CN102680528B - Silver and indium oxide composite nanorod array formaldehyde air-sensitive material and preparation method thereof - Google Patents
Silver and indium oxide composite nanorod array formaldehyde air-sensitive material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a sensing material and a preparation method thereof, in particular to a silver and indium oxide composite nanorod array formaldehyde air-sensitive material and a preparation method thereof. The material is formed by hexagonally and periodically arraying silver and indium oxide composite nanorods. The preparation method comprises mixing and stirring surfactant, water and hydrochloric acid until the surfactant is dissolved totally; then adding ethyl orthosilicate in the mixture and stirring; performing hydrothermal reaction for 1-5 days at the temperature of 130 DEG C after standing; performing suction filtration, washing and drying after cooling so as to obtain white powder; using solvent to extract mesoporous silica which is a hard template; adding the mesoporous silica into ethanol solution with indium nitrate and silver nitrate, stirring and dipping; repeating the steps; and finally adding caustic soda solution in a calcined product, and centrifugally filtering to obtain an orderly silver and indium oxide composite nanorod array material after stirring. The silver and indium oxide composite nanorod array formaldehyde air-sensitive material and the preparation method thereof have the advantages of high sensitivity and fine stability.
Description
Technical field
The present invention relates to a kind of sensing material and preparation method thereof, especially relate to a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material and preparation method thereof.
Background technology
As everyone knows, formaldehyde is a kind of important industrial chemicals, be widely used in synthetic resin, surfactant, plastics, rubber, leather, papermaking, dyestuff, pharmacy, agricultural chemicals, photographic film, explosive, building materials and sterilization, the industry such as stifling and anticorrosion, but simultaneously formaldehyde gas energy intense stimulus human body mucous membrane, there is carcinogenicity, belong to high poisonous substance, so effective detection of PARA FORMALDEHYDE PRILLS(91,95) is particular importance.
At present the detection method of formaldehyde gas mainly contains spectrophotometric method, chromatography, fluorescence method, electrochemical process, but these methods still come with some shortcomings, as long in apparatus expensive, complicated operation, detection time, can not on-the-spotly detect in real time etc.Formaldehyde semiconductor gas sensor refers to the metal-oxide semiconductor (MOS) of PARA FORMALDEHYDE PRILLS(91,95) sensitivity is added to the gas sensor that top electrode and heating resistor are prepared into, it have simple in structure, highly sensitive, stable performance, cost low, be easy to the features such as miniaturization and portability, can detect in real time by PARA FORMALDEHYDE PRILLS(91,95), have great application prospect.What as the formaldehyde gas sensitive material of key component wherein, conventionally adopt is oxide or the composite oxides of the metals such as indium, tin, iron.As the people such as Li adopt In2O3 tiny balloon, as sensitive material, to 80ppm formaldehyde, sensitivity is 12(Li B.X.; Xie Y.; Jing M.; Rong G.X.; Tang Y.C.; Zhang G.Z., In2O3 hollow microspheres:Synthesis from designed In (OH) 3 precursors and applications in gas sensors and photocatalysis, Langmuir, 22 (2006) 9380-9385); The people such as Wu adopt α-Fe2O3 nanometer rods, and as sensitive material, to 50ppm formaldehyde, sensitivity is 8(Wu C.Z.; Yin P.; Zhu X.; OuYang C.Z.; Xie Y., Synthesis of hematite (α-Fe2O3) nanorods:Diameter-size and shape effects on their applications in magnetism, lithium ion battery, and gas sensors, Journal of Physical Chemistry B, 110 (2006) 17806-17812); The people such as Xu adopt the compound of ZnO and ZnSnO3, and as sensitive material, to 50ppm formaldehyde, sensitivity is 33(Xu J.; Jia X.; Lou X.; Xi G.; Han J.; Gao Q., Selective detection of HCHO gas using mixed oxides of ZnO/ZnSnO3, Sensors and Actuators B:Chemical, 120 (2007) 694-699).But formaldehyde gas sensitive material highly sensitive, good stability still needs further to be developed.
Summary of the invention
The object of the invention is to overcome the defect of above-mentioned prior art, a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material of a kind of highly sensitive, good stability and preparation method thereof is provided.
The present invention realizes in the following way:
Silver-indium oxide composite nanorod array formaldehyde gas sensitive material, is characterized in that: this formaldehyde gas sensitive material is to be formed by silver-indium oxide composite nanorod six side's periodic arrangement, and between nanometer rods, having length is that 2-5nm connects;
Described nanometer rods diameter is 5-15nm, length 20-500nm, and described silver is 0.2-20% at the quality percentage composition of composite nanorod;
The preparation method of described a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material, is characterized in that: its preparation method comprises the steps:
A, by 8.0g surfactant P123, the hydrochloric acid that 60g water is 2M with 240g concentration mixes under 35 ° of C, stir and all dissolve and be uniformly dispersed to surfactant for 1-24 hour, then add 16.72g ethyl orthosilicate, stir after 5 minutes, transfer in a teflon bottle in 35 ° of C baking ovens standing 20 hours, then at 130-150 ° of C hydro-thermal reaction 1-5 days, naturally cooling by obtaining a white powder after suction filtration, washing, natural drying at room temperature, contain the mesopore silicon oxide of surfactant;
Mesopore silicon oxide in b, use solvent extraction a: the white powder that 1.0g step a is obtained joins in 200 milliliters of solvents, again to the concentrated hydrochloric acid that adds 16 milliliters of 36wt% in solvent, in reflux, 70 ° of C stir 24h, filter, wash, be dried, obtain surfactant-free mesopore silicon oxide;
The mesopore silicon oxide that c, the 0.6g step b of take processed is hard template, be distributed in 10g ethanol, add 1.8g indium nitrate and 0.1 g silver nitrate, at 40 ° of C, stir dipping, indium salt solusion is entered in the duct of mesopore silicon oxide, continue to stir after solvent flashing, in air, in 300 ° of C calcinings 2 hours, calcine 1 ° of C/min of heating rate;
D, the powder that step c is obtained are re-dispersed in 10g ethanol, add 1.4 g indium nitrates and 0.08 g silver nitrate, at 40 ° of C, stir and flood and continue to stir after solvent flashing, in air, in 300 ° of C calcinings 2 hours, calcine 1 ° of C/min of heating rate;
E, the powder that steps d is obtained are re-dispersed in 10g ethanol, add 1 g indium nitrate and 0.06 g silver nitrate, at 40 ° of C, stir and flood and continue to stir after solvent flashing, in air, in 300 ° of C calcinings 2 hours, calcine 1 ° of C/min of heating rate;
F, in the product after step e calcining, add 2M NaOH solution, after stirring, centrifugal filtration, to remove monox template, obtains Ordered Silver-indium oxide composite Nano rod array material;
Solvent in described step b can be one or more potpourri of methyl alcohol, ethanol, ethylene glycol, propyl alcohol, butanols, ether, acetonitrile, acetone, tetrahydrofuran, or the mixed solvent of they and water, the mass ratio of described mesopore silicon oxide and described solvent is 1:5-1:200;
In described step c, the mass ratio of indium nitrate and silver nitrate and mesopore silicon oxide is 1.5-7:1, and the temperature that stirs dipping is 5-80 ℃, and calcining heat is 300-500 ℃, and heating rate is 0.5-2.5 ℃/min, and calcination time is 2-10 h;
The concentration of the sodium hydroxide solution in described step e is 2-10M.
The present invention has following effect:
1) between unique, the nanometer rods of material, space is conducive to the diffusion of gas molecule, accelerated response resume speed: silver-indium oxide composite nanorod array formaldehyde gas sensitive material provided by the invention is to be formed by silver-indium oxide composite nanorod six side's periodic arrangement, between nanometer rods, having length is that 2-5nm connects, described nanometer rods diameter is 5-15nm, length 20-500nm, the quality percentage composition of described silver in compound is 0.2-20%, between nanometer rods, space is conducive to the diffusion of gas molecule, has accelerated response resume speed.
2) strengthened thermal stability: provided by the inventionly compoundly receive that between Material cladding nanometer rods provided by the invention, to have length be that 2-5nm connects, reduced nanometer rods contact each other, can reduce the sensitivity that under high temperature, the loss of sintering phenomenon and specific surface area brings and decline, strengthen thermal stability.
3) can change its air-sensitive character: the diameter of composite nanorod provided by the invention can, by regulating the aperture of mesopore silicon oxide template to control, can change its air-sensitive character accordingly;
4) strengthen sensitivity: in material provided by the invention, the existence of argent can promote formaldehyde in the reaction on composite nanorod surface, strengthen sensitivity, in composite nanorod, the content of silver can add the ratio of silver nitrate and indium nitrate to control by adjusting, correspondingly can change its air-sensitive character.
5) preparation method is unique: preparation method provided by the invention is all dissolved for first surfactant, water and mixed in hydrochloric acid being stirred to surfactant, then add ethyl orthosilicate and stir, after standing in 130-150 ℃ of hydro-thermal reaction 1-5 days, cooling rear suction filtration, washing, dry, obtain a white powder, contain the mesopore silicon oxide of surfactant; Then use in solvent extraction the mesopore silicon oxide in step to remove surfactant wherein; The ordered meso-porous silicon oxide of processing in above step is hard template, is joined in the ethanolic solution of indium nitrate and silver nitrate and stirs dipping, so that the ethanolic solution of indium nitrate and silver nitrate enters in the duct of mesopore silicon oxide; Continue stirring until after solvent volatilizees completely, in air, calcining repeats this step once or once, in product after the most backward calcining, add sodium hydroxide solution, after stirring, centrifugal filtration, to remove mesopore silicon oxide template, obtains Ordered Silver-indium oxide composite Nano rod array material.
Accompanying drawing explanation
Fig. 1: be the XRD collection of illustrative plates of the embodiment of the present invention 1 gained Ordered Silver-indium oxide composite nanorod array;
Fig. 2: be SEM picture and the TEM picture of the embodiment of the present invention 1 gained Ordered Silver-indium oxide composite nanorod array;
Fig. 3: be the air-sensitive response curve to variable concentrations formaldehyde gas of the embodiment of the present invention 1 gained Ordered Silver-indium oxide composite nanorod array.
Embodiment
Embodiment 1: a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material, this formaldehyde gas sensitive material is to be formed by silver-indium oxide composite nanorod six side's periodic arrangement, between nanometer rods, having length is that 2-5nm connects, described nanometer rods diameter is 9 nm, length 20-500nm, the quality percentage composition of described silver in compound is 9.4%.
The preparation method of described a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material is:
8.0g surfactant P123,60 g water mix at 35 ℃ with the hydrochloric acid of 240 g 2 M, stir 12 hours until surfactant all dissolves and is uniformly dispersed, then add 16.72 g ethyl orthosilicate TEOS, stir after 5 minutes, transfer in a teflon bottle in 35 ℃ of baking ovens standing 20 hours, then 130 degree hydro-thermal reaction is 5 days, naturally cooling by suction filtration, washing, after natural drying at room temperature, obtain a white powder, contain the mesopore silicon oxide of surfactant.Surfactant P123 removes by solvent extraction method: the powdered sample that 1.0 g obtain above joins in 200 milliliters of ethanol, then adds the concentrated hydrochloric acid of 16 milliliter of 36 wt%, and in reflux, 70 ℃ are stirred 24 h, filter, and washing, dry.Ordered meso-porous silicon oxide specific surface area 365 m2/g of gained, pore volume 1.21 cm3/g, linked hole size is greater than 8-13 nm.
The mesopore silicon oxide of the above-mentioned processing of 0.6 g of take is hard template, be distributed in 10 g ethanol, add 1.8 g indium nitrates and 0.1 g silver nitrate, at 40 ℃, stir dipping, so that indium salt solusion enters in the duct of mesopore silicon oxide, continue to stir after solvent flashing, in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, adds 1.4 g indium nitrates and 0.08 g silver nitrate, at 40 ℃, stirs and floods and continue to stir after solvent flashing, and in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, adds 1 g indium nitrate and 0.06 g silver nitrate, at 40 ℃, stirs and floods and continue to stir after solvent flashing, and in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; In the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration, to remove monox template, obtains Ordered Silver-indium oxide composite Nano rod array material of the present invention, specific surface area 80 m2/g of this material, pore volume 0.27 cm3/g.As shown in Figure 2, the oldered array material of composite Nano bar construction is obtained, and the diameter of nanometer rods is about 9 nm.
If Fig. 1 is the XRD collection of illustrative plates of the present embodiment gained Ordered Silver-indium oxide composite nanorod array;
Fig. 3 is the air-sensitive response curve to variable concentrations formaldehyde gas of the present embodiment gained Ordered Silver-indium oxide composite nanorod array.
Embodiment 2: a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material, this formaldehyde gas sensitive material is to be formed by silver-indium oxide composite nanorod six side's periodic arrangement, between nanometer rods, having length is that 2-5nm connects, described nanometer rods diameter is 9nm, length 20-500nm, the quality percentage composition of described silver in compound is 0.2%.
The preparation method of described a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material is:
8.0g surfactant P123,60 g water mix at 35 ℃ with the hydrochloric acid of 240 g 2 M, stir 12 hours until surfactant all dissolves and is uniformly dispersed, then add 16.72 g ethyl orthosilicate TEOS, stir after 5 minutes, transfer in a teflon bottle in 35 ℃ of baking ovens standing 20 hours, then 130 degree hydro-thermal reaction is 5 days, naturally cooling by suction filtration, washing, after natural drying at room temperature, obtain a white powder, contain the mesopore silicon oxide of surfactant.Surfactant P123 removes by solvent extraction method: the powdered sample that 1.0 g obtain above joins in 200 milliliters of ethanol, then adds the concentrated hydrochloric acid of 16 milliliter of 36 wt%, and in reflux, 70 ℃ are stirred 24 h, filter, and washing, dry.Ordered meso-porous silicon oxide specific surface area 365 m2/g of gained, pore volume 1.21 cm3/g, linked hole size 8-13 nm.
The mesopore silicon oxide of the above-mentioned processing of 0.6 g of take is hard template, be distributed in 10 g ethanol, add 1.8 g indium nitrates and 0.003 g silver nitrate, at 40 ℃, stir dipping, so that indium salt solusion enters in the duct of mesopore silicon oxide, continue to stir after solvent flashing, in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, adds 1.4 g indium nitrates and 0.001 g silver nitrate, at 40 ℃, stirs and floods and continue to stir after solvent flashing, and in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, adds 1 g indium nitrate and 0.0008 g silver nitrate, at 40 ℃, stirs and floods and continue to stir after solvent flashing, and in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; In the product after calcining, add 2 M NaOH solution,, after stirring, centrifugal filtration, to remove monox template, obtains Ordered Silver-indium oxide composite Nano rod array material of the present invention, specific surface area 70 m2/g of this material, pore volume 0.26 cm3/g.
Embodiment 3: a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material, this formaldehyde gas sensitive material is to be formed by silver-indium oxide composite nanorod six side's periodic arrangement, between nanometer rods, having length is that 2-5nm connects, described nanometer rods diameter is 9nm, length 20-500nm, the quality percentage composition of described silver in compound is 20%.
The preparation method of described a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material is:
8.0g surfactant P123,60 g water mix at 35 ℃ with the hydrochloric acid of 240 g 2 M, stir 12 hours until surfactant all dissolves and is uniformly dispersed, then add 16.72 g ethyl orthosilicate TEOS, stir after 5 minutes, transfer in a teflon bottle in 35 ℃ of baking ovens standing 20 hours, then 130 degree hydro-thermal reaction is 5 days, naturally cooling by suction filtration, washing, after natural drying at room temperature, obtain a white powder, contain the mesopore silicon oxide of surfactant.Surfactant P123 removes by solvent extraction method: the powdered sample that 1.0 g obtain above joins in 200 milliliters of ethanol, then adds the concentrated hydrochloric acid of 16 milliliter of 36 wt%, and in reflux, 70 ℃ are stirred 24 h, filter, and washing, dry.Ordered meso-porous silicon oxide specific surface area 365 m2/g of gained, pore volume 1.21 cm3/g, linked hole size 8-13 nm.
The mesopore silicon oxide of the above-mentioned processing of 0.6 g of take is hard template, be distributed in 10 g ethanol, add 1.8 g indium nitrates and 0.2 g silver nitrate, at 40 ℃, stir dipping, so that indium salt solusion enters in the duct of mesopore silicon oxide, continue to stir after solvent flashing, in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, adds 1.4 g indium nitrates and 0.16 g silver nitrate, at 40 ℃, stirs and floods and continue to stir after solvent flashing, and in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, adds 1 g indium nitrate and 0.12 g silver nitrate, at 40 ℃, stirs and floods and continue to stir after solvent flashing, and in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; In the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration, to remove monox template, obtains Ordered Silver-indium oxide composite Nano rod array material of the present invention.
Embodiment 4: a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material, this formaldehyde gas sensitive material is to be formed by silver-indium oxide composite nanorod six side's periodic arrangement, between nanometer rods, having length is that 2-5nm connects, described nanometer rods diameter is 8 nm, length 20-500nm, the quality percentage composition of described silver in compound is 9.4%.
The preparation method of described a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material is:
8.0g surfactant P123,60 g water mix at 35 ℃ with the hydrochloric acid of 240 g 2 M, stir 12 hours until surfactant all dissolves and is uniformly dispersed, then add 16.72 g ethyl orthosilicate TEOS, stir after 5 minutes, transfer in a teflon bottle in 35 ℃ of baking ovens standing 20 hours, then 130 degree hydro-thermal reaction is 1 day, naturally cooling by suction filtration, washing, after natural drying at room temperature, obtain a white powder, contain the mesopore silicon oxide of surfactant.Surfactant P123 removes by solvent extraction method: the powdered sample that 1.0 g obtain above joins in 200 ml methanol, then adds the concentrated hydrochloric acid of 16 milliliter of 36 wt%, and in reflux, 70 ℃ are stirred 24 h, filter, and washing, dry.
The mesopore silicon oxide of the above-mentioned processing of 0.6 g of take is hard template, be distributed in 10 g ethanol, add 1.8 g indium nitrates and 0.1 g silver nitrate, at 40 ℃, stir dipping, so that indium salt solusion enters in the duct of mesopore silicon oxide, continue to stir after solvent flashing, in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, adds 1.4 g indium nitrates and 0.08 g silver nitrate, at 40 ℃, stirs and floods and continue to stir after solvent flashing, and in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, adds 1 g indium nitrate and 0.06 g silver nitrate, at 40 ℃, stirs and floods and continue to stir after solvent flashing, and in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; In the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration, to remove monox template, obtains Ordered Silver-indium oxide composite Nano rod array material of the present invention.
Embodiment 5: a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material, this formaldehyde gas sensitive material is to be formed by silver-indium oxide composite nanorod six side's periodic arrangement, between nanometer rods, having length is that 2-5nm connects, described nanometer rods diameter is 9nm, length 20-500nm, the quality percentage composition of described silver in compound is 0.2%.
The preparation method of described a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material is:
8.0g surfactant P123,60 g water mix at 35 ℃ with the hydrochloric acid of 240 g 2 M, stir 12 hours until surfactant all dissolves and is uniformly dispersed, then add 16.72 g ethyl orthosilicate TEOS, stir after 5 minutes, transfer in a teflon bottle in 35 ℃ of baking ovens standing 20 hours, then 150 degree hydro-thermal reaction is 1 day, naturally cooling by suction filtration, washing, after natural drying at room temperature, obtain a white powder, contain the mesopore silicon oxide of surfactant.Surfactant P123 removes by solvent extraction method: the powdered sample that 1.0 g obtain above joins in 200 milliliters of ethylene glycol, then adds the concentrated hydrochloric acid of 16 milliliter of 36 wt%, and in reflux, 70 ℃ are stirred 24 h, filter, and washing, dry.
The mesopore silicon oxide of the above-mentioned processing of 0.6 g of take is hard template, be distributed in 10 g ethanol, add 1.8 g indium nitrates and 0.003 g silver nitrate, at 40 ℃, stir dipping, so that indium salt solusion enters in the duct of mesopore silicon oxide, continue to stir after solvent flashing, in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, adds 1.4 g indium nitrates and 0.001 g silver nitrate, at 40 ℃, stirs and floods and continue to stir after solvent flashing, and in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, adds 1 g indium nitrate and 0.0008 g silver nitrate, at 40 ℃, stirs and floods and continue to stir after solvent flashing, and in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; In the product after calcining, add 2 M NaOH solution,, after stirring, centrifugal filtration, to remove monox template, obtains Ordered Silver-indium oxide composite Nano rod array material of the present invention.
Embodiment 6: a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material, this formaldehyde gas sensitive material is to be formed by silver-indium oxide composite nanorod six side's periodic arrangement, between nanometer rods, having length is that 2-5nm connects, described nanometer rods diameter is 9nm, length 20-500nm, the quality percentage composition of described silver in compound is 20%.
The preparation method of described a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material is:
8.0g surfactant P123,60 g water mix at 35 ℃ with the hydrochloric acid of 240 g 2 M, stir 12 hours until surfactant all dissolves and is uniformly dispersed, then add 16.72 g ethyl orthosilicate TEOS, stir after 5 minutes, transfer in a teflon bottle in 35 ℃ of baking ovens standing 20 hours, then 130 degree hydro-thermal reaction is 5 days, naturally cooling by suction filtration, washing, after natural drying at room temperature, obtain a white powder, contain the mesopore silicon oxide of surfactant.Surfactant P123 removes by solvent extraction method: the powdered sample that 1.0 g obtain above joins in 200 milliliters of acetone, then adds the concentrated hydrochloric acid of 16 milliliter of 36 wt%, and in reflux, 70 ℃ are stirred 24 h, filter, and washing, dry.
The mesopore silicon oxide of the above-mentioned processing of 0.6 g of take is hard template, be distributed in 10 g ethanol, add 1.8 g indium nitrates and 0.2 g silver nitrate, at 40 ℃, stir dipping, so that indium salt solusion enters in the duct of mesopore silicon oxide, continue to stir after solvent flashing, in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; The powder obtaining is re-dispersed in 10 g ethanol, add 1.4 g indium nitrates and 0.16 g silver nitrate, at 40 ℃, stir and flood and continue to stir after solvent flashing, in air, in 300 ℃, calcine 2 hours, in air, in 300 ℃ of calcinings 2 hours, calcining heating rate was 1 ℃/min; In the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration, to remove monox template, obtains Ordered Silver-indium oxide composite Nano rod array material of the present invention.
Claims (6)
1. silver-indium oxide composite nanorod array formaldehyde gas sensitive material, is characterized in that: this formaldehyde gas sensitive material is to be formed by silver-indium oxide composite nanorod six side's periodic arrangement, and between nanometer rods, having length is that 2-5nm connects.
2. a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material as claimed in claim 1, is characterized in that: described nanometer rods diameter is 5-15nm, length 20-500nm, and described silver is 0.2-20% at the quality percentage composition of composite nanorod.
3. the preparation method of a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material as claimed in claim 1, is characterized in that: its preparation method comprises the steps:
A, by 8.0g surfactant P123, the hydrochloric acid that 60g water is 2M with 240g concentration mixes under 35 ° of C, stir and all dissolve and be uniformly dispersed to surfactant for 1-24 hour, then add 16.72g ethyl orthosilicate, stir after 5 minutes, transfer in a teflon bottle in 35 ° of C baking ovens standing 20 hours, then at 130-150 ° of C hydro-thermal reaction 1-5 days, naturally cooling by obtaining a white powder after suction filtration, washing, natural drying at room temperature, contain the mesopore silicon oxide of surfactant;
Mesopore silicon oxide in b, use solvent extraction a: the white powder that 1.0g step a is obtained joins in 200 milliliters of solvents, again to the concentrated hydrochloric acid that adds 16 milliliters of 36wt% in solvent, in reflux, 70 ° of C stir 24h, filter, wash, be dried, obtain surfactant-free mesopore silicon oxide;
The mesopore silicon oxide that c, the 0.6g step b of take processed is hard template, be distributed in 10g ethanol, add 1.8g indium nitrate and 0.1 g silver nitrate, at 40 ° of C, stir dipping, indium salt solusion is entered in the duct of mesopore silicon oxide, continue to stir after solvent flashing, in air, in 300 ° of C calcinings 2 hours, calcine 1 ° of C/min of heating rate;
D, the powder that step c is obtained are re-dispersed in 10g ethanol, add 1.4 g indium nitrates and 0.08 g silver nitrate, at 40 ° of C, stir and flood and continue to stir after solvent flashing, in air, in 300 ° of C calcinings 2 hours, calcine 1 ° of C/min of heating rate;
E, the powder that steps d is obtained are re-dispersed in 10g ethanol, add 1 g indium nitrate and 0.06 g silver nitrate, at 40 ° of C, stir and flood and continue to stir after solvent flashing, in air, in 300 ° of C calcinings 2 hours, calcine 1 ° of C/min of heating rate;
F, in the product after step e calcining, add 2M NaOH solution, after stirring, centrifugal filtration, to remove monox template, obtains Ordered Silver-indium oxide composite Nano rod array material.
4. the preparation method of a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material as claimed in claim 3, it is characterized in that: the solvent in described step b can be one or more potpourri of methyl alcohol, ethanol, ethylene glycol, propyl alcohol, butanols, ether, acetonitrile, acetone, tetrahydrofuran, or the mixed solvent of they and water, the mass ratio of described mesopore silicon oxide and described solvent is 1:5-1:200.
5. the preparation method of a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material as claimed in claim 3, it is characterized in that: in described step c, the mass ratio of indium nitrate and silver nitrate and mesopore silicon oxide is 1.5-7:1, the temperature that stirs dipping is 5-80 ℃, calcining heat is 300-500 ℃, heating rate is 0.5-2.5 ℃/min, and calcination time is 2-10 h.
6. the preparation method of a kind of silver-indium oxide composite nanorod array formaldehyde gas sensitive material as claimed in claim 3, is characterized in that: the concentration of the sodium hydroxide solution in described step e is 2-10M.
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| CN107285392A (en) * | 2017-06-28 | 2017-10-24 | 济南大学 | A kind of NiO In2O3The preparation method of nano composite material |
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