CN106082329B - A kind of semi-conducting material containing bismuth and halogen and its preparation and analysis method - Google Patents
A kind of semi-conducting material containing bismuth and halogen and its preparation and analysis method Download PDFInfo
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- CN106082329B CN106082329B CN201610407141.4A CN201610407141A CN106082329B CN 106082329 B CN106082329 B CN 106082329B CN 201610407141 A CN201610407141 A CN 201610407141A CN 106082329 B CN106082329 B CN 106082329B
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 43
- 239000004065 semiconductor Substances 0.000 title claims abstract description 36
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 30
- 150000002367 halogens Chemical class 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000004458 analytical method Methods 0.000 title abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims description 22
- 229910052740 iodine Inorganic materials 0.000 claims description 19
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 13
- 229910052792 caesium Inorganic materials 0.000 claims description 11
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical group [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- 238000001429 visible spectrum Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 20
- 238000004448 titration Methods 0.000 description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 101710134784 Agnoprotein Proteins 0.000 description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000001144 powder X-ray diffraction data Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 241000276573 Cottidae Species 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000003708 ampul Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 3
- 235000004237 Crocus Nutrition 0.000 description 2
- 241000596148 Crocus Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000010748 Photoabsorption Effects 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000000411 transmission spectrum Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- 244000170916 Paeonia officinalis Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
- C01G29/006—Compounds containing, besides bismuth, two or more other elements, with the exception of oxygen or hydrogen
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a kind of semi-conducting material containing bismuth and halogen and its preparation and analysis method.The described semi-conducting material containing bismuth and halogen, it is characterised in that its chemical formula is Cs3Bi2BrxI9‑x, wherein, x=1 6.85.The formula of the present invention is Cs3Bi2BrxI9‑xSemi-conducting material, there is adjustable direct band gap energy, minimum is adjustable to 1.99eV in an embodiment of the present invention, less than current material Cs3Bi2Br9Or Cs3Bi2I9Band-gap energy, broader wave-length coverage in visible spectrum can be absorbed.
Description
Technical field
The invention belongs to new material, is related to a kind of semi-conducting material containing bismuth and halogen and its preparation and analysis method,
It is Cs more particularly to chemical formula formula3Bi2BrxI9-xThe new material of (wherein x=1-6.85) and its preparation and analysis method.
Background technology
Currently, as energy crisis and problem of environmental pollution become increasingly conspicuous, it is traditional to search out a kind of clean energy resource replacement
The stone energy is extremely urgent.Hydrogen Energy due to its calorific value it is high, it is in light weight, pollution-free, many advantages, such as transport can be stored, while hydrogen is
One of most abundant element on the earth, Hydrogen Energy are considered as the clean energy resource for being most hopeful to substitute traditional fossil energy.Traditional
Hydrogen Energy acquisition modes are mainly water electrolysis hydrogen production and fossil fuel hydrogen manufacturing, and water electrolysis hydrogen production can consume substantial amounts of electric energy, mineral combustion
Material hydrogen manufacturing can produce CO2Secondary pollution is caused, and photocatalytic hydrogen production by water decomposition utilizes inexhaustible, nexhaustible solar energy point
Xie Shui produces hydrogen, and reaction condition is gentle, simple to operate, pollution-free, has huge DEVELOPMENT PROSPECT.
The crucial exploitation in photochemical catalyst of hydrogen is produced using decomposing water with solar energy, and weighs the quality of photochemical catalyst,
Generally see following three points:Band-gap energy and bandedge placement meet the energy requirement of decomposition water;Solar energy can be made full use of, to visible ray
Response;Stable performance, photoetch (Abe, J.Photochem.Photobiol.C, 2010,11,179-209) can be resisted.Therefore,
Search out that a kind of band structure is suitable and the photochemical catalyst of stable performance, the popularization and application meaning for photocatalytic hydrogen production by water decomposition
Justice is great.
At present, formula A3M2X9(A is alkali metal ion, M Bi3+Or Sb3+Ion, X are halide ion) seriation
Compound mainly with study based on its structure and phase transformation (Chabot, Acta Cryst.B, 1978,34,645-648;Yamada,
J.Solid State Chem., 1997,134,319-325;Ivanov, Inorg.Mater., 2001,37,623-627).
