CN111693579A - Hydrogen sulfide gas detection method and sensor based on nanosheet composite membrane - Google Patents
Hydrogen sulfide gas detection method and sensor based on nanosheet composite membrane Download PDFInfo
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Abstract
The invention discloses a hydrogen sulfide gas detection method and a hydrogen sulfide gas detection sensor based on a nanosheet composite membrane2Nanosheet composite material and preparation method based on Au/SnO-SnO2Hydrogen sulfide gas sensor of nanosheet composite membrane and detection method H2And S. The results show that the sensor pair H2S has good sensing performance. Under the conditions of working temperature of 240 ℃ and ambient temperature of 25 ℃, the product is preparedSensor pair H2S presents a good linear response relation in the range of 1-100 ppm, and the lower detection limit is as low as 0.7 ppm. The sensor has the advantages of quick response-recovery time, 22s of response time and 63s of recovery time, is not influenced by the ambient humidity, and has good reproducibility, selectivity and stability. The sensor is applied to the atmospheric environment H2S monitoring, H within 90 days2The response signal of S is only attenuated by 4.69%, which shows that the sensor has long-term stable and continuously-operated service life and has important practical application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical/biological sensing, and particularly relates to a hydrogen sulfide gas detection method and a hydrogen sulfide gas detection sensor based on a nanosheet composite membrane.
Background
Hydrogen sulfide (H)2S) is a toxic, colorless gas, since hydrogen sulfide is an acute toxic substance, and even inhalation of small amounts of high concentrations of hydrogen sulfide can lead to death in a short period of time. Low concentrations of hydrogen sulfide also damage the eye and respiratory system as well as the central nervous system, and therefore, the development of a high performance hydrogen sulfide gas sensor is critical to environmental protection and human life health.
In recent years, metal oxide semiconductors such as SnO2、ZnO、WO3、CuO、Co3O4NiO and In2O3And the like, and is widely applied to detecting various gases such as H due to the advantages of low cost, high sensitivity, simple manufacture, good chemical stability and the like2S、NO2、NH3、CO、H2、C2H5OH, formaldehyde, volatile gases, and the like. SnO2The N-type metal oxide semiconductor material has a wide forbidden band of about 3.6eV, is low in price and non-toxic, and is known as one of the most sensitive gas sensitive materials. It has rutile crystal structure, and has special physical and chemical properties and electric characteristics, so that it can be used for monitoring gasSnO2The method has the advantages of high responsiveness, strong selectivity, good detectability and the like. Zhang et al prepared three-dimensional porous SnO2To Cl2The high response is realized mainly due to the fact that the small grain size changes the electron migration rate, and meanwhile, the specific surface area can be improved through the unique three-dimensional structure, sufficient adsorption sites are provided, and the gas-sensitive performance is improved. Zeng et al prepared SnO with n-n heterostructure by solvothermal method2-Sn3O4Material, sensor pair NO2Is very sensitive, probably because of the large specific surface area of the composite and the unique n-n heterostructure. Park et al prepared SnO having a one-dimensional high pore structure2The porous form of the CuO hollow nano fiber improves the interaction between the surface and the adsorption molecules, improves the gas-sensitive performance and can reduce the working temperature. Thus, SnO is selected according to the present invention2As a detection H2S substrate material, and H with better sensing performance is obtained by material modification2And (S) a gas sensor.
It is well known that a heterojunction is formed by forming a physical interface region between two chemically distinct semiconductor or metallic materials between which three distinct heterojunctions, namely p-p, n-n and p-n junctions, may exist. The nanostructure with the heterojunction can solve the inherent limitation of the gas sensor and can also effectively reduce the working temperature of the sensor. Therefore, heterojunctions have been developed in recent years for gas detection. Li et al synthesized flower-like SnO-SnO by one-step hydrothermal method2The gas-sensitive material shows excellent gas-sensitive performance to formaldehyde gas and can be attributed to the unique layered structure and SnO2A p-n heterojunction is formed in between. Navale et al prepared a CuO nanoparticle-ZnO nanowire heterojunction gas sensor to NO2Has good sensing performance. Thus, SnO may be treated2And the p-type metal oxide semiconductor is combined to form a p-n heterojunction to improve the gas sensing performance.
The formation of composite materials using transition metal or noble metal doping is also one of the most effective strategies to improve the performance of metal oxide gas sensors. It is widely believed that goldThe presence of a metal element (Ce, Co, Fe, Pt, Pd, Ag, Au, etc.) on the surface of the metal oxide enhances the interaction of the reducing gas with the adsorbed oxygen on the surface of the material Sui et al prepared gold nanoparticle doped grades α -MoO3The improvement of the gas-sensitive performance of the hollow sphere, the sensor to toluene and xylene can be attributed to the formation of multilayer hollow nano-structure and the 'overflow effect' and catalytic effect of Au nano-particles. Zhou et al successfully prepared Ag modified ZnO nanorods using a solvothermal method. Compared with a pure ZnO nano rod, the gas-sensitive performance of the doped sensor is improved. Au has lower cost than Pt and Pd and better thermal stability than Ag, so Au is widely applied to improving gas-sensitive performance. Therefore, the gas sensing performance of the material can be improved by doping Au. However based on Au/SnO-SnO2The nano-sheet composite membrane is not reported to be used for sensing and detecting hydrogen sulfide gas.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a hydrogen sulfide gas detection method and a hydrogen sulfide gas detection sensor based on a nanosheet composite membrane.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the method comprises the following steps:
(1) preparation of Au/SnO-SnO2Nano-sheet composite material:
SnCl2·2H2Dissolving O and urea in deionized water, and uniformly stirring to form white turbid liquid; adding chloroauric acid solution into the white turbid liquid, and changing the white turbid liquid into light pink turbid liquid; transferring the obtained light pink turbid liquid into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 10-20 h at 150-200 ℃, cooling, centrifuging, washing with deionized water and absolute ethyl alcohol for multiple times in sequence, and drying for 20-30 h at 45-55 ℃; grinding to obtain gray black powder, namely Au/SnO-SnO2Nanosheets; wherein, the SnCl2·2H2The molar ratio of O to urea is 1:3 to 1:5, and the SnCl2·2H2The molar volume ratio of O to deionized water is 0.0006mol:55mL to 0.0010mol:65mL, the molar volume ratio of urea to deionized water is 0.0025mol:55mL to 0.0040mol:65mL,the molar concentration of the chloroauric acid solution is 20-30 mM, and the volume ratio of the white turbid solution to the chloroauric acid solution is 55mL:80 muL to 65mL:130 muL.
(2) Preparation of a catalyst based on Au/SnO-SnO2Hydrogen sulfide gas sensor of the nanosheet composite membrane:
adopting an aluminum oxide ceramic tube gold electrode as a matrix electrode; the prepared Au/SnO-SnO2Mixing the nano-sheet composite film powder with water to form paste, uniformly dripping the paste on the outer surface of the alumina ceramic tube, and coating N on the outer surface of the alumina ceramic tube2Calcining for 0.5-1.5 h at the temperature of 350-450 ℃ in the atmosphere to form Au/SnO-SnO2A nano-sheet composite film alumina ceramic tube gold electrode; mixing Au/SnO-SnO2The gold electrode of the nano-sheet composite film alumina ceramic tube is welded on the six-pin rubber base at Au/SnO-SnO2A nickel-chromium alloy coil penetrates through the middle of the ceramic tube of the nanosheet composite film alumina ceramic tube gold electrode, and the purpose of controlling the working temperature of the sensor is achieved by heating the nickel-chromium alloy coil; to obtain the product based on Au/SnO-SnO2A hydrogen sulfide gas sensor of a nano-sheet composite film;
(3) and (3) detecting hydrogen sulfide: based on Au/SnO-SnO2The resistance values measured by exposing the hydrogen sulfide gas sensor of the nanosheet composite membrane in the air atmosphere and the hydrogen sulfide atmosphere are respectively recorded as RaAnd RgBased on Au/SnO-SnO2The response value S of the hydrogen sulfide gas sensor of the nanosheet composite membrane to hydrogen sulfide gas is represented by the following formula:
S(％)＝ΔR/Ra＝(Rg-Ra)/Ra×100％。；
the response/recovery time of the gas sensor is defined as the time required for the sensor to stabilize the resistance in air and for the change in the stabilized resistance in hydrogen sulfide gas to reach 90%, respectively denoted as τrepAnd τrec。
Preferably, the step (1) is to mix SnCl2·2H2Dissolving O and urea in deionized water, and uniformly stirring to form white turbid liquid; adding chloroauric acid solution into the white turbid liquid, and changing the white turbid liquid into light pink turbid liquid; transferring the obtained light pink turbid liquid into polytetrafluoroethylene high-pressure reactionReacting in a kettle at 180 ℃ for 16h, cooling, centrifuging, washing with deionized water and absolute ethyl alcohol for multiple times in sequence, and drying at 50 ℃ for 24 h; grinding to obtain gray black powder, namely Au/SnO-SnO2Nanosheets; wherein, the SnCl2·2H2The molar ratio of O to urea is 1:4, and the SnCl2·2H2The molar volume ratio of O to deionized water is 0.0008mol:60mL, the molar volume ratio of urea to deionized water is 0.0032mol:60mL, the molar concentration of chloroauric acid in the chloroauric acid solution is 24mM, and the volume ratio of white turbid liquid to the chloroauric acid solution is 60mL:108 muL.
Preferably, the calcining temperature in the step (2) is 400 ℃, and the calcining time is 1 h.
Preferably, in the step (2), Au/SnO-SnO base is obtained2The hydrogen sulfide gas sensor of the nano-sheet composite film is based on Au/SnO-SnO2The hydrogen sulfide gas sensor of the nano-sheet composite membrane is exposed in dry air and aged for 36-60 h at 200-300 ℃, preferably for 48h at 260 ℃ so as to improve the stability of the sensor.
The sensor for detecting hydrogen sulfide based on the nano-sheet composite film comprises a sensor body, the outer surface of which is provided with Au/SnO-SnO2An alumina ceramic tube gold electrode (2) of a nano-sheet composite film (5).
Preferably, the sensor also comprises a six-pin rubber base (3), and the drops are coated with Au/SnO-SnO2The aluminum oxide ceramic tube gold electrode (2) of the nano-sheet composite film is welded to six pins of the six-pin rubber base (3) through platinum wires (1).
Preferably, the outer surface is provided with Au/SnO-SnO2The aluminum oxide ceramic tube gold electrode (2) of the nanosheet composite membrane (5) comprises an aluminum oxide ceramic tube (6), a nickel-chromium alloy coil (4) penetrates through the middle of the aluminum oxide ceramic tube (6), a gold electrode (7) is arranged on the aluminum oxide ceramic tube (6), and Au/SnO-SnO2The nano-sheet composite film (5) is arranged on the outer surface of the gold electrode (7) of the alumina ceramic tube (6).
Preferably, the Au/SnO-SnO2The nano-sheet composite film (5) is composed of a plurality of SnO-SnO2Nanosheet (8) and SnO attached thereto2Au particles (9) on the nanosheets (8); the thickness of the nanosheet (8) is 0.5-1.5 nm, preferably 1.0 nm; the diameter of the Au particles is 0.5-2.5 nm, and preferably 1.5 nm; the Au/SnO-SnO2The thickness of the nano-sheet composite film (5) is 20-100 nm, preferably 60 nm.
In more detail, the platinum wire has a diameter of about 50 μm; the inner diameter of the gold electrode of the alumina ceramic tube is 2mm, the outer diameter is 3mm, and the height is 6 mm; the diameter of the nickel-chromium alloy coil is about 50 mu m; the inner diameter of the alumina ceramic pipe is 2mm, the outer diameter is 3mm, and the height is 6 mm; the gold electrode is 1mm wide and 0.1mm thick.
Preferably, the linear range of the response of the sensor to hydrogen sulfide is 1-100 ppm, and the lower detection limit reaches 0.7 ppm.
The invention is further illustrated below:
the invention adopts a one-pot hydrothermal method to prepare Au/SnO-SnO2Dropping the nano sheet material onto the gold electrode of the alumina ceramic tube by a dropping method to form a thin nano composite film on the surface, thus preparing the novel H-shaped nano composite film2And (5) an S sensor. The microstructure and morphology of the material are characterized by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and the gas-sensitive performance of the material is tested. The test result shows that Au/SnO-SnO2Nanosheet composite pair H2S has good sensing performance. Under the conditions that the working temperature is 240 ℃ and the environmental temperature is 25 ℃, the manufactured sensor pair H2S presents a good linear response relation in the range of 1-100 ppm, and the lower detection limit is as low as 0.7 ppm. The sensor has the advantages of quick response-recovery time, 22s of response time and 63s of recovery time, is not influenced by the ambient humidity, and has good reproducibility, selectivity and stability. The sensor is applied to the atmospheric environment H2S monitoring, H within 90 days2The response signal of S is only attenuated by 4.69%, which shows that the sensor has long-term stable and continuously-operated service life and has important practical application prospect.
Drawings
FIG. 1 is a diagram based on Au/SnO-SnO2A structural schematic diagram of a hydrogen sulfide gas sensor of the nanosheet composite membrane;
FIG. 2 is a schematic cross-sectional view of a composite film alumina ceramic tube gold electrode;
FIG. 3 shows Au/SnO-SnO2A schematic cross-sectional view of the nano-sheet composite film;
FIG. 4 is an SEM image of different nanomaterials; in the figure: SnO-SnO2 nanosheets (a); Au/SnO-SnO2 nanosheets (b);
FIG. 5 is a TEM image of different nanomaterials; in the figure: SnO-SnO2 nanosheets (a); Au/SnO-SnO2 nanosheets (b); high power TEM SnO2 nanosheets (c); Au/SnO-SnO2 nanosheets (d);
FIG. 6 shows Au/SnO-SnO based on different working temperatures2Hydrogen sulfide gas sensor pair of nanosheet composite membrane with 100ppm H2A response relation curve of S;
FIG. 7 shows Au/SnO-SnO based on different environmental humidities2Hydrogen sulfide gas sensor pair of nanosheet composite membrane with 100ppm H2A response relation curve of S;
FIG. 8 shows Au/SnO-SnO based on different environmental temperatures2Hydrogen sulfide gas sensor pair of nanosheet composite membrane with 100ppm H2A response relation curve of S;
FIG. 9 is a graph based on Au/SnO-SnO2Hydrogen sulfide gas sensor of nanosheet composite membrane for different concentrations of H2A dynamic response curve (A) of S and a relation curve (B) of response values and concentrations;
FIG. 10 is a graph based on Au/SnO-SnO2Hydrogen sulfide gas sensor pair H of nanosheet composite membrane2S, a dynamic response curve (A) and a response-recovery curve (B) which are continuously five times;
FIG. 11 shows Au/SnO-SnO in the same batch2Hydrogen sulfide gas sensor pair of nanosheet composite membrane with 100ppm H2A response comparison graph (A) of S and a response comparison graph (B) of the sensor to different gases of 100 ppm;
FIG. 12 is a graph based on Au/SnO-SnO2Hydrogen sulfide gas sensor pair of nanosheet composite membrane with 100ppm H2S, a stability curve graph of long-term monitoring;
FIG. 13 is a graph based on Au/SnO-SnO2Hydrogen sulfide gas sensor pair H of nanosheet composite membrane2And S response mechanism diagram.
In the figure: 1.a platinum wire; 2. an alumina ceramic tube gold electrode; 3. a six-legged rubber base; 4. a nickel-chromium alloy coil; 5. Au/SnO-SnO2A nanosheet composite membrane; 6. an alumina ceramic tube; 7. a gold electrode; 8. SnO-SnO2Nanosheets; 9. and Au particles.
Detailed Description
In the examples, the water used was ultrapure water (resistivity: 18.3 M.OMEGA.. multidot.cm).
First, the experimental process
1、Au/SnO-SnO2Preparation of nanosheet composite
Au/SnO-SnO synthesized by hydrothermal method2A nanocomposite material. 0.0008mol of SnCl2·2H2Dissolving O and 0.0032mol of urea in 60mL of deionized water, and uniformly stirring to form white turbid liquid. Then 108. mu.L of 24mM chloroauric acid solution was added to the white turbid solution, and the white turbid solution became a pale pink turbid solution. Transferring the obtained light pink turbid liquid into a 100mL polytetrafluoroethylene high-pressure reaction kettle, reacting for 16h at 180 ℃, cooling, centrifuging, washing with deionized water and absolute ethyl alcohol for multiple times in sequence, and drying for 24h at 50 ℃. Grinding to obtain gray black powder, and obtaining Au/SnO-SnO2Nanosheet (Au/SnO-SnO)2NS). For comparison, SnO-SnO was prepared by the same method as above without adding chloroauric acid2Nanosheet (SnO-SnO)2NS)。
2、Au/SnO-SnO2Preparation and testing of sensors
An alumina ceramic tube gold electrode with the inner diameter of 2mm, the outer diameter of 3mm and the height of 6mm is used as a substrate electrode. Firstly, the prepared Au/SnO-SnO2Mixing NS powder with water to form paste, and uniformly dripping the paste on the outer surface of the alumina ceramic tube2Calcining for 1h at 400 ℃ in the atmosphere to form Au/SnO-SnO2NS composite film alumina ceramic tube gold electrode, namely based on Au/SnO-SnO2A hydrogen sulfide gas sensor of the NS composite membrane; then, the electrode is welded on a six-pin rubber base, a nickel-chromium alloy coil penetrates through the middle of the ceramic tube, and the purpose of controlling the working temperature of the sensor is achieved by heating the alloy coil. The soldered sensor was exposed to dry air,aging at 260 ℃ for 48h improves the stability of the sensor. The resistance values measured when the sensor is exposed to air and the measured air are respectively recorded as RaAnd Rg. The response value (S) of the sensor to the target gas is expressed by the following equation:
S(％)＝ΔR/Ra＝(Rg-Ra)/Ra×100％
the response/recovery time of the gas sensor is defined as the time required for the stable resistance of the sensor in the air and the stable resistance variation of the gas to be measured to reach 90%, which are respectively recorded as taurepAnd τrec。
Referring to fig. 1 to 3, the sensor for detecting hydrogen sulfide comprises a sensor body with an external surface provided with Au/SnO-SnO2And the aluminum oxide ceramic tube gold electrode 2 of the nano-sheet composite film 5. The sensor also comprises a six-pin rubber base 3, and the droplets are coated with Au/SnO-SnO2The aluminum oxide ceramic tube gold electrode 2 of the nano-sheet composite film 5 is welded to six pins of the six-pin rubber base 3 through platinum wires 1. The outer surface is provided with Au/SnO-SnO2The gold electrode 2 of the alumina ceramic tube of the nano-sheet composite film 5 comprises an alumina ceramic tube 6, a nickel-chromium alloy coil 4 penetrates through the alumina ceramic tube 6, a gold electrode 7 is arranged on the alumina ceramic tube 6, and Au/SnO-SnO2The nano-sheet composite film 5 is arranged on the outer surface of a gold electrode 7 of the alumina ceramic tube 6. The Au/SnO-SnO2The nano-sheet composite film 5 is composed of a plurality of SnO-SnO2Nanosheet 8 and SnO adhered thereto2 Au particles 9 on the nanosheets 8; the thickness of the nano-sheet 8 is 1.0nm, the diameter of the Au particle 9 is 1.5nm, and the Au/SnO-SnO2The thickness of the sheet composite film 5 was 60 nm.
Second, experimental results and analysis
1. Characterization of materials
The prepared nanocomposites were characterized using Scanning Electron Microscopy (SEM). FIG. 4a shows that the prepared SnO-SnO2The composite material is in the form of a sheet. Au-doped SnO visible in FIG. 4b2The composite material is also in the form of a sheet and a plurality of particles, preferably Au in the form of particles, are attached to the sheetIs adhered on SnO-SnO2On the chip. The TEM representation of FIG. 5 also confirms that the prepared material is in the form of flakes, and from FIG. 5a it can be seen that SnO-SnO of the flakes2About 1.0nm thick, it can be seen from FIG. 5b that there are many small particles on the sheet, which may be SnO-SnO attached2Au nanoparticles on the sheet, the Au nanoparticles having a particle size of about 1.5 nm; as can be seen from FIGS. 4 and 5, Au/SnO-SnO2The thickness of the sheet composite film was about 60 nm. FIGS. 5c and 5d show SnO-SnO, respectively2Nanosheets and Au/SnO-SnO2High-power TEM images of the nanosheets, both of which show very clear lattice fringes, have lattice spacings of 0.328nm and 0.330nm respectively and correspond to SnO2The (110) crystal plane of (a).
2. Working temperature versus Au/SnO-SnO2Detection of influence of hydrogen sulfide by nanosheet sensor
An important factor in measuring the performance of a gas sensor is the operating temperature. In order to determine the optimal working temperature of the Au/SnO-SnO2 nanosheet sensor for detecting hydrogen sulfide, the response behavior of the sensor 100ppm H2S is studied within the range of 80-340 ℃. As shown in fig. 6, the response curve of the sensor to H2S shows a unimodal pattern with rising first and falling second in the above-described operating temperature range. When the working temperature is within the range of 80-240 ℃, the responsivity of the sensor is greatly increased, because the activation energy required by the adsorption of H2S and the gas sensitive material cannot be reached when the temperature is lower, the temperature rise response value is also increased. When the working temperature is in the range of 240-340 ℃, the sensitivity of the sensor is in a descending trend. Since the response values of the sensors are almost the same and the reaction times are almost the same when the operating temperatures are 240 c, 260 c and 300 c, respectively, in order to reduce the energy consumption during the experiment, 240 c is selected as the optimum operating temperature of the sensor as the lower the operating temperature is.
3. Ambient humidity vs. Au/SnO-SnO2Detection of effects of Hydrogen sulfide by nanosheets
The sensor is examined for 100ppm H within the humidity range of 10% -100%2And (5) response rule of S. As can be seen from FIG. 7, the sensor exhibited a tendency to rise and fall over the entire humidity range, but the rising and falling trends were smallThe response value is 80.15% on average, and the relative standard deviation is 3.10%, which shows that the sensor has good moisture resistance, so the influence caused by the change of the ambient humidity in the whole experiment process can be ignored.
4. Ambient temperature versus Au/SnO-SnO2Detection of influence of hydrogen sulfide by nanosheet sensor
Examine the sensor pair 100ppm H at a temperature range of 10 ℃ to 40 DEG C2S response curve. As can be seen from fig. 8, the sensor response is almost flat at temperatures between 10 c and 30 c, and after 30 c, the response drops slightly. Overall, the average response value of the sensor is 80.43%, and the relative deviation is 3.15%, which indicates that the performance of the sensor is not greatly affected by the temperature in this temperature range, and the ambient temperature of 25 ℃ is selected as the subsequent test condition because the response time is shortest at 25 ℃.
5、Au/SnO-SnO2Nanosheet sensor pair H2Linear response performance of S
Under the conditions that the working temperature is 240 ℃ and the ambient temperature is 25 ℃, the sensor is used for detecting H with the concentration range of 3ppm to 300ppm2S was tested (fig. 9A). FIG. 9B is a graph of sensor response versus concentration. The response value of the sensor increases with the increase of the concentration, but the response value tends to be stable when the concentration reaches 100 ppm. From the interpolation graph of fig. 9B, it can be seen that the response value of the sensor and the concentration exhibit a good linear relationship at concentrations of 1ppm to 100ppm, and the lower limit of detection reaches 0.7 ppm.
6. Repeatability, reproducibility and selectivity tests
Five consecutive exposures of the same sensor to the same concentration of H2In the S gas atmosphere, a corresponding recovery-response curve is obtained, and as seen from FIG. 10A, the five-time response relationship is basically consistent, and it can be seen that the repeatability of the sensor is good. Fig. 10B is a partial enlarged view thereof, and it can be seen that the response time is fast, 22s, and the recovery time is 63 s.
In addition, six sensors prepared from the same batch were exposed to 100ppm of H, respectively2S gas, as shown in FIG. 11A, six sensor responsesAlmost the same, the average was 81.76% and the relative deviation was 2.8%, indicating good reproducibility of the sensor. The sensors were exposed to 100ppm of H, respectively2S, ethanol, NH3Formaldehyde and methanol, the selectivity of the sensor was examined. As can be seen in FIG. 11B, sensor pair H2S gas response is maximal for ethanol, methanol, formaldehyde and NH3Is relatively small, indicating that the prepared sensor pair H2S has better selectivity.
7. Stability of
Test type sensor for 100ppm H within 90 days2S is tested. It can be seen from fig. 12 that the response of the sensor decreases slightly with time. The response of the sensor averaged 80.64% over 90 days, with a 4.69% decay. The sensor has good stability and long service life.
8. Sensing mechanism of sensor
The gas-sensitive test results clearly prove that the Au/SnO-SnO based on the p-n heterojunction2Gas sensor pair H of nanosheet composite membrane2The S gas has very good sensing response performance. Furthermore, Table 1 lists SnO-based catalysts2Is different from H2Sensing characteristics of S gas sensor, and other reported H' S listed in Table 12Compared with S gas sensor, Au/SnO-SnO2The nano-sheet composite film sensor has the advantages of reducing the working temperature, along with quick response time and recovery time and higher responsiveness.
TABLE 1 SnO base2Is different from H2Gas sensitivity performance comparison of S-sensor
Remarking: op.temp. refers to the operating temperature; res, refers to the response value; Res./Conc. means for corresponding concentration H2The response value of S gas; res.def. refers to response definition; t isres/TrecRefers to response-recovery time; LOD refers to the lower limit of detection.
The Au/SnO-SnO2Nanosheet sensor in detecting H2And S represents the sensing behavior of the n-type metal oxide semiconductor. In general, the sensing mechanism can be explained by the change of the sensor resistance caused by the adsorption and desorption process of gas molecules on the surface of the material. As shown in FIG. 13, when Au/SnO-SnO2When the nano-sheet is exposed in the air, oxygen molecules are adsorbed on the surface of the nano-sheet in a physical adsorption and chemical adsorption mode, and are captured from Au/SnO-SnO2Electrons are obtained from conduction band of the nano-sheet to form oxygen anions such as O2-、O-And O2 -As shown in equations (1, 2, 3). The reaction on the surfaces can form a thick electron depletion layer on the surfaces, so that Au/SnO-SnO2The concentration of free electrons in the nanosheets is reduced, the conductivity is reduced, and the resistance is increased. When Au/SnO-SnO2Nanosheet exposure to H2In S, H2S reacts with oxygen anions on the surface of the material, and the previously captured electrons return to Au/SnO-SnO2In the nano-sheet conduction band, Au/SnO-SnO is reduced2The thickness of the electron depletion layer on the surface in the conduction band of the nanosheet is increased, the conductivity is increased, and the resistance is reduced as shown in equation (4).
O2(air)→O2(ads) (1)
O2(ads)+e-→O2 -(ads) (2)
O2 -(ads)+e-→2O-(ads) (3)
H2S(g)+3O-(ads)→H2O(g)+SO2(g)+3e-(4)。
Claims (10)
1. A hydrogen sulfide gas detection method based on a nanosheet composite membrane is characterized by comprising the following steps:
(1) preparation of Au/SnO-SnO2Nano-sheet composite material:
SnCl2·2H2Dissolving O and urea in deionized water, and uniformly stirring to form white turbid liquid; then white turbid liquidAdding chloroauric acid solution, and changing white turbid liquid into light pink turbid liquid; transferring the obtained light pink turbid liquid into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 10-20 h at the temperature of 150-; grinding to obtain gray black powder, namely Au/SnO-SnO2Nanosheets; wherein, the SnCl2·2H2The molar ratio of O to urea is 1:3 to 1:5, and the SnCl2·2H2The molar volume ratio of O to deionized water is 0.0006mol:55mL to 0.0010mol:65mL, the molar volume ratio of urea to deionized water is 0.0025mol:55mL to 0.0040mol:65mL, the molar concentration of the chloroauric acid solution is 20-30 mM, and the volume ratio of the white turbid liquid to the chloroauric acid solution is 55mL:80 muL to 65 muL: 130 muL;
(2) preparation of a catalyst based on Au/SnO-SnO2Hydrogen sulfide gas sensor of the nanosheet composite membrane:
adopting an aluminum oxide ceramic tube gold electrode as a matrix electrode; the prepared Au/SnO-SnO2Mixing the nano-sheet composite film powder with water to form paste, uniformly dripping the paste on the outer surface of the alumina ceramic tube, and coating N on the outer surface of the alumina ceramic tube2Calcining for 0.5-1.5 h at the temperature of 350-450 ℃ in the atmosphere to form Au/SnO-SnO2A nano-sheet composite film alumina ceramic tube gold electrode; mixing Au/SnO-SnO2The gold electrode of the nano-sheet composite film alumina ceramic tube is welded on the six-pin rubber base at Au/SnO-SnO2A nickel-chromium alloy coil penetrates through the middle of the ceramic tube of the nanosheet composite film alumina ceramic tube gold electrode, and the purpose of controlling the working temperature of the sensor is achieved by heating the nickel-chromium alloy coil; to obtain the product based on Au/SnO-SnO2A hydrogen sulfide gas sensor of a nano-sheet composite film;
(3) and (3) detecting hydrogen sulfide: based on Au/SnO-SnO2The resistance values measured by exposing the hydrogen sulfide gas sensor of the nanosheet composite membrane in the air atmosphere and the hydrogen sulfide atmosphere are respectively recorded as RaAnd RgBased on Au/SnO-SnO2The response value S of the hydrogen sulfide gas sensor of the nanosheet composite membrane to hydrogen sulfide gas is represented by the following formula:
S (%) = ΔR/Ra= (Rg-Ra)/Ra×100 %。
2. the method of claim 1, wherein step (1) is performed by adding SnCl2·2H2Dissolving O and urea in deionized water, and uniformly stirring to form white turbid liquid; adding chloroauric acid solution into the white turbid liquid, and changing the white turbid liquid into light pink turbid liquid; transferring the obtained light pink turbid liquid into a polytetrafluoroethylene high-pressure reaction kettle, reacting for 16h at 180 ℃, cooling, centrifuging, washing with deionized water and absolute ethyl alcohol for multiple times in sequence, and drying for 24h at 50 ℃; grinding to obtain gray black powder, namely Au/SnO-SnO2Nanosheets; wherein, the SnCl2·2H2The molar ratio of O to urea is 1:4, and the SnCl2·2H2The molar volume ratio of O to deionized water is 0.0008mol:60mL, the molar volume ratio of urea to deionized water is 0.0032mol:60mL, the molar concentration of chloroauric acid in the chloroauric acid solution is 24mM, and the volume ratio of white turbid liquid to the chloroauric acid solution is 60mL:108 muL.
3. The method of claim 1, wherein the calcining temperature in step (2) is 400 ℃ and the calcining time is 1 h.
4. The method of claim 1, wherein in step (2), a catalyst based on Au/SnO-SnO is obtained2The hydrogen sulfide gas sensor of the nano-sheet composite film is based on Au/SnO-SnO2The hydrogen sulfide gas sensor of the nanosheet composite membrane is exposed in dry air and aged for 36-60 hours at the temperature of 200-300 ℃ so as to improve the stability of the sensor.
5. The method of claim 4, wherein in step (2), Au/SnO-based alloy is obtained2The hydrogen sulfide gas sensor of the nano-sheet composite film is based on Au/SnO-SnO2Exposing the hydrogen sulfide gas sensor of the nano-sheet composite membrane in dry air, and aging at 260 ℃ for 48h。
6. A sensor for detecting hydrogen sulfide based on a nanosheet composite membrane is characterized by comprising a sensor body, the outer surface of which is provided with Au/SnO-SnO2An alumina ceramic tube gold electrode (2) of a nano-sheet composite film (5).
7. The sensor according to claim 6, characterized in that it further comprises a hexapod rubber base (3), said drops being coated with Au/SnO-SnO2The aluminum oxide ceramic tube gold electrode (2) of the nano-sheet composite film is welded to six pins of the six-pin rubber base (3) through platinum wires (1).
8. The sensor of claim 7, wherein the outer surface is provided with Au/SnO-SnO2The aluminum oxide ceramic tube gold electrode (2) of the nanosheet composite membrane (5) comprises an aluminum oxide ceramic tube (6), a nickel-chromium alloy coil (4) penetrates through the middle of the aluminum oxide ceramic tube (6), a gold electrode (7) is arranged on the aluminum oxide ceramic tube (6), and Au/SnO-SnO2The nano-sheet composite film (5) is arranged on the outer surface of the gold electrode (7) of the alumina ceramic tube (6).
9. The sensor of claim 8, wherein the Au/SnO-SnO is present in the composition2The nano-sheet composite film (5) is composed of a plurality of SnO-SnO2Nanosheet (8) and SnO attached thereto2Au particles (9) on the nanosheets (8); the thickness of the nanosheet (8) is 0.5-1.5 nm, and the diameter of the Au particle is 0.5-2.5 nm; the Au/SnO-SnO2The thickness of the nano-sheet composite film (5) is 20-100 nm.
10. The sensor of any one of claims 6 to 9, wherein the sensor has a linear response to hydrogen sulfide in the range of 1 to 100ppm with a lower detection limit of 0.7 ppm.
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