CN118112071A - Hollow tubular Pt/TiN gas-sensitive electrode material, and preparation method and application thereof - Google Patents
Hollow tubular Pt/TiN gas-sensitive electrode material, and preparation method and application thereof Download PDFInfo
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- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims abstract 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
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- 238000001816 cooling Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
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- SLIOYUPLNYLSSR-UHFFFAOYSA-J tetrachloroplatinum;hydrate;dihydrochloride Chemical compound O.Cl.Cl.Cl[Pt](Cl)(Cl)Cl SLIOYUPLNYLSSR-UHFFFAOYSA-J 0.000 description 1
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Abstract
The invention belongs to the technical field of gas sensors, and particularly relates to a hollow tubular Pt/TiN gas-sensitive electrode material, and a preparation method and application thereof. The preparation method comprises the following steps: mixing a titanium source, ethylene glycol, isopropyl alcohol and benzyl alcohol, and performing ultrasonic treatment to obtain a mixed solution; heating the mixed solution for reaction, centrifuging, and vacuum drying to obtain a TiN precursor; respectively carrying out first calcination and second calcination on the obtained TiN precursor to obtain a TiN material; mixing the TiN material, glycol and H 2PtCl6 aqueous solution, carrying out ultrasonic treatment, heating, reacting, centrifuging, and vacuum drying to obtain the Pt/TiN gas-sensitive electrode material. The preparation method has the advantages of short reaction time, simple operation and the like; the Pt/TiN gas-sensitive electrode material has the advantages of high conductivity, stable electrochemical performance and the like, can be used for preparing a gas sensor for efficiently monitoring hydrogen gas, and has excellent long-term stability and quick response recovery performance.
Description
Technical Field
The invention belongs to the technical field of gas sensors, and particularly relates to a hollow tubular Pt/TiN gas-sensitive electrode material, and a preparation method and application thereof.
Background
The disclosure of this background section is intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Hydrogen (H 2) is an ideal fuel that is expected to achieve carbon dioxide zero emission targets and energy sustainability. The hydrogen has very wide application, and plays a great role in petrochemical industry, electronic products, chemical raw materials, high-efficiency fuel and the like. Hydrogen is a very flammable gas with a fire point of only 574 ℃ and burns at a volume fraction of 4% to 75% in air, and when the hydrogen concentration in air is 4.1% to 74.8%, an explosion can be caused by an open flame. Therefore, the hydrogen can be monitored rapidly, accurately and stably for a long time, and the threat of hydrogen explosion to industrial scenes and human health can be effectively avoided.
Currently, a gas sensor for hydrogen detection is a PEM fuel cell type gas sensor, but a conventional (PEM) fuel cell type gas sensor often uses porous carbon as a carrier and Pt particles as a catalyst, and the porous carbon is easily corroded and decomposed to generate carbon oxides under electrochemical oxidation conditions to cause the agglomeration phenomenon of the Pt particles, so that the active sites of the Pt are reduced, and the sensitivity of the sensor is greatly reduced or even fails. Therefore, developing a more sensitive, efficient, more stable fuel cell sensor for detecting hydrogen is a current challenge in the art.
Disclosure of Invention
Aiming at the defects of the prior art, the first aim of the invention is to provide a preparation method of a hollow tubular Pt/TiN gas-sensitive electrode material; the invention utilizes the strong interaction between the transition metal nitride and the noble metal, and prepares the gas-sensitive electrode material by taking the transition metal nitride as a carrier material; the preparation method has the advantages of short reaction time, simple operation and the like; .
The second object of the invention is to provide the hollow tubular Pt/TiN gas sensitive electrode material prepared by the method.
A third object of the present invention is to provide the use of the hollow tubular Pt/TiN gas-sensitive electrode material described above; the gas-sensitive electrode material is used for preparing a gas sensor capable of efficiently monitoring hydrogen gas, and the gas sensor has excellent long-term stability and quick response recovery performance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method of the hollow tubular Pt/TiN gas-sensitive electrode material comprises the following steps:
(1) Mixing a titanium source, ethylene glycol (CH 2 OH), isopropanol (C 3H8 O) and benzyl alcohol (C 7H8 O), and performing ultrasonic treatment to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to react, centrifuging, and vacuum drying to obtain a TiN precursor;
(3) Respectively carrying out first calcination and second calcination on the TiN precursor obtained in the step (2) to obtain a TiN material;
(4) Mixing the TiN material obtained in the step (4), glycol and H 2PtCl6 aqueous solution, performing ultrasonic treatment, heating, reacting, centrifuging, and vacuum drying to obtain the Pt/TiN gas-sensitive electrode material.
