CN113325041A - DMMP sensor based on gold-modified oxygen vacancy-rich tin dioxide and preparation method thereof - Google Patents
DMMP sensor based on gold-modified oxygen vacancy-rich tin dioxide and preparation method thereof Download PDFInfo
- Publication number
- CN113325041A CN113325041A CN202110597879.2A CN202110597879A CN113325041A CN 113325041 A CN113325041 A CN 113325041A CN 202110597879 A CN202110597879 A CN 202110597879A CN 113325041 A CN113325041 A CN 113325041A
- Authority
- CN
- China
- Prior art keywords
- tin dioxide
- rich
- gold
- modified
- dmmp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Abstract
A resistance DMMP sensor of gold-modified tin dioxide nano material rich in oxygen vacancies with gas-sensitive response characteristics and a preparation method thereof belong to the technical field of gas sensors. The sensor is of a tubular structure, and two parallel and mutually separated annular Au electrodes Al are arranged on the outer surface of the sensor2O3The gas sensor comprises a ceramic tube substrate, a gold-modified oxygen vacancy-rich tin dioxide nano material gas sensitive film coated on the outer surface of the ceramic tube and the annular Au electrode, and a nichrome heating coil penetrating through the inside of the ceramic tube. The invention can realize the regulation and control of the composition, the structure and other properties of the gold-modified oxygen vacancy-rich tin dioxide nano material by controlling the reaction temperature, the reaction time and the proportion of the reaction precursor. The nano material has excellent gas-sensitive property to DMMP, high sensitivity and fast response recovery rate, and solves the problems of low sensitivity and incapability of recovery when a pure semiconductor oxide material is used for detecting DMMP.
Description
Technical Field
The invention belongs to the technical field of gas sensors, and particularly relates to a resistance DMMP sensor made of a gold-modified tin dioxide nano material rich in oxygen vacancies and having gas-sensitive response characteristics and a preparation method thereof.
Background
The organophosphorus compound refers to a phosphoric acid or phosphate ester derivative containing organic functional groups, and can strongly inhibit the biological activity of acetylcholine enzyme in organisms, so that the nervous system of the organisms is disturbed and even dies. Organophosphorus compounds are used as nerve agents on battlefields, for example, sarin, tabun, soman, etc., on the basis of their very high toxicity. Meanwhile, the organic phosphorus compound is a high-efficiency pesticide commonly used in the agricultural field, such as dichlorvos, dimethoate and the like. Dimethyl methylphosphonate (DMMP) is a common additive type organophosphorus flame retardant, the molecular structure of which has a chemical structure similar to that of organic phosphorus compounds such as sarin and the like, and the DMMP is commonly used as a simulant of organic pesticides such as sarin and organic phosphorus compounds for research. Therefore, in recent years, a DMMP detection technique with high sensitivity, portability and high speed is urgently needed by chemical defense departments and environmental protection departments.
At present, there are many methods for detecting DMMP, including gas chromatography, spectrophotometry, electrochemical analysis, colorimetry, quartz crystal microbalance, and the like. Although these methods can achieve quantitative analysis of DMMP concentration, these methods are generally time-consuming, dependent on equipment, complex to operate, and the like. The semiconductor oxide-based resistance type gas sensor has the advantages of convenience in preparation, low cost, wide source, small volume, high sensitivity and the like, and becomes a detection technology with a great application prospect in the field of gas detection. At present, tin dioxide, zinc oxide and other micro-nano materials are used for detecting DMMP, but a semiconductor oxide gas sensor has the problems of high detection limit, poor response recovery characteristic and the like when detecting DMMP. Therefore, a novel semiconductor oxide sensitive material is designed, the sensitive characteristic of the DMMP gas sensor is improved, and the obtained DMMP gas sensor with excellent performance has practical significance and great value on public safety and environmental safety.
Disclosure of Invention
The invention aims to provide a resistance type DMMP sensor based on a gold-modified tin dioxide nano material rich in oxygen vacancies and having high-sensitivity DMMP response characteristic and a preparation method thereof.
The invention relates to a resistance DMMP sensor based on a gold-modified tin dioxide nano material rich in oxygen vacancies, which has a tubular structure and is made of Al2O3Ceramic tube substrate coated with Al2O3Two parallel and separated annular Au electrodes coated on the outer surface of the ceramic tube substrate and coated with Al2O3Gas sensitive film on ceramic tube outer surface and annular Au electrode, penetrating Al2O3A nichrome heating coil inside the ceramic tube; the method is characterized in that: the gas sensitive film is a gold-modified oxygen vacancy-rich tin dioxide nano material, and is prepared by the following steps:
(1) heat-treating 5.0-10 g of commercial tin dioxide powder (national chemical group chemical Co., Ltd.) at 80-100 ℃ for 12-24 h under vacuum;
(2) adding the tin dioxide powder obtained in the step (1) into a toluene solution, wherein the volume of the toluene is 100-150 mL, and performing ultrasonic treatment to uniformly disperse the toluene; then adding 1.0-2.0 g of dimethyltin dichloride into the solution, and stirring for 2-3 hours at room temperature to obtain a mixed solution of dimethyltin dichloride and stannic oxide;
(3) adding 8-10 mL of triethylamine into the mixed solution of dimethyltin dichloride and stannic oxide obtained in the step (2), and continuously stirring at room temperature for 2-4 h; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain an organotitanane modified stannic oxide material;
(4) calcining the stannic oxide material modified by the organic stannane obtained in the step (3) at 500-600 ℃ for 2-4 h to obtain stannic oxide nano-material powder rich in oxygen vacancies;
(5) adding 1-5 g of the oxygen vacancy-rich tin dioxide powder obtained in the step (4) into water, wherein the volume of the water is 80-100 mL, and performing ultrasonic treatment to uniformly disperse the water; then adding 1-2 mL of chloroauric acid aqueous solution into the solution, wherein the concentration of the chloroauric acid aqueous solution is 10-20 mM, and stirring at room temperature for 1-2 h to obtain a mixed solution of chloroauric acid and oxygen vacancy-enriched stannic oxide;
(6) adding 30-50 mg of sodium borohydride into the mixed solution of chloroauric acid and oxygen-rich vacancy tin dioxide obtained in the step (5), and stirring at room temperature for 0.2-0.3 h; and carrying out centrifugal separation, ethanol washing and drying on the solution to obtain the gold-modified tin dioxide material rich in oxygen vacancies.
Al2O3The length of the ceramic tube is 3-5 mm, the outer diameter is 1.1-1.3 mm, and the inner diameter is 0.7-0.9 mm; the nichrome heating coil provides working temperature for the sensor, and the resistance value of the heating coil is 30-40 omega; the width of the annular Au electrode is 0.7-0.9 mm, and the distance between the two electrodes is 1.7-1.9 mm; the thickness of the gas sensitive film is 180-220 mu m; before and after the gas sensitive film contacts the gas to be measured, the resistance of the gas sensitive film changes, and the sensitivity of the sensor can be obtained by measuring the resistance change of the two annular Au electrodes. The sensitivity is calculated by dividing the resistance between the gold torroidal electrodes in air by the resistance in the target gas.
The invention relates to a preparation method of a resistance DMMP sensor based on a gold-modified tin dioxide nano material rich in oxygen vacancies, which comprises the following steps:
(1) the method comprises the following steps of (1) mixing gold-modified oxygen vacancy-rich tin dioxide and deionized water in a mass ratio of 3-5: 1, and grinding into paste, and applying the paste to Al with two parallel and mutually separated annular Au electrodes on the outer surface2O3The surface of the ceramic tube;
(2) baking the device obtained in the step (1) for 20-40 minutes under an infrared lamp, and after the sensitive material is dried, enabling a nickel-chromium alloy heating coil with the resistance value of 30-40 omega to penetrate through Al2O3The ceramic tube is used as a heating wire and is welded and packaged according to the indirectly heated gas sensitive element;
(3) and (3) aging the device obtained in the step (2) at 280-320 ℃ for 8-12 h to obtain the resistance DMMP sensor based on the gold-modified tin dioxide nano material rich in oxygen vacancies.
The invention has the advantages that:
1) the sensitive material in the invention takes commercialized tin dioxide as a base material, has low raw material cost, high yield and good structural consistency, and is suitable for mass production.
2) The DMMP sensor based on the gold-modified oxygen vacancy-rich tin dioxide nano material has the advantages of simple manufacturing process, low cost and small volume, and is suitable for industrial mass production.
3) The prepared gold-modified tin dioxide nano material rich in oxygen vacancies has excellent gas-sensitive characteristics for DMMP, including high sensitivity and fast response recovery rate, and solves the problems of low sensitivity and incapability of recovery when a pure semiconductor oxide material is used for detecting DMMP.
4) The invention utilizes the synergistic effect of high surface oxygen vacancy concentration and surface modified gold nanoparticles to improve the sensitivity of the device.
5) The preparation method of the gold-modified tin dioxide nanomaterial rich in oxygen vacancies is easy to regulate and control the surface microstructure of tin dioxide, and can realize regulation and control of the properties such as the composition, the structure and the like of the gold-modified tin dioxide nanomaterial rich in oxygen vacancies by controlling experimental parameters such as reaction temperature, reaction time, the proportion of reaction precursors and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern of the gold-modified oxygen vacancy rich tin dioxide nanomaterial prepared in example 1;
FIG. 2 is a transmission electron micrograph of the gold-modified oxygen vacancy rich tin dioxide nanomaterial prepared in example 1;
FIG. 3 is a response recovery curve of a gold-modified oxygen vacancy rich tin dioxide nanomaterial-based sensor prepared in example 1 at 300 ℃ to 204ppb DMMP;
FIG. 4 is a response recovery curve of the gold-modified oxygen vacancy-rich tin dioxide nanomaterial-based gas sensor prepared in example 1 at 300 ℃ for different concentrations of DMMP;
FIG. 5 is the response value of the gold-modified oxygen vacancy rich tin dioxide nanomaterial-based gas sensor prepared in example 2 at 300 ℃ to 680ppb DMMP and 100ppm of other organic gases.
FIG. 6 is a response recovery curve of the gold-modified oxygen vacancy-rich tin dioxide nanomaterial-based gas sensor prepared in example 3 at 300 ℃ for different concentrations of DMMP;
FIG. 7 is a response recovery curve of the gold-modified oxygen vacancy-rich tin dioxide nanomaterial-based gas sensor prepared in example 4 at 300 ℃ for different concentrations of DMMP;
Detailed Description
Example 1
(1) 5.0g of commercial tin dioxide powder (national pharmaceutical group chemical Co., Ltd.) was heat-treated at 80 ℃ for 24 hours under vacuum;
(2) adding the tin dioxide powder obtained in the step (1) into a toluene solution, wherein the volume of the toluene is 100mL, and performing ultrasonic treatment to uniformly disperse the toluene; then adding 1.0g of dimethyltin dichloride into the solution, and stirring for 2 hours at room temperature to obtain a mixed solution of dimethyltin dichloride and tin dioxide;
(3) adding 8mL of triethylamine into the mixed solution of the dimethyltin dichloride and the tin dioxide obtained in the step (2), and continuously stirring at room temperature for 2 hours; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain an organotitanane modified stannic oxide material;
(4) calcining the stannic oxide material modified by the organic stannane obtained in the step (3) at 500 ℃ for 4h to obtain stannic oxide nano-material powder rich in oxygen vacancies;
(5) adding 1g of the oxygen vacancy-rich tin dioxide powder obtained in the step (4) into water, wherein the volume of the water is 80mL, and performing ultrasonic treatment to uniformly disperse the water; then adding 1mL of chloroauric acid aqueous solution into the solution, wherein the concentration of the chloroauric acid aqueous solution is 10mM, and stirring at room temperature for 1h to obtain a mixed solution of chloroauric acid and tin dioxide rich in oxygen vacancies;
(6) adding 30mg of sodium borohydride into the mixed solution of chloroauric acid and oxygen vacancy-rich tin dioxide obtained in the step (5), and stirring at room temperature for 0.2 h; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain a gold-modified tin dioxide material rich in oxygen vacancies;
(7) mixing the gold-modified oxygen vacancy-rich tin dioxide powder prepared in the step (6) with deionized water according to the mass ratio of 3:1, and grinding the mixture into pastePaste, applying the paste to Al with two parallel, annular and mutually separated gold electrodes on the outer surface2O3The surface of the ceramic tube. Baking the ceramic tube for 20 minutes under an infrared lamp to obtain a sensitive film based on the surface functionalized zinc oxide on the surface of the ceramic tube, wherein the thickness of the sensitive film is 180 mu m; then a nickel-chromium alloy hotter coil with a resistance value of 30 omega is passed through the Al2O3The ceramic tube is used as a heating wire, and finally welding and packaging are carried out according to the indirectly heated gas sensitive element; al (Al)2O3The length of the ceramic tube is 3mm, the outer diameter is 1.1mm, and the inner diameter is 0.7 mm; the width of the annular Au electrode is 0.7mm, and the distance between the two electrodes is 1.7 mm;
(8) and (4) carrying out aging treatment on the DMMP gas sensor based on the gold-modified tin dioxide rich in oxygen vacancies obtained in the step (7) at 280 ℃ for 12 hours to finish the aging treatment on the gas sensor, thereby obtaining the resistance DMMP sensor based on the gold-modified tin dioxide rich in oxygen vacancies.
Example 2
(1) 5.0g of commercial tin dioxide powder (national pharmaceutical group chemical Co., Ltd.) was heat-treated at 80 ℃ for 24 hours under vacuum;
(2) adding the tin dioxide powder obtained in the step (1) into a toluene solution, wherein the volume of the toluene is 150mL, and performing ultrasonic treatment to uniformly disperse the toluene; then adding 2.0g of dimethyltin dichloride into the solution, and stirring for 3 hours at room temperature to obtain a mixed solution of dimethyltin dichloride and tin dioxide;
(3) adding 10mL of triethylamine into the mixed solution of the dimethyltin dichloride and the tin dioxide obtained in the step (2), and continuously stirring at room temperature for 4 hours; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain an organotitanane modified stannic oxide material;
(4) calcining the stannic oxide material modified by the organic stannane obtained in the step (3) at 600 ℃ for 2h to obtain stannic oxide nano-material powder rich in oxygen vacancies;
(5) adding 1g of the oxygen vacancy-rich tin dioxide powder obtained in the step (4) into water, wherein the volume of the water is 90mL, and performing ultrasonic treatment to uniformly disperse the water; then adding 1mL of chloroauric acid aqueous solution into the solution, wherein the concentration of the chloroauric acid solution is 15mM, and stirring at room temperature for 1h to obtain a mixed solution of chloroauric acid and tin dioxide rich in oxygen vacancies;
(6) adding 30mg of sodium borohydride into the mixed solution of chloroauric acid and oxygen vacancy-rich tin dioxide obtained in the step (5), and stirring at room temperature for 0.3 h; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain a gold-modified tin dioxide material rich in oxygen vacancies;
(7) mixing the gold-modified oxygen vacancy-rich tin dioxide powder prepared in the step (6) with deionized water according to the mass ratio of 3:1, grinding the mixture into pasty slurry, and coating the slurry on Al with two parallel, annular and mutually-separated gold electrodes on the outer surface2O3The surface of the ceramic tube. Baking the ceramic tube for 20 minutes under an infrared lamp to obtain a sensitive film based on the surface functionalized zinc oxide on the surface of the ceramic tube, wherein the thickness of the sensitive film is 180 mu m; then a nickel-chromium alloy hotter coil with a resistance value of 40 omega is passed through the Al2O3The ceramic tube is used as a heating wire, and finally welding and packaging are carried out according to the indirectly heated gas sensitive element; al (Al)2O3The length of the ceramic tube is 4mm, the outer diameter is 1.1mm, and the inner diameter is 0.8 mm; the width of the annular Au electrode is 0.8mm, and the distance between the two electrodes is 1.8 mm;
(8) and (4) carrying out heat treatment on the DMMP gas sensor based on the gold-modified tin dioxide rich in oxygen vacancies obtained in the step (7) at 280 ℃ for 12 hours to finish the aging treatment of the gas sensor, thereby obtaining the resistance DMMP sensor based on the gold-modified tin dioxide rich in oxygen vacancies.
Example 3
(1) 7.5g of commercial tin dioxide powder (national pharmaceutical group chemical Co., Ltd.) was heat-treated at 90 ℃ for 18 hours under vacuum;
(2) adding the tin dioxide powder obtained in the step (1) into a toluene solution, wherein the volume of the toluene is 100mL, and performing ultrasonic treatment to uniformly disperse the toluene; then adding 1.0g of dimethyltin dichloride into the solution, and stirring for 2 hours at room temperature to obtain a mixed solution of dimethyltin dichloride and tin dioxide;
(3) adding 8mL of triethylamine into the mixed solution of the dimethyltin dichloride and the tin dioxide obtained in the step (2), and continuously stirring at room temperature for 2 hours; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain an organotitanane modified stannic oxide material;
(4) calcining the stannic oxide material modified by the organic stannane obtained in the step (3) at 500 ℃ for 4h to obtain stannic oxide nano-material powder rich in oxygen vacancies;
(5) adding 1g of the oxygen vacancy-rich tin dioxide powder obtained in the step (4) into water, wherein the volume of the water is 100mL, and performing ultrasonic treatment to uniformly disperse the water; then adding 1mL of chloroauric acid aqueous solution into the solution, wherein the concentration of the chloroauric acid solution is 15mM, and stirring at room temperature for 1h to obtain a mixed solution of chloroauric acid and tin dioxide rich in oxygen vacancies;
(6) adding 40mg of sodium borohydride into the mixed solution of chloroauric acid and oxygen vacancy-rich tin dioxide obtained in the step (5), and stirring at room temperature for 0.2 h; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain a gold-modified tin dioxide material rich in oxygen vacancies;
(7) mixing the gold-modified oxygen vacancy-rich tin dioxide powder prepared in the step (6) with deionized water according to the mass ratio of 4:1, grinding the mixture into pasty slurry, and coating the slurry on Al with two parallel, annular and mutually-separated gold electrodes on the outer surface2O3The surface of the ceramic tube. Baking the ceramic tube for 30 minutes under an infrared lamp to obtain a sensitive film based on the surface functionalized zinc oxide on the surface of the ceramic tube, wherein the thickness of the sensitive film is 200 mu m; then a nickel-chromium alloy hotter coil with a resistance value of 30 omega is passed through the Al2O3The ceramic tube is used as a heating wire, and finally welding and packaging are carried out according to the indirectly heated gas sensitive element; al (Al)2O3The length of the ceramic tube is 5mm, the outer diameter is 1.2mm, and the inner diameter is 0.9 mm; the width of the annular Au electrode is 0.9mm, and the distance between the two electrodes is 1.9 mm;
(8) and (4) carrying out heat treatment on the DMMP gas sensor based on the gold-modified tin dioxide rich in oxygen vacancies obtained in the step (7) at 300 ℃ for 10 hours to finish the aging treatment of the gas sensor, thereby obtaining the resistance DMMP sensor based on the gold-modified tin dioxide rich in oxygen vacancies.
Example 4
(1) 7.5g of commercial tin dioxide powder (national pharmaceutical group chemical Co., Ltd.) was heat-treated at 90 ℃ for 18 hours under vacuum;
(2) adding the tin dioxide powder obtained in the step (1) into a toluene solution, wherein the volume of the toluene is 150mL, and performing ultrasonic treatment to uniformly disperse the toluene; then adding 2.0g of dimethyltin dichloride into the solution, and stirring for 3 hours at room temperature to obtain a mixed solution of dimethyltin dichloride and tin dioxide;
(3) adding 10mL of triethylamine into the mixed solution of the dimethyltin dichloride and the tin dioxide obtained in the step (2), and continuously stirring at room temperature for 4 hours; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain an organotitanane modified stannic oxide material;
(4) calcining the stannic oxide material modified by the organic stannane obtained in the step (3) at 600 ℃ for 2h to obtain stannic oxide nano-material powder rich in oxygen vacancies;
(5) adding 1.5g of the oxygen vacancy-rich tin dioxide powder obtained in the step (4) into water, wherein the volume of the water is 80mL, and performing ultrasonic treatment to uniformly disperse the water; then adding 2mL of chloroauric acid aqueous solution into the solution, wherein the concentration of the chloroauric acid aqueous solution is 15mM, and stirring at room temperature for 2h to obtain a mixed solution of chloroauric acid and tin dioxide rich in oxygen vacancies;
(6) adding 40mg of sodium borohydride into the mixed solution of chloroauric acid and oxygen vacancy-rich tin dioxide obtained in the step (5), and stirring at room temperature for 0.3 h; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain a gold-modified tin dioxide material rich in oxygen vacancies;
(7) mixing the gold-modified oxygen vacancy-rich tin dioxide powder prepared in the step (6) with deionized water according to the mass ratio of 4:1, grinding the mixture into pasty slurry, and coating the slurry on Al with two parallel, annular and mutually-separated gold electrodes on the outer surface2O3The surface of the ceramic tube. Baking the ceramic tube for 30 minutes under an infrared lamp to obtain a sensitive film based on the surface functionalized zinc oxide on the surface of the ceramic tube, wherein the thickness of the sensitive film is 200 mu m; then a nickel-chromium alloy hotter coil with a resistance value of 40 omega is passed through the Al2O3The ceramic tube is used as a heating wire, and finally welding and packaging are carried out according to the indirectly heated gas sensitive element; al (Al)2O3The length of the ceramic tube is3mm, the outer diameter is 1.2mm, and the inner diameter is 0.7 mm; the width of the annular Au electrode is 0.7mm, and the distance between the two electrodes is 1.7 mm;
(8) and (4) carrying out heat treatment on the DMMP gas sensor based on the gold-modified tin dioxide rich in oxygen vacancies obtained in the step (7) at 300 ℃ for 10 hours to finish the aging treatment of the gas sensor, thereby obtaining the resistance DMMP sensor based on the gold-modified tin dioxide rich in oxygen vacancies.
Example 5
(1) 10g of commercial tin dioxide powder (national pharmaceutical group chemical Co., Ltd.) was heat-treated at 100 ℃ for 12 hours under vacuum;
(2) adding the tin dioxide powder obtained in the step (1) into a toluene solution, wherein the volume of the toluene is 100mL, and performing ultrasonic treatment to uniformly disperse the toluene; then adding 1.0g of dimethyltin dichloride into the solution, and stirring for 2 hours at room temperature to obtain a mixed solution of dimethyltin dichloride and tin dioxide;
(3) adding 8mL of triethylamine into the mixed solution of the dimethyltin dichloride and the tin dioxide obtained in the step (2), and continuously stirring at room temperature for 2 hours; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain an organotitanane modified stannic oxide material;
(4) calcining the stannic oxide material modified by the organic stannane obtained in the step (3) at 500 ℃ for 4h to obtain stannic oxide nano-material powder rich in oxygen vacancies;
(5) adding 1.5g of the oxygen vacancy-rich tin dioxide powder obtained in the step (4) into water, wherein the volume of the water is 90mL, and performing ultrasonic treatment to uniformly disperse the water; then adding 2mL of chloroauric acid aqueous solution into the solution, wherein the concentration of the chloroauric acid aqueous solution is 20mM, and stirring at room temperature for 2h to obtain a mixed solution of chloroauric acid and tin dioxide rich in oxygen vacancies;
(6) adding 50mg of sodium borohydride into the mixed solution of chloroauric acid and oxygen vacancy-rich tin dioxide obtained in the step (5), and stirring at room temperature for 0.2 h; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain a gold-modified tin dioxide material rich in oxygen vacancies;
(7) mixing the gold-modified oxygen vacancy-rich tin dioxide powder prepared in the step (6) with deionized water according to the mass ratio of 5:1Example mixing and grinding to a paste-like paste, applying the paste to Al with two parallel, annular and mutually separated gold electrodes on the outer surface2O3The surface of the ceramic tube. Baking the ceramic tube for 40 minutes under an infrared lamp to obtain a sensitive film based on the surface functionalized zinc oxide on the surface of the ceramic tube, wherein the thickness of the sensitive film is 220 microns; then a nickel-chromium alloy hotter coil with a resistance value of 30 omega is passed through the Al2O3The ceramic tube is used as a heating wire, and finally welding and packaging are carried out according to the indirectly heated gas sensitive element; al (Al)2O3The length of the ceramic tube is 4mm, the outer diameter is 1.3mm, and the inner diameter is 0.8 mm; the width of the annular Au electrode is 0.8mm, and the distance between the two electrodes is 1.8 mm;
(8) and (4) carrying out heat treatment on the DMMP gas sensor based on the gold-modified tin dioxide rich in oxygen vacancies obtained in the step (7) at 320 ℃ for 8 hours to finish the aging treatment of the gas sensor, thereby obtaining the resistance DMMP sensor based on the gold-modified tin dioxide rich in oxygen vacancies.
Example 6
(1) 10g of commercial tin dioxide powder (chemical reagent of national drug group, Ltd.) is subjected to heat treatment at 80-100 ℃ for 12-24 h under vacuum condition;
(2) adding the tin dioxide powder obtained in the step (1) into a toluene solution, wherein the volume of the toluene is 150mL, and performing ultrasonic treatment to uniformly disperse the toluene; then adding 2.0g of dimethyltin dichloride into the solution, and stirring for 3 hours at room temperature to obtain a mixed solution of dimethyltin dichloride and tin dioxide;
(3) adding 10mL of triethylamine into the mixed solution of the dimethyltin dichloride and the tin dioxide obtained in the step (2), and continuously stirring at room temperature for 4 hours; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain an organotitanane modified stannic oxide material;
(4) calcining the stannic oxide material modified by the organic stannane obtained in the step (3) at 600 ℃ for 2h to obtain stannic oxide nano-material powder rich in oxygen vacancies;
(5) adding 1.5g of the oxygen vacancy-rich tin dioxide powder obtained in the step (4) into water, wherein the volume of the water is 100mL, and performing ultrasonic treatment to uniformly disperse the water; then adding 2mL of chloroauric acid aqueous solution into the solution, wherein the concentration of the chloroauric acid aqueous solution is 20mM, and stirring at room temperature for 2h to obtain a mixed solution of chloroauric acid and tin dioxide rich in oxygen vacancies;
(6) adding 50mg of sodium borohydride into the mixed solution of chloroauric acid and oxygen vacancy-rich tin dioxide obtained in the step (5), and stirring at room temperature for 0.3 h; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain a gold-modified tin dioxide material rich in oxygen vacancies;
(7) mixing the gold-modified oxygen vacancy-rich tin dioxide powder prepared in the step (6) with deionized water according to the mass ratio of 5:1, grinding the mixture into pasty slurry, and coating the slurry on Al with two parallel, annular and mutually-separated gold electrodes on the outer surface2O3The surface of the ceramic tube. Baking the ceramic tube for 40 minutes under an infrared lamp to obtain a sensitive film based on the surface functionalized zinc oxide on the surface of the ceramic tube, wherein the thickness of the sensitive film is 220 microns; then a nickel-chromium alloy hotter coil with a resistance value of 40 omega is passed through the Al2O3The ceramic tube is used as a heating wire, and finally welding and packaging are carried out according to the indirectly heated gas sensitive element; al (Al)2O3The length of the ceramic tube is 5mm, the outer diameter is 1.3mm, and the inner diameter is 0.9 mm; the width of the annular Au electrode is 0.9mm, and the distance between the two electrodes is 1.9 mm;
(8) and (4) carrying out heat treatment on the DMMP gas sensor based on the gold-modified tin dioxide rich in oxygen vacancies obtained in the step (7) at 320 ℃ for 8 hours to finish the aging treatment of the gas sensor, thereby obtaining the resistance DMMP sensor based on the gold-modified tin dioxide rich in oxygen vacancies.
The X-ray electron diffraction pattern of the gold-modified oxygen vacancy rich tin dioxide nanomaterial prepared in example 1 is shown in FIG. 1. It can be seen that the prepared gold-modified tin dioxide nanomaterial rich in oxygen vacancies gives a series of characteristic diffraction peaks attributed to rutile phase tin dioxide. In addition, the nano material also gives two characteristic diffraction peaks belonging to a gold simple substance, which indicates that the gold-modified tin dioxide nano material rich in oxygen vacancies is successfully prepared.
The transmission electron micrograph of the gold-modified oxygen vacancy-rich tin dioxide nanomaterial prepared in example 1 is shown in fig. 2, and as can be seen from fig. 2, the composite material has two different crystal stripes, one is the lattice stripe of tin dioxide, and the other is the lattice stripe of a gold simple substance, which further proves that the composite material is prepared.
The response recovery curve of the gold-modified oxygen vacancy-rich tin dioxide nanomaterial prepared in example 1 at 300 ℃ to 204ppb DMMP is shown in fig. 3. The composite material has good response characteristic and recovery characteristic to 204ppb DMMP, the response value to 204ppb DMMP is 1.24, and the response time and the recovery time are respectively 26s and 32s, which shows that the gold-modified tin dioxide nano material rich in oxygen vacancies has good response to low-concentration DMMP.
The response recovery curves of the gold-modified oxygen vacancy-rich tin dioxide nanomaterial prepared in example 1 at 300 ℃ for different concentrations of DMMP of different gases are shown in FIG. 4. As can be seen, the sensor has good response to DMMP with the concentration range of 34-680 ppb, and the lowest detection concentration is 34 ppb.
The response values of the gold-modified oxygen vacancy enriched tin dioxide nanomaterial prepared in example 2 at 300 ℃ to 680ppb DMMP and 100ppm of other organic gases are shown in FIG. 5. It can be seen that the response of the cell to high concentrations of organic gas is still lower than that of low concentrations of DMMP, indicating that the cell has good selectivity.
The response recovery curve of the gold-modified oxygen vacancy-rich tin dioxide nanomaterial prepared in example 3 at 300 ℃ to 204ppb DMMP is shown in FIG. 6. The composite material has good response characteristic and recovery characteristic to 204ppb DMMP, and the response time and the recovery time to 204ppb DMMP are respectively 20s and 51 s.
The response recovery curve of the gold-modified oxygen vacancy-rich tin dioxide nanomaterial prepared in example 4 at 300 ℃ to 204ppb DMMP is shown in fig. 7. The composite material has good response characteristic and recovery characteristic to 204ppb DMMP, and the response time and the recovery time to 204ppb DMMP are respectively 40s and 61 s.
Claims (3)
1. A resistance-type DMMP sensor based on gold-modified tin dioxide nanomaterial rich in oxygen vacancies is prepared from Al2O3Ceramic tube substrate coated with Al2O3Two parallel and separated annular Au electrodes coated on the outer surface of the ceramic tube substrate and coated with Al2O3Gas sensitive film on ceramic tube outer surface and annular Au electrode, penetrating Al2O3A nichrome heating coil inside the ceramic tube; the method is characterized in that: the gas sensitive film is a gold-modified oxygen vacancy-rich tin dioxide nano material, and is prepared by the following steps:
(1) carrying out heat treatment on 5.0-10 g of tin dioxide powder for 12-24 h at 80-100 ℃ in vacuum;
(2) adding the tin dioxide powder obtained in the step (1) into a toluene solution, wherein the volume of the toluene is 100-150 mL, and performing ultrasonic treatment to uniformly disperse the toluene; then adding 1.0-2.0 g of dimethyltin dichloride into the solution, and stirring for 2-3 hours at room temperature to obtain a mixed solution of dimethyltin dichloride and stannic oxide;
(3) adding 8-10 mL of triethylamine into the mixed solution of dimethyltin dichloride and stannic oxide obtained in the step (2), and continuously stirring at room temperature for 2-4 h; carrying out centrifugal separation, ethanol washing and drying on the solution to obtain an organotitanane modified stannic oxide material;
(4) calcining the stannic oxide material modified by the organic stannane obtained in the step (3) at 500-600 ℃ for 2-4 h to obtain stannic oxide nano-material powder rich in oxygen vacancies;
(5) adding 1-5 g of the oxygen vacancy-rich tin dioxide powder obtained in the step (4) into water, wherein the volume of the water is 80-100 mL, and performing ultrasonic treatment to uniformly disperse the water; then adding 1-2 mL of chloroauric acid aqueous solution into the solution, wherein the concentration of the chloroauric acid aqueous solution is 10-20 mM, and stirring at room temperature for 1-2 h to obtain a mixed solution of chloroauric acid and oxygen vacancy-enriched stannic oxide;
(6) adding 30-50 mg of sodium borohydride into the mixed solution of chloroauric acid and oxygen-rich vacancy tin dioxide obtained in the step (5), and stirring at room temperature for 0.2-0.3 h; and carrying out centrifugal separation, ethanol washing and drying on the solution to obtain the gold-modified tin dioxide material rich in oxygen vacancies.
2. The oxygen-enriched air based on gold modification of claim 1The resistance type DMMP sensor of the tin dioxide nano material is characterized in that: al (Al)2O3The length of the ceramic tube is 3-5 mm, the outer diameter is 1.1-1.3 mm, and the inner diameter is 0.7-0.9 mm; the resistance value of the nichrome heating coil is 30-40 omega; the width of the annular Au electrode is 0.7-0.9 mm, and the distance between the two electrodes is 1.7-1.9 mm; the thickness of the gas sensitive film is 180-220 μm.
3. The preparation method of the resistance DMMP sensor based on the gold-modified tin dioxide nanomaterial rich in oxygen vacancies as claimed in claim 1 or 2, which comprises the following steps:
(1) the method comprises the following steps of (1) mixing gold-modified oxygen vacancy-rich tin dioxide and deionized water in a mass ratio of 3-5: 1, and grinding into paste, and applying the paste to Al with two parallel and mutually separated annular Au electrodes on the outer surface2O3The surface of the ceramic tube;
(2) baking the device obtained in the step (1) for 20-40 minutes under an infrared lamp, and after the sensitive material is dried, enabling a nickel-chromium alloy heating coil with the resistance value of 30-40 omega to penetrate through Al2O3The ceramic tube is used as a heating wire and is welded and packaged according to the indirectly heated gas sensitive element;
(3) and (3) aging the device obtained in the step (2) at 280-320 ℃ for 8-12 h to obtain the resistance DMMP sensor based on the gold-modified tin dioxide nano material rich in oxygen vacancies.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110597879.2A CN113325041B (en) | 2021-05-31 | 2021-05-31 | DMMP sensor based on gold-modified oxygen vacancy-rich tin dioxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110597879.2A CN113325041B (en) | 2021-05-31 | 2021-05-31 | DMMP sensor based on gold-modified oxygen vacancy-rich tin dioxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113325041A true CN113325041A (en) | 2021-08-31 |
| CN113325041B CN113325041B (en) | 2022-10-04 |
Family
ID=77422474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110597879.2A Active CN113325041B (en) | 2021-05-31 | 2021-05-31 | DMMP sensor based on gold-modified oxygen vacancy-rich tin dioxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113325041B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010126336A2 (en) * | 2009-04-30 | 2010-11-04 | 주식회사 아모그린텍 | Gas sensor using metal oxide nanoparticles, and method for manufacturing same |
| CN101936937A (en) * | 2010-07-06 | 2011-01-05 | 电子科技大学 | Micro-cantilever gas sensor and manufacturing method thereof |
| US20130239661A1 (en) * | 2010-09-01 | 2013-09-19 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Use of diazonium salts for the formation of thick layers on at least one surface of a substrate |
| CN109292734A (en) * | 2018-09-26 | 2019-02-01 | 吉林大学 | A kind of room temperature flexible gas sensor and preparation method thereof based on polycrystalline micro wire grain boundary effect |
| CN109342523A (en) * | 2018-10-16 | 2019-02-15 | 吉林大学 | Based on the resistor-type NO for being rich in the grapheme modified composite material of Lacking oxygen stannic oxide2Sensor, preparation method and applications |
| CN110068597A (en) * | 2019-05-05 | 2019-07-30 | 吉林大学 | A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof |
| CN110361445A (en) * | 2019-07-30 | 2019-10-22 | 西安交通大学 | A kind of highly selective CMUTs gas sensor of multi-parameter and its use and preparation method |
| CN110606503A (en) * | 2019-09-16 | 2019-12-24 | 安徽师范大学 | Gold-modified porous tin dioxide micro-nanosheet composite material and preparation method and application thereof |
-
2021
- 2021-05-31 CN CN202110597879.2A patent/CN113325041B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010126336A2 (en) * | 2009-04-30 | 2010-11-04 | 주식회사 아모그린텍 | Gas sensor using metal oxide nanoparticles, and method for manufacturing same |
| CN101936937A (en) * | 2010-07-06 | 2011-01-05 | 电子科技大学 | Micro-cantilever gas sensor and manufacturing method thereof |
| US20130239661A1 (en) * | 2010-09-01 | 2013-09-19 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Use of diazonium salts for the formation of thick layers on at least one surface of a substrate |
| CN109292734A (en) * | 2018-09-26 | 2019-02-01 | 吉林大学 | A kind of room temperature flexible gas sensor and preparation method thereof based on polycrystalline micro wire grain boundary effect |
| CN109342523A (en) * | 2018-10-16 | 2019-02-15 | 吉林大学 | Based on the resistor-type NO for being rich in the grapheme modified composite material of Lacking oxygen stannic oxide2Sensor, preparation method and applications |
| CN110068597A (en) * | 2019-05-05 | 2019-07-30 | 吉林大学 | A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof |
| CN110361445A (en) * | 2019-07-30 | 2019-10-22 | 西安交通大学 | A kind of highly selective CMUTs gas sensor of multi-parameter and its use and preparation method |
| CN110606503A (en) * | 2019-09-16 | 2019-12-24 | 安徽师范大学 | Gold-modified porous tin dioxide micro-nanosheet composite material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| DAQI CHEN: "A wireless electrodeless quartz crystal microbalance with dissipation DMMP sensor", 《SENSORS AND ACTUATORS B:CHEMICAL》 * |
| SOO CHOOL LEE: "The development of SnO2-based recoverable gas sensors for the detection of DMMP", 《SENSORS AND ACTUATORS B：CHEMICAL》 * |
| 刘刚: "金属镍掺杂二氧化锡基气体传感器的检测特性研究", 《优秀硕士论文集》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113325041B (en) | 2022-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Two-dimensional oriented growth of Zn-MOF-on-Zr-MOF architecture: A highly sensitive and selective platform for detecting cancer markers | |
| CN100592082C (en) | Formaldehyde air-sensitive material and its preparation method and preparation method for formaldehyde air-sensitive device | |
| CN108801990B (en) | CsPbBr-based3Omethoate detection method of perovskite quantum dot-molecular imprinting fluorescence sensor | |
| US20180031532A1 (en) | Methylbenzene gas sensor using palladium-containing cobalt oxide nanostructures and method for manufacturing the same | |
| Cao et al. | Photoelectrochemical determination of malathion by using CuO modified with a metal-organic framework of type Cu-BTC | |
| CN102653413A (en) | Zinc-doped indium oxide nano gas sensitive material and preparation method thereof | |
| CN105717168B (en) | A kind of preparation method and application of the these hydrogen sulfide gas sensor based on titanium dioxide nanoplate carried noble metal | |
| CN112408463A (en) | High-response-sensitivity SnO2Gas sensitive material, preparation process and application | |
| Chen et al. | Determination of gallic acid in tea by a graphene modified glassy carbon electrode | |
| CN110487778B (en) | Glow-type chemiluminescence sensor constructed based on hydrogel as well as preparation method and application thereof | |
| Zhang et al. | A novel electrochemical sensor based on Au-Dy2 (WO4) 3 nanocomposites for simultaneous determination of uric acid and nitrite | |
| CN113325041B (en) | DMMP sensor based on gold-modified oxygen vacancy-rich tin dioxide and preparation method thereof | |
| CN109187687B (en) | Preparation of conjugated organic microporous material modified electrode and application of modified electrode as peroxynitroso anion electrochemical sensor | |
| CN110068597A (en) | A kind of resistor-type NO based on stannic oxide modification zinc oxide nano material2Sensor and preparation method thereof | |
| Kia et al. | Preparation of voltammetric biosensor for tryptophan using multi-walled carbon nanotubes | |
| Xia et al. | Microplasma-assisted synthesis of a mixed-valence Ce-MOF with enhanced oxidase-like activity for colorimetric sensing of dopamine | |
| CN105929003B (en) | A kind of preparation method of catalysis filter membrane for improving gas sensor selectivity | |
| CN113075266B (en) | NGQD/Fe2O3Graphene foam composite film and preparation method and application thereof | |
| CN115015328A (en) | N-pentanol gas sensor based on PtAu alloy nanocrystalline modified flower-shaped WO3 sensitive material and preparation method thereof | |
| CN113433181A (en) | Electrochemical sensing method for simultaneously distinguishing and detecting luteolin and baicalin | |
| CN115290704A (en) | Preparation method of NiCo2O4-In2O3 composite gas-sensitive material formaldehyde sensor | |
| Chu et al. | A novel non-enzyme sensor based on a PDDA-RGO/Pt NPs nanocomposite for electrochemical detection of ascorbic acid | |
| CN113960122B (en) | Three-dimensional SnO2/Co3O4Core-shell nanocomposite and moisture-resistant acetone gas sensor prepared from same | |
| KR101526304B1 (en) | Naphthalimide amine derivates, preparation method of thereof and detection method of carbon dioxide using the same | |
| CN110208331B (en) | SrO-doped SnO2Radical NH3Method for preparing sensitive material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |