CN111825079A - Layered double hydroxide/graphene nano composite gas-sensitive material, preparation method thereof and application thereof in detection of nitrogen dioxide - Google Patents
Layered double hydroxide/graphene nano composite gas-sensitive material, preparation method thereof and application thereof in detection of nitrogen dioxide Download PDFInfo
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Abstract
The invention discloses a layered double metal hydroxide/graphene nano composite gas-sensitive material prepared by a one-step hydrothermal method process, which can realize uniform coverage of LDH nanosheets on the surfaces of lamellar graphene by regulating and controlling the temperature, the ratio of two materials and the like in the hydrothermal reaction process, form a three-dimensional composite structure with large specific surface area, high conductivity and good carrier channel, overcome the problems of disordered structure stacking and poor performance of the composite material caused by the fact that LDH is difficult to be uniformly layered and compounded with graphene in the traditional direct mixing method, remarkably improve the sensitivity, the response speed, the detection limit and other room temperature gas sensitivity of a layered double metal hydroxide-based gas sensor, and realize that the sensor can sense ppb-level trace NO2Ultra-high room temperature sensitive and ultra-fast roomAnd (4) temperature response.
Description
Technical Field
The invention belongs to the technical field of gas sensors, and relates to a layered double metal hydroxide/graphene (ZnTi-LDH/GO) nano composite gas sensitive material, a preparation method thereof and application thereof in detection of nitrogen dioxide, wherein the layered double metal hydroxide/graphene nano composite gas sensitive material has ultrahigh room temperature sensitivity and ultrafast room temperature response characteristic to the nitrogen dioxide.
Background
Due to the fact that the combustion of fuel, urban automobile exhaust and nitrogen dioxide generated in the industrial production process increase year by year, the serious and wide spreading of acid rain and photochemical smog are caused, and the ecological environment is seriously damaged. The presence of nitrogen dioxide poses a great threat to human health, lung function is impaired even if the exposure time to nitrogen dioxide is short, eyes, nose and respiratory tract are strongly stimulated when the concentration of nitrogen dioxide reaches 10ppm, and children, old people and people suffering from respiratory diseases are affected by nitrogen dioxide more greatly. In order to effectively ensure NO of human beings in real time2The protection, research of intelligent safety and excellent performance for detecting trace NO in environment2The gas sensor of (1) is highly necessary. With the success of the preparation of single-layer graphene, two-dimensional layered nanomaterials are receiving more and more attention, and the applications of the two-dimensional layered nanomaterials in the gas sensitive field are increasingly widespread, wherein the two-dimensional Layered Double Hydroxides (LDHs) are applied to the preparation of gas sensors due to the excellent characteristics of the two-dimensional layered double hydroxides, such as: the prepared NiFeAl-LDH with the molar ratio of Ni to Fe to Al of 1:1:1 is sensitive to nitrogen oxides as low as 100ppb, and NiCo-LDHs can detect 97ppm of NO at room temperature2The gas and the prepared ZnAl-LDHs/PANI multilayer film have strong selective reaction to ammonia at room temperature. However, the existing LDH-based gas-sensitive material has the problems of easy stacking and agglomeration, poor conductivity and the like, so that the existing LDH-based gas-sensitive material can be used for treating low-concentration NO2The defects of long response recovery time and low detection sensitivity, especially weak room temperature response signals of ppb level rarefied gases and the like are more difficult to meet the current requirement of continuously reducing the detection limit of the sensor. In order to meet or satisfy the performance requirements of various sensor networks and integrated systems on the sensor elements, the LDH must be further modified,the surface gas adsorption and reaction performance is regulated and controlled through modification, so that the sensitivity of the device is obviously improved, and the rapid high-sensitivity response to trace gas is realized at room temperature.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a three-dimensional layered double metal hydroxide/graphene (ZnTi-LDH/GO) nanocomposite gas-sensitive material, a preparation method thereof and application thereof in detecting nitrogen dioxide, realizes the compositing of LDH and graphene through a simple optimization process, solves the problem that LDH is difficult to uniformly and controllably assemble on the surface of graphene in the process of preparing the three-dimensional composite material, and forms the ZnTi-LDH/GO gas-sensitive material with a reasonable morphology structure and uniform growth of LDH on the surface of graphene, thereby obviously improving the sensitivity, response speed, detection limit and other room temperature gas sensitivity of an LDH-based gas sensor, and realizing the effect that the sensor is sensitive to NO gas2Ultra-high room temperature sensitivity and ultra-fast room temperature response.
