CN104891558A - Polyhedral tin dioxide nanoparticle with core-shell structure and preparation method of polyhedral tin dioxide nanoparticle - Google Patents
Polyhedral tin dioxide nanoparticle with core-shell structure and preparation method of polyhedral tin dioxide nanoparticle Download PDFInfo
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Abstract
The invention discloses a polyhedral tin dioxide nanoparticle with a core-shell structure and a preparation method of the polyhedral tin dioxide nanoparticle, belonging to the technical field of nanomaterials and solving the technical problems that a preparation method of tin dioxide nanoparticles is complex in operation and high in cost and tin dioxide nanoparticles with complex appearances cannot be prepared in the prior art. The polyhedral tin dioxide nanoparticle with the core-shell structure is composed of a hollow shell and a solid core, wherein both the hollow shell and the solid core are made of tin dioxide and have the same shape and central point; and the hollow shell is of a structure shaped like a regular hexahedron, tetradecahedron or regular octahedron. The polyhedral nanoparticle is of a hollow hierarchical structure, variable and easily-controlled in shape (which can be the regular hexahedron, tetradecahedron or regular octahedron), good in monodispersity and crystallinity, high in surface chemical activity, large in specific surface area and favorable in p-toluene gas sensibility so as to have a potential application value in the field of gas sensors.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of nucleocapsid structure tindioxide polyhedral nano particles and preparation method thereof.
Background technology
Tindioxide, as a kind of n-type semiconductor of broad-band gap, because its chemical stability is good, erosion resistance is strong, short and highly sensitive to gas adsorption desorption time, the advantages such as the specific absorption in visible-range is almost nil, are widely used in the fields such as gas sensitive, battery, Wave Guiding Optics, transistor, optical pickocff.
In prior art, the preparation method of tin oxide nano particles mainly contains hydrothermal method and liquid phase deposition etc.As 2008, tin dioxide nanocrystal (Wu, S. that the people such as Wu utilize amino acid assisting alcohol-hydrothermal method to prepare size to be less than 10nm, Cao, H., Yin, S., Liu, X., & Zhang, X.2009.The Journal of Physical Chemistry C, 113,17893-17898.); 2011, Das etc. for raw material, adopted liquid phase deposition to prepare stannic oxide particle (Das, the S. of 200nm with tin protochloride and vulkacit H, Kim, D.Y., Choi, C.M., & Hahn, Y.B.2011.46,609-614.); The same year solid stannic oxide particle (Kim, H.R., Choi, the K.I. that to have utilized water heat transfer to go out smooth such as Kim, Lee, J.H., & Akbar, S.A. (2009) .Sensors and Actuators B:Chemical, 136,138-143.).But tin oxide nano particles prepared by above-mentioned preparation method is all solid construction, the tin oxide nano particles of complex topography cannot be obtained, accordingly, also cannot possess the performance of inorganic hollow micro nano structure; And preparation process needs high temperature, or use additive, complicated operation, cost are higher.
Summary of the invention
The preparation method's complicated operation, the cost that the object of the invention is tin oxide nano particles in solution prior art are high, and the technical problem of the tin oxide nano particles of complex topography cannot be prepared, a kind of nucleocapsid structure tindioxide polyhedral nano particles and preparation method thereof is provided.
The technical scheme that the present invention solves the problems of the technologies described above employing is as follows.
A kind of nucleocapsid structure tindioxide polyhedral nano particles, be made up of hollow casing and solid kernel, the material of described solid kernel and hollow casing is tindioxide, and shape is identical, have identical central point, a face of solid kernel is parallel with a face of hollow casing;
Described hollow casing structure be regular hexahedron, the tetrakaidecahedron or regular octahedron.
Preferably, the median size of described nano particle is 800nm, and the mean thickness of hollow casing is 100nm, and the median size of solid kernel is 600-650nm.
A preparation method for nucleocapsid structure tindioxide polyhedral nano particles, comprises the following steps:
Step one, prepare solid zinc polyhedral nano particles;
Step 2, the solid zinc polyhedral nano particles high temperature annealing that step one is obtained, cooling, obtains solid mixing polyhedral nano particles;
Step 3, solid mixing polyhedral nano particles is added in aqueous nitric acid, after leaving standstill 24-96h, washing, dry, obtain nucleocapsid structure tindioxide polyhedral nano particles;
In described aqueous nitric acid, the concentration of nitric acid is 0.25-1 mol/L.
Preferably, the polyhedral preparation method of described solid zinc is: by SnCl
45H
2o and ZnCl
2dissolve in a solvent, mix, obtain mixing solutions, then to dropping aqueous solution of sodium, be stirred to oyster white, leave standstill 12-48h, by washing of precipitate, drying, obtain solid zinc polyhedron;
Described solvent is water, or be water and ethanol is (2-10) by volume: 1 mixture.
Preferably, in described mixing solutions, SnCl
45H
2o and ZnCl
2mol ratio be 1:1, when the solid zinc polyhedral nano particles prepared is regular hexahedron, SnCl in sodium hydroxide and mixing solutions in aqueous sodium hydroxide solution
45H
2the mol ratio of O is (8-15): 1; When the solid zinc polyhedral nano particles prepared is the tetrakaidecahedron, SnCl in sodium hydroxide and mixing solutions in aqueous sodium hydroxide solution
45H
2the mol ratio of O is (20-30): 1; When the solid zinc polyhedral nano particles prepared is regular octahedron, SnCl in sodium hydroxide and mixing solutions in aqueous sodium hydroxide solution
45H
2the mol ratio of O is greater than 30:1, is less than or equal to 35:1.
Preferably, in described aqueous sodium hydroxide solution, the concentration of sodium hydroxide is 0.3-1.4 mol/L.
Preferably, the consumption of described aqueous sodium hydroxide solution is: every 3 milliliters of mixing solutionss add the aqueous sodium hydroxide solution of 5 milliliters.
Preferably, described stirring velocity is 1200-1600r/min, and churning time is 10-40min.
Preferably, described high temperature annealing is the 30min-4h that anneals under 700-950 DEG C of air ambient; Preferred, described annealing time is 30min.
Preferably, the consumption of described solid mixing polyhedral nano particles and aqueous nitric acid is: the solid mixing polyhedral nano particles of every 1 milligram joins in the aqueous nitric acid of 0.1 milliliter.
Compared with prior art, the invention has the beneficial effects as follows:
1, nucleocapsid structure tindioxide polyhedral nano particles of the present invention is hollow graded structure, pattern is changeable and easy to control, can be regular hexahedron, the tetrakaidecahedron and regular octahedron, monodispersity and crystallinity good, chemical mobility of the surface is high, specific surface area is large, has good gas sensing property, have potential using value in gas sensor field to toluene gas;
2, preparation method's preparation cost of the present invention low, reproducible, easy and simple to handle, easily control.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of solid zinc 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 nucleocapsid structure tindioxide regular hexahedron nano particle prepared by embodiment 1;
Fig. 4 is the transmission scanning electron microscope figure of nucleocapsid structure tindioxide regular hexahedron nano particle prepared by embodiment 1;
Fig. 5 is the scanning electron microscope (SEM) photograph of solid zinc 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 nucleocapsid structure tindioxide tetrakaidecahedron nano particle prepared by embodiment 4;
Fig. 8 is the transmission surface sweeping Electronic Speculum figure of nucleocapsid structure tindioxide tetrakaidecahedron nano particle prepared by embodiment 4;
Fig. 9 is the scanning electron microscope (SEM) photograph of solid zinc 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 nucleocapsid structure tindioxide regular octahedron nano particle prepared by embodiment 7;
Figure 12 is the transmission scanning electron microscope figure of nucleocapsid structure tindioxide regular octahedron nano particle prepared by embodiment 7;
Figure 13 is the X-ray diffractogram of nucleocapsid structure tindioxide regular hexahedron nano particle prepared by embodiment 1;
Figure 14 is that the nucleocapsid structure tindioxide regular hexahedron nano particle prepared of the solid tin oxide nano particles of comparative example 1 and embodiment 1 is to the sensitivity map of toluene gas.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just in order to further illustrate spy of the present invention just with advantage instead of limiting to the claimed invention.
Nucleocapsid structure tindioxide polyhedral nano particles of the present invention, be 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 is tindioxide, solid kernel is arranged in the inner chamber of hollow casing formation, solid kernel and hollow casing have identical central point, arrange from the inside to the outside, and solid kernel face is parallel with a face of hollow casing, the material of solid kernel is also tindioxide.The specific surface area of polyhedral nano particles of the present invention is 40-70m
2g
– 1, be 65-75 to the sensitivity of 100ppm toluene gas, the median size of nano particle is 800nm, and the mean thickness of hollow casing is 100nm, and the median size of solid kernel is 600-650nm.
In the present invention, definition regular hexahedron and the particle diameter of regular octahedron are the length of body diagonal, and the particle diameter of the tetrakaidecahedron is geometric centre through the tetrakaidecahedron and the longest in all line segments of contacting with the face of the tetrakaidecahedron respectively of two ends.The tetrakaidecahedron of the present invention refers to the tetrakaidecahedron structure of crystalline structure, is prior art, general claims cuboctahedron structure, and the hexagon identical with eight by six identical squares forms; Wherein, hexagon is made up of the minor face that three identical long limits are identical with three, and long limit is alternately connected with minor face, and the straight line at adjacent place, two long limits becomes 60 degree of angles; Each foursquare four edges is hexagonal long limit conllinear with respectively, adjacent two hexagonal minor face conllinear.
The preparation method of above-mentioned nucleocapsid structure tindioxide polyhedral nano particles, comprises the following steps:
Step one, prepare solid zinc polyhedral nano particles
Solid zinc polyhedral nano particles be prepared as prior art, the invention provides a kind of preparation method of solid zinc polyhedral nano particles, but be not limited thereto: by SnCl
45H
2o and ZnCl
2dissolve in a solvent, be uniformly mixed, generally stir 10-40min with the stirring velocity of 1200-1600r/min, obtain mixing solutions, then be the aqueous sodium hydroxide solution of 0.3-1.4 mol/L to mixed solution and dripping concentration, the consumption of aqueous sodium hydroxide solution can be the aqueous sodium hydroxide solution that every 3 milliliters of mixing solutionss add 5 milliliters, be stirred to oyster white, generally stir 10-40min with the stirring velocity of 1200-1600r/min, leave standstill 12-48h in atmosphere, the precipitation obtained is through using deionized water respectively, dehydrated alcohol eccentric cleaning each 3 times (centrifugal rotational speed 6500 turns/min, centrifugation time 3min) after, 60 DEG C of oven dry, obtain solid zinc polyhedral nano particles,
Wherein, solvent generally selects water, when the mixture of water and ethanol selected by solvent, and SnCl
45H
2o and ZnCl
2dispersiveness in mixing solutions is better, so preferred solvent is the mixture of water and ethanol, both volume ratios are (2-10): 1, and water of the present invention is good with deionized water; SnCl
45H
2o, ZnCl
2and sodium hydroxide stoichiometrically reacts, for avoiding wastage of material, in mixing solutions, SnCl
45H
2o, ZnCl
2mol ratio be 1:1; When the solid zinc polyhedral nano particles prepared is regular hexahedron, SnCl in the sodium hydroxide contained in the total amount of the aqueous sodium hydroxide solution of dropping and mixing solutions
45H
2the mol ratio of O is (8-15): 1; When the solid zinc polyhedral nano particles prepared is the tetrakaidecahedron, SnCl in the sodium hydroxide contained in the total amount of the aqueous sodium hydroxide solution of dropping and mixing solutions
45H
2the mol ratio of O is (20-30): 1; When the solid zinc polyhedral nano particles prepared is regular octahedron, SnCl in the sodium hydroxide contained in the total amount of the aqueous sodium hydroxide solution of dropping and mixing solutions
45H
2the mol ratio of O is greater than 30:1, is less than or equal to 35:1;
Step 2, prepare solid mixing polyhedral nano particles
Solid zinc polyhedral nano particles step one obtained is annealed 30min-4h under 700-950 DEG C of air ambient, preferred 30min, in this process, solid mixing polyhedral nano particles at high temperature generates the mixed phase of tindioxide and zinc, but the pattern of polyhedral nano particles is constant, be still polyhedral structure, naturally cool to room temperature, obtain solid mixing polyhedral nano particles;
Step 3, solid mixing polyhedral nano particles etch
Solid mixing polyhedral nano particles step 2 prepared adds in aqueous nitric acid, preferably the solid mixing polyhedral nano particles of every 1 milligram adds in the aqueous nitric acid of 0.1 milliliter, leave standstill 24-96h in atmosphere, due to tindioxide and the zinc dissolubility difference in aqueous nitric acid, zinc in mixed phase is dissolved, tindioxide retains, do not destroy former polyhedral structure, after leaving standstill, deionized water wash, 60 DEG C of oven dry, obtain hollow structure tindioxide polyhedral nano particles;
Wherein, in aqueous nitric acid, the concentration of nitric acid is 0.25-1 mol/L, if lower than 0.25 mol/L, cannot obtain pure phase polyhedral nano particles, if higher than 1 mol/L, the hollow structure of polyhedral nano particles can be destroyed; It should be noted that, because polyhedral nano particles needs to etch under relatively gentle environment, so etching must be carried out under static condition, otherwise polyhedral pattern cannot be kept.
The present invention is further illustrated below in conjunction with embodiment and comparative example.
Comparative example 1
To solid construction tin oxide nano particles (Beijing Deco Dao Jin Science and Technology Ltd., the specific surface area: 14.2m of comparative example 1
2/ g) to carry out air-sensitive ability and test, test result is as shown in figure 14.
Embodiment 1
The preparation of nucleocapsid structure tindioxide regular hexahedron nano particle:
Step one, by the SnCl of 5mL 0.2M
45H
2the ZnCl of O ethanolic soln and 10mL 0.1M
2the aqueous solution is uniformly mixed, obtain mixing solutions, by in 25mL 0.4M NaOH aqueous solution instillation mixing solutions, after 1500r/min stirs 10min, by solution left standstill 24h, be separated, after deionized water and the centrifugal respectively eccentric cleaning of dehydrated alcohol three times, dry solid zinc regular hexahedron nano particle at 60 DEG C, its scanning electron microscope (SEM) photograph is as shown in Figure 1;
Step 2, by preparation solid zinc regular hexahedron nano particle at 850 DEG C, carry out the high temperature anneal 30min in air atmosphere, obtain solid mixing regular hexahedron nano particle after cooling, its scanning electron microscope (SEM) photograph is as shown in Figure 2;
Step 3, the solid mixing regular hexahedron nano particle prepared by 50mg are dissolved in 5mL 0.25M aqueous nitric acid, leave standstill 96h, be separated, after deionized water eccentric cleaning, dry at 60 DEG C, obtain nucleocapsid structure tindioxide regular hexahedron nano particle, as shown in Figure 3, transmission electron microscope picture as shown in Figure 4 for its scanning electron microscope (SEM) photograph.
As can be seen from Fig. 1-4; solid zinc regular hexahedron nano grain surface is smooth; profile is regular hexahedron; median size is 800nm; there is not considerable change in solid mixing regular hexahedron nano particle size pattern; surface roughen; there is not raw considerable change in nucleocapsid structure tindioxide regular hexahedron nano particle size pattern; surface particlesization is more obvious and present nucleocapsid structure; median size is still 800nm; the mean thickness of hollow casing is 100nm, and the median size of solid kernel is 650nm.
X-ray diffraction sign is carried out to the nucleocapsid structure tindioxide regular hexahedron nano particle of embodiment 1, result as shown in figure 13, be JCPDS 41-1445 in conjunction with PDF standard card, as can be seen from Figure 13, sample peak type conforms to substantially with standard card, there is no assorted peak to avoid the peak hour appearance, and peak type is comparatively sharp-pointed and peak is strong, illustrates that nucleocapsid structure tindioxide regular hexahedron nano particle of the present invention has good crystallinity.
Carry out air-sensitive ability to the nucleocapsid structure tindioxide regular hexahedron nano particle of embodiment 1 to test, Figure 14 is that the nucleocapsid structure tindioxide regular hexahedron nano particle prepared of the solid construction tin oxide nano particles of comparative example 1 and embodiment 1 is to the sensitivity of the toluene gas of different concns, as can be seen from Figure 14, polyhedral nano particles of the present invention to the sensitivity of the toluene gas of different concns all higher than prior art.In figure, Ra is the aerial functional resistance value of gas sensor, and Rg is the resistance value of gas sensor in gas to be measured.
The specific surface area of the nucleocapsid structure tindioxide regular hexahedron nano particle of testing example 1 is 66.85m
2g
– 1.
Embodiment 2
The preparation of nucleocapsid structure tindioxide regular hexahedron nano particle:
Step one, by the SnCl of 5mL 0.2M
45H
2the ZnCl of O ethanolic soln and 10mL 0.1M
2the aqueous solution is uniformly mixed, obtain mixing solutions, by in 25mL 0.32M NaOH aqueous solution instillation mixing solutions, after 1600r/min stirs 20min, by solution left standstill 48h, be separated, after deionized water and the centrifugal respectively eccentric cleaning of dehydrated alcohol three times, dry solid zinc regular hexahedron nano particle at 60 DEG C;
Step 2, by preparation solid zinc regular hexahedron nano particle at 950 DEG C, carry out the high temperature anneal 30min in air atmosphere, after cooling, obtain solid mixing regular hexahedron nano particle;
Step 3, the solid mixing regular hexahedron nano particle prepared by 50mg are dissolved in 5mL 0.5M aqueous nitric acid, leave standstill 48h, are separated, after deionized water eccentric cleaning, dry at 60 DEG C, obtain nucleocapsid structure tindioxide regular hexahedron nano particle.
Embodiment 3
The preparation of nucleocapsid structure tindioxide regular hexahedron nano particle:
Step one, by the SnCl of 5mL 0.2M
45H
2the ZnCl of O ethanolic soln and 10mL 0.1M
2the aqueous solution is uniformly mixed, obtain mixing solutions, by in 25mL 0.6M NaOH aqueous solution instillation mixing solutions, after 1500r/min stirs 10min, by solution left standstill 12h, be separated, after deionized water and the centrifugal respectively eccentric cleaning of dehydrated alcohol three times, dry solid zinc regular hexahedron nano particle at 60 DEG C;
Step 2, by preparation solid zinc regular hexahedron nano particle at 700 DEG C, carry out the high temperature anneal 30min in air atmosphere, after cooling, obtain solid mixing regular hexahedron nano particle;
Step 3, the solid mixing regular hexahedron nano particle prepared by 50mg are dissolved in 5mL 0.75M aqueous nitric acid, leave standstill 72h, are separated, after deionized water eccentric cleaning, dry at 60 DEG C, obtain nucleocapsid structure tindioxide regular hexahedron nano particle.
Embodiment 4
The preparation of nucleocapsid structure tindioxide tetrakaidecahedron nano particle:
Step one, by the SnCl of 5mL 0.2M
45H
2the ZnCl of O ethanolic soln and 10mL 0.1M
2the aqueous solution is uniformly mixed, obtain mixing solutions, by in 25mL 1.12M NaOH aqueous solution instillation mixing solutions, after 1200r/min stirs 30min, by solution left standstill 24h, be separated, after deionized water and the centrifugal respectively eccentric cleaning of dehydrated alcohol three times, dry solid zinc tetrakaidecahedron nano particle at 60 DEG C, its scanning electron microscope (SEM) photograph is as shown in Figure 5;
Step 2, by preparation solid zinc tetrakaidecahedron nano particle at 850 DEG C, carry out the high temperature anneal 30min in air atmosphere, obtain solid mixing tetrakaidecahedron nano particle after cooling, its scanning electron microscope (SEM) photograph is as shown in Figure 6;
Step 3, the solid mixing tetrakaidecahedron nano particle prepared by 50mg are dissolved in 5mL 0.25M aqueous nitric acid, leave standstill 96h, be separated, after deionized water eccentric cleaning, dry at 60 DEG C, obtain nucleocapsid structure tindioxide tetrakaidecahedron nano particle, as shown in Figure 7, transmission electron microscope picture as shown in Figure 8 for its scanning electron microscope (SEM) photograph.
As can be seen from Fig. 5-8; solid zinc tetrakaidecahedron nano grain surface is smooth; profile is the tetrakaidecahedron; median size is 800nm; there is not considerable change in solid mixing tetrakaidecahedron nano particle size pattern; surface roughen; there is not raw considerable change in nucleocapsid structure tindioxide tetrakaidecahedron nano particle size pattern; surface particlesization is more obvious and present nucleocapsid structure; median size is still 800nm; the mean thickness of hollow casing is 100nm, and the median size of solid kernel is 600nm.
By test, the specific surface area obtaining tetrakaidecahedron nano particle prepared by embodiment 4 is about 57.39m
2g
– 1, be 69.5 to the sensitivity of 100ppm toluene gas.
Embodiment 5
The preparation of nucleocapsid structure tindioxide tetrakaidecahedron nano particle:
Step one, by the SnCl of 5mL 0.2M
45H
2the ZnCl of O ethanolic soln and 10mL 0.1M
2the aqueous solution is uniformly mixed, obtain mixing solutions, by in 25mL 0.8M NaOH aqueous solution instillation mixing solutions, after 1500r/min stirs 10min, by solution left standstill 24h, be separated, after deionized water and the centrifugal respectively eccentric cleaning of dehydrated alcohol three times, dry solid zinc tetrakaidecahedron nano particle at 60 DEG C;
Step 2, by preparation solid zinc tetrakaidecahedron nano particle at 850 DEG C, carry out the high temperature anneal 1h in air atmosphere, after cooling, obtain solid mixing tetrakaidecahedron nano particle;
Step 3, the solid mixing tetrakaidecahedron nano particle prepared by 50mg are dissolved in 5mL 0.5M aqueous nitric acid, leave standstill 24h, are separated, after deionized water eccentric cleaning, dry at 60 DEG C, obtain nucleocapsid structure tindioxide tetrakaidecahedron nano particle.
Embodiment 6
The preparation of nucleocapsid structure tindioxide tetrakaidecahedron nano particle:
Step one, by the SnCl of 5mL 0.2M
45H
2the ZnCl of O ethanolic soln and 10mL 0.1M
2the aqueous solution is uniformly mixed, obtain mixing solutions, by in 25mL 1.2M NaOH aqueous solution instillation mixing solutions, after 1600r/min stirs 10min, by solution left standstill 24h, be separated, after deionized water and the centrifugal respectively eccentric cleaning of dehydrated alcohol three times, dry solid zinc tetrakaidecahedron nano particle at 60 DEG C;
Step 2, by preparation solid zinc tetrakaidecahedron nano particle at 850 DEG C, carry out the high temperature anneal 1.5h in air atmosphere, after cooling, obtain solid mixing tetrakaidecahedron nano particle;
Step 3, the solid mixing tetrakaidecahedron nano particle prepared by 50mg are dissolved in 5mL 1M aqueous nitric acid, leave standstill 96h, are separated, after deionized water eccentric cleaning, dry at 60 DEG C, obtain nucleocapsid structure tindioxide tetrakaidecahedron nano particle.
Embodiment 7
The preparation of nucleocapsid structure tindioxide regular octahedron nano particle:
Step one, by the SnCl of 5mL 0.2M
45H
2the ZnCl of O ethanolic soln and 10mL 0.1M
2the aqueous solution is uniformly mixed, obtain mixing solutions, by in 25mL 1.36M NaOH aqueous solution instillation mixing solutions, after 1500r/min stirs 10min, by solution left standstill 24h, be separated, after deionized water and the centrifugal respectively eccentric cleaning of dehydrated alcohol three times, dry solid zinc regular octahedron nano particle at 60 DEG C, its scanning electron microscope (SEM) photograph is as shown in Figure 9;
Step 2, by preparation solid zinc regular octahedron nano particle at 850 DEG C, carry out the high temperature anneal 30min in air atmosphere, obtain solid mixing regular octahedron nano particle after cooling, its scanning electron microscope (SEM) photograph is as shown in Figure 10;
Step 3, the solid mixing regular octahedron nano particle prepared by 50mg are dissolved in 5mL 0.25M aqueous nitric acid, leave standstill 96h, be separated, after deionized water eccentric cleaning, dry at 60 DEG C, obtain nucleocapsid structure tindioxide regular octahedron nano particle, as shown in figure 11, transmission electron microscope picture as shown in figure 12 for its scanning electron microscope (SEM) photograph.
As can be seen from Fig. 9-12; solid zinc regular octahedron nano grain surface is smooth; profile is regular octahedron; median size is 800nm; there is not considerable change in solid mixing regular octahedron nano particle size pattern; surface roughen; there is not raw considerable change in nucleocapsid structure tindioxide regular octahedron nano particle size pattern; surface particlesization is more obvious and present nucleocapsid structure; median size is still 800nm; the mean thickness of hollow casing is 100nm, and the median size of solid kernel is 600nm.
By test, the specific surface area obtaining tetrakaidecahedron nano particle prepared by embodiment 7 is about 43.89m
2g
– 1, be 65.8 to the sensitivity of 100ppm toluene gas.
Embodiment 8
The preparation of nucleocapsid structure tindioxide regular octahedron nano particle:
Step one, by the SnCl of 5mL 0.2M
45H
2the ZnCl of O ethanolic soln and 10mL 0.1M
2the aqueous solution is uniformly mixed, obtain mixing solutions, by in 25mL 1.24M NaOH aqueous solution instillation mixing solutions, after 1500r/min stirs 10min, by solution left standstill 24h, be separated, after deionized water and the centrifugal respectively eccentric cleaning of dehydrated alcohol three times, dry solid zinc regular octahedron nano particle at 60 DEG C;
Step 2, by preparation solid zinc regular octahedron nano particle at 900 DEG C, carry out the high temperature anneal 30min in air atmosphere, after cooling, obtain solid mixing regular octahedron nano particle;
Step 3, the solid mixing regular octahedron nano particle prepared by 50mg are dissolved in 5mL 0.25M aqueous nitric acid, leave standstill 96h, are separated, after deionized water eccentric cleaning, dry at 60 DEG C, obtain nucleocapsid structure tindioxide regular octahedron nano particle.
Obviously, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. nucleocapsid structure tindioxide polyhedral nano particles, is characterized in that, is made up of hollow casing and solid kernel, the material of described solid kernel and hollow casing is tindioxide, and shape is identical, have identical central point, a face of solid kernel is parallel with a face of hollow casing;
Described hollow casing structure be regular hexahedron, the tetrakaidecahedron or regular octahedron.
2. nucleocapsid structure tindioxide polyhedral nano particles according to claim 1, is characterized in that, the median size of described nano particle is 800nm, and the mean thickness of hollow casing is 100nm, and the median size of solid kernel is 600-650nm.
3. the preparation method of nucleocapsid structure tindioxide polyhedral nano particles, is characterized in that, comprises the following steps:
Step one, prepare solid zinc polyhedral nano particles;
Step 2, the solid zinc polyhedral nano particles high temperature annealing that step one is obtained, cooling, obtains solid mixing polyhedral nano particles;
Step 3, solid mixing polyhedral nano particles is added in aqueous nitric acid, after leaving standstill 24-96h, washing, dry, obtain nucleocapsid structure tindioxide polyhedral nano particles;
In described aqueous nitric acid, the concentration of nitric acid is 0.25-1 mol/L.
4. the preparation method of nucleocapsid structure tindioxide polyhedral nano particles according to claim 3, is characterized in that, the polyhedral preparation method of described solid zinc is: by SnCl
45H
2o and ZnCl
2dissolve in a solvent, mix, obtain mixing solutions, then to dropping aqueous solution of sodium, be stirred to oyster white, leave standstill 12-48h, by washing of precipitate, drying, obtain solid zinc polyhedron;
Described solvent is water, or be water and ethanol by volume (2-10): the mixture of 1.
5. the preparation method of nucleocapsid structure tindioxide polyhedral nano particles according to claim 4, is characterized in that, in described mixing solutions, and SnCl
45H
2o and ZnCl
2mol ratio be 1:1, when the solid zinc polyhedral nano particles prepared is regular hexahedron, SnCl in sodium hydroxide and mixing solutions in aqueous sodium hydroxide solution
45H
2the mol ratio of O is (8-15): 1; When the solid zinc polyhedral nano particles prepared is the tetrakaidecahedron, SnCl in sodium hydroxide and mixing solutions in aqueous sodium hydroxide solution
45H
2the mol ratio of O is (20-30): 1; When the solid zinc polyhedral nano particles prepared is regular octahedron, SnCl in sodium hydroxide and mixing solutions in aqueous sodium hydroxide solution
45H
2the mol ratio of O is greater than 30:1, is less than or equal to 35:1.
6. the preparation method of nucleocapsid structure tindioxide polyhedral nano particles according to claim 4, is characterized in that, in described aqueous sodium hydroxide solution, the concentration of sodium hydroxide is 0.3-1.4 mol/L.
7. the preparation method of nucleocapsid structure tindioxide polyhedral nano particles according to claim 4, is characterized in that, the consumption of described aqueous sodium hydroxide solution is: every 3 milliliters of mixing solutionss add the aqueous sodium hydroxide solution of 5 milliliters.
8. the preparation method of nucleocapsid structure tindioxide polyhedral nano particles according to claim 4, is characterized in that, described stirring velocity is 1200-1600r/min, and churning time is 10-40min.
9. the preparation method of nucleocapsid structure tindioxide polyhedral nano particles according to claim 3, is characterized in that, described high temperature annealing is the 30min-4h that anneals under 700-950 DEG C of air ambient.
10. the preparation method of nucleocapsid structure tindioxide polyhedral nano particles according to claim 3, it is characterized in that, the consumption of described solid mixing polyhedral nano particles and aqueous nitric acid is: the solid mixing polyhedral nano particles of every 1 milligram joins in the aqueous nitric acid of 0.1 milliliter.
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| 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 |
| CN112479155A (en) * | 2020-11-26 | 2021-03-12 | 同济大学 | Method for enhancing nonlinear optical performance of tin disulfide nanosheet |
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| 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 |
| CN112479155A (en) * | 2020-11-26 | 2021-03-12 | 同济大学 | Method for enhancing nonlinear optical performance of tin disulfide nanosheet |
| CN112479155B (en) * | 2020-11-26 | 2024-04-26 | 同济大学 | Method for enhancing nonlinear optical performance of tin disulfide nanosheets |
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