CN110161091A - Gas sensing module and its preparation method and application - Google Patents
Gas sensing module and its preparation method and application Download PDFInfo
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- CN110161091A CN110161091A CN201810956342.9A CN201810956342A CN110161091A CN 110161091 A CN110161091 A CN 110161091A CN 201810956342 A CN201810956342 A CN 201810956342A CN 110161091 A CN110161091 A CN 110161091A
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Abstract
The present invention relates to new function material field, a kind of gas sensing module and its preparation method and application is disclosed, which includes microsensor chip and the noble-metal-supported gas sensing materials that are supported on the microsensor chip；Wherein, the noble-metal-supported gas sensing materials include stannic oxide carrier and the noble metal being supported on the stannic oxide carrier, and the noble metal is selected from one of metallic element of IB race and VIII group or a variety of.Gas sensing module provided by the invention has the features such as material preparation method is easy, and yield is big, and carried noble metal mode is simple, and dosage is few, and sensitivity and stability are good, and resistance is lower.
Description
Technical field
The present invention relates to new function material fields, and in particular to a kind of gas sensing module and preparation method thereof and answers
With.
Background technique
In a variety of gas sensing materials known at present, stannic oxide be it is most commonly used, repeatability preferably,
Most stable of one kind is responded, but it is also a kind of material that specificity is poor.Since stannic oxide is to such as H2、CO、H2S、
NOxThere is different degrees of response etc. all kinds of gases, is not suitable for the sensitive material detected as pure gas.In recent years, with
The development of the technologies such as intelligent measurement, multicomponent gas sensor are increasingly becoming the indispensable technical tool in analysis detection field.
Based on extensive gas sensor array, there is the exploitation of the intelligent measurement device of big data feature and integrate, for the more function of a new generation
Sensor-based system can be integrated and provide advantageous strategy support.Spectral response characteristic based on stannic oxide carries out your gold of differentiation
Belong to (such as Ag, Au, Pd, Pt) doping, modification, load and modified, provide for it is a kind of meet simultaneously air-sensitive response broad spectrum activity with
The solution of otherness.The development and application of the comprehensive state identification sensor of integrated form, by revolutionary alternative functions list
One, information dispersion cannot achieve the contemporary sensor device of complicated atmosphere monitoring and warning.Integrated, data mart modeling, letter by device
The means extracted are ceased, can be won comprehensively in detection sensitivity, the indexs such as response speed and complex environment assessment accuracy
Current commercial apparatus.But the problem that the existing gas sensing module based on stannic oxide is single there are still type, it cannot
Meet the needs of above-mentioned detection.
Summary of the invention
The purpose of the invention is to overcome, material yield of the existing technology is low, mode of carried noble metal obtains
Noble metal granule is larger, material stability and the problem of poor sensitivity, provides a kind of gas sensing module and preparation method thereof
And application, the gas sensing module have material preparation method easy, yield is big, and carried noble metal mode is simple, and dosage is few, spirit
The features such as sensitivity and stability are good, and resistance is lower.
To achieve the goals above, one aspect of the present invention provides a kind of gas sensing module, which includes
Microsensor chip and the noble-metal-supported gas sensing materials being supported on the microsensor chip；Wherein, the noble metal
Load gas sensing materials include stannic oxide carrier and the noble metal being supported on the stannic oxide carrier, the noble metal
One of metallic element selected from IB race and VIII group is a variety of.
Preferably, the noble metal is selected from one of Ag, Au, Pd and Pt or a variety of.
Preferably, the stannic oxide carrier is stannic oxide microballoon.
It is highly preferred that the diameter of the stannic oxide microballoon is 0.5-2.5 μm.
It is highly preferred that the stannic oxide microballoon has flower-like structure.
It is highly preferred that the load capacity of the noble metal is in terms of precious metal element relative to 1 parts by weight stannic oxide carrier
0.005-0.03 parts by weight.
Preferably, the microsensor chip includes the sensing electrode of substrate and setting over the substrate.
It is highly preferred that the microsensor chip further includes heating electrode.
Preferably, the microsensor chip include the electrode layer stacked gradually, it is insulating layer, heating layer, supporting layer, hanging
Layer and substrate layer, the region corresponding with the heating layer on the hanging layer and the substrate layer have through-hole.
Second aspect of the present invention provides a kind of preparation method of gas sensing module, this method comprises:
1) by sn-containing compound, the organic dibasic acid of C2-C6, hydrazine hydrate and mixed in hydrochloric acid and hydro-thermal reaction is carried out, then
It is separated by solid-liquid separation, obtains stannic oxide carrier；
2) by noble-metal-supported on the stannic oxide carrier, noble-metal-supported gas sensing materials are obtained；
3) the noble-metal-supported gas sensing materials are supported on microsensor chip；
Wherein, the noble metal is selected from one of metallic element of IB race and VIII group or a variety of.
Preferably, the noble metal is selected from one of Ag, Au, Pd and Pt or a variety of.
Preferably, the sn-containing compound in dichloride stannous, tin tetrachloride, stannous oxide and stannous oxalate one
Kind is a variety of.