2015, have been reported that (Lehner, Chem.Mater., 2015,27,7137-7148;Brandt, MRS Commun., 2015,5,
265-275;Park, Adv.Mater., 2015,27,6806-6813) it have studied Cs3Sb2I9And Cs3Bi2I9In solar cell side
The application in face.However, in known A3M2X9In type compound, containing Sb3+Material hydrolabil, Cs3Bi2Br9To be bright orange
Color only absorbs the blue light in visible ray, and Cs3Bi2I9At room temperature by isolated Bi2I9 3-Ion forms, without perovskite-like
Structure.These existing materials are not the catalyst materials of preferable photolysis water hydrogen.
The content of the invention
The present invention is directed to above mentioned problem existing for current material, and it is an object of the invention to provide one kind to be free of Sb3+And it can inhale
Receive the perovskite-like material and its preparation, analysis method of most of visible spectrum.
In order to achieve the above object, the invention provides a kind of semi-conducting material containing bismuth and halogen, it is characterised in that
Its chemical formula is Cs3Bi2BrxI9-x, wherein, x=1-6.85.
Further, the semi-conducting material containing bismuth and halogen has quasi-calcium titanium ore crystal structure, and space group is
P-3m1。
Present invention also offers the preparation method of the above-mentioned semi-conducting material containing bismuth and halogen, it is characterised in that bag
Include:By Cs3Bi2Br9And Cs3Bi2I9Mix according to a certain percentage, heating response obtains Cs3Bi2BrxI9-x;Or will contain Cs,
The reactant of Bi and I elements reacts with hydrobromic acid, crystallisation by cooling, obtains Cs3Bi2BrxI9-x。
Preferably, the reactant containing Cs, Bi and I element is CsBr and BiI3。
Preferably, the reactant containing Cs, Bi and I element is CsI and Bi2O3。
Preferably, the reactant containing Cs, Bi and I element is Cs3Bi2I9。
Preferably, the mol ratio of Cs elements and Bi elements is 3: 2 in described reactant.
Preferably, described Cs3Bi2Br9And Cs3Bi2I9Mol ratio be x: 9-x, x=1-6.85.
It is preferably, described that " heating response obtains Cs3Bi2BrxI9-x" in heating-up temperature be 550-640 DEG C, during heating
Between be 2 hours.
It is highly preferred that described, " heating response obtains Cs3Bi2BrxI9-x" in reaction carry out under nitrogen protection.
Preferably, the reaction temperature described in described " reacting the reactant containing Cs, Bi and I element and hydrobromic acid "
For 75 DEG C.
Present invention also offers the analysis method of the above-mentioned semi-conducting material containing bismuth and halogen, it is characterised in that bag
Include:By Cs3Bi2BrxI9-xSolution to be measured is configured to, uses AgNO3Solution carries out constant-current titration, by during potential break twice
AgNO3The consumption or titration time of solution, calculate the absolute or relative amount of Br and I in sample.
Preferably, the compound method of described solution to be measured includes:Grind Cs3Bi2BrxI9-xSample simultaneously adds phosphoric acid,diluted and stirred
Mix, add deionized water and supporting electrolyte solution, obtain solution to be measured.
It is highly preferred that described supporting electrolyte solution is NaNO3Solution.
It is highly preferred that the concentration of described phosphoric acid,diluted is 1% (mass ratio).
Preferably, described constant-current titration uses constant flow pump.
It is highly preferred that described constant flow pump is syringe pump or peristaltic pump.
Preferably, described AgNO3The consumption of solution is AgNO3The consumption volume of solution, if during first time potential break
AgNO3AgNO when the consumption volume of solution and second of potential break3The consumption volume integral of solution Wei not V1And V2, pass through
Calculation formula:X=9 (1-V1/V2) calculate Cs3Bi2BrxI9-xThe x values of sample, and then obtain the relative of Br and I in sample and contain
Amount.
Preferably, when carrying out described constant-current titration, described AgNO3Solution is at the uniform velocity added dropwise, if first time current potential is dashed forward
Titration time during titration time and second of potential break during jump is respectively t1And t2, pass through calculation formula:X=9 (1-
t1/t2) calculate Cs3Bi2BrxI9-xThe x values of sample, and then obtain the relative amount of Br and I in sample.
Preferably, when titration process closes on potential break, AgNO is added dropwise in first pause3Solution & stir, then recover drop
Add.
Compared with prior art, the beneficial effects of the invention are as follows:
1st, formula of the invention is Cs3Bi2BrxI9-xSemi-conducting material, there is adjustable direct band gap energy, in this hair
Minimum is adjustable to 1.99eV in bright embodiment, less than current material Cs3Bi2Br9Or Cs3Bi2I9Band-gap energy, can absorb
Broader wave-length coverage in visible spectrum, and be free of Sb3+, moisture-stable.
2nd, formula of the invention is Cs3Bi2BrxI9-xSemi-conducting material preparation method, from the raw material that is easy to get, reaction
Mild condition, product characteristicses are stably and controllable, are adapted to large-scale production.
3rd, formula of the invention is Cs3Bi2BrxI9-xSemi-conducting material analysis method, using Continuous potentiometric titration, lead to
Cross AgNO when measuring potential break twice3The ratio between consumption can directly calculate the x values in sample.This analysis method need not
Accurate weighing solid prepares solution, also without cumbersome sample separation or enriching step, compared with prior art more fast,
It is easy and accurate.
Brief description of the drawings
Fig. 1:Cs3Bi2BrxI9-xSingle crystal X-ray diffraction crystal structure.
Fig. 2:Cs3Bi2BrxI9-xThe diffusing reflection spectrum of series of samples, x values corresponding to from (a) to (g) are followed successively by 1,3,0,
4.8th, 6,6.85 and 9.
Fig. 3:Cs3Bi2Br4I5The transmission spectrum of monocrystalline.
Fig. 4:Cs3Bi2Br3I6(a) potential-time curve and (b) current potential of Continuous potentiometric titration are led to the single order of time
Number.
Fig. 5:Cs3Bi2Br3I6X-ray diffractogram of powder and refine result.(a) curve is experiment spectrogram in figure, and (b) is bent
Line is fitting spectrogram, and each short vertical line in middle part is fitting peak position, and bottom fine rule is experiment and the difference of fitting data.
Fig. 6:Cs3Bi2BrI8X-ray diffractogram of powder and refine result, legend it is identical with Fig. 5.
Fig. 7:Cs3Bi2Br6I3X-ray diffractogram of powder and refine result, legend it is identical with Fig. 5.
Fig. 8:Cs3Bi2Br4.8I4.2X-ray diffractogram of powder and refine result, legend it is identical with Fig. 5.
Fig. 9:Cs3Bi2Br6.85I2.15X-ray diffractogram of powder and refine result, legend it is identical with Fig. 5.
Figure 10:Cs3Bi2I9X-ray diffractogram of powder and refine result, legend it is identical with Fig. 5.
Figure 11:Cs3Bi2Br9X-ray diffractogram of powder and refine result, legend it is identical with Fig. 5.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Initiation material:With reference to Aleshin, Russ.J.Inorg.Chem., 1978,23,1713-1716, by bismuth and iodine list
Directly reaction obtains grey black BiI to matter in vacuum sealing tube3Flat crystal.With reference to Chabot, Acta Cryst.B, 1978,34,
645-648, by Bi2O3, CsX (X=Br, I) reacts in the 1M HX aqueous solution and obtains Cs3Bi2X9Crystal.
Embodiment 1:Cs3Bi2Br3I6
A kind of semi-conducting material containing bismuth and halogen, chemical formula Cs3Bi2Br3I6, there is quasi-calcium titanium ore crystal structure,
Space group is P-3m1, and its preparation method is:
The accurate Cs for weighing 588mg (0.300mmol)3Bi2I9With 230mg (0.150mmol) Cs3Bi2Br9Ground and mixed
Uniformly it is fitted into glass ampule, is evacuated to below 20Pa, sealed after being filled with the nitrogen of 1/3 atmospheric pressure, is added under nitrogen protection
Heat obtains reddish black solid in 6 hours to 640 DEG C of reactions.
It can be seen that diffusing reflection spectrum is as shown in curve b in Fig. 2, optical band gap Eg=2.07eV.
Powder xrd pattern is as shown in figure 5, structure cell refine result:Trigonal system, P-3m1 space groups (No.164), lattice parameterMolecule co-volumeThis structure cell refine result shows that this contains
There is the semi-conducting material of bismuth and halogen that there is crystal structure and Cs shown in Fig. 13Bi2BrxI9-xChemical formula formula.
The analysis method of the above-mentioned semi-conducting material containing bismuth and halogen is:
(1) by sample preparation into solution to be measured:
Grind 14.8mg Cs3Bi2BrxI9-xSample and add 10ml 1% (mass concentration) phosphoric acid,diluted stir 1 hour,
Make the halide ion in sample completely into the phosphoric acid solution in dilute phosphoric acid solution, having been dissolved sample.It is above-mentioned molten to measure 1ml
The phosphoric acid solution of sample has been solved, has added 10ml deionized waters and 0.5ml 5M NaNO3Supporting electrolyte solution, obtain to be measured
Solution.
(2) AgNO is used3Solution carries out constant-current titration, passes through AgNO during potential break twice3The titration time of solution, meter
Calculate the relative amount of Br and I in sample:
1mM AgNO are added dropwise with 8 μ l/s speed into this solution using syringe pump3Solution carries out constant-current titration, and uses
Silver electrode monitors the variation tendency of solution electrode potential in real time, obtains potential-time curve as shown in Figure 4.During by current potential pair
Between seek first derivative, titration time during potential break twice is obtained, if titration time during first time potential break and second
Titration time during potential break is respectively t1And t2, measure t1And t2Respectively 636 seconds and 957 seconds, pass through calculation formula:X=
9·(1-t1/t2) calculate Cs3Bi2BrxI9-xThe x values of sample are 3.02, i.e. Br: I content mol ratio is x: 9-x=3.02:
5.98。
Above analysis result explanation, the Cs that the present embodiment obtains3Bi2Br3I6The Cs obtained with comparative examples 13Bi2I9Phase
Than space group is different, and photo absorption performance is more preferable, is a kind of novel semiconductor material with structure-improved and performance.
Embodiment 2:Cs3Bi2BrI8
A kind of semi-conducting material containing bismuth and halogen, chemical formula Cs3Bi2BrI8, there is quasi-calcium titanium ore crystal structure,
Space group is P-3m1, and its preparation method is:
The accurate Cs for weighing 784mg (0.400mmol)3Bi2I9With 76.8mg (0.0500mmol) Cs3Bi2Br9Grinding is mixed
Conjunction is uniformly fitted into glass ampule, is evacuated to below 20Pa, is sealed after being filled with the nitrogen of 1/3 atmospheric pressure, under nitrogen protection
It is heated to 550 DEG C of reactions and obtains reddish black solid in 6 hours.
It can be seen that diffusing reflection spectrum is as shown in curve a in Fig. 2, optical band gap Eg=1.99eV.
Powder xrd pattern is as shown in fig. 6, structure cell refine result:Trigonal system, P-3m1 space groups (No.164), lattice parameterMolecule co-volumeThis structure cell refine result shows that this contains
There is the semi-conducting material of bismuth and halogen that there is crystal structure and Cs shown in Fig. 13Bi2BrxI9-xChemical formula formula.
The analysis method of the above-mentioned semi-conducting material containing bismuth and halogen is:
(1) by sample preparation into solution to be measured:
Grind 14.9mg Cs3Bi2BrxI9-xSample and add 10ml 1% (mass concentration) phosphoric acid,diluted stirring and dissolving 1 it is small
When, make the halide ion in sample completely into the phosphoric acid solution in dilute phosphoric acid solution, having been dissolved sample.Measure on 1ml
The phosphoric acid solution for having dissolved sample is stated, adds 10ml deionized waters and 0.5ml 5M NaNO3Supporting electrolyte solution, obtain
Solution to be measured.
(2) AgNO is used3Solution carries out constant-current titration, passes through AgNO during potential break twice3The consumption volume of solution, meter
Calculate the relative amount of Br and I in sample:
Using constant flow pump (syringe pump) into this solution with 8 μ l/s speed slowly, 1mM AgNO are at the uniform velocity added dropwise3Solution enters
Row constant-current titration, and the variation tendency of solution electrode potential is monitored using silver electrode in real time.When closing on hop, first pause is added dropwise
AgNO3Solution is simultaneously sufficiently stirred solution 5 minutes, then recovers to be added dropwise.Measure AgNO corresponding to potential break twice3Solution consumption
Volume, if consumption volume integral during consumption volume and second of potential break during first time potential break Wei not V1And V2, V1With
V2Respectively 6.59ml and 7.48ml, passes through calculation formula:X=9 (1-V1/V2) calculate Cs3Bi2BrxI9-xThe x values of sample
For 1.07, i.e. Br: I content mol ratio is x: 9-x=1.07: 7.93.
Above analysis result explanation, the Cs that the present embodiment obtains3Bi2BrI8The Cs obtained with comparative examples 13Bi2I9Phase
Than space group is different, and photo absorption performance is more preferable, is a kind of novel semiconductor material with structure-improved and performance.
Embodiment 3:Cs3Bi2Br6I3
A kind of semi-conducting material containing bismuth and halogen, chemical formula Cs3Bi2Br6I3, there is quasi-calcium titanium ore crystal structure,
Space group is P-3m1, and its preparation method is:
The accurate Cs for weighing 294mg (0.150mmol)3Bi2I9With 461mg (0.300mmol) Cs3Bi2Br9Ground and mixed
Uniformly it is fitted into glass ampule, is evacuated to below 20Pa, sealed after being filled with the nitrogen of 1/3 atmospheric pressure, is heated to 640 DEG C of reactions
Obtain Chinese red solid within 6 hours.
It can be seen that diffusing reflection spectrum is as shown in curve e in Fig. 2, optical band gap Eg=2.23eV.
Powder xrd pattern is as shown in fig. 7, structure cell refine result:Trigonal system, P-3m1 space groups (No.164), lattice parameterMolecule co-volumeThis structure cell refine result shows that this contains
There is the semi-conducting material of bismuth and halogen that there is crystal structure and Cs shown in Fig. 13Bi2BrxI9-xChemical formula formula.
Analyzed using the analysis method in embodiment 2, measure V1And V2Respectively 2.91ml and 8.64ml, is calculated
It is 5.97, Br: I content mol ratio x: 9-x 5.97: 3.03 to x values.
Embodiment 4:Cs3Bi2Br4.8I4.2
A kind of semi-conducting material containing bismuth and halogen, chemical formula Cs3Bi2Br4.8I4.2, there is quasi-calcium titanium ore crystal knot
Structure, space group P-3m1, its preparation method are:
CsBr+BiI3+HBr→Cs3Bi2Br4.8I4.2
(1) reactant containing Cs, Bi and I element and hydrobromic acid are reacted:
Precise 590mg (1.00mmol) BiI3Solid, in the 75 DEG C of 1M for being dissolved completely in 18ml HBr under stirring,
Then it will be added dropwise and reacted in 1M HBr solution that 1ml contains 319mg (1.50mmol) CsBr, separated out at once a large amount of red
Color little crystal grain.
(2) crystallisation by cooling:
2 hours natural cooling crystallizations are stood, after temperature is down to room temperature, are filtered under diminished pressure, are rinsed with deionized water, absolute ethyl alcohol
Afterwards, cerise hexagonal crystal is dried to obtain in atmosphere.
It can be seen that diffusing reflection spectrum is as shown in curve d in Fig. 2, optical band gap Eg=2.17eV.
Powder xrd pattern is as shown in figure 8, structure cell refine result:Trigonal system, P-3m1 space groups (No.164), lattice parameterMolecule co-volumeThis structure cell refine result shows that this contains
The semi-conducting material of bismuth and halogen has crystal structure and the Cs shown in Fig. 13Bi2BrxI9-xChemical formula formula.
Analyzed using the analysis method in embodiment 2, measure V1And V2Respectively 3.78ml and 8.10ml, is calculated
It is 4.80 to x values, obtains Br: I content mol ratio x: 9-x 4.80: 4.20.
Embodiment 5:Cs3Bi2Br6.85I2.15
A kind of semi-conducting material containing bismuth and halogen, chemical formula Cs3Bi2Br6.85I2.15, there is quasi-calcium titanium ore crystal
Structure, space group P-3m1, its preparation method are:
CsI+Bi2O3+HBr→Cs3Bi2Br6.85I2.15
(1) reactant containing Cs, Bi and I element and hydrobromic acid are reacted:
Precise 233mg (0.500mmol) Bi2O3Solid, 18ml 1M is dissolved completely under stirring at 75 DEG C
HBr, it then will be added dropwise and reacted in 1M HBr solution that 1ml contains 390mg (1.50mmol) CsI, separated out at once big
Measure crocus little crystal grain.
(2) crystallisation by cooling:
2 hours natural cooling crystallizations are stood, after temperature is down to room temperature, are filtered under diminished pressure, are rushed with deionized water, absolute ethyl alcohol
After washing, crocus hexagonal crystal is dried to obtain in atmosphere.
It can be seen that diffusing reflection spectrum is as shown in curve f in Fig. 2, optical band gap Eg=2.30eV.
