CN103776870A - ZnO/SnO2 nano composite gas-sensitive material with flower-shaped grading structure and preparation method of material - Google Patents
ZnO/SnO2 nano composite gas-sensitive material with flower-shaped grading structure and preparation method of material Download PDFInfo
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Abstract
The invention provides a ZnO/SnO2 nano composite gas-sensitive material with a flower-shaped grading structure. The ZnO/SnO2 nano composite gas-sensitive material is prepared by the following steps: dripping a sodium hydroxide water solution into an ethanol solution of cetyl trimethyl ammonium bromide and stannous chloride dihydrate under electromagnetic stirring; after dripping, preparing a precursor solution by the continuous electromagnetic stirring; adding the precursor solution into a reaction kettle, reacting at 130 DEG C; carrying out centrifuging on a reactant, washing and drying to obtain a flower-shaped stannous oxide sacrifice template; adding the flower-shaped stannous oxide sacrifice template into a zinc acetate solution; agitating and carrying out ultrasonic treatment; removing a solvent to obtain a ZnO/SnO2 precursor; and carrying out heat preservation on the ZnO/SnO2 precursor for 2-4 hours in an air atmosphere of 700 DEG to obtain the composite gas-sensitive material. According to the ZnO/SnO2 nano composite gas-sensitive material with the flower-shaped grading structure, the controllable preparation of the composite gas-sensitive material on the appearance and components can be realized; the mass percent content of zinc oxide in the composite gas-sensitive material is 5%-15%; a flower shape is assembled by sheet-shaped tin dioxide and zinc oxide nano particles; the ZnO/SnO2 nano composite gas-sensitive material has a good gas sensitive performance and has a wide application prospect in the aspect of manufacturing a novel high-efficient gas sensor.
Description
Technical field
The present invention relates to a kind of nano composite material, specifically a kind of flower-shaped hierarchy zinc paste/tin ash (ZnO/SnO
2) nano composite air-sensitive material and preparation method thereof.
Background technology
in environment, the quick and precisely detection of toxic and harmful is significant to environmental protection.The advantages such as the gas sensor based on Metal oxide semiconductor gas-sensitiveness material is highly sensitive with it, response is fast, method for making is simple, volume is little, low price have become a kind of important gas detection means.Metal oxide semiconductor gas-sensitiveness material is the core component of such gas sensor, and its gas sensitization performance directly has influence on performance and the application of gas sensor.Therefore, it is significant to improving the performance of gas sensor that the novel metal oxide that Design & preparation has an efficient air-sensitive performance is partly led material, become one of the primary study direction in semiconductor gas sensor field.
Zinc paste (ZnO) and tin ash (SnO
2) be two kinds of typical N-shaped wide bandgap semiconductor materials, this bi-material is subject to extensive concern because having good gas sensitization performance in gas sensor field, is also to study at present two more class gas sensitives.For further improving ZnO and the SnO of one-component
2the deficiency that nano material exists at aspects such as gas-selectively, response recovery time, sensitivity, thus bi-material is carried out to compound making ZnO/SnO
2nano composite material is a kind of effective method.The advantage of the method is can effectively improve by fully utilizing the cooperative effect of bi-material between advantage and the bi-material aspect air-sensitive performance the air-sensitive performance of material.At present about ZnO/SnO
2the report of nano composite material comprises: SnO
2/ ZnO compound hollow microballoon (CN 103364453 A), ZnO/SnO
2nuclear shell structure nano line (
sensors and Actuators B 148 (2010) 595-600), SnO
2nano particle/ZnO nanorod nano composite material (
sensors and Actuators B 162 (2012) 82 – 88), nanofiber-nano wire stem/branch heterojunction structure (
sensors and Actuators B 181 (2012) 787 – 794) etc.And for by ZnO nano particulate and SnO
2the three-dimensional flower-shaped ZnO/SnO that nanometer sheet assembles
2the current document of method of nano composite material and preparation thereof has no report.
Summary of the invention
The present invention seeks to the deficiency for solving the problems of the technologies described above, a kind of zinc paste (ZnO) nano particle and tin ash (SnO are provided
2) the flower-shaped hierarchical Z nO/SnO that assembles of nanometer sheet
2nano composite air-sensitive material, preparation method, prepared ZnO/SnO
2composite air-sensitive material has good sensitivity characteristic to ethanol, aspect the new and effective gas sensor of manufacture, is having broad application prospects.
A kind of flower-shaped hierarchical Z nO/SnO
2nano composite air-sensitive material, described composite air-sensitive material is by sheet stannous oxide and ZnO nanoparticle is compound forms, the shared mass percentage content of zinc paste is 5-15%, described sheet stannous oxide is assembled into flower-shaped, ZnO nanoparticle is evenly grown on the petal of sheet stannous oxide formation, and wherein ZnO nanoparticle is of a size of 10～30 nanometers.
A kind of flower-shaped hierarchical Z nO/SnO
2nano composite air-sensitive material, wherein the mass percentage content of zinc paste is 5-15%; Its concrete preparation process is:
Step 1, by NaOH (NaOH) aqueous solution, under electromagnetic agitation, be added drop-wise to cetyl trimethyl ammonium bromide (CTAB) and stannous chloride dihydrate (SnCl
22H
2o) in ethanolic solution, dropwise rear continuation electromagnetic agitation 10-20 minute, prepare precursor solution, for subsequent use; The mol ratio of wherein said NaOH, cetyl trimethyl ammonium bromide and stannous chloride dihydrate is 3:1:1, and the volume ratio of water and ethanol is 1:7-1:10;
Step 2, precursor solution prepared above-mentioned steps one is packed in reactor, at 130 ℃, react 12-24 hour; Then reactant is taken out and carry out centrifugally, centrifugal gained precipitation successively after ethanol and deionized water washing, is then dried, obtain flower-shaped stannous oxide and sacrifice template, for subsequent use;
Step 3, according to two water zinc acetate (Zn (CH
3cOO)
22H
2o) with above-mentioned steps two in the stannous oxide that obtains to sacrifice the mol ratio of stannous oxide in template be 0.1-0.3:1, get two water zinc acetates, be added in its quality 5-10 deionized water or ethanol doubly, obtain acetic acid zinc solution, for subsequent use;
Step 4, prepared above-mentioned steps two flower-shaped stannous oxide is sacrificed to template add in the prepared acetic acid zinc solution of above-mentioned steps three, then through stirring, ultrasonic processing is after 5-20 minute, adopt low-temperature heat evaporation or distillation under vacuum to remove solvent, obtain ZnO/SnO
2presoma, for subsequent use;
Step 5, by above-mentioned steps three gained ZnO/SnO
2presoma is incubated after 2-4 hour in the air atmosphere of 700 ℃, obtains flower-shaped hierarchical Z nO/SnO
2nano composite air-sensitive material.
Beneficial effect is:
1, the present invention adopts the synthetic flower-shaped stannous oxide of solvent heat for sacrificing template, and two water zinc acetates are zinc source, can realize flower-shaped hierarchical Z nO/SnO by heat treatment method
2the controlled preparation of nano composite air-sensitive material in pattern and component; Utilize stannous oxide to sacrifice the pattern hereditary capacity of template, can prepare the SnO with stannous oxide sacrifice template with identical shape characteristic
2material, through heat treatment process, SnO is SnO by complete oxidation
2, and its shape characteristic has intactly been entailed SnO by SnO sacrifice template
2, can control by controlling the addition of each reagent the pattern of stannous oxide sacrifice template, thereby control prepared flower-shaped hierarchical Z nO/SnO
2the shape of nano composite air-sensitive material.
2, prepared flower-shaped hierarchical Z nO/SnO
2nano composite material is by SnO
2nanometer sheet and ZnO nano particulate assemble.Wherein, ZnO nano particulate is evenly grown in sheet SnO
2on petal, and ZnO nano particle size is 10-30 nanometer, and content is easily controlled.Can obtain by controlling the addition of zinc acetate dihydrate the ZnO/SnO of different ZnO contents
2compound substance; ZnO content is in the time that quality percentage composition is less than or equal to 10%, and in gained compound substance, ZnO nano particle is at sheet SnO
2surface presents good dispersiveness.And in the time that ZnO content is more than or equal to 15%, SnO
2can there is obvious reunion in epontic ZnO nano particle, thereby cause the specific surface area of compound substance to decline, and finally causes the ethanol air-sensitive performance of material to reduce.Sensitivity the best between ZnO quality percentage composition 5%-15% time, can need to adjust according to sensitivity the content of ZnO.
3, SnO
2between nanometer sheet and ZnO nano particulate, form the raising that heterojunction is conducive to material air-sensitive performance; The inner a large amount of holes that exist of flower-shaped hierarchy are convenient to gas molecule and are transported therein, and then can improve its response-recovery speed to gas; By changing the specific surface area that the content of ZnO nano particle can Effective Regulation compound substance, and then regulate and control its Adsorption, make it have better gas sensitization performance, having broad application prospects manufacturing aspect new and effective gas sensor.
Accompanying drawing explanation
The flower-shaped hierarchical Z nO/SnO of Fig. 1, different ZnO contents
2the XRD spectra of nano composite material:
The flower-shaped hierarchical Z nO/SnO that Fig. 2, ZnO mass content are 10%
2the overall microscopic appearance stereoscan photograph of nano composite material;
The flower-shaped hierarchical Z nO/SnO that Fig. 3, ZnO mass content are 10%
2the microscopic appearance stereoscan photograph of the sheet petal of nano composite material;
The flower-shaped hierarchical Z nO/SnO of Fig. 4, different ZnO contents
2nano composite material is the sensitivity curve to different concentration ethanol steam under 300 degree;
Fig. 5. the flower-shaped hierarchical Z nO/SnO that ZnO content is 10%
2nano composite material is the response-recovery curve to different concentration ethanol steam under 300 degree.
Embodiment
A kind of flower-shaped hierarchical Z nO/SnO
2nano composite air-sensitive material, described composite air-sensitive material is by sheet tin ash and ZnO nanoparticle is compound forms, the shared mass percentage content of zinc paste is 5-15%, described sheet tin ash is assembled into flower-shaped, ZnO nanoparticle is evenly grown on the petal of sheet tin ash formation, and wherein ZnO nanoparticle is of a size of 10～30 nanometers.
A kind of flower-shaped hierarchical Z nO/SnO
2nano composite air-sensitive material, wherein the mass percentage content of zinc paste is 5-15%; Its concrete preparation process is:
Step 1, by NaOH (NaOH) aqueous solution, under electromagnetic agitation, be added drop-wise to cetyl trimethyl ammonium bromide (CTAB) and stannous chloride dihydrate (SnCl
22H
2o) in ethanolic solution, dropwise rear continuation electromagnetic agitation 10-20 minute, prepare precursor solution, for subsequent use; The mol ratio of wherein said NaOH, cetyl trimethyl ammonium bromide and stannous chloride dihydrate is 3:1:1, and the volume ratio of water and ethanol is 1:7-1:10;
Step 2, precursor solution prepared above-mentioned steps one is packed in reactor, at 130 ℃, react 12-24 hour; Then product is taken out and carry out centrifugally, centrifugal gained precipitation successively after ethanol and deionized water washing, is then dried, obtain flower-shaped stannous oxide and sacrifice template, for subsequent use;
Step 3, according to two water zinc acetate (Zn (CH
3cOO)
22H
2o) with above-mentioned steps two in the stannous oxide that obtains to sacrifice the mol ratio of stannous oxide in template be 0.1-0.3:1, get two water zinc acetates, be added in its quality 5-10 deionized water or ethanol doubly, obtain acetic acid zinc solution, for subsequent use;
Step 4, prepared above-mentioned steps two flower-shaped stannous oxide is sacrificed to template add in the prepared acetic acid zinc solution of above-mentioned steps three, then through stirring, ultrasonic processing is after 5-20 minute, adopt low-temperature heat evaporation or distillation under vacuum to remove solvent, obtain ZnO/SnO
2presoma, for subsequent use;
Step 5, by above-mentioned steps three gained ZnO/SnO
2presoma is incubated after 2-4 hour in the air atmosphere of 700 ℃, obtains flower-shaped hierarchical Z nO/SnO
2nano composite air-sensitive material.
embodiment 1
Accurately weigh 1.822 g CTAB and 1.286 g SnCl
22H
2o adds in 40mL absolute ethyl alcohol, is stirred to solid and dissolves completely.The NaOH aqueous solution of 5 mL 3 M is under agitation dropwise joined in above-mentioned solution, dropwise and continue to stir 10 min.In gained solution reaction cartridge still, in 130 ℃ of reaction 15 h, reaction finishes rear reactor and naturally cools to room temperature, and gained precipitate with deionized water and ethanol wash respectively 4 times, and after centrifuging, at the temperature of 60 ℃, dry 12 h, prepare SnO
powder.Add 20 ml to contain 0.66 g Zn (CH 0.5 g SnO powder of above-mentioned preparation
3cOO)
2 .2H
2in O aqueous solution, after ultrasonic processing 10 min, solvent is removed in decompression distillation, obtains ZnO/SnO
2the presoma of nano composite material.Gained ZnO/SnO in air atmosphere
2the thermal treatment 2 hours at 700 ℃ of nano composite material presoma, obtains ZnO mass content and is 10% flower-shaped classification ZnO/SnO
2nano composite air-sensitive material, its XRD spectra as shown in Figure 1.Fig. 2 and Fig. 3 are respectively the overall microscopic appearance of this sample and the microscopic appearance electron microscope photo scanning of sheet petal; In this sample, the particle diameter of ZnO nano particle is in 10-30 nanometer left and right, and ZnO nano particle is at SnO
2sheet petal surface favorable dispersibility.Its specific surface area is 25.132 m
2g
-1.
Prepared material is made to air-sensitive original paper, on WS-60A type gas sensor tester, test air-sensitive performance.The sensitivity S of gas sensor is expressed as:
s=
r a/
r g, wherein S is sensitivity,
r afor the aerial resistance of gas sensor,
r gfor the resistance of gas sensor in gas to be measured.The response time of element to test gas and be respectively certain density gas inject to be measured release time or separating sensor starts to reach and stablize resistance 90% or return to the required time of resistance 10% in normal air to resistance of sensor.As shown in Figure 4 and Figure 5, test result shows its result, at 300 ℃, is 43 to the sensitivity S of 100 ppm ethanol, responds and is respectively release time 19 seconds and 5 seconds.
embodiment 2
Accurately weigh 2.733 g CTAB and 1.929 g SnCl
22H
2o adds in 60mL absolute ethyl alcohol, is stirred to solid and dissolves completely.The NaOH aqueous solution of 7.5 mL 3 M is under agitation dropwise joined in above-mentioned solution, dropwise and continue to stir 10 min.In gained solution reaction cartridge still, in 130 ℃ of reaction 12 h, reaction finishes rear reactor and naturally cools to room temperature, and gained precipitate with deionized water and ethanol wash respectively 4 times, and after centrifuging, at the temperature of 60 ℃, dry 12 h, prepare SnO
powder.0.8 g SnO powder of above-mentioned preparation is scattered in to 20 ml and contains 1.07 g Zn (CH
3cOO)
2 .2H
2in O aqueous solution, after ultrasonic processing 10 min, Low Temperature Thermal evaporative removal solvent, obtains ZnO/SnO
2the presoma of nano composite material.Gained ZnO/SnO in air atmosphere
2the thermal treatment 4 hours at 700 ℃ of nano composite material presoma, obtains ZnO mass content and is 10% flower-shaped classification ZnO/SnO
2nano composite air-sensitive material, its XRD spectra as shown in Figure 1.In this sample, the particle diameter of ZnO nano particle is in 10～30 nanometer left and right, and ZnO nano particle is at SnO sheet petal surface favorable dispersibility.Its specific surface area is 24.672 m
2g
-1.
Adopt the prepared flower-shaped classification ZnO/SnO of method of testing test of air-sensitive performance in example 1
2nano composite air-sensitive material, its result as shown in Figure 4 and Figure 5, draw this material at 300 ℃ the sensitivity to 100 ppm ethanol and the response-recovery time close with example.
embodiment 3
Accurately weigh 1.822 g CTAB and 1.286 g SnCl
22H
2o adds in 40mL absolute ethyl alcohol, is stirred to solid and dissolves completely.The NaOH aqueous solution of 5 mL 3 M is under agitation dropwise joined in above-mentioned solution, dropwise and continue to stir 10 min.In gained solution reaction cartridge still, in 130 ℃ of reaction 15 h, reaction finishes rear reactor and naturally cools to room temperature, and gained precipitate with deionized water and ethanol wash respectively 4 times, and after centrifuging, at the temperature of 60 ℃, dry 12 h, prepare SnO
powder.0.5 g SnO powder of above-mentioned preparation is scattered in to 20 ml and contains 0.32 g Zn (CH
3cOO)
2 .2H
2in O aqueous solution, after ultrasonic processing 10 min, solvent is removed in decompression distillation, obtains ZnO/SnO
2the presoma of nano composite material.Gained ZnO/SnO in air atmosphere
2the thermal treatment 3 hours at 700 ℃ of nano composite material presoma, obtains ZnO mass content and is 5% flower-shaped classification ZnO/SnO
2nano composite air-sensitive material, its XRD spectra as shown in Figure 1.In this sample, the particle diameter of ZnO nano particle is in 10～30 nanometer left and right, and ZnO nano particle is at SnO sheet petal surface favorable dispersibility.Its specific surface area is 22.146 m
2g
-1.
Adopt the prepared flower-shaped classification ZnO/SnO of method of testing test of air-sensitive performance in example 1
2nano composite air-sensitive material, its result as shown in Figure 4 and Figure 5, show that this material is 33.1 to the sensitivity of 100 ppm ethanol at 300 ℃.Respond and be respectively release time 14 seconds and 12 seconds.
embodiment 4
Accurately weigh 1.822 g CTAB and 1.286 g SnCl
22H
2o adds in 40mL absolute ethyl alcohol, is stirred to solid and dissolves completely.The NaOH aqueous solution of 5 mL 3 M is under agitation dropwise joined in above-mentioned solution, dropwise and continue to stir 10 min.In gained solution reaction cartridge still, in 150 ℃ of reaction 15 h, reaction finishes rear reactor and naturally cools to room temperature, and gained precipitate with deionized water and ethanol wash respectively 4 times, and after centrifuging, at the temperature of 60 ℃, dry 12 h, prepare SnO
powder.0.5 g SnO powder of above-mentioned preparation is scattered in to 20 ml and contains 1.06 g Zn (CH
3cOO)
2 .2H
2in O aqueous solution, after ultrasonic processing 10 min, solvent is removed in decompression distillation, obtains ZnO/SnO
2the presoma of nano composite material.Gained ZnO/SnO in air atmosphere
2the thermal treatment 3 hours at 700 ℃ of nano composite material presoma, obtains ZnO content and is 15% flower-shaped classification ZnO/SnO
2nano composite air-sensitive material, its XRD spectra as shown in Figure 1.In this sample, the particle diameter of ZnO nano particle is in 10～30 about nanometers, and between ZnO nano particle, starts to occur part and reunite.Its specific surface area is 14.438 m
2g
-1.
Adopt the prepared flower-shaped classification ZnO/SnO of method of testing test of air-sensitive performance in example 1
2nano composite air-sensitive material, its result as shown in Figure 4 and Figure 5, show that this material is 14.2 to the sensitivity of 100 ppm ethanol at 300 ℃, responds and is respectively release time 24 seconds and 27 seconds.
Claims (5)
1. a flower-shaped hierarchical Z nO/SnO
2the preparation method of nano composite air-sensitive material, is characterized in that: its concrete preparation process is:
Step 1, by sodium hydrate aqueous solution, under electromagnetic agitation, be added drop-wise in the ethanolic solution of cetyl trimethyl ammonium bromide and stannous chloride dihydrate, dropwise rear continuation electromagnetic agitation 10-20 minute, prepare precursor solution, for subsequent use; The mol ratio of wherein said NaOH, cetyl trimethyl ammonium bromide and stannous chloride dihydrate is 3:1:1, and the volume ratio of water and ethanol is 1:7-1:10;
Step 2, precursor solution prepared above-mentioned steps one is packed in reactor, at 130 ℃, react 12-24 hour; Then reactant is taken out and carry out centrifugally, centrifugal gained precipitation successively after ethanol and deionized water washing, is then dried, obtain flower-shaped stannous oxide and sacrifice template, for subsequent use;
The mol ratio that step 3, the stannous oxide obtaining according to two water zinc acetates and above-mentioned steps two are sacrificed stannous oxide in template is 0.1-0.3:1, gets two water zinc acetates, is added in its quality 5-10 deionized water or ethanol doubly, obtains acetic acid zinc solution, for subsequent use;
Step 4, prepared above-mentioned steps two flower-shaped stannous oxide sacrificed to template add in the prepared acetic acid zinc solution of above-mentioned steps three, then successively through stir and ultrasonic processing after, removal solvent, obtains ZnO/SnO
2presoma, for subsequent use;
Step 5, by above-mentioned steps three gained ZnO/SnO
2presoma after thermal treatment 2-4 hour, obtains flower-shaped hierarchical Z nO/SnO in the air atmosphere of 700 ℃
2nano composite air-sensitive material.
2. flower-shaped hierarchical Z nO/SnO as claimed in claim 1
2the preparation method of nano composite air-sensitive material, is characterized in that: the removal solvent method described in step 4 is, low-temperature heat evaporation or distillation under vacuum.
3. flower-shaped hierarchical Z nO/SnO as claimed in claim 1
2the preparation method of nano composite air-sensitive material, is characterized in that: the time of ultrasonic processing described in step 4 is 5-20 minute.
4. flower-shaped hierarchical Z nO/SnO as claimed in claim 1
2the preparation method of nano composite air-sensitive material, is characterized in that: the rotating speed stirring described in step 4 is 4000r/min, and the time is 5-20 minute.
5. the flower-shaped hierarchical Z nO/SnO that prepared by the method for claim 1
2nano composite air-sensitive material, it is characterized in that: described composite air-sensitive material is by sheet tin ash and ZnO nanoparticle is compound forms, the shared mass percentage content of zinc paste is 5-15%, described sheet tin ash is assembled into flower-shaped, ZnO nanoparticle is evenly grown on the petal of sheet tin ash formation, and wherein ZnO nanoparticle is of a size of 10～30 nanometers.
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