CN103091369A - Preparation method of Pd-nanoparticle-modified porous ZnO nanosheet gas-sensitive material and gas sensor - Google Patents
Preparation method of Pd-nanoparticle-modified porous ZnO nanosheet gas-sensitive material and gas sensor Download PDFInfo
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Abstract
The invention discloses a preparation method of a Pd-nanoparticle-modified porous ZnO nanosheet gas-sensitive material, which comprises the following steps: mixing and grinding porous monocrystalline ZnO nanosheets and Pd nanoparticles, wherein the weight of the Pd nanoparticles accounts for 0.3-0.8% of the total weight of the porous monocrystalline ZnO nanosheets and Pd nanoparticles; and calcining at 550-650 DEG C for 1-2 hours to obtain the Pd-nanoparticle-modified porous ZnO nanosheet gas-sensitive material. The Pd-nanoparticle-modified porous ZnO nanosheet gas-sensitive material has high sensitivity: the sensitivity for 100ppm acetone gas is up to 70, the sensitivity for 500ppm acetone gas is up to 222, and the sensitivity for 10ppm acetone gas is up to 8 or so. The operating temperature is low: the optimum temperature of the ZnO nanosheet composite material modified by the Pd nanoparticles is 340 DEG C, and is greatly lowered as compared with 420 DEG C of the single ZnO nanosheets. The selectivity is high: the gas sensor is less sensitive to some common organic solvents, such as ethanol, methanol, benzene, toluene and the like, than acetone.
Description
Technical field
The present invention relates to the preparation method of a kind of Novel composite nano gas sensitive and gas sensor thereof.
Background technology
Acetone is as a kind of important industrial chemicals and industrial solvent, and the status is very important in the modern chemical industry commercial production.Wherein 2011, global acetone demand reached 6,310,000 tons, and the acetone consumption of China has surpassed 1/5th of the whole world.And acetone is also a kind of inflammable and explosive, and the liquid of poisonous highly volatile in use easily produces a large amount of acetone steams, has report to point out that the above acetone steam of concentration 500 ppm can cause obvious harm to human body, and its lower explosive limit is only 2.6%.Therefore, exploitation is fast efficient, and sensitive acetone sensor is significant.At present, acetone air-sensitive material is mainly take the ZnO material as main, but it exists sensitivity low, the shortcomings such as operating temperature height.And traditional doping modification method can make the sensitivity of material greatly improve, yet operating temperature is still undesirable, as: the WO after doping
3-ZnO and MoO
3-ZnO has reached 60 left and right to the sensitivity of 20 ppm acetone gas, and the response-recovery time was respectively 30 and 20 seconds, but its operating temperature but up to 500 ℃ (Chinese patent CN 101162211A), this has brought constant to practical application.And without the SnO of template preparation
2Square nano wire, operation under 300 ℃ is 11 (Nanotechnology. 2008,19,185705) to the sensitivity of the acetone steam of 100 ppm concentration.
Summary of the invention
Purpose of the present invention aims to provide a kind ofly has response fast to acetone gas, and highly sensitive, operating temperature is low, requires simultaneously acetone gas is had higher optionally novel gas sensitive and the preparation method of gas sensor thereof.
Technical scheme of the present invention is: a kind of preparation method of Pd Nanoparticle Modified porous ZnO nanometer sheet gas sensitive, with porous monocrystalline ZnO nano sheet and Pd nano particle mixed grinding, the quality of Pd nano particle accounts for 0.3 ~ 0.8% of porous monocrystalline ZnO nano sheet and Pd nano particle gross mass, then calcine 1-2h under the condition of 550-650 ℃, obtain the gas sensitive of Pd Nanoparticle Modified porous ZnO nanometer sheet.
The thickness of described porous monocrystalline ZnO nano sheet is 10-50 nm, and the diameter of Pd nano particle is 5-20nm.
Described porous monocrystalline ZnO nano sheet and Pd nano particle mixed grinding time are 0.5-1h.
The gas sensitive of Pd Nanoparticle Modified porous ZnO nanometer sheet is mixed into slurry in terpinol, evenly be coated in again the aluminium oxide ceramics tube-surface with forked gold electrode, first toast 30-60min under the condition of 80-120 ℃ in baking oven, put into again muffle furnace, calcine 1-2h under the condition of 400-600 ℃, then welding, packing, aging obtain Pd Nanoparticle Modified porous ZnO nanometer sheet gas sensor.
Technical scheme of the present invention comprises that gas sensitive and gas sensor prepared for two steps:
Concrete steps are as follows:
(1) gas sensitive preparation: adopt porous monocrystalline ZnO nano sheet, after Pd nano particle mixed grinding, Pd content is between 0.3-0.8%, in air, under 600 ℃, calcining 1-2 h, namely prepare Pd Nanoparticle Modified porous ZnO nanometer sheet gas sensitive.
(2) gas sensor preparation: prepared gas sensitive is mixed into the aluminium oxide ceramics tube-surface that evenly is coated in again after slurry with forked gold electrode in terpinol, then calcine 1-2h under 400-600 ℃ in air, then again by the preparation method of traditional heater-type gas sensor weld, packing, aging this gas sensor of namely making.
The present invention prepares the compound substance of the nanoparticle surface modified two-dimentional porous monocrystalline ZnO nano sheet of Pd first, and is applied to gas sensing.Because noble metal nano particles modification one-dimensional nano material has report more, rarely has in addition report but modify the two-dimensional nano material preparation with application.
The heater-type gas sensor of preparation, the sensing capabilities of test gas sensor in HW-30A type air-sensitive test macro, test atmosphere adopts static distribution to send out and measures.Definition gas sensor sensitivity S=Ra/Rg, the response-recovery time be the device resistance value reach the required time of change in resistance maximal value 90% (Ra is the aerial resistance of gas sensor, Rg by gas sensor the resistance in survey gas).
The invention has the advantages that:
(1) highly sensitive: the sensitivity to 100 ppm acetone gas reaches 8 left and right up to 70,500 ppm up to 222,10ppm.
(2) (operating temperature is low: through the ZnO nano sheet compound substance after the Pd Nanoparticle Modified, optimum temperature is 340 ℃, and 420 ℃ of more single ZnO nano sheets have significantly and reduce.
(3) the response-recovery time is fast: the response-recovery time of this gas sensor in 10-500 ppm scope is all in 10 s.
(4) good cycling stability: the single crystal ZnO material has good thermal stability than polycrystalline ZnO, but the sensitivity meeting is weaker, yet selects porous monocrystalline ZnO material, can increase specific surface area, is conducive to improve sensitivity.When increasing sensitivity, can reduce operating temperature after modification Pd nano particle, namely further guarantee its stability, so in the continuous firing of 60 days, sensitivity swims in 2%.
(5) selectivity is good: relative acetone, this gas sensor common are machine solvent such as ethanol, methyl alcohol, benzene and toluene etc. and insensitive to some.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) photo and the electronic diffraction photo of the monocrystalline porous ZnO nanometer sheet of preparation;
Fig. 2 is TEM photo and the energy spectrogram after the compound Pd nano particle of porous ZnO nanometer sheet;
Fig. 3 is gas sensor of the present invention response to 100 ppm acetone gas at different temperature;
Fig. 4 is that gas sensor of the present invention is to the response curve of variable concentrations acetone gas;
Fig. 5 is the air-sensitive selectivity test of gas sensor of the present invention;
Fig. 6 is the stability test of gas sensor of the present invention.
Embodiment
Embodiment 1
Prepared porous ZnO nanometer sheet is mixed with the Pd nano particle, and the Pd nanoparticle content is 0.5%, grinds 1 h in agate mortar, after 600 ℃ of calcining 2h, makes the compound substance of Pd Nanoparticle Modified ZnO.Then, this material is made slurry in terpinol, evenly be coated in the ceramic pipe surface, then dry 1 h under 100 ℃ in baking oven, then put into 540 ℃ of calcining 2 h of muffle furnace, then again according to the heater-type common process, weld, encapsulation, aging, make gas sensor.The air-sensitive test result shows that it has reached 222 to the sensitivity of 100 ppm acetone steams up to the sensitivity of 70,500 ppm, and the response-recovery time is respectively 7 s and 8 s, as shown in Figure 4.
Prepared porous ZnO nanometer sheet is mixed with the Pd nano particle, and the Pd nanoparticle content is 0.4%, grinds 30min in agate mortar, after 550 ℃ of calcining 1.5h, makes the compound substance of Pd Nanoparticle Modified ZnO.Make slurry, evenly be coated in the ceramic pipe surface, then dry 1h under 80 ℃ in baking oven, then put into 560 ℃ of calcining 1.5 h of muffle furnace then again according to the heater-type common process, welds, encapsulation, aging, makes gas sensor.The air-sensitive test result shows that it has reached 216 to the sensitivity of 100 ppm acetone steams up to the sensitivity of 71,500 ppm, and the response-recovery time is respectively 8 s and 9 s.
Embodiment 3
Prepared porous ZnO nanometer sheet is mixed with the Pd nano particle, and the Pd nanoparticle content is 0.3%, grinds 40min in agate mortar, after 550 ℃ of calcining 1h, makes the compound substance of Pd Nanoparticle Modified ZnO.This material is made slurry in terpinol, evenly be coated in the ceramic pipe surface, then dry 1h under 90 ℃ in baking oven, put into again 500 ℃ of calcining 1.8 h of muffle furnace, then again according to the heater-type common process, weld, encapsulation, aging, make gas sensor.The air-sensitive test result shows that it has reached 209 to the sensitivity of 100 ppm acetone steams up to the sensitivity of 68,500 ppm, and the response-recovery time is respectively 10s and 10 s.
Embodiment 4
Prepared porous ZnO nanometer sheet is mixed with the Pd nano particle, and the Pd nanoparticle content is 0.6%, grinds 50min in agate mortar, after 580 ℃ of calcining 1.2h, makes the compound substance of Pd Nanoparticle Modified ZnO.Then, this material is made slurry in terpinol, evenly be coated in the ceramic pipe surface, then dry 30min under 120 ℃ in baking oven, then put into 440 ℃ of calcining 1.5 h of muffle furnace, then again according to the heater-type common process, weld, encapsulation, aging, make gas sensor.The air-sensitive test result shows that it has reached 232 to the sensitivity of 100 ppm acetone steams up to the sensitivity of 78,500 ppm, and the response-recovery time is respectively 8 s and 7 s.
Embodiment 5
Prepared porous ZnO nanometer sheet is mixed with the Pd nano particle, and the Pd nanoparticle content is 0.7%, grinds 1 h in agate mortar, after 650 ℃ of calcining 1.5h, makes the compound substance of Pd Nanoparticle Modified ZnO.Make slurry, evenly be coated in the ceramic pipe surface, then dry 30min under 100 ℃ in baking oven, then put into 480 ℃ of calcining 1.2 h of muffle furnace then again according to the heater-type common process, welds, encapsulation, aging, makes gas sensor.The air-sensitive test result shows that it has reached 240 to the sensitivity of 100 ppm acetone steams up to the sensitivity of 88,500 ppm, and the response-recovery time is respectively 6 s and 7 s.
Embodiment 6
Prepared porous ZnO nanometer sheet is mixed with the Pd nano particle, and the Pd nanoparticle content is 0.8%, grinds 40min in agate mortar, after 620 ℃ of calcining 1.8h, makes the compound substance of Pd Nanoparticle Modified ZnO.Then this material is ground in terpinol and make slurry, evenly be coated in the ceramic pipe surface, then dry 1 h under 120 ℃ in baking oven, put into again 600 ℃ of calcining 1.4 h of muffle furnace, then again according to the heater-type common process, weld, encapsulation, aging, make gas sensor.The air-sensitive test result shows that it has reached 252 to the sensitivity of 100 ppm acetone steams up to the sensitivity of 95,500 ppm, and the response-recovery time is respectively 5 s and 6 s.
Claims (4)
1. the preparation method of a Pd Nanoparticle Modified porous ZnO nanometer sheet gas sensitive, it is characterized in that: with porous monocrystalline ZnO nano sheet and Pd nano particle mixed grinding, the quality of Pd nano particle accounts for 0.3 ~ 0.8% of porous monocrystalline ZnO nano sheet and Pd nano particle gross mass, then calcine 1-2h under the condition of 550-650 ℃, obtain the gas sensitive of Pd Nanoparticle Modified porous ZnO nanometer sheet.
2. the preparation method of Pd Nanoparticle Modified porous ZnO nanometer sheet gas sensitive according to claim 1, it is characterized in that: the thickness of described porous monocrystalline ZnO nano sheet is 10-50 nm, the diameter of Pd nano particle is 5-20nm.
3. the preparation method of Pd Nanoparticle Modified porous ZnO nanometer sheet gas sensitive according to claim 1, it is characterized in that: described porous monocrystalline ZnO nano sheet and Pd nano particle mixed grinding time are 0.5-1h.
4. the preparation method of Pd Nanoparticle Modified porous ZnO nanometer sheet gas sensor according to claim 1, it is characterized in that: the gas sensitive of Pd Nanoparticle Modified porous ZnO nanometer sheet is mixed into slurry in terpinol, evenly be coated in again the aluminium oxide ceramics tube-surface with forked gold electrode, first toast 30-60min under the condition of 80-120 ℃ in baking oven, put into again muffle furnace, calcine 1-2h under the condition of 400-600 ℃, then welding, packing, aging obtain Pd Nanoparticle Modified porous ZnO nanometer sheet gas sensor.
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| CN103901075A (en) * | 2014-03-13 | 2014-07-02 | 郑州轻工业学院 | Preparation methods for three-dimensional porous ZnO nano sheet ball gas sensitive material and gas sensitive element |
| CN104237464A (en) * | 2014-09-09 | 2014-12-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Gas-sensitive sensing material with nano-zinc oxide supported palladium-copper porous structure and preparation method of gas-sensitive sensing material |
| CN106541143A (en) * | 2016-11-02 | 2017-03-29 | 山东大学 | A kind of porous zinc bloom nanometer sheet loads the synthetic method of high-dispersion nano noble metal composite air-sensitive material |
| CN108802116A (en) * | 2018-06-19 | 2018-11-13 | 扬州睿德石油机械有限公司 | A kind of preparation method of acetone gas sensitive material |
| CN105784775B (en) * | 2016-02-01 | 2018-12-25 | 山东科技大学 | A kind of preparation method of ethyl acetate gas sensitive material |
| CN109725039A (en) * | 2019-01-10 | 2019-05-07 | 沈阳化工大学 | A kind of preparation and its application of Pd modification ZnO nano-rod array |
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| CN117960168A (en) * | 2024-04-01 | 2024-05-03 | 国网安徽省电力有限公司电力科学研究院 | Zinc oxide ultrathin nanosheet capable of performing photocatalytic conversion on sulfur hexafluoride as well as preparation method and application thereof |
| CN117960168B (en) * | 2024-04-01 | 2024-06-25 | 国网安徽省电力有限公司电力科学研究院 | Zinc oxide ultrathin nanosheet capable of performing photocatalytic conversion on sulfur hexafluoride as well as preparation method and application thereof |
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| CN103901075B (en) * | 2014-03-13 | 2016-02-24 | 郑州轻工业学院 | The preparation method of a kind of three-dimensional porous ZnO nano sheet ball gas sensitive and gas sensor |
| CN103901075A (en) * | 2014-03-13 | 2014-07-02 | 郑州轻工业学院 | Preparation methods for three-dimensional porous ZnO nano sheet ball gas sensitive material and gas sensitive element |
| CN104237464A (en) * | 2014-09-09 | 2014-12-24 | 上海纳米技术及应用国家工程研究中心有限公司 | Gas-sensitive sensing material with nano-zinc oxide supported palladium-copper porous structure and preparation method of gas-sensitive sensing material |
| CN104237464B (en) * | 2014-09-09 | 2016-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | The gas sensing materials of nano zine oxide supported palladium-copper porous structure and preparation |
| CN105784775B (en) * | 2016-02-01 | 2018-12-25 | 山东科技大学 | A kind of preparation method of ethyl acetate gas sensitive material |
| CN106541143A (en) * | 2016-11-02 | 2017-03-29 | 山东大学 | A kind of porous zinc bloom nanometer sheet loads the synthetic method of high-dispersion nano noble metal composite air-sensitive material |
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| CN109725039A (en) * | 2019-01-10 | 2019-05-07 | 沈阳化工大学 | A kind of preparation and its application of Pd modification ZnO nano-rod array |
| CN112268940A (en) * | 2020-10-30 | 2021-01-26 | 郑州轻工业大学 | MO for aniline gas sensor2/MO3NMNPs hollow microsphere material and preparation method thereof |
| CN112268940B (en) * | 2020-10-30 | 2024-04-16 | 郑州轻工业大学 | MO for aniline gas sensor 2 /MO 3 NMNPs hollow microsphere material and preparation method thereof |
| CN117960168A (en) * | 2024-04-01 | 2024-05-03 | 国网安徽省电力有限公司电力科学研究院 | Zinc oxide ultrathin nanosheet capable of performing photocatalytic conversion on sulfur hexafluoride as well as preparation method and application thereof |
| CN117960168B (en) * | 2024-04-01 | 2024-06-25 | 国网安徽省电力有限公司电力科学研究院 | Zinc oxide ultrathin nanosheet capable of performing photocatalytic conversion on sulfur hexafluoride as well as preparation method and application thereof |
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Application publication date: 20130508 |