Powder xrd pattern is as shown in figure 9, structure cell refine result:Trigonal system, P-3m1 space groups (No.164), lattice parameterMolecule co-volumeThis structure cell refine result shows that this contains
There is the semi-conducting material of bismuth and halogen that there is crystal structure and Cs shown in Fig. 13Bi2BrxI9-xChemical formula formula.
Analyzed using the analysis method in embodiment 2, measure V1And V2Respectively 2.00ml and 8.38ml, is calculated
It is 6.85 to x values, obtains Br: I content mol ratio x: 9-x 6.85: 2.15.
Embodiment 6:Cs3Bi2Br4I5Monocrystalline
A kind of semi-conducting material containing bismuth and halogen, chemical formula Cs3Bi2Br4I5, there is quasi-calcium titanium ore crystal structure,
Space group is P-3m1, and its preparation method is:
Cs3Bi2I9+HBr→Cs3Bi2Br4I5+HI
(1) reactant containing Cs, Bi and I element and hydrobromic acid are reacted:By 194mg Cs3Bi2I9Adding 6ml's
1M HBr solution and being completely dissolved in 75 DEG C is reacted;
(2) crystallisation by cooling:With 1 DEG C per hour of speed crystallisation by cooling, 30 DEG C are reduced to temperature, it is 0.5- to obtain width
1mm hexagon peony monocrystalline.
Transmission spectrum is as shown in figure 3, optical band gap Eg=2.03eV.
Monocrystalline XRD structures are as shown in figure 1, trigonal system, P-3m1 space groups (No.164), cell parameter areMolecule co-volumeThis structure elucidation result shows that this contains
The semi-conducting material for having bismuth and halogen has Cs3Bi2BrxI9-xChemical formula formula.
Analyzed using the analysis method in embodiment 2, measure V1And V2Respectively 4.68ml and 8.38ml, is calculated
It is 4.14 to x values, obtains Br: I content mol ratio x: 9-x 3.97: 5.03.
Comparative examples 1:Cs3Bi2I9
With reference to Chabot, Acta Cryst.B, 1978,34,645-648, by Bi2O3, CsI reacts in the 1M HI aqueous solution
Obtain red sheet Cs3Bi2I9Crystal.
Powder xrd pattern is as shown in Figure 10, structure cell refine result:Trigonal system, P63/ mmc space groups (No.194), lattice
ParameterMolecule co-volumeIt can be seen that diffusing reflection spectrum such as Fig. 2
Shown in middle curve c, optical band gap Eg=2.08eV.
Comparative examples 2:Cs3Bi2Br9
With reference to Chabot, Acta Cryst.B, 1978,34,645-648, by Bi2O3, CsBr it is anti-in the 1M HBr aqueous solution
Glassy yellow sheet Cs should be obtained3Bi2Br9Crystal.
Powder xrd pattern is as shown in figure 11, structure cell refine result:Trigonal system, P-3m1 space groups (No.164), lattice ginseng
NumberMolecule co-volumeIt is it can be seen that bent in diffusing reflection spectrum such as Fig. 2
Shown in line g, optical band gap Eg=2.61eV.
Claims (6)
1. a kind of semi-conducting material containing bismuth and halogen, it is characterised in that its chemical formula is Cs3Bi2Br x I9–x , wherein,x =
1–6.85。
2. the semi-conducting material containing bismuth and halogen as claimed in claim 1, it is characterised in that described contains bismuth and halogen
Semi-conducting material there is quasi-calcium titanium ore crystal structure, space group isP−3m1。
3. the preparation method of the semi-conducting material containing bismuth and halogen described in claim 1 or 2, it is characterised in that including:Will
Cs3Bi2Br9And Cs3Bi2I9Mix according to a certain percentage, heating response obtains Cs3Bi2Br x I9–x ;Or Cs, Bi and I will be contained
The reactant of element reacts with hydrobromic acid, crystallisation by cooling, obtains Cs3Bi2Br x I9–x 。
4. the preparation method of the semi-conducting material as claimed in claim 3 containing bismuth and halogen, it is characterised in that described contains
The reactant for having Cs, Bi and I element is CsBr and BiI3。
5. the preparation method of the semi-conducting material as claimed in claim 3 containing bismuth and halogen, it is characterised in that described contains
The reactant for having Cs, Bi and I element is CsI and Bi2O3。
6. the preparation method of the semi-conducting material as claimed in claim 3 containing bismuth and halogen, it is characterised in that described contains
The reactant for having Cs, Bi and I element is Cs3Bi2I9。
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