CN111115716A - NiO gas-sensitive material for methane detection and preparation method thereof - Google Patents
NiO gas-sensitive material for methane detection and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a NiO gas-sensitive material for methane detection, which comprises the following steps: slowly dripping oxalic acid ethanol solution into Ni (NO) according to the mixture ratio3)2·6H2Stirring the solution of O in water and ethanol to obtain a nickel oxalate precursor solution; heating and stirring the nickel oxalate precursor solution, naturally cooling to room temperature, washing for multiple times and carrying out centrifugal separation to obtain a precipitate, and drying the precipitate to obtain a nickel oxalate precursor; then calcining is carried out to obtain the NiO gas sensitive material. The invention adopts oxalate precipitation method to prepare nickel oxalate precursor, and the nickel oxalate precursor is subjected to nickel oxalate precipitationThe precursor is used as a sacrificial template, NiO porous rods and nano-particle gas-sensitive materials with different morphological structures are prepared by utilizing the characteristics of the sacrificial template, and the prepared NiO porous rods and NiO nano-particle gas-sensitive materials have good sensitivity to methane and have wide application prospect in the aspect of manufacturing novel efficient gas sensors.
Description
Technical Field
The invention belongs to the technical field of application of nano materials, and particularly relates to a NiO gas-sensitive material for methane detection and a preparation method thereof.
Background
Methane (CH)4) Is a simple colorless and tasteless organic matter, and is also the main component of household natural gas and coal mine gas. Methane is used as natural gas, and provides important energy for industrial production and living needs of human beings. Methane is a fuel widely used in civil and industrial production; in addition, methane can be used as a raw material for hydrogen production, carbon black, carbon monoxide, and methane as acetylene and formaldehyde. However, the characteristics of methane such as no color, no smell, flammability and explosiveness also bring great threat to the personal safety of people. Is reported to be when CH4At too high a concentration, the oxygen content can be greatly reduced, which can lead to headache, dizziness, inattention and suffocation. In addition, methane, as a climate-changing gas, produces a greenhouse effect 25 times greater than carbon dioxide. More seriously, in the coal mine production process, when the volume concentration of methane reaches 4.9 to 15.4 percent, violent explosion easily occurs. Thus, implementing the pair CH4Fast real-time detection of the same becomes increasingly important.
Among the numerous approaches to methane detection, Metal Oxide Semiconductor (MOS) sensors are receiving increasing attention due to their simple fabrication, portability, low power consumption, low cost, and superior response characteristics. Until now, various morphologically structured MOS have been developed and used as gas sensor materials. NiO, a typical p-type MOS, shows wide applicability in the fields of catalysts, sensors and the like. However, NiO with a general morphology is rarely used as a sensitive element material in a sensor due to low NiO responsiveness. Because the gas-sensitive performance of the MOS depends on the microstructure to a great extent, the construction of a micro-nano structure with a novel form becomes one of the main means for improving the material performance. In recent years, reports on manufacturing a MOS structure with multiple pores by a sacrificial template method are increasing, for example, a Metal Organic Framework (MOF) sacrificial template method is used for synthesizing porous MOS, but the operation flow for synthesizing the MOF sacrificial template is complicated and complicated, which hinders the application of the MOF sacrificial template in the rapid synthesis of porous MOS nano-materials to some extent; the oxalate can be easily prepared by a simple precipitation method, the synthesis method is simple, no impurity ions are introduced, the environment is friendly and pollution-free, and the oxalate can be easily decomposed at high temperature and can be used for synthesizing the porous MOS material.
Although there are reports of NiO materials for use in the detection of methane gas, there are few reports of NiO produced by oxalate as a sacrificial template and used in the detection of methane gas.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a NiO gas-sensitive material for methane detection and a preparation method thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a NiO gas-sensitive material for methane detection preferably comprises the following steps:
the method comprises the following steps: mixing Ni (NO)3)2·6H2Dissolving O in a mixed solution of water and ethanol under the stirring condition to obtain a first solution, slowly dripping the oxalic acid ethanol solution into the first solution according to the proportion under the stirring condition, and continuously stirring to obtain a nickel oxalate precursor solution;
step two: heating and stirring the nickel oxalate precursor solution obtained in the step one, then naturally cooling to room temperature, washing for multiple times through deionized water and absolute ethyl alcohol, centrifugally separating to obtain a precipitate, and drying the precipitate to obtain a nickel oxalate precursor, namely a sacrificial template;
step three: and gradually heating the sacrificial template obtained in the step two to a certain temperature in an air atmosphere for calcining to obtain the NiO gas-sensitive material.
In the above method for preparing a NiO gas-sensitive material for methane detection, as a preferred scheme, the third step specifically is: gradually heating the sacrificial template obtained in the step two to 350-380 ℃ at a heating rate of 1-3 ℃/min in an air atmosphere, and calcining for 2-4 h to obtain a NiO gas-sensitive material;
the NiO gas sensitive material is a NiO porous rod gas sensitive material.
In the above method for preparing a NiO gas-sensitive material for methane detection, as a preferred scheme, the third step specifically is: gradually heating the sacrificial template obtained in the step two to 420-500 ℃ at a heating rate of 1-3 ℃/min in an air atmosphere, and calcining for 2-4 h to obtain a NiO gas-sensitive material;
the NiO gas sensitive material is a NiO nano-particle gas sensitive material.
In the preparation method of the NiO gas-sensitive material for methane detection, as a preferable scheme, the volume ratio of the first solution to the oxalic acid ethanol solution in the first step is 3: 1;
preferably, the Ni (NO)3)2·6H2The mass concentration of O in the first solution is 0.033 mol/L;
more preferably, the substance amount concentration of the oxalic acid ethanol solution is 0.2 mol/L.
In the preparation method of the NiO gas-sensitive material for methane detection, as a preferable scheme, the volume ratio of water to ethanol in the first solution in the step one is 2: 1.
In the preparation method of the NiO gas-sensitive material for methane detection, as a preferred scheme, the heating temperature in the step two is 40-60 ℃, and the stirring time is 6-9 h.
In the above-described method for preparing a NiO gas-sensitive material for methane detection, as a preferred embodiment, the number of times of washing with deionized water and absolute ethyl alcohol in step two is four.
In the preparation method of the NiO gas-sensitive material for methane detection, as a preferred scheme, the drying temperature in the step two is 60-80 ℃, and the drying time is 8-12 h.
The NiO gas-sensitive material for methane detection preferably comprises a NiO porous rod gas-sensitive material and a NiO nano particle gas-sensitive material.
In the NiO gas-sensitive material for methane detection, as a preferable scheme, both the NiO porous rod gas-sensitive material and the NiO nanoparticle gas-sensitive material are prepared by the preparation method of the NiO gas-sensitive material for methane detection.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
according to the invention, the nickel oxalate precursor is prepared by adopting an oxalate precipitation method, the nickel oxalate precursor is used as a sacrificial template, and NiO porous rods and nanoparticle gas-sensitive materials with different morphological structures are prepared by adjusting the calcining temperature.
