CN115290704A - Preparation method of NiCo2O4-In2O3 composite gas-sensitive material formaldehyde sensor - Google Patents

Preparation method of NiCo2O4-In2O3 composite gas-sensitive material formaldehyde sensor Download PDF

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CN115290704A
CN115290704A CN202210393111.8A CN202210393111A CN115290704A CN 115290704 A CN115290704 A CN 115290704A CN 202210393111 A CN202210393111 A CN 202210393111A CN 115290704 A CN115290704 A CN 115290704A
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孟丹
康嘉琪
伞晓广
张磊
谢宗昇
张越
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Shenyang University of Chemical Technology
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    • 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 preparation method of a NiCo2O4-In2O3 composite gas-sensitive material formaldehyde sensor relates to a preparation method of a formaldehyde sensor, and adopts a simple and efficient two-step hydrothermal method In the design and preparation process of a gas-sensitive material, and constructs NiCo by changing the ratio of raw materials 2 O 4 ‑In 2 O 3 The composite material has an optimal structure, so that the composite material has excellent application performance. The whole production process has the advantages of simple process, low cost, good controllability, no toxicity and no harm, and the prepared material has high purity, good crystallization and good dispersibility, and is suitable for large-scale industrial production. NiCo prepared by the invention 2 O 4 ‑In 2 O 3 The composite material has higher sensitivity, good selectivity and stability to formaldehyde at room temperature, and has wide application prospect in the aspect of detecting organic volatile gas in indoor environment.

Description

Preparation method of NiCo2O4-In2O3 composite gas-sensitive material formaldehyde sensor
Technical Field
The invention relates to a preparation method of a formaldehyde sensor, in particular to a preparation method of a NiCo2O4-In2O3 composite gas-sensitive material formaldehyde sensor.
Background
Formaldehyde is a colorless gas, has a very strong pungent taste, is very easy to volatilize, and is a carcinogen with strong toxicity. Formaldehyde has been identified by the world health organization as an intangible substance that causes deformity, leading to cancer. Formaldehyde is recognized as a highly-polluted and highly-toxic chemical product in China, and can cause very strong stimulation to the skin, mucous membranes, eyes and the like of people, possibly cause the problem of system dysfunction, possibly cause the problem of damage to nerve centers and livers, and cause the problems of deformity, chronic respiratory diseases, leukemia, nasopharyngeal carcinoma, acute dysthymia, female menstrual disorder and the like of fetuses. Therefore, the method has very important significance for effectively and real-timely monitoring the concentration of the formaldehyde.
In recent years, with the rapid development of the internet of things, the gas sensor has a huge application prospect in the fields of industrial production safety detection, atmospheric environmental pollution monitoring, intelligent mobile terminals, emerging intelligent homes and the like. The metal oxide semiconductor gas sensor has low cost and excellent gas-sensitive property, and is widely used as a commercial gas sensor, but the metal oxide semiconductor gas sensor still has the defects of high working temperature, poor selectivity, poor stability and the like, so that the requirement of obtaining environmental information and integrating the environmental information into the technology of the internet of things cannot be met. Therefore, the room-temperature metal oxide gas sensor with low power consumption, integration and intelligence is developed, the toxic, combustible and explosive gases are identified and detected, and new vitality can be injected into the environment monitoring field in the era of the Internet of things.
Indium oxide (In) 2 O 3 ) Is an n-type semiconductor material having a direct bandgap of 3.55-3.75 eV and an indirect bandgap of 2.62 eV. Due to In 2 O 3 Has good conductivity, unique gas adsorption and catalysis characteristics, low electron affinity and wide application prospect in the field of microelectronics. Thus, in is utilized 2 O 3 As a gas sensitive material, the gas sensitive material has important commercial value for researching the sensitive performance of the gas sensitive material to formaldehyde and other volatile organic compounds. With the rise and vigorous development of nanotechnology, advanced nano-technology is utilizedTechnique, synthesis of In with excellent Properties 2 O 3 The nano-structure sensitive material and the design and construction of the gas sensing platform by regulating and controlling the microstructure and the composition of the material are effective technical means for improving the gas sensitivity performance.
Disclosure of Invention
The invention aims to provide a preparation method of a NiCo2O4-In2O3 composite gas-sensitive material formaldehyde sensor, and NiCo assembled by nano sheets is prepared by a hydrothermal synthesis method 2 O 4 -In 2 O 3 The material has good detection characteristic on formaldehyde gas, has the greatest advantage of room temperature detection, provides a simple and quick technical means for on-site on-line monitoring of indoor air pollutants, has simple equipment, low cost and high product purity, and is suitable for large-scale industrial production.
The purpose of the invention is realized by the following technical scheme:
the invention has the advantages and effects that:
(1) The method takes indium chloride, cobalt nitrate, nickel nitrate and urea as raw materials to prepare NiCo by a two-step hydrothermal method 2 O 4 -In 2 O 3 A composite material. The method has the advantages of low cost, good controllability, high purity of the prepared material, good crystallization and good dispersibility, and is suitable for large-scale industrial production.
(2) The NiCo prepared by the invention 2 O 4 -In 2 O 3 The gas sensor prepared by the composite material as the gas sensitive material has higher sensitivity, good selectivity and stability to formaldehyde at room temperature, and has wide application prospect in the aspect of detecting organic volatile gas in indoor environment.
(3) NiCo prepared by the invention 2 O 4 -In 2 O 3 The formaldehyde gas sensor has simple manufacturing process and low cost, and is suitable for industrial mass production.
Drawings
FIG. 1 is a schematic structural view of a formaldehyde sensor according to the present invention;
FIG. 2 is a graph showing the sensitivity of the gas sensor of the present invention to 10 ppm of formaldehyde gas at room temperature;
FIG. 3 is a graph showing the response recovery of a sensor according to example 3 of the present invention to 10 ppm of formaldehyde gas at room temperature;
FIG. 4 is a graph showing the selectivity of a sensor according to example 3 of the present invention to 10 ppm of gas at room temperature.
Detailed Description
The present invention will be described in detail with reference to the embodiments shown in the drawings.
The starting raw materials of the invention are cheap and easily available indium chloride, cobalt nitrate, nickel nitrate and urea, and the raw materials are treated by hydrothermal reaction, centrifugation, washing, drying, calcination and the like. Mixing NiCo 2 O 4 -In 2 O 3 The gas sensor prepared from the composite material has a unique spatial structure, and shows high sensitivity, good selectivity and good stability to formaldehyde at a low working temperature.
NiCo 2 O 4 -In 2 O 3 The preparation method of the composite material comprises the following steps:
the method comprises the following steps: weighing indium chloride and terephthalic acid, dissolving the indium chloride and the terephthalic acid in a 10 mLN, N-dimethylacetamide solution, adding an anhydrous sodium acetate solution, and stirring all mixed solutions for 30 minutes at 100 ℃ by using a constant-temperature water bath to obtain a precursor reaction solution;
step two: centrifugally separating the solution reacted in the step one to obtain a reaction product, and repeatedly washing the reaction product by using distilled water and absolute ethyl alcohol; then putting the washed reaction product into a drying oven with constant temperature, drying at 60 ℃ for 12 hours to obtain white powder;
step three: adding deionized water into the powder obtained in the step two for ultrasonic treatment, then adding nickel nitrate, cobalt nitrate and urea, and stirring all mixed solutions for 30 minutes by using a constant-temperature water bath kettle at 100 ℃ to obtain a reaction product;
step four: centrifugally separating the solution obtained after the reaction in the step three to obtain a reaction product, and repeatedly washing the reaction product by using distilled water and absolute ethyl alcohol;
step five: putting the reaction product washed in the step four into a drying box with constant temperature, drying at 60 ℃ for 12 hours, and cooling after drying;
step six: putting the product dried in the fifth step into a clean crucible, putting the crucible into a muffle furnace, and calcining for 4 hours at 500 ℃ to obtain NiCo 2 O 4 -In 2 O 3 Composite material, which is stored in a desiccator to be assayed.
Example 1
Preparation of In 2 O 3 Material
The method comprises the following steps: weighing indium chloride 0.3810 g and terephthalic acid 0.1661 g, dissolving the indium chloride 0.3810 g and the terephthalic acid 0.1661 g in 10 mL of N, N-dimethylacetamide solution, adding anhydrous sodium acetate solution, and stirring all mixed solutions for 30 minutes at 100 ℃ in a constant-temperature water bath to obtain precursor reaction solution;
step two: centrifugally separating the solution reacted in the step one to obtain a reaction product, and repeatedly washing the reaction product by using distilled water and absolute ethyl alcohol; then putting the washed reaction product into a drying oven with constant temperature, drying at 60 ℃ for 12 hours to obtain white powder;
step three: putting the product dried In the step two into a clean crucible, putting the crucible into a muffle furnace, and calcining for 4 hours at 500 ℃ to obtain In 2 O 3 The material, which is stored in a desiccator to be assayed.
Example 2
Preparation of NiCo 2 O 4 -In 2 O 3 Composite material
The method comprises the following steps: weighing indium chloride 0.3810 g and terephthalic acid 0.1661 g, dissolving the indium chloride 0.3810 g and the terephthalic acid 0.1661 g in a 10 mLN, N-dimethylacetamide solution, adding an anhydrous sodium acetate solution, and stirring all mixed solutions for 30 minutes at 100 ℃ by using a constant-temperature water bath to obtain a precursor reaction solution;
step two: centrifugally separating the solution reacted in the step one to obtain a reaction product, and repeatedly washing the reaction product by using distilled water and absolute ethyl alcohol; then putting the washed reaction product into a drying oven with constant temperature, drying at 60 ℃ for 12 hours to obtain white powder;
step three: adding deionized water into the powder 0.0895 g obtained in the second step for ultrasonic treatment, then adding nickel nitrate 0.0020 g, cobalt nitrate 0.0073 g and urea 0.0112 g, and stirring all mixed solutions for 30 minutes at 100 ℃ by using a constant-temperature water bath to obtain a reaction product;
step four: centrifugally separating the solution obtained after the reaction in the step three to obtain a reaction product, and repeatedly washing the reaction product by using distilled water and absolute ethyl alcohol;
step five: putting the reaction product washed in the step four into a drying oven with constant temperature, drying at 60 ℃ for 12 hours, and cooling after drying;
step six: putting the product dried in the fifth step into a clean crucible, putting the crucible into a muffle furnace, and calcining for 4 hours at 500 ℃ to obtain NiCo 2 O 4 -In 2 O 3 Composite material, which is stored in a desiccator to be assayed.
Example 3
Preparation of NiCo 2 O 4 -In 2 O 3 Composite material
The first, second, fourth, fifth and sixth steps are the same as those of the example 2.
Step three: adding deionized water into the powder 0.0895 g obtained in the second step for ultrasonic treatment, then adding nickel nitrate 0.0045 g, cobalt nitrate 0.0014 g and urea 0.0219 g, and stirring all mixed solutions for 30 minutes at 100 ℃ by using a constant-temperature water bath to obtain a reaction product;
example 4
Preparation of NiCo 2 O 4 -In 2 O 3 Composite material
The first, second, fourth, fifth and sixth steps are the same as those of the embodiment 2.
Step three: adding deionized water into the powder 0.0895 g obtained in the second step for ultrasonic treatment, then adding nickel nitrate 0.0045 g, cobalt nitrate 0.0014 g and urea 0.0219 g, and stirring all mixed solutions for 30 minutes at 100 ℃ by using a constant-temperature water bath to obtain a reaction product;
to obtain NiCo 2 O 4 -In 2 O 3 The composite material product is prepared into a gas sensor, and the gas sensor is used for carrying out related gas-sensitive performance test on formaldehyde:
weighing a certain amount of NiCo 2 O 4 -In 2 O 3 CompoundingThe material product is added with water to prepare slurry, and the slurry is coated on an alumina ceramic tube, two gold electrodes and four platinum leads are arranged on the alumina ceramic tube, and a nickel-chromium heating wire is arranged in the tube. The ceramic tube was welded to a six-legged base to produce a gas sensor element, as shown in fig. 1.
The sensitivity profile of the gas sensor to 10 ppm formaldehyde gas at room temperature is shown in fig. 2. As is apparent from the figure, several gas sensors all have response characteristics to formaldehyde gas at room temperature, and the sensitivities of the sensors are respectively embodiment 1 sensor 2.6, embodiment 2 sensor 2.9 and embodiment 3 sensor 3.1; example 4 sensor 2. By comparison, the sensor of example 3 exhibited more excellent response characteristics. The sensor of example 3 was chosen here as the best sensor for further analysis of its sensitivity performance. FIG. 3 is a graph showing the response-recovery curve of the sensor of example 3 for 10 ppm of formaldehyde gas at room temperature. As can be seen, the sensor of example 3 has good response-recovery characteristics for formaldehyde. Fig. 4 shows the results of the gas selectivity test of the sensor of example 3 to 6 gas of 10 ppm at room temperature, and it can be seen that the sensitivity of the sensor to formaldehyde gas is higher than that of methanol, ethanol, toluene, benzene, acetone gas, indicating that the sensor has excellent selectivity to formaldehyde.

Claims (1)

1. NiCo 2 O 4 -In 2 O 3 The preparation method of the composite gas-sensitive material formaldehyde sensor is characterized by comprising the following preparation processes:
preparation of NiCo 2 O 4 -In 2 O 3 The composite material comprises the following steps:
(1) Weighing indium chloride and terephthalic acid, dissolving the indium chloride and the terephthalic acid in 10 mL of N, N-dimethylacetamide solution, adding anhydrous sodium acetate solution, and stirring all mixed solutions for 30 minutes at 100 ℃ in a constant-temperature water bath to obtain precursor reaction solution;
(2) Centrifugally separating the reacted solution to obtain a reaction product, and repeatedly washing the reaction product by using distilled water and absolute ethyl alcohol; then putting the washed reaction product into a drying oven with constant temperature, drying at 60 ℃ for 12 hours to obtain white powder;
(3) Adding deionized water into the powder for ultrasonic treatment, then adding nickel nitrate, cobalt nitrate and urea, and stirring all mixed solutions for 30 minutes by using a constant-temperature water bath kettle at 100 ℃ to obtain a reaction product;
(4) Centrifugally separating the reacted solution to obtain a reaction product, and repeatedly washing the reaction product by using distilled water and absolute ethyl alcohol;
(5) Putting the washed reaction product into a drying box with constant temperature, drying at 60 ℃ for 12 hours, and cooling after drying;
(6) Putting the dried product into a clean crucible, putting the crucible into a muffle furnace, and calcining for 4 hours at 500 ℃ to obtain NiCo 2 O 4 -In 2 O 3 A composite material, which is stored in a desiccator to be analyzed and detected;
mixing the NiCo with the mixture 2 O 4 -In 2 O 3 The composite material is used as a gas sensitive material to manufacture a gas sensor, and the steps are as follows:
(1) Mixing NiCo with a solvent 2 O 4 -In 2 O 3 Adding water into the composite material to prepare slurry, and coating the slurry on the outer wall of an alumina ceramic tube with two gold electrodes and four platinum leads;
(2) The nickel-chromium alloy heating wire penetrates through the alumina ceramic tube stuck with the sample, and the heating wire is parallel to the ceramic tube and is far away from the ceramic tube;
(3) Respectively welding four electric leads of the ceramic tube and two ends of the heating wire on the six-pin base to obtain a gas sensor element;
(4) A WS-30A gas-sensitive tester is adopted to test the gas sensitivity characteristic of the sensor; the test temperature was room temperature.
CN202210393111.8A 2022-04-15 2022-04-15 Preparation method of NiCo2O4-In2O3 composite gas-sensitive material formaldehyde sensor Pending CN115290704A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117949500A (en) * 2024-01-09 2024-04-30 兰州理工大学 Preparation and application of high-response zinc cobaltate/indium trioxide composite gas-sensitive material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117949500A (en) * 2024-01-09 2024-04-30 兰州理工大学 Preparation and application of high-response zinc cobaltate/indium trioxide composite gas-sensitive material

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