Further, in the step (1), the titanium source is titanyl sulfate (TiOSO 4).
Further, in the step (1), the mass-volume ratio of the titanium source, the ethylene glycol, the isopropyl alcohol and the benzyl alcohol is (1.5-4.5) g: (7.5-22.5) mL: (10-30) mL: (7.5-22.5) mL.
Further, in the step (1), the time of the ultrasonic treatment is 30-40 min.
Further, in the step (2), the temperature of the heating reaction is 140-180 ℃ and the time is 4-8 h.
Further, in the step (2), the rotational speed of the centrifugation is 8000-10000 r/min, and the time is 5-8 min.
Further, in the step (2), the temperature of the vacuum drying is 50-60 ℃ and the time is 8-12 h.
Further, in the step (3), the first calcination is performed under an air atmosphere at a temperature of 500-800 ℃ for 4-8 h ℃ and at a heating rate of 5-8 ℃/min.
Further, in step (3), the first calcination is cooled to room temperature.
Further, in the step (3), the second calcination is performed under an ammonia atmosphere; the temperature of the second calcination is 700-800 ℃, the time is 1-2 h, the temperature-raising program is to raise the temperature to 300 ℃ at 5 ℃/min, then raise the temperature to 700 ℃ at 2 ℃/min, and finally raise the temperature to 800 ℃ at 1 ℃/min.
Further, in the step (3), cooling to room temperature is required after the second calcination, and argon gas 1 h is introduced; the purpose of argon is to ensure complete removal of NH 3.
Further, in the step (4), the mass concentration of the H 2PtCl6 aqueous solution is 100 mg/L;
The H 2PtCl6 aqueous solution is prepared by the following steps: 1g chloroplatinic acid hydrate was added to a 100mL volumetric flask and subsequently sized to 100mL with deionized water.
Further, in the step (4), the mass-volume ratio of the TiN material, the glycol and the H 2PtCl6 aqueous solution is (4-5) mg: (4-5) mL: (30-34) mu L.
Further, in the step (4), the time of the ultrasonic treatment is 30-60 min.
Further, in the step (4), the temperature of the heating reaction is 140-180 ℃ and the time is 3-6 h.
Further, in the step (4), the reaction is cooled to room temperature after the heating reaction.
Further, in the step (4), the rotational speed of the centrifugation is 8000-10000 r/min, and the time is 5-8 min.
Further, in the step (4), the temperature of the vacuum drying is 50-60 ℃ and the time is 8-12 h.
The Pt/TiN gas-sensitive electrode material prepared by the method.
The Pt/TiN gas-sensitive electrode material is applied to preparing a gas sensor.
Further, the gas sensor is used for detecting hydrogen.
The beneficial effects are that: the invention uses Transition Metal Nitride (TMNs) to prepare gas-sensitive electrode material, and the preparation method has the advantages of short reaction time, simple operation and the like; and the prepared transition metal nitride has the advantages of strong corrosion resistance, high conductivity, stable electrochemical performance and the like. The transition metal nitride and the noble metal have strong interaction, and the gas sensor prepared by taking the transition metal nitride as a carrier material can be used for efficiently monitoring hydrogen gas and has excellent long-term stability and quick response recovery performance.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. Embodiments of the present invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is an XRD pattern of TiN material prepared in example 1;
Fig. 2 is an SEM image of TiN material prepared in example 1;
FIG. 3 is a graph of response current statistics of a Pt/TiN sensor at 500 ppm H 2 and other interfering gases;
FIG. 4 is a graph showing the response current statistics of Pt/TiN sensors with different Pt loadings prepared in examples 1-3.
Detailed Description
In the following description, specific details of the invention are set forth in order to provide a thorough understanding of the invention. The terminology used in the description of the invention herein is for the purpose of describing the advantages and features of the invention only and is not intended to be limiting of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The medicines or reagents used in the present invention are used according to the product instructions or by the conventional methods of use in the art unless specifically stated. The technical scheme of the invention is further described according to the attached drawings and the specific embodiments.
Example 1 (1), 3g titanyl sulfate, 15 mL ethylene glycol, 20 mL isopropyl alcohol, and 15 mL benzyl alcohol were placed in a 100 mL beaker; placing the beaker into an ultrasonic instrument, and performing ultrasonic treatment for 30 min to obtain a mixed solution;
(2) Transferring the mixed solution obtained in the step (1) into a polytetrafluoroethylene lining of 100mL, loading the mixed solution into a stainless steel high-pressure reaction kettle, reacting 4 h at 140 ℃ in an oven, and centrifugally collecting reactants after naturally cooling to room temperature, wherein the centrifugal collecting conditions are as follows: 8000 r/min, time: 5 min; washing the collected sample with deionized water for 3 times, and centrifugally collecting each time; washing the sample with absolute ethanol for 3 times, and centrifugally collecting each time; placing the collected sample into a vacuum drying oven, and drying at 60 ℃ for 8-12 h to obtain white powdery solid, namely the hollow tubular TiN precursor;
(3) Putting the TiN precursor obtained in the step (2) into a porcelain boat, shaking to uniformly disperse the TiN precursor, then putting the porcelain boat into a muffle furnace, heating to 500 ℃ at 5 ℃/min under the air atmosphere, maintaining for 4 h, naturally cooling to room temperature after the program is finished, and finally obtaining white product titanium dioxide;
(4) Taking the white product obtained in the step (3) of 200-300 mg, shaking to uniformly disperse the white product in a porcelain boat, then placing the porcelain boat in a tube furnace, heating the porcelain boat to room temperature to 300 ℃,5 ℃/min,300 ℃ to 700 ℃,2 ℃/min,700 ℃ to 800 ℃,1 ℃/min, heating the porcelain boat to 800 ℃ and then maintaining the porcelain boat for 1h, naturally cooling the porcelain boat to room temperature after the procedure is finished, then introducing argon gas 1h, ensuring complete removal of NH 3, and finally obtaining the black product hollow tubular TiN material;
(5) Adding 50 mg of the TiN material obtained in the step (4) and 340 mu L of H 2PtCl6 aqueous solution with the mass concentration of 100 mg/L into 50 mL of ethylene glycol, wherein the mass ratio of TiN to Pt is 4:1, ultrasonic treatment is carried out for 30 min to uniform mixing, then the mixed solution is transferred into a polytetrafluoroethylene lining, then is transferred into a stainless steel high-pressure reaction kettle, is placed into an oven for heating at 140 ℃ for 3 h, and after the mixture is naturally cooled to room temperature, reactants are centrifugally collected under the following centrifugal collection conditions: 10000 r/min, time: 5 min, drying 8-12 h in a vacuum drying oven at 60 ℃; washing the collected sample with deionized water for 3 times, centrifugally collecting each time, washing the sample with absolute ethyl alcohol for 3 times, centrifugally collecting each time, placing the collected sample into a vacuum drying oven, and drying at 60 ℃ for 8-12 h to obtain black powdery solid, namely the Pt/TiN material, wherein the Pt load is 20%.
Fig. 1 is an XRD pattern of the TiN material prepared in example 1, and shows successful synthesis of TiN material.
Fig. 2 is an SEM image of the TiN material prepared in example 1, and the result shows that the TiN material has a hollow tubular shape.
Example 2 steps (1) to (4) are all the same as example 1;
(5) Adding 50mg of the TiN material obtained in the step (4) and 28 mu L of H 2PtCl6 aqueous solution with the mass concentration of 100mg/L into 50 mL of ethylene glycol, wherein the mass ratio of TiN to Pt is 49:1, ultrasonic treatment is carried out for 30min to uniform mixing, then the mixed solution is transferred into a polytetrafluoroethylene lining, then is transferred into a stainless steel high-pressure reaction kettle, is placed into an oven for heating at 140 ℃ for 3h, and after the mixture is naturally cooled to room temperature, reactants are centrifugally collected under the following centrifugal collection conditions: 10000 r/min, time: 5min, drying 8-12 h in a vacuum drying oven at 60 ℃; washing the collected sample with deionized water for 3 times, centrifugally collecting each time, washing the sample with absolute ethyl alcohol for 3 times, centrifugally collecting each time, placing the collected sample into a vacuum drying oven, and drying at 60 ℃ for 8-12 h to obtain black powdery solid, namely Pt/TiN material, wherein the Pt load is 2%.
Example 3 steps (1) to (4) are all the same as example 1;
(5) Adding 50 mg of the TiN material obtained in the step (4) and 152 mu L of H 2PtCl6 aqueous solution with the mass concentration of 100 mg/L into 50 mL of ethylene glycol, wherein the mass ratio of TiN to Pt is 9:1, ultrasonic treatment is carried out for 30 min to uniform mixing, then the mixed solution is transferred into a polytetrafluoroethylene lining, then is transferred into a stainless steel high-pressure reaction kettle, is placed into an oven for heating at 140 ℃ for 3 h, and after the mixture is naturally cooled to room temperature, reactants are centrifugally collected under the following centrifugal collection conditions: 10000 r/min, time: 5 min, drying 8-12 h in a vacuum drying oven at 60 ℃; washing the collected sample with deionized water for 3 times, centrifugally collecting each time, washing the sample with absolute ethyl alcohol for 3 times, centrifugally collecting each time, placing the collected sample into a vacuum drying oven, and drying at 60 ℃ for 8-12 h to obtain black powdery solid, namely the Pt/TiN material, wherein the Pt load is 10%.
Comparative example 1
Adding 50mg carbon black and 340 mu L of H 2PtCl6 solution with the mass concentration of 100 mg/L into 50 mL ethylene glycol, carrying out ultrasonic treatment for 30 min until the mixture is uniformly mixed, transferring the mixed solution into a polytetrafluoroethylene lining, transferring into a stainless steel high-pressure reaction kettle, placing the stainless steel high-pressure reaction kettle into an oven, heating for 3H at 140 ℃, and after the mixture is naturally cooled to room temperature, centrifugally collecting reactants, wherein the centrifugal collection condition is that the rotating speed is as follows: 10000 r/min, time: 5min, drying 8-12 h in a vacuum drying oven at 60 ℃; washing the collected sample with deionized water for 3 times, centrifugally collecting each time, washing the sample with absolute ethyl alcohol for 3 times, centrifugally collecting each time, placing the collected sample into a vacuum drying oven, and drying at 60 ℃ for 8-12 h to obtain black powdery solid, namely the Pt/C material.
Example 41 preparation of gas sensor and Performance test
(1) Preparation of Pt/TiN gas sensor:
The Pt/TiN material prepared in example 1, 5mg, was dissolved in 460. Mu.L of isopropanol solution and 40. Mu.L of Nafion solution (5 wt%) and thoroughly sonicated to obtain a catalyst ink. The obtained Pt/TiN catalyst ink was uniformly dropped on two pieces of 1.5 x 1.5 cm carbon paper, after being sufficiently dried, 20. Mu.L of 5 wt% Nafion solution was uniformly dropped on the catalyst layer, and then dried again in an oven. The treated carbon paper was cut into a round shape with a diameter of 1 cm a. Finally, two layers of carbon paper and one layer of Nafion membrane were hot pressed at 90 ℃ and 1.5 MPa to obtain a Membrane Electrode Assembly (MEA). And then bonding the MEA with a stainless steel electrode cap and a water storage tank to obtain the Pt/TiN sensor to be operated.
(2) The preparation method of the Pt/C gas sensor comprises the following steps:
The Pt/C prepared in comparative example 1, 5mg, was dissolved in 460. Mu.L of isopropanol solution and 40. Mu.L of Nafion solution (5 wt%) and sufficiently sonicated to obtain a catalyst ink. The obtained Pt/C catalyst ink was uniformly dropped on two pieces of 1.5 x 1.5 cm carbon paper, and after sufficient drying, 20. Mu.L of 5 wt% Nafion solution was uniformly dropped on the catalyst layer, and then dried again in an oven. The treated carbon paper was cut into a round shape with a diameter of 1 cm a. Finally, two layers of carbon paper and one layer of Nafion membrane were hot pressed at 90 ℃ and 1.5 MPa to obtain a Membrane Electrode Assembly (MEA). And then bonding the MEA with a stainless steel electrode cap and a water storage tank to obtain the Pt/C sensor to be operated.
(3) Performance testing of gas sensors
Method for detecting H 2 gas:
The testing equipment of the gas sensor consists of a gas distribution system, a testing device, an electrochemical workstation, a computer and the like. The concentration of the target gas is obtained through a self-built gas distribution system, air is adopted as background gas in the invention, the whole experiment is carried out at room temperature, an electrochemical workstation is connected with a computer, and the computer is used for collecting and processing output data of a gas sensor. Before testing, the sensor is stabilized in the air for a period of time to stabilize the output of the sensor, then a certain concentration of target gas is introduced into a testing device, the output current of the sensor is collected, and the gas-sensitive performance of the prepared sensor is evaluated by recording the current changes of different sensors in various gases. The sensor response is defined as Δi=i 2-I1, where I 1 and I 2 represent the current of the sensor in air and target gas, respectively.
① . The response currents of the prepared Pt/TiN sensor and the Pt/C gas sensor under 1000 ppm H 2 and other interference gases are detected, wherein the other interference gases are CH 3OH,Acetone,NO,NO2,CO,H2 S, and the concentrations of the other interference gases are 50 ppm. FIG. 3 is a graph of the response current statistics of the Pt/TiN sensor at 1000 ppm H 2 and other interfering gases, showing that the Pt/TiN sensor has the best selectivity to H 2, the highest response current to H 2, the response current being about 54.6 μA, and the response current of the Pt/TiN sensor to other interfering gases being negligible. In addition, the response current statistics of the Pt/C gas sensor show that the response current to H 2 is significantly lower than that of the Pt/TiN sensor.
② . The response current was measured for Pt/TiN sensors and Pt/C gas sensors with Pt loadings of 2%,10% and 20%, and fig. 4 is a graph of response current statistics for Pt/TiN sensors, where 0.1% means that H 2 concentration is 1000 ppm,0.2% means that H 2 concentration is 2000 ppm,0.5% means that H 2 concentration is 5000 ppm,1% means that H 2 concentration is 10000 ppm,2% means that H 2 concentration is 20000 ppm,4% means that H 2 concentration is 40000 ppm, and the results show that Pt/TiN sensors with Pt loadings of 10% and 20% have higher response currents, and Pt loading of 2% of Pt/TiN sensors has lower response currents. In addition, the response current results of the Pt/C gas sensor showed that the response current to H 2 was significantly lower than those of Pt/TiN sensors with Pt loadings of 2%,10% and 20%.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the essence of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the hollow tubular Pt/TiN gas-sensitive electrode material is characterized by comprising the following steps of:
(1) Mixing a titanium source, ethylene glycol, isopropyl alcohol and benzyl alcohol, and performing ultrasonic treatment to obtain a mixed solution;
(2) Heating the mixed solution obtained in the step (1) to react, centrifuging, and vacuum drying to obtain a TiN precursor;
(3) Respectively carrying out first calcination and second calcination on the TiN precursor obtained in the step (2) to obtain a TiN material;
(4) Mixing the TiN material obtained in the step (4), glycol and H 2PtCl6 aqueous solution, performing ultrasonic treatment, heating, reacting, centrifuging, and vacuum drying to obtain the Pt/TiN gas-sensitive electrode material.
2. The method of claim 1, wherein in step (1), the titanium source is titanyl sulfate;
The mass volume ratio of the titanium source, the ethylene glycol, the isopropyl alcohol and the benzyl alcohol is (1.5-4.5) g: (7.5-22.5) mL: (10-30) mL: (7.5-22.5) mL;
The ultrasonic treatment time is 30-40 min.
3. The method according to claim 1, wherein in the step (2), the heating reaction is carried out at a temperature of 140 to 180 ℃ for a time of 4 to 8h;
the rotational speed of the centrifugation is 8000-10000 r/min, and the time is 5-8 min;
The vacuum drying temperature is 50-60 ℃ and the time is 8-12 h.
4. The method according to claim 1, wherein in the step (3), the first calcination is performed under an air atmosphere at a temperature of 500 to 800 ℃ for a time of 4 to 8h and a temperature rise rate of 5 to 8 ℃/min;
The first calcination also requires cooling to room temperature.
5. The method according to claim 1, wherein in the step (3), the second calcination is performed under an ammonia atmosphere; the temperature of the second calcination is 700-800 ℃, the time is 1-2 h, the temperature-raising program is that the temperature is raised to 300 ℃ at 5 ℃/min, then raised to 700 ℃ at 2 ℃/min, and finally raised to 800 ℃ at 1 ℃/min;
And cooling to room temperature after the second calcination, and introducing argon gas 1-2 h.
6. The method according to claim 1, wherein in the step (4), the mass concentration of the aqueous solution of H 2PtCl6 is 100 mg/L;
the mass volume ratio of the TiN material to the glycol to the H 2PtCl6 aqueous solution is (4-5) mg: (4-5) mL: (30-34) mu L.
7. The method of claim 1, wherein in step (4), the time of the ultrasonic treatment is 30 to 60 min;
The temperature of the heating reaction is 140-180 ℃ and the time is 3-6 h;
Cooling to room temperature after the heating reaction;
the rotational speed of the centrifugation is 8000-10000 r/min, and the time is 5-8 min;
The vacuum drying temperature is 50-60 ℃ and the time is 8-12 h.
8. A Pt/TiN gas sensitive electrode material prepared by the method of any one of claims 1 to 7.
9. Use of the Pt/TiN gas-sensitive electrode material prepared by the method according to any one of claims 1 to 7 and/or the Pt/TiN gas-sensitive electrode material according to claim 8 for the preparation of a gas sensor.
10. The use according to claim 9, wherein the gas sensor is used for detecting hydrogen.
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