CN109060889A - A kind of three-layer laminated CoAl double-metal hydroxide composite material and preparation method and application - Google Patents
A kind of three-layer laminated CoAl double-metal hydroxide composite material and preparation method and application Download PDFInfo
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Abstract
A kind of three-layer laminated CoAl double-metal hydroxide composite material and preparation method and application are related to a kind of double-metal hydroxide composite material and preparation method and application.The present invention is in order to solve existing NOxThe problems such as sensor is at high cost.The three-layer laminated CoAl double-metal hydroxide composite material of the present invention is made of cobalt nitrate, aluminum nitrate, ammonium fluoride, precipitating reagent.Preparation method: weighing raw material, adds the raw material into and obtains mixed solution in deionized water, and mixed solution carries out hydro-thermal reaction, obtains removing impurity by means of precipitation washing drying to get three-layer laminated CoAl double-metal hydroxide composite material is arrived.The three-layer laminated CoAl double-metal hydroxide composite material high sensitivity of the present invention, the response time is short, and preparation method is simple, has reversibility of adsorption, the interference performance of anti-external environment is good, at low cost.The present invention is suitable for preparing three-layer laminated CoAl double-metal hydroxide composite material.
Description
Technical field
The present invention relates to a kind of double-metal hydroxide composite material and preparation method and applications.
Background technique
With being constantly progressive for social development, atmosphere pollution is increasingly severe in city, especially nitrogen oxides.Many institute's weeks
Know, nitrogen oxides is a kind of typical air pollutants, and nitrogen oxides can stimulate the lung of human body, makes one to generate and is difficult to resist
Respiratory disease；Oxides of nitrogen gas can react to form acid rain with the moisture in air；With other pollutants certain
Under the conditions of generate photochemical fog, great threat is constituted to environment and human health.
Therefore, develop various types of gas sensors carry out at room temperature quickly, accurately detect poisonous and hazardous nitrogen
Oxide, it is most important to life, production of the mankind etc. and environmental protection.Layered hydroxide is due to rich in unique layer structure
The rich presence of ion and the presence of transition metal is provided for the advantage of active site and electron channel abundant, through too long
The research and development of phase is widely used in the industries such as environment, food, medical treatment, house ornamentation.
The double-metal hydroxide composite material of layer structure is a kind of new inorganic material with abundant layer structure,
The characteristics such as acid-base property, thermal stability, interlayer anion interchangeability and memory effect have been widely used for catalyst,
The fields such as anion-exchange material, fire retardant, adsorbent and drug dispensing, however it is applied to the seldom of air-sensitive field；It answers at present
Material for air-sensitive field is mainly SnO2Class material, noble-metal-supported material etc., higher cost price is bimetallic hydrogen
The tens of oxide composite are to hundred times.
Summary of the invention
The present invention is in order to solve existing NOxThe problems such as sensor is at high cost provides a kind of three-layer laminated CoAl bimetallic hydrogen
The preparation method and application of oxide composite.
The three-layer laminated CoAl double-metal hydroxide composite material of the present invention is by cobalt nitrate, aluminum nitrate, ammonium fluoride and precipitating
Agent is made；
The precipitating reagent is aqueous solution of urea, and concentration of aqueous solution of urea is 0.5~1mol/L；The cobalt nitrate and aluminum nitrate
Molar ratio is (1~4): 1；The aluminum nitrate and ammonium fluoride molar ratio are 1:(5~15)；The aluminum nitrate and precipitating reagent molar ratio
For 1:(60~80)；
The preparation method of above-mentioned three-layer laminated CoAl double-metal hydroxide composite material specifically sequentially includes the following steps:
One, cobalt nitrate, aluminum nitrate, ammonium fluoride and precipitating reagent are weighed as raw material, is added the raw material into equipped with deionized water
Container in carry out 5~10min of ultrasonic treatment, then stir 20~30min, obtain mixed solution；The gross mass of the raw material with
The mass ratio of deionized water is (2.0~2.5): 40；
Two, the mixed solution for obtaining step 1 pours into stainless steel autoclave, and stainless steel autoclave is placed in 80~200
4~20h is heated in DEG C water-bath, and stainless steel autoclave is then cooled to room temperature；
Three, solution obtained in step 2 stainless steel autoclave is filtered and is precipitated, the precipitating that will be obtained by filtration
Removal of impurities washing is carried out, finally the precipitating after removal of impurities washing is placed in drying box and is dried to get bis- to three-layer laminated CoAl
Metal hydroxides composite material；
The method of the removal of impurities washing are as follows: the pH that the sediment being obtained by filtration first is washed with deionized to cleaning solution is
Then neutrality is washed 2~3 times with dehydrated alcohol again；The method of the drying are as follows: dry 10 at 50~90 DEG C~for 24 hours；
Above-mentioned three-layer laminated CoAl double-metal hydroxide composite material is in NOxApplication in detection；
The three-layer laminated CoAl double-metal hydroxide composite material detects NOxMethod sequentially include the following steps: by
Three-layer laminated CoAl double-metal hydroxide composite material prepares gas sensor as sensitive material, and the gas sensor of preparation is set
To NO under conditions of temperature is 18~35 DEG C, humidity is 20%~70%xIt is detected；
The method for preparing gas sensor are as follows: disperse three-layer laminated CoAl double-metal hydroxide compound material ultrasound
In the ethanol solution of 5~7 times of volumes, finely dispersed suspension is obtained, then suspension is spin-coated in Au interdigital electrode,
Dry 4~6h is placed at 60~80 DEG C to get gas sensor is arrived.
Reaction principle of the present invention are as follows:
In water-heat process, aluminium salt and cobalt salt form Co (OH) (H in the solution3O)+ n-1With Al (OH) (H3O)2+ n-1, with
The progress of reaction, urea, which decomposes, generates hydroxide ion, makes solution alkaline, final Co (OH) (H3O)+ n-1, Al (OH) (H3O
)2+ n-1,OH-And CO3 2-Reaction forms double-metal hydroxide.
The present invention have it is following the utility model has the advantages that
1, in the three-layer laminated CoAl double-metal hydroxide composite material preparation process of the present invention, carbanion is as layer
Plate anion is inserted into laminate, and the insertion of carbanion, which is equivalent to, struts metal cation layer, so that interlamellar spacing is changed, with
This forms the channel for being more conducive to gas adsorption desorption, improves gas-sensitive property；And the present invention uses simple hydrolysis of urea legal system
It is simple for three-layer laminated double-metal hydroxide presoma, preparation method；The three-layer laminated CoAl bimetal hydroxide of the present invention
The cost of cobalt nitrate, aluminum nitrate or ammonium fluoride that the preparation of object composite material uses is far below SnO2Class material or noble metal, therefore
It is at low cost；
2, the three-layer laminated CoAl double-metal hydroxide composite material of the present invention has layer structure abundant, and layer and layer form
The specific surface area of flower-shaped composite material, the double-metal hydroxide of flower-shaped layering is bigger, is capable of providing more active sites and goes
It is reacted with gas molecule, while flower-shaped layering double-metal hydroxide has certain hole between layers, it is advantageous in this way
It enters in gas molecule and is wherein reacted；Therefore flower-shaped layering duplex metal hydroxide nanometer structure has higher gas
Sensibility and response speed can be improved the sensitivity of gas sensor, shorten the response time；
The gas sensor prepared at room temperature using three-layer laminated CoAl double-metal hydroxide composite material of the invention
The NO for being 100ppm to concentrationxGas sensitivity is up to 6.05, to NOxThe gas sensitivity of concentration down to 0.05ppm are greater than 1.08,
Response time is less than 7s, and has reversibility of adsorption；
3, the gas sensor that the three-layer laminated CoAl double-metal hydroxide composite material of the present invention is prepared as sensitive material
For detecting NO in airxDetection process do not need heating system, can be 20% in room temperature i.e. 18~35 DEG C and humidity~
It is operated under conditions of 70%, application method is simple；
4, the three-layer laminated CoAl double-metal hydroxide composite material of the present invention is flower-shaped layering hydroxide nano structure,
And the thin and tall crystallinity for illustrating composite material of its XRD diffraction maximum is preferable, therefore increases the interference performance of its anti-external environment, makes
Its performance is obtained to stablize.
Detailed description of the invention
Fig. 1 is the SEM figure for the three-layer laminated CoAl double-metal hydroxide composite material that embodiment 1 obtains；
Fig. 2 is 6,000 times of transmission electron microscopes of the three-layer laminated CoAl double-metal hydroxide composite material that embodiment 1 obtains
Figure；
Fig. 3 is the sensitivity curve that gas sensor prepared by embodiment 1 detects nitrogen oxides；
Fig. 4 is the gas-selectively test chart of the gas sensor of the preparation of embodiment 1 at room temperature；
Fig. 5 is 500,000 times of transmission electron microscopes of the three-layer laminated CoAl double-metal hydroxide composite material that embodiment 2 obtains
Figure；
Fig. 6 is the X-ray diffractogram for the three-layer laminated CoAl double-metal hydroxide composite material that embodiment 2 obtains；
Fig. 7 is the gas reperformance test figure of the gas sensor of the preparation of embodiment 2 at room temperature；
Fig. 8 is the veneer structure schematic diagram of three-layer laminated CoAl double-metal hydroxide composite material prepared by embodiment 2.
Specific embodiment:
The technical solution of the present invention is not limited to the following list, further includes between each specific embodiment
Any reasonable combination.
Specific embodiment 1: the three-layer laminated CoAl double-metal hydroxide composite material of present embodiment by cobalt nitrate,
Aluminum nitrate, ammonium fluoride and precipitating reagent are made；The precipitating reagent is aqueous solution of urea.
Present embodiment have it is following the utility model has the advantages that
1, the three-layer laminated CoAl double-metal hydroxide composite material of present embodiment has layer structure abundant, layer and layer
Flower-shaped composite material is formed, the specific surface area of the double-metal hydroxide of flower-shaped layering is bigger, is capable of providing more active sites
Point goes to be reacted with gas molecule, while flower-shaped layering double-metal hydroxide has certain hole between layers, in this way
Be conducive to gas molecule and enter wherein reacted；Therefore flower-shaped layering duplex metal hydroxide nanometer structure has higher
Vapor sensitivity and response speed can be improved the sensitivity of gas sensor, shorten the response time；
The gas sensor prepared at room temperature using three-layer laminated CoAl double-metal hydroxide composite material of the invention
The NO for being 100ppm to concentrationxGas sensitivity is up to 6.05, to NOxThe gas sensitivity of concentration down to 0.05ppm are greater than 1.08,
Response time is less than 7s, and has reversibility of adsorption；
3, the air-sensitive that the three-layer laminated CoAl double-metal hydroxide composite material of present embodiment is prepared as sensitive material
Element is for detecting NO in airxDetection process do not need heating system, can be in room temperature i.e. 18~35 DEG C and humidity
It is operated under conditions of 20%~70%, application method is simple；
4, the three-layer laminated CoAl double-metal hydroxide composite material of present embodiment is flower-shaped layering hydroxide nano
Structure, and the thin and tall crystallinity for illustrating composite material of its XRD diffraction maximum is preferable, therefore increases the interference energy of its anti-external environment
Power, so that its performance is stablized.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: the cobalt nitrate and aluminum nitrate
Molar ratio is (1~4): 1.Other steps and parameter are same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: the aluminum nitrate and fluorine
Change ammonium molar ratio is 1:(5~15).Other steps and parameter are the same as one or two specific embodiments.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: the aluminum nitrate
It is 1:(60~80 with precipitating reagent molar ratio).Other steps and parameter are identical as one of specific embodiment one to three.
Specific embodiment 5: the preparation method of the three-layer laminated CoAl double-metal hydroxide composite material of present embodiment
It follows the steps below:
One, cobalt nitrate, aluminum nitrate, ammonium fluoride and precipitating reagent are weighed as raw material, is added the raw material into equipped with deionized water
Container in carry out 5~10min of ultrasonic treatment, then stir 20~30min, obtain mixed solution；
The gross mass of the raw material and the mass ratio of deionized water are (2.0~2.5): 40；
Two, the mixed solution for obtaining step 1 pours into stainless steel autoclave, and stainless steel autoclave is placed in 80~200
4~20h is heated in DEG C water-bath, and stainless steel autoclave is then cooled to room temperature；
Three, solution obtained in step 2 stainless steel autoclave is filtered and is precipitated, the precipitating that will be obtained by filtration
Removal of impurities washing is carried out, finally the precipitating after removal of impurities washing is placed in drying box and is dried to get bis- to three-layer laminated CoAl
Metal hydroxides composite material.
The present invention have it is following the utility model has the advantages that
1, in the three-layer laminated CoAl double-metal hydroxide composite material preparation process of present embodiment, carbanion is made
It is inserted into laminate for laminate anion, the insertion of carbanion, which is equivalent to, struts metal cation layer, to change interlayer
Away from improving gas-sensitive property so as to form the channel of more conducively gas adsorption desorption；And the present invention uses simple hydrolysis of urea
Method is prepared for three-layer laminated double-metal hydroxide presoma, and preparation method is simple；The bis- gold of the three-layer laminated CoAl of present embodiment
The cost for belonging to cobalt nitrate, aluminum nitrate or ammonium fluoride that hydroxide composite material preparation uses is far below SnO2Class material or your gold
Belong to, therefore at low cost；
2, the three-layer laminated CoAl double-metal hydroxide composite material of present embodiment preparation has layer structure abundant,
Layer forms flower-shaped composite material with layer, and the specific surface area of the double-metal hydroxide of flower-shaped layering is bigger, is capable of providing more
Active site goes to be reacted with gas molecule, while flower-shaped layering double-metal hydroxide has certain hole between layers
Gap is conducive to gas molecule and enters wherein reacted in this way；Therefore flower-shaped layering duplex metal hydroxide nanometer structure tool
There are higher vapor sensitivity and response speed, can be improved the sensitivity of gas sensor, shortens the response time；
The gas sensor prepared at room temperature using three-layer laminated CoAl double-metal hydroxide composite material of the invention
The NO for being 100ppm to concentrationxGas sensitivity is up to 6.05, to NOxThe gas sensitivity of concentration down to 0.05ppm are greater than 1.08,
Response time is less than 7s, and has reversibility of adsorption；
3, the three-layer laminated CoAl double-metal hydroxide composite material of present embodiment preparation is prepared as sensitive material
Gas sensor for detecting NO in airxDetection process do not need heating system, can be in room temperature i.e. 18~35 DEG C and wet
Degree operates under conditions of being 20%~70%, and application method is simple；
Specific embodiment 6: present embodiment is unlike specific embodiment five: the method for the removal of impurities washing
Are as follows: it is neutrality that the sediment being obtained by filtration, which is first washed with deionized to the pH of cleaning solution, then washs 2 with dehydrated alcohol again
~3 times.Other steps and parameter are identical as specific embodiment five.
Specific embodiment 7: present embodiment is unlike specific embodiment five or six: the method for the drying
Are as follows: dry 10 at 50~90 DEG C~for 24 hours.Other steps and parameter are identical as specific embodiment five or six.
Specific embodiment 8: the three-layer laminated CoAl double-metal hydroxide composite material of present embodiment is in NOxDetection
In application.
Present embodiment have it is following the utility model has the advantages that
1, the gas prepared at room temperature using the three-layer laminated CoAl double-metal hydroxide composite material of present embodiment
The NO that quick element is 100ppm to concentrationxGas sensitivity is up to 6.05, to NOxThe gas sensitivity of concentration down to 0.05ppm are greater than
1.08, the response time is less than 7s, and has reversibility of adsorption；
2, the air-sensitive that the three-layer laminated CoAl double-metal hydroxide composite material of present embodiment is prepared as sensitive material
Element is for detecting NO in airxDetection process do not need heating system, can be in room temperature i.e. 18~35 DEG C and humidity
It is operated under conditions of 20%~70%, application method is simple；
Specific embodiment 9: present embodiment is unlike specific embodiment eight: the three-layer laminated CoAl is bis-
Metal hydroxides composite material detects NOxMethod sequentially include the following steps:
Gas sensor is prepared using three-layer laminated CoAl double-metal hydroxide composite material as sensitive material, by preparation
Gas sensor be placed in temperature be 18~35 DEG C, under conditions of humidity is 20%~70% to NOxIt is detected.Other steps and ginseng
Number is identical as specific embodiment eight.
Specific embodiment 10: present embodiment is unlike specific embodiment eight or nine: described to prepare gas sensitive element
The method of part are as follows: disperse three-layer laminated CoAl double-metal hydroxide compound material ultrasound in the ethanol solution of 5~7 times of volumes
In, finely dispersed suspension is obtained, then suspension is spin-coated in Au interdigital electrode, is placed at 60~80 DEG C dry 4
~6h to get arrive gas sensor.Other steps and parameter are identical as specific embodiment eight or nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment 1:
The preparation method of the three-layer laminated CoAl double-metal hydroxide composite material of the present embodiment specifically according to the following steps into
Row:
One, 150mg aluminum nitrate, 233mg cobalt nitrate, 150mg ammonium fluoride and 1700mg precipitating reagent are weighed as raw material, it will be former
Material, which is added in the container equipped with 40mL deionized water, carries out ultrasonic treatment 10min, then stirs 30min, obtains mixed solution；Institute
Stating precipitating reagent is aqueous solution of urea, and the concentration of aqueous solution of urea is 0.875mol/L；
Two, the mixed solution for obtaining step 1 pours into stainless steel autoclave, and stainless steel autoclave is placed in 90 DEG C of water
6h is heated in bath, and stainless steel autoclave is then cooled to room temperature；
Three, solution obtained in step 2 stainless steel autoclave is filtered and is precipitated, the precipitating that will be obtained by filtration
Removal of impurities washing is carried out, finally the precipitating after removal of impurities washing is placed in drying box and is dried to get bis- to three-layer laminated CoAl
Metal hydroxides；
The method of the removal of impurities washing are as follows: the pH that the sediment being obtained by filtration first is washed with deionized to cleaning solution is
Then neutrality is washed 2 times with dehydrated alcohol again；The method of the drying are as follows: the dry 20h at 80 DEG C.
Fig. 1 is the SEM figure for the three-layer laminated CoAl double-metal hydroxide composite material that embodiment 1 obtains；It can from Fig. 1
To find out, three-layer laminated CoAl double-metal hydroxide composite material is to assemble the flower-like structure grown by multiple nanometer sheets,
This is conducive to improve sensitivity, shortens response；Fig. 2 is that the three-layer laminated CoAl double-metal hydroxide that embodiment 1 obtains is compound
6,000 times of transmission electron microscope pictures of material；It can be clearly seen that this three-layer laminated CoAl double-metal hydroxide is compound from Fig. 2
Material has abundant layer structure, and layer and layer form flower-shaped composite material, is more advantageous to raising to vapor sensitivity and selectivity.
Three-layer laminated CoAl double-metal hydroxide composite material prepared by embodiment 1 is as the sensitive material of gas sensor
Expect in the detection to nitrogen oxides, method particularly includes: the three-layer laminated CoAl double-metal hydroxide for preparing embodiment 1 is compound
Material ultrasonic disperse obtains finely dispersed suspension in the ethanol solution of 6 times of volumes, and suspension is then spin-coated on Au fork
Refer on electrode, is placed at 70 DEG C dry 5h to get gas sensor is arrived.
Gas sensitive detection, specific steps are as follows: first by air-sensitive to be measured are carried out using gas sensor of the static volumetric method to preparation
Element is installed in gas chamber and connect with information collection and analytical equipment, in the case where detection temperature is 22 DEG C, detection humidity is 25%,
Start the NO of injection 100ppmx, starting small fan makes NOxIt is uniformly distributed in gas chamber, is fed back when according to data collection system quickly
Information observe air-sensitive response stablize when, then using air pump be evacuated, make NOxIt excludes, device under test returns original state, i.e., complete
It is recycled at a gas injection；Then 50ppm, 30ppm, 10ppm, 5ppm, 3ppm, 1ppm, 0.5ppm and 0.3ppm are successively carried out
NOxGas injection circulation；The sensitivity curve of gas sensor detection nitrogen oxides prepared by embodiment 1 is obtained after completing gas injection circulation,
As shown in Figure 3, wherein curve 1~11 respectively correspond 100ppm, 50ppm, 30ppm, 10ppm, 5ppm, 3ppm, 1ppm,
The NO of 0.5ppm, 0.3ppm, 0.1ppm and 0.05ppmx.From figure 3, it can be seen that NOxConcentration is the sensitive of 100ppm gas
Degree is up to 6.05, to NOxConcentration down to 0.05ppm gas sensitivity be greater than 1.08, sensitive membrane from injection NOxResistance when gas
Start to change to the time used in its resistance complete stability less than 7s, fast response time, reversibility of adsorption are good.
Fig. 4 is the gas-selectively test chart of the gas sensor of the preparation of embodiment 1 at room temperature；, wherein test gas packet
It includes: NOx、NH3、H2、CH4And CO, remove NOxImplantation concentration is outside 100ppm, and the implantation concentration of remaining gas is 1000ppm；Fig. 4 knot
Fruit it is found that embodiment 1 prepare gas sensor at room temperature to NOxWith selectivity very outstanding.
Embodiment 2:
The preparation method of the three-layer laminated CoAl double-metal hydroxide composite material of the present embodiment specifically according to the following steps into
Row:
One, 150mg aluminum nitrate, 233mg cobalt nitrate, 150mg ammonium fluoride and 1700mg precipitating reagent are weighed as raw material, it will be former
Material, which is added in the container equipped with 40mL deionized water, carries out ultrasonic treatment 10min, then stirs 30min, obtains mixed solution；Institute
Stating precipitating reagent is aqueous solution of urea, and the concentration of aqueous solution of urea is 0.875mol/L；
Two, the mixed solution for obtaining step 1 pours into stainless steel autoclave, and stainless steel autoclave is placed in 120 DEG C of water
6h is heated in bath, and stainless steel autoclave is then cooled to room temperature；
Three, solution obtained in step 2 stainless steel autoclave is filtered and is precipitated, the precipitating that will be obtained by filtration
Removal of impurities washing is carried out, finally the precipitating after removal of impurities washing is placed in drying box and is dried to get bis- to three-layer laminated CoAl
Metal hydroxides；The method of the removal of impurities washing are as follows: the sediment being obtained by filtration first is washed with deionized to cleaning solution
PH be neutrality, then washed 2 times with dehydrated alcohol again；The method of the drying are as follows: the dry 20h at 80 DEG C；
Fig. 5 is 500,000 times of transmission electron microscopes of the three-layer laminated CoAl double-metal hydroxide composite material that embodiment 2 obtains
Figure；From figure 5 it can be seen that three-layer laminated CoAl double-metal hydroxide composite material intergranular for 0.258nm away from corresponding to
CoAl double-metal hydroxide (012) crystal face, is proved each other with XRD, has been prepared for the higher CoAl bimetallic hydrogen-oxygen of purity
Compound；Fig. 6 is the X-ray diffractogram for the three-layer laminated CoAl double-metal hydroxide composite material that embodiment 2 obtains；From Fig. 6
In as can be seen that three-layer laminated CoAl double-metal hydroxide composite material crystallinity it is preferable；In figure 2 θ angle value be 11.6 °,
23.32 °, 34.25 °, 46.2 ° (003) (006) (012) for corresponding to CoAl double-metal hydroxide and (018) crystal face, and
(003) and the diffraction maximum of (006) crystal face be it is very strong, show CoAl double-metal hydroxide during formation along one
Fixed direction growth.Meanwhile all diffraction maximums show that CoAl double-metal hydroxide crystal phase is Co in Fig. 66Al2CO3(OH)16·
H2O；Fig. 8 is the veneer structure schematic diagram of three-layer laminated CoAl double-metal hydroxide composite material prepared by embodiment 2.
Three-layer laminated CoAl double-metal hydroxide composite material prepared by embodiment 2 is as the sensitive material of gas sensor
Expect in the detection to nitrogen oxides, method particularly includes: the three-layer laminated CoAl double-metal hydroxide for preparing embodiment 1 is compound
Material ultrasonic disperse obtains finely dispersed suspension in the ethanol solution of 6 times of volumes, and suspension is then spin-coated on Au fork
Refer on electrode, is placed at 70 DEG C dry 5h to get gas sensor is arrived；
Gas sensitive detection, specific steps are as follows: first by air-sensitive to be measured are carried out using gas sensor of the static volumetric method to preparation
Element is installed in gas chamber and connect with information collection and analytical equipment, in the case where detection temperature is 20 DEG C, detection humidity is 25%,
Start the NO of injection 100ppmx, starting small fan makes NOxIt is uniformly distributed in gas chamber, is fed back when according to data collection system quickly
Information observe air-sensitive response stablize when, then using air pump be evacuated, make NOxIt excludes, device under test returns original state, i.e., complete
It is recycled at a gas injection；Fig. 7 is the gas reperformance test figure for the gas sensor that at room temperature prepared by embodiment 2.From figure it is found that
After three-layer laminated CoAl double-metal hydroxide composite material is formed by sensitive membrane nitric oxide adsorption, resistance is rapider
Ground reduces, and after continuous 5 circulation absorptions-desorption ammonia, sensitivity is slightly reduced, and repeatability is preferably.
Table 1 is sensitivity and response time of the gas sensor of the preparation of testing example 2 under different nitrous oxides concentrations,
As it can be seen from table 1 concentration constantly reduces, and the response time is respectively less than when nitrous oxides concentration is from 100ppm to 0.05ppm
7s, i.e. response time are rapid, and sensitivity is higher, wherein Calculation of Sensitivity formula is S=R0/Rg, R0For the initial electricity of sensitive membrane
Resistance, RgFor NOxThe resistance of sensitive membrane under atmosphere.
Table 1
Claims (10)
1. a kind of three-layer laminated CoAl double-metal hydroxide composite material, it is characterised in that: three-layer laminated CoAl bimetallic hydrogen
Oxide composite is made of cobalt nitrate, aluminum nitrate, ammonium fluoride and precipitating reagent；The precipitating reagent is aqueous solution of urea.
2. three-layer laminated CoAl double-metal hydroxide composite material according to claim 1, it is characterised in that: the nitre
Sour cobalt and nitric acid al mole ratio are (1~4): 1.
3. three-layer laminated CoAl double-metal hydroxide composite material according to claim 1 or 2, it is characterised in that: institute
It states aluminum nitrate and ammonium fluoride molar ratio is 1:(5~15).
4. three-layer laminated CoAl double-metal hydroxide composite material according to claim 3, it is characterised in that: the nitre
Sour aluminium and precipitating reagent molar ratio are 1:(60~80).
5. the preparation method of three-layer laminated CoAl double-metal hydroxide composite material as described in claim 1, feature exist
In: the preparation method follows the steps below:
One, cobalt nitrate, aluminum nitrate, ammonium fluoride and precipitating reagent are weighed as raw material, adds the raw material into the appearance equipped with deionized water
5~10min of ultrasonic treatment is carried out in device, is then stirred 20~30min, is obtained mixed solution；
The gross mass of the raw material and the mass ratio of deionized water are (2.0~2.5): 40；
Two, the mixed solution for obtaining step 1 pours into stainless steel autoclave, and stainless steel autoclave is placed in 80~200 DEG C of water
4~20h is heated in bath, and stainless steel autoclave is then cooled to room temperature；
Three, solution obtained in step 2 stainless steel autoclave is filtered and is precipitated, the precipitating being obtained by filtration is carried out
Precipitating after removal of impurities washing is finally placed in drying box and is dried to get three-layer laminated CoAl bimetallic is arrived by removal of impurities washing
Hydroxide composite material.
6. the preparation method of three-layer laminated CoAl double-metal hydroxide composite material according to claim 5, feature
It is: the method for the removal of impurities washing are as follows: during the pH that the sediment being obtained by filtration first is washed with deionized to cleaning solution is
Property, then washed 2~3 times with dehydrated alcohol again.
7. the preparation method of three-layer laminated CoAl double-metal hydroxide composite material according to claim 5, feature
It is: the method for the drying are as follows: dry 10 at 50~90 DEG C~for 24 hours.
8. three-layer laminated CoAl double-metal hydroxide composite material as described in claim 1 is in NOxApplication in detection.
9. application according to claim 8, it is characterised in that: the three-layer laminated CoAl double-metal hydroxide composite wood
Material detection NOxMethod sequentially include the following steps:
Gas sensor is prepared using three-layer laminated CoAl double-metal hydroxide composite material as sensitive material, by the air-sensitive of preparation
Element be placed in temperature be 18~35 DEG C, under conditions of humidity is 20%~70% to NOxIt is detected.
10. application according to claim 9, it is characterised in that: the method for preparing gas sensor are as follows: will be three-layer laminated
CoAl double-metal hydroxide compound material ultrasound is scattered in the ethanol solution of 5~7 times of volumes, is obtained finely dispersed suspended
Then suspension is spin-coated in Au interdigital electrode by liquid, be placed at 60~80 DEG C dry 4~6h to get gas sensor is arrived.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110736778A (en) * | 2019-06-04 | 2020-01-31 | 黑龙江大学 | Preparation method of three-dimensional layered CoAl bimetal hydroxide nano material and application of three-dimensional layered CoAl bimetal hydroxide nano material in detection of heavy metal ions in water body |
| CN110862575A (en) * | 2019-11-15 | 2020-03-06 | 南京理工大学 | Composite intumescent flame retardant, flame-retardant high impact polystyrene material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665233A (en) * | 2009-09-15 | 2010-03-10 | 北京化工大学 | Layered double hydroxide and preparation method thereof |
| CN104445364A (en) * | 2014-10-04 | 2015-03-25 | 吴晓红 | Method for synthesizing ZnAl-layered double hydroxide |
| CN106517359A (en) * | 2016-11-15 | 2017-03-22 | 大连理工大学 | Method for one-step compounding of cobalt manganese laminated double-metal hydroxide at large interlayer interval |
| CN106876150A (en) * | 2017-03-10 | 2017-06-20 | 上海应用技术大学 | A kind of porous C oAl bimetallic oxides two dimension hierarchical structure electrode material and preparation method thereof |
| CN107195485A (en) * | 2017-06-01 | 2017-09-22 | 上海应用技术大学 | A kind of preparation method of flower-shaped CoAl double-metal hydroxides electrode material |
-
2018
- 2018-06-06 CN CN201810575816.5A patent/CN109060889A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665233A (en) * | 2009-09-15 | 2010-03-10 | 北京化工大学 | Layered double hydroxide and preparation method thereof |
| CN104445364A (en) * | 2014-10-04 | 2015-03-25 | 吴晓红 | Method for synthesizing ZnAl-layered double hydroxide |
| CN106517359A (en) * | 2016-11-15 | 2017-03-22 | 大连理工大学 | Method for one-step compounding of cobalt manganese laminated double-metal hydroxide at large interlayer interval |
| CN106876150A (en) * | 2017-03-10 | 2017-06-20 | 上海应用技术大学 | A kind of porous C oAl bimetallic oxides two dimension hierarchical structure electrode material and preparation method thereof |
| CN107195485A (en) * | 2017-06-01 | 2017-09-22 | 上海应用技术大学 | A kind of preparation method of flower-shaped CoAl double-metal hydroxides electrode material |
Non-Patent Citations (2)
| Title |
|---|
| HONGXIN SUN ET AL.: "Three-dimensional hierarchical flower-like Mg-Al-layered double hydroxides: Fabrication, characterization and enhanced sensing properties to NOx at room temperature", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| 常兴: "基于钴铝层双金属氢氧化物制备的电极材料及其电容性能", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110736778A (en) * | 2019-06-04 | 2020-01-31 | 黑龙江大学 | Preparation method of three-dimensional layered CoAl bimetal hydroxide nano material and application of three-dimensional layered CoAl bimetal hydroxide nano material in detection of heavy metal ions in water body |
| CN110862575A (en) * | 2019-11-15 | 2020-03-06 | 南京理工大学 | Composite intumescent flame retardant, flame-retardant high impact polystyrene material and preparation method thereof |
| CN110862575B (en) * | 2019-11-15 | 2022-03-18 | 南京理工大学 | Composite intumescent flame retardant, flame-retardant high impact polystyrene material and preparation method thereof |
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