CN104569075A - Fe-doped bimodal mesoporous nickel oxide formaldehyde gas sensitive material and preparation method thereof - Google Patents
Fe-doped bimodal mesoporous nickel oxide formaldehyde gas sensitive material and preparation method thereof Download PDFInfo
- Publication number
- CN104569075A CN104569075A CN201510004492.6A CN201510004492A CN104569075A CN 104569075 A CN104569075 A CN 104569075A CN 201510004492 A CN201510004492 A CN 201510004492A CN 104569075 A CN104569075 A CN 104569075A
- Authority
- CN
- China
- Prior art keywords
- nickel oxide
- sensitive material
- formaldehyde gas
- gas sensitive
- nitrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a sensing material and a preparation method of the sensing material and in particular relates to a Fe-doped bimodal mesoporous nickel oxide formaldehyde gas sensitive material and a preparation method of the Fe-doped bimodal mesoporous nickel oxide formaldehyde gas sensitive material. The Fe-doped bimodal mesoporous nickel oxide formaldehyde gas sensitive material is formed by Fe-doped nickel oxide spiral nanowires through cubic periodic arrangement; the preparation method of the Fe-doped bimodal mesoporous nickel oxide formaldehyde gas sensitive material comprises the steps of mixing surface active agents, water and hydrochloric acid until the surface active agents are completely dissolved, adding with n-butyl alcohol, stirring for 2h, then adding with tetraethoxysilane and stirring for one day, carrying out hydrothermal reaction for one day at 35-100 DEG C, cooling, performing suction filtration, washing, and drying to obtain white powder; calcining in air to remove the surface active agent; by using the calcined ordered mesoporous silica as a hard template, adding the hard template into ethanol solution of nickel nitrate and ferric nitrate, and calcining in air; and adding sodium hydroxide solution into the calcined product, stirring, centrifuging, and filtering to obtain the Fe-doped bimodal mesoporous nickel oxide material. The Fe-doped bimodal mesoporous nickel oxide formaldehyde gas sensitive material has high sensitivity and good stability.
Description
Technical field
The present invention relates to a kind of gas sensitive and preparation method thereof, especially relate to two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping 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, construction material 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, therefore effective detection of PARA FORMALDEHYDE PRILLS(91,95) is particular importance.
The detection method of current formaldehyde gas mainly contains AAS, 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.Formaldehyde semiconductor gas sensor refers to the gas sensor metal-oxide semiconductor (MOS) of PARA FORMALDEHYDE PRILLS(91,95) sensitivity being added top electrode and heating resistor and be prepared into, it has that structure is simple, highly sensitive, stable performance, cost are low, be easy to the features such as miniaturized and portability, can detect in real time by PARA FORMALDEHYDE PRILLS(91,95), have great application prospect.Oxide or the composite oxides of what the formaldehyde gas sensitive material as wherein key component adopted usually is metals such as indium, tin, iron.As the people such as Li adopt In
2o
3tiny balloon is 12(Li B.X. as sensitive material to the sensitivity of 80ppm formaldehyde; Xie Y.; Jing M.; Rong G.X.; Tang Y.C.; Zhang G.Z., In
2o
3hollow microspheres:Synthesis from designed In (OH)
3precursors and applications in gas sensors and photocatalysis,
langmuir , 22 (2006) 9380-9385); The people such as Wu adopt α-Fe
2o
3nanometer rods is 8(Wu C.Z. as sensitive material to the sensitivity of 50ppm formaldehyde; Yin P.; Zhu X.; OuYang C.Z.; Xie Y., Synthesis of hematite (α-Fe
2o
3) 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 ZnO and ZnSnO
3compound be 33(Xu J. as sensitive material to the sensitivity of 50ppm formaldehyde; Jia X.; Lou X.; Xi G.; Han J.; Gao Q., Selective detection of HCHO gas using mixed oxides of ZnO/ZnSnO
3,
sensors and Actuators B:Chemical , 120 (2007) 694-699); The people such as Lai adopt Ordered Silver-indium oxide composite nanorod array to be that sensitive material reaches 110(Lai when operating temperature is 300 DEG C to the sensitivity of 85ppm formaldehyde, X., et al., Ordered array of Ag – In2O3 composite nanorods with enhanced gas-sensing properties
scripta Materialia , 67 (2012): 293-296).But also there is no highly sensitive, good stability formaldehyde gas sensitive material at present.
Summary of the invention:
The object of the invention is to the defect overcoming above-mentioned prior art, two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of a kind of Fe2O3 doping that is highly sensitive, good stability and preparation method thereof is provided.
The present invention realizes in the following way:
The two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping, is characterized in that: this material is arranged by Fe2O3 doping nickel oxide spiral nanometer line cubic periodic to form;
In described material, the mol ratio of iron and nickel is 1-50:100, has the connection of length 2-5 nanometer between nano wire, and the diameter of nano wire is 4-8 nanometer, has different mesoporous of two kinds of sizes simultaneously;
The preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of described a kind of Fe2O3 doping, is characterized in that: its preparation method comprises the steps:
A, by 6.0g surfactant P123,216g water mixes at 35 DEG C with 11.8g concentrated hydrochloric acid, stir 1-12 hour until surfactant all dissolves and is uniformly dispersed, then add 6g n-butanol, stir after 2 hours, add 12.9g ethyl orthosilicate TEOS, stir after 24 hours, transfer in a polytetrafluoroethylene (PTFE) bottle, then 35-100 DEG C of hydro-thermal reaction 1 day, naturally through suction filtration, washing, natural drying at room temperature after cooling, the mesopore silicon oxide containing surfactant is obtained;
B, by a step gained sample surfaces activating agent P123 by after 550 DEG C of calcinings removing in 6 hours in atmosphere not containing the mesopore silicon oxide of surfactant;
C, with the mesopore silicon oxide of 1g step b process for hard template, be distributed in 10 g ethanol, add 0.999 g nickel nitrate, 0.042g ferric nitrate stirs dipping at 40 DEG C, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min;
D, by step c gained sample dispersion in 10 g ethanol, add 0.936g nickel nitrate, 0.039 g ferric nitrate stirs dipping at 40 DEG C, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min;
E, in the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration is remove mesopore silicon oxide template, namely obtains Fe2O3 doping of the present invention pair mesoporous nickel oxide material;
Hydrothermal temperature 35-100 DEG C in described step a;
In described step c and d, the volume of nitrate is 0.5-0.8:1 with the ratio of the pore volume of mesopore silicon oxide, the mol ratio of ferric nitrate and nickel nitrate is 1-50:100, the temperature stirring dipping is 5-80 DEG C, calcining heat is 300-500 DEG C, heating rate is 0.5-2.5 DEG C/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) material unique, there are two kinds different be mesoporously distributed with the diffusion being beneficial to gas molecule; accelerate response resume speed: the two mesoporous nickel oxide of Fe2O3 doping provided by the invention is arranged by Fe2O3 doping nickel oxide spiral nanometer line cubic periodic and forms; there is between nano wire the connection of length 2-5 nanometer; two kinds of mesoporous distribution proportions can be controlled with the ratio of the pore volume of mesopore silicon oxide by the aperture and the volume of connectivity and nitrate regulating mesopore silicon oxide template; space between nano wire is conducive to the diffusion of gas molecule, accelerates response resume speed;
2) heat endurance is enhanced: having length between the nano wire in material provided by the invention is that 2-5nm connects, decrease nano wire contact each other, the sensitivity that sintering phenomenon and specific area loss are brought under high temperature can be reduced decline, enhance heat endurance;
3) its air-sensitive character can be changed: the diameter of the nano wire in material provided by the invention can control by regulating the aperture of mesopore silicon oxide template, can change its air-sensitive character accordingly;
4) sensitivity is strengthened: in material provided by the invention, the existence of ferric ion reduces hole in nickel oxide, strengthen the sensitivity of PARA FORMALDEHYDE PRILLS(91,95) gas, in material, the content of ferric ion can control by regulating the ratio adding nickel nitrate and ferric nitrate, can change its air-sensitive character accordingly.
Accompanying drawing explanation
Fig. 1 is the pore size distribution collection of illustrative plates of the two mesoporous nickel oxide of the embodiment of the present invention 1 gained Fe2O3 doping;
Fig. 2 is the TEM picture of the two mesoporous nickel oxide of the embodiment of the present invention 1 gained Fe2O3 doping;
Fig. 3 is that the two mesoporous nickel oxide of the embodiment of the present invention 1 gained Fe2O3 doping is to the air-sensitive response curve of variable concentrations formaldehyde gas.
Detailed description of the invention:
Embodiment 1: the preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping, its preparation method comprises as follows:
By 6.0g surfactant P123,216g water mixes at 35 DEG C with 11.8g concentrated hydrochloric acid, stir 1-12 hour until surfactant all dissolves and is uniformly dispersed, then add 6g n-butanol, stir after 2 hours, add 12.9g ethyl orthosilicate TEOS, stir after 24 hours, transfer in a polytetrafluoroethylene (PTFE) bottle, then 40 degree of hydro-thermal reactions 1 day, naturally through suction filtration, washing, natural drying at room temperature after cooling, namely containing the mesopore silicon oxide of surfactant.Gained sample surfaces activating agent P123 obtains a white powder after passing through 550 degree of calcinings removing in 6 hours in atmosphere above.Ordered meso-porous silicon oxide specific area 736 m of gained
2/ g, pore volume 0. 64cm
3/ g, hole dimension is about 4.8 nm.
With the mesopore silicon oxide of the above-mentioned process of 1g for hard template, be distributed in 10 g ethanol, add 0.784 g nickel nitrate and 0.218g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 20:100, dipping is stirred, to make nitrate solution enter in the duct of mesopore silicon oxide, after Keep agitation solvent flashing at 40 DEG C, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; Again by above-mentioned gained sample dispersion in 10 g ethanol, add 0.737g nickel nitrate and 0.205 g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 20:100, dipping is stirred at 40 DEG C, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; In the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration is to remove mesopore silicon oxide template, namely obtains the two mesoporous nickel oxide material of Fe2O3 doping of the present invention, this material specific surface area 140 m
2/ g, pore volume 0.32 cm
3/ g.
As the pore size distribution collection of illustrative plates that Fig. 1 is the two mesoporous nickel oxide of the present embodiment gained Fe2O3 doping, show the mesoporous distribution that it has 2 kinds of different sizes; As the TEM picture that Fig. 2 is the two mesoporous nickel oxide of the present embodiment gained Fe2O3 doping, confirm that it has orderly meso-hole structure; If Fig. 3 is that the two mesoporous nickel oxide of the present embodiment gained Fe2O3 doping responds the air-sensitive of variable concentrations formaldehyde gas, 554 are reached to 90ppm formaldehyde gas susceptibility, and the nonferrous two susceptibility of mesoporous nickel oxide to the formaldehyde gas of same concentration only has 8.6, show that it strengthens effect significantly.
Embodiment 2: the preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping, its preparation method comprises as follows:
By 6.0g surfactant P123,216g water mixes at 35 DEG C with 11.8g concentrated hydrochloric acid, stir 1-12 hour until surfactant all dissolves and is uniformly dispersed, then add 6g n-butanol, stir after 2 hours, add 12.9g ethyl orthosilicate TEOS, stir after 24 hours, transfer in a polytetrafluoroethylene (PTFE) bottle, then 40 degree of hydro-thermal reactions 1 day, naturally through suction filtration, washing, natural drying at room temperature after cooling, namely containing the mesopore silicon oxide of surfactant.Gained sample surfaces activating agent P123 obtains a white powder after passing through 550 degree of calcinings removing in 6 hours in atmosphere above.Ordered meso-porous silicon oxide specific area 736 m of gained
2/ g, pore volume 0. 64cm
3/ g, hole dimension is about 4.8 nm.
With the mesopore silicon oxide of the above-mentioned process of 1g for hard template, be distributed in 10 g ethanol, add 1.03 g nickel nitrates and 0.0143g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 1:100, dipping is stirred, to make nitrate solution enter in the duct of mesopore silicon oxide, after Keep agitation solvent flashing at 40 DEG C, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; Again by above-mentioned gained sample dispersion in 10 g ethanol, add 0.967g nickel nitrate and 0.0134 g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 1:100, dipping is stirred at 40 DEG C, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; In the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration is to remove mesopore silicon oxide template, namely obtains the two mesoporous nickel oxide material of Fe2O3 doping of the present invention.
Embodiment 3: the preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping, its preparation method comprises as follows:
6.0g surfactant P123,216g water mixes at 35 DEG C with 11.8g concentrated hydrochloric acid, stir 1-12 hour until surfactant all dissolves and is uniformly dispersed, then add 6g n-butanol, stir after 2 hours, add 12.9g ethyl orthosilicate TEOS, stir after 24 hours, transfer in a polytetrafluoroethylene (PTFE) bottle, then 40 degree of hydro-thermal reactions 1 day, naturally through suction filtration, washing, natural drying at room temperature after cooling, namely containing the mesopore silicon oxide of surfactant.Gained sample surfaces activating agent P123 obtains a white powder after passing through 550 degree of calcinings removing in 6 hours in atmosphere above.Ordered meso-porous silicon oxide specific area 736 m of gained
2/ g, pore volume 0. 64cm
3/ g, hole dimension is about 4.8 nm.
With the mesopore silicon oxide of the above-mentioned process of 1g for hard template, be distributed in 10 g ethanol, add 0.999 g nickel nitrate and 0.042g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 3:100, dipping is stirred, to make nitrate solution enter in the duct of mesopore silicon oxide, after Keep agitation solvent flashing at 40 DEG C, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; Again by above-mentioned gained sample dispersion in 10 g ethanol, add 0.936g nickel nitrate and 0.039 g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 3:100, dipping is stirred at 40 DEG C, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; In the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration is to remove mesopore silicon oxide template, namely obtains the two mesoporous nickel oxide material of Fe2O3 doping of the present invention.
Embodiment 4: the preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping, its preparation method comprises as follows:
By 6.0g surfactant P123,216g water mixes at 35 DEG C with 11.8g concentrated hydrochloric acid, stir 1-12 hour until surfactant all dissolves and is uniformly dispersed, then add 6g n-butanol, stir after 2 hours, add 12.9g ethyl orthosilicate TEOS, stir after 24 hours, transfer in a polytetrafluoroethylene (PTFE) bottle, then 40 degree of hydro-thermal reactions 1 day, naturally through suction filtration, washing, natural drying at room temperature after cooling, namely containing the mesopore silicon oxide of surfactant.Gained sample surfaces activating agent P123 obtains a white powder after passing through 550 degree of calcinings removing in 6 hours in atmosphere above.Ordered meso-porous silicon oxide specific area 736 m of gained
2/ g, pore volume 0. 64cm
3/ g, hole dimension is about 4.8 nm.
With the mesopore silicon oxide of the above-mentioned process of 1g for hard template, be distributed in 10 g ethanol, add 0.897 g nickel nitrate and 0.125g ferric nitrate (ferric nitrate and nickel nitrate mol ratio are 10:100) to stir at 40 DEG C and flood, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; Again by above-mentioned gained sample dispersion in 10 g ethanol, add 0.842g nickel nitrate and 0.117g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 10:100, dipping is stirred at 40 DEG C, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; In the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration is to remove mesopore silicon oxide template, namely obtains the two mesoporous nickel oxide material of Fe2O3 doping of the present invention.
Embodiment 5: the preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping, its preparation method comprises as follows:
By 6.0g surfactant P123,216g water mixes at 35 DEG C with 11.8g concentrated hydrochloric acid, stir 1-12 hour until surfactant all dissolves and is uniformly dispersed, then add 6g n-butanol, stir after 2 hours, add 12.9g ethyl orthosilicate TEOS, stir after 24 hours, transfer in a polytetrafluoroethylene (PTFE) bottle, then 40 degree of hydro-thermal reactions 1 day, naturally through suction filtration, washing, natural drying at room temperature after cooling, namely containing the mesopore silicon oxide of surfactant.Gained sample surfaces activating agent P123 obtains a white powder after passing through 550 degree of calcinings removing in 6 hours in atmosphere above.Ordered meso-porous silicon oxide specific area 736 m of gained
2/ g, pore volume 0. 64cm
3/ g, hole dimension is about 4.8 nm.
With the mesopore silicon oxide of the above-mentioned process of 1g for hard template, be distributed in 10 g ethanol, add 0.659 g nickel nitrate and 0.32g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 35:100, dipping is stirred, to make nitrate solution enter in the duct of mesopore silicon oxide, after Keep agitation solvent flashing at 40 DEG C, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; Again by above-mentioned gained sample dispersion in 10 g ethanol, add 0.62g nickel nitrate and 0.302 g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 35:100, dipping is stirred at 40 DEG C, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; In the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration is to remove mesopore silicon oxide template, namely obtains the two mesoporous nickel oxide material of Fe2O3 doping of the present invention.
Embodiment 6: the preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping, its preparation method comprises as follows:
6.0g surfactant P123,216g water mixes at 35 DEG C with 11.8g concentrated hydrochloric acid, stir 1-12 hour until surfactant all dissolves and is uniformly dispersed, then add 6g n-butanol, stir after 2 hours, add 12.9g ethyl orthosilicate TEOS, stir after 24 hours, transfer in a polytetrafluoroethylene (PTFE) bottle, then 100 degree of hydro-thermal reactions 1 day, naturally through suction filtration, washing, natural drying at room temperature after cooling, namely containing the mesopore silicon oxide of surfactant.Gained sample surfaces activating agent P123 obtains a white powder after passing through 550 degree of calcinings removing in 6 hours in atmosphere above.Ordered meso-porous silicon oxide specific area 877 m of gained
2/ g, pore volume 1cm
3/ g, hole dimension is about 7.9 nm.
With the mesopore silicon oxide of the above-mentioned process of 1g for hard template, be distributed in 10 g ethanol, add 0.999 g nickel nitrate and 0.042g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 20:100, dipping is stirred, to make nitrate solution enter in the duct of mesopore silicon oxide, after Keep agitation solvent flashing at 40 DEG C, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; Again by above-mentioned gained sample dispersion in 10 g ethanol, add 0.936g nickel nitrate and 0.039 g ferric nitrate, ferric nitrate and nickel nitrate mol ratio are 20:100, dipping is stirred at 40 DEG C, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min; In the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration is to remove mesopore silicon oxide template, namely obtains the two mesoporous nickel oxide material of Fe2O3 doping of the present invention.
Claims (6)
1. the two mesoporous nickel oxide formaldehyde gas sensitive material of Fe2O3 doping, is characterized in that: this material is arranged by Fe2O3 doping nickel oxide spiral nanometer line cubic periodic to form.
2. the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping as claimed in claim 1, it is characterized in that: in described material, the mol ratio of iron and nickel is 1-50:100, there is between nano wire the connection of length 2-5 nanometer, the diameter of nano wire is 4-8 nanometer, has different mesoporous of two kinds of sizes simultaneously.
3. the preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping as claimed in claim 1, is characterized in that: its preparation method comprises the steps:
A, by 6.0g surfactant P123,216g water mixes at 35 DEG C with 11.8g concentrated hydrochloric acid, stir 1-12 hour until surfactant all dissolves and is uniformly dispersed, then add 6g n-butanol, stir after 2 hours, add 12.9g ethyl orthosilicate TEOS, stir after 24 hours, transfer in a polytetrafluoroethylene (PTFE) bottle, then 35-100 DEG C of hydro-thermal reaction 1 day, naturally through suction filtration, washing, natural drying at room temperature after cooling, the mesopore silicon oxide containing surfactant is obtained;
B, by a step gained sample surfaces activating agent P123 by after 550 DEG C of calcinings removing in 6 hours in atmosphere not containing the mesopore silicon oxide of surfactant;
C, with the mesopore silicon oxide of 1g step b process for hard template, be distributed in 10 g ethanol, add 0.999 g nickel nitrate, 0.042g ferric nitrate stirs dipping at 40 DEG C, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min;
D, by step c gained sample dispersion in 10 g ethanol, add 0.936g nickel nitrate, 0.039 g ferric nitrate stirs dipping at 40 DEG C, enter in the duct of mesopore silicon oxide to make nitrate solution, after Keep agitation solvent flashing, in atmosphere in 300 DEG C of calcinings 3 hours, calcining heating rate is 1 DEG C/min;
E, in the product after calcining, add 2 M NaOH solution, after stirring, centrifugal filtration is remove mesopore silicon oxide template, namely obtains Fe2O3 doping of the present invention pair mesoporous nickel oxide material.
4. the preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping as claimed in claim 3, is characterized in that: hydrothermal temperature 35-100 DEG C in described step a.
5. the preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping as claimed in claim 3, it is characterized in that: in described step c and d, the volume of nitrate is 0.5-0.8:1 with the ratio of the pore volume of mesopore silicon oxide, the mol ratio of ferric nitrate and nickel nitrate is 1-50:100, the temperature stirring dipping is 5-80 DEG C, calcining heat is 300-500 DEG C, heating rate is 0.5-2.5 DEG C/min, and calcination time is 2-10 h.
6. the preparation method of the two mesoporous nickel oxide formaldehyde gas sensitive material of a kind of Fe2O3 doping as claimed in claim 3, is characterized in that: the concentration of the sodium hydroxide solution in described step e is 2-10M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510004492.6A CN104569075B (en) | 2015-01-06 | 2015-01-06 | Double mesoporous nickel oxide formaldehyde gas sensitive materials of a kind of Fe2O3 doping and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510004492.6A CN104569075B (en) | 2015-01-06 | 2015-01-06 | Double mesoporous nickel oxide formaldehyde gas sensitive materials of a kind of Fe2O3 doping and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104569075A true CN104569075A (en) | 2015-04-29 |
| CN104569075B CN104569075B (en) | 2017-10-17 |
Family
ID=53085638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510004492.6A Expired - Fee Related CN104569075B (en) | 2015-01-06 | 2015-01-06 | Double mesoporous nickel oxide formaldehyde gas sensitive materials of a kind of Fe2O3 doping and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104569075B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107132252A (en) * | 2017-05-23 | 2017-09-05 | 徐靖才 | A kind of preparation method of tin dope nickel oxide gas sensitive |
| CN107399767A (en) * | 2017-08-28 | 2017-11-28 | 四川理工学院 | A kind of Fe doping NiO composites and semiconductor gas sensor |
| CN108508155A (en) * | 2018-04-03 | 2018-09-07 | 宁夏大学 | A kind of high specific surface area ordered mesoporous nickel oxide acetone air-sensitive material and preparation method thereof greatly |
| CN108508065A (en) * | 2018-04-03 | 2018-09-07 | 宁夏大学 | A kind of order mesoporous nickel ferrite based magnetic loaded toluene gas sensitive of ultra-fine skeleton and preparation method thereof |
| CN109772334A (en) * | 2018-12-28 | 2019-05-21 | 宁夏大学 | A kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area and preparation method thereof |
| CN113219006A (en) * | 2021-04-16 | 2021-08-06 | 华南理工大学 | Gas sensor, preparation method thereof and wearable electronic device |
| CN114235904A (en) * | 2021-12-17 | 2022-03-25 | 电子科技大学 | Ppb-level hydrogen sensor and preparation method thereof |
| CN115385387A (en) * | 2022-08-03 | 2022-11-25 | 武汉大学 | Defect-rich mesoporous metal oxide with high specific surface area and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958158A (en) * | 2006-09-20 | 2007-05-09 | 南京大学 | Catalysis materials of cobalt oxide, nickel oxide, preparation method and application |
| CN101219908A (en) * | 2007-09-21 | 2008-07-16 | 南京大学 | Multi-component metal oxide semiconductor mesoporous material and synthesizing method thereof |
| CN101391753A (en) * | 2008-11-05 | 2009-03-25 | 中国科学院上海硅酸盐研究所 | Method for preparing mesoporous metallic oxide material |
| US20090098442A1 (en) * | 2007-10-16 | 2009-04-16 | Samsung Sdi Co., Ltd. | Hierarchical mesoporous carbon, method of manufacturing the same, and fuel cell using the same |
| CN104048996A (en) * | 2014-03-31 | 2014-09-17 | 济南大学 | Preparation method of crystal-non-crystal metal oxide composite gas-sensitive material |
| CN104183392A (en) * | 2014-07-29 | 2014-12-03 | 上海应用技术学院 | Mesoporous nickel oxide and carbon composite nano-material and preparation method thereof |
-
2015
- 2015-01-06 CN CN201510004492.6A patent/CN104569075B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958158A (en) * | 2006-09-20 | 2007-05-09 | 南京大学 | Catalysis materials of cobalt oxide, nickel oxide, preparation method and application |
| CN101219908A (en) * | 2007-09-21 | 2008-07-16 | 南京大学 | Multi-component metal oxide semiconductor mesoporous material and synthesizing method thereof |
| US20090098442A1 (en) * | 2007-10-16 | 2009-04-16 | Samsung Sdi Co., Ltd. | Hierarchical mesoporous carbon, method of manufacturing the same, and fuel cell using the same |
| CN101391753A (en) * | 2008-11-05 | 2009-03-25 | 中国科学院上海硅酸盐研究所 | Method for preparing mesoporous metallic oxide material |
| CN104048996A (en) * | 2014-03-31 | 2014-09-17 | 济南大学 | Preparation method of crystal-non-crystal metal oxide composite gas-sensitive material |
| CN104183392A (en) * | 2014-07-29 | 2014-12-03 | 上海应用技术学院 | Mesoporous nickel oxide and carbon composite nano-material and preparation method thereof |
Non-Patent Citations (7)
| Title |
|---|
| DOMINIK KLAUS ET AL.: "One-step synthesis of multi-modal pore systems in mesoporous In2O3:A detailed study", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| ZHONG ZHENG ET AL.: "Large-scale synthesis of mesoporous CoO-doped NiO hexagonal nanoplatelets with improved electrochemical performance", 《SOLID STATE SCIENCE》 * |
| 孙艳艳等: "基于模板技术的介孔金属氧化物的生长机理及应用", 《化学进展》 * |
| 杨晓梅等: "介孔氧化铟纳米粒子的制备及其气敏性质", 《辽东学院学报（自然科学版）》 * |
| 王剑等: "锌掺杂氧化镍纳米线的制备及氧化镍基气敏传感器性能的研究", 《西华大学学报（自然科学版）》 * |
| 董家丽等: "双介孔二氧化硅制备研究进展", 《无机盐工业》 * |
| 马占华等: "硬模板法合成晶态介孔金属氧化物研究进展", 《现代工业》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107132252A (en) * | 2017-05-23 | 2017-09-05 | 徐靖才 | A kind of preparation method of tin dope nickel oxide gas sensitive |
| CN107399767A (en) * | 2017-08-28 | 2017-11-28 | 四川理工学院 | A kind of Fe doping NiO composites and semiconductor gas sensor |
| CN107399767B (en) * | 2017-08-28 | 2019-05-03 | 四川理工学院 | A kind of Fe doping NiO composite material and semiconductor gas sensor |
| CN108508155A (en) * | 2018-04-03 | 2018-09-07 | 宁夏大学 | A kind of high specific surface area ordered mesoporous nickel oxide acetone air-sensitive material and preparation method thereof greatly |
| CN108508065A (en) * | 2018-04-03 | 2018-09-07 | 宁夏大学 | A kind of order mesoporous nickel ferrite based magnetic loaded toluene gas sensitive of ultra-fine skeleton and preparation method thereof |
| CN109772334A (en) * | 2018-12-28 | 2019-05-21 | 宁夏大学 | A kind of big mesoporous nickel cobalt glucose-sensitive material of high-specific surface area and preparation method thereof |
| CN113219006A (en) * | 2021-04-16 | 2021-08-06 | 华南理工大学 | Gas sensor, preparation method thereof and wearable electronic device |
| CN114235904A (en) * | 2021-12-17 | 2022-03-25 | 电子科技大学 | Ppb-level hydrogen sensor and preparation method thereof |
| CN114235904B (en) * | 2021-12-17 | 2022-11-01 | 电子科技大学 | Ppb-level hydrogen sensor and preparation method thereof |
| CN115385387A (en) * | 2022-08-03 | 2022-11-25 | 武汉大学 | Defect-rich mesoporous metal oxide with high specific surface area and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104569075B (en) | 2017-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104569075A (en) | Fe-doped bimodal mesoporous nickel oxide formaldehyde gas sensitive material and preparation method thereof | |
| CN106732818B (en) | Double layer hollow material based on titanium dioxide and preparation method thereof and the application in hydrogen sulfide photocatalysis treatment | |
| Bian et al. | Facile preparation of fluorescent Au nanoclusters-based test papers for recyclable detection of Hg2+ and Pb2+ | |
| Hiramatsu et al. | pH-controlled assembly and disassembly of electrostatically linked CdSe− SiO2 and Au− SiO2 nanoparticle clusters | |
| Hussain | Magnetic nanomaterials for environmental analysis | |
| CN104495912B (en) | A kind of triple mesoporous indium oxide formaldehyde gas sensitive materials and preparation method thereof | |
| CN103203467B (en) | Method for preparing silver nanowires | |
| Kuai et al. | Aerosol-spray diverse mesoporous metal oxides from metal nitrates | |
| CN106841326A (en) | A kind of zinc oxide cobalt hollow nano polyhedron film to alcohol sensible | |
| CN109916966B (en) | alpha-Fe2O3/TiO2Nanocomposite and H prepared therefrom2S gas sensor | |
| Tosun et al. | Polymeric template assisted synthesis of monodisperse-porous manganese oxide microspheres: a new nanozyme with oxidase-like activity allowing biomolecule determination via bimodal sensing | |
| CN108212147A (en) | A kind of rare-earth-doped modification mangano-manganic oxide and its preparation method and application | |
| CN107261857A (en) | Modified graphene film separated for monovalence with polyvalent metal ion and preparation method thereof | |
| CN104014807A (en) | Silver nanocrystalline preparation method with surface raman enhancing effect | |
| CN106670500A (en) | Method for manufacturing silver nanowire by utilizing organic amine reduction | |
| Devadas et al. | Controlled electrochemical synthesis of yttrium (III) hexacyanoferrate micro flowers and their composite with multiwalled carbon nanotubes, and its application for sensing catechin in tea samples | |
| Xu et al. | Tubular Au-TTF solid contact layer synthesized in a microfluidic device improving electrochemical behaviors of paper-based potassium potentiometric sensors | |
| CN101813654A (en) | Method for preparing ethanol sensitive material with fine graded porous structure | |
| Divagar et al. | Surface imprinted Ag decorated MnO2 thin film electrodes for the synergic electrochemical detection of bacterial pathogens | |
| CN102680528B (en) | Silver and indium oxide composite nanorod array formaldehyde air-sensitive material and preparation method thereof | |
| Yu et al. | Gas sensing and electrochemical behaviors of Ag-doped 3D spherical WO3 assembled by nanostrips to formaldehyde | |
| Khan et al. | Sol–gel synthesis of poly (o-toluidine)@ Sn (II) silicate/CNT composites for ion selective membrane electrodes | |
| CN105067579A (en) | Preparation and application of single-layer g-C3N4 fluorescence sensor | |
| Abdel-Atty et al. | The fabrication of a highly sensitive nano green carbon paste electrode modified with yttrium doped manganese oxide (Mn2O3/Y2O3) for electrochemical determination of marbofloxacin and its residues in bovine meat and milk samples | |
| CN106082352B (en) | A kind of FeAsO4/Fe2O3Composite material and preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171017 Termination date: 20220106 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |