CN106629824B - A kind of preparation method of graded hollow cubic tin oxide nano particles - Google Patents
A kind of preparation method of graded hollow cubic tin oxide nano particles Download PDFInfo
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- CN106629824B CN106629824B CN201611215406.7A CN201611215406A CN106629824B CN 106629824 B CN106629824 B CN 106629824B CN 201611215406 A CN201611215406 A CN 201611215406A CN 106629824 B CN106629824 B CN 106629824B
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- C01—INORGANIC CHEMISTRY
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- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The present invention is a kind of preparation method for the graded hollow cubic tin oxide nano particles being made up of superfine nanometer rods, belong to the technical field of nano material preparation, this method is using solid cubic zinc hydroxyl stannate as predecessor, hydro-thermal reaction through a period of time, hydroxyl stannate zinc surface covering one layer of nanometer tin dioxide rod of growth, decomposed simultaneously with internal hydroxyl groups zinc stannate, so as to obtain the graded hollow cubic tin oxide nano particles being made up of superfine nanometer rods similar with zinc hydroxyl stannate shape.The present invention is compared with conventional template method, with cost is low, step is few, simple operation and other advantages, and the hollow stannic oxide particle prepared has obvious graded structure and meso-hole structure, it is not easy to reunite, crystallinity is good, and specific surface area is big, and Debye length is closely sized to by the nanometer bar construction and nanometer rods of a large amount of ordered arrangements, good gas-sensitive property is shown, there is potential application value in gas sensor field.
Description
Technical field
The invention belongs to technical field prepared by nano material, and in particular to a kind of graduation being made up of superfine nanometer rods
The preparation method of hollow cube shape tin oxide nano particles, such graded hollow structure table in gas sensor field
Reveal excellent air-sensitive performance.
Background technology
The graded hollow structure nano material with varied pattern is in basic research and practical application in recent years
Field receives more and more attention.Its application includes medicament transport, catalysis, gas sensing, clean energy resource conversion, the energy
Storage etc..Now, the optimum way that preparing has good hollow-core construction, which is included on removable removing template, coats material requested, or according to
Different principle (chemical displacement method, Kinkendal Effect, soda acid etching etc.) is converted into through pre-formed granules.It is although existing a lot
The notable example of hollow-core construction is successfully prepared, but hollow process is generally complicated, need to be through multiple steps.Only based on Oswald that
Moral cures the hollow-core construction that not prepared hard template just can be simply prepared with seldom certain methods such as soft templates, but result is usual
All it is that hollow ball shape structure is in the majority.This respect is considered, explores new feasible method, it is better simply to prepare aspherical point
Grade hollow-core construction still has very high value.
Tin ash, as a kind of broad-band gap (Eg=3.6eV, at 300K) n-type semiconductor, there is high electrical conductivity
The stability become reconciled is current research most extensively and earliest applied to sensitive material in practice.And because tin ash exists
Absorptivity in visible-range is almost nil so transmitance is high, so being also widely used in optical field.And with
The development that nanometer technology is advanced by leaps and bounds, answering in terms of being confined to gas-sensitive property and battery incessantly is studied for tin ash
With.Such as in terms of Wave Guiding Optics, transistor, optical sensor, all there is very big application prospect in tin ash.And with dioxy
Change the widely studied of tin, including thermal evaporation, laser ablation method, solid-phase synthesis solwution method etc. are all employed for preparing titanium dioxide
Tin nanoparticles.2009, Xu et al. synthesized diameter 90nm tin ash using hydro-thermal method to crystallize sodium stannate as raw material
Hollow stannic oxide nanometer ball (Xu, the J.Q. of nanometer rods and diameter 120nm；Wang,D.；Qin, L.P.；Yu, W.J.；Pan,
Q.Y.Sens.Actuators,B 2009,137,490-495)；2010, Yin et al. was using stannous sulfate as raw material, hydro-thermal method
Hollow nano-sphere (Yin, the X.M. being made up of the wide 30nm of thick 6nm stannic oxide nanometer piece are synthesized；Li,C.C.；Zhang,
M.；Hao,Q.Y.；Liu,S.；Chen, L.B.；Wang, T.H.J.Phys.Chem.C 2010,114,8084-8088)；2014
Year, Liu et al., using sodium citrate assisting alcohol-hydrothermal method, has been synthesized by very thin titanium dioxide sijna using crystallizing stannous chloride as raw material
Nano flower (Liu Yang, Jiao Yang, Zhang Zhenglin, Qu Fengyu, Ahmad Uar, the and Wu of rice piece composition
Xiang, ACS Appl.Mater.Interfaces 2014,6,2174-2184).But above hydrothermal synthesis method all fails
Prepare graduate aspherical hollow nanostructured tin oxide nano particles.