The technical purpose of the invention is realized by the following technical scheme.
A layered double metal hydroxide/graphene (ZnTi-LDH/GO) nano composite gas-sensitive material and a preparation method thereof are carried out according to the following steps:
uniformly dispersing graphene oxide into an ethanol aqueous solution to obtain a graphene oxide dispersion solution, fully dissolving titanium tetrachloride, zinc nitrate hexahydrate and urea into deionized water to obtain a mixed salt solution, uniformly mixing the mixed salt solution and the graphene oxide dispersion solution to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction at the temperature of 130-150 ℃ for 20-30h, wherein the concentration of the graphene oxide in the reaction solution is 16-17mg/ml, and the molar ratio of the titanium tetrachloride to the zinc nitrate hexahydrate to the urea is (1-3): (4-7): 50.
The concentration of graphene oxide in the reaction solution is preferably 16.4mg/ml, the molar ratio of titanium tetrachloride, zinc nitrate hexahydrate and urea is preferably 3:5:50, the hydrothermal reaction temperature is preferably 140 ℃, and the reaction time is preferably 24 hours.
The volume ratio of ethanol to water in the ethanol water solution is 1: 1; uniformly dispersing graphene oxide in an ethanol water solution by ultrasonic stirring for 1-2 h; stirring at a constant speed of 100r/min for 0.5-1.5h to fully dissolve titanium tetrachloride, zinc nitrate hexahydrate and urea in deionized water; and uniformly mixing the mixed salt solution and the graphene oxide dispersion liquid by ultrasonic stirring for 1-2 h.
After the hydrothermal reaction is finished, cooling the reaction kettle to room temperature, then respectively centrifugally washing the obtained sample by using ethanol and deionized water, and finally drying the obtained sample in a drying oven at 60 ℃ for 10-14h to obtain the layered double metal hydroxide/graphene nano composite gas-sensitive material.
The chemical reagents used in each step are analytically pure AR.
The invention has the beneficial effects that:
the invention discloses a method for three-dimensionally assembling layered double metal oxide and graphene through a one-step hydrothermal process, wherein uniform coverage of LDH nanosheets on the surfaces of lamellar graphene can be realized by regulating and controlling the temperature, the ratio of two materials and the like in the hydrothermal reaction process, a three-dimensional ZnTi-LDH/GO nano composite material with controllable morphology is prepared, LDH nanosheets uniformly grow on the surfaces of the graphene nanosheets to form a three-dimensional composite structure with large specific surface area, high conductivity and good carrier channels, the problems of disordered stacking and poor performance of the composite material structure caused by the difficulty in uniform layered compounding of LDH and graphene in the traditional direct mixing method are solved, the sensitivity, the response speed, the detection limit and other room temperature gas sensitivity of a layered double metal hydroxide based gas sensor are obviously improved, and the sensor is capable of realizing the room temperature gas sensitivity to ppb level trace NO2Ultra-high room temperature sensitivity and ultra-fast room temperature response. The layered double metal hydroxide/graphene (ZnTi-LDH/GO) nano composite gas sensitive material prepared by the invention can be used for resisting 50ppb and 500ppb NO at room temperature2The response sensitivity S (S ═ Rg-Ra |/Ra × 100%) of (a) is: 3%, 29%; for 10ppm of NO2The gas sensitive material can achieve a near saturation response of 97%, and can achieve an instantaneous response with a response time of 1-3 s. In addition, the LDH/GO composite material has a three-dimensional structure with large-layer graphene as a framework carrier and LDH nanosheets uniformly grown on the graphene layersGood stability, reliable repeatability and other properties, and is suitable for low-concentration NO at room temperature2Detection of (3).
