CN103588242B - Biological polymer assists the preparation method of a step hydrothermal synthesis of stephanoporate stannic oxide nanometer ball - Google Patents
Biological polymer assists the preparation method of a step hydrothermal synthesis of stephanoporate stannic oxide nanometer ball Download PDFInfo
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- CN103588242B CN103588242B CN201310598509.6A CN201310598509A CN103588242B CN 103588242 B CN103588242 B CN 103588242B CN 201310598509 A CN201310598509 A CN 201310598509A CN 103588242 B CN103588242 B CN 103588242B
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Abstract
The invention discloses the preparation method that a kind of biological polymer assists a step hydrothermal synthesis of stephanoporate stannic oxide nanometer ball, belong to technical field of inorganic nano-material preparation; Its step under agitation by a certain percentage tin tetrachloride and complexing agent is dissolved in the settled solution forming the stannate radicle ion containing complexing in deionized water, then biological polymer sodium alginate is under agitation added, be stirred to and dissolve completely, this reaction system being transferred to liner is in the stainless steel cauldron of tetrafluoroethylene; Be placed in loft drier, hydro-thermal reaction certain hour, then naturally cools to room temperature, and by gained precipitate with deionized water and dehydrated alcohol rinsing respectively, centrifugation, in loft drier inner drying, can obtain porous SnO 2 (SnO
2) nanometer ball; Synthetic method of the present invention has that technique is simple, and cost is low, product pattern and size uniform, can synthesize in a large number and the high advantage of productive rate, and the porous SnO 2 nanosphere size of synthesis and pattern even, mean diameter is 80nm ~ 350nm.
Description
Technical field
The present invention relates to a kind of preparation method of nano material, be specifically related to a kind of preparation method of porous SnO 2 nanometer ball, belong to technical field of inorganic nano-material preparation.
Background technology
There is the constructional feature of inorganic nano material due to its uniqueness of vesicular structure and the widespread use at gas sensor, effective catalyst, drug release carrier and cause people to pay close attention to greatly.Tindioxide (SnO
2) be a kind of important n-type semiconductor, there is wide band gap (under room temperature 3.62eV), be widely used in the fields such as opto-electronic device, gas sensor, energy storage and conversion.
There is the tin dioxide nanometer material of vesicular structure, because of its unique texture, there is the catalytic activity and electrochemical activity that are better than its solid material, thus cause the strong interest of people.At present, the preparation method with the tin dioxide nanometer material of vesicular structure has many kinds.As Velasquez etc. with a kind of organo-tin compound for presoma, employing Surfactant CTAB is structure directing agent, obtains stannic oxide (C. Velasquez, the Nanotechnology with nano-pore structure by hydrolysis and heat treating process, 2005,1278); Zhang etc. take stannous sulfate as reactant, and employing trisodium citrate is complexing agent, with water/ethanol for mixed solvent, obtain porous oxidation tin nanometer ball (H. J. Zhang, CystEngComm, 2012,3169) by solvent-thermal method and heat treating process; Chen etc. are reactant with sodium stannate, take oleic acid as structure directing agent, obtain mesoporous tin oxide nanometer ball (Y. J. Chen, CystEngComm, 2012,6170) by thermal evaporation; Huang etc. first to prepare hydroxyl stannate copper, then with it for precursor, by high-temperature roasting and pickling, prepare porous oxidation tin cubes and nanometer rod (J. R. Huang, CystEngComm, 2012,3283).Jia etc. take carbon nanotube as hard template, remove carbon nanotube by high-temperature calcination, obtain the tin oxide nano tube (Y. Jia, Journal of Physical Chemistry C, 2009,9581) of vesicular structure.Wang etc. take glucose as carbon source, by water heat transfer stannic oxide/carbon composite nano ball, are then obtained the stannic oxide (F. Wang, Journal of Alloys and Commpounds, 2011,5969) with macroporous structure by calcining.But in above preparation method or need organic salt costly or organic reagent, or the more and complex process of preparation process is as needed hard template (carbon nanotube or carbon ball or polymer microballoon), presoma and high-temperature heat treatment program subsequently.
Sodium alginate is a kind of polysaccharide (biological polymer) extracted from natural seaweed, is also a kind of common foodstuff additive, stablizer and thickening material.Its backbone can form network in aqueous, and is wherein rich in the functional group such as carboxyl, hydroxyl, can interact with metal ion, as pattern and the structure regulator of preparing metal oxide or sulfide micro Nano material.This use tin tetrachloride is reactant, with inexpensively and the less sodium alginate of consumption for structure regulator, take sodium hydroxide as alkali source and complexing agent, adopt the method for stannic oxide nanometer ball that one step hydro thermal method to synthesize pattern and size uniform within a short period of time in a large number, that have vesicular structure to yet there are no open report.
The present invention adopts biological polymer to assist a step hydrothermal synthesis of stephanoporate stannic oxide nanometer ball, technique is simple, with low cost, quick, energy-conservation, efficient, and the porous SnO 2 nanometer ball excellent property of synthesis, this product is expected to obtain in fields such as lithium ion battery electrode material, photoelectric and biosensors apply widely.
Summary of the invention
The object of the present invention is to provide a kind of method of synthesizing porous stannic oxide nanometer ball, under lower temperature condition, adopt raw material cheap and easy to get and simple process, rapid, high volume synthesis be dispersed better, pattern and the comparatively uniform porous SnO 2 nanometer ball of size.
For realizing the object of foregoing invention, the technical scheme that the present invention takes is as follows:
Biological polymer assists the preparation method of a step hydrothermal synthesis of stephanoporate stannic oxide nanometer ball, comprises the steps:
(1) tin tetrachloride is dissolved in deionized water, then adds sodium hydroxide and stir formation settled solution A; The mol ratio of sodium hydroxide and tin ion is 6.0 ~ 8.0:1;
(2) pattern and structure regulator sodium alginate are dissolved in deionized water, stir and form solution B,
(3) under vigorous stirring, solution A dropwise joined in solution B, form solution C, in final solution, sodium alginate mass concentration is 6 ~ 30mg/ml;
(4) the reaction system solution C that step (3) obtains is transferred in reactor, be placed in loft drier, hydro-thermal reaction 2 ~ 24 hours, then room temperature is naturally cooled to, gained precipitation dehydrated alcohol and deionized water are washed three times respectively, and centrifugation, vacuum drying oven inner drying, can obtain porous SnO 2 nanometer ball;
The add-on of the tin tetrachloride described in step (1) is: the volumetric molar concentration of tin ion is 0.01 ~ 0.1mol/L;
The add-on of the sodium hydroxide described in step (1) is: the mol ratio of sodium hydroxide and tin ion is 6.0 ~ 8.0:1;
Pattern described in step (2) and structure regulator are sodium alginate; Described pattern and the add-on of structure regulator are mass concentration is 6 ~ 30mg/ml;
The temperature of the hydro-thermal reaction described in step (4) is 160 ~ 200 DEG C;
The time of the hydro-thermal reaction described in step (4) is 2 ~ 24 hours;
Vacuum drying temperature described in step (4) is 60 ~ 80 DEG C;
10 ~ 12 hours vacuum drying time described in step (4);
In preparation process of the present invention, adopt sodium alginate as pattern and structure regulator, adopt sodium hydroxide as alkali source and complexing agent.
The present invention regulates the size of porous SnO 2 nanometer ball by changing tin ion concentration or sodium alginate concentration or reaction times or temperature of reaction.The reaction process that the present invention relates to is as follows:
Sn
4++ 6OH
-→[Sn(OH)
6]
2-(1)
[Sn(OH)
6]
2-→SnO
2+2OH
-+2H
2O (2)
Beneficial effect of the present invention is:
(1) have that preparation technology is simple, with low cost, product pattern and size uniform, can synthesize in a large number and the high advantage of product yield.
(2) the porous SnO 2 nanometer ball mean diameter prepared is between 80nm ~ 350nm; This product is expected to obtain in fields such as lithium ion battery electrode material, photoelectric and biosensors apply widely.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the porous SnO 2 nanometer ball that the present invention obtains;
Fig. 2 is scanning electron microscope and the transmission electron microscope picture of the porous SnO 2 nanometer ball that the present invention obtains;
Fig. 3 is the scanning electron microscope (SEM) photograph of the porous SnO 2 nanometer ball that the present invention obtains.
Embodiment
Be described in further details the present invention below by embodiment, these embodiments are only used for the present invention is described, do not limit the scope of the invention.
Embodiment 1
Be dissolved in by the tin tetrachloride of 2mmol in 15ml deionized water, then add the sodium hydroxide of 14mmol, solution produced white precipitate before this, and this precipitation fades away under vigorous stirring, finally forms transparent clear soln A.Under vigorous stirring 0.5g sodium alginate is dissolved in 20ml water, forms solution B.Under vigorous stirring solution A is dropwise joined in solution B.Final solution being transferred to 50ml liner is in the stainless steel cauldron of tetrafluoroethylene.Be placed in loft drier, hydro-thermal reaction 24 hours at 180 DEG C.Then room temperature is naturally cooled to, by the rinsing three times respectively of gained precipitate with deionized water and dehydrated alcohol, centrifugation, 80 DEG C of dryings 12 hours in vacuum drying oven.Porous SnO 2 nanometer ball can be obtained.SnO
2the X-ray diffractogram of product is shown in Fig. 1, and in figure, each diffraction peak position and intensity are all consistent with standard diffraction card (JCPDS41-1445).Its scanning electron microscope (SEM) photograph is shown in Fig. 2 (A), and Fig. 2 (A) shows SnO
2product is the very uniform nanometer ball of scale topography, mean diameter 141nm and better dispersed.Fig. 2 (B) and (C) are its transmission electron microscope picture, and display nanometer ball is assembled by many little nanoparticles to form, and its internal structure is comparatively loose, there is comparatively concrete dynamic modulus.
Embodiment 2
Be dissolved in by the tin tetrachloride of 2mmol in 15ml deionized water, then add the sodium hydroxide of 14mmol, solution produced white precipitate before this, and this precipitation fades away under vigorous stirring, finally forms transparent clear soln A.Under vigorous stirring 0.5g sodium alginate is dissolved in 20ml water, forms solution B.Under vigorous stirring solution A is dropwise joined in solution B.Final solution being transferred to 50ml liner is in the stainless steel cauldron of tetrafluoroethylene.Be placed in loft drier, hydro-thermal reaction 24 hours at 180 DEG C.Then room temperature is naturally cooled to, by the rinsing three times respectively of gained precipitate with deionized water and dehydrated alcohol, centrifugation, 80 DEG C of dryings 12 hours in vacuum drying oven.Porous SnO 2 nanometer ball can be obtained.SnO
2the scanning electron microscope (SEM) photograph of product is shown in Fig. 3, display SnO
2product is the very uniform nanometer ball of scale topography, mean diameter 195nm and better dispersed.
Embodiment 3
Be dissolved in by the tin tetrachloride of 1mmol in 15ml deionized water, then add the sodium hydroxide of 8mmol, solution produced white precipitate before this, and this precipitation fades away under vigorous stirring, finally forms transparent clear soln A.Under vigorous stirring 0.8g sodium alginate is dissolved in 20ml water, forms solution B.Under vigorous stirring solution A is dropwise joined in solution B.Final solution being transferred to 50ml liner is in the stainless steel cauldron of tetrafluoroethylene.Be placed in loft drier, hydro-thermal reaction 24 hours at 180 DEG C.Then naturally cool to room temperature, by the rinsing three times respectively of gained precipitate with deionized water and dehydrated alcohol, centrifugation, in vacuum drying oven, 80 DEG C of dryings 12 hours, can obtain porous SnO 2 nanometer ball, SnO
2nanometer ball mean diameter 102nm.
Embodiment 4
Be dissolved in by the tin tetrachloride of 2mmol in 15ml deionized water, then add the sodium hydroxide of 14mmol, solution produced white precipitate before this, and this precipitation fades away under vigorous stirring, finally forms transparent clear soln A.Under vigorous stirring 0.8g sodium alginate is dissolved in 20ml water, forms solution B.Under vigorous stirring solution A is dropwise joined in solution B.Final solution being transferred to 50ml liner is in the stainless steel cauldron of tetrafluoroethylene.Be placed in loft drier, hydro-thermal reaction 2 hours at 180 DEG C.Then naturally cool to room temperature, by the rinsing three times respectively of gained precipitate with deionized water and dehydrated alcohol, centrifugation, in vacuum drying oven, 80 DEG C of dryings 12 hours, can obtain porous SnO 2 nanometer ball, SnO
2nanometer ball mean diameter 124nm.
Embodiment 5
Be dissolved in by the tin tetrachloride of 2mmol in 15ml deionized water, then add the sodium hydroxide of 14mmol, solution produced white precipitate before this, and this precipitation fades away under vigorous stirring, finally forms transparent clear soln A.Under vigorous stirring 0.8g sodium alginate is dissolved in 20ml water, forms solution B.Under vigorous stirring solution A is dropwise joined in solution B.Final solution being transferred to 50ml liner is in the stainless steel cauldron of tetrafluoroethylene.Be placed in loft drier, hydro-thermal reaction 24 hours at 200 DEG C.Then naturally cool to room temperature, by the rinsing three times respectively of gained precipitate with deionized water and dehydrated alcohol, centrifugation, in vacuum drying oven, 80 DEG C of dryings 12 hours, can obtain porous SnO 2 nanometer ball, SnO
2nanometer ball mean diameter 161nm.
Claims (1)
1. biological polymer assists the preparation method of a step hydrothermal synthesis of stephanoporate stannic oxide nanometer ball, it is characterized in that: comprise the steps:
(1) tin tetrachloride is dissolved in deionized water, then adds sodium hydroxide and stir formation settled solution A; The mol ratio of sodium hydroxide and tin ion is 6.0 ~ 8.0:1, and the volumetric molar concentration of tin ion is 0.01 ~ 0.1mol/L;
(2) be dissolved in deionized water by pattern and structure regulator sodium alginate, stir and form solution B, pattern and structure regulator are sodium alginate, and its add-on is mass concentration is 6 ~ 30mg/ml;
(3) under vigorous stirring, solution A dropwise joined in solution B, form solution C, in final solution, sodium alginate mass concentration is 6 ~ 30mg/ml;
(4) the reaction system solution C that step (3) obtains is transferred in reactor, be placed in loft drier, room temperature is naturally cooled to after 2 ~ 24 hours 160 ~ 200 DEG C of hydro-thermal reactions, gained precipitation dehydrated alcohol and deionized water are washed three times respectively, and centrifugation, 60 ~ 80 DEG C of vacuum drying oven inner dryings 10 ~ 12 hours, can obtain porous SnO 2 nanometer ball.
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|---|---|---|---|---|
| KR20100027454A (en) * | 2008-09-02 | 2010-03-11 | 한양대학교 산학협력단 | Method for fabricating tin dioxide nano sol and porous composite using the same |
| CN102674439A (en) * | 2012-05-28 | 2012-09-19 | 重庆大学 | Method for preparing stannic oxide porous microsphere |
| CN103121708A (en) * | 2013-03-12 | 2013-05-29 | 大连理工大学 | Porous tin dioxide material as well as preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100027454A (en) * | 2008-09-02 | 2010-03-11 | 한양대학교 산학협력단 | Method for fabricating tin dioxide nano sol and porous composite using the same |
| CN102674439A (en) * | 2012-05-28 | 2012-09-19 | 重庆大学 | Method for preparing stannic oxide porous microsphere |
| CN103121708A (en) * | 2013-03-12 | 2013-05-29 | 大连理工大学 | Porous tin dioxide material as well as preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| Low temperature synthesis of porous tin oxide anode for high-performance lithium-ion battery;Alok Kumar Rai等;《Electrochimica Acta》;20130731;第109卷;461-467页 * |
| Micrometer-sized nanoporous tin dioxide spheres for gas sensing;J.-H. Smått等;《Sensors and Actuators B: Chemical》;20101230;第155卷;483-488页 * |
| Porous SnO2 nanospheres as sensitive gas sensors for volatile organic compounds detection;Zhipeng Li等;《Nanoscale》;20110131;1646-1652页 * |
| Template-free synthesis and gas sensing properties of well-controlled porous tin oxide nanospheres;S.C. Yeow等;《Sensors and Actuators B: Chemical》;20090903;第143卷;295-301页 * |
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