CN106277040A - Tin ash microsphere that a kind of crystallite dimension is controlled and preparation method and application - Google Patents
Tin ash microsphere that a kind of crystallite dimension is controlled and preparation method and application Download PDFInfo
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- CN106277040A CN106277040A CN201610695746.8A CN201610695746A CN106277040A CN 106277040 A CN106277040 A CN 106277040A CN 201610695746 A CN201610695746 A CN 201610695746A CN 106277040 A CN106277040 A CN 106277040A
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- microsphere
- tin ash
- crystallite dimension
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- 239000004005 microsphere Substances 0.000 title claims abstract description 106
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 230000004044 response Effects 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 25
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 18
- 238000013019 agitation Methods 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 11
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- 239000001119 stannous chloride Substances 0.000 claims description 7
- 235000011150 stannous chloride Nutrition 0.000 claims description 7
- 229910001432 tin ion Inorganic materials 0.000 claims description 6
- 239000011941 photocatalyst Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000033228 biological regulation Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- 238000005119 centrifugation Methods 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000008187 granular material Substances 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- -1 energy gap is 3.6eV Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- SFXJSNATBHJIDS-UHFFFAOYSA-N disodium;dioxido(oxo)tin;trihydrate Chemical compound O.O.O.[Na+].[Na+].[O-][Sn]([O-])=O SFXJSNATBHJIDS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000000877 morphologic effect Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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Abstract
The present invention relates to controlled tin ash microsphere of a kind of crystallite dimension and preparation method and application, this tin ash microsphere is formed by the tin ash crystallite self assembly that crystallinity is good, the crystallite dimension of tin ash crystallite is adjustable in the range of 5 30nm, a diameter of 200 400nm, specific surface area ＞ 40m of tin ash microsphere2/g；During preparation, in the normal propyl alcohol mixed solution with water, it is sequentially added into concentrated hydrochloric acid, Xi Yuan, forms clear homogeneous solution；Carry out solvent thermal reaction；After question response terminates, taking out precipitation, washing separates,.Compared with prior art, present invention process route is easy, it is not necessary to surfactant, uses one-step method to can be prepared by even size distribution, by the multilevel hierarchy SnO of nano microcrystalline self assembly2Microsphere, and SnO can be regulated and controled by alcohol/water ratio in regulation reaction system2The size of crystallite, microsphere possesses the characteristic of specific area and submicrometer scale, has wide practical use in solaode, lithium ion battery and photocatalysis field.
Description
Technical field
The invention belongs to inorganic advanced technical field of nanometer material preparation, relate to the tin ash that a kind of crystallite dimension is controlled
Microsphere and preparation method and application.
Background technology
SnO2Being a kind of broad-band gap n-type semiconductor, energy gap is 3.6eV, and chemical stability is good, electron transfer energy
Power is fast, and has high visible light transmissivity, novel solar battery, lithium ion battery, gas sensor, electrically conducting transparent with
And photocatalysis field has wide application prospect, therefore, the tin dioxide nanometer material tool of synthesis size, pattern, structure-controllable
Significant.
Grain size is a few nanometer or the SnO of tens nanometers2Granule has high specific surface area and more avtive spot,
Therefore, its more physics and chemical characteristic can be given.But, there is a lot of problem in small-size grains: example when reality is applied
As, little crystal grain is easily reunited, and reduces its reactivity；The size of little crystal grain is much smaller than visible wavelength, uses it for the sun
The capture of sunlight it is unfavorable for during energy battery light anode material；For the material of (sub-) micron-scale, nano-scale
Little crystal grain is not easy to reclaim；Little granule dense accumulation, is unfavorable for the infiltration of ion, electrolyte solution or other reaction systems.Closely
Research over Nian shows, prepares the SnO of multilevel hierarchy2Microsphere can expand SnO significantly2The range of nano material.Multilevel hierarchy
SnO2Microsphere is by SnO2Nano-crystalline granule self assembly gathering forms, and it remains SnO2The advantage of nano-particle high-specific surface area, with
Time be also equipped with easily the reclaiming of micronsize material, the advantage of high light scattering, additionally the hole of multilevel hierarchy microsphere is by nanocrystalline
Grain stacking obtains, usually mesopore size, contributes to the abundant infiltration of electrolyte.Therefore, synthesis multilevel hierarchy SnO2Microsphere has
There is significant application value, especially the cyclical stability of the photoelectric transformation efficiency and lithium ion battery that improve solaode is had weight
Want meaning.
