CN104891558B - A kind of core shell structure tin ash polyhedral nano particles and preparation method thereof - Google Patents
A kind of core shell structure tin ash polyhedral nano particles and preparation method thereof Download PDFInfo
- Publication number
- CN104891558B CN104891558B CN201510288725.XA CN201510288725A CN104891558B CN 104891558 B CN104891558 B CN 104891558B CN 201510288725 A CN201510288725 A CN 201510288725A CN 104891558 B CN104891558 B CN 104891558B
- Authority
- CN
- China
- Prior art keywords
- nano particles
- preparation
- solid
- polyhedral
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of core shell structure tin ash polyhedral nano particles and preparation method thereof, belong to technical field of nano material.Preparation method complex operation, the cost for solving tin oxide nano particles in the prior art are high, and can not prepare the technical problem of the tin oxide nano particles of complex topography.The core shell structure tin ash polyhedral nano particles of the present invention are made up of hollow casing and solid kernel, wherein, the material of solid kernel and hollow casing is tin ash, and shape is identical, with identical central point；The structure of hollow casing is regular hexahedron, the tetrakaidecahedron or regular octahedron.The polyhedral nano particles are hollow graded structure, pattern is changeable and easy to control, can be regular hexahedron, the tetrakaidecahedron and regular octahedron, monodispersity and crystallinity are good, chemical mobility of the surface is high, specific surface area is big, has good gas sensing property to toluene gas, has potential application value in gas sensor field.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of core shell structure tin ash polyhedral nano particles
And preparation method thereof.
Background technology
Tin ash, as a kind of n-type semiconductor of broad-band gap, because its chemical stability is good, corrosion resistance is strong, to gas
The body adsorption/desorption time is short and sensitivity is high, and the advantages of absorptivity in visible-range is almost nil is widely used in
The fields such as gas sensitive, battery, Wave Guiding Optics, transistor, optical sensor.
In the prior art, the preparation method of tin oxide nano particles mainly has hydro-thermal method and liquid phase deposition etc..Such as
2008, Wu et al. using amino acid assisting alcohol-hydrothermal method prepare size less than 10nm tin dioxide nanocrystal (Wu, S.,
Cao,H.,Yin,S.,Liu,X.,&Zhang,X.2009.The Journal of Physical Chemistry C,113,
17893-17898.)；2011, Das etc. was prepared using stannous chloride and hexa as raw material using liquid phase deposition
200nm stannic oxide particle (Das, S., Kim, D.Y., Choi, C.M., ＆Hahn, Y.B.2011.46,609-614.)；
The same year Kim etc. using hydro-thermal method synthesized smooth solid stannic oxide particle (Kim, H.R., Choi, K.I., Lee,
J.H.,&Akbar,S.A.(2009).Sensors and Actuators B:Chemical,136,138-143.).But, on
The tin oxide nano particles for stating preparation method preparation are all solid construction, it is impossible to obtain the stannic oxide nanometer of complex topography
Grain, accordingly, can not also possess the performance of inorganic hollow micro nano structure；And preparation process needs high temperature, or use addition
Agent, complex operation, cost are higher.
The content of the invention
Present invention solves the technical problem that being how to provide a kind of with hollow graded structure, pattern is changeable and easily-controllable
System, can be regular hexahedron, the tetrakaidecahedron and regular octahedron, and monodispersity and crystallinity are good, and chemical mobility of the surface is high, compares table
Area is big, has core shell structure tin ash polyhedral nano particles of good gas sensing property and preparation method thereof to toluene gas
With application.
The technical scheme that the present invention solves above-mentioned technical problem use is as follows.
A kind of core shell structure tin ash polyhedral nano particles, are made up of hollow casing and solid kernel, described solid
The material of kernel and hollow casing is tin ash, and shape is identical, with identical central point, a face of solid kernel
It is parallel with a face of hollow casing；
The structure of the hollow casing is regular hexahedron, the tetrakaidecahedron or regular octahedron.
It is preferred that, the average grain diameter of the nano particle is 800nm, and the average thickness of hollow casing is 100nm, solid interior
The average grain diameter of core is 600-650nm.
A kind of preparation method of core shell structure tin ash polyhedral nano particles, comprises the following steps：
Step 1: preparing solid zinc stannate polyhedral nano particles；
Step 2: the solid zinc stannate polyhedral nano particles high annealing that step one is obtained, cooling, obtain solid mixed
Close polyhedral nano particles；
Step 3: solid mixing polyhedral nano particles are added in aqueous solution of nitric acid, stand after 24-96h, wash, do
It is dry, obtain core shell structure tin ash polyhedral nano particles；
In the aqueous solution of nitric acid, the concentration of nitric acid is 0.25-1 mol/Ls.
