CN112255278B - Based on Ti 3 C 2 T x /WO 3 Room-temperature ammonia gas sensor made of composite nano material, and preparation method and application thereof - Google Patents
Based on Ti 3 C 2 T x /WO 3 Room-temperature ammonia gas sensor made of composite nano material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Ti 3 C 2 T x /WO 3 The sensor sequentially comprises an alumina ceramic substrate, an Ag/Pd interdigital electrode layer and Ti from bottom to top 3 C 2 T x /WO 3 A composite material thin film layer of Ti 3 C 2 T x /WO 3 The composite film is made by drop coating onto a preformed interdigital electrode. WO selected in the invention 3 The nano particles have the advantages of sensitivity to ammonia gas, quick response time, good long-term stability, easy synthesis, rich oxygen active sites and the like; ti 3 C 2 T x The material is a novel two-dimensional material, has large specific surface area and high carrier concentration, and the surface contains rich ammonia adsorption functional groups, so the Ti 3 C 2 T x The material has excellent ammonia adsorption capacity; the combination of the two can greatly improve the response sensitivity of the sensor to ammonia gas.
Description
Technical Field
The invention relates to the technical field of gas sensors and nano materials,in particular to Ti 3 C 2 T x /WO 3 A room temperature ammonia gas sensor made of composite nano material, a preparation method and application.
Background
With the rapid development of industry and agriculture in recent years, ammonia gas is used in large quantities for chemical raw materials and fertilizer production. However, because of its strong irritation, human beings can cause skin allergy, respiratory tract damage and other injuries after being contacted for a long time. Therefore, the design and development of the ammonia gas sensor which has the advantages of room temperature operation, large response value, high response speed, low detection concentration limit and the like has very important value for industrial and agricultural production.
Metal oxide semiconductors are commonly used materials in the gas sensing field, and are widely used for gas detection due to their easy preparation and low cost. Among them, tungsten oxide is a common material having excellent sensitivity to ammonia, and has a large response value to ammonia and a high response speed. However, since the metal oxide is not sensitive to gas at room temperature, a heat treatment is required to work. Therefore, the power consumption of the sensor is increased, and the miniaturization and intelligent development of the current sensor is not facilitated. And the metal oxide has strong cross sensitivity to gas, has response to various gases, and is difficult to accurately identify the type and concentration of target gas. These disadvantages greatly limit the application of metal oxides in the gas sensing field.
The novel two-dimensional material has the characteristics of large specific surface area, high carrier concentration and the like, so that the room temperature detection of gas can be realized. Through the calculation of a first principle, the two-dimensional materials have larger difference of binding energy of different gases, and each two-dimensional material generally has a characteristic gas corresponding to the two-dimensional material. The characteristics can well make up the defects of the metal oxide semiconductor in the gas sensitive field, and the metal oxide semiconductor and the two-dimensional material are compounded, so that the action temperature of the metal oxide semiconductor on gas can be reduced, and meanwhile, the composite material has excellent gas selection characteristics.
Disclosure of Invention
The invention aims to: providing a Ti 3 C 2 T x /WO 3 Room temperature ammonia gas sensor of composite nano material andthe preparation method and the application solve the problems of high working temperature, poor ammonia sensitivity, low selectivity and the like of the conventional ammonia sensor at present.
The technical scheme adopted by the invention is as follows:
based on Ti 3 C 2 T x /WO 3 Room temperature ammonia sensor of composite nanomaterial, ti 3 C 2 T x /WO 3 The room-temperature ammonia gas sensor made of the composite nano material sequentially comprises an alumina ceramic substrate layer, an Ag/Pd interdigital electrode layer and Ti from bottom to top 3 C 2 T x /WO 3 A composite material thin film layer of Ti 3 C 2 T x /WO 3 The composite film is prepared on a prefabricated interdigital electrode by a drop coating method.
Further, the Ti 3 C 2 T x /WO 3 The thickness of the composite material film layer is 1-5 μm.
Further, said one Ti 3 C 2 T x /WO 3 The thickness of the Ag/Pd interdigital electrode layer is 100-200nm, the number of pairs of fingers of the Ag/Pd interdigital electrode layer is 5, and the distance between the fingers is 200 mu m.
Ti 3 C 2 T x /WO 3 The preparation method of the room-temperature ammonia gas sensor made of the composite nano material comprises the following steps:
the method comprises the following steps: preparation of Ti by direct ultrasonic compounding 3 C 2 T x /WO 3 A composite nanomaterial;
step two: preparation based on Ti 3 C 2 T x /WO 3 The room temperature ammonia gas sensor of the composite nano material comprises the following specific steps:
A. taking 10mg of prepared Ti 3 C 2 T x /WO 3 The nano composite material is prepared by dispersing the material in 50 mu L of absolute ethyl alcohol, and performing ultrasonic treatment for 5min (power 150W) to obtain a uniform dispersion liquid.
B. Taking 3 mu L of the dispersion liquid obtained in the step A by using a liquid transfer device, and uniformly coating the dispersion liquid on the alumina ceramicOn the prefabricated interdigital electrode of the ceramic substrate bottom layer and the Ag/Pd interdigital electrode layer, ti is obtained 3 C 2 T x /WO 3 A room temperature ammonia gas sensor of composite nano material.
Further, the first step specifically comprises the following steps:
(1) weighing 2g of Ti 3 AlC 2 40ml of hydrofluoric acid (40% by mass) was measured and poured into a polytetrafluoroethylene beaker, and the obtained Ti was poured into the beaker 3 AlC 2 Slowly adding into the beaker, stirring at room temperature (25 deg.C) at 200rpm for 24 hr, repeatedly centrifuging and washing the solution with deoxygenated water until pH is 6, and vacuum drying the precipitate to obtain Ti 3 C 2 T x And (5) standby.
(2) Taking 50mg of Ti in the step (1) 3 C 2 T x Dispersing the Ti powder into 30ml of deoxygenated water, and carrying out ultrasonic treatment for 30min to obtain uniform Ti 3 C 2 T x And (3) dispersing the mixture.
(3) Taking 50mgWO3 nano-particles, dispersing the nano-particles into 30ml of deoxygenated water, and carrying out ultrasonic treatment for 30min to obtain uniform WO3 3 And (3) dispersing the mixture.
(4) Ti in the step (2) 3 C 2 T x The dispersion is dropwise added to WO in the step (3) 3 In the dispersion liquid, the mixed solution is placed in a cell crusher for ultrasonic treatment for 3 hours to obtain Ti 3 C 2 T x /WO 3 A composite nanomaterial dispersion.
(5) And (3) respectively centrifuging the solution obtained in the step (4) with deoxygenated water and ethanol (8000rpm, 5min) for three times, washing the solution, and drying the precipitate to obtain Ti 3 C 2 T x /WO 3 A composite nanomaterial.
Further, in the step (4), the distance between an ultrasonic probe of the cell crusher and the bottom of the cup is 1cm, the ultrasonic power is 150W, and the ultrasonic pulse interval is 3s. .
Further, ti in the step (4) 3 C 2 T x The dropping time of the dispersion was controlled to 1min.
Further, the drying temperature and time in the step (5) are 60 ℃ and 12h.
A kind ofTi 3 C 2 T x /WO 3 Application of room-temperature ammonia gas sensor made of composite nano material, and Ti 3 C 2 T x /WO 3 The room-temperature ammonia gas sensor made of the composite nano material can measure Ti at room temperature 3 C 2 T x /WO 3 The resistance change of the composite nano material is used for detecting the ammonia concentration in industrial and agricultural production.
The working principle is as follows: the composite materials are all semiconductor type materials, and the Ti prepared by the preparation method of the invention 3 C 2 T x /WO 3 The resistance of the room-temperature ammonia gas sensor made of the composite nano material is stable in the air, the resistance is about tens of kilo-ohms, electrons in ammonia gas molecules can be captured when the ammonia gas molecules are contacted, and the conductivity of the ammonia gas sensor is reduced and the resistance is increased due to the fact that the composite material integrally presents the property of a P-type semiconductor.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. WO selected by the invention 3 The nano particles have the advantages of sensitivity to ammonia gas, quick response time, good long-term stability, easy synthesis, rich oxygen active sites and the like; ti 3 C 2 T x The material is a novel two-dimensional material, has large specific surface area and high carrier concentration, and the surface contains rich ammonia adsorption functional groups, so that Ti 3 C 2 T x The material has excellent ammonia adsorption capacity; the combination of the two can greatly improve the response sensitivity of the sensor to ammonia gas.
2. Ti of the invention 3 C 2 T x /WO 3 The room-temperature ammonia gas sensor made of the composite nano material has good repeatability, selectivity, sensitivity and long-term stability, can normally work at room temperature, and can accurately and quickly monitor the ammonia gas concentration in industrial and agricultural production.
Drawings
FIG. 1 shows Ti prepared by the present invention 3 C 2 T x /WO 3 Room temperature ammonia gas sensor made of composite nano materialA schematic structural diagram of (a);
FIG. 2 shows Ti of the present invention 3 C 2 T x /WO 3 Scanning Electron Microscope (SEM) images of the composite nanomaterials;
FIG. 3 shows Ti of the present invention 3 C 2 T x /WO 3 X-ray photoelectron spectroscopy (XPS) of the composite nanomaterial on Ti 2 p;
FIG. 4 shows Ti of the present invention 3 C 2 T x /WO 3 X-ray photoelectron spectroscopy (XPS) images of the composite nanomaterial on W4 f;
FIG. 5 shows Ti prepared by the present invention 3 C 2 T x /WO 3 A real-time resistance change curve diagram of a room-temperature ammonia gas sensor of the composite nano material to 1-5 ppm;
FIG. 6 shows Ti prepared by the present invention 3 C 2 T x /WO 3 A real-time response change curve diagram of the room-temperature ammonia gas sensor of the composite nano material to 1 ppm;
FIG. 7 shows Ti prepared by the present invention 3 C 2 T x /WO 3 A room-temperature ammonia gas sensor selectivity test curve graph of the composite nano material;
FIG. 8 shows Ti prepared by the present invention 3 C 2 T x /WO 3 A long-term stability test curve diagram of a room-temperature ammonia gas sensor made of a composite nano material.
Labeled as: 1-alumina ceramic substrate layer, 2-Ag/Pd interdigital electrode layer and 3-Ti 3 C 2 T x /WO 3 A composite film layer.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to fig. 1 to 8 in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in FIG. 1, a Ti-based alloy 3 C 2 T x /WO 3 Room temperature ammonia sensor of composite nanomaterial, ti 3 C 2 T x /WO 3 The room-temperature ammonia gas sensor made of the composite nano material sequentially comprises an alumina ceramic substrate layer 1, an Ag/Pd interdigital electrode layer 2 and Ti from bottom to top 3 C 2 T x /WO 3 A composite material thin film layer 3 of Ti 3 C 2 T x /WO 3 The composite material film is prepared on an alumina ceramic substrate by a dripping coating method, the thickness of the Ti3C2Tx/WO3 composite material film layer 3 is 1-5 mu m, the thickness of the Ag/Pd interdigital electrode layer 2 is 100-200nm, the number of pairs of fingers of the Ag/Pd interdigital electrode layer 2 is 5 pairs, and the distance between the fingers is 200 mu m.
The above Ti 3 C 2 T x /WO 3 The preparation method of the room-temperature ammonia gas sensor made of the composite nano material comprises the following steps:
the method comprises the following steps: preparation of Ti by direct ultrasonic compounding 3 C 2 T x /WO 3 A composite nanomaterial;
(1) weighing 2g of Ti 3 AlC 2 40ml of hydrofluoric acid (40%) was measured and poured into a Teflon beaker, and the Ti obtained was poured 3 AlC 2 Slowly adding into the beaker, stirring at room temperature (25 deg.C) at 200rpm for 24 hr, repeatedly centrifuging and washing the solution with deoxygenated water until pH is 6, and vacuum drying the precipitate to obtain Ti 3 C 2 T x And (5) standby.
(2) Taking 50mg of Ti in the step (1) 3 C 2 T x Dispersing the Ti into 30ml of deoxygenated water, and carrying out ultrasonic treatment for 30min to obtain uniform Ti 3 C 2 T x And (3) dispersing the mixture.
(3) Taking 50mgWO 3 Dispersing the nano particles into 30ml of deoxygenated water, and performing ultrasonic treatment for 30min to obtain uniform WO 3 And (3) dispersing the mixture.
(4) Ti in the step (2) 3 C 2 T x Dropwise adding the dispersion into the WO in the step (3) within 1min 3 In the dispersion, the mixed solution is placed in a cell disruptorUltrasonic treatment in a machine for 3 hours to obtain Ti 3 C 2 T x /WO 3 The ultrasonic probe of the cell crusher is 1cm away from the cup bottom, the ultrasonic power is 150W, and the ultrasonic pulse interval is 3s.
(5) And (3) respectively centrifuging the solution obtained in the step (4) with deoxygenated water and ethanol (8000rpm, 5min) for three times, and drying the precipitate at 60 ℃ for 12 hours to obtain Ti 3 C 2 T x /WO 3 A composite nanomaterial.
Step two: preparation based on Ti 3 C 2 T x /WO 3 Room temperature ammonia sensor made of composite nano material
A. Taking 10mg of prepared Ti 3 C 2 T x /WO 3 The nano composite material is prepared by dispersing the material in 50 mu L of absolute ethyl alcohol and performing ultrasonic treatment for 5min (power is 150W) to obtain uniform dispersion liquid.
B. Taking 3 mu L of the dispersion liquid obtained in the step A by using a liquid transfer device, and uniformly coating the dispersion liquid on a prefabricated interdigital electrode of an alumina ceramic substrate layer and an Ag/Pd interdigital electrode layer to obtain Ti 3 C 2 T x /WO 3 A room temperature ammonia gas sensor of composite nano material.
Ti described in the example 3 C 2 T x /WO 3 The Scanning Electron Microscope (SEM) image of the composite nano material is shown in FIG. 2, which shows that the film has an obvious lamellar structure, and WO 3 Nanoparticles are attached to Ti 3 C 2 T x A surface.
The working principle is as follows: the composite materials are all semiconductor type materials, and the Ti prepared by the preparation method of the invention 3 C 2 T x /WO 3 The resistance of the room-temperature ammonia gas sensor of the composite nano material is stabilized to about ten kilohms in the air, electrons in ammonia gas molecules can be captured when the ammonia gas molecules are contacted, and the conductivity of the ammonia gas sensor is reduced and the resistance is increased due to the fact that the composite material integrally presents the property of a P-type semiconductor and the obtained electrons.
WO selected by the invention 3 The nano-particles are sensitive to ammonia gas, have quick response time, good long-term stability, easy synthesis and the property ofRich oxygen active sites and the like; ti (titanium) 3 C 2 T x The material is a novel two-dimensional material, has large specific surface area and high carrier concentration, and the surface contains rich ammonia adsorption functional groups, so that Ti 3 C 2 T x The material has excellent ammonia adsorption capacity; the combination of the two can greatly improve the response sensitivity of the sensor to ammonia gas.
Example 2
Ti 3 C 2 T x /WO 3 Performance test of room-temperature ammonia gas sensor made of composite nano material
And carrying out peak separation treatment on peaks obtained by XPS characterization through peak separation software to obtain peak separation XPS energy spectrograms of Ti 2p peaks and W4f peaks of the composite material. As shown in FIG. 3, ti 3 C 2 T x /WO 3 The Ti 2p peak of the composite nanomaterial can be subdivided into 3 types of peaks, and it can be seen that this corresponds to Ti 3 C 2 T x The Ti-C and Ti-X peaks of the material can be obviously observed, further explaining that Ti 3 C 2 T x /WO 3 Ti in composite nano material 3 C 2 T x Of the cell. On the other hand, as shown in FIG. 4, from Ti 3 AlC 2 As can be seen from the W4f peak energy spectrum of the composite material, the W4f peak can be subdivided into 4 peaks at 35.69eV and 37.83eV, which correspond to W 6+ . The results further confirm Ti 3 C 2 T x /WO 3 WO in composite materials 3 Presence of (a).
Ti prepared in example 1 3 C 2 T x /WO 3 The room-temperature ammonia gas sensor of the composite nano material is stabilized in a nitrogen atmosphere, different ammonia gases are introduced, and the resistance change of the sensor is monitored.
Ti described in the example 3 C 2 T x /WO 3 The dynamic response curve of the room temperature ammonia sensor of the composite nano material to 1-5ppm ammonia is shown in figure 5, and Ti can be seen 3 C 2 T x /WO 3 The composite nano material film has high sensitivity and high resolution response to 1-5ppm ammonia gas.
Ti described in the present example 3 C 2 T x /WO 3 The repeated response curve of the room-temperature ammonia sensor made of the composite nano material to 1ppm ammonia is shown in FIG. 6, and Ti can be seen 3 C 2 T x /WO 3 The composite nano material film has good repeated response characteristics.
Ti described in the present example 3 C 2 T x /WO 3 The selectivity curve of the room temperature ammonia gas sensor of the composite nano material is shown in FIG. 7, and Ti can be seen 3 C 2 T x /WO 3 The composite nanometer material film has excellent selectivity.