Drawings
FIG. 1 is a scanning electron microscope photomicrograph of the ZnTi-LDH/GO nanocomposite prepared in example 1.
FIG. 2 is a scanning electron micrograph of the ZnTi-LDH/GO nanocomposite prepared in example 2
FIG. 3 is a scanning electron microscope photomicrograph of the ZnTi-LDH/GO nanocomposite prepared in example 3.
FIG. 4 is an XRD spectrum of ZnTi-LDH, RGO and ZnTi-LDH/GO prepared in accordance with the present invention.
FIG. 5 shows ZnTi-LDH/GO gas-sensitive sensing elements prepared by the invention for 50ppb, 100ppb, 200ppb, 300ppb and 500ppb of NO2The dynamic response curve of (2).
FIG. 6 shows ZnTi-LDH/GO gas-sensitive sensor element pairs prepared by the invention with NO of 0.2ppm, 0.5ppm, 1ppm, 5ppm, 10ppm, 20ppm, 50ppm and 100ppm2The dynamic response curve of (2).
FIG. 7 is a schematic of the long-term stability of ZnTi-LDH/GO gas sensors prepared in accordance with the present invention.
Detailed Description
The raw materials used in the present invention are all commercially available chemical pure reagents, and the present invention will be further described in detail with reference to specific examples.
Example 1
Step 1: preparation of graphene oxide
Graphene oxide was prepared by a conventional Hummers method. Placing a 250ml reaction bottle in an ice water bath, slowly pouring 30ml concentrated sulfuric acid, adding 1g of graphite powder and 0.5g of sodium nitrate under uniform stirring, then slowly adding 5g of potassium permanganate, and controlling the reaction temperature to be not more than 20 ℃. Stirring for 30 minutes, heating to 35 ℃, continuing stirring for 30 minutes, then adding 40ml of deionized water, heating to 98 ℃, continuing heating for 20 minutes to obtain a brownish yellow solution, then adding 5ml of hydrogen peroxide, filtering the hot sample, washing with hydrochloric acid and deionized water, and finally fully drying in a drying oven at 60 ℃.
Step 2: preparation of ZnTi-LDH/GO nano composite material
The method is characterized in that urea is used as an alkali source, and a hydrothermal method is adopted to prepare ZnTi-LDH/GO with a three-dimensional structure. Measuring 1.64g of graphene oxide obtained in the step (1) and dissolving the graphene oxide in 40ml of ethanol water solution (ethanol: water is 1:1), carrying out ultrasonic stirring for 1H to prepare a graphene oxide dispersion liquid, measuring 3mmol of TiCl4, 5mmol of Zn (NO3) 2.6H 2O and 50mmol of urea and dissolving the mixture in 60ml of deionized water, and carrying out uniform stirring for 60 minutes until a mixed salt solution is uniform. And slowly dripping the mixed salt solution into the graphene oxide dispersion liquid under stirring at a constant speed by using a rubber head dropper, ultrasonically stirring for 1h, transferring into a 100ml Teflon-lined autoclave, and carrying out hydrothermal reaction for 24h at 140 ℃. After the hydrothermal process is finished, cooling the autoclave to room temperature, putting the obtained sample into a large test tube, respectively centrifugally cleaning the sample for a plurality of times by using ethanol and deionized water, and finally drying the sample in a drying oven at 60 ℃ for 12 hours to obtain the ZnTi-LDH/GO sample.
And step 3: preparation of gas-sensitive sensor element
(1) Substrate cleaning
And (3) placing the ceramic wafer with the size specification of 2.5 x 1.0cm2 in acetone, absolute ethyl alcohol and deionized water in sequence for ultrasonic cleaning for 10 min. Drying in a drying oven after cleaning;
(2) electrode preparation
High-purity Pt is adopted as an electrode material, and an interdigital electrode is prepared on a cleaned substrate by magnetron sputtering by utilizing an interdigital mask. Magnetron sputtering conditions: the sputtering power is 100W, and the sputtering time is 2 min;
(3) sample smear
And dispersing the powder sample obtained by the experiment in deionized water to obtain a uniform solution, uniformly coating the solution on the prepared interdigital electrode ceramic chip by using a dropper, and placing the interdigital electrode ceramic chip in an infrared drying box for drying to obtain the gas sensitive element.