It is preferred that, the solid polyhedral preparation method of zinc stannate is：By SnCl4·5H2O and ZnCl2It is dissolved in solvent
In, it is well mixed, obtains mixed solution, then to dropping aqueous solution of sodium, stirring to milky is stood
12-48h, by washing of precipitate, drying, obtains solid zinc stannate polyhedron；
The solvent is water, or is that water is (2-10) by volume with ethanol:1 mixture.
It is preferred that, in the mixed solution, SnCl4·5H2O and ZnCl2Mol ratio be 1:1, when the solid stannic acid of preparation
When zinc polyhedral nano particles are regular hexahedron, sodium hydroxide and SnCl in mixed solution in sodium hydrate aqueous solution4·5H2O's
Mol ratio is (8-15):1；When the solid zinc stannate polyhedral nano particles of preparation are the tetrakaidecahedron, sodium hydrate aqueous solution
Middle sodium hydroxide and SnCl in mixed solution4·5H2O mol ratio is (20-30):1；When the solid zinc stannate polyhedron of preparation
When nano particle is regular octahedron, sodium hydroxide and SnCl in mixed solution in sodium hydrate aqueous solution4·5H2O mol ratio is big
In 30:1, less than or equal to 35:1.
It is preferred that, the concentration of sodium hydroxide is 0.3-1.4 mol/Ls in the sodium hydrate aqueous solution.
It is preferred that, the consumption of the sodium hydrate aqueous solution is：Every 3 milliliters of mixed solutions add 5 milliliters of sodium hydroxide
The aqueous solution.
It is preferred that, the mixing speed is 1200-1600r/min, and mixing time is 10-40min.
It is preferred that, the high annealing is the 30min-4h that annealed under 700-950 DEG C of air ambient；It is furthermore preferred that described
Annealing time is 30min.
It is preferred that, the consumption of solid the mixing polyhedral nano particles and aqueous solution of nitric acid is：Every 1 milligram solid mixed
Polyhedral nano particles are closed to be added in 0.1 milliliter of aqueous solution of nitric acid.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, core shell structure tin ash polyhedral nano particles of the invention are hollow graded structure, and pattern is changeable and easy
Control, can be regular hexahedron, the tetrakaidecahedron and regular octahedron, and monodispersity and crystallinity are good, and chemical mobility of the surface is high, than
Surface area is big, has good gas sensing property to toluene gas, has potential application value in gas sensor field；
2nd, preparation method of the invention preparation cost is low, reproducible, easy to operate, be easily controlled.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of solid zinc stannate regular hexahedron nano particle prepared by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of solid mixing regular hexahedron nano particle prepared by embodiment 1；
Fig. 3 is the scanning electron microscope (SEM) photograph of core shell structure tin ash regular hexahedron nano particle prepared by embodiment 1；
Fig. 4 is the transmission scanning electron microscope figure of core shell structure tin ash regular hexahedron nano particle prepared by embodiment 1；
Fig. 5 is the scanning electron microscope (SEM) photograph of solid zinc stannate tetrakaidecahedron nano particle prepared by embodiment 4；
Fig. 6 is the scanning electron microscope (SEM) photograph of solid mixing tetrakaidecahedron nano particle prepared by embodiment 4；
Fig. 7 is the scanning electron microscope (SEM) photograph of core shell structure tin ash tetrakaidecahedron nano particle prepared by embodiment 4；
Fig. 8 is the transmission surface sweeping electron microscope of core shell structure tin ash tetrakaidecahedron nano particle prepared by embodiment 4；
Fig. 9 is the scanning electron microscope (SEM) photograph of solid zinc stannate regular octahedron nano particle prepared by embodiment 7；
Figure 10 is the scanning electron microscope (SEM) photograph of solid mixing regular octahedron nano particle prepared by embodiment 7；
Figure 11 is the scanning electron microscope (SEM) photograph of core shell structure tin ash regular octahedron nano particle prepared by embodiment 7；
Figure 12 is the transmission scanning electron microscope figure of core shell structure tin ash regular octahedron nano particle prepared by embodiment 7；
Figure 13 is the X-ray diffractogram of core shell structure tin ash regular hexahedron nano particle prepared by embodiment 1；
Figure 14 be the core shell structure tin ash for preparing of solid tin oxide nano particles and embodiment 1 of comparative example 1 just
Sensitivity map of the hexahedron nano particle to toluene gas.
Embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are retouched with reference to embodiment
State, but it is to be understood that these descriptions are intended merely to further illustrate the spy of the present invention just with advantage rather than to present invention power
The limitation that profit is required.
The core shell structure tin ash polyhedral nano particles of the present invention, are made up of hollow casing and solid kernel, wherein
Solid kernel is identical with the shape of hollow casing, can be regular hexahedron, the tetrakaidecahedron or regular octahedron, the material of hollow casing
Expect for tin ash, solid kernel is arranged in the inner chamber of hollow casing formation, solid kernel has identical with hollow casing
Central point, is arranged from the inside to the outside, and a face of solid kernel and a face of hollow casing are parallel, the material of solid kernel
For tin ash.The specific surface area of the polyhedral nano particles of the present invention is 40-70m2g–1, to the sensitive of 100ppm toluene gas
Spend for 65-75, the average grain diameter of nano particle is 800nm, the average thickness of hollow casing is 100nm, solid kernel is averaged
Particle diameter is 600-650nm.
