", 《J. PHYS. CHEM. LETT.》 * |
| SATYAWAN NAGANE等: ""CH3NH3PbI(3_x)(BF4)x: molecular ion substituted hybrid perovskite"", 《CHEM. COMMUN.》 * |
| 吕思刘: ""具有钙钛矿结构的有机铅卤化物的制备及其光电性能的研究"", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107316668A (en) * | 2017-08-02 | 2017-11-03 | 北京大学 | A kind of X-ray protection structure based on perovskite material and preparation method thereof |
| CN109206449A (en) * | 2018-08-01 | 2019-01-15 | 南京航空航天大学 | A kind of organic and inorganic perovskite crystal material and the preparation method and application thereof |
| CN109921043A (en) * | 2019-02-26 | 2019-06-21 | 五邑大学 | A kind of elctro-catalyst and preparation method thereof of B adulterated with Ca and Ti ore type oxide |
| CN109921043B (en) * | 2019-02-26 | 2021-10-08 | 五邑大学 | Electro-catalyst of B-doped perovskite oxide and preparation method thereof |
| WO2020249927A1 (en) * | 2019-06-11 | 2020-12-17 | Oxford University Innovation Limited | Optoelectronic device |
| CN115286513A (en) * | 2022-08-11 | 2022-11-04 | 哈尔滨工业大学 | Methylamine lead iodide perovskite powder and preparation method and application thereof |
| CN115304982A (en) * | 2022-08-11 | 2022-11-08 | 哈尔滨工业大学 | Shielding coating for satellite-borne integrated circuit packaging and preparation method thereof |
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