CN119086661B - Ammonia gas-sensitive material and preparation method and application thereof - Google Patents
Ammonia gas-sensitive material and preparation method and application thereof Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000000463 material Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000011777 magnesium Substances 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 5
- 229940116411 terpineol Drugs 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 25
- 230000007774 longterm Effects 0.000 abstract description 11
- 230000004048 modification Effects 0.000 abstract description 10
- 238000012986 modification Methods 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 238000011068 loading method Methods 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 52
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- -1 silver-modified samarium cobalt magnesium oxide Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012306 spectroscopic technique Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
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- C01—INORGANIC CHEMISTRY
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention discloses an ammonia gas-sensitive material, a preparation method and application thereof, and relates to the technical field of gas sensors. The chemical formula of the ammonia gas-sensitive material is Xwt% Ag-SmCo 1‑yMgyO3, wherein 0<X is less than or equal to 20, and y is more than or equal to 0 and less than or equal to 0.5. The preparation method is prepared by carrying out surface loading and modification on the Ag element and carrying out B-site doping on the Mg element on the basis of SmCoO 3 materials by a hydrothermal method. The prepared ammonia gas-sensitive material shows excellent sensitivity in detecting ammonia gas through the composite doping modification of noble metal and B site, especially shows good response to low-concentration ammonia gas, and particularly has a response value of 7.53 to 2ppm of ammonia gas at the working temperature of 150 ℃, and meanwhile shows good selectivity to ammonia gas and good long-term stability.
Description
Technical Field
The invention relates to the technical field of gas sensors, in particular to an ammonia gas-sensitive material, a preparation method and application thereof.
Background
Ammonia is a common colorless gas, has a strong pungent odor, is readily soluble in water, and has alkalinity. Ammonia gas is widely applied to a plurality of fields such as chemical industry, agriculture, pharmacy and the like, and has important industrial application in the production of chemical fertilizers, refrigeration systems and wastewater treatment processes. In addition, ammonia is also used as a diagnostic reagent in the medical industry. However, ammonia is also a potentially toxic substance, and high concentrations of ammonia have serious irritation to the human respiratory system, eyes and skin, and long-term exposure may even lead to poisoning. Therefore, real-time monitoring of ammonia gas leakage is of great importance in the fields of industrial safety, environmental protection and public health.
Currently, methods for detecting ammonia include chemical absorption methods, electrochemical sensors, spectroscopic techniques, and the like. However, these methods have limitations such as complicated detection process, complicated operation steps, expensive and difficult movement of the spectrum detection device, and electrochemical sensors are easily affected by factors such as ambient humidity and temperature in practical applications, although they have good sensitivity. Furthermore, these techniques still have room for optimization in terms of response time, lower detection limit, selectivity, and long-term stability. Based on this, the development of ammonia gas-sensitive materials with high sensitivity, rapid response, good selectivity and environmental suitability has become a hot spot of research. Particularly in the detection of low-concentration ammonia gas, the gas-sensitive material is required to maintain reliable performance under complex environments.
In the prior art, CN111204798A discloses a high-sensitivity two-dimensional nanometer strontium titanate gas-sensitive material with low working temperature, a preparation method and application thereof, and the ultrathin two-dimensional nanometer sheet-shaped strontium titanate gas-sensitive material prepared by adopting n-butyl titanate and strontium chloride as raw materials can have good response to 100ppm ammonia gas at the working temperature of 20 ℃ and has the sensitivity of more than 5. Although the perovskite material strontium titanate prepared in the patent can realize good response to ammonia gas at room temperature, the concentration of the ammonia gas is 0-10ppm when the ammonia gas leaks, so that the strontium titanate does not show good response to low-concentration ammonia gas. The preparation of SmCoO 3 nano material and its gas-sensitive property research (Li Jiang et al, modern chemical industry, 9 months in 2008, volume 28, 9 th stage) disclose that synthesizing SmCoO 3 nano material with perovskite structure by adopting citric acid sol-gel method, its nano particles are well dispersed, its average grain size is about 30nm, and its sensitivity to H 2 S at 200 deg.C is 20.5, and the SmCoO 3 nano material only shows good response to H 2 S gas, but not to NH 3.
Therefore, the research and development of the ammonia gas-sensitive material which has high detection precision and adapts to complex environments is used for detecting low-concentration ammonia, and has important application value for improving the efficiency and safety of ammonia leakage monitoring.
Disclosure of Invention
Aiming at the prior art, the invention aims to provide an ammonia gas-sensitive material, and a preparation method and application thereof. The chemical formula of the ammonia gas-sensitive material is Xwt% Ag-SmCo 1-yMgyO3, wherein 0<X is less than or equal to 20, and y is more than or equal to 0 and less than or equal to 0.5. The preparation method is prepared by carrying out surface loading and modification on the Ag element and carrying out B-site doping on the Mg element on the basis of SmCoO 3 materials by a hydrothermal method. The prepared ammonia gas-sensitive material shows excellent sensitivity in detecting ammonia gas through the composite doping modification of noble metal and B site, especially shows good response to low-concentration ammonia gas, and particularly has a response value of 7.53 to 2ppm of ammonia gas at the working temperature of 150 ℃, and meanwhile shows good selectivity to ammonia gas and good long-term stability.
In order to achieve the above purpose, the invention adopts the following technical scheme:
In a first aspect of the invention, an ammonia gas-sensitive material is provided, wherein the chemical formula of the ammonia gas-sensitive material is Xwt% Ag-SmCo 1-yMgyO3, and 0<X is less than or equal to 20, and 0< y is less than or equal to 0.5.
Preferably, the ammonia gas-sensitive material has an average particle size of 55-200nm.
In a second aspect of the present invention, there is provided a method for producing an ammonia gas-sensitive material, comprising the steps of:
(1) Mixing samarium nitrate, magnesium nitrate, cobalt nitrate, silver nitrate, citric acid and dilute nitric acid according to the addition amount of (0.01-5) mol, (0.01-100) g, (20-100) g and (5-100) mL, adding into 10-150mL deionized water, and stirring to obtain a mixed solution;
(2) Cooling the mixed solution to room temperature after hydrothermal reaction to obtain a solid product, washing the solid product, and drying to obtain precursor powder, wherein the hydrothermal reaction temperature is 120-200 ℃ and the hydrothermal reaction time is 10-14h;
(3) Calcining the precursor powder at 500-1000 ℃ for 1-5h, and grinding to obtain Xwt% Ag-SmCo 1-yMgyO3 ammonia gas-sensitive material.
Preferably, in step (1), the stirring time is 1.5-2.5 hours.
Preferably, in the step (2), the washing treatment is to wash the solid product with deionized water 2 to 3 times to remove the remaining impurities therein.
Preferably, in step (2), the drying temperature is 40-80 ℃ and the drying time is 2-8h.
In a third aspect of the invention, there is provided the use of the ammonia gas-sensitive material in the detection of ammonia and/or in the preparation of an ammonia gas-sensitive sensor.
Preferably, the ammonia gas has a gas concentration of 1 to 10ppm.
Preferably, the ammonia gas-sensitive material is prepared by the following method:
Mixing an ammonia gas-sensitive material, deionized water and terpineol to obtain slurry, spin-coating the slurry on an alumina substrate to form a gas-sensitive film, and aging the gas-sensitive film to obtain the ammonia gas-sensitive sensor.
Further preferably, the addition ratio of the ammonia gas sensitive material, deionized water and terpineol is (1-5) g (3-15) mL (1-5) mL.
Further preferably, the gas-sensitive film has a thickness of 80 to 200. Mu.m.
Further preferably, the aging temperature is 200-240 ℃ and the aging time is 10-24 hours.
The invention has the beneficial effects that:
according to the invention, the ammonia gas sensitive material Xwt% Ag-SmCo 1-yMgyO3 is synthesized by a hydrothermal method, and the prepared ammonia gas sensitive material has excellent gas correspondence to low-concentration ammonia gas. Specifically, at the working temperature of 150 ℃, the response value of the prepared ammonia gas-sensitive material to 2ppm of ammonia gas is 7.53, the ammonia gas-sensitive material shows good selectivity to ammonia gas, and meanwhile, the ammonia gas-sensitive material has long-term stability to ammonia gas.
According to the invention, on the basis of SmCoO 3 materials, ag element is adopted to carry out surface loading and modification, mg element is adopted to carry out B-site doping, and noble metal and B-site composite doping modification is adopted, so that the prepared ammonia gas-sensitive material shows excellent sensitivity in detecting ammonia gas, and ammonia gas and other interference gases can be effectively distinguished. Meanwhile, the ammonia gas-sensitive material prepared by the invention can reduce the working temperature of the sensor to 80-220 ℃, reduce the energy consumption of the sensor, and is suitable for portable or low-power-consumption equipment.
The ammonia gas-sensitive material prepared by the invention has a nano particle structure, and the structure provides more active sites, so that the gas adsorption and reaction speed is effectively improved, and the response time of the ammonia gas-sensitive material to ammonia gas is only tens of seconds. Meanwhile, the ammonia gas-sensitive material prepared by the sol-gel method has simple and controllable process, and the material has better stability in long-term use.
Drawings
FIG. 1 is an XRD pattern of the silver-modified samarium cobalt magnesium oxide-based ammonia gas sensitive material prepared in example 1;
FIG. 2 is an SEM image of a silver-modified samarium cobalt magnesium oxide-based ammonia gas-sensitive material obtained in example 1;
FIG. 3 is a graph showing the relationship between the gas-sensitive properties and the temperature of the ammonia gas-sensitive material prepared in example 1 and comparative examples 1 to 3 with respect to 2 ppm NH 3 gas;
FIG. 4 is a graph showing the response of the ammonia gas-sensitive material prepared in example 1 to a plurality of gases of 2 ppm;
FIG. 5 is a schematic diagram showing the long-term gas-sensitive stability of the ammonia gas-sensitive material prepared in example 1 against 2 ppm of ammonia gas.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
Ammonia is used as a gas having a pungent odor, and is applied to various fields of chemical industry, agriculture, pharmacy, etc., and ammonia is also used as a diagnostic reagent in the medical industry. However, ammonia gas is used as a toxic pollutant, which can affect the immune system of human body or inhibit the growth of cells, and because ammonia gas is widely applied and produced in various fields, certain leakage is inevitably produced in the production process, when tiny leakage occurs, the concentration of ammonia gas is 0-10ppm, and the ammonia gas-sensitive material in the prior art can only detect 100ppm ammonia gas, and does not show good response to low-concentration ammonia gas.
Based on the above, the invention provides an ammonia gas-sensitive material Xwt% Ag-SmCo 1-yMgyO3. The ammonia gas-sensitive material is prepared by carrying out surface loading and modification on the ammonia gas-sensitive material by adopting Ag element and carrying out B-site doping on the ammonia gas-sensitive material by adopting Mg element on the basis of SmCoO 3 material. The prepared ammonia gas-sensitive material shows excellent sensitivity in detecting ammonia gas through the composite doping modification of noble metal and B site, particularly shows good response to low-concentration ammonia gas, particularly has a response value of 7.53 to 2ppm ammonia gas, and can effectively distinguish ammonia gas and other interference gases. Meanwhile, the ammonia gas-sensitive material prepared by the invention can reduce the working temperature of the sensor to 80-220 ℃, reduce the energy consumption of the sensor, and is suitable for portable or low-power-consumption equipment.
In the invention, ag element not only improves the gas-sensitive performance of the material through the traditional electron sensitization and chemical sensitization mechanism, but also interacts with the crystal structure of SmCoO 3, enhances the number and distribution of surface active sites of the material, and particularly shows higher surface energy in the adsorption process of ammonia molecules. The Ag loading initiates an electron transfer effect on the surface of the material, so that the reactivity of ammonia molecules under low concentration is obviously improved, and the overall gas-sensitive performance is further improved. In addition, ag also has good oxidation resistance, which helps to extend the life and stability of the material.
The B-site doping of Mg not only increases the number of oxygen vacancies by adjusting lattice distortion, but also remarkably regulates and controls the electrical conductivity of the material. The doping of Mg changes the electron distribution of the material and promotes the dissociation process of ammonia molecules, thereby improving the response speed and sensitivity in the detection of low-concentration ammonia. In addition, the addition of Mg enhances the gas-sensitive performance of the material in a wider temperature range, so that the material can still maintain higher detection efficiency under the condition of low temperature (80-220 ℃).
Through the synergistic effect of Ag element and Mg element, the material shows excellent detection capability on low-concentration ammonia gas. Specifically, the response value at 2ppm ammonia is 7.53, and the selectivity is good, so that ammonia and other interference gases can be effectively distinguished. The material realizes lower working temperature and lower energy consumption at the same time, and is particularly suitable for portable or low-power consumption gas sensor equipment.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
The experimental materials used in the embodiment of the invention are all conventional in the field and can be purchased through commercial channels.
Example 1 preparation of Ammonia gas sensitive Material 10wt% Ag-SmCo 0.5Mg0.5O3
(1) 44.442G of samarium nitrate, 7.415g of magnesium nitrate, 9.147g of cobalt nitrate, 3.75g of silver nitrate, 50g of citric acid and 10mL of dilute nitric acid are mixed, added into 50mL of deionized water, and stirred for 2h at room temperature to ensure that the mixture is fully dissolved and forms a uniform solution, so as to obtain a mixed solution;
(2) Transferring the mixed solution into hydrothermal reactivity, performing hydrothermal reaction at 180 ℃ for 12 hours, cooling to room temperature, filtering to obtain a solid product, washing the solid product with deionized water for 3 times to remove residual impurities, and drying at 60 ℃ for 6 hours to obtain precursor powder;
(3) The precursor powder was calcined at 700 ℃ for 3 hours to enhance its crystallinity and gas-sensitive properties, and the calcined product was ground to fine powder to obtain 10wt% Ag-SmCo 0.5Mg0.5O3 ammonia gas-sensitive material.
The ammonia gas-sensitive material prepared in this example was subjected to structural characterization of 10wt% Ag-SmCo 0.5Mg0.5O3, and the results are shown in FIGS. 1-2.
As can be seen from fig. 1, the crystallization peaks correspond to the (200), (020) and (220) crystalline phases of SmCoO 3 (No. 25-1071), and the (101) characteristic peak of Mg element and the (111) characteristic peak of Ag element can be clearly seen, whereby it can be seen that Ag element and Mg element are present in the material.
As can be seen from fig. 2, the ammonia gas-sensitive material has a typical nanoparticle structure, the specific surface area of the material is 13.8 m 2/g, and the pore diameter is 30-80: 80 nm, so that the ammonia gas-sensitive material prepared by the invention has larger specific surface area and larger pores, and the reaction sites and transmission channels of gas molecules in the ammonia gas-sensitive material are more.
Example 2 preparation of Ammonia gas sensitive Material 5 wt% Ag-SmCo 0.3Mg0.7O3
(1) 44.442G of samarium nitrate, 10.381g of magnesium nitrate, 5.488g of cobalt nitrate, 1.81g of silver nitrate, 60g of citric acid and 20mL of dilute nitric acid are mixed, added into 60mL of ionized water, and stirred for 1.5h at room temperature to ensure sufficient dissolution and form a uniform solution, so as to obtain a mixed solution;
(2) Transferring the mixed solution into hydrothermal reactivity, performing hydrothermal reaction at 120 ℃ for 10 hours, cooling to room temperature, filtering to obtain a solid product, washing the solid product with deionized water for 3 times to remove residual impurities, and drying at 40 ℃ for 8 hours to obtain precursor powder;
(3) The precursor powder is calcined at 700 ℃ for 5 hours to enhance the crystallinity and gas-sensitive property, and the calcined product is ground into fine powder to obtain 5 wt percent Ag-SmCo 0.3Mg0.7O3 ammonia gas-sensitive material.
Example 3 preparation of Ammonia gas sensitive Material 15 wt% Ag-SmCo 0.7Mg0.3O3
(1) 44.442G of samarium nitrate, 4.449g of magnesium nitrate, 12.805g of cobalt nitrate, 5.84g of silver nitrate, 55g of citric acid and 15mL of dilute nitric acid are mixed, added into 55mL of ionized water, and stirred at room temperature for 2.5h to ensure sufficient dissolution and form a uniform solution, so as to obtain a mixed solution;
(2) Transferring the mixed solution into hydrothermal reactivity, performing hydrothermal reaction at 200 ℃ for 14 hours, cooling to room temperature, filtering to obtain a solid product, washing the solid product with deionized water for 3 times to remove residual impurities, and drying at 80 ℃ for 2 hours to obtain precursor powder;
(3) The precursor powder is calcined at 1000 ℃ for 1h to enhance the crystallinity and gas-sensitive property, and the calcined product is ground into fine powder to obtain 15 wt percent Ag-SmCo 0.7Mg0.3O3 gas-sensitive material.
Example 4 preparation of Ammonia gas sensor
Uniformly mixing the ammonia gas-sensitive material prepared in the embodiment 1, deionized water and terpineol according to the addition ratio of 1g to 3mL to 1mL to obtain slurry, spin-coating the slurry on the surface of a ceramic tube of aluminum oxide at the rotating speed of 600 rpm to form a 208 mu m gas-sensitive film, placing the gas-sensitive film in air, and aging for 20h at 220 ℃ to obtain the ammonia gas-sensitive sensor.
Comparative example 1 preparation of Ammonia gas sensitive Material SmCoO 3
The difference between this comparative example and example 1 is that silver nitrate and magnesium nitrate were not added in step (1), and a gas-sensitive material of SmCoO 3 was produced.
Comparative example 2 preparation of Ammonia gas sensitive Material SmCo 0.5Mg0.5O3
The difference between this comparative example and example 1 is that in step (1), silver nitrate was not added, and the gas-sensitive material was SmCo 0.5Mg0.5O3.
Comparative example 3 preparation of Ammonia gas sensitive Material 10 wt% Ag-SmCoO 3
The difference between this comparative example and example 1 is that in step (1), magnesium nitrate was not added, and a gas-sensitive material of 10 wt% Ag-SmCoO 3 was produced.
Test example gas sensitivity test
The ammonia gas-sensitive materials prepared in example 1 and comparative examples 1 to 3 were coated on a sensing film, and their gas-sensitive responses (Rg/Ra) to 2ppm of gases such as NH 3, CO, etc., were measured, respectively, and the results are shown in FIGS. 3 to 4. Wherein Ra is the resistance of the sensor in the air, and Rg is the resistance of the measured gas. The experimental environment is RH of 20% and the ambient temperature of 20 ℃.
As can be seen from FIG. 3, the ammonia gas-sensitive material prepared by the present invention has an optimum operating temperature of 150 ℃. At the working temperature of 150 ℃, the response value of the prepared ammonia gas sensitive material to NH 3 gas of 2 ppm is 7.53, the response value of the prepared ammonia gas sensitive material SmCoO 3 of comparative example 1 to NH 3 gas of 2 ppm is 1.98, the response value of the prepared ammonia gas sensitive material SmCo 0.5Mg0.5O3 of comparative example 2 to NH 3 gas of 2 ppm by B-site doping of only Mg element to SmCoO 3 material is 2.78, the response value of the prepared ammonia gas sensitive material 10 wt% Ag-SmCoO 3 to NH 3 gas of 2 ppm by Ag element to SmCoO 3 material is 5.81, and the prepared ammonia gas sensitive material has a synergistic effect on improving the response value of the ammonia gas sensitive material to NH 3 gas by loading and modifying surface noble metal of SmCoO 3 material and doping Mg element to B site.
As can be seen from fig. 4, when contacting with various gases, the selectivity of the Ag-SmCo 0.5Mg0.5O3 of the ammonia gas-sensitive material 10 wt% to the 2 ppm NH 3 gas is obviously higher than that of gases including CO, CO 2 and the like, so that the ammonia gas-sensitive material prepared by the invention has good selectivity.
Long-term stability is another important property of gas sensitive materials. The higher the long-term stability, the longer the replacement cycle of the gas sensitive material, the more economical and energy-efficient. Fig. 5 shows the long-term stability of 10 wt% Ag-SmCo 0.5Mg0.5O3 to 2 ppm NH 3 gas of the ammonia gas-sensitive material made in accordance with the present invention. It can be seen that in one month, the response value change rate of 10 wt% Ag-SmCo 0.5Mg0.5O3 to 2 ppm NH 3 gas of the ammonia gas-sensitive material prepared by the invention is within 2%, which indicates that the material has extremely high gas-sensitive long-term stability.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. An ammonia gas-sensitive material is characterized in that the chemical formula of the ammonia gas-sensitive material is Xwt percent Ag-SmCo 1- yMgyO3, wherein 0<X is less than or equal to 20,0< y is less than or equal to 0.5, and the average granularity of the ammonia gas-sensitive material is 55-200nm;
the ammonia gas-sensitive material is prepared by the following method:
(1) Mixing samarium nitrate, magnesium nitrate, cobalt nitrate, silver nitrate, citric acid and dilute nitric acid according to the addition amount of (0.01-5) mol, (0.01-100) g, (20-100) g and (5-100) mL, adding into 10-150mL deionized water, and stirring to obtain a mixed solution;
(2) Cooling the mixed solution to room temperature after hydrothermal reaction to obtain a solid product, washing the solid product, and drying to obtain precursor powder, wherein the hydrothermal reaction temperature is 120-200 ℃ and the hydrothermal reaction time is 10-14h;
(3) Calcining the precursor powder at 500-1000 ℃ for 1-5h, and grinding to obtain Xwt% Ag-SmCo 1-yMgyO3 ammonia gas-sensitive material.
2. The ammonia gas-sensitive material of claim 1, wherein in step (1), the stirring time is 1.5 to 2.5 hours.
3. The ammonia gas-sensitive material of claim 1, wherein in step (2), the drying temperature is 40 to 80 ℃ and the drying time is 2 to 8 hours.
4. Use of an ammonia gas-sensitive material according to any one of claims 1-3 for detecting ammonia and/or for producing an ammonia gas-sensitive sensor.
5. The use according to claim 4, wherein the ammonia gas has a gas concentration of 1 to 10ppm.
6. The use according to claim 4, wherein the ammonia gas sensor is prepared by the following method:
Mixing the ammonia gas-sensitive material, deionized water and terpineol according to any one of claims 1-3 to obtain slurry, spin-coating the slurry on an alumina substrate to form a gas-sensitive film, and aging the gas-sensitive film to obtain the ammonia gas-sensitive sensor.
7. The method according to claim 6, wherein the ammonia gas-sensitive material, deionized water and terpineol are added in a ratio of (1-5) g (3-15) mL (1-5) mL, the aging temperature is 200-240 ℃, and the aging time is 10-24h.
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