CN104502413A - Copper oxide doped stannic oxide based hydrogen sulfide gas sensitive material as well as preparation and application - Google Patents
Copper oxide doped stannic oxide based hydrogen sulfide gas sensitive material as well as preparation and application Download PDFInfo
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Abstract
The invention relates to a copper oxide doped stannic oxide based hydrogen sulfide gas sensitive material as well as preparation and application. The preparation is as follow: the mass ratio of tin chloride dehydrate to copper chloride of the reaction raw materials is controlled, and the one-step solvent process is carried out to obtain copper oxide doped stannic oxide nano-particles. The stannic oxide nano-particles are uniform in size, being not greater than 500nm in particle size and olive-shaped. The stannic oxide nano-particles show good selectivity and responsiveness for toxic and harmful hydrogen sulfide. The copper oxide doped stannic oxide based hydrogen sulfide gas sensitive material has the characteristics that the preparation method is simple and easy to be carried out, and the product is high in performances; the copper oxide doped stannic oxide based hydrogen sulfide gas sensitive material has a good application prospect in the field of gas sensitive sensors, the cost can be minimized and the personal safety can be ensured in the actual production.
Description
Technical field
The invention belongs to metal oxide semiconductor sensor material preparation process technical field, belong to doping type metal-oxide semiconductor (MOS), be conducive to improving performance.
Background technology
One of semiconductor gas sensor material the earliest studied by tin ash.Have the advantages such as good conductivity, crystal structure and applicability because of it, make it in semiconductor gas sensor field, be the focus of investigation and application always.And should have highly sensitive as a kind of good gas sensitive, selectivity is strong, and air-sensitive working temperature is low, and structure is simple, the advantages such as cost is low, good stability.In view of the inferior position of pure tin dioxide gas-sensitive material in response and selectivity, the improvement of suitable adjuvant to the air-sensitive performance of its gas sensor of adulterating is necessary.So the performance in order to improve tin dioxide gas sensor, oxide semiconductor gas sensor material is mixed with noble metal catalyst at majority of case, as platinum (Pt), and palladium (Pd) and gold (Au) etc.But noble metal is expensive but also serious environment pollution not only, so the mantoquita of choice for use cheapness of the present invention is as alloy, through a step hydro-thermal reaction, can realize the preparation of cupric oxide doped tin ash, air-sensitive result shows the stink damp dependent sensor that the present invention can obtain performance reinforcement equally.
Summary of the invention
For overcoming the deficiencies in the prior art, this provides a kind of cupric oxide doped tin ash sulfuretted hydrogen gas sensitive and Synthesis and applications.
A preparation method for cupric oxide doped tin ash sulfuretted hydrogen gas sensitive, is characterized in that, comprise following steps:
(1) take surfactant polyvinylpyrrolidone, k=30,1.0 grams and two oxalic acid hydrates 3.5 grams, be dissolved in 30 ml deionized water, and magnetic agitation is to dissolving completely;
(2) take cupric chloride and two hydrated stannous chlorides, mass ratio is 1% ~ 10%, is dissolved in settled solution in step (1), and magnetic agitation is to dissolving completely;
(3) pour in the hydrothermal reaction kettle of 50 milliliters by the solution of above-mentioned steps (2), hydrothermal temperature is 200 DEG C, 12 hours hydro-thermal reaction time;
(4), after question response terminates, the precipitation in centrifuging (3), obtains product, and with absolute ethanol washing for several times; Finally use constant temperature blast drier desciccate.
The mean grain size of described gas sensitive is within 500nm, and pattern is the cupric oxide doped tin ash of " olive shape ".
The filling rate of the water heating kettle in step (3) is 60%.
A cupric oxide doped tin ash sulfuretted hydrogen gas sensitive, is characterized in that, prepares according to above-mentioned arbitrary described method.
Described cupric oxide doped tin ash sulfuretted hydrogen gas sensitive is applied preparing in stink damp dependent sensor.
Advantage of the present invention:
1, due to the restriction of technology and technique, the market price of common commercial stink damp dependent sensor in a few unit to unit up to a hundred not etc., far above the gas sensor of ethanol, ammonia and steam.This experiment is by the preparation scheme of a step hydro-thermal, obtain cupric oxide doped tin dioxide gas-sensitive material, simple for process, and abundant raw material, with low cost, by means of only the mass ratio of control two hydrated stannous chloride and cupric chloride, the gas sensitive of cupric oxide doped tin ash sulfuretted hydrogen to good selectivity and responsiveness just can be obtained.
2, common commercial stink damp dependent sensor generally responds concentration >=5ppm to sulfuretted hydrogen, and is subject to the restriction of factors in use procedure.The cupric oxide doped tin oxide nano particles that this experiment is prepared, have extraordinary response and selectivity to sulfuretted hydrogen in air-sensitive test, minimum response concentration is 2ppm and very poor to other gas responses, shows extraordinary selectivity.
3, this assay reproducibility is good, is applicable to large-scale production, at utmost ensures the personal security be exposed in sulfuretted hydrogen atmosphere.Technique is simple, overcomes conventional precious metal and to adulterate the problems such as contaminated environment with high costs.Semiconductor gas sensors material prepared by the present invention is applicable to and manufactures stink damp dependent sensor.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram that embodiment 1 obtains cupric oxide doped tin oxide nano particles.
Fig. 2 is the scanning electron microscope diagram (50,000 times) that embodiment 1 obtains cupric oxide doped tin oxide nano particles.
Fig. 3 is that embodiment 1 obtains cupric oxide doped tin ash gas sensor at 240 DEG C to 1-15ppm sulfuretted hydrogen response sensitivity.
Fig. 4 is that embodiment 1 obtains the sensitivity of cupric oxide doped tin oxide nano particles to the gas with various of 10ppm at optimal response temperature 240 DEG C.
Embodiment
embodiment 1:
(1) surfactant polyvinylpyrrolidone (k=30) 1.0 grams is taken and two oxalic acid hydrates 3.5 grams add 50ml beaker, measure 30 ml deionized water with graduated cylinder and add beaker as solvent, beaker is placed on magnetic agitation on magnetic stirring apparatus and extremely dissolves completely;
(2) take 0.226g bis-hydrated stannous chloride and 0.0068g cupric chloride, be dissolved in settled solution in (1), on magnetic stirring apparatus, magnetic agitation is to again dissolving completely;
(3) poured in the hydrothermal reaction kettle of 50 milliliters by the solution of above-mentioned steps (2), put into incubation water heating case, setting hydrothermal temperature is 200 DEG C, 12 hours hydro-thermal isothermal reaction time; Water heating kettle after having reacted naturally cools in incubation water heating case;
(4) centrifuge is separated the precipitation in (3), obtains pulverous product bottom 10ml plastic centrifuge tube.Absolute ethyl alcohol is poured into, supersound washing products several times in centrifuge tube; Clean product finally with constant temperature blast drier at 60 DEG C of desciccates until alcohol volatilizees completely;
(5) heater-type H is prepared
2s gas sensor, adopts WS-30A type Testing system of gas-sensor built to test its air-sensitive performance.
Fig. 1 is the X-ray diffraction spectrogram that embodiment 1 obtains cupric oxide doped tin oxide nano particles, with cubic rutile SnO
2standard card 41-1445 mate completely, this SnO
2nano particle crystallinity is good, and its diffraction peak sharply wherein detects the diffraction peak of two cupric oxide, proves to be doped with cupric oxide composition in tin ash.
Fig. 2 is the scanning electron microscope diagram that embodiment 1 obtains cupric oxide doped tin oxide nano particles, and product morphology is the nano particle of particle diameter within 500nm, and particle presents olive shape, and size uniform dispersion degree is good.
Fig. 3 is that embodiment 1 obtains cupric oxide doped tin ash gas sensor at 240 DEG C to 1-15ppm sulfuretted hydrogen response sensitivity curve; The optimum working temperature of this gas sensor between 240-270 DEG C, at the sulfuretted hydrogen response sensitivity of about 15ppm close to 90.Minimum response concentration is at about 2ppm.
Fig. 4 is that embodiment 1 obtains cupric oxide doped tin oxide nano particles respectively to the response sensitivity of the methyl alcohol to 10ppm, sulfuretted hydrogen, formaldehyde, acetone and ethanol at 240 DEG C, and this gas sensor shows unique selectivity to sulfuretted hydrogen.
embodiment 2:
(1) surfactant polyvinylpyrrolidone (k=30) 1.0 grams is taken and two oxalic acid hydrates 3.5 grams add 50ml beaker, measure 30 ml deionized water with graduated cylinder and add beaker as solvent, beaker is placed on magnetic agitation on magnetic stirring apparatus and extremely dissolves completely;
(2) take 0.226g bis-hydrated stannous chloride and 0.0136g cupric chloride, be dissolved in settled solution in (1), on magnetic stirring apparatus, magnetic agitation is to again dissolving completely;
(3) poured in the hydrothermal reaction kettle of 50 milliliters by the solution of above-mentioned steps (2), put into incubation water heating case, setting hydrothermal temperature is 200 DEG C, 12 hours hydro-thermal isothermal reaction time; Water heating kettle after having reacted naturally cools in incubation water heating case;
(4) centrifuge is separated the precipitation in (3), obtains pulverous product bottom 10ml plastic centrifuge tube.Absolute ethyl alcohol is poured into, supersound washing products several times in centrifuge tube; Clean product finally with constant temperature blast drier at 60 DEG C of desciccates until alcohol volatilizees completely;
(5) heater-type H is prepared
2s gas sensor, adopts WS-30A type Testing system of gas-sensor built to test its air-sensitive performance.
embodiment 3:
(1) surfactant polyvinylpyrrolidone (k=30) 1.0 grams is taken and two oxalic acid hydrates 3.5 grams add 50ml beaker, measure 30 ml deionized water with graduated cylinder and add beaker as solvent, beaker is placed on magnetic agitation on magnetic stirring apparatus and extremely dissolves completely;
(2) take 0.226g bis-hydrated stannous chloride and 0.0271g cupric chloride, be dissolved in settled solution in (1), on magnetic stirring apparatus, magnetic agitation is to again dissolving completely;
(3) poured in the hydrothermal reaction kettle of 50 milliliters by the solution of above-mentioned steps (2), put into incubation water heating case, setting hydrothermal temperature is 200 DEG C, 12 hours hydro-thermal isothermal reaction time; Water heating kettle after having reacted naturally cools in incubation water heating case;
(4) centrifuge is separated the precipitation in (3), obtains pulverous product bottom 10ml plastic centrifuge tube.Absolute ethyl alcohol is poured into, supersound washing products several times in centrifuge tube; Clean product finally with constant temperature blast drier at 60 DEG C of desciccates until alcohol volatilizees completely;
(5) heater-type H is prepared
2s gas sensor, adopts WS-30A type Testing system of gas-sensor built to test its air-sensitive performance.
The cupric oxide doped stannic oxide nanometer gas sensitive of table 1 prepared by embodiment 1-3, to the response sensitivity of 10ppm hydrogen sulfide gas.
As can be seen from Table 1, the cupric oxide doped stannic oxide nanometer gas sensitive prepared by embodiment 1-3 is for the H of 10ppm
2the sensitivity of S all reaches more than 20, for H
2s has good response.The invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and amendment all should within protection scope of the present invention.
Claims (5)
1. a preparation method for cupric oxide doped tin ash sulfuretted hydrogen gas sensitive, is characterized in that, comprise following steps:
(1) take surfactant polyvinylpyrrolidone, k=30,1.0 grams and two oxalic acid hydrates 3.5 grams, be dissolved in 30 ml deionized water, and magnetic agitation is to dissolving completely;
(2) take cupric chloride and two hydrated stannous chlorides, mass ratio is 1% ~ 10%, is dissolved in settled solution in step (1), and magnetic agitation is to dissolving completely;
(3) pour in the hydrothermal reaction kettle of 50 milliliters by the solution of above-mentioned steps (2), hydrothermal temperature is 200 DEG C, 12 hours hydro-thermal reaction time;
(4), after question response terminates, the precipitation in centrifuging (3), obtains product, and with absolute ethanol washing for several times; Finally use constant temperature blast drier desciccate.
2. the preparation method of tin ash sulfuretted hydrogen gas sensitive cupric oxide doped according to claim 1, is characterized in that: the mean grain size of described gas sensitive is within 500nm, and pattern is the cupric oxide doped tin ash of " olive shape ".
3. the preparation method of tin ash sulfuretted hydrogen gas sensitive cupric oxide doped according to claim 1, is characterized in that: the filling rate of the water heating kettle in step (3) is 60%.
4. a cupric oxide doped tin ash sulfuretted hydrogen gas sensitive, is characterized in that, method prepares according to above-mentioned arbitrary claim.
5. cupric oxide doped tin ash sulfuretted hydrogen gas sensitive according to claim 4 is applied preparing in stink damp dependent sensor.
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| CN104990959A (en) * | 2015-07-10 | 2015-10-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of hydrogen sulfide gas sensitive material composited by copper and tin oxide |
| CN105417572A (en) * | 2015-11-09 | 2016-03-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing p-n type SnO2/CuO composite microspheres |
| CN106093140A (en) * | 2016-07-19 | 2016-11-09 | 山东大学 | For NO2the composite construction doped air-sensitive material of gas, gas sensor and preparation method thereof and application |
| CN108318542A (en) * | 2017-11-30 | 2018-07-24 | 苏州慧闻纳米科技有限公司 | The preparation method of tin dioxide gas sensitive and these hydrogen sulfide gas sensor chip, these hydrogen sulfide gas sensor |
| CN110161097A (en) * | 2019-06-02 | 2019-08-23 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation of the modified tin dioxide nanometer material of di-iron trioxide-silver for gas sensor and product and application |
| CN112067666A (en) * | 2020-08-13 | 2020-12-11 | 东北电力大学 | Preparation method of silver phosphate doped tin dioxide gas sensor gas sensitive material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104990959A (en) * | 2015-07-10 | 2015-10-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of hydrogen sulfide gas sensitive material composited by copper and tin oxide |
| CN104990959B (en) * | 2015-07-10 | 2018-07-13 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of copper and the compound hydrogen sulfide gas sensitive of tin oxide |
| CN105417572A (en) * | 2015-11-09 | 2016-03-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing p-n type SnO2/CuO composite microspheres |
| CN105417572B (en) * | 2015-11-09 | 2017-10-27 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of p n-types SnO2The preparation method of/CuO complex microspheres |
| CN106093140A (en) * | 2016-07-19 | 2016-11-09 | 山东大学 | For NO2the composite construction doped air-sensitive material of gas, gas sensor and preparation method thereof and application |
| CN106093140B (en) * | 2016-07-19 | 2019-10-25 | 山东大学 | For NO2The composite construction doped air-sensitive material of gas, gas sensor and preparation method thereof and application |
| CN108318542A (en) * | 2017-11-30 | 2018-07-24 | 苏州慧闻纳米科技有限公司 | The preparation method of tin dioxide gas sensitive and these hydrogen sulfide gas sensor chip, these hydrogen sulfide gas sensor |
| CN110161097A (en) * | 2019-06-02 | 2019-08-23 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation of the modified tin dioxide nanometer material of di-iron trioxide-silver for gas sensor and product and application |
| CN110161097B (en) * | 2019-06-02 | 2021-09-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation of ferric oxide-silver modified tin dioxide nano material for gas sensor, product and application |
| CN112067666A (en) * | 2020-08-13 | 2020-12-11 | 东北电力大学 | Preparation method of silver phosphate doped tin dioxide gas sensor gas sensitive material |
| CN112067666B (en) * | 2020-08-13 | 2024-03-29 | 东北电力大学 | Preparation method of silver phosphate doped tin dioxide gas sensor gas-sensitive material |
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