In the present invention, length of the particle diameter of regular hexahedron and regular octahedron for body diagonal, the particle diameter of the tetrakaidecahedron are defined
To be most long in all line segments for being contacted respectively with the face of the tetrakaidecahedron through the geometric center of the tetrakaidecahedron and two ends.The present invention
The tetrakaidecahedron refer to the tetrakaidecahedron structure of crystal structure, be prior art, commonly referred to as cuboctahedron structure is identical by six
Square with eight identical hexagonal groups into；Wherein, hexagon is by three long sides of identical and three identical short side groups
Into and long side and short side be alternately connected, and the straight line where two adjacent long sides is into 60 degree of angles；The four edges point of each square
Conllinear not with the long side of a hexagon, the short side of two adjacent hexagons is conllinear.
The preparation method of above-mentioned core shell structure tin ash polyhedral nano particles, comprises the following steps：
Step 1: preparing solid zinc stannate polyhedral nano particles
Solid zinc stannate polyhedral nano particles are prepared as prior art, and the present invention provides a kind of solid zinc stannate multiaspect
The preparation method of body nano particle, but not limited to this：By SnCl4·5H2O and ZnCl2In a solvent, stirring mixing is equal for dissolving
It is even, 10-40min is typically stirred with 1200-1600r/min mixing speed, mixed solution is obtained, then dripped into mixed solution
Plus the sodium hydrate aqueous solution that concentration is 0.3-1.4 mol/Ls, the consumption of sodium hydrate aqueous solution can be every 3 milliliters mixing
Solution adds 5 milliliters of sodium hydrate aqueous solution, and stirring to milky is typically stirred with 1200-1600r/min mixing speed
10-40min, stands 12-48h in atmosphere, obtained precipitation through using deionized water, absolute ethyl alcohol eccentric cleaning each 3 times respectively
After (6500 turns of centrifugal rotational speed/min, centrifugation time 3min), 60 DEG C of drying obtain solid zinc stannate polyhedral nano particles；
Wherein, solvent typically selects water, when solvent selects the mixture of water and ethanol, SnCl4·5H2O and ZnCl2
More preferably, it is advantageous to the mixture that solvent is water and ethanol, both volume ratios are (2-10) to dispersiveness in mixed solution:1, this
The water of invention is preferred with deionized water；SnCl4·5H2O、ZnCl2And sodium hydroxide stoichiometrically reacts, to avoid raw material
Waste, in mixed solution, SnCl4·5H2O、ZnCl2Mol ratio be 1:1；When the solid zinc stannate polyhedron nanometer of preparation
When grain is regular hexahedron, SnCl in the sodium hydroxide and mixed solution that contain in the total amount of the sodium hydrate aqueous solution of dropwise addition4·
5H2O mol ratio is (8-15):1；When the solid zinc stannate polyhedral nano particles of preparation are the tetrakaidecahedron, the hydrogen of dropwise addition
SnCl in the sodium hydroxide and mixed solution that contain in the total amount of aqueous solution of sodium oxide4·5H2O mol ratio is (20-30):1；
When the solid zinc stannate polyhedral nano particles of preparation are regular octahedron, contain in the total amount of the sodium hydrate aqueous solution of dropwise addition
Sodium hydroxide and mixed solution in SnCl4·5H2O mol ratio is more than 30:1, less than or equal to 35:1；
Step 2: preparing solid mixing polyhedral nano particles
The solid zinc stannate polyhedral nano particles that step one is obtained are annealed 30min- under 700-950 DEG C of air ambient
4h, preferably 30min, should during, solid mixing polyhedral nano particles generate the mixed of tin ash and zinc stannate at high temperature
Phase is closed, but the pattern of polyhedral nano particles is constant, is still polyhedral structure, naturally cools to room temperature, obtains solid mixing many
Face body nano particle；
Step 3: solid mixing polyhedral nano particles etching
Solid mixing polyhedral nano particles prepared by step 2 are added in aqueous solution of nitric acid, preferably every 1 milligram of reality
Heart mixing polyhedral nano particles are added in 0.1 milliliter of aqueous solution of nitric acid, 24-96h are stood in atmosphere, due to tin ash
With dissolubility difference of the zinc stannate in aqueous solution of nitric acid, dissolve the zinc stannate in mixed phase, tin ash retains, and does not destroy
After former polyhedral structure, standing, deionized water washing, 60 DEG C of drying obtain hollow-core construction tin ash polyhedral nano particles；
Wherein, the concentration of nitric acid is 0.25-1 mol/Ls in aqueous solution of nitric acid, if less than 0.25 mol/L, it is impossible to
To pure phase polyhedral nano particles, if above 1 mol/L, the hollow-core construction of polyhedral nano particles can be destroyed；Need
It is bright, because polyhedral nano particles need to etch under relatively mild environment, so etching must be under static condition
Carry out, otherwise can not keep polyhedral pattern.