The content of the invention
The technical problem to be solved in the present invention is, compared to spherical structure, due to lacking aspherical template, and to need tediously long
Preparation process and adjoint high cost, and in these highly difficult reasons of template higher curvature marginal growth designing material, it is non-
The preparation of spherical tin ash is still difficult.Difficult to solve this, some new self-template methods have successfully been prepared more
The aspherical stannic oxide particle of kind.It is rarely found orderly and this kind of particle is generally reunited and formed at random by the nano crystal of 0 dimension
Monodimension nano stick, component units as two-dimensional nano piece.But this kind of nanometer rods or piece form hollow knot as construction unit
Structure has the characteristics of uniqueness, such as controllable appearance, the anisotropy possessed by exposed crystal face and in order porous.Therefore carry
For it is a kind of it is simple to operate, product structure is excellent, the low graded hollow cubic being made up of superfine nanometer rods of production cost
The preparation method of tin oxide nano particles.
The concrete technical scheme that the present invention takes is as follows：
A kind of preparation method of graded hollow cubic tin oxide nano particles, including step in detail below：
The first step, the solution for including solid cubic hydroxyl stannate zinc nanoparticles is prepared, using coprecipitation in room
Temperature is lower to be mixed comprising zinc source, tin source, alkali, the aqueous solution of surface protectant；
Second step, above-mentioned solution is moved into hydrothermal reaction kettle, is put into constant temperature convection oven, and set baking oven constant temperature temperature
Degree；
3rd step, hydro-thermal reaction for a period of time after, directly generate the graded hollow cube being made up of superfine nanometer rods
Shape tin oxide nano particles.
The first step, it is described prepare comprising solid cubic hydroxyl stannate zinc nanoparticles solution the step of be：Room temperature
Under, the aqueous solution containing ZnO, NaOH, CTAB is configured first, and its concentration is respectively the ZnO of 0.003~0.01 mol/L；；
The CTAB of 0.02~0.04 mol/L；The NaOH of 0.2~0.4 mol/L；
The aqueous solution containing SnCl4 is reconfigured at, its concentration is 0.1~0.3 mol/L, SnCl4 solution is added dropwise to above-mentioned
The aqueous solution containing ZnO, NaOH, CTAB, a period of time is stood after being sufficiently stirred.
Second and third step, is moved into a 50ml hydrothermal reaction kettles, 160- after mixed solution obtained by the first step is sufficiently stirred
210 DEG C of hydro-thermal reaction 8-15h；Gained precipitation uses deionized water, absolute ethyl alcohol eccentric cleaning each 3 times respectively after reaction is terminated,
6500 revs/min of centrifugation 3-5 minutes, last 60 DEG C of drying obtain the graded hollow cubic two being made up of superfine nanometer rods
Tin oxide nanoparticles.
The aqueous solution of the configuration containing SnCl4：With deionized water dissolving ZnO, NaOH, CTAB, it is sufficiently stirred.
With deionized water dissolving SnCl4, after the aqueous solution containing ZnO, NaOH, CTAB is added dropwise in SnCl4 solution, fill
A period of time is stood after dividing stirring.
The time being sufficiently stirred is 5min.
It is described be sufficiently stirred 10min after stand 24h.
The present invention has following benefit：
1st, the excellent tin oxide nano particles of composite structure, the hollow graded structure being made up of monodimension nano stick, no
Easily reunite, anisotropy, there is large specific surface area and higher chemism, there are a large amount of faces to contact between particle, air-sensitive performance is excellent
It is different.
2nd, cost is low, and test use is Experiment of General Chemistry medicine, cheap.
3rd, it is simple to operate, one pot of process, it is not necessary to separate predecessor, it is not necessary to template.
Brief description of the drawings
Fig. 1 is the graded hollow cubic stannic oxide nanometer being made up of monodimension nano stick prepared by embodiment 1
The stereoscan photograph figure of particle.
Fig. 2 is the graded hollow cubic stannic oxide nanometer being made up of monodimension nano stick prepared by embodiment 1
The transmission electron microscope photo figure of particle.
Fig. 3 is the graded hollow cubic stannic oxide nanometer being made up of monodimension nano stick prepared by embodiment 1
The X-ray diffractogram of particle.
Fig. 4 is the graded hollow cubic stannic oxide nanometer being made up of monodimension nano stick prepared by embodiment 1
The sensitivity map of particle and hollow ball-shape tin oxide nano particles in contrast to n-butanol gas.
The graded hollow cubic tin oxide nano particles that Fig. 5 is made up of nanometer sheet and nanometer rods mixing are swept
Trace designs piece.
Fig. 6 mixes the saturating of the graded hollow cubic tin oxide nano particles formed by nanometer sheet and nanometer rods
Penetrate scanned picture.