Ti described in the example 3 C 2 T x /WO 3 The long-term stability curve of the room temperature ammonia gas sensor made of the composite nano material is shown in FIG. 8, and Ti can be seen 3 C 2 T x /WO 3 The composite nano material film has good long-term stability.
Ti of the example 3 C 2 T x /WO 3 The room-temperature ammonia gas sensor made of the composite nano material has good repeatability, selectivity, sensitivity and long-term stability, can normally work at room temperature, and can accurately and quickly monitor the ammonia gas concentration in industrial and agricultural production.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for some of the features thereof, and any modifications, equivalents, improvements and the like, which fall within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (2)
1.Ti 3 C 2 Tx/WO 3 A method for preparing a room-temperature ammonia gas sensor made of composite nano materials, and Ti 3 C 2 T x /WO 3 The room-temperature ammonia gas sensor of the composite nano material sequentially comprises an alumina ceramic substrate layer (1), an Ag/Pd interdigital electrode layer (2) and Ti from bottom to top 3 C 2 T x /WO 3 A composite film layer (3);
the Ti 3 C 2 T x /WO 3 The thickness of the composite material film layer (3) is 1-5 μm;
the thickness of the Ag/Pd interdigital electrode layer (2) is 100-200nm, the number of pairs of fingers of the Ag/Pd interdigital electrode layer (2) is 5, and the distance between the fingers is 200 mu m;
the method is characterized by comprising the following steps:
the method comprises the following steps: preparation of Ti by direct ultrasonic compounding 3 C 2 T x /WO 3 A composite nanomaterial;
the materials in the first step are prepared according to the following proportion:
(1) weighing 2g of Ti 3 AlC 2 40ml of a 40% hydrofluoric acid solution was measured and poured into a polytetrafluoroethylene beaker, and the obtained Ti was poured into the beaker 3 AlC 2 Slowly adding into the beaker, stirring at room temperature at 200rpm for 24 hr, repeatedly centrifuging and washing the solution with deoxygenated water until pH is 6, and vacuum drying the precipitate to obtain Ti 3 C 2 T x Standby;
(2) taking 50mg of Ti in the step (1) 3 C 2 T x Dispersing the Ti powder into 30ml of deoxygenated water, and carrying out ultrasonic treatment for 30min to obtain uniform Ti 3 C 2 T x A dispersion liquid;
(3) taking 50mgWO 3 Dispersing the nano particles into 30ml of deoxygenated water, and performing ultrasonic treatment for 30min to obtain uniform WO 3 A dispersion liquid;
(4) ti in the step (2) 3 C 2 T x The dispersion is dropped dropwise into WO in the step (3) 3 In the dispersion, ti 3 C 2 T x The dropping time of the dispersion liquid is controlled to be 1min; putting the mixed solution in a cell crusher for ultrasonic treatment for 3 hours to obtain Ti 3 C 2 Tx/WO 3 A composite nanomaterial dispersion; the distance between an ultrasonic probe of the cell crusher and the cup bottom is 1cm, the ultrasonic power is 150W, and the ultrasonic pulse interval is 3s;
(5) respectively centrifugally washing the solution obtained in the step (4) by using deoxygenated water and ethanolThirdly, drying the precipitate to obtain Ti 3 C 2 Tx/WO 3 A composite nanomaterial; the drying temperature and time are 60 ℃ and 12 hours;
step two: preparation based on Ti 3 C 2 T x /WO 3 The room temperature ammonia gas sensor of the composite nano material comprises the following specific steps:
A. 10mg of prepared Ti3C2Tx/WO is taken 3 Compounding nanometer material, dispersing the material in 50 μ L absolute ethyl alcohol, and performing ultrasonic treatment for 5min at power of 150W to obtain uniform dispersion liquid;
B. taking 3 mu L of dispersion liquid obtained in the step A by using a liquid transfer machine, and uniformly coating the dispersion liquid on a prefabricated interdigital electrode of the alumina ceramic substrate layer (1)/Ag/Pd interdigital electrode layer (2) to obtain Ti 3 C 2 T x /WO 3 A room temperature ammonia gas sensor of composite nano material.
2. Ti obtained by the production method according to claim 1 3 C 2 Tx/WO 3 The application of the room-temperature ammonia gas sensor of the composite nano material is characterized in that the sensor is used for detecting the ammonia gas concentration.
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