CN105158303B - Noble metal/base metal oxide/graphene tri compound gas sensitive and preparation - Google Patents
Noble metal/base metal oxide/graphene tri compound gas sensitive and preparation Download PDFInfo
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- CN105158303B CN105158303B CN201510570223.6A CN201510570223A CN105158303B CN 105158303 B CN105158303 B CN 105158303B CN 201510570223 A CN201510570223 A CN 201510570223A CN 105158303 B CN105158303 B CN 105158303B
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Abstract
The present invention relates to a kind of noble metal/base metal oxide/graphene tri compound gas sensitive materials and preparation method thereof.The preparation of noble metal/base metal oxide/graphene tri compound gas sensitive material is realized by series of process.The composite material combines each own excellent specific property of component, and the gas-sensitive property of sensor is further improved while the shortcomings of overcoming low INVENTIONConventional metal-oxide sensitive material sensitivity, poor selectivity, big resistance.The gas sensor made using this trielement composite material is used to detect acetone gas has higher sensitivity, faster response, shorter recovery time and stronger selectivity than metal oxide/graphene composite material and metal oxide/noble metal semi-conducting material as the sensor of sensitive material, has broad application prospects.
Description
Technical field
The invention belongs to gas sensitive material technical fields, and in particular to a kind of noble metal/base metal oxide/graphene
Tri compound gas sensitive material and preparation method thereof.The invention further relates to one kind being based on noble metal/base metal oxide/graphite
The gas sensor of alkene tri compound gas sensitive material.
Background technology
Metal-oxide semiconductor (MOS) gas sensor be used as " gas-electricity " transcriber part, have detection speed soon, at
This low advantage.But the pure phase of metal-oxide semiconductor (MOS) is broad spectrum activity sensitive material, selectivity relatively low with sensitivity
The shortcomings of poor and resistance is big.To metal-oxide semiconductor (MOS) gas sensor, more stringent requirements are proposed for the development of modern science and technology,
The sensor will not only have higher sensibility, it is also necessary to have higher gas-selectively and stability.
Tradition improve gas sensor selectivity and stability method mainly have using doping techniques, optimization manufacture craft,
Sintering process, improvement component structure etc..Common dopant is mainly noble metal such as gold, silver, platinum, ruthenium, rhodium, osmium, iridium.Noble metal
With catalytic activity, the activation energy of tested aerochemistry absorption can be reduced, thus can effectively improve element sensitivity and
Shorten the response time, but it also increases the unstability of material.
Graphene is a kind of newfound carbon group material, has excellent physics, chemical property.It is multiple with metal oxide
Composite material is widely used in the every field such as photocatalysis, gas sensitization, the energy made of closing.Although being carried significantly in terms of air-sensitive
Its high sensitivity, but it is still not highly desirable in terms of selectivity.
Although metal oxide exists with noble metal composite air-sensitive material and graphene with metal oxide composite air-sensitive material
The stability and selectivity of gas sensor are improved to a certain extent, but so far, metal-oxide semiconductor (MOS) gas
The problem of selectivity and the stability difference of sensor can't solve well.Therefore, presently, there are the problem of be badly in need of research
Develop a kind of multiple elements design gas sensitive material that can improve gas sensor sensibility, gas-selectively and stability.
Invention content
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide a kind of noble metal/base metal oxygen
Compound/graphene tri compound gas sensing materials and preparation method thereof.This method is with precious metal salt, base-metal salt and oxidation stone
Black alkene is noble metal/base metal oxide/graphene tri compound gas sensing materials that function admirable is made in raw material, multiple with this
Gas sensor made of condensation material, to the high selectivity of gas, sensitivity is good, response is fast, and recovery time is short.
For this purpose, first aspect present invention provides a kind of gas sensitive material, it is noble metal, base metal oxide and stone
Black alkene trielement composite material.
According to the present invention, the trielement composite material is by graphene oxide solution and base metal salt solution and precious metal salt
It is made after solution mixing through being heat-treated, in the mixture of graphene oxide solution and base metal salt solution and precious metal salt solution
In, the mass ratio of precious metal salt, base-metal salt and graphene oxide is (0.3-0.7):(170-190):(0.24-0.28)；It is excellent
It is (0.48-0.57) to select the mass ratio of the precious metal salt, base-metal salt and graphene oxide:(171-180):(0.25-
0.26)。
In some embodiments of the invention, the noble metal includes at least one in gold, silver, platinum, ruthenium, rhodium, osmium and iridium
Kind.It is preferred that the noble metal is silver.
In other embodiments of the present invention, the base metal oxide includes tin oxide, indium oxide, zinc oxide, oxygen
Change at least one of manganese, iron oxide, titanium oxide, zirconium oxide, aluminium oxide, tungsten oxide and vanadium oxide.It is preferred that the base metal oxygen
Compound is tin oxide.
Second aspect of the present invention provides a kind of preparation method of sensitive material as described in the first aspect of the invention, including：
Noble metal/low-priced is made in step A after mixing graphene oxide solution with base metal salt solution and precious metal salt solution
Metal oxide/graphene precursor mixture；
Step B carries out being heat-treated obtained gas sensitization to noble metal/base metal oxide/graphene precursor mixture
Material.
In some embodiments of the invention, a concentration of 5.04-5.88mg/mL of the graphene oxide solution；It is preferred that
A concentration of 5.3-5.5mg/mL of the graphene oxide solution.
In other embodiments of the present invention, a concentration of 187.89-210.00mg/mL of the base metal salt solution；
It is preferred that a concentration of 189.47-198.95mg/mL of the base metal salt solution.
In other embodiments of the invention, a concentration of 6.3-14.7mg/mL of the precious metal salt solution；It is preferred that described
A concentration of 10-12mg/mL of precious metal salt solution.
According to the present invention, the graphene oxide solution is to carry out ultrasonic wave after being mixed with ethyl alcohol by graphene oxide again
Reason is made.The base metal salt solution is to be dissolved in ethyl alcohol to be made by base-metal salt.Your gold the precious metal salt solution is by
Category salt, which is dissolved in ethyl alcohol, to be made.
In some embodiments of the invention, the base-metal salt include in base metal oxide corresponding base metal institute it is right
The acetate and/or metal halide answered.
In other embodiments of the present invention, the precious metal salt is the nitrate corresponding to noble metal.
In some embodiments of the invention, in stepb, the temperature of the heat treatment is 250-400 DEG C.It is preferred that described
The temperature of heat treatment is 290-300 DEG C.The time of the heat treatment is 1-6 hours.It is preferred that the time of the heat treatment is that 2-3 is small
When.
Third aspect present invention provides a kind of gas sensitization sensor comprising substrate is provided on the bottom surfaces substrate a
The broach of Ith comb shape sensing electrode and the IIth comb shape sensing electrode, two comb shape sensing electrodes is interspersed and gap therebetween
It is interior to be coated with gas sensitive material coating, it is respectively set that there are one be connected with comb shape sensing electrode at the both ends of the bottom surfaces substrate a
Bar shaped sensing electrode, and be connected with a gold thread on each bar shaped sensing electrode, wherein the gas sensitive material coating
The gas prepared by the gas sensitive material described in first aspect present invention or preparation method as described in respect of the second aspect of the invention
Bottom surface of the sensitive material coated on substrate a is formed.
In a preferred embodiment of the invention, the sensing electrode further includes being provided with heating on the bottom surfaces substrate b
Layer is respectively set at the both ends of the bottom surfaces substrate b there are one the bar shaped sensing electrode being connected with heating layer, and each bar shaped passes
A gold thread is connected on sense electrode.
Description of the drawings
It is next below in conjunction with the accompanying drawings that invention is further described in detail.
Fig. 1 is the gas sensor schematic diagram in 3-7 of the embodiment of the present invention；The meaning of Fig. 1 reference numerals is as follows：101 gas
Body sensitive sensor；1 substrate；2 faces substrate a；3 the Ith comb shape sensing electrodes；4 the IIth comb shape sensing electrodes；5 broach；6 gases are quick
Feel material；7 bar shaped sensing electrodes；8 gold threads；9 bottom surfaces substrate b；10 heating layers.
Fig. 2 is gas sensitive material (noble metal/base metal oxide/graphene three obtained in the embodiment of the present invention 1
First composite material) transmission electron microscope (TEM) photo.
Fig. 3 is X-ray energy spectrum (EDS) figure of the black region on the circular granular in Fig. 2.
Fig. 4 is to set the gas sensor made of the gas sensitive material in the embodiment of the present invention 1 respectively in embodiment 3
The measured sensitivity characteristic curve in the acetone of a concentration of 0.005ppm, 15ppm, 150ppm, 600ppm and 3000ppm
Figure.
Fig. 5 is in embodiment 4 by existing SnO2/ graphene gas sensor and by the gas in the embodiment of the present invention 1
Gas sensor made of sensitive material is respectively placed in sensitivity characteristic measured in the acetone gas atmosphere of a concentration of 150ppm
Curve graph.
Fig. 6 is to set the gas sensor made of the gas sensitive material in the embodiment of the present invention 1 respectively in embodiment 5
The measured sensitivity characteristic curve graph in the acetone of a concentration of 150ppm, ammonia, furans, formaldehyde and chlorobenzene gas atmosphere.
Fig. 7 is dense to be placed in the gas sensor made of the gas sensitive material in the embodiment of the present invention 1 in embodiment 6
Degree is in the acetone gas atmosphere of 150ppm, is respectively 250 DEG C, 300 DEG C and 350 DEG C conditions in the operating temperature of gas sensor
Lower measured sensitivity characteristic curve graph.
Specific implementation mode
To keep the present invention easier to understand, below in conjunction with embodiment and attached drawing, the present invention will be described in detail, these realities
Apply example only serve it is illustrative, it is not limited to application range of the invention.
As previously mentioned, there are sensibility, selectivity and stability are poor for existing metal-oxide semiconductor (MOS) gas sensor
The problem of, and cannot all be well solved always.In consideration of it, the present inventor is directed to metal-oxide semiconductor (MOS) gas
Body sensing material has carried out a large amount of research and has found, is combined and can be formed with graphene with noble metal, base metal oxide
A kind of novel tertiary composite air-sensitive material, the composite material are each own excellent by noble metal, base metal oxide and graphene
Different characteristic is organically combined, and low INVENTIONConventional metal-oxide sensitive material sensitivity, poor selectivity, resistance can be overcome big etc. and lacked
Point.Synergistic effect can also be generated between each ingredient especially in the composite material, this composite material is used to prepare air-sensitive
Sensor can further be obviously improved the gas-sensitive property of sensor.
Therefore, first aspect present invention is related to a kind of gas sensitive material, is noble metal, base metal oxide and graphite
Alkene trielement composite material.Wherein, noble metal plays the role of powerful catalyst, graphene can reduce the loss of electronics in the transmission with
And the ability of enhancing absorption, to improve selectivity and the sensitivity of material.
In some embodiments of the invention, the noble metal includes at least one in gold, silver, platinum, ruthenium, rhodium, osmium and iridium
Kind.It is preferred that the noble metal is silver.
In other embodiments of the present invention, the base metal oxide includes tin oxide, indium oxide, zinc oxide, oxygen
Change at least one of manganese, iron oxide, titanium oxide, zirconium oxide, aluminium oxide, tungsten oxide and vanadium oxide.It is preferred that the base metal oxygen
Compound is tin oxide.
According to the present invention, the trielement composite material is by graphene oxide solution and base metal salt solution and precious metal salt
It is made through centrifugal treating, the heat treatment annealing that cools down again after solution mixing, in graphene oxide solution and base metal salt solution and expensive
In the mixture of metal salt solution, the mass ratio of precious metal salt, base-metal salt and graphene oxide is (0.3-0.7):(170-
190):(0.24-0.28).It is preferred that the mass ratio of the precious metal salt, base-metal salt and graphene oxide is (0.48-0.57):
(171-180):(0.25-0.26).More preferably, the mass ratio of the precious metal salt, base-metal salt and graphene oxide is
0.48:171:0.25。
Second aspect of the present invention is related to a kind of preparation method of sensitive material as described in the first aspect of the invention, including：
Step A, after graphene oxide solution is mixed with base metal salt solution and precious metal salt solution successively, by centrifugation
Noble metal/base metal oxide/graphene precursor mixture is made in processing；
Step B is heat-treated (calcining) to noble metal/base metal oxide/graphene precursor mixture, then through stove
Cold (cooling) anneals, and gas sensitive material is made.
In some embodiments of the invention, a concentration of 5.04-5.88mg/mL of the graphene oxide solution.It is preferred that
A concentration of 5.3-5.5mg/mL of the graphene oxide solution.More preferably, the preferably described graphene oxide solution is dense
Degree is 5.3mg/mL.
In other embodiments of the present invention, a concentration of 187.89-210.00mg/mL of the base metal salt solution.
It is preferred that a concentration of 189.47-198.95mg/mL of the base metal salt solution.More preferably, the base metal salt solution
A concentration of 189.47mg/mL.
In other embodiments of the invention, a concentration of 6.3-14.7mg/mL of the precious metal salt solution.It is preferred that described
A concentration of 10-12mg/mL of precious metal salt solution.More preferably, a concentration of 10mg/mL of the precious metal salt solution.
According to the method for the present invention, in step, the graphene oxide solution is after being mixed with ethyl alcohol by graphene oxide
Ultrasonication is carried out again to be made.The base metal salt solution is to be dissolved in ethyl alcohol to be made by base-metal salt.The noble metal
Salting liquid is to be dissolved in ethyl alcohol to be made by precious metal salt.
In some embodiments of the invention, the base-metal salt include in base metal oxide corresponding base metal institute it is right
The acetate and/or metal halide answered.The metal halide includes metal chloride, metal bromide and metal fluoride
At least one of.It is preferred that metal halide is metal chloride, for example, metal halide can be Tin tetrachloride pentahydrate.
In other embodiments of the present invention, the precious metal salt is the nitrate corresponding to noble metal.
In certain specific embodiments of the invention, in step A, noble metal/base metal oxide/graphene presoma
The preparation method of mixture is：Ethyl alcohol is added into graphene oxide, and it is molten that mixture ultrasound 80-100min obtained graphene
Liquid；Base-metal salt is dissolved in ethanol and above-mentioned graphene solution is added and stirs 4-6h；Nitre is added after mixed liquor is stirred
The lysate of sour silver, is stirred for 4-7min；Obtained mixture centrifugal treating is obtained into noble metal/base metal oxide/stone
Black alkene precursor mixture.
In the further specific embodiment of the present invention, noble metal/base metal oxide/graphite in step A
The preparation method of alkene precursor mixture is：5.3g graphene oxides are taken to be added in the ethyl alcohol of 1L, and by mixture ultrasound 90
Minute, obtain graphene solution.The dissolving metal salts of 3.6g are in the ethyl alcohol of 19mL and the above-mentioned graphene solutions of 1mL are added.It will
10mg/mL silver nitrate ethyl alcohol lysate 1mL are added after stirring 5h in mixed liquor, are stirred for 5min.By obtained mixture with 8000
Rev/min centrifugal treating 5min is to get to noble metal/base metal oxide/graphene precursor mixture.
According to the method for the present invention, in stepb, the temperature of the calcining is 250-400 DEG C.It is preferred that the temperature of the calcining
It is 290-300 DEG C.More preferably, the temperature of the calcining is 300 DEG C.The time of the calcining is 1-6 hours.It is preferred that described
The time of calcining is 2-3 hours.More preferably, the time of the calcining is 2 hours.
In the specific embodiment of the present invention, noble metal/base metal oxide/graphene ternary is multiple in step B
The preparation method of condensation material is：Noble metal/base metal oxide/graphene precursor mixture will be obtained to calcine at 300 DEG C
2h obtains gas sensitive material.
Further include step C after stepb according to the present invention, it is quick that powdered gas is made in gas sensitive material smashing
Feel material.The grain size of the powdered gas sensitive material is 1-3 μm.Preferably 2 μm.
The present invention of source in to(for) graphene oxide is not particularly limited, and can be obtained by commercially available mode,
It can voluntarily prepare, it is preferred to use the graphene oxide that following manner is prepared.For example, by graphite powder, sodium nitrate, dense sulphur
Reaction mixture is made after acid, potassium permanganate and water mixing；Hydrogen peroxide is added thereto, filter, then respectively with hydrochloric acid and go from
Sub- water washing；In deionized water by filter cake dissolving, ultrasonication is used in combination；Obtained mixture is centrifuged and washed, will be washed
The graphene oxide obtained after washing is dried in vacuo, and dry graphene oxide is made.
In the specific embodiment of the present invention, the preparation method of graphene oxide is：By 1g graphite and 1g nitric acid
Sodium is added in the concentrated sulfuric acid of 46mL, and is stirred in ice bath 3 minutes, and 6g potassium permanganate is then slowly added.It will after 1 hour
Reaction mixture is transferred in 35 DEG C of oil bath and stirs 2 hours, and temperature is slowly increased to 60 DEG C later, is stirred for 2 hours.Most
Afterwards, the water of 200mL is added into reaction mixture and is warming up to 90 DEG C and stirs 5 hours, quality is added thereto after reaction
The hydrogen peroxide 10mL that score is 30%, the color of solution become brown by yellow.Solution is slowly filtered, with 5% hydrochloric acid
Washing, then be washed with deionized water.In deionized water by filter cake dissolving, ultrasonic wave stripping reaction product is used in combination.It is mixed by what is obtained
It closes object and centrifuges all visible particles of 5min removals at 2000 revs/min first, then centrifuged 10 minutes with 8000 revs/min.
The graphene oxide obtained after washing is dried in vacuo 12 hours at 60 DEG C, obtains needing graphene oxide to be prepared.
Third aspect present invention is related to a kind of gas sensitization sensor 101 comprising substrate 1 is set on the bottom surfaces substrate a 2
The broach 5 for being equipped with the Ith comb shape sensing electrode 3 and the IIth 4, two comb shape sensing electrodes of comb shape sensing electrode be interspersed and
It is coated with gas sensitive material coating 6 in its gap, is respectively set at the both ends of the bottom surfaces substrate a 2 electric there are one being sensed with comb shape
The bar shaped sensing electrode 7 that pole is connected, and it is connected with a gold thread 8 on each bar shaped sensing electrode 7；On the bottom surfaces substrate b 9
It is provided with heating layer 10, is respectively set there are one the bar shaped sensing electrode 7 being connected with heating layer at the both ends of the bottom surfaces substrate b 9,
And it is connected with a gold thread 8 on each bar shaped sensing electrode 7；Wherein, the gas sensitive material coating 6 is by the present invention first
Gas sensitive material coating prepared by the gas sensitive material described in aspect or preparation method as described in respect of the second aspect of the invention
It is formed in the bottom surface of substrate a.
In the present invention, the material of the preferably described substrate is ceramics or other insulating materials.
The present invention is further directed to a kind of preparation method of gas sensitization sensor, is matched above-mentioned gas sensitive with solvent
Gas sensitive suspension is made, the substrate bottom surface being then coated between two comb shape sensing electrodes of gas sensor and with two
A comb shape sensing electrode is connected and forms gas sensitization coating, to which gas sensitization sensor be made.
In the present invention, during preparing gas sensor, a concentration of 12-18mg/ of the gas sensitive suspension
mL.It is preferred that a concentration of 15mg/mL of the gas sensitive suspension.
According to certain embodiments of the present invention, in the above-mentioned method for preparing gas sensitization sensor, the solvent includes
But it is not limited to experiment ethyl alcohol.
Heretofore described term " trielement composite material gas sensitization sensor " refers to by noble metal/low-priced gold of the present invention
Belong to gas sensitization sensor made of oxide/graphene trielement composite material.
Experiment material involved in the present invention is bought from market or is made using conventional method, and it is equal to test chemical reagent used
To analyze pure grade, reagent is purchased from Sinopharm Chemical Reagent Co., Ltd.；Pico-ampere table (Keithley 6487) is used for providing electricity
The variation of the electric current and record current in source is purchased from Keithley instrument company；Transmission electron microscope (TEM), instrument model
JEM-2011 is purchased from Jeol Ltd..
The performance evaluation test condition of gas sensor of the present invention is：The test voltage at gas sensor both ends is constant to be
0.3V, operating temperature are 200-350 DEG C.It is preferred that operating temperature is 250-350 DEG C.The further preferred operating temperature is 300
℃。
The present invention is aoxidized by the noble metal made by raw material/base metal of precious metal salt, base-metal salt and graphene oxide
Object/graphene tri compound gas sensitive material, by noble metal, base metal oxide and each own excellent specific property of graphene
The shortcomings of being organically combined, low INVENTIONConventional metal-oxide sensitive material sensitivity, poor selectivity, big resistance can be overcome.Especially
It is can also to generate synergistic effect between each ingredient in the composite material, which is used to prepare gas sensor
It has been obviously improved the gas-sensitive property of sensor, has reduced minimum gas concentrations；Response time and extensive is substantially reduced simultaneously
The multiple time.
With gas sensor made of this trielement composite material for detecting ketone gas ratio with base metal oxide/graphite
Alkene composite material has higher sensitivity, faster response and shorter recovery time as the sensor of sensitive material.Example
Such as, when the test voltage at the gas sensor both ends made with this trielement composite material is constant for 0.3V, operating temperature is 300 DEG C
When, stronger selectivity is shown to acetone gas, faster response and resume speed, concentration limit are
0.005ppm, relatively known graphene/metal oxide have lower concentrations to acetone gas context of detection.
Embodiment
Embodiment 1：The preparation of noble metal/base metal oxide/graphene tri compound gas sensitive material
(1) preparation of graphene oxide：
1g graphite and 1g sodium nitrate are added in the concentrated sulfuric acid of 46mL, and stir 3 minutes in ice bath, then slowly
6g potassium permanganate is added.Reaction mixture is transferred in 35 DEG C of oil bath after 1 hour and is stirred 2 hours, it is later that temperature is slow
60 DEG C are risen to, is stirred for 2 hours.Finally, into reaction mixture be added 200mL water and be warming up to 90 DEG C stir 5 hours, instead
The hydrogen peroxide 10mL that mass fraction is 30% is added after answering thereto, the color of solution becomes brown by yellow.By solution
Slowly filtering with 5% salt acid elution, then is washed with deionized water.In deionized water by filter cake dissolving, it is used in combination ultrasonic wave to shell
From graphene oxide.Obtained mixture is centrifuged into 5min at 2000 revs/min first and removes all visible particles, then with
8000 revs/min centrifuge 10 minutes.The graphene oxide obtained after washing is dried in vacuo 12 hours at 60 DEG C, obtains needing to make
Standby graphene oxide.
(2) preparation of noble metal/base metal oxide/graphene precursor mixture：
5.3g is taken to be added in the ethyl alcohol of 1L by the graphene oxide that the above method is prepared, and mixture is ultrasonic
90 minutes.The Tin tetrachloride pentahydrate of 3.6g is dissolved in the ethyl alcohol of 19mL and the above-mentioned graphene oxide solutions of 1mL is added.It will mix
The ethyl alcohol lysate 1mL that liquid stirs addition 10mg/mL silver nitrates after 5h is closed, 5min is stirred for.By obtained mixture with 8000
Rev/min centrifugation 5min is to get to noble metal/base metal oxide/graphene precursor mixture.
(3) preparation of noble metal/base metal oxide/graphene trielement composite material：
Obtained noble metal/base metal oxide/graphene precursor mixture is calcined 2 hours at 300 DEG C, furnace cooling is moved back
Fire obtains white tri compound gas sensitive material.
(4) powdered tri compound gas sensitive material is made in the smashing of tri compound gas sensitive material.
Using the microstructure of the transmission electron microscope observing gas sensitive material, the results are shown in Figure 2.Fig. 2 is of the invention
Transmission electron microscope (TEM) photo of tri compound gas sensitive material, from fig. 2 it can be seen that existing on circular granular in Fig. 2
Black region.
X-ray energy spectrometer detection further is carried out to the black region on the circular granular in Fig. 2, the results are shown in Figure 3.
Fig. 3 is X-ray energy spectrum (EDS) figure of the black region on the circular granular in Fig. 2, which proves on circular granular
Substance in black region is silver-colored simple substance.
It can be obtained further combined with transmission electron microscope (TEM) photo of the gas sensitive material of Fig. 2, it is a diameter of in Fig. 2
The circular granular of 40nm is tin oxide, and the atrament depended on tin oxide is silver-colored simple substance, and bottom is graphene, and part is irregular
Shade may be the graphene of overlapping, it was demonstrated that the gas sensitive material is silver/tin oxide/graphene tri compound gas sensitization material
Material.
Embodiment 2：The preparation of noble metal/base metal oxide/graphene tri compound gas sensitive material
(1) the preparation method is the same as that of Example 1 for graphene oxide.
(2) preparation of noble metal/base metal oxide/graphene precursor mixture：
5.5g is taken to be added in the ethyl alcohol of 1L by the graphene oxide that the above method is prepared, and mixture is ultrasonic
90 minutes.The Tin tetrachloride pentahydrate of 3.78g is dissolved in the ethyl alcohol of 19mL and the above-mentioned graphene oxide solutions of 1mL is added.It will
Mixed liquor stirs the ethyl alcohol lysate 1mL of addition 12mg/mL silver nitrates after 5h, is stirred for 5min.By obtained mixture with
8000 revs/min of centrifugation 5min are to get to noble metal/base metal oxide/graphene precursor mixture.
(3) preparation of noble metal/base metal oxide/graphene trielement composite material：
Obtained noble metal/base metal oxide/graphene precursor mixture is calcined 3 hours at 290 DEG C, furnace cooling is moved back
Fire obtains white tri compound gas sensitive material.
(4) powdered tri compound gas sensitive material is made in the smashing of tri compound gas sensitive material.
It is further carried out by the microstructure of the transmission electron microscope observing gas sensitive material, and in conjunction with X-ray energy spectrometer
Analysis, it is as a result similar with embodiment 1, it was demonstrated that the gas sensitive material is that silver/tin oxide/graphene tri compound gas is quick
Feel material.
Embodiment 3：The performance evaluation of gas sensitization sensor
(1) gas sensitization sensor is prepared with gas sensitive material obtained in embodiment 1
Gas sensitive material obtained in embodiment 1 is dissolved in the air-sensitive that a concentration of 15mg/mL is configured in ethyl alcohol
Material suspension, then by the suspension be coated on gas sensor two comb shape sensing electrodes between substrate bottom surface and with
Two comb shape sensing electrodes are connected and form gas sensitization coating, to which gas sensitization sensor be made.
(2) sensitivity characteristic of detection gas sensitive sensor
The voltage that gas sensor both ends are arranged is 0.3V, and operating temperature is 300 DEG C, is placed it in respectively a concentration of
In the acetone gas atmosphere of 0.005ppm, 15ppm, 150ppm, 600ppm and 3000ppm, its sensitivity characteristic is detected, as a result as schemed
Shown in 4.
From fig. 4, it can be seen that noble metal/base metal oxide/minimum inspection of graphene tri compound gas sensitization sensor
Go out a concentration of 0.005ppm, its response curve continues to increase with the increase of concentration.And it can from summary responses curve graph
To obtain, which has good repeatability.Sensor is instantly available response, fastest response when being contacted under test gas
Time is average response time 1s within 0.5s.When inputting fresh air, response current value quickly returns to baseline immediately
Position.
Embodiment 4
The preparation method of gas sensitization sensor is the same as embodiment 3.
The voltage that gas sensor both ends are arranged is 0.3V, and operating temperature is 300 DEG C, respectively by itself and existing SnO2/
Graphene gas sensor is placed in the acetone gas atmosphere of a concentration of 150ppm, detects its sensitivity characteristic, as a result such as Fig. 5 institutes
Show.
From fig. 5, it can be seen that noble metal/base metal oxide/graphene tri compound gas sensitization sensor is to acetone
The sensitivity of gas is higher than existing SnO2/ graphene gas sensor, and respond faster, recovery time it is shorter.
Embodiment 5
The preparation method of gas sensitization sensor is the same as embodiment 3.
The voltage that gas sensor both ends are arranged is 0.3V, and operating temperature is 300 DEG C, is placed it in respectively a concentration of
In the acetone of 150ppm, ammonia, furans, formaldehyde and chlorobenzene gas atmosphere, its sensitivity characteristic is detected, the results are shown in Figure 6.
From fig. 6, it can be seen that noble metal/base metal oxide/graphene tri compound gas sensitization sensor is to acetone
Gas has preferable selectivity.
Embodiment 6
The preparation method of gas sensitization sensor is the same as embodiment 3.
The voltage that gas sensor both ends are arranged is 0.3V, and operating temperature is 300 DEG C, places it in a concentration of 150ppm's
In acetone gas atmosphere, its sensitivity is detected under the conditions of the operating temperature of gas sensor is 250 DEG C, 300 DEG C and 350 DEG C respectively
Characteristic, the results are shown in Figure 7.
From figure 7 it can be seen that noble metal/base metal oxide/graphene tri compound gas sensitization sensor is to acetone
Response be incremented by with the raising of operating temperature during 250-300 DEG C, 300-350 DEG C its response with temperature
Raising declines instead, so 300 DEG C are best for noble metal/base metal oxide/graphene tri compound gas sensitization sensor
Operating temperature.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (10)
- It is noble metal, base metal oxide and graphene trielement composite material 1. a kind of acetone gas sensitive material, described three First composite material is to be made after being mixed with base metal salt solution and precious metal salt solution by graphene oxide solution through being heat-treated, In the mixture of graphene oxide solution and base metal salt solution and precious metal salt solution, precious metal salt, base-metal salt and oxidation The mass ratio of graphene is (0.3-0.7):(170-190):(0.24-0.28), the noble metal are silver, the base metal oxidation Object is tin oxide.
- 2. sensitive material according to claim 1, which is characterized in that the precious metal salt, base-metal salt and graphite oxide The mass ratio of alkene is (0.48-0.57):(171-180):(0.25-0.26).
- 3. a kind of preparation method of sensitive material as claimed in claim 1 or 2, including：Noble metal/base metal is made in step A after mixing graphene oxide solution with base metal salt solution and precious metal salt solution Oxide/graphene precursor mixture；Step B carries out being heat-treated obtained gas sensitive material to noble metal/base metal oxide/graphene precursor mixture；Wherein, a concentration of 5.04-5.88mg/mL of the graphene oxide solution；The temperature of the heat treatment is 290-300 ℃。
- 4. preparation method according to claim 3, which is characterized in thatA concentration of 187.89-210.00mg/mL of the base metal salt solution；A concentration of 6.3- of the precious metal salt solution 14.7mg/mL。
- 5. preparation method according to claim 4, which is characterized in thatA concentration of 5.3-5.5mg/mL of the graphene oxide solution；A concentration of 189.47-198.95mg/mL of the base metal salt solution；A concentration of 10-12mg/mL of the precious metal salt solution.
- 6. according to the preparation method described in any one of claim 3-5, which is characterized in thatThe graphene oxide solution is to carry out ultrasonication again after being mixed with ethyl alcohol by graphene oxide to be made；The base metal salt solution is to be dissolved in ethyl alcohol to be made by base-metal salt；The precious metal salt solution is to be dissolved in ethyl alcohol to be made by precious metal salt.
- 7. preparation method according to claim 6, which is characterized in thatThe base-metal salt includes the acetate and/or metal halide corresponding to corresponding base metal in base metal oxide；The precious metal salt is the nitrate corresponding to noble metal.
- 8. preparation method according to claim 7, which is characterized in that the time of the heat treatment is 1-6 hours.
- 9. preparation method according to claim 8, which is characterized in that the time of the heat treatment is 2-3 hours.
- 10. a kind of acetone gas sensitive sensor comprising substrate, be provided on the bottom surfaces substrate a the Ith comb shape sensing electrode and The broach of IIth comb shape sensing electrode, two comb shape sensing electrodes is interspersed and is coated with gas sensitization material in gap therebetween Expect coating, is respectively set that there are one the bar shaped sensing electrodes that are connected with comb shape sensing electrode at the both ends of the bottom surfaces substrate a, and It is connected with a gold thread on each bar shaped sensing electrode, wherein the gas sensitive material coating is described in claims 1 or 2 Gas sensitive material or any one of claim 3-9 described in the gas sensitive material for preparing of preparation method be coated on base The bottom surface of bottom a is formed.
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