CN109490386A - It is a kind of using brownmillerite structure oxide as the current mode NH of sensitive electrode material3Sensor - Google Patents
It is a kind of using brownmillerite structure oxide as the current mode NH of sensitive electrode material3Sensor Download PDFInfo
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Abstract
The invention discloses a kind of using brownmillerite structure oxide as the current mode NH of sensitive electrode material3Sensor and preparation method thereof, the chemical formula of the brownmillerite structure oxide sensitive electrode material are Sr1+xSm2‑xO4+δ(wherein, 0 < x≤0.2,0 < δ < 1), the brownmillerite structure Sr of synthesis1+xSm2‑xO4+δSensitive electrode slurry can be made with ethyl cellulose, graphite and alpha-terpineol ball milling mixing, then using YSZ as solid electrolyte, prepare current mode NH3Sensor.The present invention can be realized sensor to NH3High response and restorability.
Description
Technical field
The invention belongs to sensitive electrode field of material preparation, and in particular to one kind is using brownmillerite structure oxide as sensitive electrical
The current mode NH of pole material3Sensor and preparation method thereof.
Background technique
With economic growth, car ownership persistently rises, brings convenience to people's lives, but vehicle exhaust
Imperfect combustion can generate the substances such as CO, nitrogen oxides, lead, solids suspension, in a certain range of atmospheric environment, when
The amount of these substances increases suddenly, often has an adverse effect and endangers to people, animal, plant etc..Currently, vehicle exhaust is dirty
Dye has become the primary pollution source of China large- and-medium size cities air pollution, and the nitrogen oxides indissoluble that wherein imperfect combustion generates
Yu Shui, it is toxic, stimulation can be generated to the respiratory apparatus of people, be exposed to the NO of high concentration in short term2In even can cause death.
Therefore, extremely urgent for the improvement of vehicle exhaust.
By preparing SCR system in automobile exhaust systems, make NOxPass through SCR system and NH3Reaction, which is reduced, generates N2
And H2O can reduce NOxHarm to environment.But the NH in SCR system3Amount should be appropriate, and system should be at full closeding state,
Otherwise additional pollution can be brought, so NH3Sensor comes into being.NH for vehicle exhaust monitoring3Sensor is located at SCR
The downstream of system, operating condition is more harsh, but it is in temperature (600-900 DEG C), high humidity and interference gas (HC, CO etc.)
Not only there is good sensitivity characteristic, and with good stability and reliability when coexisting.Existing detection NH3Method have
The chromatography of ions, gas chromatography etc. limit it in real life since equipment volume is big, at high cost, analytical cycle is long
Application, and NH3Sensor is easy to carry, and cost is relatively low, high reliablity, by extensive concern.Common NH3Sensor has metal
Semiconductor transducer, conduction high polymer sensor, electrochemical sensor, nano material sensor, light sensor etc..At these
In sensor, most of is all to work under lower temperature conditions, and liquid electrolyte type traditional in electrochemical sensor passes
Since volatilization, service life greatly shorten, in contrast improved solid electrolyte type electrochemical sensor more meets sensor
Vehicle exhaust exacting terms has faster response speed, high sensitivity, low-detection lower limit and preferable selectivity etc. excellent
Point.
Common sensitive electrode material includes using Pt, Pd and Au as the noble metal electrode of representative, with ZnO, SnO2、In2O3、
WO3、TiO2、CuO、Fe2O3、Mn3O4、Co3O4、Cr2O3, NiO be representative simple metal oxide electrode and with perovskite, point
Spar is the composite oxides electrode of representative.Compared to noble metal electrode, simple oxide electrode, composite oxides electrode more has
Beneficial to improving selectivity, sensitivity and the influence for eliminating humidity of sensor.Sr1+xSm2-xO4+δFor brownmillerite structure composite oxygen
Compound belongs to orthorhombic system, is n-type semiconductor, thermal stability is good, to NH3Etc. reproducibilities electron gas there is preferable selection
Property, can yet be regarded as NH3One potential candidate of sensor.
Currently, existing NH3Sensor is mostly applied to the monitoring of gas in atmosphere at room temperature environment, and about hot operation
The NH of automobile-used type under environment3Sensor is most of in order to meet complicated, harsh operating condition, meeting and NO in vehicle exhaustxSensor
And SCR system is worked in coordination, and an organic whole is constituted.The hot spot of research often concentrates on the whole sexual function of three, to list
Only NH3The performance study of sensor is less, and the research in terms of sensitive electrode material is even more fewer and fewer.In the prior art
It is primarily present the related NH of following items3The patent of sensor:
104359959 A of CN discloses one kind with Ni3V2O8Electric potential type NH is blended together for the YSZ base of sensitive electrode3Sensor and its
Preparation method.The sensor is mainly used for the detection of vehicle exhaust, changes the microcosmic shape of sensitive electrode by changing calcination temperature
Looks, to improve the sensitivity and selectivity of sensor.
107748191 A of CN discloses a kind of automobile-used nitrogen oxides ammonia integrated sensor.The sensor can guarantee nitrogen oxygen
On the basis of compound and ammonia measure at the same time and measurement result is not interfere with each other, but constructs complex, the skill for needing to put into
The cost is relatively high for art.
107941885 A of CN discloses a kind of gas sensor.The sensor can be surveyed simultaneously at a temperature of a control
Determine the concentration of nitrogen oxides and ammonia, and can also measure in conversion, precision compare it is more excellent, but when testing to work
There is certain requirement as temperature, greatly limits its application in industrialization.
That there are sensor life-times is short, at high cost for the above patent, structure is complicated, preparation process is cumbersome etc. urgently to be resolved asks
Topic.
Summary of the invention
In view of this, the purpose of the present invention is to propose to a kind of using brownmillerite structure oxide as the electric current of sensitive electrode material
Type NH3Sensor and preparation method thereof can realize sensor to NH3High response and restorability.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of current mode NH prepared using brownmillerite structure oxide as sensitive electrode material3Sensor, the brownmillerite structure
The chemical formula of oxide is Sr1+xSm2-xO4+δ, wherein 0 < x≤0.2,0 < δ < 1.
The preparation method of the brownmillerite structure oxide the following steps are included:
1) 4.23-5.08 g Sr (NO is weighed respectively according to stoichiometric ratio3)2、16.00-17.78 g Sm(NO3)3·6H2O,
It is dissolved in 150-300 mL deionized water, is sufficiently stirred, obtains salting liquid；
2) 50-100 mL deionized water is added in surfactant, heating stirring 5-15 min obtains 0.005-0.1 mol/L
Surfactant solution；Then salting liquid obtained by step 1) is added in surfactant solution, is sufficiently stirred, keeps salting liquid equal
It is even to be scattered in surfactant, obtain solution A；
3) precipitating reagent is added in 100-300 mL deionized water and is dissolved, and stir 10-30 min, obtain 0.1-5 mol/L precipitating
Agent solution；Step 2 acquired solution A is added drop-wise in precipitant solution by peristaltic pump, 2-6 h is stirred to react, is precipitated
Object；The revolving speed control of peristaltic pump is 15-100 r/min, and the revolving speed of stirring is 600-1000 r/min；
4) 15.13-25.22 g citric acid is weighed, is dissolved in 50-75 mL deionized water, citric acid and urea are then pressed
Molar ratio be that urea is added in 1:0-2 in gained citric acid solution, 60-100 DEG C of heating water bath 10-30 under agitation
Min obtains solution B；
5) step 3) gained sediment is added in step 4) acquired solution B, and the pH to 6-8 that precipitating reagent adjusts solution is added
Afterwards, in being stirred to react 3-8 h in 60-100 DEG C, presoma wet gel is obtained；
6) gained presoma wet gel is placed in baking oven, after 100-180 DEG C of heating 10-24 h, through temperature-programmed calcination, is obtained
To brownmillerite structure oxide；Described program heating specifically: be warming up to 300 DEG C with the rate of 0.5-5 DEG C/min, roasting
0.5-1 h；, 600 DEG C are then heated to, 2-4 h is roasted；, then be warming up to 800 DEG C of roasting 3-10 h, finally with 2-10 DEG C/
The rate of min is warming up to 1100-1400 DEG C, roasts 2-10 h, then be down to room temperature with the rate of 2-10 DEG C/min.
Wherein, the surfactant is one of lauric acid, stearic acid, polyvinyl alcohol or polyethylene glycol or a variety of.
The precipitating reagent is one of sodium carbonate, ammonium carbonate, ammonium hydrogen carbonate, urea or ammonium hydroxide or a variety of.
The current mode NH3The preparation method of sensor is by gained brownmillerite structure oxide and ethyl cellulose, stone
Sensitive electrode slurry is made in ink and alpha-terpineol ball milling mixing, and using YSZ as solid electrolyte, the electric current is further made
Type NH3Sensor.
Wherein, the mass ratio of brownmillerite structure oxide and ethyl cellulose is (2-5): (0.034-0.36), brownmillerite
The mass ratio of structure oxide and graphite is 1:(0.01-0.1), the mass ratio of brownmillerite structure oxide and alpha-terpineol is 1:
(0.1-0.3).
The time of ball milling is 0.5-5 h, and revolving speed is 300-800 r/min.
Compared with prior art, the invention has the following beneficial effects:
1. the present invention provides a kind of novel brownmillerite structure oxide Sr1+xSm2-xO4+δAs sensitive electrode material, from structure
On see, Sr1+xSm2-xO4+δBelong to orthorhombic system, general formula AB2O4, without high secondary axes, wherein B atom and O atom will form two kinds
The B-O of distortion is octahedra, generates Lacking oxygen by increasing the turbulence of structure；In addition, by changing two kinds of elements of Sr, Sm
Stoichiometric ratio makes excessive Sr2+It is doped to Sm3+On position, Lacking oxygen can be also generated, ion conductivity is further increased.
2. Sr1+xSm2-xO4+δFor n-type semiconductor, and NH3For reproducibility electron gas.When sensor is exposed to NH3In
When, NH3It is adsorbed on sensitive electrode surfaces, NH3In extra electronics promptly move to Sr1+xSm2-xO4+δConduction band, can be effective
Improve the response and selectivity of sensor.Sensitive electrode using n-type semiconductor as sensor detects reducibility gas, improves
The response and selectivity of sensor, a kind of this good method of can yet be regarded as.
3. the NH made of the sensitive electrode3Sensor, under the conditions of simulated automotive tail gas, when there is response and restoring
Between short, high sensitivity, steady performance, be a kind of NH suitable for large-scale promotion application3Detection method.
Detailed description of the invention
Fig. 1 is Sr in the embodiment of the present invention1.05Sm1.95O4.025Sensitive electrode material roasts 5 h at 1100-1400 DEG C
The XRD spectra of sample afterwards.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Embodiment 1
Brownmillerite structure oxide Sr1.05Sm1.95O4.025The preparation of powder:
(1) 4.44 g Sr (NO are weighed respectively according to stoichiometric ratio3)2、17.33 g Sm(NO3)3·6H2O(nSr: nSm=
1.05:1.95, i.e. x=0.05), it is dissolved in 200 mL deionized waters, is sufficiently stirred, obtains salting liquid.It is hard to weigh 0.51 g
100 mL deionized waters are added in 1000 mL conical flasks in resin acid, and 10 min of heating stirring obtains surfactant solution；Then
Above-mentioned salting liquid is poured into surfactant solution and is sufficiently stirred, salting liquid is dispersed in surfactant, obtains
Solution A.It weighs 5g ammonium hydrogen carbonate and measures 5 mL, 28% ammonium hydroxide, 200 mL deionized water dissolvings of addition, heating stirring 10min,
Obtain precipitant solution；Solution A is added drop-wise in the precipitant solution being stirred continuously by peristaltic pump, 4 h of reaction is vigorously stirred, obtains
To sediment (the revolving speed control of peristaltic pump is 75 r/min, and the revolving speed of electric mixer is transferred to 700 r/min).
(2) 17.65 g citric acids are weighed, are dissolved in 50 mL deionized waters, heating water bath and are continuously stirred at 85 DEG C
30 min, are then added urea thereto, so that nCitric acid: nUrea=1:1.5 is further continued for 60 min of stirring, obtains solution B.
(3) sediment that step (1) obtains is added in step (2) acquired solution B, is adjusted with ammonium hydrogen carbonate-ammonium hydroxide
The pH value of solution is 7-8, and at 85 DEG C, magnetic agitation reacts 5 h for temperature control, obtains presoma wet gel；Place it in baking oven
In, after 130 DEG C of 18 h of heating, 300 DEG C are warming up to the rate of 2 DEG C/min, roasts 0.5 h；600 DEG C are then heated to,
Roast 3 h；It is warming up to 800 DEG C again, roasts 5 h, be finally warming up to 1100 DEG C with the rate of 4 DEG C/min, roast 5 h, then with
The rate of 4 DEG C/min is down to room temperature, obtains Sr1.05Sm1.95O4.025。
Embodiment 2
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that Sr1.05Sm1.95O4.025It is final
Maturing temperature is changed to 1200 DEG C from 1100 DEG C.
Embodiment 3
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that Sr1.05Sm1.95O4.025It is final
Maturing temperature is changed to 1250 DEG C from 1100 DEG C.
Embodiment 4
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that Sr1.05Sm1.95O4.025It is final
Maturing temperature is changed to 1300 DEG C from 1100 DEG C.
Embodiment 5
The specific preparation method of the present embodiment is substantially the same manner as Example 1, the difference is that Sr1.05Sm1.95O4.025It is final
Maturing temperature is changed to 1400 DEG C from 1100 DEG C.
Embodiment 6
The specific preparation method of the present embodiment is substantially the same manner as Example 3, the difference is that brownmillerite structure oxide is
Sr1.01Sm1.99O4.005(i.e. nSr: nSm=1.01:1.99, i.e. x=0.01).
Embodiment 7
The specific preparation method of the present embodiment is substantially the same manner as Example 3, the difference is that brownmillerite structure oxide is
Sr1.2Sm1.8O4.1(i.e. nSr: nSm=1.2:1.8, i.e. x=0.2).
Embodiment 8
The specific preparation method of the present embodiment is substantially the same manner as Example 3, the difference is that changing stearic acid in synthesis process
For lauric acid.
Embodiment 9
The specific preparation method of the present embodiment is substantially the same manner as Example 3, the difference is that will heat up rate 4 in roasting process
DEG C/min is changed to 10 DEG C/min.
Embodiment 10
The specific preparation method of the present embodiment is substantially the same manner as Example 3, the difference is that by rate of temperature fall in roasting process
Natural cooling is changed to for 4 DEG C/min.
Embodiment 11
The specific preparation method of the present embodiment is substantially the same manner as Example 3, the difference is that the reaction temperature 85 of step (3)
DEG C it is changed to 60 DEG C.
Embodiment 12
The specific preparation method of the present embodiment is substantially the same manner as Example 3, the difference is that the reaction temperature 85 of step (3)
DEG C it is changed to 100 DEG C.
Embodiment 13
The specific preparation method of the present embodiment is substantially the same manner as Example 12, the difference is that electric mixer in step (1)
Revolving speed increase to 1000 r/min by 700 r/min.
Embodiment 14
The specific preparation method of the present embodiment is substantially the same manner as Example 12, the difference is that being not added with urea in step (2).
Application Example
Weigh 3 g of brownmillerite structure oxide, 0.052 g of ethyl cellulose, 0.4 g of graphite and alpha-terpineol obtained above
0.6 g ball milling mixing in ball grinder, revolving speed be 500 r/min, Ball-milling Time be 3 h, obtain sensitive electrode slurry, then with
YSZ is solid electrolyte, prepares current mode NH3Sensor.
Properties of product test:
In laboratory simulation vehicle exhaust, that is, it is passed through 0.18 % CO, 350 ppm C3H6, 4.7% CO2, 5% H2O, 600 ppm
NO2, 500 ppm NH3, 14 % O2, balanced gas N2, connect measurement route.Institute is tested using IM6 electrochemical analyser
Obtain current mode NH3Sensor is to NH3Response and response and recovery time, the results are shown in Table 1.
Response of 1 sensor of table at 700 DEG C and its to NH3Response and recovery time
As it can be seen from table 1 when maturing temperature is 1250 DEG C, with Sr1.05Sm1.95O4.025(i.e. nSr: nSm=1.05:1.95, i.e. x
=0.05) be sensitive electrode when, sensor is to NH3With relatively high quick, reversible response-recovery；By further excellent
It is combined to process, sensor is to NH3Response and response dynamics process obtained apparent improvement.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (10)
1. a kind of current mode NH prepared using brownmillerite structure oxide as sensitive electrode material3Sensor, it is characterised in that: institute
The chemical formula for stating brownmillerite structure oxide is Sr1+xSm2-xO4+δ, wherein 0 < x≤0.2,0 < δ < 1.
2. current mode NH according to claim 13Sensor, it is characterised in that: the preparation of the brownmillerite structure oxide
Method the following steps are included:
1) 4.23-5.08 g Sr (NO is weighed respectively according to stoichiometric ratio3)2、16.00-17.78 g Sm(NO3)3·6H2O,
It is dissolved in 150-300 mL deionized water, obtains salting liquid；
2) gained salting liquid is added in surfactant solution, is sufficiently stirred, obtains solution A；
3) acquired solution A is added drop-wise in precipitant solution by peristaltic pump, is stirred to react 2-6 h, obtains sediment；
4) 15.13-25.22 g citric acid is weighed, is dissolved in 50-75 mL deionized water, citric acid and urea are then pressed
Molar ratio be 1:0-2 urea is added in gained citric acid solution, under agitation, 60-100 DEG C of heating water bath 10-30
Min obtains solution B；
5) after the pH for step 3) gained sediment being added in step 4) acquired solution B, and precipitating reagent being used to adjust solution, in
It is stirred to react 3-8 h in 60-100 DEG C, obtains presoma wet gel；
6) gained presoma wet gel is placed in baking oven, after 100-180 DEG C of heating 10-24 h, through temperature-programmed calcination, is obtained
To brownmillerite structure oxide.
3. current mode NH according to claim 23Sensor, it is characterised in that: surfactant described in step 2 is the moon
One of cinnamic acid, stearic acid, polyvinyl alcohol or polyethylene glycol are a variety of.
4. current mode NH according to claim 23Sensor, it is characterised in that: precipitating reagent described in step 3) is carbonic acid
One of sodium, ammonium carbonate, ammonium hydrogen carbonate, urea or ammonium hydroxide are a variety of.
5. current mode NH according to claim 23Sensor, it is characterised in that: the revolving speed of peristaltic pump is 15- in step 3)
100 r/min, the revolving speed of blender are 600-1000 r/min.
6. current mode NH according to claim 23Sensor, it is characterised in that: the pH value of solution is 6- after step 5) is adjusted
8。
7. current mode NH according to claim 23Sensor, it is characterised in that: temperature programming described in step 6) is specific
Are as follows: 300 DEG C are warming up to the rate of 0.5-5 DEG C/min, roasts 0.5-1 h, then heats to 600 DEG C, roasts 2-4 h,
It is warming up to 800 DEG C of roasting 3-10 h again, is finally warming up to 1100-1400 DEG C with the rate of 2-10 DEG C/min, roasts 2-10
H, then room temperature is down to the rate of 2-10 DEG C/min.
8. a kind of current mode NH as described in claim 13The preparation method of sensor, it is characterised in that: by gained brownmillerite knot
Sensitive electrode slurry is made in structure oxide and ethyl cellulose, graphite and alpha-terpineol ball milling mixing, and using YSZ as solid electricity
The current mode NH is further made in Xie Zhi3Sensor.
9. current mode NH according to claim 83The preparation method of sensor, it is characterised in that: brownmillerite structure oxide
Mass ratio with ethyl cellulose is (2-5): the mass ratio of (0.034-0.36), brownmillerite structure oxide and graphite is 1:
The mass ratio of (0.01-0.1), brownmillerite structure oxide and alpha-terpineol is 1:(0.1-0.3).
10. current mode NH according to claim 83The preparation method of sensor, it is characterised in that: the time of ball milling is
0.5-5 h, revolving speed are 300-800 r/min.
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Cited By (1)
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| CN111924895A (en) * | 2020-07-29 | 2020-11-13 | 福州大学 | Spinel type oxide, preparation method thereof and application thereof in solid oxide ammonia fuel cell |
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