CN106082329A - A kind of containing bismuth and the semi-conducting material of halogen and preparation thereof and the method for analysis - Google Patents
A kind of containing bismuth and the semi-conducting material of halogen and preparation thereof and the method for analysis Download PDFInfo
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- CN106082329A CN106082329A CN201610407141.4A CN201610407141A CN106082329A CN 106082329 A CN106082329 A CN 106082329A CN 201610407141 A CN201610407141 A CN 201610407141A CN 106082329 A CN106082329 A CN 106082329A
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 47
- 239000004065 semiconductor Substances 0.000 title claims abstract description 40
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 34
- 150000002367 halogens Chemical class 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000004458 analytical method Methods 0.000 title claims abstract description 20
- 238000005658 halogenation reaction Methods 0.000 title abstract description 4
- 238000000034 method Methods 0.000 title description 6
- 239000000126 substance Substances 0.000 claims abstract description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 239000013078 crystal Substances 0.000 claims description 22
- 238000004448 titration Methods 0.000 claims description 20
- 229910052740 iodine Inorganic materials 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 13
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 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
- 101710134784 Agnoprotein Proteins 0.000 claims description 9
- 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
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000001429 visible spectrum Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 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
- 238000000985 reflectance 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 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 241000276573 Cottidae Species 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000003115 supporting electrolyte Substances 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
- 239000011521 glass Substances 0.000 description 3
- 239000011941 photocatalyst Substances 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
- 238000004364 calculation method Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 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
- 238000001914 filtration Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000736199 Paeonia Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000009191 jumping Effects 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
- 239000000203 mixture 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
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing 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 containing bismuth and the semi-conducting material of halogen and preparation thereof and analysis method.Described containing bismuth and the semi-conducting material of 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, it is possible to absorb broader wave-length coverage in visible spectrum.
Description
Technical field
The invention belongs to new material, relate to a class and contain bismuth and the semi-conducting material of halogen and preparation thereof and analysis method,
Being specifically related to chemical formula formula is Cs3Bi2BrxI9-xThe new material of (wherein x=1-6.85) and preparation thereof and the method for analysis.
Background technology
Currently, along with energy crisis and problem of environmental pollution become increasingly conspicuous, search out a kind of clean energy resource and substitute traditional
The stone energy is extremely the most urgent.Hydrogen Energy is owing to its calorific value is high, lightweight, pollution-free, can store the plurality of advantages such as transport, and hydrogen is simultaneously
One of element the abundantest on the earth, Hydrogen Energy is considered as to be hopeful most to substitute the clean energy resource of traditional fossil energy.Traditional
Hydrogen Energy obtains mode and is mainly water electrolysis hydrogen production and fossil fuel hydrogen manufacturing, and water electrolysis hydrogen production can consume substantial amounts of electric energy, and mineral fire
Material hydrogen manufacturing can produce CO2Cause secondary pollution, and photocatalytic hydrogen production by water decomposition utilizes inexhaustible, nexhaustible solar energy to divide
Xie Shui produces hydrogen, and reaction condition is gentle, simple to operate, pollution-free, has huge DEVELOPMENT PROSPECT.
Utilize decomposing water with solar energy to produce the key exploitation at photocatalyst of hydrogen, and weigh the quality of photocatalyst,
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, can resist photoetch (Abe, J.Photochem.Photobiol.C, 2010,11,179-209).Therefore,
Searching out that a kind of band structure is suitable and the photocatalyst of stable performance, the popularization and application for photocatalytic hydrogen production by water decomposition are anticipated
Justice is great.
At present, formula is A3M2X9(A is alkali metal ion, and M is Bi3+Or Sb3+Ion, X is halide ion) seriation
Compound mainly with study its structure with become mutually main (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) have studied Cs3Sb2I9And Cs3Bi2I9In solar cell side
The application in face.But, at known A3M2X9In type compound, containing Sb3+Material hydrolabil, Cs3Bi2Br9For bright orange
Color only absorbs the blue light in visible ray, and Cs3Bi2I9At room temperature by the Bi isolated2I9 3-Ion forms, and does not have perovskite-like
Structure.These existing materials are not the most the catalyst materials of preferable photolysis water hydrogen.
Summary of the invention
The present invention is directed to the problems referred to above that current material exists, it is an object of the invention to provide a class without Sb3+, and can inhale
Receive perovskite-like material and preparation, the analysis method of major part visible spectrum.