With reference to embodiments the present invention is further illustrated with comparative example.
Comparative example 1
To the solid construction tin oxide nano particles of comparative example 1, (Beijing Deco Dao Jin Science and Technology Ltd.s, compare surface
Product:14.2m2/ g) carry out air-sensitive ability tested, test result is as shown in figure 14.
Embodiment 1
The preparation of core shell structure tin ash regular hexahedron nano particle：
Step 1: by 5mL 0.2M SnCl4·5H2The ZnCl of O ethanol solutions and 10mL 0.1M2Aqueous solution stirring mixing
Uniformly, mixed solution is obtained, the 25mL 0.4M NaOH aqueous solution is instilled in mixed solution, after 1500r/min stirrings 10min,
By solution left standstill 24h, separation is dry at 60 DEG C after deionized water and absolute ethyl alcohol centrifugation respectively eccentric cleaning three times
Solid zinc stannate regular hexahedron nano particle, its scanning electron microscope (SEM) photograph is as shown in Figure 1；
Moved back Step 2: carrying out high temperature by the solid zinc stannate regular hexahedron nano particle of preparation at 850 DEG C, in air atmosphere
Fire processing 30min, obtains solid mixing regular hexahedron nano particle after cooling, its scanning electron microscope (SEM) photograph is as shown in Figure 2；
Step 3: solid mixing regular hexahedron nano particle prepared by 50mg is dissolved in into 5mL 0.25M aqueous solution of nitric acid
In, 96h is stood, separation after deionized water eccentric cleaning, is dried at 60 DEG C, obtains positive six face of core shell structure tin ash
Body nano particle, its scanning electron microscope (SEM) photograph is as shown in figure 3, transmission electron microscope picture is as shown in Figure 4.
From Fig. 1-4 as can be seen that solid zinc stannate regular hexahedron nano grain surface is smooth, profile is regular hexahedron, is put down
Equal particle diameter is 800nm, and significant change does not occur for solid mixing regular hexahedron nano particle size pattern, and surface is roughening, nucleocapsid
Structure tin ash regular hexahedron nano particle size pattern does not give birth to significant change, and surface particles become apparent and presented
Core shell structure, average grain diameter is still 800nm, and the average thickness of hollow casing is 100nm, and the average grain diameter of solid kernel is
650nm。
X-ray diffraction sign is carried out to the core shell structure tin ash regular hexahedron nano particle of embodiment 1, as a result such as
It is JCPDS 41-1445, as can be seen from Figure 13, sample peak type and the basic phase of standard card with reference to PDF standard cards shown in Figure 13
Symbol, has no miscellaneous peak and avoids the peak hour appearances, and peak type more sharp and peak intensity is strong, is illustrating core shell structure tin ash of the invention just
Hexahedron nano particle has good crystallinity.
Core shell structure tin ash regular hexahedron nano particle progress air-sensitive ability to embodiment 1 is tested, Figure 14
Core shell structure tin ash regular hexahedron prepared by solid construction tin oxide nano particles and embodiment 1 for comparative example 1 is received
Sensitivity of the rice grain to the toluene gas of various concentrations, it is seen from figure 14 that the polyhedral nano particles of the present invention are not to
Sensitivity with the toluene gas of concentration is above prior art.In figure, Ra is the aerial operating resistance of gas sensor
Value, Rg is resistance value of the gas sensor under test gas.
The specific surface area of the core shell structure tin ash regular hexahedron nano particle of testing example 1, is 66.85m2g–1。
Embodiment 2
The preparation of core shell structure tin ash regular hexahedron nano particle：
Step 1: by 5mL 0.2M SnCl4·5H2The ZnCl of O ethanol solutions and 10mL 0.1M2Aqueous solution stirring mixing
Uniformly, mixed solution is obtained, the 25mL 0.32M NaOH aqueous solution is instilled in mixed solution, after 1600r/min stirrings 20min,
By solution left standstill 48h, separation is dry at 60 DEG C after deionized water and absolute ethyl alcohol centrifugation respectively eccentric cleaning three times
Solid zinc stannate regular hexahedron nano particle；
Moved back Step 2: carrying out high temperature by the solid zinc stannate regular hexahedron nano particle of preparation at 950 DEG C, in air atmosphere
Fire processing 30min, obtains solid mixing regular hexahedron nano particle after cooling；
Step 3: solid mixing regular hexahedron nano particle prepared by 50mg is dissolved in into 5mL 0.5M aqueous solution of nitric acid
In, 48h is stood, separation after deionized water eccentric cleaning, is dried at 60 DEG C, obtains positive six face of core shell structure tin ash
Body nano particle.
