CN114813858A - Formaldehyde gas sensor based on neodymium oxide modified indium trioxide rod-shaped composite material and preparation method thereof - Google Patents
Formaldehyde gas sensor based on neodymium oxide modified indium trioxide rod-shaped composite material and preparation method thereof Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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Abstract
A formaldehyde gas sensor based on a neodymium oxide modified indium trioxide rod-shaped composite material and a preparation method thereof belong to the technical field of gas sensors. The sensor is made of Al with Pd metal interdigital electrodes 2 O 3 Substrate, Pd-coated metal interdigital electrode and Al 2 O 3 The sensitive material layer on the substrate is composed of an indium oxide rod-shaped composite material modified based on neodymium oxide. In the present invention, In is templated by self-sacrificial organometallic framework (MOF) 2 O 3 And Nd (OH) 3 The precursor is mixed and annealed to synthesize the sensitive material, so that the specific surface area of the precursor is increased, a large number of surface active sites are brought, the larger resistance value change caused by the p-n heterojunction can be effectively utilized to improve the gas sensitive response, and the sensitive material has good detection performance on formaldehyde gas. Meanwhile, the method has simple process, and the prepared device has small volume and is suitable for mass production, thereby having important application value.
Description
Technical Field
The invention belongs to the technical field of gas sensors, and particularly relates to a formaldehyde gas sensor based on a neodymium oxide modified indium trioxide rod-shaped composite material and a preparation method thereof.
Background
Along with the leap of science and technology and the development of society, people continuously enjoy the convenience of science and technology, and the problem of environmental pollution is increasingly prominent. In particular, there is a greater chance that people will be exposed to dangerous gases, such as natural gas containing carbon monoxide and methane as main components, organic toxic volatile gases such as formaldehyde, benzene and xylene generated during new decoration, and sulfur dioxide and nitrogen oxides emitted from coal combustion and automobile exhaust. Once these colorless, tasteless, toxic, harmful, flammable and explosive gases are leaked, they pose serious threats to the health and life safety of people. Therefore, it is very important to develop a gas sensor with low cost, high responsivity and high detection speed.
Formaldehyde is a major indoor air pollutant and is classified as a carcinogen by the world health organization. If exposed to a certain amount of formaldehyde gas, problems such as sore throat and nose, headache, nausea, cough, etc. may be caused. Even at low concentrations, exposure to formaldehyde gas can cause irreversible damage to the human body. Therefore, it is urgently needed to develop a gas sensor with good selectivity, high response and low price for rapidly detecting formaldehyde.
When some metal oxide semiconductor nano materials are contacted with certain gases, the electrical properties and the like of the metal oxide semiconductor nano materials are obviously changed, and the change of the electrical properties (electrical signals) of the materials can be detected through a peripheral detection circuit, so that the gases are monitored. The gas sensor based on the metal oxide semiconductor gas sensitive material has the advantages of high responsiveness, high response recovery speed, low detection lower limit and the like.
The gas-sensitive performance of the metal oxide semiconductor nano material has a great relationship with the surface activity and the surface state of the material, and the morphology, the size and the surface modification of the material can influence the surface activity and the catalytic activity of the material. In general, composite sensitive materials, while exhibiting the physicochemical properties possessed by phase-pure materials, may also exhibit unique properties superior to their single component materials. Due to different work functions, n-n, p-p and n-p heterojunction structures can be formed at an interface when two semiconductor oxide sensitive materials are compounded, and due to different Fermi level positions of the two materials, carriers of the material at one end are transferred to the other end, a space charge layer is formed at the interface, so that energy bands are bent to generate potential barriers. Because the transfer of the current carrier in the material needs to cross the interface potential barrier, the mobility of the current carrier is directly influenced, the resistance of the material is further influenced, the reaction capability of the material and the gas is improved, and the sensitivity characteristic of the material to the gas is improved.
Indium (In) oxide 2 O 3 ) The material is a common n-type semiconductor material, the forbidden band width of the material is 3.55-3.75 eV, and the material has good gas-sensitive performance to formaldehyde gas. And neodymium oxide (Nd) 2 O 3 ) The band gap of the crystal is 4.7 eV, and the crystal has stronger activity. Thus, by pairing In 2 O 3 Nd of sensitive material 2 O 3 Modification, because a p-n junction is formed between the two, the responsivity and the stability of the gas sensor in the process of detecting formaldehyde gas can be further improved.
Disclosure of Invention
The invention aims to provide a formaldehyde gas sensor based on a neodymium oxide modified indium trioxide rod-shaped composite material and a preparation method thereof. The method is simple, low in cost and low in equipment requirement, is suitable for mass production, can improve the gas sensitivity of the gas sensor to formaldehyde gas, and has important practical value.
The invention relates to a formaldehyde gas sensor based on a neodymium oxide modified indium trioxide rod-shaped composite material, which is composed of Al with Pd metal interdigital electrodes 2 O 3 Substrate, Pd-coated metal interdigital electrode and Al 2 O 3 A layer of sensitive material on a substrate.
The invention relates to a preparation method of a formaldehyde gas sensor based on a neodymium oxide modified indium trioxide rod-shaped composite material, which comprises the following steps:
1. and (3) processing the Pd metal interdigital electrode:
respectively wiping Al with Pd metal interdigital electrode by using acetone and ethanol cotton balls 2 O 3 Cleaning the substrate, and then putting Al with Pd metal interdigital electrode 2 O 3 Sequentially placing the substrate in acetone, ethanol and deionized water, respectively ultrasonically cleaning for 5-10 minutes, and finally drying at 100-120 ℃;
the invention uses the silk-screen printing technology to print Al 2 O 3 The method for preparing the Pd metal interdigital electrode on the substrate comprises the following steps: mixing the ink [ Jiahua JX07500487]Pd powder and a diluent are mixed according to the proportion of 1: 1: 2, mixing and stirring to prepare paste; then, injecting the paste on a silk screen plate with an interdigital electrode pattern, scraping the paste under the conditions of an inclination angle of 30-45 degrees and a pressure of 5-10 newtons, and adding Al 2 O 3 Printing interdigital electrodes on a substrate, drying, and curing by ultraviolet light to finish the preparation of the Pd metal interdigital electrodes, wherein the width and the electrode spacing of the Pd metal interdigital electrodes are 0.15-0.20 mm, the thickness is 100-150 nm, and the number of pairs of interdigital electrodes is 5-10.
2. Pure In 2 O 3 Micron rod, Nd 2 O 3 Modified In 2 O 3 Preparing a formaldehyde gas sensor made of a rod-shaped composite material:
(1) preparing a pure indium oxide precursor: firstly, dissolving 0.60-0.62 g of anhydrous indium nitrate and 0.39-0.41 g of terephthalic acid in a mixed solution consisting of 10-15 mL of ethanol and 30-35 mL of N, N-dimethylformamide, and stirring for 2-3 h; then transferring the obtained mixed solution into a counter-pressure kettle, and carrying out hydrothermal reaction at 100-110 ℃ for 18-24 h; finally, centrifugally cleaning the reaction product by using ethanol, and drying the centrifugal product at 60-80 ℃ to obtain white pure indium oxide precursor powder, namely CPP-3(In) powder;
(2) pure In 2 O 3 Preparing the micron rods: annealing the CPP-3(In) powder obtained In the step (1) at 480-500 ℃ for 2-3 h to obtain yellow pure In 2 O 3 A micron rod;
(3)Nd 2 O 3 modified In 2 O 3 Preparation of a rod-shaped composite material:
firstly, dissolving 2-3 mL and 14-16 mol/L concentrated nitric acid in 8-12 mL of water, adding 0.82-0.84 g of neodymium oxide, and stirring until the neodymium oxide is completely dissolved; then dropwise adding 10-12 mL of 9-11% by mass of sodium hydroxide solution until white precipitate appears; then transferring the obtained mixed solution into a counter-pressure kettle, and carrying out hydrothermal reaction at 160-180 ℃ for 10-12 hours; and then centrifugally cleaning the reaction product by using ethanol, and drying the centrifugal product at the temperature of 60-80 ℃ to obtain purple Nd (OH) 3 A precursor powder;
100-110 mg of CPP-3(In) powder obtained In the step (1) and 2-10 mg of Nd (OH) are taken 3 Placing the precursor powder in 40-45 mL of ethanol solution, performing ultrasonic treatment for 0.25-0.5 h, and centrifuging; drying the centrifugal product at 60-80 ℃, and then annealing at 480-500 ℃ for 2-3 h to obtain light green Nd 2 O 3 Modified In 2 O 3 A rod-shaped composite material.
3. Based on Nd 2 O 3 Modified In 2 O 3 Preparing a formaldehyde gas sensor made of a rod-shaped composite material:
adding Nd 2 O 3 Modified In 2 O 3 Putting the rod-shaped composite material into a mortar, and grinding for 20-30 minutes to obtain nano material powder; then, dropping deionized water into the mortar, and continuing grinding for 20-30 minutes to obtain viscous slurry; the mass ratio of the nano material powder to the deionized water is 5: 1-3; dipping a small amount of slurry by using a hairbrush, and coating the slurry on Al with Pd metal interdigital electrodes 2 O 3 On the substrate, the Pd metal interdigital electrode and Al are completely covered by the slurry 2 O 3 A substrate;then drying at 60-80 ℃ to obtain Nd with the thickness of 2-4 mu m 2 O 3 Modified In 2 O 3 A rod-like composite material sensitive layer; finally, aging for 48-72 hours under the direct current of 80-120 mA in the environment with the relative humidity of 20-40% RH and the temperature of 20-35 ℃, thereby obtaining the Nd-based material 2 O 3 Modified In 2 O 3 A formaldehyde gas sensor made of a rod-shaped composite material.
The invention utilizes a CGS-1TP type gas-sensitive performance tester produced by Beijing Elite technology Limited to test the formaldehyde gas-sensitive performance.
Compared with the prior art, the invention has the advantages and positive effects that:
in the invention, In derived from Metal Organic Framework (MOF) 2 O 3 Not only the morphology of the precursor is kept, but also the specific surface area is larger. Passing through Nd 2 O 3 After modification, on one hand, the specific surface area of the material is increased due to the existence of neodymium oxide, a large number of surface active sites are formed, and more formaldehyde molecules can be adsorbed; on the other hand, the formation of the p-n heterojunction raises the initial resistance of the device, thereby enhancing the responsivity to formaldehyde. Meanwhile, the method has simple process, and the prepared formaldehyde gas sensor has small volume and is suitable for mass production, so the method has important application value for detecting formaldehyde gas. In a word, the invention not only has excellent detection performance for formaldehyde gas, but also has the advantages of simple preparation method, low cost, high response speed and being expected to produce in large scale.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a scanning electron micrograph of a pure indium oxide MOF precursor CPP-3 (In); the synthesized CPP-3(In) was observed to be a 10-20 μm micron rod, having a hexagonal prism shape as a whole and a smooth surface.
FIG. 2 shows pure In 2 O 3 Scanning electron microscope images of the micron rods; it can be seen that pure In 2 O 3 The micrometer rod inherits the morphological characteristics of an MOF precursor CPP-3(In), is still hexagonal prism-shaped, but is damaged after annealing, and has a smooth surface and a length of 5-15 micrometers.
FIG. 3 is based on Nd 2 O 3 Modified In 2 O 3 Scanning electron microscope images of the rod-shaped composite materials; it can be seen that the surface of the indium oxide becomes rough after the neodymium oxide is modified, and many rod-shaped neodymium oxides of 200 to 400 nm appear.
FIG. 4 is based on Nd 2 O 3 Modified In 2 O 3 XRD pattern of the rod-like composite; wherein, S1-S4 respectively represent indium oxide composite materials with different neodymium oxide modification amounts. As can be seen in (a), the XRD peaks of all samples match those of the standard card JCPDS:06-0416 of indium oxide; and (b) is a partially enlarged XRD pattern, and it can be seen that the (222) peak of neodymium oxide standard card JCPDS:21-0579 gradually appears in XRD diffraction peaks along with the increase of neodymium content. But its peak is weaker, probably due to the smaller content of neodymium oxide. In addition, no other impurity peaks were observed. Therefore, the synthesized materials S2, S3, and S4 include only indium oxide and neodymium oxide.
FIG. 5 is based on Nd 2 O 3 Modified In 2 O 3 XPS plots of rod composites; the full spectrum of sample S3 In FIG. (a) shows that S3 contains only three elements of Nd, In and O. Plot (b) is the In 3d spectrum for samples S1 and S3, which shows pure indium oxide (S1) and based on Nd 2 O 3 Modified In 2 O 3 Rod-like composite materials (S3), In 3d thereof 3/2 Peak sum In 3d 5/2 The peaks are shifted by 0.3eV, which shows that a heterojunction is formed between the neodymium oxide and the indium oxide, and the characteristic peaks are shifted. In the graph (c), which is a spectrum of Nd 3d of the sample S3, two peaks appearing at 998.76eV and 975.65eV are observed, corresponding to Nd 3d 3/2 And Nd 3d 5/2 They areBelong to Nd 3+ Characteristic peak of (2).
FIG. 6 is a schematic view of a device fabricated according to the present invention; from bottom to top in the order of Al 2 O 3 Substrate 1, Pd metal interdigital electrode 3, Pd metal interdigital electrode and Al coated on 2 O 3 Nd-based on substrate 2 O 3 Modified In 2 O 3 The sensitive material layer 2 of the rod-shaped composite material.
FIG. 7 is a graph of responsivity versus formaldehyde concentration characteristics for devices S1 and S3 of the present invention at an operating temperature of 119 ℃; responsivity (R) of gas sensor a /R g ) Defined as the resistance R of the sensor in air a And resistance R in Formaldehyde g The ratio of (a) to (b). As shown in FIG. 7, when the operating temperature is 119 ℃ and the formaldehyde gas is changed within the range of 1-100 ppm, the responsivity of the gas sensors S3 and S1 is increased along with the increase of the formaldehyde concentration. In addition, it can be observed that the response of sample S3 is much higher than that of sample S1 due to the p-n junction formed between the neodymium oxide and the indium oxide, pulling up the initial resistance of the sensor, which shows a more pronounced change in resistance when encountering formaldehyde.
FIG. 8 is a graph of the responsivity of a device of the invention to 100ppm formaldehyde at different temperatures; the optimal operating temperature for the four devices was found to be 119 c. Among them, the sensor showed the highest response to formaldehyde at 119 ℃ with a neodymium oxide modification amount of 5mg (device S3).
FIG. 9 is a graph showing the recovery curves of the response of the devices S1 to S4 according to the present invention at an operating temperature of 119 ℃ and a formaldehyde gas concentration of 100 ppm. It can be seen that the response time of devices S2 to S4 was shortened and the recovery time was significantly accelerated compared to device S1 after modification of the neodymium oxide. The response recovery time of S3 is the shortest, and is 3S and 12S, respectively.
FIG. 10 is a schematic representation of the selectivity of the devices S1-S4 of the present invention at an operating temperature of 119 deg.C and a test gas concentration of 100 ppm. It can be found that the devices S1-S4 all have excellent selectivity to formaldehyde.
Detailed Description
Next, the technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the drawings in the embodiments of the present invention. It should be apparent that the described embodiments are only a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived from the embodiments of the present invention by a person skilled in the art without any creative effort, should be included in the protection scope of the present invention.
Examples 1 to 2:
1. and (3) processing the Pd metal interdigital electrode:
respectively wiping Al with Pd metal interdigital electrode by using acetone and ethanol cotton balls 2 O 3 Cleaning the substrate, and then putting Al with Pd metal interdigital electrode 2 O 3 The substrate is sequentially placed in acetone, ethanol and deionized water, respectively cleaned by ultrasonic for 5 minutes, and finally dried in an environment of 100 ℃.
The invention uses the silk-screen printing technology to print Al 2 O 3 The method for preparing the Pd metal interdigital electrode on the substrate comprises the following steps: mixing the ink [ Jiahua JX07500487]Pd powder and a diluent are mixed according to the proportion of 1: 1: 2, mixing and stirring to prepare paste; then, the paste was poured onto a screen plate having an interdigital electrode pattern, scraped at an inclination angle of 30 ℃ and under a pressure of 5N, and applied to Al 2 O 3 Printing interdigital electrodes on a substrate, drying, and finishing the preparation of the Pd metal interdigital electrodes after ultraviolet curing, wherein the width and the electrode spacing of the Pd metal interdigital electrodes are both 0.15mm, the thickness is 150nm, and the number of pairs of interdigital electrodes is 5.
2. Pure In 2 O 3 Micron rod, Nd 2 O 3 Modified In 2 O 3 Preparing a formaldehyde gas sensor made of a rod-shaped composite material:
(1) preparing a pure indium oxide precursor: first, 0.6g of anhydrous indium nitrate and 0.4g of terephthalic acid were dissolved in a mixed solution composed of 10mL of ethanol and 30mL of N, N-dimethylformamide, and stirred for 2.5 hours. Then the mixed solution is transferred to a counter-pressure kettle and undergoes hydrothermal reaction for 24 hours at 100 ℃. And finally, centrifugally cleaning the reaction product by using ethanol, and drying the centrifugal product at 60 ℃ to obtain white pure indium oxide precursor powder, namely CPP-3(In) powder.
(2) Pure In 2 O 3 Preparing the micron rods: annealing the white CPP-3(In) powder obtained In the step (1) at the temperature of 500 ℃ for 3h to obtain yellow pure In 2 O 3 A micron rod.
(3)Nd 2 O 3 Modified In 2 O 3 Preparation of a rod-shaped composite material:
first, 2mL of 15mol/L concentrated nitric acid was dissolved in 8mL of water, and 0.84g of neodymium oxide was added thereto and stirred until all neodymium oxide was dissolved. Then, 10mL of 10% sodium hydroxide solution was added dropwise until a white precipitate appeared. The mixed solution was then transferred to a back pressure reactor and subjected to hydrothermal reaction at 180 ℃ for 12 hours. Then centrifugally washing the reaction product by ethanol, and drying the centrifugal product at 60 ℃ to obtain purple Nd (OH) 3 A precursor powder.
Taking 100mg of CPP-3(In) powder obtained In step (1) and 2mg of purple Nd (OH) 3 The powder was placed in 40mL of ethanol solution, sonicated for 0.5h and centrifuged. Drying the centrifugal product at 60 ℃, and then annealing the centrifugal product at 500 ℃ for 3h to obtain light green Nd 2 O 3 Modified In 2 O 3 A rod-shaped composite material.
3. Preparing a formaldehyde gas sensor:
(1) based on pure In 2 O 3 Preparation of a formaldehyde gas sensor made of a rod-shaped material: 375mg of pure In was added 2 O 3 Putting the rod-shaped gas-sensitive material into a mortar, and grinding for 30 minutes to obtain powder of the nano material; and then, 150 mu L of deionized water is dripped into the mortar, and the grinding is continued for 30 minutes to obtain viscous slurry, wherein the mass ratio of the nano material to the deionized water is 5: 2; dipping a small amount of slurry by using a hairbrush, and coating the slurry on Al with Pd metal interdigital electrodes 2 O 3 Drying the substrate at 80 deg.C to obtain pure In with thickness of 2 μm on the surface of Pd metal interdigital electrode 2 O 3 A rod-shaped gas sensitive material sensitive layer; finally, aging the mixture for 48 hours under the direct current of 100mA In an environment with the relative humidity of 30 percent RH and the temperature of 25 ℃, thereby obtaining pure In 2 O 3 A gas sensor of rod-shaped material, labeled S1 (example 1).
(2) Based on Nd 2 O 3 Modified In 2 O 3 Preparing a formaldehyde gas sensor made of a rod-shaped composite material:
375mg of Nd 2 O 3 Modified In 2 O 3 Putting the rod-shaped composite material into a mortar, and grinding for 30 minutes to obtain powder of the nano material; then 150 mul of deionized water is dripped into the mortar, and the mixture is ground for 30 minutes to obtain viscous slurry; the mass ratio of the nano material to the deionized water is 5: 2; dipping a small amount of slurry by using a hairbrush, and coating the slurry on Al with Pd metal interdigital electrodes 2 O 3 Drying the substrate at 80 deg.C, and coating on Al with Pd metal interdigital electrode 2 O 3 Nd with a thickness of 2 μm was obtained on the substrate 2 O 3 Modified In 2 O 3 A rod-like composite material sensitive layer; finally, the mixture is aged for 48 hours under the direct current of 100mA in an environment with the relative humidity of 30 percent RH and the temperature of 25 ℃, thereby obtaining the Nd-based alloy 2 O 3 Modified In 2 O 3 A formaldehyde gas sensor of a rod composite, designated S2 (example 2).
After the gas sensor is prepared, the formaldehyde gas-sensitive performance of the gas sensor is tested. (the invention uses CGS-1TP type gas-sensitive performance tester produced by Beijing Elite technology Limited company to test the formaldehyde gas-sensitive performance.)
Example 3
The Pd metal interdigital electrode is processed in the same way as in example 2.
Preparation of pure indium oxide MOF precursors CPP-3(In) and Nd (OH) by hydrothermal method 3 The experimental procedure for the precursors was the same as in example 2.
Nd 2 O 3 The modification process comprises the following steps: first, 100mg of white CPP-3(In) powder and 5mg of purple Nd (OH) 3 The powder was placed in 40mL of ethanol solution, sonicated for 0.5h and centrifuged. Drying the centrifuged product at 60 ℃, and then annealing the dried product at 500 ℃ for 3 hours to obtain light green Nd 2 O 3 Modified In 2 O 3 A rod-shaped composite material.
Nd 2 O 3 Modified In 2 O 3 Preparing a formaldehyde gas sensor made of a rod-shaped composite material: the experimental procedure was as in example 2, and a device prepared based on this material was labeled as S3 (example 3).
Example 4
The Pd metal interdigital electrode is processed in the same way as in example 2.
Preparation of pure indium oxide MOF precursors CPP-3(In) and Nd (OH) by hydrothermal method 3 The experimental procedure for the precursors was the same as in example 2.
Nd 2 O 3 The modification process comprises the following steps: first, 100mg of white CPP-3(In) powder and 10mg of purple Nd (OH) 3 The powder was placed in 40mL of ethanol solution, sonicated for 0.5h and centrifuged. Drying the centrifugal product at 60 ℃, and then annealing the centrifugal product at 500 ℃ for 3h to obtain light green Nd 2 O 3 Modified In 2 O 3 A rod-shaped composite material.
Nd 2 O 3 Modified In 2 O 3 Preparing a formaldehyde gas sensor made of a rod-shaped composite material: the experimental procedure was as in example 2, and a device prepared based on this material was labeled as S4 (example 4).
Nd prepared in examples 1 to 4 2 O 3 Modified In 2 O 3 The gas-sensitive performance of the gas sensor taking the rod-shaped composite material as the sensitive layer and Pd as the metal Pd metal interdigital electrode is tested by a CGS-1TP type gas-sensitive performance tester of Elite technologies, Inc. of Beijing.
After the gas sensor is prepared, the formaldehyde gas-sensitive performance of the gas sensor is tested.
At 119.21 deg.C, the responsivity of device S1 to 100ppm formaldehyde was 33.75 with a response time of 5S. At 119.21 deg.C, the device S2 had a response of 324.3 to 100ppm formaldehyde with a response time of 3S. At 119.21 deg.C, the device S3 had a response of 850.3 to 100ppm formaldehyde with a response time of 3S. At 119.21 deg.C, the device S4 had a response of 534.4 to 100ppm formaldehyde with a response time of 4S.
The above description is only an embodiment of the present invention, and the scope of the present invention should not be limited thereto, but all equivalent changes and modifications made within the scope of the present invention should still fall within the scope covered by the present invention.
Claims (5)
1. A formaldehyde gas sensor based on neodymium oxide modified rod-shaped indium oxide composite material is composed of Al with Pd metal interdigital electrode 2 O 3 Substrate, Pd-coated metal interdigital electrode and Al 2 O 3 Sensitive material layer composition on a substrate, characterized by: the sensitive material is an indium oxide rod-shaped composite material modified based on neodymium oxide and is prepared by the following steps,
(1) preparing a pure indium oxide precursor: firstly, dissolving 0.60-0.62 g of anhydrous indium nitrate and 0.39-0.41 g of terephthalic acid in a mixed solution consisting of 10-15 mL of ethanol and 30-35 mL of N, N-dimethylformamide, and stirring for 2-3 h; then transferring the obtained mixed solution into a counter-pressure kettle, and carrying out hydrothermal reaction at 100-110 ℃ for 18-24 h; finally, centrifugally cleaning the reaction product by using ethanol, and drying the centrifugal product at 60-80 ℃ to obtain white pure indium oxide precursor powder, namely CPP-3(In) powder;
(2)Nd 2 O 3 modified In 2 O 3 Preparation of a rod-shaped composite material: firstly, dissolving 2-3 mL and 14-16 mol/L concentrated nitric acid in 8-12 mL of water, adding 0.82-0.84 g of neodymium oxide, and stirring until the neodymium oxide is completely dissolved; then dropwise adding 10-12 mL of 9-11% by mass of sodium hydroxide solution until white precipitate appears; then transferring the obtained mixed solution into a counter-pressure kettle, and carrying out hydrothermal reaction at 160-180 ℃ for 10-12 hours; and centrifugally cleaning the reaction product by using ethanol, and drying the centrifugal product at the temperature of 60-80 ℃ to obtain purple Nd (OH) 3 A precursor powder;
(3) 100-110 mg of CPP-3(In) powder obtained In the step (1) and 2-10 mg of Nd (OH) obtained In the step (2) 3 Placing the precursor powder in 40-45 mL of ethanol solution, performing ultrasonic treatment for 0.25-0.5 h, and centrifuging; drying the centrifugal product at 60-80 ℃, and then annealing at 480-500 ℃ for 2-3 h to obtain light green Nd 2 O 3 Modified In 2 O 3 A rod-shaped composite material.
2. The formaldehyde gas sensor based on the neodymium oxide modified indium oxide rod-shaped composite material as claimed in claim 1, wherein: the thickness of the sensitive material layer is 2-4 mu m.
3. The formaldehyde gas sensor based on the neodymium oxide modified indium oxide rod-shaped composite material as claimed in claim 1, wherein: the width and the electrode spacing of the Pd metal interdigital electrode are both 0.15-0.20 mm, the thickness is 100-150 nm, and the number of pairs of interdigital electrodes is 5-10.
4. The method for preparing the formaldehyde gas sensor based on the neodymium oxide modified indium oxide rod-shaped composite material according to any one of claims 1 to 3, which comprises the following steps:
(1) and (3) processing the Pd metal interdigital electrode:
respectively wiping Al with Pd metal interdigital electrode by using acetone and ethanol cotton balls 2 O 3 Cleaning the substrate, and then putting Al with Pd metal interdigital electrode 2 O 3 Sequentially placing the substrate in acetone, ethanol and deionized water, respectively ultrasonically cleaning for 5-10 minutes, and finally drying at 100-120 ℃;
(2) based on Nd 2 O 3 Modified In 2 O 3 Preparing a formaldehyde gas sensor made of a rod-shaped composite material:
adding Nd 2 O 3 Modified In 2 O 3 Putting the rod-shaped composite material into a mortar, and grinding for 20-30 minutes to obtain nano material powder; then, dripping deionized water into the mortar, and continuously grinding for 20-30 minutes to obtain viscous slurry; dipping a small amount of slurry by using a hairbrush, and coating the slurry on Al with Pd metal interdigital electrodes 2 O 3 On the substrate, the Pd metal interdigital electrode and Al are completely covered by the slurry 2 O 3 A substrate; then drying at 60-80 ℃ to obtain Nd 2 O 3 Modified In 2 O 3 A rod-like composite material sensitive layer; finally, aging for 48-72 hours under the direct current of 80-120 mA in the environment with the relative humidity of 20-40% RH and the temperature of 20-35 ℃, thereby obtaining the Nd-based material 2 O 3 Modified In 2 O 3 A formaldehyde gas sensor made of a rod-shaped composite material.
5. The method for preparing the formaldehyde gas sensor based on the neodymium oxide modified indium trioxide rod-shaped composite material as claimed in claim 4, wherein the method comprises the following steps: in the step (2), the mass ratio of the nano material powder to the deionized water is 5: 1 to 3.
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