CN101704505B - Method for preparing high-thermostability tin oxide nano-powder on Ca-doped basis - Google Patents

Method for preparing high-thermostability tin oxide nano-powder on Ca-doped basis Download PDF

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CN101704505B
CN101704505B CN200910154719XA CN200910154719A CN101704505B CN 101704505 B CN101704505 B CN 101704505B CN 200910154719X A CN200910154719X A CN 200910154719XA CN 200910154719 A CN200910154719 A CN 200910154719A CN 101704505 B CN101704505 B CN 101704505B
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powder
solution
tin oxide
ion
thermostability
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CN101704505A (en
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郭艳群
李月
杨晔
谭瑞琴
宋伟杰
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention discloses a method for preparing high-thermostability tin oxide nano-powder on Ca-doped basis, mainly taking inorganic tin salt, inorganic calcium salt and alkali source as raw materials. The experimental process mainly comprises the following steps: precursor preparation, hydrothermal reaction, precipitate washing and drying and the like, and the invention further analyzes the thermostability of the Ca-doped tin oxide nano-powder through high-temperature thermal treatment. The invention has the main advantages as follows: Ca is evenly doped into SnO2 by using the low-temperature hydrothermal method, so that the prepared Ca-doped tin oxide nano-powder has small particle size and large specific surface area; compared with the undoped tin oxide, the invention obviously increases the thermostability of the Ca-doped tin oxide nano-powder prepared by the method to 900 DEG C, therefore, the invention has wide prospect of application in the fields of gas-sensing, catalysis and the like; and the method dispenses with surfactant and has the advantages of simple and easily-available materials, simple and pollution-free process, short preparation period, mild conditions and low cost, therefore, the method is suitable for large-scale production and is an environment-friendly synthesis method.

Description

The preparation method of the high-thermostability tin oxide nano-powder that mixes based on calcium
Technical field
The present invention relates to a kind of preparation of nanomaterials, especially relate to a kind of preparation method of the high-thermostability tin oxide nano-powder that mixes based on calcium.
Background technology
Existing tin oxide (SnO 2) have fabulous photoelectric characteristic and to the sensitive property of reducibility gas, be widely used in fields such as gas sensor material, conductive powder body and catalysis material at present.Work as SnO 2After the crystal particle scale of material gets into nanoscale, owing to the exclusive small-size effect of nano material, skin effect and quantum size effect etc. show many special physicochemical character, SnO 2Nano particle shows very big advantage in application facet such as air-sensitive, conduction and photocatalysis, but because SnO 2The nano particle specific surface energy is high, belongs to thermodynamic unstable system, in order to reach stable state, the spontaneous reunion of particle meeting; Unadulterated in addition SnO 2The nano particle heat endurance is relatively poor, can grow up with the rising crystal grain of temperature; Particle agglomeration or grain growth all can weaken SnO because of size increases 2The performance of nano material advantage.So SnO 2The key issue that nano material will solve in actual high temperature environment of applications is how to improve its heat endurance, and this is very important for the performance that improves material with recycling the life-span.Numerous researchs show, to pure SnO 2The different element that mixes in the nano material is the effective way of head it off.Elements C a is SnO 2A kind of effective grain growth inhibitor of nano material, SnO 2The relative SnO of the CaO that the crystal boundary place exists 2The growth of crystal grain can be played the obvious suppression effect, thereby can control SnO 2The size of crystal grain, improve its heat endurance (Bong-Ki Min, Soon-Don Choi, Sensors andActuators B, 2004,99,288-296).
Relevant Ca doping SnO 2The research report of nano powder preparation is less, and wherein, Choi research group has reported a kind of preparation Ca doping SnO 2The wet chemical method of nano material, they are Xi Yuan with the stannous chloride, obtain moisture SnO earlier 2Deposition, again deposition is carried out drying, the calcining, ball milling obtains pure SnO 2Nano material finally obtains the SnO that Ca mixes through the method for in the acetate solution of Ca, flooding then 2Nano material (Soon-Don Choi, Duk-Dong Lee, Sensors and Actuators B, 2001,77,335-338; Bong-Ki Min, Soon-Don Choi, Sensorsand Actuators B, 2004,99,288-296; Bong-Ki Min, Soon-Don Choi, Sensors andActuators B, 2005,108,119-124).People such as Liu Wei are primary raw material with stannous chloride and calcium nitrate, utilize sol-gel process to prepare the SnO that Ca mixes 2Nano material (LIU Wei, CAO Lili, SCIENCE IN CHINA (Series B), 2001,44,63-67).
Yet, above-mentioned Ca doping SnO 2There is following deficiency in the preparation method of nano-powder:
1), heat treatment temperature is higher among the above-mentioned preparation method; The high-temperature calcination process introduces impurity easily, cause growing up and reuniting of nano-powder particle; And cause the migration or the segregation of the calcium constituent that is mixed, thereby it is inhomogeneous to cause calcium to mix, and influences the final performance of powder.
2), the method operation more (comprising deposition, drying, calcining, ball milling, dipping) that adopts of Choi, manufacturing cycle is very long.
Summary of the invention
The method of the high-thermostability tin oxide nano-powder that technical problem to be solved by this invention provides that a kind of technology is simple, the preparation of mild condition is mixed based on calcium
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of preparation method of the high-thermostability tin oxide nano-powder that mixes based on calcium, and concrete steps are followed successively by:
Step 1; Pink salt is dissolved in deionized water or the absolute ethyl alcohol; Through stirring formation Sn ion concentration is the tin-salt solution of 0.2 ~ 1mol/L; Calcium salt is dissolved in the deionized water, is the calcium salt soln of 0.1 ~ 0.5mol/L through stir forming the Ca ion concentration, and described pink salt is a kind of in stannous chloride, stannic chloride or the nitric acid tin; Described calcium salt is a kind of in calcium chloride or the calcium nitrate;
Step 2, according to the mol ratio of Ca ion and Sn ion 0.5: 100 ~ 10: 100, the calcium salt soln with step 1 preparation when stirring joined in the tin-salt solution, continues to stir 10 ~ 30min then, forms mixed solution;
Step 3 adds to the alkali source drips of solution in the described mixed solution of step 2 when stirring, and between 9 ~ 13, and then stirs 10 ~ 50min, the formation precursor solution until pH value; Described alkali source solution is that the aqueous solution or the mass concentration of the potassium hydroxide that concentration is the aqueous solution of the urea of 0.4 ~ 1mol/L, the aqueous solution that concentration is the NaOH of 0.4 ~ 1mol/L, concentration is 0.4 ~ 1mol/L is a kind of in 1 ~ 8% the ammoniacal liquor;
Step 4 is transferred to the precursor solution of step 3 gained in the autoclave, at 100 ~ 200 ℃ of following hydro-thermal reaction 4 ~ 24h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 5 is used deionized water and absolute ethanol washing repeatedly successively with the sediment of step 4 gained, and to remove the ion of solubility wherein, 60 ~ 100 ℃ of oven dry under vacuum condition of the sediment after will washing then obtain the SnO that Ca mixes 2Nano-powder.
Described stirring is a magnetic agitation, and the stirring intensity when dripping alkali source solution is bigger than other processes.
Washing methods described in the step 5 is: adopt centrifugation or the method for filtering spends deionised water 3 ~ 4 times successively with product, with absolute ethanol washing 1 ~ 2 time, with the ion of removal solubility wherein.
The ion of described solubility is one or more in chlorion, nitrate ion, sodium ion, the potassium ion.
In washing process, through AgNO 3Solution detects supernatant liquor or whether filtrating produces the residual volume that white precipitate is judged chlorion, described AgNO 3The concentration of solution is 0.1mol/L.
Compared with prior art, the invention has the advantages that: adopt hydrothermal reaction at low temperature to realize that Ca is at SnO 2In even doping; Can directly generate crystal through water-heat process; Do not need follow-up high-temperature heat treatment; The migration or the segregation of the calcium constituent of having avoided the introducing of the growing up of crystal grain in the high-temperature heat treatment process, impurity and having been mixed, gained Ca doped tin oxide nano-powder particle diameter little (several approximately nanometer), the big (160 ~ 190m of specific area 2/ g); Compare with unadulterated tin oxide, adopt the heat endurance of the Ca doped tin oxide nano-powder of this method preparation obviously to improve, its heat endurance can reach 900 ℃.In a word, this method is not added any surfactant, and raw material is simple and easy to, and technology is simply pollution-free, and manufacturing cycle is short, mild condition, and cost is low, and suitability for scale production is a kind of environmentally friendly synthetic method.
Description of drawings
Fig. 1 is preparation method's of the present invention process chart;
Fig. 2 is the X-ray diffractogram of products therefrom under the different heat treatment temperature in the practical implementation instance 1 of the present invention;
Fig. 3 is the products therefrom in the practical implementation instance 1 of the present invention and 2 and the comparison diagram of the average grain size of doped tin oxide nano-powder under the different heat treatment temperature not.
The specific embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Practical implementation instance 1
Step 1 is with the SnCl of 3.506g 4.5H 2O is dissolved in the deionized water, forms Sn through stirring 4+Concentration is the tin chloride solution of 0.3mol/L; According to Ca 2+With Sn 4+Mol ratio be 10% to take by weighing the CaCl of 0.1109g 2Be dissolved in the deionized water, stir then and form Ca 2+Concentration is the CaCl of 0.5mol/L 2Solution;
Step 2, the CaCl that when stirring, step 1 is prepared 2Solution joins SnCl 4In the solution, continue to stir 20min then, form mixed solution;
Step 3 when stirring is that 7% ammoniacal liquor drops in the described mixed solution of step 2 with mass concentration, is 10 until pH value, and then stirs 30min, the formation precursor solution;
Step 4 is transferred to the precursor solution of step 3 gained in the autoclave, at 200 ℃ of following hydrothermal treatment consists 4h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 5 is used deionized water and absolute ethanol washing repeatedly successively with sediment, and to remove the ion of solubility wherein, the 70 ℃ of dry 2h under vacuum condition of the sediment after will washing then obtain the SnO that white Ca mixes 2Nano-powder, its average grain size is approximately 3.7nm, and specific area is about 176m 2/ g.
Practical implementation instance 2
Step 1 is with the SnCl of 3.506g 4.5H 2O is dissolved in the deionized water, forms Sn through stirring 4+Concentration is the tin chloride solution of 0.3mol/L; According to Ca 2+With Sn 4+Mol ratio be 3% to take by weighing the CaCl of 0.0333g 2Be dissolved in the deionized water, stir then and form Ca 2+Concentration is the CaCl of 0.5mol/L 2Solution;
Step 2, the CaCl that when stirring, step 1 is prepared 2Solution joins SnCl 4In the solution, and then stir 20min, form mixed solution;
Step 3 when stirring is that 7% ammoniacal liquor drops in the described mixed solution of step 2 with mass concentration, is 10 until pH value, and then stirs 30min, the formation precursor solution;
Step 4 is transferred to the described precursor solution of step 3 in the autoclave, at 200 ℃ of following hydrothermal treatment consists 4h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 5 is used deionized water and absolute ethanol washing repeatedly successively with sediment, and to remove the ion of solubility wherein, the 70 ℃ of dry 2h under vacuum condition of the sediment after will washing then obtain the SnO that white Ca mixes 2Nano-powder, its average grain size is approximately 3.5nm, and specific area is about 188m 2/ g.
Practical implementation instance 3
Step 1 is with the SnCl of 2.7078g 2.2H 2O is dissolved in the 40ml absolute ethyl alcohol, forms Sn through stirring 2+Concentration is the stannous chloride solution of 0.3mol/L; According to Ca 2+With Sn 2+Mol ratio be 5% to take by weighing the CaCl of 0.0665g 2Be dissolved in the deionized water, stir then and form Ca 2+Concentration is the CaCl of 0.5mol/L 2Solution;
Step 2, the CaCl that when stirring, step 1 is prepared 2Solution joins SnCl 2In the solution, continue to stir 20min then, form mixed solution;
Step 3 when stirring is that 7% ammoniacal liquor drops in the described mixed solution of step 2 with mass concentration, is 10 until pH value, and then stirs 30min, the formation precursor solution;
Step 4 is transferred to the described precursor solution of step 3 in the autoclave, at 200 ℃ of following hydrothermal treatment consists 4h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 5 is used deionized water and absolute ethanol washing repeatedly successively with sediment, and to remove the ion of solubility wherein, the 70 ℃ of dry 2h under vacuum condition of the sediment after will washing then obtain the SnO that white Ca mixes 2Nano-powder, its average grain size is approximately 3.6nm, and specific area is about 185m 2/ g.
Practical implementation instance 4
Step 1 is with the SnCl of 2.7078g 2.2H 2O is dissolved in the 20ml absolute ethyl alcohol, forms Sn through stirring 2+Concentration is the stannous chloride solution of 0.6mol/L; According to Ca 2+With Sn 2+Mol ratio be 5% to take by weighing the Ca (NO of 0.0984g 3) 2Be dissolved in the deionized water, stir then and form Ca 2+Concentration is the Ca (NO of 0.2mol/L 3) 2Solution;
Step 2, the Ca (NO that when stirring, step 1 is prepared 3) 2Solution joins SnCl 2In the solution, continue to stir 30min then, form mixed solution;
Step 3 when stirring is that the aqueous solution of the NaOH of 0.5mol/L drops in the described mixed solution of step 2 with concentration, is 12 until pH value, and then stirs 40min, the formation precursor solution;
Step 4 is transferred to the described precursor solution of step 3 in the autoclave, at 180 ℃ of following hydrothermal treatment consists 12h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 5 is used deionized water and absolute ethanol washing repeatedly successively with sediment, and to remove the ion of solubility wherein, the 90 ℃ of dry 1h under vacuum condition of the sediment after will washing then obtain the SnO that white Ca mixes 2Nano-powder, its average grain size is approximately 3.8nm, and specific area is about 172m 2/ g.
Further, mix to the influence of tin oxide nano-powder heat endurance, with the SnO of above-mentioned each embodiment gained in order to analyze Ca 2At 400 ℃, 600 ℃, 700 ℃, 900 ℃ following heat treatment 3h, the heating rate in the heat treatment process is 5 ℃/min to nano-powder respectively.Be illustrated in figure 2 as the SnO that gained 10mol%Ca mixes in the practical implementation instance 1 2Under the different heat treatment temperature, the anneal X-ray diffractogram of 3h of nano-powder can be seen the SnO of the corresponding tetragonal crystal system Rutile structure of each diffraction maximum in publishing picture 2The relevant dephasign of Ca does not appear in phase; Be illustrated in figure 3 as unadulterated SnO 2The SnO that gained Ca mixes in nano-powder and practical implementation instance 1 and 2 2The average grain size of nano-powder under the different heat treatment temperature, the average grain size here are by the mean value of the Scherrer formula crystallite dimension that estimation obtains according to the half-peak breadth of 110,101 and 211 diffraction maximums, can find out the SnO that Ca mixes 2With unadulterated SnO 2Compare heat endurance and obviously improve, Ca mixes and has suppressed SnO under the high temperature effectively 2The growth of crystal grain, its heat endurance can reach 900 ℃ (even through 900 ℃ of heat treatment 3h, less increase also only takes place crystallite dimension, still remains on about 10nm).
Got by last, the present invention adopts hydrothermal reaction at low temperature to realize that Ca is at SnO 2Even doping in the nano material; Compare with unadulterated tin oxide, adopt the heat endurance of the Ca doped tin oxide nano-powder of this method preparation obviously to improve.
More than be the description of this invention and non-limiting, based on other embodiment of inventive concept, all among protection scope of the present invention.

Claims (5)

1. the preparation method of a high-thermostability tin oxide nano-powder that mixes based on calcium is characterized in that concrete steps are followed successively by:
Step 1; Pink salt is dissolved in deionized water or the absolute ethyl alcohol; Through stirring formation Sn ion concentration is the tin-salt solution of 0.2～1mol/L; Calcium salt is dissolved in the deionized water, is the calcium salt soln of 0.1～0.5mol/L through stir forming the Ca ion concentration, and described pink salt is a kind of in stannous chloride, stannic chloride or the nitric acid tin; Described calcium salt is a kind of in calcium chloride or the calcium nitrate;
Step 2, according to the mol ratio of Ca ion and Sn ion 0.5: 100～10: 100, the calcium salt soln with step 1 preparation when stirring joined in the tin-salt solution, continues to stir 10～30min then, forms mixed solution;
Step 3 adds to the alkali source drips of solution in the described mixed solution of step 2 when stirring, and between 9～13, and then stirs 10～50min, the formation precursor solution until pH value; Described alkali source solution is that the aqueous solution or the mass concentration of the potassium hydroxide that concentration is the aqueous solution of the urea of 0.4～1mol/L, the aqueous solution that concentration is the NaOH of 0.4～1mol/L, concentration is 0.4～1mol/L is a kind of in 1～8% the ammoniacal liquor;
Step 4 is transferred to the precursor solution of step 3 gained in the autoclave, at 100～200 ℃ of following hydro-thermal reaction 4～24h, naturally cools to room temperature then, after the filtering supernatant, obtains sediment;
Step 5 is used deionized water and absolute ethanol washing repeatedly successively with the sediment of step 4 gained, and to remove the ion of solubility wherein, 60～100 ℃ of oven dry under vacuum condition of the sediment after will washing then obtain the SnO that Ca mixes 2Nano-powder.
2. the preparation method of the high-thermostability tin oxide nano-powder that mixes based on calcium according to claim 1, it is characterized in that: described stirring is a magnetic agitation, the stirring intensity when dripping alkali source solution is bigger than other processes.
3. the preparation method of the high-thermostability tin oxide nano-powder that mixes based on calcium according to claim 1; It is characterized in that: the washing methods described in the step 5 is: adopt the method for centrifugation or filtration that sediment is spent deionised water 3～4 times successively; With absolute ethanol washing 1～2 time, to remove the ion of solubility wherein.
4. the preparation method of the high-thermostability tin oxide nano-powder that mixes based on calcium according to claim 1, it is characterized in that: the ion of described solubility is one or more in chlorion, nitrate ion, sodium ion, the potassium ion.
5. the preparation method of the high-thermostability tin oxide nano-powder that mixes based on calcium according to claim 1 is characterized in that: in washing process, through AgNO 3Solution detects supernatant liquor or whether filtrating produces the residual volume that white precipitate is judged chlorion, described AgNO 3The concentration of solution is 0.1mol/L.
CN200910154719XA 2009-12-03 2009-12-03 Method for preparing high-thermostability tin oxide nano-powder on Ca-doped basis Expired - Fee Related CN101704505B (en)

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CN106179346A (en) * 2016-07-07 2016-12-07 深圳市尤佳环境科技有限公司 A kind of metal-oxide preparation method with photocatalytic activity
CN111017988B (en) * 2019-12-31 2022-07-05 深圳爱多科传感技术有限公司 Formaldehyde gas-sensitive material based on recovery treatment of tin mud and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN1652259A (en) * 2005-03-03 2005-08-10 昆明理工大学 Process for preparing nano-oxide conducting powder
CN1724383A (en) * 2005-06-21 2006-01-25 电子科技大学 Process for preparing one-dimensional nano tin dioxide material
KR100724807B1 (en) * 2006-08-21 2007-06-04 고려대학교 산학협력단 Method for preparing tin oxide nano particle and the tin oxide nano particle prepared by the same, and method for preparing metal-doped tin oxide nano particle and the metal-doped tin oxide nano particle prepared by the same
CN101037224A (en) * 2007-02-15 2007-09-19 苏州大学 Preparation process of antimony doped stannum oxide nano-crystal
EP2048116A1 (en) * 2007-10-09 2009-04-15 ChemIP B.V. Dispersion of nanoparticles in organic solvents

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1652259A (en) * 2005-03-03 2005-08-10 昆明理工大学 Process for preparing nano-oxide conducting powder
CN1724383A (en) * 2005-06-21 2006-01-25 电子科技大学 Process for preparing one-dimensional nano tin dioxide material
KR100724807B1 (en) * 2006-08-21 2007-06-04 고려대학교 산학협력단 Method for preparing tin oxide nano particle and the tin oxide nano particle prepared by the same, and method for preparing metal-doped tin oxide nano particle and the metal-doped tin oxide nano particle prepared by the same
CN101037224A (en) * 2007-02-15 2007-09-19 苏州大学 Preparation process of antimony doped stannum oxide nano-crystal
EP2048116A1 (en) * 2007-10-09 2009-04-15 ChemIP B.V. Dispersion of nanoparticles in organic solvents

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