Embodiment 3
The preparation of core shell structure tin ash regular hexahedron nano particle：
Step 1: by 5mL 0.2M SnCl4·5H2The ZnCl of O ethanol solutions and 10mL 0.1M2Aqueous solution stirring mixing
Uniformly, mixed solution is obtained, the 25mL 0.6M NaOH aqueous solution is instilled in mixed solution, after 1500r/min stirrings 10min,
By solution left standstill 12h, separation is dry at 60 DEG C after deionized water and absolute ethyl alcohol centrifugation respectively eccentric cleaning three times
Solid zinc stannate regular hexahedron nano particle；
Moved back Step 2: carrying out high temperature by the solid zinc stannate regular hexahedron nano particle of preparation at 700 DEG C, in air atmosphere
Fire processing 30min, obtains solid mixing regular hexahedron nano particle after cooling；
Step 3: solid mixing regular hexahedron nano particle prepared by 50mg is dissolved in into 5mL 0.75M aqueous solution of nitric acid
In, 72h is stood, separation after deionized water eccentric cleaning, is dried at 60 DEG C, obtains positive six face of core shell structure tin ash
Body nano particle.
Embodiment 4
The preparation of core shell structure tin ash tetrakaidecahedron nano particle：
Step 1: by 5mL 0.2M SnCl4·5H2The ZnCl of O ethanol solutions and 10mL 0.1M2Aqueous solution stirring mixing
Uniformly, mixed solution is obtained, the 25mL 1.12M NaOH aqueous solution is instilled in mixed solution, after 1200r/min stirrings 30min,
By solution left standstill 24h, separation is dry at 60 DEG C after deionized water and absolute ethyl alcohol centrifugation respectively eccentric cleaning three times
Solid zinc stannate tetrakaidecahedron nano particle, its scanning electron microscope (SEM) photograph is as shown in Figure 5；
Moved back Step 2: carrying out high temperature by the solid zinc stannate tetrakaidecahedron nano particle of preparation at 850 DEG C, in air atmosphere
Fire processing 30min, obtains solid mixing tetrakaidecahedron nano particle after cooling, its scanning electron microscope (SEM) photograph is as shown in Figure 6；
Step 3: solid mixing tetrakaidecahedron nano particle prepared by 50mg is dissolved in into 5mL 0.25M aqueous solution of nitric acid
In, 96h is stood, separation after deionized water eccentric cleaning, is dried at 60 DEG C, obtains the four sides of core shell structure tin ash ten
Body nano particle, its scanning electron microscope (SEM) photograph is as shown in fig. 7, transmission electron microscope picture is as shown in Figure 8.
From Fig. 5-8 as can be seen that solid zinc stannate tetrakaidecahedron nano grain surface is smooth, profile is the tetrakaidecahedron, is put down
Equal particle diameter is 800nm, and significant change does not occur for solid mixing tetrakaidecahedron nano particle size pattern, and surface is roughening, nucleocapsid
Structure tin ash tetrakaidecahedron nano particle size pattern does not give birth to significant change, and surface particles become apparent and presented
Core shell structure, average grain diameter is still 800nm, and the average thickness of hollow casing is 100nm, and the average grain diameter of solid kernel is
600nm。
By test, the specific surface area about 57.39m of the tetrakaidecahedron nano particle of the preparation of embodiment 4 is obtained2g–1, it is right
The sensitivity of 100ppm toluene gas is 69.5.
Embodiment 5
The preparation of core shell structure tin ash tetrakaidecahedron nano particle：
Step 1: by 5mL 0.2M SnCl4·5H2The ZnCl of O ethanol solutions and 10mL 0.1M2Aqueous solution stirring mixing
Uniformly, mixed solution is obtained, the 25mL 0.8M NaOH aqueous solution is instilled in mixed solution, after 1500r/min stirrings 10min,
By solution left standstill 24h, separation is dry at 60 DEG C after deionized water and absolute ethyl alcohol centrifugation respectively eccentric cleaning three times
Solid zinc stannate tetrakaidecahedron nano particle；
Moved back Step 2: carrying out high temperature by the solid zinc stannate tetrakaidecahedron nano particle of preparation at 850 DEG C, in air atmosphere
Fire processing 1h, obtains solid mixing tetrakaidecahedron nano particle after cooling；
Step 3: solid mixing tetrakaidecahedron nano particle prepared by 50mg is dissolved in into 5mL 0.5M aqueous solution of nitric acid
In, 24h is stood, separation after deionized water eccentric cleaning, is dried at 60 DEG C, obtains the four sides of core shell structure tin ash ten
Body nano particle.