Example 2
The present embodiment is different from embodiment 1 in that: the amount of graphene oxide in step 2 was increased to 4.92 g.
Example 3
The present embodiment is different from embodiment 1 in that: the amount of graphene oxide in step (2) was reduced to 0.55 g.
As shown in fig. 1, LDH of the ZnTi-LDH/GO nanocomposite prepared in example 1 grows on graphene nanosheets in the form of nanosheets, is uniformly and densely distributed, and has a large specific surface area of a formed three-dimensional structure; as shown in fig. 2, the ZnTi-LDH/GO nanocomposite with increased graphene oxide amount prepared in example 2 has a phenomenon of local lamellar stacking and agglomeration into particles with the increase of graphene oxide; as shown in fig. 3, the ZnTi-LDH/GO nanocomposite with reduced graphene oxide amount prepared in example 3 shows the phenomena of lamellar accumulation and disordered structure as the graphene oxide increases and decreases. In conclusion, when the concentration of the graphene oxide in the reaction solution is about 16.4mg/ml, the prepared ZnTi-LDH/GO nano composite material has the best structural morphology.
As shown in fig. 4, rGO is a graphene oxide sample prepared by the method of the present invention, ZnTi-LDH is a layered double metal hydroxide (ZnTi-LDH) sample prepared by the method of the present invention, and ZnTi-LDH/GO is a layered double metal hydroxide/graphene nanocomposite gas sensitive material (ZnTi-LDH/GO) sample prepared by the method of the present invention, diffraction peaks on (003), (006), (012), (101), (009), (018), (110), (113) planes of the ZnTi-LDH sample can be observed, showing the formation of a typical LDHs structure; the main characteristic peak of rGO appears in a broad band around 24.5 °, 24.5 ° corresponding to the diffraction of the graphene (200) crystal plane, indicating that the size of the layer after redox is reduced, the integrity and order of the crystal structure is reduced; in the XRD spectrum of the ZnTi-LDH/GO composite material, a broad peak belonging to the (200) diffraction peak of the rGO appears at 24.5 degrees, the existence of the rGO in the composite material is confirmed, and meanwhile, LDHs structure diffraction peaks on the (009), (018), (110) and (113) planes also confirm the existence of LDHs in the composite material, thereby proving that the ZnTi-LDH/GO nano composite gas-sensitive material is successfully synthesized.
As shown in FIG. 5, the ZnTi-LDH/GO nano composite gas-sensitive material prepared by the invention has NO2Lowest detection lower limit of<50ppb, even in such a low concentration gas, the gas sensor is excellentGood gas-sensitive properties for 50ppb, 100ppb, 200ppb and 300ppb NO2The sensitivities of the ZnTi-LDH/GO nano composite gas-sensitive material are respectively 3 percent, 11 percent, 14 percent and 29 percent, and the response times are respectively 2.0s, 1.0s and 2.0s, thereby proving that the ZnTi-LDH/GO nano composite gas-sensitive material prepared by the invention has ppb level concentration of NO2The detection response is good, the response time is fast, and the method has important significance in practical application.
The test of the gas-sensitive performance of the ZnTi-LDH/GO nano composite gas-sensitive material prepared by the invention is completed by using a gas-sensitive test system self-made by a subject group, and a static gas distribution method is adopted, namely, in a gas reaction chamber with the volume of 30L, the change of gas atmosphere is realized through the injection and diffusion of gas, and the specific operation process is as follows: firstly, placing a prepared gas-sensitive sensing element on a sample table of a gas reaction chamber, connecting the sensing element and a test ammeter by using a probe, then injecting target gas to be tested with different concentrations into the gas reaction chamber, opening a cover above the reaction chamber when the resistance value of the element to be tested tends to be stable, carrying out gas diffusion to recover the resistance value of the sample, and continuously monitoring and recording the resistance change of the sensing element in the whole process, namely, dynamic response. The sampling interval is 1s, the testing process is carried out at the room temperature of 25-27 ℃ and the relative humidity of the environment is within the range of 30-35%. As shown in FIG. 6, NO was present at various concentrations (0.2-100ppm)2Under the gas atmosphere, the ZnTi-LDH/GO nano composite gas-sensitive material prepared by the invention has good reversibility and recoverability.
FIG. 7 shows that the ZnTi-LDH/GO nano composite gas-sensitive material prepared by the invention has a fixed concentration of 10ppm NO2The transient resistance response can observe that the dynamic characteristics of each air inlet and outlet cycle are basically the same, so that the ZnTi-LDH/GO nano composite gas-sensitive material prepared by the method has good reversibility and stability.
According to the content of the invention, the adjustment of the process parameters can realize the preparation of the layered double metal hydroxide/graphene (ZnTi-LDH/GO) nano composite gas-sensitive material, and the performance of the material is basically consistent with that of the embodiment of the invention.
Although the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or rearrangements of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. A layered double metal hydroxide/graphene nano composite gas-sensitive material is characterized in that: is prepared by the following steps:
uniformly dispersing graphene oxide into an ethanol aqueous solution to obtain a graphene oxide dispersion solution, fully dissolving titanium tetrachloride, zinc nitrate hexahydrate and urea into deionized water to obtain a mixed salt solution, uniformly mixing the mixed salt solution and the graphene oxide dispersion solution to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction at the temperature of 130-150 ℃ for 20-30h, wherein the concentration of the graphene oxide in the reaction solution is 16-17mg/ml, and the molar ratio of the titanium tetrachloride to the zinc nitrate hexahydrate to the urea is (1-3): (4-7): 50.
2. The layered double hydroxide/graphene nanocomposite gas-sensitive material according to claim 1, wherein: the concentration of graphene oxide in the reaction solution is 16.4mg/ml, and the molar ratio of titanium tetrachloride to zinc nitrate hexahydrate to urea is 3:5: 50.
3. The layered double hydroxide/graphene nanocomposite gas-sensitive material according to claim 1, wherein: the volume ratio of ethanol to water in the ethanol water solution is 1: 1; uniformly dispersing graphene oxide in an ethanol water solution by ultrasonic stirring for 1-2 h; stirring at a constant speed of 100r/min for 0.5-1.5h to fully dissolve titanium tetrachloride, zinc nitrate hexahydrate and urea in deionized water; and uniformly mixing the mixed salt solution and the graphene oxide dispersion liquid by ultrasonic stirring for 1-2 h.
4. The layered double hydroxide/graphene nanocomposite gas-sensitive material according to claim 1, wherein: after the hydrothermal reaction is finished, cooling the reaction kettle to room temperature, then respectively centrifugally washing the obtained sample by using ethanol and deionized water, and finally drying the obtained sample in a drying oven at 60 ℃ for 10-14h to obtain the layered double metal hydroxide/graphene nano composite gas-sensitive material.
5. The layered double hydroxide/graphene nanocomposite gas-sensitive material according to claim 1, wherein: the hydrothermal reaction temperature is 140 ℃, and the reaction time is 24 h.
6. A preparation method of a layered double metal hydroxide/graphene nano composite gas-sensitive material is characterized by comprising the following steps: the method comprises the following steps:
uniformly dispersing graphene oxide into an ethanol aqueous solution to obtain a graphene oxide dispersion solution, fully dissolving titanium tetrachloride, zinc nitrate hexahydrate and urea into deionized water to obtain a mixed salt solution, uniformly mixing the mixed salt solution and the graphene oxide dispersion solution to obtain a reaction solution, transferring the reaction solution into a high-pressure reaction kettle, and carrying out hydrothermal reaction at the temperature of 130-150 ℃ for 20-30h, wherein the concentration of the graphene oxide in the reaction solution is 16-17mg/ml, and the molar ratio of the titanium tetrachloride to the zinc nitrate hexahydrate to the urea is (1-3): (4-7): 50.
7. The preparation method of the layered double hydroxide/graphene nanocomposite gas-sensitive material according to claim 6, wherein: the concentration of graphene oxide in the reaction solution is 16.4mg/ml, and the molar ratio of titanium tetrachloride to zinc nitrate hexahydrate to urea is 3:5: 50.
8. The preparation method of the layered double hydroxide/graphene nanocomposite gas-sensitive material according to claim 6, wherein: the volume ratio of ethanol to water in the ethanol water solution is 1: 1; uniformly dispersing graphene oxide in an ethanol water solution by ultrasonic stirring for 1-2 h; stirring at a constant speed of 100r/min for 0.5-1.5h to fully dissolve titanium tetrachloride, zinc nitrate hexahydrate and urea in deionized water; and uniformly mixing the mixed salt solution and the graphene oxide dispersion liquid by ultrasonic stirring for 1-2 h.
9. The preparation method of the layered double hydroxide/graphene nanocomposite gas-sensitive material according to claim 6, wherein: the hydrothermal reaction temperature is 140 ℃, and the reaction time is 24 hours; after the hydrothermal reaction is finished, cooling the reaction kettle to room temperature, then respectively centrifugally washing the obtained sample by using ethanol and deionized water, and finally drying the obtained sample in a drying oven at 60 ℃ for 10-14h to obtain the layered double metal hydroxide/graphene nano composite gas-sensitive material.
10. The use of the layered double hydroxide-graphene nanocomposite gas-sensitive material of any one of claims 1 to 5 in the detection of nitrogen dioxide gas, wherein: at room temperature, the detection limit of the nitrogen dioxide gas is 50ppb, the response time is 1-3s, and the response sensitivity of the nitrogen dioxide gas to 10ppm can reach 97%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113155915A (en) * | 2021-05-07 | 2021-07-23 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Titanium mesh supported cobalt-based metal organic framework graphene nanosheet array and application thereof |
| CN113546628A (en) * | 2021-06-22 | 2021-10-26 | 南京工业大学 | Preparation method of bimetallic hydroxide-graphene aerogel electrocatalyst |
| CN113758976A (en) * | 2021-09-14 | 2021-12-07 | 北京化工大学 | Preparation and application of hydrotalcite-based ammonia gas-sensitive material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864010A (en) * | 2014-03-05 | 2014-06-18 | 南京理工大学 | Nitrogen-doped graphene/cobalt ferrite nano composite material and preparation method thereof |
| CN107681132A (en) * | 2017-09-03 | 2018-02-09 | 河南师范大学 | Zinc-nickel secondary batteries negative material zinc titanium binary layered hydroxide and preparation method thereof and the battery using the negative material |
-
2019
- 2019-10-28 CN CN201911032447.6A patent/CN111825079A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864010A (en) * | 2014-03-05 | 2014-06-18 | 南京理工大学 | Nitrogen-doped graphene/cobalt ferrite nano composite material and preparation method thereof |
| CN107681132A (en) * | 2017-09-03 | 2018-02-09 | 河南师范大学 | Zinc-nickel secondary batteries negative material zinc titanium binary layered hydroxide and preparation method thereof and the battery using the negative material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113155915A (en) * | 2021-05-07 | 2021-07-23 | 山东鲁泰控股集团有限公司石墨烯高分子复合材料研发中心 | Titanium mesh supported cobalt-based metal organic framework graphene nanosheet array and application thereof |
| CN113546628A (en) * | 2021-06-22 | 2021-10-26 | 南京工业大学 | Preparation method of bimetallic hydroxide-graphene aerogel electrocatalyst |
| CN113758976A (en) * | 2021-09-14 | 2021-12-07 | 北京化工大学 | Preparation and application of hydrotalcite-based ammonia gas-sensitive material |
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Application publication date: 20201027 |