Xiongwen Lou et al. with crystallization stannous chloride as Xi Yuan, sodium hydroxide as alkali source, add carbamide as pattern
Adjusting control agent, the multilevel hierarchy microsphere that solvent-thermal process is assembled by tin oxide nano sheet, this microsphere is used for lithium-ion electric
Specific capacity that Chi Shiyou is higher and the biggest electric current density, it is most important to the formation of microsphere, instead that they also find that carbamide adds
Answer the microsphere (J.Phys.Chem.C 2011,115,24605 that then cannot obtain size uniform in thing without carbamide
24610).Peining Zhu et al. use crystallization stannic chloride be Xi Yuan, lithium salts as pore creating material, synthesized Jie by molten-salt growth method
Hole multilevel hierarchy SnO2Microsphere, had both possessed high surface absorbing dye sub-micro meter ruler simultaneously after DSSC
The very little light scattering ability that improve battery, but the Microsphere Size that this high temperature solid-state method obtains is the most uneven, can be also in microsphere
Can residual impurity (Chem.Commun., 2012,48,10865 10867).Yu-Fen Wang et al. uses crystallization stannous chloride
For Xi Yuan, with ethylenediamine for Morphological control agent, synthesize mesoporous multilevel hierarchy SnO by combination of ultrasound solvent thermal two step2Microsphere,
But the Microsphere Size that this method obtains is relatively big (about 2.2 microns), and Microsphere Size uneven (J.Power Sources,
2015,280,476–482).Guanglu Shang et al. with stannous sulfate as Xi Yuan, solvent-thermal process multilevel hierarchy SnO2
Microsphere, but Microsphere Size distribution is the most uneven, and diameter Distribution is wider, from 100 to 800nm, in addition as microsphere group substantially
The nano-crystalline granule crystallinity becoming unit is not the most preferable (J.Phys.Chem.C 2012,116,20140-20145).
More than research shows, multilevel hierarchy SnO2Microsphere has wide practical use, but the most good method
The SnO of synthesis even size distribution (single dispersing or quasi-single dispersing)2Microsphere, additionally as constituting the nanocrystalline of microsphere elementary cell
The size of granule regulates and controls also few people and mentions that actually this is to affect the long-pending key component with active site of microsphere surface.Cause
This, be highly desirable to develop a kind of easy wet-chemical that need not extra additive (such as pore creating material, Morphological control agent)
Method synthesizes the SnO of even size distribution2Microsphere.
Authorization Notice No. is that the Chinese invention patent of CN102060321B discloses a kind of tin ash self-assembled nanometer knot
The preparation method of structure microsphere, the method step: a. is 1:2-1:3 sodium stannate trihydrate by mol ratio and surfactant joins second
Alcohol is with the mixed solvent of water, and in mixed solvent, ethanol and water volume ratio are 1:3.5-3:1；It is subsequently adding ethanolamine, ethanolamine
Addition is every 1mmol sodium stannate trihydrate 2-5ml ethanolamine；B. the Glass rod of the solvent solute mixing in step a is stirred,
To finely dispersed mixed solution；C. by step b gained mixed solution 140-200 DEG C of temperature hydro-thermal 1-48h in reactor, instead
Room temperature should be naturally cooled to after terminating；D. by step c gained precipitation water and dehydrated alcohol centrifuge washing, tin ash
Self-assembled nano structures microsphere.Compared with above-mentioned patented technology, preparation method of the present invention need not use surfactant, and
The size of the tin ash microsphere prepared is more uniform.
Summary of the invention
Defect that the purpose of the present invention is contemplated to overcome above-mentioned prior art to exist and a kind of dispersibility and crystallization are provided
Property good, photoelectric properties are excellent, have controlled tin ash microsphere of the crystallite dimension of bigger serface and preparation method thereof with
Application.
The purpose of the present invention can be achieved through the following technical solutions:
The tin ash microsphere that a kind of crystallite dimension is controlled, this tin ash microsphere is micro-by the tin ash that crystallinity is good
Brilliant self assembly forms, and the crystallite dimension of described tin ash crystallite is adjustable in the range of 5-30nm, and described tin ash is micro-
A diameter of 200-400nm of ball, specific surface area ＞ 40m2/g。
The preparation method of the tin ash microsphere that a kind of crystallite dimension is controlled, the method comprises the following steps:
(1) under agitation, in the normal propyl alcohol mixed solution with water, it is sequentially added into concentrated hydrochloric acid, Xi Yuan, is formed transparent
Homogeneous phase solution；
(2) clear homogeneous solution addition reactor step (1) prepared carries out solvent thermal reaction；
(3) after question response terminates, taking out precipitation, washing separates, i.e. prepares the tin ash microsphere that crystallite dimension is controlled.
Normal propyl alcohol described in step (1) is 0-20% with the volume fraction of water in the mixed solution of water
Normal propyl alcohol described in step (1) and the mixed solution of water are 100:2-5 with the volume ratio of concentrated hydrochloric acid.
Xi Yuan described in step (1) includes one or both in stannous chloride or stannous chloride dihydrate.
In described clear homogeneous solution, the molar concentration of tin ion is 0.01-0.06mol/L.
The filling rate of the reactor described in step (2) is 50-80%.
The temperature of the solvent thermal reaction described in step (2) is 160-250 DEG C, and the response time is 12-18h.
The application of the tin ash microsphere that a kind of crystallite dimension is controlled, described tin ash microsphere is used for preparing pure dioxy
Change tinbase DSSC, lithium ion battery or photocatalyst.
The present invention use stannous chloride be Xi Yuan, normal propyl alcohol and water mixed system as reaction dissolvent, size can be obtained
The SnO distributed very evenly2Microsphere, and the size of nano microcrystalline can be regulated by the ratio changing normal propyl alcohol and water.
Common stannous chloride easily fast hydrolyzing in neutral or alkaline pure water solution, obtains the most uneven white of distribution of sizes
Amorphous SnO2Precipitation；It addition, divalent tin ion hydrolysis easily forms lamellar structure SnO, further by O2Oxidation obtains lamella knot
The SnO of structure2, therefore, it is readily obtained lamellar structure product with Bivalent Tin for Xi Yuan.The present invention, mainly with normal propyl alcohol as solvent, drops
Low divalent tin ion hydrolysis rate, so the overall transparent state of precursor solution, the addition of the most a small amount of concentrated hydrochloric acid also rises
Arrive the effect of suppression hydrolysis.During follow-up solvent thermal, tin ion can separate out uniformly from solution, such that it is able to
Homogeneous nucleation, finally gives the microsphere of size uniform.The regulation and control of alcohol/water ratio can change tin ion nucleating growth speed, water
Ratio improve, SnO can be promoted2The nucleating growth of crystallite, thus the SnO that size is bigger can be obtained2Crystallite.
Compared with prior art, present invention process route is easy, it is not necessary to surfactant, uses one-step method the most available
Distribution of sizes is highly uniform, by the multilevel hierarchy SnO of nano microcrystalline self assembly2Microsphere, and can be by regulation reaction system
Middle alcohol/water ratio regulates and controls SnO2The size of crystallite, microsphere is provided simultaneously with the characteristic of specific area and submicrometer scale, too
Sun energy battery, lithium ion battery and photocatalysis field have wide application prospects, and have the following characteristics that
(1) preparation technology is simple: the present invention use wet chemistry method simple, efficient synthesized distribution of sizes highly uniform,
By the multilevel hierarchy SnO of nano microcrystalline self assembly2Microsphere, process route is easy, and energy consumption is low, and product yield is high；
(2) crystallite dimension is controlled: the present invention can regulate and control SnO by alcohol/water ratio in regulation reaction system2The one-tenth of crystallite
Nucleus growth, thus flexible can prepare the SnO of diverse microcosmic structure2Microsphere；
(3) with low cost: compared with previous methods, the present invention can need not surfactant or other additives
Under the conditions of prepare the more preferable SnO of performance2Microsphere, this not only lowers cost, also provides a kind of new preparation method；
(4) excellent product performance: the SnO of present invention synthesis2The specific surface area of microsphere is more than 40 square metres every gram, higher than often
Rule block materials, additionally, the tin ash microsphere dispersibility of synthesis is good with crystallinity, photoelectric properties are excellent, quick for dyestuff
The photoelectric transformation efficiency of 4.2% is obtained after changing solaode.
Accompanying drawing explanation
Fig. 1 is the field emission scanning electron microscope figure of the tin ash microsphere of embodiment 1 preparation；
Fig. 2 is the field emission scanning electron microscope figure of the tin ash microsphere of embodiment 2 preparation；
Fig. 3 is the field emission scanning electron microscope figure of the tin ash microsphere of embodiment 3 preparation；
Fig. 4 is the field emission scanning electron microscope figure of the tin ash microsphere of embodiment 4 preparation；
Fig. 5 is the XRD figure spectrum of tin ash microsphere prepared by embodiment 1～4 (a～d in corresponding diagram respectively)；
Fig. 6 is the field emission scanning electron microscope figure of the tin ash microsphere of embodiment 5 preparation；
Fig. 7 is the transmission electron microscope picture of the tin ash microsphere of embodiment 5 preparation；
Fig. 8 is the field emission scanning electron microscope figure of the tin ash microsphere of embodiment 6 preparation；
Fig. 9 is the transmission electron microscope picture of the tin ash microsphere of embodiment 6 preparation；
Figure 10 is the isothermal nitrogen adsorption desorption curve of the tin ash microsphere of embodiment 7 preparation；
Figure 11 is the current-voltage curve of DSSC prepared by tin ash microsphere in embodiment 7.
Detailed description of the invention
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
Measure 50 milliliters of normal propyl alcohols, under the conditions of magnetic agitation, be sequentially added into 1.5 milliliters of concentrated hydrochloric acid and 0.4513 gram of two water
Stannous chloride, forms transparent homogeneous phase solution；Above-mentioned clear solution is transferred to carry out in reactor solvent thermal reaction, reactor
Filling rate be 60%, reaction temperature controls at 200 DEG C, and the response time is 12 hours；Question response takes out precipitation, with pure after terminating
Water cyclic washing, centrifugation.
Fig. 1 is the field emission scanning electron microscope figure of tin ash microsphere of embodiment 1 preparation, it can be seen that microsphere from figure
Dispersibility is preferable, even size distribution, a diameter of 200～300 nanometers of single microsphere；Also may be used from the scanning electron microscope (SEM) photograph of high power
To see that microsphere is to be assembled by little crystal grain to form, the crystallite dimension of crystallite about 10 nanometer.
Embodiment 2
By 2.5 milliliters of pure water and 47.5 milliliters of normal propyl alcohol mixing, under the conditions of magnetic agitation, it is sequentially added into 1.5 milliliters of dense salt
Acid and 0.4513 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Transfer to above-mentioned clear solution reactor is carried out
Solvent thermal reaction, the filling rate of reactor is 60%, and reaction temperature controls at 200 DEG C, and the response time is 12 hours；Question response is tied
Precipitation is taken out, with pure water cyclic washing, centrifugation after bundle.
Fig. 2 is the field emission scanning electron microscope figure of tin ash microsphere of embodiment 2 preparation, it can be seen that microsphere from figure
Dispersibility is preferable, even size distribution, a diameter of 200～300 nanometers of single microsphere；Also may be used from the scanning electron microscope (SEM) photograph of high power
To see that microsphere is to be assembled by little crystal grain to form, the crystallite dimension of crystallite about 15 nanometer.
Embodiment 3
By 5 milliliters of pure water and the mixing of 45 milliliters of normal propyl alcohols, be sequentially added under the conditions of magnetic agitation 1.5 milliliters of concentrated hydrochloric acid and
0.4513 gram of stannous chloride dihydrate, forms transparent homogeneous phase solution；Above-mentioned clear solution is transferred to carry out in reactor solvent
Thermal response, the filling rate of reactor is 60%, and reaction temperature controls at 200 DEG C, and the response time is 12 hours；After question response terminates
Take out precipitation, with pure water cyclic washing, centrifugation.
Fig. 3 is the field emission scanning electron microscope figure of tin ash microsphere of embodiment 3 preparation, it can be seen that microsphere from figure
Dispersibility is preferable, and size is highly uniform, a diameter of 250 nanometers of single microsphere.
Embodiment 4
By 7.5 milliliters of pure water and 42.5 milliliters of normal propyl alcohol mixing, under the conditions of magnetic agitation, it is sequentially added into 1.5 milliliters of dense salt
Acid and 0.4513 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Transfer to above-mentioned clear solution reactor is carried out
Solvent thermal reaction, the filling rate of reactor is 60%, and reaction temperature controls at 200 DEG C, and the response time is 12 hours；Question response is tied
Precipitation is taken out, with pure water cyclic washing, centrifugation after bundle.
Fig. 4 is the field emission scanning electron microscope figure of tin ash microsphere of embodiment 4 preparation, it can be seen that microsphere from figure
Dispersibility is preferable, and size is highly uniform, a diameter of 300～400 nanometers of single microsphere.
Fig. 5 is the XRD figure spectrum of tin ash microsphere prepared by embodiment 1～4 (a～d in corresponding diagram respectively), from collection of illustrative plates
It can be seen that all of diffraction maximum all with Rutile Type SnO2(JCPDS No.41-1445) standard card is consistent, and does not has other miscellaneous
Peak, illustrates that the product obtained is pure SnO2.Additionally, the diffraction maximum of all microspheres all has widthization phenomenon, the crystalline substance of stannum oxide is described
Particle size is less, can illustrate that microsphere is to be formed by nanocrystalline little particle aggregation further.Scherrer formula is utilized to calculate SnO2Micro-
Brilliant crystallite dimension, respectively 10.0 nanometers, 11.8 nanometers, 14.5 nanometers, 15.4 nanometers, it appeared that constitute the SnO of microsphere2
The size of crystallite is being gradually increased, consistent with scanning electron microscopic observation result.So the present invention can easily by regulation alcohol/
Water ratio regulates and controls the size of crystallite, and the ratio of water is the highest, and the size of crystallite is the biggest.
Embodiment 5
Measure 50 milliliters of normal propyl alcohols, under the conditions of magnetic agitation, be sequentially added into 1.5 milliliters of concentrated hydrochloric acid and 0.225 gram of two water chlorine
Change stannous, form transparent homogeneous phase solution；Transfer to above-mentioned clear solution reactor carries out solvent thermal reaction, reactor
Filling rate is 60%, and reaction temperature controls at 200 DEG C, and the response time is 12 hours；Question response takes out precipitation after terminating, and uses pure water
Cyclic washing, centrifugation.
Fig. 6 is the field emission scanning electron microscope figure of tin ash microsphere of embodiment 5 preparation, it can be seen that microsphere from figure
Dispersibility is preferable, even size distribution, a diameter of 200～300 nanometers of single microsphere.
Fig. 7 is the transmission electron microscope picture of tin ash microsphere of embodiment 5 preparation, from figure it is apparent that microsphere be by
Nano-crystalline granule gathering forms, the size of single crystal grain about 10 nanometer.
Embodiment 6
By 2.5 milliliters of pure water and 47.5 milliliters of normal propyl alcohol mixing, under the conditions of magnetic agitation, it is sequentially added into 1.5 milliliters of dense salt
Acid and 0.225 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Transfer to reactor is carried out molten by above-mentioned clear solution
Agent thermal response, the filling rate of reactor is 60%, and reaction temperature controls at 200 DEG C, and the response time is 12 hours；Question response terminates
Rear taking-up is precipitated, with pure water cyclic washing, centrifugation.
Fig. 8 is the field emission scanning electron microscope figure of tin ash microsphere of embodiment 6 preparation, it can be seen that microsphere from figure
Dispersibility is preferable, even size distribution, a diameter of 200～300 nanometers of single microsphere.
Fig. 9 is the transmission electron microscope picture of tin ash microsphere of embodiment 6 preparation, from figure it is apparent that microsphere be by
Nano-crystalline granule gathering forms, the size of single crystal grain about 15 nanometer.
In conjunction with the embodiments 5 and 6, it appeared that the size of crystallite improves with the ratio of water in reaction system and becomes big.
Embodiment 7
By 2.5 milliliters of pure water and 47.5 milliliters of normal propyl alcohol mixing, under the conditions of magnetic agitation, it is sequentially added into 1.5 milliliters of dense salt
Acid and 0.4513 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Transfer to above-mentioned clear solution reactor is carried out
Solvent thermal reaction, the filling rate of reactor is 80%, and reaction temperature controls at 180 DEG C, and the response time is 15 hours；Question response is tied
Precipitation is taken out, with pure water cyclic washing, centrifugation after bundle.
Figure 10 is the SnO that embodiment 7 prepares2The isothermal nitrogen adsorption desorption curve of microsphere, test result shows microsphere
Specific surface area be 43 square metres every gram, aperture size is about 9 nanometers, so the SnO that the present invention obtains2Microsphere is typical Jie
Hole multilevel structure material.
By the SnO in the present embodiment2Microsphere makes pure tin dioxide DSSC, the light of test battery
Electrical property, the current-voltage curve of battery as shown in figure 11: battery short circuit electric current density reaches 12.2 milliamperes every square centimeter, electricity
Pond efficiency reaches 4.2%；The battery efficiency that this efficiency is prepared higher than conventional tin oxide nano particles, fully demonstrates in the present invention
SnO2Advantage in terms of the dye adsorption and light capture that the good crystallinity of microsphere, high-specific surface area and light scattering effect bring,
Indicate its broad prospect of application.
Embodiment 8
By 10 milliliters of pure water and 40 milliliters of normal propyl alcohol mixing, under the conditions of magnetic agitation, it is sequentially added into 2.5 milliliters of concentrated hydrochloric acid
With 0.113 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Above-mentioned clear solution is transferred to carry out in reactor solvent
Thermal response, the filling rate of reactor is 50%, and reaction temperature controls at 250 DEG C, and the response time is 18 hours；After question response terminates
Take out precipitation, with pure water cyclic washing, centrifugation.
Embodiment 9
By 10 milliliters of pure water and 20 milliliters of normal propyl alcohols and 20 milliliters of n-butyl alcohol mixing, it is sequentially added under the conditions of magnetic agitation
2.5 milliliters of concentrated hydrochloric acid and 0.113 gram of stannous chloride dihydrate, form transparent homogeneous phase solution；Above-mentioned clear solution is transferred to instead
Answering and carry out solvent thermal reaction in still, the filling rate of reactor is 50%, and reaction temperature controls at 240 DEG C, and the response time is 12 little
Time；Question response takes out precipitation, with pure water cyclic washing, centrifugation after terminating.
The above-mentioned description to embodiment is to be understood that for ease of those skilled in the art and use invention.
These embodiments obviously easily can be made various amendment by person skilled in the art, and described herein typically
Principle is applied in other embodiments without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel should be the present invention's according to the announcement of the present invention, the improvement made without departing from scope and amendment
Within protection domain.
Claims (9)
1. the tin ash microsphere that a crystallite dimension is controlled, it is characterised in that this tin ash microsphere is good by crystallinity
Tin ash crystallite self assembly forms, and the crystallite dimension of described tin ash crystallite is adjustable in the range of 5-30nm, described
A diameter of 200-400nm of tin ash microsphere, specific surface area ＞ 40m2/g。
The preparation method of the tin ash microsphere that a kind of crystallite dimension the most as claimed in claim 1 is controlled, it is characterised in that should
Method comprises the following steps:
(1) under agitation, in the normal propyl alcohol mixed solution with water, it is sequentially added into concentrated hydrochloric acid, Xi Yuan, forms clear homogeneous
Solution；
(2) clear homogeneous solution addition reactor step (1) prepared carries out solvent thermal reaction；
(3) after question response terminates, taking out precipitation, washing separates, i.e. prepares the tin ash microsphere that crystallite dimension is controlled.
The preparation method of the tin ash microsphere that a kind of crystallite dimension the most according to claim 2 is controlled, it is characterised in that
Normal propyl alcohol described in step (1) is 0-20% with the volume fraction of water in the mixed solution of water.
The preparation method of the tin ash microsphere that a kind of crystallite dimension the most according to claim 2 is controlled, it is characterised in that
Normal propyl alcohol described in step (1) and the mixed solution of water are 100:2-5 with the volume ratio of concentrated hydrochloric acid.
The preparation method of the tin ash microsphere that a kind of crystallite dimension the most according to claim 2 is controlled, it is characterised in that
Xi Yuan described in step (1) includes one or both in stannous chloride or stannous chloride dihydrate.
The preparation method of the tin ash microsphere that a kind of crystallite dimension the most according to claim 5 is controlled, it is characterised in that
In described clear homogeneous solution, the molar concentration of tin ion is 0.01-0.06mol/L.
The preparation method of the tin ash microsphere that a kind of crystallite dimension the most according to claim 2 is controlled, it is characterised in that
The filling rate of the reactor described in step (2) is 50-80%.
The preparation method of the tin ash microsphere that a kind of crystallite dimension the most according to claim 2 is controlled, it is characterised in that
The temperature of the solvent thermal reaction described in step (2) is 160-250 DEG C, and the response time is 12-18h.
The application of the tin ash microsphere that a kind of crystallite dimension the most as claimed in claim 1 is controlled, it is characterised in that described
Tin ash microsphere is used for preparing pure tin dioxide DSSC, lithium ion battery or photocatalyst.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336332A (en) * | 2018-01-22 | 2018-07-27 | 山西大学 | A kind of tin dioxide powder and preparation method thereof |
| CN109682867A (en) * | 2019-01-23 | 2019-04-26 | 陕西科技大学 | A kind of micron order tin dioxide gas-sensitive material and its preparation method and application |
| CN110828187A (en) * | 2019-11-19 | 2020-02-21 | 南昌航空大学 | Preparation method of large-particle zinc oxide and mesoporous tin oxide double-layer photo-anode |
| CN115475634A (en) * | 2022-09-21 | 2022-12-16 | 上海市农业科学院 | Preparation method of core-shell structure photocatalyst for reducing carbon dioxide emission in environment |
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| CN105271374A (en) * | 2015-11-21 | 2016-01-27 | 河南师范大学 | Preparation method of stannic oxide microspheres of oriented connection microstructure |
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| CN105271374A (en) * | 2015-11-21 | 2016-01-27 | 河南师范大学 | Preparation method of stannic oxide microspheres of oriented connection microstructure |
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| D. SOLĹS-CASADOS ET AL.: ""Characterization and Photocatalytic Performance of Tin Oxide"", 《IND. ENG. CHEM. RES.》 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336332A (en) * | 2018-01-22 | 2018-07-27 | 山西大学 | A kind of tin dioxide powder and preparation method thereof |
| CN108336332B (en) * | 2018-01-22 | 2020-08-04 | 山西大学 | Tin dioxide powder material and preparation method thereof |
| CN109682867A (en) * | 2019-01-23 | 2019-04-26 | 陕西科技大学 | A kind of micron order tin dioxide gas-sensitive material and its preparation method and application |
| CN110828187A (en) * | 2019-11-19 | 2020-02-21 | 南昌航空大学 | Preparation method of large-particle zinc oxide and mesoporous tin oxide double-layer photo-anode |
| CN115475634A (en) * | 2022-09-21 | 2022-12-16 | 上海市农业科学院 | Preparation method of core-shell structure photocatalyst for reducing carbon dioxide emission in environment |
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