CN103613123A - Method for preparing monodisperse stannic oxide nanocrystalline particles - Google Patents

Abstract

The invention belongs to the technical field of preparation of nano materials and relates to a method for preparing monodisperse stannic oxide nanocrystalline particles. The method comprises the following steps: uniformly mixing deionized water with ethanol or isopropanol to serve as a solvent, and then respectively dissolving SnCl4.5H2O and benzimidazole in the solvent to obtain a mixed solution; transferring the mixed solution into a stainless steel reaction kettle lined with polytetrafluoroethylene to react to obtain a white sample; and then, sequentially cleaning the white sample with deionized water and ethanol, and drying to obtain the monodisperse stannic oxide nanocrystalline particles; the preparation method is simple in preparation process, simple and convenient to operate, reliable in principle, low in production cost, high in product yield and is environmental-friendly, and the prepared nanocrystalline particles are small in size, good in monodispersity, large in specific surface area and high in purity, has a wide application prospect on the aspects of gas sensors and can be put into large-scale industrial production easily.

Description

A kind of single preparation method who disperses tin dioxide nanocrystal particle

Technical field:

The invention belongs to nano material preparing technical field, relate to a kind of benzoglyoxaline that utilizes and do controlled bigger serface, the single technique of disperseing tin dioxide nanocrystal particle prepared of mineralizer, particularly a single preparation method who disperses tin dioxide nanocrystal particle, can be used for the fields such as catalyzer, gas sensor and electrode materials.

Background technology:

Tindioxide is a kind of wide bandgap semiconductor oxide compound (energy gap is 3.6eV), in its actual building-up process, there is oxygen room, present N-shaped characteristic of semiconductor, tindioxide has unique gas sensing property, electroconductibility and light transmission, in fields such as photoelectricity and gas sensors, have broad application prospects, its potential using value has caused people's extensive concern, the brilliant particle of tindioxide of dispersed nano size has larger specific surface area, there are many defects in higher activity and surface, its photoelectric property and air-sensitive performance show the excellent properties that is different from block materials, and its sensitivity, selectivity can be improved by other element that adulterates, therefore, many researchists are devoted to study single preparation method who disperses tin dioxide nanocrystal particle.At present, SnO ₂the preparation method of nano particle comprises physics synthesis method and chemical synthesis, and wherein, physics synthesis method comprises sputtering method, vapour deposition process and plasma method, and these methods require high to plant and instrument, and productive expense is expensive, and it is high to consume energy; Compare with traditional physics synthesis method, the cost of material of chemical synthesis process is cheap, and plant and instrument is simple, and building-up process is easy to control, and existing chemical synthesis has developed hydrothermal method (H.C.Chiu; C.S.Yeh.J.Phys.Chem.C.2007,111,7256; H.L.Zhu; D.Yang; G.X.Yu; H.Zhang; K.H.Yao.Nanotechnology, 2006,17,2386), sol-gel method (F.Gu.; S.F.Wang.; M.K.Lu; G.J.Zhou.; D.Xu.; D.R.Yuan.J.Phys.Chem.B, 2004,108,8119), ultrasonic synthetic (J.J.Zhu; Z.H.Lu; S.T.Aruna; D.Aurbach; A.Gedanken.Chem.Mater., 2000,12,2557) and the methods such as synthetic (CN1887722) of burning, the SnO that wherein prepared by hydrothermal method ₂nano particle has the advantages such as crystal grain growth is complete, narrow particle size distribution, reunion mild degree, has greatly improved the performance of material, is considered to a kind of important means of preparing tin oxide nano particles.Yet traditional hydrothermal synthesis method need to be prepared monodispersed tin oxide nano particles by means of tensio-active agent; owing to having introduced tensio-active agent; the purity of prepared stannic oxide particle is not high, must for example, by follow-up further processing (high-temperature calcination), just can obtain high purity, single tin oxide nano particles (Y.D.Wang. that disperses; C.L.Ma.; X.D.Sun.; H.D.Li.Nanotechnology, 2002,13,565), energy consumption is high, complicated process of preparation.Therefore, develop a kind of single stage method and prepare that diameter littlely, single disperses, the method tool of highly purified tin dioxide nanocrystal particle is of great significance.

Summary of the invention:

The object of the invention is to overcome the shortcoming that prior art exists, and provides a kind of benzoglyoxaline that utilizes for the method for the tin dioxide nanocrystal particle of the dispersion of the controlled preparation list of mineralizer, high purity, bigger serface.

In order to realize foregoing invention object, the present invention is with SnCl ₄5H ₂o is raw material, and benzoglyoxaline is made mineralizer, and the mixed solution of water and ethanol or propyl alcohol is solvent, the single tin dioxide nanocrystal particle that disperses of preparation, and its concrete technology step comprises:

(1), using deionized water and ethanol or propyl alcohol by volume for the ratio of 1:1 mixes as solvent, then by SnCl ₄5H ₂o and benzoglyoxaline are dissolved in solvent and obtain mixing solutions, wherein, and SnCl ₄5H ₂the weight ratio of O and solvent is 1:100, SnCl ₄5H ₂the weight ratio of O and benzoglyoxaline is 7:2-12;

(2), mixing solutions that step (1) is obtained transfers in teflon-lined stainless steel cauldron, at 160-200 ℃, reacts 12-24 hour, obtains white sample;

(3), white sample that step (2) is obtained dries after cleaning with deionized water and ethanol successively at 60-150 ℃, obtains single tin dioxide nanocrystal particle that disperses.

Compared with prior art, its preparation technology is simple, easy and simple to handle in the present invention, principle is reliable, production cost is low, and product yield is high, environmental friendliness, the nano-crystalline granule size of preparation is little, monodispersity is good, and specific surface area is large, and purity is high, aspect gas sensor, have broad application prospects, be easy to carry out large-scale commercial production.

Accompanying drawing explanation:

Fig. 1. be the SnO of the embodiment of the present invention 1 preparation ₂the XRD figure spectrum of nano particle, shows that material is the monocrystalline SnO of tetragonal crystal structure ₂particle.

Fig. 2 is the SnO of the embodiment of the present invention 2 preparations ₂the XRD figure spectrum of nano particle, shows that material is the monocrystalline SnO of tetragonal crystal structure ₂particle.

Fig. 3 is the SnO of the embodiment of the present invention 3 preparations ₂the XRD figure spectrum of nano particle, shows that material is the monocrystalline SnO of tetragonal crystal structure ₂particle.

Fig. 4 is the SnO of the embodiment of the present invention 1 preparation ₂the transmission electron microscope photo of nano-crystalline granule, wherein (a) is SnO ₂the low power transmission electron microscope photo of nano-crystalline granule, (b) is SnO ₂the high power transmission electron microscope photo of nano-crystalline granule; Show that this material is the brilliant particle of monodispersed ball shaped nano, particle size is more even, and mean diameter is 3.4nm greatly.

Fig. 5 is the SnO of the embodiment of the present invention 2 preparations ₂the transmission electron microscope photo of nano-crystalline granule, wherein (a) is SnO ₂the low power transmission electron microscope photo of nano-crystalline granule, (b) is SnO ₂the high power transmission electron microscope photo of nano-crystalline granule; Show that this material is monodispersed elliposoidal nano-crystalline granule, particle size is more even, its major diameter average out to 7.4nm, minor axis average out to 4.8nm.

Fig. 6 is the SnO of the embodiment of the present invention 3 preparations ₂the transmission electron microscope photo of nano-crystalline granule, wherein (a) is SnO ₂the low power transmission electron microscope photo of nano-crystalline granule, (b) is SnO ₂the high power transmission electron microscope photo of nano-crystalline granule; Show that this material is the brilliant particle of ball shaped nano, and occur clustering phenomena, mean diameter is about 5.2nm.

Fig. 7 is the SnO of the embodiment of the present invention 1 preparation ₂the size distribution plot of nano-crystalline granule, shows the SnO preparing ₂the size of particle is more even, is distributed in 2.3-4.5nm.

Fig. 8 is the SnO of the embodiment of the present invention 2 preparations ₂the size distribution plot of nano-crystalline granule, shows the SnO preparing ₂the size of particle is more even, and major diameter is distributed in 6.8-8.0nm, and minor axis is distributed in 4.5-6.0nm.

Fig. 9 is the SnO of the embodiment of the present invention 3 preparations ₂the size distribution plot of nano-crystalline granule, shows the SnO preparing ₂the distribution of sizes of particle is at 3.5-6.0nm.

Figure 10 is the SnO of the embodiment of the present invention 1 preparation ₂the N of nano-crystalline granule ₂adsorption-desorption thermoisopleth and graph of pore diameter distribution, show that this material has typical meso-hole structure.

Figure 11 is the SnO of the embodiment of the present invention 2 preparations ₂the N of nano-crystalline granule ₂adsorption-desorption thermoisopleth and graph of pore diameter distribution, show that this material has typical meso-hole structure.

Figure 12 is the SnO of the embodiment of the present invention 3 preparations ₂the N of nano-crystalline granule ₂adsorption-desorption thermoisopleth and graph of pore diameter distribution, show that this material has typical meso-hole structure.

Embodiment:

Below by embodiment, be also described further by reference to the accompanying drawings.

The present embodiment is with SnCl ₄5H ₂o is raw material, and benzoglyoxaline is made mineralizer, and the mixed solution of water and ethanol or propyl alcohol is solvent, prepares single dispersion, bigger serface, highly purified tin dioxide nanocrystal particle, and its concrete technology step comprises:

(1), using deionized water and ethanol or propyl alcohol by volume for the ratio of 1:1 mixes as solvent, then by SnCl ₄5H ₂o and benzoglyoxaline are dissolved in solvent and obtain mixing solutions, wherein, and SnCl ₄5H ₂the weight ratio of O and solvent is 1:100, SnCl ₄5H ₂the weight ratio of O and benzoglyoxaline is 7:2-12;

(2), mixing solutions that step (1) is obtained transfers in teflon-lined stainless steel cauldron, at 160-200 ℃, reacts 12-24 hour, obtains white sample;

(3), white sample that step (2) is obtained dries after cleaning with deionized water and ethanol successively at 60-150 ℃, obtains single tin dioxide nanocrystal particle that disperses.

Embodiment 1:

The present embodiment is with SnCl ₄5H ₂o is raw material, and benzoglyoxaline is made mineralizer, and the mixed solution of water and ethanol is solvent, under 180 ℃ of conditions, reacts 20 hours, makes single dispersion, bigger serface, highly purified tin dioxide nanocrystal particle, and its concrete technology step comprises:

(1), 20mL deionized water and 20mL ethanol are mixed as solvent, by 0.35gSnCl ₄5H ₂o and 0.1g benzoglyoxaline are also dissolved in and in solvent, obtain mixing solutions;

(2), the mixing solutions of gained is transferred in 50mL teflon-lined stainless steel cauldron, at 180 ℃, react 20h and obtain white sample;

(3), the white sample of gained is cleaned with deionized water and ethanol successively, then in air, 100 ℃ of oven dry obtain single SnO of dispersion that mean diameter is about 3.4nm ₂the brilliant particle of ball shaped nano, its specific surface area is 223.6m ²g ^-1, aperture is 5.6nm.

Embodiment 2:

In the present embodiment, the consumption of benzoglyoxaline is 0.3g, and other experiment condition is identical with embodiment 1, prepares single SnO of dispersion of elliposoidal ₂nano-crystalline granule, its major diameter average out to 7.4nm, minor axis is on average about 4.8nm, and specific surface area is 181.2m ²g ^-1, aperture is 6.4nm.

Embodiment 3:

In the present embodiment, the consumption of benzoglyoxaline is 0.6g, and other experiment condition is identical with embodiment 1, the SnO preparing ₂there is clustering phenomena in nano-crystalline granule, particle is spherical, and its mean diameter is about 5.2nm, and specific surface area is 109.7m ²g ^-1, compare specific surface area with embodiment 1 with 2 and obviously decline; Aperture is 4.3nm.

The present embodiment is by regulating the consumption regulation and control SnO of mineralizer benzoglyoxaline ₂nanocrystalline particle size and pattern, under the regulating and controlling effect of benzoglyoxaline, the SnO of preparation ₂the advantages such as nano particle has size homogeneous, and monodispersity is good, and degree of crystallinity is high, and reference area is large, and have potential application in fields such as catalyzer, gas sensor and electrode materialss.

Claims (1)

1. a single preparation method who disperses tin dioxide nanocrystal particle, is characterized in that with SnCl ₄5H ₂o is raw material, and benzoglyoxaline is made mineralizer, and the mixed solution of water and ethanol or propyl alcohol is solvent, and the single concrete technology step of tin dioxide nanocrystal particle of disperseing of preparation comprises:

(1), using deionized water and ethanol or propyl alcohol by volume for the ratio of 1:1 mixes as solvent, then by SnCl ₄5H ₂o and benzoglyoxaline are dissolved in solvent and obtain mixing solutions, wherein, and SnCl ₄5H ₂the weight ratio of O and solvent is 1:100, SnCl ₄5H ₂the weight ratio of O and benzoglyoxaline is 7:2-12;

(2), mixing solutions that step (1) is obtained transfers in teflon-lined stainless steel cauldron, at 160-200 ℃, reacts 12-24 hour, obtains white sample;

(3), white sample that step (2) is obtained dries after cleaning with deionized water and ethanol successively at 60-150 ℃, obtains single tin dioxide nanocrystal particle that disperses.

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