Embodiment 6
The preparation of core shell structure tin ash tetrakaidecahedron nano particle：
Step 1: by 5mL 0.2M SnCl4·5H2The ZnCl of O ethanol solutions and 10mL 0.1M2Aqueous solution stirring mixing
Uniformly, mixed solution is obtained, the 25mL 1.2M NaOH aqueous solution is instilled in mixed solution, after 1600r/min stirrings 10min,
By solution left standstill 24h, separation is dry at 60 DEG C after deionized water and absolute ethyl alcohol centrifugation respectively eccentric cleaning three times
Solid zinc stannate tetrakaidecahedron nano particle；
Moved back Step 2: carrying out high temperature by the solid zinc stannate tetrakaidecahedron nano particle of preparation at 850 DEG C, in air atmosphere
Fire processing 1.5h, obtains solid mixing tetrakaidecahedron nano particle after cooling；
Step 3: solid mixing tetrakaidecahedron nano particle prepared by 50mg is dissolved in 5mL 1M aqueous solution of nitric acid,
96h is stood, separation after deionized water eccentric cleaning, is dried at 60 DEG C, obtains the core shell structure tin ash tetrakaidecahedron and receive
Rice grain.
Embodiment 7
The preparation of core shell structure tin ash regular octahedron nano particle：
Step 1: by 5mL 0.2M SnCl4·5H2The ZnCl of O ethanol solutions and 10mL 0.1M2Aqueous solution stirring mixing
Uniformly, mixed solution is obtained, the 25mL 1.36M NaOH aqueous solution is instilled in mixed solution, after 1500r/min stirrings 10min,
By solution left standstill 24h, separation is dry at 60 DEG C after deionized water and absolute ethyl alcohol centrifugation respectively eccentric cleaning three times
Solid zinc stannate regular octahedron nano particle, its scanning electron microscope (SEM) photograph is as shown in Figure 9；
Step 2: the solid zinc stannate regular octahedron nano particle of preparation is carried out into high temperature at 850 DEG C in air atmosphere
30min is made annealing treatment, solid mixing regular octahedron nano particle is obtained after cooling, its scanning electron microscope (SEM) photograph is as shown in Figure 10；
Step 3: solid mixing regular octahedron nano particle prepared by 50mg is dissolved in into 5mL 0.25M aqueous solution of nitric acid
In, 96h is stood, separation after deionized water eccentric cleaning, is dried at 60 DEG C, obtains the positive octahedral of core shell structure tin ash
Body nano particle, as shown in figure 11, transmission electron microscope picture is as shown in figure 12 for its scanning electron microscope (SEM) photograph.
From Fig. 9-12 as can be seen that solid zinc stannate regular octahedron nano grain surface is smooth, profile is regular octahedron, is put down
Equal particle diameter is 800nm, and significant change does not occur for solid mixing regular octahedron nano particle size pattern, and surface is roughening, nucleocapsid
Structure tin ash regular octahedron nano particle size pattern does not give birth to significant change, and surface particles become apparent and presented
Core shell structure, average grain diameter is still 800nm, and the average thickness of hollow casing is 100nm, and the average grain diameter of solid kernel is
600nm。
By test, the specific surface area about 43.89m of the tetrakaidecahedron nano particle of the preparation of embodiment 7 is obtained2g–1, it is right
The sensitivity of 100ppm toluene gas is 65.8.
Embodiment 8
The preparation of core shell structure tin ash regular octahedron nano particle：
Step 1: by 5mL 0.2M SnCl4·5H2The ZnCl of O ethanol solutions and 10mL 0.1M2Aqueous solution stirring mixing
Uniformly, mixed solution is obtained, the 25mL 1.24M NaOH aqueous solution is instilled in mixed solution, after 1500r/min stirrings 10min,
By solution left standstill 24h, separation is dry at 60 DEG C after deionized water and absolute ethyl alcohol centrifugation respectively eccentric cleaning three times
Solid zinc stannate regular octahedron nano particle；
Moved back Step 2: carrying out high temperature by the solid zinc stannate regular octahedron nano particle of preparation at 900 DEG C, in air atmosphere
Fire processing 30min, obtains solid mixing regular octahedron nano particle after cooling；
Step 3: solid mixing regular octahedron nano particle prepared by 50mg is dissolved in into 5mL 0.25M aqueous solution of nitric acid
In, 96h is stood, separation after deionized water eccentric cleaning, is dried at 60 DEG C, obtains the positive octahedral of core shell structure tin ash
Body nano particle.
Obviously, the explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should refer to
Go out, under the premise without departing from the principles of the invention, can also be to this hair for the those of ordinary skill of the technical field
Bright to carry out some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
1. core shell structure tin ash polyhedral nano particles, it is characterised in that be made up of hollow casing and solid kernel, described
The material of solid kernel and hollow casing is tin ash, and shape is identical, with identical central point, the one of solid kernel
Individual face is parallel with a face of hollow casing；
The structure of the hollow casing is regular hexahedron, the tetrakaidecahedron or regular octahedron；
The core shell structure tin ash polyhedral nano particles are prepared by the following method：
Step 1: preparing solid zinc stannate polyhedral nano particles；
The polyhedral preparation method of solid zinc stannate is：By SnCl4·5H2O and ZnCl2In a solvent, mixing is equal for dissolving
It is even, mixed solution is obtained, then to dropping aqueous solution of sodium, stirring to milky stands 12-48h, will
Washing of precipitate, drying, obtain solid zinc stannate polyhedron；
The solvent is water, or for water and ethanol by volume (2-10):1 mixture；
In the mixed solution, SnCl4·5H2O and ZnCl2Mol ratio be 1:1, when the solid zinc stannate polyhedron of preparation is received
When rice grain is regular hexahedron, sodium hydroxide and SnCl in mixed solution in sodium hydrate aqueous solution4·5H2O mol ratio is
(8-15):1；When the solid zinc stannate polyhedral nano particles of preparation are the tetrakaidecahedron, hydroxide in sodium hydrate aqueous solution
Sodium and SnCl in mixed solution4·5H2O mol ratio is (20-30):1；When the solid zinc stannate polyhedral nano particles of preparation
During for regular octahedron, sodium hydroxide and SnCl in mixed solution in sodium hydrate aqueous solution4·5H2O mol ratio is more than 30:1,
Less than or equal to 35:1；
Step 2: the solid zinc stannate polyhedral nano particles high annealing that step one is obtained, cooling, obtain solid mixing many
Face body nano particle；
Step 3: solid mixing polyhedral nano particles are added in aqueous solution of nitric acid, stand after 24-96h, wash, dry, obtain
To core shell structure tin ash polyhedral nano particles；
In the aqueous solution of nitric acid, the concentration of nitric acid is 0.25-1 mol/Ls.
2. core shell structure tin ash polyhedral nano particles according to claim 1, it is characterised in that the nanometer
The average grain diameter of grain is 800nm, and the average thickness of hollow casing is 100nm, and the average grain diameter of solid kernel is 600-650nm.
3. the preparation method of core shell structure tin ash polyhedral nano particles, it is characterised in that comprise the following steps：
Step 1: preparing solid zinc stannate polyhedral nano particles；
Step 2: the solid zinc stannate polyhedral nano particles high annealing that step one is obtained, cooling, obtain solid mixing many
Face body nano particle；
Step 3: solid mixing polyhedral nano particles are added in aqueous solution of nitric acid, stand after 24-96h, wash, dry, obtain
To core shell structure tin ash polyhedral nano particles；
In the aqueous solution of nitric acid, the concentration of nitric acid is 0.25-1 mol/Ls.
4. the preparation method of core shell structure tin ash polyhedral nano particles according to claim 3, it is characterised in that
The polyhedral preparation method of solid zinc stannate is：By SnCl4·5H2O and ZnCl2Dissolving in a solvent, is well mixed, obtained
To mixed solution, then to dropping aqueous solution of sodium, stirring to milky stands 12-48h, will precipitated
Wash, dry, obtain solid zinc stannate polyhedron；
The solvent is water, or for water and ethanol by volume (2-10):1 mixture.
5. the preparation method of core shell structure tin ash polyhedral nano particles according to claim 4, it is characterised in that
In the mixed solution, SnCl4·5H2O and ZnCl2Mol ratio be 1:1, when the solid zinc stannate polyhedron nanometer of preparation
When grain is regular hexahedron, sodium hydroxide and SnCl in mixed solution in sodium hydrate aqueous solution4·5H2O mol ratio is (8-
15):1；When the solid zinc stannate polyhedral nano particles of preparation are the tetrakaidecahedron, in sodium hydrate aqueous solution sodium hydroxide with
SnCl in mixed solution4·5H2O mol ratio is (20-30):1；When the solid zinc stannate polyhedral nano particles of preparation is just
When octahedra, sodium hydroxide and SnCl in mixed solution in sodium hydrate aqueous solution4·5H2O mol ratio is more than 30:1, it is less than
Equal to 35:1.
6. the preparation method of core shell structure tin ash polyhedral nano particles according to claim 4, it is characterised in that
The concentration of sodium hydroxide is 0.3-1.4 mol/Ls in the sodium hydrate aqueous solution.
7. the preparation method of core shell structure tin ash polyhedral nano particles according to claim 4, it is characterised in that
The consumption of the sodium hydrate aqueous solution is：Every 3 milliliters of mixed solutions add 5 milliliters of sodium hydrate aqueous solution.
8. the preparation method of core shell structure tin ash polyhedral nano particles according to claim 4, it is characterised in that
The mixing speed is 1200-1600r/min, and mixing time is 10-40min.
9. the preparation method of core shell structure tin ash polyhedral nano particles according to claim 3, it is characterised in that
The high annealing is the 30min-4h that annealed under 700-950 DEG C of air ambient.
10. the preparation method of core shell structure tin ash polyhedral nano particles according to claim 3, its feature exists
In the consumption of solid the mixing polyhedral nano particles and aqueous solution of nitric acid is：Every 1 milligram of solid mixing polyhedron nanometer
Particle is added in 0.1 milliliter of aqueous solution of nitric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510288725.XA CN104891558B (en) | 2015-05-29 | 2015-05-29 | A kind of core shell structure tin ash polyhedral nano particles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510288725.XA CN104891558B (en) | 2015-05-29 | 2015-05-29 | A kind of core shell structure tin ash polyhedral nano particles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104891558A CN104891558A (en) | 2015-09-09 |
| CN104891558B true CN104891558B (en) | 2017-09-22 |
Family
ID=54024597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510288725.XA Expired - Fee Related CN104891558B (en) | 2015-05-29 | 2015-05-29 | A kind of core shell structure tin ash polyhedral nano particles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104891558B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107352577B (en) * | 2017-06-28 | 2020-06-02 | 齐鲁工业大学 | Micro-nano net structure In2O3/SnO2Composite material and growing method thereof |
| 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 |
| CN108107083B (en) * | 2017-12-05 | 2020-06-05 | 广东美的制冷设备有限公司 | SnO2 gas-sensitive material with hierarchical structure and preparation method thereof |
| CN108598426A (en) * | 2018-04-26 | 2018-09-28 | 吉林大学 | The method for improving its charge/discharge capacity by preparing cobalt acid manganese/N doping carbon/manganese dioxide nucleocapsid |
| CN110857928A (en) * | 2018-08-23 | 2020-03-03 | 吉福有限公司 | Semiconductor-type gas sensor, multi-sensor device, and method for identifying the same |
| CN112479155B (en) * | 2020-11-26 | 2024-04-26 | 同济大学 | Method for enhancing nonlinear optical performance of tin disulfide nanosheets |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863507B (en) * | 2010-06-02 | 2012-08-22 | 中山大学 | Preparation method of gradated stannic oxide octahedrons |
| CN101928037B (en) * | 2010-09-08 | 2012-01-04 | 西安交通大学 | Preparation method of hollow cube of tin dioxide |
| KR20120063925A (en) * | 2010-12-08 | 2012-06-18 | 한국전자통신연구원 | Method of manufacturing porous metal oxides |
| 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 |
-
2015
- 2015-05-29 CN CN201510288725.XA patent/CN104891558B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104891558A (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104891558B (en) | A kind of core shell structure tin ash polyhedral nano particles and preparation method thereof | |
| CN104891557B (en) | Tin dioxide nanoflower with hollow structure and preparation method of tin dioxide nanoflower | |
| CN101333002B (en) | Titanium dioxide nanometer powder with special appearance and method for preparing same | |
| CN104569075B (en) | Double mesoporous nickel oxide formaldehyde gas sensitive materials of a kind of Fe2O3 doping and preparation method thereof | |
| CN102764897B (en) | Method for preparing submicron silver powder for electro-conductive paste | |
| CN106311190A (en) | Preparation method of porous manganese-based lithium ion sieve adsorbent | |
| CN103506630A (en) | Method for preparing flaky silver powder with ultralow apparent density | |
| CN105800684A (en) | Monodispersive porous crystal titanium oxide nanosphere with size smaller than 100 nm and preparation method thereof | |
| CN104492367B (en) | Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof | |
| CN108483474A (en) | A kind of preparation method of nano-level sphere aluminium oxide | |
| CN115974550A (en) | Preparation method of tetragonal-phase nano-doped zirconia ceramic powder material with particle size D50 smaller than 100nm | |
| CN107792887A (en) | A kind of high-specific surface area ZnMn2O4Preparation method | |
| CN102774875A (en) | Preparation method of octahedral zinc oxide crystals with micrometer-nanometer pore micro structures | |
| CN101993115B (en) | Preparation method of ferroferric oxide magnetic nanoparticles | |
| CN102718256B (en) | Preparation method for titania microspheres with adjustable grain sizes | |
| CN105271371A (en) | Flower-shaped indium oxide microrod material, and preparation method and application thereof | |
| CN101840743B (en) | Method for preparing transparent conductive oxide nano powder slurry | |
| CN101597022A (en) | A kind of preparation method of antimony doped stannic oxide nano powder | |
| CN105858721A (en) | Preparation method of monoatomic layer titanium oxide nanosheet colloidal solution | |
| CN106698498B (en) | A kind of preparation method of nano cuprous oxide catalyst | |
| CN101786649B (en) | Method for preparing rare-earth fluoride nanometer mesoporous spheres | |
| CN103159252B (en) | Aluminum-doped zinc oxide electric conduction powder and preparation method thereof | |
| CN111392780A (en) | Composite oxide nano-particles capable of emitting THz frequency and preparation method thereof | |
| CN107170891A (en) | A kind of wide spectrum perovskite solar cell and preparation method thereof | |
| CN100384522C (en) | MnO film for filtering carbon nanotube effluent, its prepn. and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170922 Termination date: 20200529 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |