CN114917864A - Hollow gas-sensitive material and preparation method and application thereof - Google Patents
Hollow gas-sensitive material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 11
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- 238000000034 method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
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- 239000002904 solvent Substances 0.000 claims description 6
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- 238000010438 heat treatment Methods 0.000 claims description 5
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 claims description 5
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 4
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- 238000002604 ultrasonography Methods 0.000 claims description 4
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- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
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- 238000005245 sintering Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 46
- 239000000243 solution Substances 0.000 description 10
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- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/28016—Particle form
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- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
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- 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
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Abstract
The invention discloses a hollow gas-sensitive material and a preparation method and application thereof, belonging to the technical field of formaldehyde test 2 O 3 /BiFeO 3 The hollow sphere structure is formed. Bi exemplified in the present invention 2 O 3 /BiFeO 3 The hollow gas-sensitive material has higher sensitivity to formaldehyde, and researches show that: the molar ratio Bi to Fe in the raw materials is 2:3, the gas-sensitive material prepared at the sintering temperature of 450 ℃ has good gas-sensitive performance, the optimal working temperature is 240 ℃, the response value to 100ppm formaldehyde is 45.9, the response recovery time is 34s and 21s respectively, and the gas-sensitive material is detectedThe detection limit reaches 1ppm, and the method has better repeatability and selectivity.
Description
Technical Field
The invention relates to the technical field of formaldehyde testing, in particular to a hollow gas-sensitive material with high sensitivity to formaldehyde and a preparation method and application thereof.
Background
With the rapid development of industry, some environmental issues, especially indoor health issues, have received great attention. Formaldehyde is one of the most representative indoor air pollutants, is a colorless, inflammable and pungent gas at room temperature, can enter a human body through a respiratory tract system, a digestive tract system and a skin system, further influences a nervous system, makes people feel uncomfortable and pay attention toDisperse, reduced work efficiency, headache, nausea, fatigue, red and swollen skin, and the like, which may cause deformity, leukemia and various cancers of infants if serious. Indoor decoration, carpets, wood and plastic products, etc. release formaldehyde. Although the indoor formaldehyde exceeds the standard, the concentration is not high enough, the irritant odor is hardly smelled, the indoor environment is safe, and the release period of the formaldehyde is 3-15 years. Indoor formaldehyde pollution has become an "invisible killer" that is harmful to human health. The World Health Organization (WHO) has set a maximum average of 0.08ppm over 30 minutes of exposure to formaldehyde, and the occupational safety and health standards (OSHA) have also set a formaldehyde allowable exposure limit of 0.7ppm for an 8 hour work period. Therefore, how to accurately and effectively detect formaldehyde becomes an important topic in the field of environmental pollution at present. The metal semiconductor gas sensor is concerned in a plurality of formaldehyde detection modes due to the advantages of small equipment volume, convenient operation, simple device preparation, low detection cost and the like. BiFeO 3 The perovskite structure with trigonal system distortion has wide application in spinning electron, information storage, microelectronics and other aspects due to the excellent physical properties of the perovskite structure, and meanwhile, the research in the gas sensitive field is also one of the research focuses of scientific researchers. At present, a small amount of BiFeO is reported 3 Gas sensitive property to gases such as ethanol, acetone, formaldehyde and the like, but Bi 2 O 3 /BiFeO 3 The gas-sensitive property to formaldehyde is not reported.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a hollow gas-sensitive material which is Bi 2 O 3 /BiFeO 3 The hollow sphere structure is adopted, and the gas-sensitive performance of the material is tested by using a static gas distribution method.
The technical scheme adopted by the invention for solving the technical problems is as follows:
provides a hollow gas-sensitive material which is prepared from Bi 2 O 3 /BiFeO 3 The hollow sphere structure is formed.
A preparation method of a hollow gas-sensitive material comprises the following steps:
s1: dissolving saccharides in water at room temperature, stirring, heating to 185 deg.C at 2 deg.C/min, maintaining for 5-8 hr, cooling to room temperature after reaction, cleaning, and drying at 75-85 deg.C to obtain C ball;
s2: carrying out ultrasonic dispersion on the C balls in a solvent at room temperature and then continuing to carry out ultrasonic treatment to obtain a solution A;
s3: adding bismuth nitrate pentahydrate (Bi (NO) 3 ) 2 ·5H 2 O) dissolving in a solvent, stirring and dissolving to obtain a solution B, slowly dropwise adding the solution B into the solution A under the ultrasonic condition, and continuing ultrasonic treatment after dropwise adding is finished;
s4: adding potassium hexacyanoferrate (K) 3 [Fe(CN) 6 ]) Dissolving in water, stirring to obtain solution C, slowly adding dropwise the solution C into the solution obtained in step S3 under ultrasonic condition, continuing ultrasonic treatment after dropwise addition is finished, aging at room temperature, cleaning, drying at 80 deg.C for 11-13h, heating to 450 deg.C at a speed of 1 deg.C/min in a muffle furnace, and calcining for 2 h.
Specifically, the diameter of the C ball is 80-200 nm.
Further, the molar ratio of the bismuth nitrate pentahydrate to the potassium hexacyanoferrate is 1:3 or 2:3 or 1:1 or 3: 2.
Further, the saccharide is glucose, sucrose or starch; alternatively, the solvent is N, N-dimethylacetamide.
Further, in step S1, the mixture was magnetically stirred for 30min and then transferred to a hydrothermal reaction vessel to be heated.
Further, in step S1, deionized water and absolute ethyl alcohol are respectively used for cleaning, and the drying time is 12 hours.
Further, in step S2, the ultrasound is ultrasound for 30 min.
Further, in step S3, the dropping speed is 20S per drop; and (4) performing ultrasonic treatment for 30min after the dropwise addition is finished.
Further, in step S4, the ultrasonic time is 30min after the dropwise addition, the aging time is 24h, and the mixture is washed with deionized water and absolute ethyl alcohol respectively, and dried for 12h at 80 ℃.
The hollow gas-sensitive material is applied to detecting formaldehyde.
Compared with the prior art, the invention has the beneficial effects that:
bi exemplified in the present invention 2 O 3 /BiFeO 3 The gas-sensitive material with the hollow sphere structure has higher sensitivity to formaldehyde, and researches show that: the gas-sensitive material prepared by the raw materials with the molar ratio Bi: Fe of 2:3 at the sintering temperature of 450 ℃ has good gas-sensitive performance, the optimal working temperature is 240 ℃, the response value to 100ppm formaldehyde is 45.9, the response recovery time is 34s and 21s respectively, the detection limit reaches 1ppm, and the gas-sensitive material has good repeatability and selectivity.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
FIG. 1 shows Bi prepared by different raw material ratios 2 O 3 /BiFeO 3 XRD spectrum of (1);
FIG. 2 shows Bi 2 O 3 /BiFeO 3 A TEM image of (B);
FIG. 3 is a graph of the sensitivity of the samples to 100ppm formaldehyde at different temperatures;
FIG. 4 is a graph showing the dynamic response of sample BF23 to different concentrations of formaldehyde at an optimum operating temperature of 240 ℃;
FIG. 5 is a graph showing the reproducibility of BF23 element in comparison with 100ppm formaldehyde at 240 ℃ for sample BF 23;
FIG. 6 shows the sensitivity of BF23 cell to 100ppm of different gases at 240 ℃ for sample BF 23.
Detailed Description
The present application will be described in further detail with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention. It should be noted that, for convenience of description, only the portions related to the present invention are shown in the drawings.
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
The first embodiment is as follows: bi 2 O 3 /BiFeO 3 Hollow gas-sensitive material and preparation method and application thereof
One, Bi 2 O 3 /BiFeO 3 Preparation of hollow gas-sensitive material
1. C ball preparation
At room temperature, 7g of glucose was dissolved in 60mL of H 2 And O, magnetically stirring for 30min, transferring to a hydrothermal reaction kettle, heating to 180 ℃ at the speed of 2 ℃/min, preserving heat for 6h, cooling to room temperature after complete reaction, respectively washing with deionized water and absolute ethyl alcohol for 3 times, and drying at 80 ℃ for 12h to obtain the C balls.
2、Bi 2 O 3 /BiFeO 3 Preparation of hollow spheres
0.2g C spheres were sonicated into 50mL of N, N-dimethylacetamide at room temperature for 30 min. 0.3mmol of Bi (NO) 3 ) 2 ·5H 2 O (0.0892g) was dissolved in 10mL of N, N-dimethylacetamide and dissolved with stirring. Under the ultrasonic condition, Bi (NO) is added 3 ) 2 The N, N-dimethylacetamide solution is slowly dripped into the N, N-dimethylacetamide solution of the C ball at the speed of 20s per drop, and the ultrasonic treatment is continued for 30min after the dripping is finished. 0.2mmol of K 3 [Fe(CN) 6 ](0.0970g) dissolved in 10mL of H 2 And O, stirring and dissolving. Under the ultrasonic condition, K is added 3 [Fe(CN) 6 ]The aqueous solution is slowly dripped into the solution at the speed of 20s per drop, and the ultrasonic treatment is continued for 1 hour after the dripping is finished. Aging at room temperature for 24h, washing with deionized water and anhydrous ethanol for 3 times, and drying at 80 deg.C for 12 h. Finally, the temperature is increased to 450 ℃ in a muffle furnace at the speed of 1 ℃/min, the calcination is carried out for 2h, and the C balls are burnt after the calcination to obtain Bi 2 O 3 /BiFeO 3 And (3) a hollow gas-sensitive material.
Preparing Bi with different raw material ratios according to the method 2 O 3 /BiFeO 3 As shown in table 1.
TABLE 1 Bi of different raw material ratios 2 O 3 /BiFeO 3
Second, test analysis
1. X-ray diffraction analysis (XRD)
As shown in FIG. 1, Bi prepared for different raw material ratios 2 O 3 /BiFeO 3 XRD spectrum of (a).
The XRD spectrogram shows that Bi is contained in the prepared sample 2 O 3 /BiFeO 3 A composite material.
2. TEM analysis
As shown in FIG. 2, is prepared Bi 2 O 3 /BiFeO 3 Wherein (a) is BF 13; (b) BF 23; (c) BF 33; (d) is BF 32.
As can be seen from the TEM image of FIG. 2, Bi prepared by different raw material ratios 2 O 3 /BiFeO 3 The shapes of the materials are not obviously different, hollow and porous structures exist, the size of the porous microspheres is not uniform and is between 50 nm and 200nm, and some small nano particles exist. From the graph (b) it can be seen that the hollow sphere structure is evident, and the small nanoparticles are likely to be the breakup of the hollow spheres due to the generation of gas during calcination. The hollow and porous structure enables the material to have larger specific surface area and more active sites, and improves the gas-sensitive performance of the material.
3. Gas sensor fabrication
The gas sensor is manufactured by a sintering type indirectly-heated process, sample powder and a proper amount of terpineol are mixed in an agate mortar and ground, and then the mixture is uniformly coated on Al 2 O 3 And (3) the ceramic tube is externally arranged. Two ends of the ceramic tube are respectively coated with a circle of gold electrode, and two platinum wires are fixed on the gold electrode. And drying the coated ceramic tube at 80 ℃, calcining the ceramic tube at 500 ℃ for 2h, and welding the platinum wire of the ceramic tube on the hexagonal base of the element. The working temperature is controlled by the nickel-chromium alloy wire as a heating wire through the ceramic tube.
4. Gas sensitive Performance test
A static gas distribution method is adopted to carry out gas sensitivity test on a WS-30A gas sensitive element tester produced by Zhengzhou weisheng electronic technology limited. The sensitivity of the element in the reducing gas is defined as Ra/Rg, wherein Ra and Rg are resistance values of the element in the air and the gas to be measured respectively. The response-recovery time is the time required for the resistance value of the device to reach 90% of the maximum value of the resistance change.
1) Effect of operating temperature on element sensitivity
FIG. 3 shows the sensitivity profiles of the samples to 100ppm formaldehyde at different temperatures. It can be seen that the optimum operating temperature for samples BF23, BF33, BF32 was 240 deg.C, when the response values to 100ppm formaldehyde were 45.9, 35.4, 26.5, respectively. The optimum operating temperature for sample BF13 was 200 ℃ and the response value was 11.7. Sample BF23 showed the highest sensitivity to formaldehyde.
2) Influence of gas concentration on element sensitivity
As shown in fig. 4, it is a dynamic response curve of sample BF23 for different concentrations of formaldehyde at the optimum operating temperature of 240 ℃.
As shown in fig. 4, the large graph is the dynamic response curve of sample BF23 to different concentrations of formaldehyde at the optimum operating temperature of 240 ℃. It can be seen that the response recovery time of the material is longer when the gas concentration is smaller. As the gas concentration increases, the response value starts to increase and the response-recovery time starts to decrease. The response-recovery time of the element to 10ppm formaldehyde was 62s and 59s, respectively; response-recovery times for 50ppm formaldehyde were 29s and 30s, respectively; the response-recovery times for 100ppm formaldehyde were 34s and 21s, respectively. The graph in fig. 4 is a linear concentration curve of sample BF23 for different concentrations of formaldehyde. It can be seen from the figure that the sensitivity of the element increases with increasing gas concentration. At low concentrations, the sensitivity increases more rapidly, and at gas concentrations above 100ppm, the sensitivity increases slowly, primarily as the adsorption of gas in the active sites of the material tends to saturate. The sample also showed a clear response to 1ppm formaldehyde gas with a response value of 4.2 and a response value of 7.5 and 11.8 for the lower 5ppm and 10ppm concentrations, respectively. It can be seen that Bi 2 O 3 /BiFeO 3 The gas sensitive material has a lower detection limit.
3) Repeatability test
FIG. 5 shows the repeatability curve for sample BF23 at 240 ℃ for 100ppm formaldehyde.
FIG. 5 is a graph showing the repeatability of sample BF23 at 240 ℃ for 100ppm formaldehyde. It can be seen from the figure that the samples were subjected to five cycles of repeated experiments and the elements showed satisfactory reproducibility with the response of four consecutive cycles remaining almost unchanged. This indicates that the sensor has good cycling stability and the ability to continuously detect formaldehyde.
4) Comparative experiment
As shown in Table 2, comparative analyses were performed on different gas-sensitive materials at 240 ℃ and a formaldehyde concentration of 100 ppm.
TABLE 2 comparative analysis table for different gas-sensitive materials
Wherein, BiFeO 3 The microspheres were prepared from TK.M.Zhu, S.Y.Ma, S.T.Pei, Y.Tie, Q.X.Zhang, W.Q.Wang, X.L.Xu.preparation, chromatography and chromatography gas sensing properties of warp shaped BiFeO 3 materials Letters,2019,246: 107-;
pr doped BiFeO 3 Hollow nanofibers are used in the documents y.tie, s.y.ma, s.t.pei, q.x.zhang, k.m.zhu, r.zhang, x.h.xu, t.han, w.w.liu.pr ordered BiFeO feo 3 hollow nanofifibers via electrospinning method as a formaldehyde sensor.Sensors&Actuators B.chemical,2020,308: 127689.
According to the experimental results, the BF23 sample has higher response value to formaldehyde compared with the comparison example.
5) Selective testing
As shown in FIG. 6, which is a sample of BF23 at 240 deg.C, the BF23 cell was sensitive to 100ppm of different gases.
The figure shows that the sensitivity of the element to 100ppm formaldehyde is far greater than that of gases such as acetone, methanol, ethanol, triethylamine, ammonia water, benzene, toluene and the like, and the element shows good gas selectivity.
It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Claims (10)
1. The hollow gas-sensitive material is characterized in that the hollow gas-sensitive material is Bi 2 O 3 /BiFeO 3 The hollow sphere structure is formed.
2. A method for preparing the hollow gas-sensitive material according to claim 1, comprising the steps of:
s1: dissolving saccharides in water at room temperature, stirring, heating to 185 ℃ at the speed of 2 ℃/min, preserving heat for 5-8h, cooling to room temperature after complete reaction, cleaning, and drying at 75-85 ℃ to obtain a C ball;
s2: carrying out ultrasonic dispersion on the C spheres in a solvent at room temperature and then continuing to carry out ultrasonic treatment to obtain a solution A;
s3: dissolving bismuth nitrate pentahydrate in a solvent, stirring and dissolving to obtain a solution B, slowly dropwise adding the solution B into the solution A under the ultrasonic condition, and continuing ultrasonic treatment after dropwise adding is finished;
s4: dissolving potassium hexacyanoferrate in water, stirring and dissolving to obtain a solution C, slowly dropwise adding the solution C into the solution obtained in the step S3 under the ultrasonic condition, continuing ultrasonic after dropwise adding, aging at room temperature, cleaning, drying at 80 ℃ for 11-13h, increasing the temperature to 450 ℃ in a muffle furnace at the speed of 1 ℃/min, and calcining for 2h to obtain the potassium hexacyanoferrate.
3. The method for preparing the hollow gas-sensitive material according to claim 2, wherein the molar ratio of the bismuth nitrate pentahydrate to the potassium hexacyanoferrate is 1:3 or 2:3 or 1:1 or 3: 2.
4. The method for preparing the hollow gas-sensitive material according to claim 2, wherein the saccharide is glucose, sucrose or starch;
alternatively, the solvent is N, N-dimethylacetamide.
5. The method for preparing the hollow gas-sensitive material according to claim 2, wherein in step S1, the hollow gas-sensitive material is transferred to a hydrothermal reaction kettle for temperature rise after being magnetically stirred for 30 min.
6. The method for preparing the hollow gas-sensitive material according to claim 2, wherein in step S1, the hollow gas-sensitive material is washed with deionized water and absolute ethyl alcohol respectively, and the drying time is 12 hours.
7. The hollow gas-sensitive material according to claim 2, wherein in step S2, the ultrasound is ultrasound for 30 min.
8. The hollow gas-sensitive material according to claim 2, wherein in step S3, the dropping speed is 20S per drop; and (4) performing ultrasonic treatment for 30min after the dropwise addition is finished.
9. The hollow gas-sensitive material of claim 2, wherein in step S4, the ultrasonic time after the end of the dropwise addition is 30min, the aging time is 24h, and the hollow gas-sensitive material is washed with deionized water and absolute ethanol respectively, and dried at 80 ℃ for 12 h.
10. Use of the hollow gas-sensitive material of any of claims 1 to 9 for detecting formaldehyde.
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