It is highly preferred that in terms of tin element, the organic dibasic acid of the sn-containing compound and the C2-C6, the hydrazine hydrate,
The molar ratio of the hydrochloric acid is 1:3-5.5:3-25:0.2-0.48.
It is highly preferred that the organic dibasic acid of the C2-C6 is in oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid
It is one or more.
It is highly preferred that the organic dibasic acid of the C2-C6 is oxalic acid.
Preferably, it is 160-200 DEG C that the condition of the hydro-thermal reaction, which includes: temperature, time 4-20h.
Preferably, by infusion process by noble-metal-supported on the stannic oxide carrier.
Preferably, stannic oxide carrier noble metal precursor body is impregnated, and carries out ultraviolet light irradiation, your gold
Belonging to presoma is water-soluble precious metal salt one or more in the metallic element selected from IB race and VIII group.
Preferably, the noble metal precursor body is selected from AgNO3、AuCl3、Pd(OAc)2、K2PtCl4、PdCl2And Pd
(acac)2One of or it is a variety of.
Preferably, relative to 1 parts by weight stannic oxide carrier, the dosage of the noble metal precursor body in terms of precious metal element
Preferably 0.005-0.03 parts by weight.
Preferably, the condition of the ultraviolet light irradiation include: the time be 10-60min.
Preferably, the microsensor chip includes the sensing electrode of substrate and setting over the substrate.
It is highly preferred that the microsensor chip further includes heating electrode.
Preferably, the microsensor chip include the electrode layer stacked gradually, it is insulating layer, heating layer, supporting layer, hanging
Layer and substrate layer, the region corresponding with the heating layer on the hanging layer and the substrate layer have through-hole.
The present invention also provides a kind of gas sensing module array, the gas sensing module array is by more than two described above
The gas sensing module composition that gas sensing module or above-mentioned preparation method obtain, the gas sensing module load have not
Same noble-metal-supported gas sensing materials.
The gas sensing module that is obtained the present invention also provides above-mentioned gas sensing module, above-mentioned preparation method or above-mentioned
Application of the gas sensing module array in leak detection field, hazardous gas detection field or physical protection field.
Through the above technical solutions, noble-metal-supported stannic oxide flower-like structure of the invention has uniform assembling ruler
Very little, biggish specific surface area has the response of significant air-sensitive.The load has the stannic oxide structure of noble metal to have higher than SnO2
The response sensitivity of bulk material；Dependent on the difference of carried metal, it is poor that material generates the gases such as carbon monoxide and hydrogen sulfide
Anisotropic air-sensitive response；It is expected to, in conjunction with advanced simulated algorithm, realize to mixed gas by constructing various dimensions sensor array
Accurate sensing, can be widely used in that Petrochemical Area etc. is poisonous and harmful, flammable explosive gas is distributed opposite close quarters, can
Realize monitoring, ingredient identification and the alert applications to complicated atmosphere state.
Preparation method proposed by the present invention is easy, and low energy consumption, is easily enlarged production.It can also lead in the preparation process of laboratory
Temperature, reaction time and raw material proportioning are overregulated to regulate and control the size of noble-metal-supported stannic oxide flower-like nanostructure.In reality
In the production process of border, production can be scaled up as the case may be.
Detailed description of the invention
Fig. 1 is the resulting Ag@SnO of embodiment 12, the resulting Au@SnO of embodiment 42, the resulting Pd@SnO of embodiment 52, it is real
Apply the resulting Pt@SnO of example 62And the resulting unsupported SnO of comparative example 12X ray diffracting spectrum；
Fig. 2 is the resulting Ag@SnO of embodiment 12The resulting unsupported SnO of (a, b) and comparative example 12The scanning electron microscope of (c, d)
Photo；
Fig. 3 is the resulting Ag@SnO of embodiment 12(a) and the resulting unsupported SnO of comparative example 12(b) transmission electron microscope shines
Piece；
Fig. 4 is the resulting Ag@SnO of embodiment 125 gained Pd@SnO of (left figure), embodiment2(right figure) is to various concentration
CO、H2The response curve of S gas and the two mixed gas；
Fig. 5 is the structural schematic diagram for the microsensor chip that preparation example 1 obtains.
Description of symbols
1, sensing electrode 2, heating electrode
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
Gas sensing module according to the present invention, the gas sensing module include microsensor chip and are supported on micro- biography
Noble-metal-supported gas sensing materials on sensor chip；Wherein, the noble-metal-supported gas sensing materials include titanium dioxide
Tin carrier and the noble metal being supported on the stannic oxide carrier, the noble metal are selected from the metallic element of IB race and VIII group
One of or it is a variety of.
Preferably, the noble metal is selected from one of Ag, Au, Pd and Pt or a variety of.
In the present invention, by the way that above-mentioned noble-metal-supported on stannic oxide carrier, can not only be obviously improved dioxy
Change the air-sensitive response speed and sensitivity of tin, be more capable of differentiation is embodying the response relative intensity to gas with various component
On.Gas sensing module i.e. of the invention can generate response simultaneously to gas with various, by having different air-sensitives to pass selected from load
The two or more gas sensing modules of the invention felt in the material gas sensitive of the same race different with load capacity cooperate, shape
At gas sensing module array, and using the data analysis algorithm of rear end, the gas sensing based on this series material is allowed for
Module array is possibly realized the component resolving of complicated gas；So that synthesis of the gas sensing module under practical atmosphere
Recognition capability greatly promotes, and with high sensitivity and detection speed.The gas of above-mentioned gas sensing material response, example
It such as can be H2、CO、H2S、NOx, toluene, butane etc., the need to poisonous and harmful flammable explosive gas detection can be adapted to extensively
It asks.
According to the present invention, there is no particular limitation for the shape of the stannic oxide carrier, as long as can reach to different gas
Body response purpose, the preferably described stannic oxide carrier be stannic oxide microballoon, more preferably have flower-like structure, described two
The diameter of tin oxide microballoon for example can be 0.5-2.5 μm, preferably 0.5-2 μm.
In order to further increase the air-sensitive response speed and sensitivity of resulting materials, as the load capacity of the noble metal,
Relative to 1 parts by weight stannic oxide carrier, the load capacity of the noble metal is 0.005-0.03 parts by weight in terms of precious metal element,
Preferably 0.007-0.02 parts by weight, more preferably 0.01-0.002 parts by weight.
According to the present invention, there is no particular limitation for the structure of the microsensor chip, as long as your gold can be loaded
Belong to load gas sensing materials and realizes the response to gas with various.
As a kind of preferred microsensor chip of the present invention, such as shown in Fig. 5, the micro sensing chip may include base
The sensing electrode 1 of piece and setting over the substrate.By loading gas sensing materials on the sensing electrode, so as to reality
Now to the highly sensitive detection of gas.Preferably, the microsensor chip further includes heating electrode 2, such as resistance wire, described to add
Thermode 2 is used to provide the described gas sensing module operating temperature appropriate.Gas sensing materials are connected to by sensing electrode 1
External circuit has between electrode heating electrode 2 to pass through, can be by changing the voltage applied on heating electrode 2 come the temperature of controlled material.
As the preferred microsensor chip of another of the invention, which includes the electricity stacked gradually
Pole layer (including sensing electrode), insulating layer, heating layer (including heating electrode), supporting layer, hanging layer and substrate layer, described outstanding
Region corresponding with the heating layer on dead level and the substrate layer has through-hole.It, can be with by forming above-mentioned hanging structure
Reducing heat dissipation reduces power consumption, improves response sensitivity, reduces the response time.
The preparation method of gas sensing module according to the present invention, this method comprises:
1) by sn-containing compound, the organic dibasic acid of C2-C6, hydrazine hydrate and mixed in hydrochloric acid and hydro-thermal reaction is carried out, then
It is separated by solid-liquid separation, obtains stannic oxide carrier；
2) by noble-metal-supported on the stannic oxide carrier, noble-metal-supported gas sensing materials are obtained；
3) the noble-metal-supported gas sensing materials are supported on microsensor chip；
Wherein, the noble metal is selected from one of the metallic element or a variety of of IB race, VIII group.
Preferably, the noble metal is selected from one of Ag, Au, Pd and Pt or a variety of.
In step 1), as long as the sn-containing compound dissolution can obtain tin cation (Sn in acidic aqueous solution4+Or
Sn2+), preferably stanniferous inorganic salts or oxide.The sn-containing compound can be selected from dichloride stannous, four chlorinations
One of tin, stannous oxide and stannous oxalate are a variety of, wherein preferably two hydration dichloride stannous.
In addition, stannic oxide carrier of uniform size in order to obtain, of good performance, it is preferable that described to contain in terms of tin element
The organic dibasic acid of tin compound and the C2-C6, the hydrazine hydrate, the hydrochloric acid molar ratio be 1:3-5.5:3-25:
0.2-0.48, more preferably 1:3.5-5.5:3-20:0.35-0.45.
In step 1), there is no particular limitation for the organic dibasic acid of the C2-C6, can be selected from oxalic acid, malonic acid, fourth
It is one or more in diacid, glutaric acid and adipic acid, wherein preferably oxalic acid.The hydrochloric acid used is preferably concentrated hydrochloric acid, more
The concentrated hydrochloric acid of preferably 35% (mass concentration, similarly hereinafter).
Stannic oxide carrier of uniform size in order to obtain, of good performance preferably has by water-soluble pink salt, C2-C6
After machine binary acid, hydrazine hydrate and mixed in hydrochloric acid, hydro-thermal process is being carried out after being uniformly mixing to obtain homogeneous system.As the hydro-thermal
The condition of reaction includes: that temperature is 160-200 DEG C, time 4-30h, it is preferable that temperature is 170-180 DEG C, time 16-
24h.By carrying out hydro-thermal reaction, the titanium dioxide of the available flower-like structure with uniform package size under the above conditions
Tin, the stannic oxide have bigger specific surface area, have the response of significant air-sensitive, while being also convenient for the load of noble metal.
In order to remove the impurity adsorbed on stannic oxide carrier, further with deionized water to two preferably after separation of solid and liquid
Tin oxide carrier is washed, and specifically, after deionized water ultrasonic disperse can be added, is collected by centrifugation again, and repeats 2
More than secondary.
, according to the invention it is preferred to by infusion process by noble-metal-supported on the stannic oxide carrier.It specifically, can be with
Stannic oxide carrier noble metal precursor body is impregnated, and carries out ultraviolet light irradiation, the noble metal precursor body be selected from
One or more water-soluble precious metal salt in the metallic element of IB race and VIII group.It is preferable to use the noble metal precursor
Body, such as can enumerate selected from AgNO3、AuCl3、Pd(OAc)2、K2PtCl4、PdCl2With Pd (acac)2In (bis-acetylacetonate palladium)
It is one or more.
In order to reach suitable load capacity, relative to 1 parts by weight stannic oxide carrier, your gold in terms of precious metal element
The dosage for belonging to presoma is preferably 0.005-0.03 parts by weight, preferably 0.007-0.02 parts by weight, more preferably 0.01-
0.002 parts by weight.It as the concentration of noble metal precursor body in above-mentioned dipping process, such as can be 0.1-2mg/mL, preferably
0.15-0.5mg/mL.The process of dipping can be using the existing impregnated carrier that can be used in of saturation dipping, incipient impregnation etc.
Mode, as long as the combination of noble metal precursor body and stannic oxide carrier can be completed.
After the completion of above-mentioned dipping, preferably obtained gas sensor material is washed and dried, the side as washing
Formula, such as deionized water cleaning can be added, it is then centrifugated again, washing is repeated twice above；As dry mode,
It can be carried out in the baking oven of 65-75 DEG C (such as 70 DEG C).By washing and drying, can remove in gas sensor material
Soluble impurity reaches the interference for reducing impurity, improves the stability of material and the purpose of sensitivity.
In order to obtain precious metal simple substance (such as Ag, Pd) or metal oxide containing precious metals from noble metal precursor body, preferably in ultraviolet light
Noble metal precursor body is set to decompose under conditions of irradiation, to obtain precious metal simple substance.The condition packet of the ultraviolet light irradiation
Include: time 10-60min, power 150-500W, it is preferable that the condition of the ultraviolet light irradiation include: the time be 10-
40min, power 250-350W, for example, the ultraviolet light irradiation condition may include: the time be 10-40min, power 280-
300W。
According to the present invention, there is no particular limitation for the structure of the microsensor chip, as long as your gold can be loaded
Belong to load gas sensing materials and realize the response to gas with various, for example including H2、CO、H2S、NOx, toluene, butane etc.
Deng.
As a kind of preferred microsensor chip of the present invention, such as shown in Fig. 5, the micro sensing chip may include base
The sensing electrode 1 of piece and setting over the substrate.By loading gas sensing materials on the sensing electrode, so as to reality
Now to the highly sensitive detection of gas.Preferably, the microsensor chip further includes heating electrode 2, such as resistance wire, described to add
Thermode 2 is used to provide the described gas sensing module operating temperature appropriate.Gas sensing materials are connected to by sensing electrode 1
External circuit has between electrode heating electrode 2 to pass through, can be by changing the voltage applied on heating electrode 2 come the temperature of controlled material.
Above-mentioned microsensor chip can be carried out using the existing method that can be used in the preparation of microsensor chip, such as can be in substrate
On prepared with micro-processing method, such as photoetching and vapor deposition the methods of.
As another preferred microsensor chip of the invention, which includes the electrode stacked gradually
Layer, insulating layer, heating layer, supporting layer, hanging layer and substrate layer, on the hanging layer and the substrate layer with the heating
The corresponding region of layer has through-hole.By forming above-mentioned hanging structure, it is possible to reduce heat dissipation reduces power consumption, and it is sensitive to improve response
Degree reduces the response time.It, can be as supporting layer, hanging layer and substrate layer as the preparation method of the microsensor chip
The silicon wafer (such as p-type (100) monocrystalline silicon piece of silica twin polishing) with silicon oxide layer on steamed by photoetching and vacuum
Plating mode prepares metal heating wire and connects the heating electrode of heater strip as heating layer；Recycle vapor deposition (such as PECVD)
Grow SiO2As insulating layer；Then the mode for reusing photoetching and hot evaporation prepares interdigital electrode (sensing electrode) as electricity
Pole layer；The subsequently corresponding hanging layer of removal electrode zone and substrate layer, the method that can specifically use chemical etching, such as with
BOE solution (HF and NH4F-scale is 1:7) etching isolation layer, tetramethyl ammonium hydroxide solution (the tetramethyl hydrogen-oxygen of 5wt%
Change the aqueous solution of ammonium) the hanging layer of etching, to form the micro sensing chip with hanging structure.
In the present invention, it is not limited particularly in the method that the microsensor chip loads the upper gas sensing materials
It is fixed, such as microsensor core can will be supported on modes such as dropwise addition, sprays after gas sensing materials solvent appropriate dissolution
On piece is dried.Before use, it is preferred that thering is the chip of gas sensing materials to be heat-treated load, such as at 300-500 DEG C
1-5h is heated, preferably in 400-500 DEG C of heating 1.5-3h, such as can be in 440 DEG C of heating 2h.
In the gas sensing module use process of the invention, preferably by external circuits to microsensor chip into
Row power supply, to make gas sensing materials be detected under its operating temperature needed, as above-mentioned gas sensing materials
Operating temperature, for example, 200-300 DEG C.For more acurrate measurement, before preferably measurement starts, to gas sensing module of the invention
Carry out aging process.It as the condition of aging, such as may include 250-500 DEG C, 1-24h preferably includes 280-320 DEG C, 1-
6h。
Gas sensing module array according to the present invention, wherein the gas sensing module array is by more than two above-mentioned gas
The gas sensing module composition that body sensing module or above-mentioned preparation method obtain, the gas sensing module load have different
The noble-metal-supported gas sensing materials.The different noble-metal-supported gas sensing materials refer to that air-sensitive passes
The type and/or content of the noble metal loaded in sense material are different.By using the different noble-metal-supported gas sensings
The gas sensing module array that material is formed, can be completed the detection of gas with various ingredient during one-time detection,
Be greatly improved the efficiency of detection, and final result is calculated by the testing result of gas with various sensing module, accuracy with can
By property height.
The gas sensing module that is obtained the present invention also provides above-mentioned gas sensing module, above-mentioned preparation method or on
State application of the gas sensing module array in leak detection field, hazardous gas detection field or physical protection.
The present invention will be described in detail by way of examples below.In following embodiment, X-ray diffraction is purchased from Dutch pa
Section's company model of receiving is X'Pert Pro；Scanning electron microscope is purchased from Hitachi, Ltd model S4800；Transmission electron microscope
It is purchased from Japan Electronics Corporation model JEOL2100.
Preparation example 1
Finger-like as shown in Figure 5, which is prepared, in silicon chip surface by the micro-processing method of photoetching and vapor deposition intersects Au electrode
(10 microns of width) is used as sensing electrode 1, and heating to use Au resistance wire (5 microns of width) as heating electrode 2, to obtain
Microsensor chip.And the microsensor integrated chip is connected in one piece of control circuit board by 3.
Embodiment 1
(1) 1g bis- is hydrated dichloride stannous, 2g oxalic acid to mix with 100mL deionized water, 0.1mL concentrated hydrochloric acid is added
(35%), 2.16g hydrazine hydrate (50wt%), stirring form clear homogeneous mixed liquor；
(2) above-mentioned mixed liquor is put into reaction kettle, 160 DEG C of hydro-thermal process 20h are centrifugated after cooling；
(3) solid precipitating is collected, adds deionized water ultrasonic disperse 10min, is collected by centrifugation, is repeated 3 times again, obtain dioxy
Change tin microballoon；
(4) the above-mentioned stannic oxide microballoon of 0.1g is weighed, the AgNO that 10mL concentration is 1mmol/L is added into3In aqueous solution,
The xenon lamp ultraviolet light irradiation 20min of power 300W, makes AgNO3It decomposes, subsequent 10000 revs/min of centrifugations 5min, separates filter residue, add
Enter deionized water cleaning, is centrifugated filter residue again, and be repeated 2 times；
(5) final solid is collected, dry, acquisition Ag load stannic oxide microballoon gas sensing materials are placed in 80 DEG C of baking ovens
(i.e. Ag@SnO2)；
(6) above-mentioned gas sensing materials and terpinol are mixed to form slurry with the weight ratio of 1:1.72, take 20 microlitres of slurries
Drop is added on the finger-like crossed electrode of 10 microns of spacing, dry in 120 DEG C of baking ovens；Electrode package is sealed in polytetrafluoroethylene (PTFE)
In closed chamber body, and it is connect by connecting circuit with external control system；
(7) operating temperature of gas sensing materials is controlled at 300 ± 5 DEG C by adjusting the load voltage on resistance wire
In range, stablizes aging 2h, obtain gas sensing module 1.
As shown in Figure 1, compareing the Ag@SnO2With unsupported SnO2X-ray diffraction spectrum and standard substance card it is found that Ag@
SnO2Ag particle of diffraction maximum of the sample near 44 ° and 79 ° from load.
As shown in Fig. 2, compareing unsupported SnO2Stereoscan photograph it is found that Ag@SnO2The package assembly of sample is not shown
Variation is write, the feature of 3 micrometre-sized spherical package assemblies, and the composed structure unit of the visible a large amount of sheets in surface are maintained.
As shown in figure 3, compareing unsupported SnO2Transmission electron microscope photo it is found that Ag@SnO2The final structure of sample has occurred
Variation, surface visible size is in 5nm little particle enrichment below.
Embodiment 2
(1) 1.6g bis- is hydrated dichloride stannous, 2g oxalic acid to mix with 100mL deionized water, 0.1mL concentrated hydrochloric acid is added
(35%), 2.4g hydrazine hydrate (50wt%), stirring form clear homogeneous system；
(2) above-mentioned mixed liquor is put into reaction kettle, 180 DEG C of hydro-thermal process 12h are centrifugated after cooling；
(3) solid precipitating is collected, adds deionized water ultrasonic disperse 10min, is collected by centrifugation again, which is simultaneously repeated 3 times,
Obtain stannic oxide microballoon；
(4) the above-mentioned stannic oxide microballoon of 0.1g is weighed, the AgNO that 10mL concentration is 1.3mmol/L is added into3Aqueous solution
In, xenon lamp ultraviolet light irradiation 20min makes AgNO3It decomposes, subsequent 10000 revs/min of centrifugations 5min, separates filter residue, deionization is added
Water cleaning, is centrifugated filter residue, and be repeated 2 times again；
(5) final solid is collected, dry, acquisition Ag load stannic oxide microballoon gas sensing materials are placed in 80 DEG C of baking ovens
(i.e. Ag@SnO2)。
The XRD diagram of the gas sensing materials is similar to Example 1, relatively unsupported SnO2Diffraction near 44 ° and 79 °
Ag particle of the peak from load.The SEM figure and TEM figure result of product are similar to Example 1, are the three-dimensional of micron order size
Spherical package assembly, structural unit are the particle of 2-15nm size.
(6) gas sensing module 2 is obtained according to step (6)-(7) method in embodiment 1.
Embodiment 3
(1) 1.3g bis- is hydrated dichloride stannous, 2g oxalic acid to mix with 100mL deionized water, 0.1mL concentrated hydrochloric acid is added
(35%), 3.25g hydrazine hydrate (50%), stirring form clear homogeneous system；
(2) above-mentioned mixed liquor is put into reaction kettle, 200 DEG C of hydro-thermal process 4h are centrifugated after cooling；
(3) solid precipitating is collected, adds deionized water ultrasonic disperse 10min, is collected by centrifugation again, which is simultaneously repeated 3 times,
Obtain stannic oxide microballoon；
(4) the above-mentioned stannic oxide microballoon of 0.1g is weighed, the AgNO that 10mL concentration is 0.9mmol/L is added into3Aqueous solution
In, xenon lamp ultraviolet light irradiation 20min makes AgNO3It decomposes, subsequent 10000 revs/min of centrifugations 5min, separates filter residue, deionization is added
Water cleaning, is centrifugated filter residue, and be repeated 2 times again；
(5) final solid is collected, dry, acquisition Ag load stannic oxide microballoon gas sensing materials are placed in 80 DEG C of baking ovens
(i.e. Ag@SnO2)。
The XRD diagram of the gas sensing materials is similar to Example 1, and the diffraction maximum near 44 ° and 79 ° is from load
Ag particle.The SEM figure and TEM figure result of the gas sensing materials are similar to Example 1, are that the three-dimensional of micron order size is spherical
Package assembly, structural unit are the particle of tens nanosizeds.
(6) gas sensing module 3 is obtained according to step (6)-(7) method in embodiment 1.
Embodiment 4
(1) 1g bis- is hydrated dichloride stannous, 2g oxalic acid to mix with 100mL deionized water, 0.1mL concentrated hydrochloric acid is added
(35%), 2.16g hydrazine hydrate (50wt%), stirring form clear homogeneous system；
(2) above-mentioned mixed liquor is put into reaction kettle, 160 DEG C of hydro-thermal process 20h are centrifugated after cooling；
(3) solid precipitating is collected, adds deionized water ultrasonic disperse 10min, is collected by centrifugation again, which is simultaneously repeated 3 times,
Obtain stannic oxide microballoon；
(4) the above-mentioned stannic oxide microballoon of 0.1g is weighed, the AuCl that 10mL concentration is 1mmol/L is added into3In aqueous solution,
Xenon lamp ultraviolet light irradiation 20min, makes AuCl3It decomposes, subsequent 10000 revs/min of centrifugations 5min, separates filter residue, deionized water is added
Cleaning, is centrifugated filter residue, and be repeated 2 times again；
(5) final solid is collected, dry, acquisition Au load stannic oxide microballoon gas sensing materials are placed in 80 DEG C of baking ovens
(i.e. Au@SnO2)。
The XRD diagram of the gas sensing materials is similar to Example 1, and the diffraction maximum near 44 ° and 79 ° is from load
Au particle.The SEM figure and TEM figure result of the gas sensing materials are similar to Example 1, are that the three-dimensional of micron order size is spherical
Package assembly, structural unit are the particle of tens nanosizeds.
(6) gas sensing module 4 is obtained according to step (6)-(7) method in embodiment 1.
Embodiment 5
(1) 1g bis- is hydrated dichloride stannous, 2g oxalic acid to mix with 100mL deionized water, 0.1mL concentrated hydrochloric acid is added
(35%), 2.16g hydrazine hydrate (50wt%), stirring form clear homogeneous system；
(2) above-mentioned mixed liquor is put into reaction kettle, 160 DEG C of hydro-thermal process 20h are centrifugated after cooling；
(3) solid precipitating is collected, adds deionized water ultrasonic disperse 10min, is collected by centrifugation again, which is simultaneously repeated 3 times,
Obtain stannic oxide microballoon；
(4) the above-mentioned stannic oxide microballoon of 0.1g is weighed, the Pd (OAc) that 10mL concentration is 1mmol/L is added into2Aqueous solution
In, xenon lamp ultraviolet light irradiation 20min makes Pd (OAc)2It decomposes, subsequent 10000 revs/min of centrifugations 5min, separates filter residue, addition is gone
Ionized water cleaning, is centrifugated filter residue, and be repeated 2 times again；
(5) final solid is collected, dry, acquisition Pd load stannic oxide microballoon gas sensing materials are placed in 80 DEG C of baking ovens
(i.e. Pd@SnO2)。
The XRD diagram of the gas sensing materials is similar to Example 1, relatively unsupported SnO2Near 40 °, 47 ° and 69 °
Pd particle of the diffraction maximum from load.The SEM figure and TEM figure result of the gas sensing materials are similar to Example 1, are micron
The spherical package assembly of the three-dimensional of grade size, structural unit are the particle of tens nanosizeds.
(6) gas sensing module 5 is obtained according to step (6)-(7) method in embodiment 1.
Embodiment 6
(1) 1g bis- is hydrated dichloride stannous, 2g oxalic acid to mix with 100mL deionized water, 0.1mL concentrated hydrochloric acid is added
(35%), 2.16g hydrazine hydrate (50wt%), stirring form clear homogeneous system；
(2) above-mentioned mixed liquor is put into reaction kettle, 160 DEG C of hydro-thermal process 20h are centrifugated after cooling；
(3) solid precipitating is collected, adds deionized water ultrasonic disperse 10min, is collected by centrifugation again, which is simultaneously repeated 3 times,
Obtain stannic oxide microballoon；
(4) the above-mentioned stannic oxide microballoon of 0.1g is weighed, the K that 10mL concentration is 1mmol/L is added into2PtCl4Aqueous solution
In, xenon lamp ultraviolet light irradiation 20min makes K2PtCl4Decompose, subsequent 10000 revs/min of centrifugations 5min, separate filter residue, be added go from
Sub- water cleaning, is centrifugated filter residue, and be repeated 2 times again；
(5) final solid is collected, dry, acquisition Pt load stannic oxide microballoon gas sensing materials are placed in 80 DEG C of baking ovens
(i.e. Pt@SnO2)。
The XRD diagram of the gas sensing materials is similar to Example 1, relatively unsupported SnO2Near 40 °, 47 ° and 69 °
Pt particle of the diffraction maximum from load.The SEM figure and TEM figure result of the gas sensing materials are similar to Example 1, are micron
The spherical package assembly of the three-dimensional of grade size, structural unit are the particle of tens nanosizeds.
(6) gas sensing module 6 is obtained according to step (6)-(7) method in embodiment 1.
Test case
It is tested using above-mentioned gas sensing module 1-6, prescribed concentration is injected into polytetrafluoroethylene (PTFE) closed cavity
CO, H to be measured2The mixed gas of S and the two, the resistance variations that detection gas sensitive is injected with gas, obtain corresponding number of responses
According to concrete outcome is as shown in table 1-2 and Fig. 4.
Table 1
Table 2
It can be seen that by above-mentioned Tables 1 and 2 and change the relevant parameters such as precious metal salt presoma type and solution concentration,
The noble-metal-supported gas sensing materials of preparation, pattern, microstructure and its CO/H2Without aobvious in terms of the response characteristic of S gas
Difference is write, illustrates that gas sensing block preparation method of the invention can be effectively synthesized broad spectrum response material；Meanwhile different metal
The stannic oxide of load is to CO and H2Otherness is presented in terms of the response sensitivity of S gas, can be used for constructing various dimensions complexity
Gas sensor array is simulated by iterative algorithm, can get the composition information of complexity gas.
Fig. 4 left figure is 1 gained Ag@SnO of embodiment2To the CO and H of various concentration2The sound of S gas and the two mixed gas
Curve is answered, right figure is 5 gained Pd@SnO of embodiment2To the CO and H of various concentration2The response of S gas and the two mixed gas is bent
Line.It can be seen that in a certain concentration section, Ag@SnO2With Pd@SnO2To CO and H2The response of S gas has approximately linear special
Sign, while the response of mixed gas is substantially less than the sum of the response of single composition gas.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (13)
1. a kind of gas sensing module, which is characterized in that the gas sensing module includes microsensor chip and to be supported on this micro-
The noble-metal-supported gas sensing materials of sensor core on piece；
Wherein, the noble-metal-supported gas sensing materials include stannic oxide carrier and are supported on the stannic oxide carrier
Noble metal, the noble metal is selected from one of metallic element of IB race and VIII group or a variety of.
2. gas sensing module according to claim 1, wherein the noble metal is selected from one of Ag, Au, Pd and Pt
Or it is a variety of.
3. gas sensing module according to claim 1, wherein the stannic oxide carrier is stannic oxide microballoon,
Preferably, the diameter of the stannic oxide microballoon is 0.5-2.5 μm；
Preferably, the stannic oxide microballoon has flower-like structure；
Preferably, relative to 1 parts by weight stannic oxide carrier, the load capacity of the noble metal is 0.005- in terms of precious metal element
0.03 parts by weight.
4. gas sensing module according to claim 1, wherein the microsensor chip includes substrate and is arranged at this
Sensing electrode on substrate；
Preferably, microsensor chip further includes heating electrode.
5. gas sensing module according to claim 1, wherein the microsensor chip includes the electrode stacked gradually
Layer, insulating layer, heating layer, supporting layer, hanging layer and substrate layer, on the hanging layer and the substrate layer with the heating
The corresponding region of layer has through-hole.
6. a kind of preparation method of gas sensing module, which is characterized in that this method comprises:
1) by sn-containing compound, the organic dibasic acid of C2-C6, hydrazine hydrate and mixed in hydrochloric acid and hydro-thermal reaction is carried out, then carried out
It is separated by solid-liquid separation, obtains stannic oxide carrier；
2) by noble-metal-supported on the stannic oxide carrier, noble-metal-supported gas sensing materials are obtained；
3) the noble-metal-supported gas sensing materials are supported on microsensor chip；
Wherein, the noble metal is selected from one of metallic element of IB race and VIII group or a variety of.
7. preparation method according to claim 6, wherein the noble metal is selected from one of Ag, Au, Pd and Pt or more
Kind.
8. preparation method according to claim 6, wherein the sn-containing compound be selected from dichloride stannous, tin tetrachloride,
One of stannous oxide and stannous oxalate are a variety of；
Preferably, in terms of tin element, organic dibasic acid, the hydrazine hydrate, the salt of the sn-containing compound and the C2-C6
The molar ratio of acid is 1:3-5.5:3-25:0.2-0.48；
Preferably, the organic dibasic acid of the C2-C6 it is a kind of in oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid or
It is a variety of；
Preferably, the organic dibasic acid of the C2-C6 is oxalic acid；
Preferably, it is 160-200 DEG C that the condition of the hydro-thermal reaction, which includes: temperature, time 4-20h.
9. preparation method according to claim 6, wherein carried noble-metal-supported in the stannic oxide by infusion process
On body；
Preferably, stannic oxide carrier noble metal precursor body is impregnated, and carries out ultraviolet light irradiation, before the noble metal
Driving body is water-soluble precious metal salt one or more in the metallic element selected from IB race and VIII group；
Preferably, the noble metal precursor body is selected from AgNO3、AuCl3、Pd(OAc)2、K2PtCl4、PdCl2With Pd (acac)2In
It is one or more；
Preferably, relative to 1 parts by weight stannic oxide carrier, the dosage of the noble metal precursor body is in terms of precious metal element
0.005-0.03 parts by weight；
Preferably, the condition of the ultraviolet light irradiation include: the time be 10-60min.
10. preparation method according to claim 6, wherein the microsensor chip includes substrate and is arranged in the base
The sensing electrode of on piece；
Preferably, the microsensor chip further includes heating electrode.
11. preparation method according to claim 6, wherein the microsensor chip include the electrode layer stacked gradually,
Insulating layer, heating layer, supporting layer, hanging layer and substrate layer, on the hanging layer and the substrate layer with the heating layer
Corresponding region has through-hole.
12. a kind of gas sensing module array, which is characterized in that the gas sensing module array is by more than two claim 1-
The gas that preparation method described in any one of gas sensing module or claim 6-11 described in any one of 5 obtains
Sensing module composition, the gas sensing module load have different noble-metal-supported gas sensing materials.
13. according to claim 1 described in any one of gas sensing module, claim 6-11 described in any one of -5
Gas sensing module array described in the gas sensing module or claim 12 that preparation method obtains is led in leak detection
Application in domain, hazardous gas detection field or physical protection field.
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| CN113820363A (en) * | 2021-08-27 | 2021-12-21 | 山东大学 | Platinum-loaded porous tin oxide nanosphere gas-sensitive material and preparation method and application thereof |
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| CN104880490A (en) * | 2015-05-20 | 2015-09-02 | 吉林大学 | Pd-SnO2 oxide semiconductor sensor for carbon monoxide as well as preparation and application |
| CN105823800A (en) * | 2016-03-23 | 2016-08-03 | 云南大学 | Sensitive material for detecting methyl alcohol gas |
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| CN104880490A (en) * | 2015-05-20 | 2015-09-02 | 吉林大学 | Pd-SnO2 oxide semiconductor sensor for carbon monoxide as well as preparation and application |
| CN105823800A (en) * | 2016-03-23 | 2016-08-03 | 云南大学 | Sensitive material for detecting methyl alcohol gas |
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| CN113511646A (en) * | 2020-04-10 | 2021-10-19 | 中国石油化工股份有限公司 | Self-heating gas sensor, gas-sensitive material, and preparation method and application thereof |
| CN113820363A (en) * | 2021-08-27 | 2021-12-21 | 山东大学 | Platinum-loaded porous tin oxide nanosphere gas-sensitive material and preparation method and application thereof |
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