CN105158303A - Precious metal/base metal oxide/graphene ternary composite gas sensitive material and preparation method thereof - Google Patents

Precious metal/base metal oxide/graphene ternary composite gas sensitive material and preparation method thereof Download PDF

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CN105158303A
CN105158303A CN201510570223.6A CN201510570223A CN105158303A CN 105158303 A CN105158303 A CN 105158303A CN 201510570223 A CN201510570223 A CN 201510570223A CN 105158303 A CN105158303 A CN 105158303A
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oxide
metal salt
graphene
sensitive material
base metal
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CN105158303B (en
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孙宇峰
孟凡利
葛胜
赵丽洁
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Anhui Polytechnic University
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Anhui Polytechnic University
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Abstract

The invention relates to a precious metal/base metal oxide/graphene ternary composite gas sensitive material and a preparation method thereof. The preparation of the precious metal/base metal oxide/graphene ternary composite gas sensitive material is realized by a series of processes; the composition material is combined with excellent properties of various components; by using the composition material, the gas sensitive property of a sensor is further improved while the defects of low sensitivity, poor selectivity, high resistance and the like of a conventional metal oxide sensitive material are overcome; a gas sensitive sensor prepared from the ternary composite material is used for detecting acetone gas; compared with a sensor prepared from a metal oxide/graphene composite material and a metal oxide/precious metal semiconducting material as gas sensitive materials, the gas sensitive sensor prepared from the ternary composite material has the advantages of higher sensitivity, quicker response, shorter recovery time and higher selectivity and broader application prospect.

Description

Noble metal/base metal oxide/Graphene tri compound gas sensitive and preparation
Technical field
The invention belongs to gas sensitive material technical field, be specifically related to a kind of noble metal/base metal oxide/Graphene tri compound gas sensitive material and preparation method thereof.The invention still further relates to a kind of gas sensor based on noble metal/base metal oxide/Graphene tri compound gas sensitive material.
Background technology
Metal-oxide semiconductor (MOS) gas sensor, as " gas-electricity " transcriber part, has that detection speed is fast, low cost and other advantages.But the pure phase of metal-oxide semiconductor (MOS) is broad spectrum activity sensitive material, it has, and sensitivity is lower, poor selectivity and the shortcoming such as resistance is large.The development of modern science and technology is had higher requirement to metal-oxide semiconductor (MOS) gas sensor, and this sensor not only will have higher susceptibility, also needs higher gas-selectively and stability.
The method that tradition improves gas sensor selectivity and stability mainly contains and utilizes doping techniques, optimizes manufacture craft, sintering process, improvement component structure etc.Conventional alloy mainly noble metal as gold, silver, platinum, ruthenium, rhodium, osmium, iridium.Noble metal has catalytic activity, can reduce the energy of activation of tested aerochemistry absorption, thus effectively can improve the sensitivity of element and shorten the response time, but it too increases the instability of material.
Graphene is a kind of newfound carbon group material, has excellent physics, chemical property.Itself and the compounded compound substance of metal oxide are widely used in the every field such as photocatalysis, gas sensitization, the energy.Although substantially increase its sensitivity in air-sensitive, still not bery desirable in selectivity.
Although metal oxide and noble metal composite air-sensitive material and Graphene and metal oxide composite air-sensitive material improve stability and the selectivity of gas sensor to a certain extent, but up to now, the selectivity of metal-oxide semiconductor (MOS) gas sensor and the problem of poor stability can't well solve.Therefore, current Problems existing is badly in need of a kind of multiple elements design gas sensitive material that can improve gas sensor susceptibility, gas-selectively and stability of research and development.
Summary of the invention
Technical matters to be solved by this invention is for the deficiencies in the prior art, provides a kind of noble metal/base metal oxide/Graphene tri compound gas sensing materials and preparation method thereof.The method with precious metal salt, base-metal salt and graphene oxide for the noble metal/base metal oxide/Graphene tri compound gas sensing materials of function admirable made by raw material, with the gas sensor that this compound substance is made, high to the selectivity of gas, sensitivity good, response is fast, and release time is short.
For this reason, first aspect present invention provides a kind of gas sensitive material, and it is noble metal, base metal oxide and Graphene trielement composite material.
According to the present invention, described trielement composite material obtains through thermal treatment after being mixed with base metal salt solution and precious metal salt solution by graphene oxide solution, in the potpourri of graphene oxide solution and base metal salt solution and precious 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); The mass ratio of preferred described precious metal salt, base-metal salt and graphene oxide is (0.48-0.57): (171-180): (0.25-0.26).
In some embodiments of the invention, described noble metal comprises at least one in gold, silver, platinum, ruthenium, rhodium, osmium and iridium.Preferred described noble metal is silver.
In other embodiments of the present invention, described base metal oxide comprises at least one in tin oxide, indium oxide, zinc paste, manganese oxide, iron oxide, titanium dioxide, zirconia, aluminium oxide, tungsten oxide and vanadium oxide.Preferred described base metal oxide is tin oxide.
Second aspect present invention provides a kind of preparation method of sensitive material as described in the first aspect of the invention, comprising:
Steps A, obtained noble metal/base metal oxide/Graphene precursor mixture after graphene oxide solution is mixed with base metal salt solution and precious metal salt solution;
Step B, heat-treats obtained gas sensitive material to noble metal/base metal oxide/Graphene precursor mixture.
In some embodiments of the invention, the concentration of described graphene oxide solution is 5.04-5.88mg/mL; The concentration of preferred described graphene oxide solution is 5.3-5.5mg/mL.
In other embodiments of the present invention, the concentration of described base metal salt solution is 187.89-210.00mg/mL; The concentration of preferred described base metal salt solution is 189.47-198.95mg/mL.
In other embodiments of the invention, the concentration of described precious metal salt solution is 6.3-14.7mg/mL; The concentration of preferred described precious metal salt solution is 10-12mg/mL.
According to the present invention, described graphene oxide solution carries out ultrasound wave process after being mixed with ethanol by graphene oxide again to obtain.Described base metal salt solution is dissolved in ethanol obtained by base-metal salt.Described precious metal salt solution is dissolved in ethanol obtained by precious metal salt.
In some embodiments of the invention, described base-metal salt comprises corresponding acetate corresponding to base metal and/or metal halide in base metal oxide.
In other embodiments of the present invention, the nitrate of described precious metal salt corresponding to noble metal.
In some embodiments of the invention, in stepb, described heat treated temperature is 250-400 DEG C.Preferred described heat treated temperature is 290-300 DEG C.The described heat treated time is 1-6 hour.The preferred described heat treated time is 2-3 hour.
Third aspect present invention provides a kind of gas sensitization sensor, it comprises substrate, substrate a bottom surface is provided with the Ith comb shape sensing electrode and the IIth comb shape sensing electrode, the comb of two comb shape sensing electrodes is interspersed and is coated with gas sensitive material coating in gap betwixt, a bar shaped sensing electrode be connected with comb shape sensing electrode is respectively arranged with at the two ends of substrate a bottom surface, and each bar shaped sensing electrode is connected with a gold thread, wherein, the bottom surface that the gas sensitive material that described gas sensitive material coating is prepared by the gas sensitive material described in first aspect present invention or preparation method is as described in respect of the second aspect of the invention coated on substrate a is formed.
In a preferred embodiment of the invention, described sensing electrode is also included on substrate b bottom surface and is provided with zone of heating, be respectively arranged with a bar shaped sensing electrode be connected with zone of heating at the two ends of substrate b bottom surface, and each bar shaped sensing electrode is connected with a gold thread.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Fig. 1 is the gas sensor schematic diagram in embodiment of the present invention 3-7; The implication of Fig. 1 Reference numeral is as follows: 101 gas sensitization sensors; 1 substrate; 2 substrate a faces; 3 the Ith comb shape sensing electrodes; 4 the IIth comb shape sensing electrodes; 5 comb; 6 gas sensitive materials; 7 bar shaped sensing electrodes; 8 gold threads; 9 substrate b bottom surfaces; 10 zones of heating.
Fig. 2 is transmission electron microscope (TEM) photo of gas sensitive material (noble metal/base metal oxide/Graphene trielement composite material) obtained in the embodiment of the present invention 1.
Fig. 3 is X-ray energy spectrum (EDS) figure of the black region on the circular granular in Fig. 2.
The gas sensor be made up of the gas sensitive material in the embodiment of the present invention 1 is placed in the sensitivity characteristic curve map measured by acetone that concentration is 0.005ppm, 15ppm, 150ppm, 600ppm and 3000ppm by Fig. 4 respectively in embodiment 3.
Fig. 5 is by existing SnO in embodiment 4 2/ Graphene gas sensor and the gas sensor be made up of the gas sensitive material in the embodiment of the present invention 1 are placed in the sensitivity characteristic curve map measured by acetone gas atmosphere that concentration is 150ppm respectively.
The gas sensor be made up of the gas sensitive material in the embodiment of the present invention 1 is placed in the sensitivity characteristic curve map measured by acetone, ammonia, furans, formaldehyde and chlorobenzene gas atmosphere that concentration is 150ppm by Fig. 6 respectively in embodiment 5.
The gas sensor be made up of the gas sensitive material in the embodiment of the present invention 1 is placed in the acetone gas atmosphere that concentration is 150ppm in embodiment 6 by Fig. 7, sensitivity characteristic curve map measured under the working temperature of gas sensor is 250 DEG C, 300 DEG C and 350 DEG C of conditions respectively.
Embodiment
For making the present invention easier to understand, describe the present invention in detail below in conjunction with embodiment and accompanying drawing, these embodiments only play illustrative effect, are not limited to range of application of the present invention.
As previously mentioned, there is the problem of susceptibility, selectivity and poor stability in existing metal-oxide semiconductor (MOS) gas sensor, and all can not be well solved always.Given this, the present inventor has carried out large quantifier elimination for metal-oxide semiconductor (MOS) gas sensing material and has found, to combine with Graphene with noble metal, base metal oxide and can form a kind of novel tertiary composite air-sensitive material, each to noble metal, base metal oxide and Graphene own excellent specific property organically combines by this compound substance, can overcome the shortcomings such as the sensitivity of INVENTIONConventional metal-oxide sensitive material is low, poor selectivity, resistance are large.Especially can also produce synergy between each composition in this compound substance, this compound substance significantly can be promoted further the gas-sensitive property of sensor for the preparation of gas sensor.
Therefore, first aspect present invention relates to a kind of gas sensitive material, and it is noble metal, base metal oxide and Graphene trielement composite material.Wherein, noble metal plays powerful catalyst effect, and Graphene can reduce electronics loss in the transmission and the ability of enhancing absorption, thus improves selectivity and the sensitivity of material.
In some embodiments of the invention, described noble metal comprises at least one in gold, silver, platinum, ruthenium, rhodium, osmium and iridium.Preferred described noble metal is silver.
In other embodiments of the present invention, described base metal oxide comprises at least one in tin oxide, indium oxide, zinc paste, manganese oxide, iron oxide, titanium dioxide, zirconia, aluminium oxide, tungsten oxide and vanadium oxide.Preferred described base metal oxide is tin oxide.
According to the present invention, described trielement composite material lowers the temperature to anneal through centrifugal treating, thermal treatment after being mixed with base metal salt solution and precious metal salt solution by graphene oxide solution to obtain again, in the potpourri of graphene oxide solution and base metal salt solution and precious 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).The mass ratio of preferred described precious metal salt, base-metal salt and graphene oxide is (0.48-0.57): (171-180): (0.25-0.26).More preferred, the mass ratio of described precious metal salt, base-metal salt and graphene oxide is 0.48:171:0.25.
Second aspect present invention relates to a kind of preparation method of sensitive material as described in the first aspect of the invention, comprising:
Steps A, after graphene oxide solution being mixed with base metal salt solution and precious metal salt solution successively, obtains noble metal/base metal oxide/Graphene precursor mixture through centrifugal treating;
Step B, heat-treats (calcining) noble metal/base metal oxide/Graphene precursor mixture, then through stove cold (cooling) annealing, obtained gas sensitive material.
In some embodiments of the invention, the concentration of described graphene oxide solution is 5.04-5.88mg/mL.The concentration of preferred described graphene oxide solution is 5.3-5.5mg/mL.More preferred, the concentration of preferred described graphene oxide solution is 5.3mg/mL.
In other embodiments of the present invention, the concentration of described base metal salt solution is 187.89-210.00mg/mL.The concentration of preferred described base metal salt solution is 189.47-198.95mg/mL.More preferred, the concentration of described base metal salt solution is 189.47mg/mL.
In other embodiments of the invention, the concentration of described precious metal salt solution is 6.3-14.7mg/mL.The concentration of preferred described precious metal salt solution is 10-12mg/mL.More preferred, the concentration of described precious metal salt solution is 10mg/mL.
According to the inventive method, in step, described graphene oxide solution carries out ultrasound wave process after being mixed with ethanol by graphene oxide again to obtain.Described base metal salt solution is dissolved in ethanol obtained by base-metal salt.Described precious metal salt solution is dissolved in ethanol obtained by precious metal salt.
In some embodiments of the invention, described base-metal salt comprises corresponding acetate corresponding to base metal and/or metal halide in base metal oxide.Described metal halide comprises at least one in metal chloride, metal bromide and metal fluoride.Preferable alloy halogenide is metal chloride, and such as, metal halide can be Tin tetrachloride pentahydrate.
In other embodiments of the present invention, the nitrate of described precious metal salt corresponding to noble metal.
In embodiments more of the present invention, in steps A, the preparation method of noble metal/base metal oxide/Graphene precursor mixture is: in graphene oxide, add ethanol, and ultrasonic for potpourri 80-100min is obtained graphene solution; Base-metal salt is dissolved in ethanol and adds above-mentioned graphene solution and stir 4-6h; Add the lysate of silver nitrate after being stirred by mixed liquor, then stir 4-7min; Namely the potpourri centrifugal treating obtained is obtained noble metal/base metal oxide/Graphene precursor mixture.
In a further concrete embodiment of the present invention, in steps A, the preparation method of noble metal/base metal oxide/Graphene precursor mixture is: get 5.3g graphene oxide and add in the ethanol of 1L, and by ultrasonic for potpourri 90 minutes, obtain graphene solution.The dissolving metal salts of 3.6g is in the ethanol of 19mL and add the above-mentioned graphene solution of 1mL.Add 10mg/mL silver nitrate ethanol lysate 1mL after mixed liquor being stirred 5h, then stir 5min.By the potpourri that obtains with 8000 revs/min of centrifugal treating 5min, namely obtain noble metal/base metal oxide/Graphene precursor mixture.
According to the inventive method, in stepb, the temperature of described calcining is 250-400 DEG C.The temperature of preferred described calcining is 290-300 DEG C.More preferred, the temperature of described calcining is 300 DEG C.The time of described calcining is 1-6 hour.The time of preferred described calcining is 2-3 hour.More preferred, the time of described calcining is 2 hours.
In a specific embodiment of the present invention, in step B, the preparation method of noble metal/base metal oxide/Graphene trielement composite material is: will obtain noble metal/base metal oxide/Graphene precursor mixture and at 300 DEG C, calcine 2h, obtain gas sensitive material.
According to the present invention, also comprise step C after stepb, gas sensitive material is shattered and makes Powdered gas sensitive material.The particle diameter of described Powdered gas sensitive material is 1-3 μm.Be preferably 2 μm.
Source for graphene oxide in the present invention has no particular limits, and can be obtained, also can prepare voluntarily, the graphene oxide preferably prepared in the following ways by commercially available mode.Such as, reaction mixture is made after dag, sodium nitrate, the concentrated sulphuric acid, potassium permanganate and water being mixed; Add hydrogen peroxide wherein, filter, more respectively with hydrochloric acid and deionized water washing; Filter cake is dissolved in deionized water, and uses ultrasound wave process; By centrifugal for obtained potpourri and wash, the graphene oxide obtained after washing is carried out vacuum drying, obtained dry graphene oxide.
In a specific embodiment of the present invention, the preparation method of graphene oxide is: 1g graphite and 1g sodium nitrate are added in the concentrated sulphuric acid of 46mL, and stirs 3 minutes in ice bath, then adds 6g potassium permanganate slowly.After 1 hour, reaction mixture is transferred in the oil bath of 35 DEG C and stir 2 hours, afterwards temperature is slowly risen to 60 DEG C, then stir 2 hours.Finally, in reaction mixture, add the water of 200mL and be warmed up to 90 DEG C of stirrings 5 hours, add the hydrogen peroxide 10mL that massfraction is 30% wherein after reaction terminates, the color from yellow of solution becomes brown.Solution is filtered slowly, with the salt acid elution of 5%, then washes with deionized water.Filter cake is dissolved in deionized water, and with ultrasound wave stripping reaction product.First the potpourri obtained is removed all visible particles at 2000 revs/min of centrifugal 5min, then centrifugal 10 minutes with 8000 revs/min.By the graphene oxide that obtains after washing 60 DEG C of vacuum drying 12 hours, obtain the graphene oxide needing preparation.
Third aspect present invention relates to a kind of gas sensitization sensor 101, it comprises substrate 1, on substrate a bottom surface 2, be provided with the comb 5 of the Ith comb shape sensing electrode 3 and the IIth comb shape sensing electrode 4, two comb shape sensing electrodes is interspersed and is coated with gas sensitive material coating 6 in gap betwixt, be respectively arranged with a bar shaped sensing electrode 7 be connected with comb shape sensing electrode at the two ends of substrate a bottom surface 2, and each bar shaped sensing electrode 7 is connected with a gold thread 8; Substrate b bottom surface 9 is provided with zone of heating 10, is respectively arranged with a bar shaped sensing electrode 7 be connected with zone of heating at the two ends of substrate b bottom surface 9, and each bar shaped sensing electrode 7 is connected with a gold thread 8; Wherein, the bottom surface that the gas sensitive material that described gas sensitive material coating 6 is prepared by the gas sensitive material described in first aspect present invention or preparation method is as described in respect of the second aspect of the invention coated on substrate a is formed.
In the present invention, the material of preferred described substrate is pottery or other insulating material.
The present invention also relates to a kind of preparation method of gas sensitization sensor further, with solvent, above-mentioned gas sensitive is mixed with gas sensitive suspension, then the substrate bottom surface between two the comb shape sensing electrodes being coated on gas sensor is also connected with two comb shape sensing electrodes and forms gas sensitization coating, thus obtained gas sensitization sensor.
In the present invention, in the process preparing gas sensor, the concentration of described gas sensitive suspension is 12-18mg/mL.The concentration of preferred described gas sensitive suspension is 15mg/mL.
According to certain embodiments of the present invention, above-mentionedly prepare in the method for gas sensitization sensor, described solvent includes but not limited to test ethanol.
Term described in the present invention " trielement composite material gas sensitization sensor " refers to the gas sensitization sensor be made up of noble metal/base metal oxide/Graphene trielement composite material of the present invention.
Relate to experiment material in the present invention buy from market or adopt conventional method to obtain, test chemical reagent used and be the pure level of analysis, reagent is all purchased from Chemical Reagent Co., Ltd., Sinopharm Group; Pi Anbiao (Keithley6487) is used to provide the electric current of power supply and the change of record current, purchased from Keithley instrument company; Transmission electron microscope (TEM), INSTRUMENT MODEL JEM-2011, purchased from Jeol Ltd..
The performance evaluation test condition of gas sensor of the present invention is: the test voltage at gas sensor two ends is constant is 0.3V, and working temperature is 200-350 DEG C.Preferred working temperature is 250-350 DEG C.Further preferred described working temperature is 300 DEG C.
The present invention is with precious metal salt, base-metal salt and the graphene oxide noble metal/base metal oxide made by raw material/Graphene tri compound gas sensitive material, each to noble metal, base metal oxide and Graphene own excellent specific property is organically combined, the shortcomings such as the sensitivity of INVENTIONConventional metal-oxide sensitive material is low, poor selectivity, resistance are large can be overcome.Especially can also produce synergy between each composition in this compound substance, this compound substance significantly be improved the gas-sensitive property of sensor for the preparation of gas sensor, reduce minimum gas concentrations; Substantially reduce response time and release time simultaneously.
The gas sensor made with this trielement composite material has higher sensitivity, faster response and shorter release time for detecting ketone gas than the sensor using base metal oxide/graphene composite material as sensitive material.Such as, be 0.3V when the test voltage at the gas sensor two ends made with this trielement composite material is constant, when working temperature is 300 DEG C, it shows stronger selectivity to acetone gas, response and resume speed faster, its concentration limit is 0.005ppm, and more known graphene/metal oxide has 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 sulphuric acid of 46mL, and stirs 3 minutes in ice bath, then add 6g potassium permanganate slowly.After 1 hour, reaction mixture is transferred in the oil bath of 35 DEG C and stir 2 hours, afterwards temperature is slowly risen to 60 DEG C, then stir 2 hours.Finally, in reaction mixture, add the water of 200mL and be warmed up to 90 DEG C of stirrings 5 hours, add the hydrogen peroxide 10mL that massfraction is 30% wherein after reaction terminates, the color from yellow of solution becomes brown.Solution is filtered slowly, with the salt acid elution of 5%, then washes with deionized water.Filter cake is dissolved in deionized water, and peels off graphene oxide with ultrasound wave.First the potpourri obtained is removed all visible particles at 2000 revs/min of centrifugal 5min, then centrifugal 10 minutes with 8000 revs/min.By the graphene oxide that obtains after washing 60 DEG C of vacuum drying 12 hours, obtain the graphene oxide needing preparation.
(2) preparation of noble metal/base metal oxide/Graphene precursor mixture:
Get the graphene oxide that 5.3g prepared by said method to add in the ethanol of 1L, and by ultrasonic for potpourri 90 minutes.The Tin tetrachloride pentahydrate of 3.6g to be dissolved in the ethanol of 19mL and to add the above-mentioned graphene oxide solution of 1mL.Add the ethanol lysate 1mL of 10mg/mL silver nitrate after mixed liquor being stirred 5h, then stir 5min.By the potpourri that obtains with 8000 revs/min of centrifugal 5min, namely obtain noble metal/base metal oxide/Graphene precursor mixture.
(3) preparation of noble metal/base metal oxide/Graphene trielement composite material:
Calcined 2 hours at 300 DEG C by the noble metal/base metal oxide/Graphene precursor mixture obtained, the cold annealing of stove, obtains white tri compound gas sensitive material.
(4) tri compound gas sensitive material is shattered make Powdered tri compound gas sensitive material.
Adopt the micromechanism of this gas sensitive material of transmission electron microscope observing, result as shown in Figure 2.Fig. 2 is transmission electron microscope (TEM) photo of tri compound gas sensitive material of the present invention, as can see from Figure 2, the circular granular in Fig. 2 exists black region.
Carry out X-ray energy spectrometer detection to the black region on the circular granular in Fig. 2 further, result as shown in Figure 3.Fig. 3 is X-ray energy spectrum (EDS) figure of the black region on the circular granular in Fig. 2, and this testing result proves that the material in the black region on circular granular is silver-colored simple substance.
Transmission electron microscope (TEM) photo further combined with the gas sensitive material of Fig. 2 can draw, in Fig. 2, diameter is the circular granular of 40nm is tin oxide, the atrament that tin oxide depends on is silver-colored simple substance, bottom is Graphene, the irregular shade of part may be overlapping Graphene, proves that this gas sensitive material is silver/tin oxide/Graphene tri compound gas sensitive material.
Embodiment 2: the preparation of noble metal/base metal oxide/Graphene tri compound gas sensitive material
(1) preparation method of graphene oxide is with embodiment 1.
(2) preparation of noble metal/base metal oxide/Graphene precursor mixture:
Get the graphene oxide that 5.5g prepared by said method to add in the ethanol of 1L, and by ultrasonic for potpourri 90 minutes.The Tin tetrachloride pentahydrate of 3.78g to be dissolved in the ethanol of 19mL and to add the above-mentioned graphene oxide solution of 1mL.Add the ethanol lysate 1mL of 12mg/mL silver nitrate after mixed liquor being stirred 5h, then stir 5min.By the potpourri that obtains with 8000 revs/min of centrifugal 5min, namely obtain noble metal/base metal oxide/Graphene precursor mixture.
(3) preparation of noble metal/base metal oxide/Graphene trielement composite material:
Calcined 3 hours at 290 DEG C by the noble metal/base metal oxide/Graphene precursor mixture obtained, the cold annealing of stove, obtains white tri compound gas sensitive material.
(4) tri compound gas sensitive material is shattered make Powdered tri compound gas sensitive material.
By the micromechanism of this gas sensitive material of transmission electron microscope observing, and analyze further in conjunction with X-ray energy spectrometer, similar in result and embodiment 1, prove that this gas sensitive material is silver/tin oxide/Graphene tri compound gas sensitive 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 ethanol and is mixed with the gas sensitive suspension that concentration is 15mg/mL, then the substrate bottom surface between two the comb shape sensing electrodes this suspension being coated on gas sensor is also connected with two comb shape sensing electrodes and forms gas sensitization coating, thus obtained gas sensitization sensor.
(2) sensitivity characteristic of gas sensitization sensor is detected
The voltage arranging gas sensor two ends is 0.3V, and working temperature is 300 DEG C, and being placed on concentration is respectively in the acetone gas atmosphere of 0.005ppm, 15ppm, 150ppm, 600ppm and 3000ppm, and detect its sensitivity characteristic, result as shown in Figure 4.
As can be seen from Figure 4, noble metal/base metal oxide/Graphene tri compound gas sensitization sensor concentration limit is 0.005ppm, along with its response curve of increase of concentration continues to increase.And can draw from summary responses curve map, this sensor has good repeatability.Sensor meets with a response when contacting with gas to be measured immediately, and the fastest response time is within 0.5s, and average response time is 1s.When inputting fresh air, response current value gets back to baseline position immediately fast.
Embodiment 4
The preparation method of gas sensitization sensor is with embodiment 3.
The voltage arranging gas sensor two ends is 0.3V, and working temperature is 300 DEG C, respectively by itself and existing SnO 2/ Graphene gas sensor is placed in the acetone gas atmosphere that concentration is 150ppm, and detect its sensitivity characteristic, result as shown in Figure 5.
As can be seen from Figure 5, the noble metal/base metal oxide/sensitivity of Graphene tri compound gas sensitization sensor to acetone gas is higher than existing SnO 2/ Graphene gas sensor, and response is faster, release time is shorter.
Embodiment 5
The preparation method of gas sensitization sensor is with embodiment 3.
The voltage arranging gas sensor two ends is 0.3V, and working temperature is 300 DEG C, and be placed on respectively in acetone, ammonia, furans, formaldehyde and the chlorobenzene gas atmosphere that concentration is 150ppm, detect its sensitivity characteristic, result as shown in Figure 6.
As can be seen from Figure 6, noble metal/base metal oxide/Graphene tri compound gas sensitization sensor has good selectivity to acetone gas.
Embodiment 6
The preparation method of gas sensitization sensor is with embodiment 3.
The voltage arranging gas sensor two ends is 0.3V, working temperature is 300 DEG C, being placed on concentration is in the acetone gas atmosphere of 150ppm, and under the working temperature of gas sensor is 250 DEG C, 300 DEG C and 350 DEG C of conditions, detect its sensitivity characteristic respectively, result as shown in Figure 7.
As can be seen from Figure 7, noble metal/base metal oxide/Graphene tri compound gas sensitization sensor increases progressively along with the rising of working temperature in the process of 250-300 DEG C the response of acetone, 300-350 DEG C of its response along with the rising of temperature declines, on the contrary so 300 DEG C is noble metal/base metal oxide/Graphene tri compound gas sensitization sensor optimum working temperature.
It should be noted that above-described embodiment only for explaining the present invention, not forming any limitation of the invention.By referring to exemplary embodiments, invention has been described, but to should be understood to word wherein used be descriptive and explanatory vocabulary, instead of limited vocabulary.Can modify the present invention by the scope being defined in the claims in the present invention, and the present invention be revised not deviating from scope and spirit of the present invention.Although the present invention wherein described relates to specific method, material and embodiment, and do not mean that the present invention is limited to particular case disclosed in it, on the contrary, easily extensible of the present invention is to other all methods and applications with identical function.

Claims (10)

1. a gas sensitive material, it is noble metal, base metal oxide and Graphene trielement composite material.
2. sensitive material according to claim 1, it is characterized in that, described trielement composite material obtains through thermal treatment after being mixed with base metal salt solution and precious metal salt solution by graphene oxide solution, in the potpourri of graphene oxide solution and base metal salt solution and precious 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); The mass ratio of preferred described precious metal salt, base-metal salt and graphene oxide is (0.48-0.57): (171-180): (0.25-0.26).
3. sensitive material according to claim 1 and 2, is characterized in that, described noble metal comprises at least one in gold, silver, platinum, ruthenium, rhodium, osmium and iridium; Preferred described noble metal is silver.
4. sensitive material according to claim 1 and 2, is characterized in that, described base metal oxide comprises at least one in tin oxide, indium oxide, zinc paste, manganese oxide, iron oxide, titanium dioxide, zirconia, aluminium oxide, tungsten oxide and vanadium oxide; Preferred described base metal oxide is tin oxide.
5., as a preparation method for sensitive material as described in any one in claim 1-4, comprising:
Steps A, obtained noble metal/base metal oxide/Graphene precursor mixture after graphene oxide solution is mixed with base metal salt solution and precious metal salt solution;
Step B, heat-treats obtained gas sensitive material to noble metal/base metal oxide/Graphene precursor mixture.
6. preparation method according to claim 5, is characterized in that,
The concentration of described graphene oxide solution is 5.04-5.88mg/mL; The concentration of preferred described graphene oxide solution is 5.3-5.5mg/mL;
The concentration of described base metal salt solution is 187.89-210.00mg/mL; The concentration of preferred described base metal salt solution is 189.47-198.95mg/mL;
The concentration of described precious metal salt solution is 6.3-14.7mg/mL; The concentration of preferred described precious metal salt solution is 10-12mg/mL.
7. the preparation method according to claim 5 or 6, is characterized in that,
Described graphene oxide solution carries out ultrasound wave process after being mixed with ethanol by graphene oxide again to obtain;
Described base metal salt solution is dissolved in ethanol obtained by base-metal salt;
Described precious metal salt solution is dissolved in ethanol obtained by precious metal salt.
8., according to the preparation method in claim 5-7 described in any one, it is characterized in that,
Described base-metal salt comprises corresponding acetate corresponding to base metal and/or metal halide in base metal oxide;
The nitrate of described precious metal salt corresponding to noble metal.
9. according to the preparation method in claim 5-8 described in any one, it is characterized in that, in stepb, described heat treated temperature is 250-400 DEG C; Preferred described heat treated temperature is 290-300 DEG C; The described heat treated time is 1-6 hour; The preferred described heat treated time is 2-3 hour.
10. a gas sensitization sensor, it comprises substrate, substrate a bottom surface is provided with the Ith comb shape sensing electrode and the IIth comb shape sensing electrode, the comb of two comb shape sensing electrodes is interspersed and is coated with gas sensitive material coating in gap betwixt, a bar shaped sensing electrode be connected with comb shape sensing electrode is respectively arranged with at the two ends of substrate a bottom surface, and each bar shaped sensing electrode is connected with a gold thread, wherein, the bottom surface that the gas sensitive material that described gas sensitive material coating is prepared by the preparation method in the gas sensitive material in claim 1-4 described in any one or claim 5-9 described in any one is coated on substrate a is formed.
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