The method utilizes the characteristics of the sacrificial template to prepare the high-purity nano material with the same appearance characteristics as the sacrificial template, and the prepared NiO porous rod and NiO nano-particle gas-sensitive material have good sensitivity to methane and have wide application prospect in the aspect of manufacturing novel high-efficiency gas sensors.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a thermogravimetric analysis of a nickel oxalate precursor in example 1 of the present invention;
FIG. 2 is an XRD spectrum of a nickel oxalate precursor, a NiO porous rod gas-sensitive material and a NiO nano-particle gas-sensitive material in examples 1 and 2 of the present invention; wherein a and b are XRD spectrograms of the nickel oxalate precursor and the NiO porous rod gas-sensitive material in the embodiment 1 respectively; c is the XRD spectrogram of the NiO nano-particle gas-sensitive material in the example 2;
FIG. 3 is a scanning electron microscope image and a transmission electron microscope photograph of the overall micro-morphology of the nickel oxalate precursor, the NiO porous rod gas-sensitive material and the NiO nanoparticle gas-sensitive material in examples 1 and 2 of the present invention; wherein, (a) and (d) are scanning electron microscope and transmission electron microscope photographs of the precursor nickel oxalate prepared in examples 1 and 2, respectively; (b) and (e) are respectively the scanning electron microscope and transmission electron microscope photographs of the NiO porous rod gas-sensitive material prepared in example 1; (c) and (f) are respectively the scanning electron microscope and transmission electron microscope photographs of the NiO nanoparticle gas-sensitive material prepared in example 2;
fig. 4 is a sensitivity curve of the NiO porous rod gas-sensitive material and the NiO nanoparticle gas-sensitive material prepared in embodiments 1 and 2 of the present invention responding to methane gas of different concentrations in real time at 320 ℃;
FIG. 5 is a resistance curve diagram of real-time response of NiO porous rod gas-sensitive material and NiO nano-particle gas-sensitive material prepared in embodiments 1 and 2 of the present invention to methane gas of different concentrations at 320 ℃;
fig. 6 is a relationship curve of methane gas concentration and response value at 320 ℃ of the NiO porous rod gas-sensitive material and the NiO nanoparticle gas-sensitive material prepared in the specific examples 1 and 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, 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 that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
According to the nanometer NiO gas sensitive material for methane detection and the preparation method thereof, the nickel oxalate precursor is obtained by adopting an oxalate precipitation method, the nickel oxalate precursor is used as a sacrificial template, the morphological structure of the product is adjusted by controlling different calcination temperatures, and the high-purity NiO porous rod gas sensitive material and the NiO nanometer particle gas sensitive material which have the same morphological characteristics as the template are prepared by utilizing the characteristics of the sacrificial template.
The invention provides a preparation method of a NiO gas-sensitive material for methane detection, which comprises the following steps:
the method comprises the following steps: mixing Ni (NO)3)2·6H2Dissolving O in a mixed solution of water and ethanol under the stirring condition to obtain a first solution, slowly dripping the oxalic acid ethanol solution into the first solution according to the proportion under the stirring condition, and continuously stirring to obtain a nickel oxalate precursor solution;
in the specific embodiment of the invention, the volume ratio of the first solution to the oxalic acid ethanol solution in the first step is 3: 1; preferably, Ni (NO)3)2·6H2The mass concentration of O in the first solution is 0.033 mol/L; more preferably, the substance amount concentration of the oxalic acid ethanol solution is 0.2 mol/L. Wherein, the mass concentration of the oxalic acid ethanol solution is 0.2mol/L, which is the ratio of the mass of the oxalic acid to the total volume of the oxalic acid ethanol solution.
In a specific embodiment of the present invention, the volume ratio of water to ethanol in the first solution in step one is 2: 1.
Step two: heating and stirring the nickel oxalate precursor solution obtained in the step one, then naturally cooling to room temperature, washing for multiple times through deionized water and absolute ethyl alcohol, centrifugally separating to obtain a precipitate, and drying the precipitate to obtain a nickel oxalate precursor, namely a sacrificial template;
in the embodiment of the invention, the heating temperature in the second step is 40-60 ℃ (such as 40 ℃, 42 ℃, 44 ℃, 45 ℃, 47 ℃, 49 ℃, 50 ℃, 52 ℃, 54 ℃, 55 ℃, 57 ℃, 59 ℃ and 60 ℃), and the stirring time is 6-9 h (such as 6h, 6.2h, 6.5h, 6.7h, 7.0h, 7.2h, 7.5 h, 7.8h, 8.0h, 8.2h, 8.5h, 8.8h and 9.0 h). Preferably, the number of repeated washing by deionized water and absolute ethyl alcohol in the second step is four.
In the embodiment of the invention, the drying temperature in the second step is 60-80 ℃ (such as 60 ℃, 62 ℃, 65 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 75 ℃, 76 ℃, 78 ℃ and 80 ℃), and the drying time is 8-12 h (such as 8h, 8.2h, 8.5h, 8.8h, 9h, 9.2h, 9.5h, 9.8h, 10h, 10.2h, 10.5h, 10.8h, 11h, 11.2h, 11.5h, 11.8h and 12 h).
Step three: and gradually heating the sacrificial template obtained in the step two to a certain temperature in an air atmosphere for calcining to obtain the NiO gas-sensitive material.
In the specific embodiment of the present invention, the third step specifically is: gradually heating the sacrificial template obtained in the second step to 350-380 ℃ (such as 350 ℃, 352 ℃, 355 ℃, 358 ℃, 360 ℃, 362 ℃, 365 ℃, 367 ℃, 372 ℃, 375 ℃, 378 ℃ and 380 ℃) at a heating rate of 1-3 ℃/min (such as 1 ℃/min, 1.2 ℃/min, 1.4 ℃/min, 1.6 ℃/min, 2.8 ℃/min, 2.9 ℃/min, 2.3 ℃/min, 2.4 ℃/min, 2.5 ℃/min, 2.6 ℃/min, 2.3 ℃/min, 2.1 ℃/min, 2.2 ℃/min, 2.3 ℃/min, 2.4 ℃/min, 2.5 ℃/min, 2.8 ℃/min and 3 ℃/min) in an air atmosphere, and calcining for 2-4 h (such as 2h, 2.2h, 2.5h, 2.6h, 2.8h, 3h, 3.2h, 3.5h, 3.8h and 4h) to obtain a NiO gas-sensitive material; the NiO gas sensitive material is a NiO porous rod gas sensitive material.
In the specific embodiment of the present invention, the third step specifically is: gradually heating the sacrificial template obtained in the second step to 420-500 ℃ (such as 420 ℃, 425 ℃, 430 ℃, 435 ℃, 440 ℃, 445 ℃, 450 ℃, 455 ℃, 460 ℃, 465 ℃, 470 ℃, 475 ℃, 480 ℃, 485 ℃, 490 ℃, 495 ℃ and 500 ℃) at a heating rate of 1-3 ℃/min (such as 1 ℃/min, 1.2 ℃/min, 1.4 ℃/min, 1.6 ℃/min, 1.8 ℃/min, 2 ℃/min, 2.1 ℃/min, 2.2 ℃/min, 2.3 ℃/min, 2.4 ℃/min, 2.5 ℃/min, 2.6 ℃/min, 2.8h, 3h, 3.2h, 3.5h, 3.8h, 4h) in an air atmosphere, obtaining NiO gas-sensitive material; the NiO gas sensitive material is a NiO nano-particle gas sensitive material.
The invention also provides a NiO gas-sensitive material for methane detection, which comprises a NiO porous rod gas-sensitive material and a NiO nano-particle gas-sensitive material.
In the specific embodiment of the invention, the NiO porous rod and the NiO nano-particle gas-sensitive material are both prepared by adopting the preparation method of the NiO gas-sensitive material for methane detection.
Example 1
The embodiment provides a preparation method of a NiO gas-sensitive material for methane detection, which comprises the following steps:
the method comprises the following steps: 0.87g of Ni (NO)3)2·6H2Dissolving O in a mixed solution of 60ml of water and 30ml of ethanol under the stirring condition to obtain a first solution, slowly dripping 30ml of oxalic acid ethanol solution into the first solution according to the proportion under the stirring condition (the mass concentration of the oxalic acid ethanol solution is 0.2mol/L), and continuously stirring to obtain a nickel oxalate precursor solution;
step two: transferring the nickel oxalate precursor solution obtained in the step one into a water bath, heating at 60 ℃, stirring for 9 hours, naturally cooling to room temperature, washing for four times by using deionized water and absolute ethyl alcohol, carrying out centrifugal separation to obtain a precipitate, and drying the precipitate at 70 ℃ for 10 hours to obtain a nickel oxalate precursor, namely a sacrificial template;
step three: and gradually heating the sacrificial template obtained in the step two to 370 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and calcining for 3h to obtain the NiO porous rod gas-sensitive material.
The characterization results of the nickel oxalate precursor obtained in the second step of the specific embodiment and the finally prepared NiO porous rod gas-sensitive material are as follows:
as shown in fig. 1, which is a thermogravimetric analysis diagram of the nickel oxalate precursor in this example, it can be seen from the diagram that the nickel oxalate undergoes two weight loss processes during the temperature rising process, in which C and H in the nickel oxalate are CO respectively2And H2The form of O is lost and after 350 ℃, the final weight does not change any more, resulting in the final product.
As shown in fig. 2, a and b are XRD spectrograms of the nickel oxalate precursor and the NiO porous rod gas-sensitive material in this example, respectively, and it can be seen from a that the obtained precursor is nickel oxalate and no other phase is found; from b it can be seen that the product obtained after calcination at 370 ℃ is a pure phase of nickel oxide without any impurity peaks.
As shown in fig. 3, (a) and (d) are scanning electron microscope and transmission electron microscope photographs of the precursor nickel oxalate prepared in this example, respectively; (b) and (e) are respectively the scanning electron microscope and transmission electron microscope photographs of the NiO porous rod gas-sensitive material prepared in the embodiment; the combination of a scanning electron microscope and a transmission electron microscope clearly shows that the nickel oxalate precursor is a solid nanorod with the size of about 50 nm-150 nm. And NiO obtained after calcination at 370 ℃ is in a porous rod structure, and porosity is formed due to the loss of C and H in nickel oxalate, so that pores are left in the original positions.
In order to evaluate the sensitivity of the NiO gas-sensitive material to real-time response of methane gas with different concentrations when the NiO gas-sensitive material is used for methane detection, a CGS-4TPs intelligent gas-sensitive analysis system instrument is selected to test the sensitivity of the NiO gas-sensitive material to response of the methane gas with different concentrations (the concentration range of the methane gas is 100-4000 ppm) at the working temperature of 320 ℃.
As shown in fig. 4 to 6, the sensitivity curve of the NiO porous rod gas-sensitive material prepared in this embodiment responding to methane gas with different concentrations in real time at 320 ℃, the resistance curve of the NiO porous rod gas-sensitive material responding to methane gas with different concentrations in real time, and the relationship curve between the methane gas concentration and the response value are shown. From the analysis in the figure, the response value of the gas sensitive device is expressed as S ═ Ra-Rg |/Ra 100. Wherein Ra is the resistance of the device in air, and Rg is the resistance of the device in methane gas. The test result shows that the response value of the NiO porous rod gas-sensitive material to methane gradually increases with the increase of the concentration of the detected methane gas, and the NiO porous rod gas-sensitive material shows a linear increasing trend at lower concentration. The response value of the NiO porous rod gas-sensitive material to 4000ppm of methane gas is 26.9%.
The sensitivity response value of the NiO porous rod gas-sensitive material in the embodiment to 2000ppm methane gas at 320 ℃ is 16.8%.
Example 2
The embodiment provides a preparation method of a NiO gas-sensitive material for methane detection, which is different from the preparation method of embodiment 1 in that in the third step, the temperature is gradually increased to 450 ℃ at a temperature increase rate of 2 ℃/min in an air atmosphere, and calcination is performed for 3 hours, so that a NiO nanoparticle gas-sensitive material is obtained.
Other steps are the same as embodiment 1 and are not described herein again.
The characterization results of the NiO porous rod gas-sensitive material prepared by the specific embodiment are as follows:
as shown in fig. 2, c is the XRD spectrum of the NiO nanoparticle gas sensitive material prepared in this example, and it can be seen from the XRD spectrum that the product obtained after calcination at 450 ℃ is also pure-phase NiO without any impurity peak. Compared with the diffraction peak of a NiO porous rod, the diffraction peak of the material obtained after calcination at 450 ℃ is stronger, sharper and better in crystallinity.
As shown in fig. 3, (c) and (f) are respectively the scanning electron microscope and transmission electron microscope photographs of the NiO nanoparticle gas-sensitive material prepared in this example, it can be seen from the photographs that NiO obtained by calcination at 450 ℃ is uniform nanoparticles, the particle size is about 20nm, and no other morphological structures are found.
As shown in fig. 4 to 6, the sensitivity curve of the NiO nanoparticle gas-sensitive material prepared in this embodiment responding to methane gas with different concentrations in real time at 320 ℃, the resistance curve of the NiO nanoparticle gas-sensitive material responding to methane gas with different concentrations in real time, and the relationship curve between the methane gas concentration and the response value are shown. The gas-sensitive device is shown in the same manner as in example 1. From the analysis in the figure, the response value of the NiO nanoparticle gas sensitive material to methane gradually increases with the increase of the detected methane gas concentration, and under the same methane concentration condition, the response value of the NiO nanoparticle gas sensitive material is higher than that of the porous rod gas sensitive material, for example, when the detected methane concentration is 3000ppm, the response value of the NiO nanoparticle gas sensitive material is 48.3% and is 2.2 times that of the porous rod gas sensitive material (the response value is 21.9%). And after multiple cycles, the resistance value of the material can be restored to the initial state.
The sensitivity response value of the NiO nano-particle gas-sensitive material in the embodiment to 2000ppm methane gas at 320 ℃ is 38.4%.
Example 3
The embodiment provides a preparation method of a NiO gas-sensitive material for methane detection, which comprises the following steps:
the method comprises the following steps: 0.29g of Ni (NO)3)2·6H2Dissolving O in a mixed solution of 20ml of water and 10ml of ethanol under the stirring condition to obtain a first solution, slowly dripping 10ml of oxalic acid ethanol solution into the first solution according to the proportion under the stirring condition (the mass concentration of the oxalic acid ethanol solution is 0.2mol/L), and continuously stirring to obtain a nickel oxalate precursor solution;
step two: transferring the nickel oxalate precursor solution obtained in the step one into a water bath, heating at 40 ℃ and stirring for 9 hours, then naturally cooling to room temperature, repeatedly washing by deionized water and absolute ethyl alcohol and centrifugally separating to obtain a precipitate, and drying the precipitate at 60 ℃ for 12 hours to obtain a nickel oxalate precursor, namely a sacrificial template;
step three: and (4) gradually heating the sacrificial template obtained in the step two to 350 ℃ at the heating rate of 2 ℃/min in the air atmosphere, and calcining for 4h to obtain the NiO porous rod gas-sensitive material.
The sensitivity response value of the NiO porous rod gas-sensitive material in the embodiment to 2000ppm methane gas at 320 ℃ is 16.4%.
Example 4
The embodiment provides a preparation method of a NiO gas-sensitive material for methane detection, which is different from the preparation method of embodiment 3 in that in the third step, the temperature is gradually increased to 420 ℃ at a temperature increase rate of 2 ℃/min in an air atmosphere, and calcination is performed for 4 hours, so that a NiO nanoparticle gas-sensitive material is obtained.
Other steps are the same as embodiment 3 and are not described herein.
The sensitivity response value of the NiO nano-particle gas-sensitive material in the embodiment to 2000ppm methane gas at 320 ℃ is 36.2%.
Example 5
The embodiment provides a preparation method of a NiO gas-sensitive material for methane detection, which comprises the following steps:
the method comprises the following steps: 0.58g of Ni (NO)3)2·6H2Dissolving O in a mixed solution of 40ml of water and 20ml of ethanol under the stirring condition to obtain a first solution, slowly dripping 20ml of oxalic acid ethanol solution into the first solution according to the proportion under the stirring condition (the mass concentration of the oxalic acid ethanol solution is 0.2mol/L), and continuously stirring to obtain a nickel oxalate precursor solution;
step two: transferring the nickel oxalate precursor solution obtained in the step one into a water bath, heating at 55 ℃ and stirring for 9 hours, then naturally cooling to room temperature, repeatedly washing by deionized water and absolute ethyl alcohol and centrifugally separating to obtain a precipitate, and drying the precipitate at 75 ℃ for 10 hours to obtain a nickel oxalate precursor, namely a sacrificial template;
step three: and gradually heating the sacrificial template obtained in the step two to 360 ℃ at the heating rate of 3 ℃/min in the air atmosphere, and calcining for 2h to obtain the NiO porous rod gas-sensitive material.
The sensitivity response value of the NiO porous rod gas-sensitive material in the embodiment to 2000ppm methane gas at 320 ℃ is 15.9%.
Example 6
The embodiment provides a preparation method of a NiO gas-sensitive material for methane detection, which is different from the preparation method of embodiment 5 in that in the third step, the temperature is gradually increased to 480 ℃ at a temperature increase rate of 3 ℃/min in an air atmosphere, and calcination is performed for 2 hours, so that a NiO nanoparticle gas-sensitive material is obtained.
The other steps are the same as those in embodiment 5, and are not described herein again.
The sensitivity response value of the NiO nano-particle gas-sensitive material in the embodiment to 2000ppm methane gas at 320 ℃ is 35.6%.
Example 7
The embodiment provides a preparation method of a NiO gas-sensitive material for methane detection, which comprises the following steps:
the method comprises the following steps: 0.44g of Ni (NO)3)2·6H2Dissolving O in a mixed solution of 30ml of water and 15ml of ethanol under the stirring condition to obtain a first solution, slowly dripping 15ml of oxalic acid ethanol solution into the first solution according to the proportion under the stirring condition (the mass concentration of the oxalic acid ethanol solution is 0.2mol/L), and continuously stirring to obtain a nickel oxalate precursor solution;
step two: transferring the nickel oxalate precursor solution obtained in the step one into a water bath, heating at 50 ℃ and stirring for 8 hours, then naturally cooling to room temperature, repeatedly washing by deionized water and absolute ethyl alcohol and centrifugally separating to obtain a precipitate, and drying the precipitate at 80 ℃ for 9 hours to obtain a nickel oxalate precursor, namely a sacrificial template;
step three: and (4) gradually heating the sacrificial template obtained in the step two to 380 ℃ at the heating rate of 2.5 ℃/min in the air atmosphere, and calcining for 3h to obtain the NiO porous rod gas-sensitive material.
The sensitivity response value of the NiO porous rod gas-sensitive material in the embodiment to 2000ppm methane gas at 320 ℃ is 15.3%.
Example 8
The embodiment provides a preparation method of a NiO gas-sensitive material for methane detection, which is different from the preparation method of embodiment 7 in that in the third step, the temperature is gradually increased to 500 ℃ at a temperature increase rate of 2.5 ℃/min in an air atmosphere, and calcination is performed for 3 hours, so that a NiO nanoparticle gas-sensitive material is obtained.
The other steps are the same as those in embodiment 7, and are not described herein again.
The sensitivity response value of the NiO nano-particle gas-sensitive material in the embodiment to 2000ppm methane gas at 320 ℃ is 34.9%.
In conclusion, the NiO porous rods and the NiO nano-particle gas-sensitive materials with different morphological structures are prepared by changing the calcination temperature of the nickel oxalate precursor of the sacrificial template, the prepared NiO porous rods and the NiO nano-particle gas-sensitive materials have good sensitivity characteristics to methane gas, and the sensitivity response values of the NiO nano-particle gas-sensitive materials to the methane gas are higher than the sensitivity response values of the NiO porous rods to the methane gas, so that the method has wide application prospects in the aspect of manufacturing stable methane sensors.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.
Claims (10)
1. A preparation method of a NiO gas-sensitive material for methane detection is characterized by comprising the following steps:
the method comprises the following steps: mixing Ni (NO)3)2·6H2Dissolving O in a mixed solution of water and ethanol under the stirring condition to obtain a first solution, slowly dripping the oxalic acid ethanol solution into the first solution according to the proportion under the stirring condition, and continuously stirring to obtain a nickel oxalate precursor solution;
step two: heating and stirring the nickel oxalate precursor solution obtained in the step one, then naturally cooling to room temperature, washing for multiple times through deionized water and absolute ethyl alcohol, centrifugally separating to obtain a precipitate, and drying the precipitate to obtain a nickel oxalate precursor, namely a sacrificial template;
step three: and gradually heating the sacrificial template obtained in the step two to a certain temperature in an air atmosphere for calcining to obtain the NiO gas-sensitive material.
2. The method for preparing the NiO gas-sensitive material for methane detection according to claim 1, wherein the third step is specifically: gradually heating the sacrificial template obtained in the step two to 350-380 ℃ at a heating rate of 1-3 ℃/min in an air atmosphere, and calcining for 2-4 h to obtain a NiO gas-sensitive material;
the NiO gas sensitive material is a NiO porous rod gas sensitive material.
3. The method for preparing the NiO gas-sensitive material for methane detection according to claim 1, wherein the third step is specifically: gradually heating the sacrificial template obtained in the step two to 420-500 ℃ at a heating rate of 1-3 ℃/min in an air atmosphere, and calcining for 2-4 h to obtain a NiO gas-sensitive material;
the NiO gas sensitive material is a NiO nano-particle gas sensitive material.
4. The method for preparing the NiO gas-sensitive material for methane detection according to claim 2 or 3, wherein the volume ratio of the first solution to the ethanol oxalate solution in the first step is 3: 1;
preferably, the Ni (NO)3)2·6H2The mass concentration of O in the first solution is 0.033 mol/L;
more preferably, the substance amount concentration of the oxalic acid ethanol solution is 0.2 mol/L.
5. The method for preparing the NiO gas-sensitive material for methane detection according to claim 4, wherein the volume ratio of water to ethanol in the first solution in the first step is 2: 1.
6. The method for preparing the NiO gas-sensitive material for methane detection according to claim 2 or 3, wherein the heating temperature in the second step is 40-60 ℃, and the stirring time is 6-9 h.
7. The method for preparing the NiO gas-sensitive material for methane detection according to claim 2 or 3, wherein in the second step, the number of washing times by the deionized water and the absolute ethyl alcohol is four.
8. The method for preparing the NiO gas-sensitive material for methane detection according to claim 2 or 3, wherein the drying temperature in the second step is 60-80 ℃, and the drying time is 8-12 h.
9. The NiO gas-sensitive material for methane detection is characterized by comprising a NiO porous rod gas-sensitive material and a NiO nano particle gas-sensitive material.
10. The NiO gas-sensitive material for methane detection of claim 9, wherein the NiO porous rod gas-sensitive material and the NiO nanoparticle gas-sensitive material are both prepared by the method for preparing the NiO gas-sensitive material for methane detection of any one of claims 1 to 8.
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| CN114308041A (en) * | 2020-09-30 | 2022-04-12 | 天津理工大学 | Preparation method of black nickel oxide and application of black nickel oxide in catalyzing oxidation reaction of 1, 2-diol for breaking C-C bond |
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