Embodiment
A kind of preparation method for the graded hollow cubic tin oxide nano particles being made up of superfine nanometer rods, step
Suddenly have：The aqueous solution containing ZnO, NaOH, CTAB is configured first, and its concentration is respectively the ZnO of 0.005 mol/L；0.03 rubs
You/liter CTAB；The NaOH of 0.24 mol/L.The aqueous solution containing SnCl4 is reconfigured at, its concentration is 0.12 mol/L.Will
Above-mentioned SnCl4 solution is added dropwise to the above-mentioned aqueous solution containing ZnO, NaOH, CTAB, and a period of time is stood after being sufficiently stirred.Afterwards will
Above-mentioned mixed solution is moved into after being sufficiently stirred in a 50ml hydrothermal reaction kettles, 180 DEG C of hydro-thermal reaction 12h.Reaction is terminated into rear institute
It must precipitate respectively with deionized water, absolute ethyl alcohol eccentric cleaning each 3 times (6500 revs/min centrifuge 3 minutes).Last 60 DEG C of drying
Obtain the graded hollow cubic tin oxide nano particles being made up of superfine nanometer rods.It is separately that above-mentioned mixed solution is abundant
Moved into after stirring in a 50ml hydrothermal reaction kettles, 200 DEG C of hydro-thermal reaction 12h.By reaction terminate after gained precipitation spend respectively from
Sub- water, absolute ethyl alcohol eccentric cleaning each 3 times (6500 revs/min centrifuge 3 minutes).Last 60 DEG C of drying obtain by nanometer sheet and received
The graded hollow cubic tin oxide nano particles of rice rod composition.
The operating procedure of the present invention is broadly divided into three phases：The first step includes solid cubic hydroxyl stannate to prepare
The solution of zinc nanoparticles, mixed at room temperature using coprecipitation comprising zinc source, tin source, alkali, surface protectant water
Solution obtains；Second step, above-mentioned solution is moved into hydrothermal reaction kettle, is put into constant temperature convection oven, and set baking oven constant temperature temperature
Degree；3rd step, hydro-thermal reaction for a period of time after, directly generate the graded hollow cubic dioxy being made up of superfine nanometer rods
Change tin nanoparticles.
Embodiment 1：
17mg ZnO, 240mg NaOH, 292mg CTAB and 210mg SnCl is weighed respectively4, gone afterwards with 25mL
Ionized water dissolves ZnO, and NaOH, CTAB are sufficiently stirred 5min, then with 5ml deionized water dissolvings SnCl4, after by SnCl4 solution by
The aqueous solution containing ZnO, NaOH, CTAB is added dropwise to, 24h is stood after being sufficiently stirred 10min, after solution then is stirred into 5min again
Move into hydrothermal reaction kettle, 180 DEG C of hydro-thermal reaction 12h.Reaction uses deionized water and absolute ethyl alcohol eccentric cleaning each three after terminating
Precipitation is dried for 60 DEG C in air atmosphere after secondary, the graded hollow cubic dioxy for collecting to be made up of superfine nanometer rods
Change tin nanoparticles, its scanned picture is shown in accompanying drawing 1, and transmission scan picture is shown in accompanying drawing 2.
The graded hollow cubic tin oxide nano particles being made up of monodimension nano stick prepared by embodiment 1
X-ray diffractogram is shown in accompanying drawing 3, it can be seen that sample prepared by embodiment 1 comprises only a kind of material of tin ash and with good
Good crystallinity, corresponding PDF standard cards are JCPDS 41-1445.To the graded hollow being made up of monodimension nano stick
Cubic tin oxide nano particles are tested for the air-sensitive ability of n-butanol gas, and test result is shown in Fig. 4.It can see
Going out, the hollow-core construction stannic oxide nanometer flower particle being made up of monodimension nano stick is excellent for the air-sensitive performance of n-butanol gas,
And better than the hollow ball-shape stannic oxide particle being made up of zero-dimension nano particle.
Embodiment 2：
17mg ZnO, 240mg NaOH, 292mg CTAB and 210mg SnCl is weighed respectively4, gone afterwards with 25mL
Ionized water dissolves ZnO, and NaOH, CTAB are sufficiently stirred 5min, then with 5ml deionized water dissolvings SnCl4, after by SnCl4 solution by
The aqueous solution containing ZnO, NaOH, CTAB is added dropwise to, 24h is stood after being sufficiently stirred 10min, after solution then is stirred into 5min again
Move into hydrothermal reaction kettle, 200 DEG C of hydro-thermal reaction 12h.Reaction uses deionized water and absolute ethyl alcohol eccentric cleaning each three after terminating
Precipitation is dried for 60 DEG C in air atmosphere after secondary, collects and obtains being stood by the graded hollow that nanometer sheet and nanometer rods mixing form
Cube shape tin oxide nano particles, its scanned picture are shown in accompanying drawing 5, and transmission scan picture is shown in accompanying drawing 6.
Claims (5)
1. a kind of preparation method of graded hollow cubic tin oxide nano particles, it is characterised in that including following tool
Body step：
The first step, the solution for including solid cubic hydroxyl stannate zinc nanoparticles is prepared, using coprecipitation at room temperature
Mix comprising zinc source, tin source, alkali, the aqueous solution of surface protectant；
Second step, above-mentioned solution is moved into hydrothermal reaction kettle, is put into constant temperature convection oven, and set baking oven thermostat temperature；
3rd step, hydro-thermal reaction for a period of time after, directly generate the graded hollow cubic two being made up of superfine nanometer rods
Tin oxide nanoparticles；
It is described prepare comprising solid cubic hydroxyl stannate zinc nanoparticles solution the step of be：At room temperature, configure first
The aqueous solution containing ZnO, NaOH, CTAB, its concentration are respectively the ZnO of 0.003~0.01 mol/L；0.02~0.04 mole/
The CTAB risen；The NaOH of 0.2~0.4 mol/L；
Be reconfigured at the aqueous solution containing SnCl4, its concentration is 0.1~0.3 mol/L, by SnCl4 solution be added dropwise to it is above-mentioned containing
ZnO, NaOH, CTAB aqueous solution, a period of time is stood after being sufficiently stirred；
Mixed solution obtained by the first step is sufficiently stirred, rear to move into a 50ml hydrothermal reaction kettles, 160-210 DEG C of hydro-thermal reaction 8-
15h；Gained precipitation uses deionized water, absolute ethyl alcohol eccentric cleaning each 3 times respectively after reaction is terminated, 6500 revs/min of centrifugations
3-5 minutes, last 60 DEG C of drying obtain the graded hollow cubic tin oxide nano particles being made up of superfine nanometer rods.
2. a kind of preparation method of graded hollow cubic tin oxide nano particles according to claim 1, its
It is characterised by：
The aqueous solution of the configuration containing SnCl4：With deionized water dissolving ZnO, NaOH, CTAB, it is sufficiently stirred.
3. a kind of preparation method of graded hollow cubic tin oxide nano particles according to claim 1, its
It is characterised by：
With deionized water dissolving SnCl4, after the aqueous solution containing ZnO, NaOH, CTAB is added dropwise in SnCl4 solution, fully stir
A period of time is stood after mixing.
4. a kind of preparation method of graded hollow cubic tin oxide nano particles according to claim 2, its
It is characterised by：
The time being sufficiently stirred is 5min.
5. a kind of preparation method of graded hollow cubic tin oxide nano particles according to claim 3, its
It is characterised by：
It is described be sufficiently stirred 10min after stand 24h.
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| CN107445211A (en) * | 2017-09-15 | 2017-12-08 | 吉林大学 | A kind of preparation method of cube of double layer hollow tin ash surface heterogeneous medium growth di-iron trioxide nanometer rods |
| CN108545770B (en) * | 2018-07-02 | 2020-06-16 | 河北镭传科技有限责任公司 | Surface-modified Pd-SnO2Preparation method and application of microspheres |
| CN110048096A (en) * | 2019-03-25 | 2019-07-23 | 天津大学 | For lithium/sodium-ion battery cathode tin oxide/carbon fibre composite and preparation method |
| CN111777095B (en) * | 2020-07-20 | 2022-09-09 | 洛阳布鲁姆电子科技有限公司 | Synthesis method of tin disulfide microspheres |
| CN113667349B (en) * | 2021-08-06 | 2023-03-17 | 叶向东 | Super-hydrophilic coating and preparation method thereof |
| CN113930029B (en) * | 2021-10-25 | 2023-06-20 | 云南锡业集团（控股）有限责任公司研发中心 | Halogen-free nano composite flame retardant and preparation method thereof |
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| CN102502794B (en) * | 2011-10-28 | 2014-01-29 | 安徽师范大学 | Preparation method of porous nano tin dioxide |
| CN103395828A (en) * | 2013-07-22 | 2013-11-20 | 安徽师范大学 | Preparation method of porous hollow micro-cube blocky tin dioxide |
| CN104310463B (en) * | 2014-10-08 | 2016-08-31 | 吉林大学 | A kind of preparation method of hollow cubic body structure tin ash |
| CN104891556B (en) * | 2015-05-29 | 2017-05-17 | 吉林大学 | Zinc hydroxystannate in double-layer hollow cubic structure and preparation method thereof |
| CN104891557B (en) * | 2015-05-29 | 2017-05-17 | 吉林大学 | Tin dioxide nanoflower with hollow structure and preparation method of tin dioxide nanoflower |
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