In order to achieve the above object, the invention provides a kind of containing bismuth with the semi-conducting material of halogen, it is characterised in that
Its chemical formula is Cs3Bi2BrxI9-x, wherein, x=1-6.85.
Further, the described semi-conducting material containing bismuth and halogen has quasi-calcium titanium ore crystal structure, and space group is
P-3m1。
Present invention also offers above-mentioned containing bismuth and the preparation method of the semi-conducting material of halogen, it is characterised in that bag
Include: by Cs3Bi2Br9And Cs3Bi2I9Mixing according to a certain percentage, reacting by heating obtains Cs3Bi2BrxI9-x；Or, will containing Cs,
The reactant of Bi and I element reacts with hydrobromic acid, and crystallisation by cooling obtains Cs3Bi2BrxI9-x。
Preferably, the described reactant containing Cs, Bi and I element is CsBr and BiI3。
Preferably, the described reactant containing Cs, Bi and I element is CsI and Bi2O3。
Preferably, the described reactant containing Cs, Bi and I element is Cs3Bi2I9。
Preferably, in described reactant, Cs element is 3: 2 with the mol ratio of Bi element.
Preferably, described Cs3Bi2Br9And Cs3Bi2I9Mol ratio be x: 9-x, x=1-6.85.
It is preferably, described that " reacting by heating obtains Cs3Bi2BrxI9-xHeating-up temperature in " is 550-640 DEG C, during heating
Between be 2 hours.
It is highly preferred that described, " reacting by heating obtains Cs3Bi2BrxI9-xReaction in " is carried out under nitrogen protection.
Preferably, the described reaction temperature described in " by reacting with hydrobromic acid containing the reactant of Cs, Bi and I element "
It it is 75 DEG C.
Present invention also offers the above-mentioned analysis method containing bismuth and the semi-conducting material of halogen, it is characterised in that bag
Include: by Cs3Bi2BrxI9-xIt is configured to solution to be measured, uses AgNO3Solution carries out constant-current titration, by during twice potential break
AgNO3The consumption of solution or titration time, calculate the absolute or relative amount of Br Yu I in sample.
Preferably, the compound method of described solution to be measured includes: grind Cs3Bi2BrxI9-xSample also adds phosphoric acid,diluted and stirs
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 time potential break3The consumer of solution is long-pending is respectively V1And V2, pass through
Computing formula: x=9 (1-V1/V2) calculate Cs3Bi2BrxI9-xThe x value of sample, and then obtain the relative of Br with I in sample and contain
Amount.
Preferably, when carrying out described constant-current titration, described AgNO3Solution at the uniform velocity drips, if current potential is dashed forward for the first time
Titration time when titration time when jumping and second time potential break is respectively t1And t2, pass through computing formula: x=9 (1-
t1/t2) calculate Cs3Bi2BrxI9-xThe x value of sample, and then obtain the relative amount of Br Yu I in sample.
Preferably, when titration process closes on potential break, first suspend dropping AgNO3Solution & stir, recovers to drip subsequently
Add.
Compared with prior art, the invention has the beneficial effects as follows:
1, the formula of the present invention is Cs3Bi2BrxI9-xSemi-conducting material, there is adjustable direct band gap energy, at this
In bright embodiment, minimum is adjustable to 1.99eV, less than current material Cs3Bi2Br9Or Cs3Bi2I9Band-gap energy, it is possible to absorb
Broader wave-length coverage in visible spectrum, and without Sb3+, moisture-stable.
2, the formula of the present invention is Cs3Bi2BrxI9-xThe preparation method of semi-conducting material, from the raw material that is easy to get, reaction
Mild condition, product characteristics is stablized controlled, is suitable for large-scale production.
3, the formula of the present invention is Cs3Bi2BrxI9-xThe analysis method of semi-conducting material, use Continuous potentiometric titration, logical
Cross AgNO when measuring twice potential break3The ratio of consumption can directly calculate the x value in sample.This analyze method without
Accurate weighing solid or preparation solution, do not have loaded down with trivial details sample to separate or enriching step yet, the most quick,
Easy and accurate.
Accompanying drawing explanation
Fig. 1: Cs3Bi2BrxI9-xSingle crystal X-ray diffraction crystal structure.
Fig. 2: Cs3Bi2BrxI9-xThe diffuse-reflectance spectrum of series of samples, be followed successively by 1 from the x value that (a) to (g) is corresponding, 3,0,
4.8,6,6.85 and 9.
Fig. 3: Cs3Bi2Br4I5The transmission spectrum of monocrystalline.
Fig. 4: Cs3Bi2Br3I6The single order of time is led by (a) potential-time curve and (b) current potential of Continuous potentiometric titration
Number.
Fig. 5: Cs3Bi2Br3I6X-ray diffractogram of powder and refine result.In figure, (a) curve is experiment spectrogram, and (b) is bent
Line is matching spectrogram, and each short vertical line of middle part is matching peak position, and bottom fine rule is the difference of experiment and fitting data.
Fig. 6: Cs3Bi2BrI8X-ray diffractogram of powder and refine result, legend is identical with Fig. 5.
Fig. 7: Cs3Bi2Br6I3X-ray diffractogram of powder and refine result, legend is identical with Fig. 5.
Fig. 8: Cs3Bi2Br4.8I4.2X-ray diffractogram of powder and refine result, legend is identical with Fig. 5.
Fig. 9: Cs3Bi2Br6.85I2.15X-ray diffractogram of powder and refine result, legend is identical with Fig. 5.
Figure 10: Cs3Bi2I9X-ray diffractogram of powder and refine result, legend is identical with Fig. 5.
Figure 11: Cs3Bi2Br9X-ray diffractogram of powder and refine result, legend is identical with Fig. 5.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, people in the art
The present invention can be made various changes or modifications by member, and these equivalent form of values fall within the application appended claims equally and limited
Scope.
Initiation material: reference Aleshin, Russ.J.Inorg.Chem., 1978,23,1713-1716, by bismuth and iodine list
Matter direct reaction in vacuum sealing tube obtains grey black BiI3Flat crystal.Reference Chabot, Acta Cryst.B, 1978,34,
645-648, by Bi2O3, CsX (X=Br, I) reacts in 1M HX aqueous solution and obtains Cs3Bi2X9Crystal.
Embodiment 1:Cs3Bi2Br3I6
A kind of containing bismuth with the semi-conducting material of halogen, chemical formula is Cs3Bi2Br3I6, there is quasi-calcium titanium ore crystal structure,
Space group is P-3m1, and its preparation method is:
Accurately weigh the Cs of 588mg (0.300mmol)3Bi2I9Cs with 230mg (0.150mmol)3Bi2Br9Ground and mixed
Uniformly load in glass ampule, be evacuated to below 20Pa, be filled with sealing by fusing after the nitrogen of 1/3 atmospheric pressure, add under nitrogen protection
Heat obtains reddish black solid in 6 hours to 640 DEG C of reactions.
Visible diffuse-reflectance spectrum as shown in curve b in Fig. 2, optical band gap Eg=2.07eV.
Powder xrd pattern is as it is shown in figure 5, structure cell refine result: trigonal system, P-3m1 space group (No.164), lattice parameterMolecular formula volumeThis structure cell refine result shows that this contains
The semi-conducting material having bismuth and halogen has the crystal structure shown in Fig. 1 and Cs3Bi2BrxI9-xChemical formula formula.
The above-mentioned analysis method containing bismuth and the semi-conducting material of halogen is:
(1) sample preparation is become solution to be measured:
Grind the Cs of 14.8mg3Bi2BrxI9-xSample and add 10ml 1% (mass concentration) phosphoric acid,diluted stir 1 hour,
Make the halide ion in sample completely in dilute phosphoric acid solution, obtain having dissolved the phosphoric acid solution of sample.Measure 1ml above-mentioned molten
Solve the phosphoric acid solution of sample, add 10ml deionized water and the 5M NaNO of 0.5ml3Supporting electrolyte solution, obtains to be measured
Solution.
(2) AgNO is used3Solution carries out constant-current titration, by AgNO during twice potential break3The titration time of solution, meter
The relative amount of Br Yu I in calculation sample:
The syringe pump speed with 8 μ l/s in this solution is used to drip 1mM AgNO3Solution carries out constant-current titration, and uses
The variation tendency of solution electrode electromotive force monitored in real time by silver electrode, obtains potential-time curve as shown in Figure 4.During by current potential pair
Between seek first derivative, obtain titration time during twice potential break, if for the first time potential break time titration time and second time
Titration time during potential break is respectively t1And t2, record t1And t2It is respectively 636 seconds and 957 seconds, passes through computing formula: x=
9·(1-t1/t2) calculate Cs3Bi2BrxI9-xThe x value of sample is 3.02, and i.e. Br: I content mol ratio is x: 9-x=3.02:
5.98。
Above analysis result illustrates, the Cs that the present embodiment obtains3Bi2Br3I6The Cs obtained with comparative examples 13Bi2I9Phase
Ratio, 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 containing bismuth with the semi-conducting material of halogen, chemical formula is Cs3Bi2BrI8, there is quasi-calcium titanium ore crystal structure,
Space group is P-3m1, and its preparation method is:
Accurately weigh the Cs of 784mg (0.400mmol)3Bi2I9Cs with 76.8mg (0.0500mmol)3Bi2Br9Grind mixed
Close and uniformly load in glass ampule, be evacuated to below 20Pa, be filled with sealing by fusing after 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.
Visible diffuse-reflectance spectrum as shown in curve a in Fig. 2, optical band gap Eg=1.99eV.
Powder xrd pattern as shown in Figure 6, structure cell refine result: trigonal system, P-3m1 space group (No.164), lattice parameterMolecular formula volumeThis structure cell refine result shows that this contains
The semi-conducting material having bismuth and halogen has the crystal structure shown in Fig. 1 and Cs3Bi2BrxI9-xChemical formula formula.
The above-mentioned analysis method containing bismuth and the semi-conducting material of halogen is:
(1) sample preparation is become solution to be measured:
Grind the Cs of 14.9mg3Bi2BrxI9-xSample to add 1% (mass concentration) phosphoric acid,diluted stirring and dissolving 1 of 10ml little
Time, make the halide ion in sample completely in dilute phosphoric acid solution, obtain having dissolved the phosphoric acid solution of sample.Measure on 1ml
State the phosphoric acid solution having dissolved sample, add 10ml deionized water and the 5M NaNO of 0.5ml3Supporting electrolyte solution, obtains
Solution to be measured.
(2) AgNO is used3Solution carries out constant-current titration, by AgNO during twice potential break3The consumption volume of solution, meter
The relative amount of Br Yu I in calculation sample:
The constant flow pump (syringe pump) speed with 8 μ l/s in this solution is used slowly, at the uniform velocity to drip 1mM AgNO3Solution enters
Row constant-current titration, and use silver electrode to monitor the variation tendency of solution electrode electromotive force in real time.When closing on hop, first suspend dropping
AgNO3Solution is also sufficiently stirred for solution 5 minutes, recovers dropping subsequently.Record twice AgNO corresponding to potential break3Solution consumption
Volume, if consumer when consuming volume and second time potential break during first time potential break amasss respectively V1And V2, V1With
V2It is respectively 6.59ml and 7.48ml, passes through computing formula: x=9 (1-V1/V2) calculate Cs3Bi2BrxI9-xThe x value of sample
Being 1.07, i.e. Br: I content mol ratio is x: 9-x=1.07: 7.93.
Above analysis result illustrates, the Cs that the present embodiment obtains3Bi2BrI8The Cs obtained with comparative examples 13Bi2I9Phase
Ratio, 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 containing bismuth with the semi-conducting material of halogen, chemical formula is Cs3Bi2Br6I3, there is quasi-calcium titanium ore crystal structure,
Space group is P-3m1, and its preparation method is:
Accurately weigh the Cs of 294mg (0.150mmol)3Bi2I9Cs with 461mg (0.300mmol)3Bi2Br9Ground and mixed
Uniformly load in glass ampule, be evacuated to below 20Pa, be filled with sealing by fusing after the nitrogen of 1/3 atmospheric pressure, be heated to 640 DEG C of reactions
Within 6 hours, obtain Chinese red solid.
Visible diffuse-reflectance spectrum as shown in curve e in Fig. 2, optical band gap Eg=2.23eV.
Powder xrd pattern is as it is shown in fig. 7, structure cell refine result: trigonal system, P-3m1 space group (No.164), lattice parameterMolecular formula volumeThis structure cell refine result shows that this contains
The semi-conducting material having bismuth and halogen has the crystal structure shown in Fig. 1 and Cs3Bi2BrxI9-xChemical formula formula.
Use the analysis method in embodiment 2 to be analyzed, record V1And V2It is respectively 2.91ml and 8.64ml, calculates
To x value be 5.97, Br: I content mol ratio x: 9-x be 5.97: 3.03.
Embodiment 4:Cs3Bi2Br4.8I4.2
A kind of containing bismuth with the semi-conducting material of halogen, chemical formula is Cs3Bi2Br4.8I4.2, there is quasi-calcium titanium ore crystal knot
Structure, space group is P-3m1, and its preparation method is:
CsBr+BiI3+HBr→Cs3Bi2Br4.8I4.2
(1) will react with hydrobromic acid containing the reactant of Cs, Bi and I element:
The BiI of precise 590mg (1.00mmol)3Solid, is dissolved completely in the 1M HBr of 18ml at 75 DEG C under stirring,
Then 1ml is contained in the 1M HBr solution of 319mg (1.50mmol) CsBr and be added dropwise over reacting, separate out the reddest at once
The little crystal grain of color.
(2) crystallisation by cooling:
Stand 2 hours natural cooling crystallization, after temperature is down to room temperature, filtration under diminished pressure, rinse with deionized water, dehydrated alcohol
After, it is dried to obtain cerise hexagonal crystal in atmosphere.
Visible diffuse-reflectance spectrum as shown in curve d in Fig. 2, optical band gap Eg=2.17eV.
Powder xrd pattern as shown in Figure 8, structure cell refine result: trigonal system, P-3m1 space group (No.164), lattice parameterMolecular formula volumeThis structure cell refine result shows that this contains
The semi-conducting material of bismuth and halogen has the crystal structure shown in Fig. 1 and Cs3Bi2BrxI9-xChemical formula formula.
Use the analysis method in embodiment 2 to be analyzed, record V1And V2It is respectively 3.78ml and 8.10ml, calculates
Being 4.80 to x value, obtaining Br: I content mol ratio x: 9-x is 4.80: 4.20.
Embodiment 5:Cs3Bi2Br6.85I2.15
A kind of containing bismuth with the semi-conducting material of halogen, chemical formula is Cs3Bi2Br6.85I2.15, there is quasi-calcium titanium ore crystal
Structure, space group is P-3m1, and its preparation method is:
CsI+Bi2O3+HBr→Cs3Bi2Br6.85I2.15
(1) will react with hydrobromic acid containing the reactant of Cs, Bi and I element:
The Bi of precise 233mg (0.500mmol)2O3Solid, is dissolved completely in the 1M of 18ml at 75 DEG C under stirring
HBr, then contains 1ml in the 1M HBr solution of 390mg (1.50mmol) CsI and is added dropwise over reacting, and separates out big at once
The amount little crystal grain of crocus.
(2) crystallisation by cooling:
Stand 2 hours natural cooling crystallization, after temperature is down to room temperature, filtration under diminished pressure, with deionized water, dehydrated alcohol punching
After washing, it is dried to obtain crocus hexagonal crystal in atmosphere.
Visible diffuse-reflectance spectrum as shown in curve f in Fig. 2, optical band gap Eg=2.30eV.
Powder xrd pattern is as it is shown in figure 9, structure cell refine result: trigonal system, P-3m1 space group (No.164), lattice parameterMolecular formula volumeThis structure cell refine result shows that this contains
The semi-conducting material having bismuth and halogen has the crystal structure shown in Fig. 1 and Cs3Bi2BrxI9-xChemical formula formula.
Use the analysis method in embodiment 2 to be analyzed, record V1And V2It is respectively 2.00ml and 8.38ml, calculates
Being 6.85 to x value, obtaining Br: I content mol ratio x: 9-x is 6.85: 2.15.
Embodiment 6:Cs3Bi2Br4I5Monocrystalline
A kind of containing bismuth with the semi-conducting material of halogen, chemical formula is Cs3Bi2Br4I5, there is quasi-calcium titanium ore crystal structure,
Space group is P-3m1, and its preparation method is:
Cs3Bi2I9+HBr→Cs3Bi2Br4I5+HI
(1) will react with hydrobromic acid containing the reactant of Cs, Bi and I element: by the Cs of 194mg3Bi2I9Adding 6ml's
1M HBr solution being completely dissolved in 75 DEG C reacts；
(2) crystallisation by cooling: with the speed crystallisation by cooling of per hour 1 DEG C, reduce to 30 DEG C to temperature, obtaining width is 0.5-
The hexagon peony monocrystalline of 1mm.
Transmission spectrum is as it is shown on figure 3, optical band gap Eg=2.03eV.
Monocrystalline XRD structure is as it is shown in figure 1, trigonal system, P-3m1 space group (No.164), and cell parameter isMolecular formula volumeThis structure elucidation result shows that this contains
The semi-conducting material having bismuth and halogen has Cs3Bi2BrxI9-xChemical formula formula.
Use the analysis method in embodiment 2 to be analyzed, record V1And V2It is respectively 4.68ml and 8.38ml, calculates
Being 4.14 to x value, obtaining Br: I content mol ratio x: 9-x is 3.97: 5.03.
Comparative examples 1:Cs3Bi2I9
Reference Chabot, Acta Cryst.B, 1978,34,645-648, by Bi2O3, CsI reacts in 1M HI aqueous solution
Obtain red lamellar Cs3Bi2I9Crystal.
Powder xrd pattern as shown in Figure 10, structure cell refine result: trigonal system, P63/ mmc space group (No.194), lattice
ParameterMolecular formula volumeVisible diffuse-reflectance spectrum such as Fig. 2
Shown in middle curve c, optical band gap Eg=2.08eV.
Comparative examples 2:Cs3Bi2Br9
Reference Chabot, Acta Cryst.B, 1978,34,645-648, by Bi2O3, CsBr anti-in 1M HBr aqueous solution
Glassy yellow lamellar Cs should be obtained3Bi2Br9Crystal.
Powder xrd pattern as shown in figure 11, structure cell refine result: trigonal system, P-3m1 space group (No.164), join by lattice
NumberMolecular formula volumeVisible diffuse-reflectance spectrum is as bent in Fig. 2
Shown in line g, optical band gap Eg=2.61eV.
Claims (10)
1. one kind contains bismuth and the semi-conducting material of halogen, it is characterised in that its chemical formula is Cs3Bi2BrxI9-x, wherein, x=
1-6.85。
2. as claimed in claim 1 containing bismuth and the semi-conducting material of halogen, it is characterised in that described containing bismuth and halogen
Semi-conducting material there is quasi-calcium titanium ore crystal structure, space group is P-3ml.
3. described in claim 1 or 2 containing bismuth and the preparation method of the semi-conducting material of halogen, it is characterised in that including: will
Cs3Bi2Br9And Cs3Bi2I9Mixing according to a certain percentage, reacting by heating obtains Cs3Bi2BrxI9-x；Or, will be containing Cs, Bi and I
The reactant of element reacts with hydrobromic acid, and crystallisation by cooling obtains Cs3Bi2BrxI9-x。
4. the preparation method of the semi-conducting material containing bismuth and halogen as claimed in claim 3, it is characterised in that described contains
The reactant having Cs, Bi and I element is CsBr and BiI3。
5. the preparation method of the semi-conducting material containing bismuth and halogen as claimed in claim 3, it is characterised in that described contains
The reactant having Cs, Bi and I element is CsI and Bi2O3。
6. the preparation method of the semi-conducting material containing bismuth and halogen as claimed in claim 3, it is characterised in that described contains
The reactant having Cs, Bi and I element is Cs3Bi2I9。
7. the analysis method containing bismuth and the semi-conducting material of halogen described in claim 1 or 2, it is characterised in that including: will
Cs3Bi2BrxI9-xIt is configured to solution to be measured, uses AgNO3Solution carries out constant-current titration, by AgNO during twice potential break3Molten
The consumption of liquid or titration time, calculate the absolute or relative amount of Br Yu I in sample.
8. the analysis method of the semi-conducting material containing bismuth and halogen as claimed in claim 7, it is characterised in that described treats
Survey solution and dissolved Cs by phosphoric acid,diluted3Bi2BrxI9-xSample obtains.
9. the analysis method of the semi-conducting material containing bismuth and halogen as claimed in claim 7, it is characterised in that described
AgNO3The consumption of solution is AgNO3The consumption volume of solution, if AgNO during first time potential break3The consumption volume of solution
With AgNO during second time potential break3The consumer of solution is long-pending is respectively V1And V2, pass through computing formula: x=9 (1-V1/
V2) calculate Cs3Bi2BrxI9-xThe x value of sample, and then obtain the relative amount of Br Yu I in sample.
10. the analysis method of the semi-conducting material containing bismuth and halogen as claimed in claim 7, it is characterised in that carrying out
During described constant-current titration, described AgNO3Solution at the uniform velocity drips, if titration time during first time potential break and second time
Titration time during potential break is respectively t1And t2, pass through computing formula: x=9 (1-t1/t2) calculate Cs3Bi2BrxI9-x
The x value of sample, and then obtain the relative amount of Br Yu I in sample.
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| CN109928426A (en) * | 2019-05-10 | 2019-06-25 | 江南大学 | A kind of nanocrystalline Rb of novel rubidium bismuth chlorine perovskite7Bi3Cl16And preparation method thereof |
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