CN103558261B - A kind of preparation method of room-temperature hydrogen sensor - Google Patents
A kind of preparation method of room-temperature hydrogen sensor Download PDFInfo
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- CN103558261B CN103558261B CN201310587206.4A CN201310587206A CN103558261B CN 103558261 B CN103558261 B CN 103558261B CN 201310587206 A CN201310587206 A CN 201310587206A CN 103558261 B CN103558261 B CN 103558261B
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Abstract
A preparation method for room-temperature hydrogen sensor, relates to hydrogen gas sensor.Annealing in process is carried out to metal oxide, by chloride, polyvinylpyrrolidone, NaI2H
2o and deionized water add and fill in the beaker of dimethyl formamide, described chloride is palladium bichloride or platinum chloride, obtain dark brown solution, transfer in reactor, then the metal oxide after annealing in process to be joined in reactor and to carry out ultrasonic disperse, after dispersion completely, reactor sealed and place under the growth temperature of setting, react complete be cooled to room temperature after, centrifugal, washing, in a solvent by product dispersion finally, obtain the metal oxide room temperature hydrogen sensitive material having palladium or Pt nanoparticle at surface deposition, ultrasonic disperse is in absolute ethyl alcohol again, then the suspension after dispersion is dropped in cleaned golden interdigital electrode, air-sensitive chip is obtained after ethanol volatilization completely, then air-sensitive chip is connected with peripheral circuit, obtain room-temperature hydrogen sensor.
Description
Technical field
The present invention relates to hydrogen gas sensor, especially relate to a kind of preparation method of room-temperature hydrogen sensor.
Background technology
Hydrogen has its energy density height and free of contamination characteristic, is described as the new forms of energy of 21 century most prospect.In recent years, a large amount of research relevant to hydrogen is as photocatalytic water, fast development such as galvanochemistry storage hydrogen and hydrogen fuel cell etc.But hydrogen is colourless, tasteless and highly flammable gas, therefore in use procedure once occur leak abnormally dangerous.Therefore the widespread use of hydrogen energy source is had higher requirement to hydrogen detection technique.
Traditional metal-oxide gas transducer generally could will work under the hot conditions more than 300 DEG C, this makes the power dissipation ratio of sensor higher on the one hand, on the other hand also with very large potential safety hazard, when the density of hydrogen in environment reaches its explosion limits (4%), be easy to generation explosion caused.Platinum group metal especially palladium (Pd) and platinum (Pt) is widely used in the low temperature hydrogen sensor lower than 200 DEG C due to outstanding catalytic performance and good stability.In most cases due to the catalytic performance of palladium or platinum itself is good not or they and metal oxide in conjunction with undertighten, can not at room temperature work well although the working temperature of sensor can significantly reduce.And the modification of palladium and platinum mostly depends on the expensive technology such as thermal evaporation, magnetron sputtering, high cost seriously limits the widespread use of this kind of material.
Summary of the invention
The object of the invention is to the deficiency overcoming the existence of above prior art, with the surperficial direct growth palladium of wet chemical method at metal oxide or the nano particle of platinum of low cost, provide under can realizing room temperature hydrogen is responded fast, highly sensitive, selectivity good, the preparation method of a kind of room-temperature hydrogen sensor with low cost.
To achieve these goals, the preparation method of room-temperature hydrogen sensor of the present invention comprises the following steps:
1) annealing in process is carried out to metal oxide;
2) by chloride, polyvinylpyrrolidone, NaI2H
2o and deionized water add simultaneously and fill in the beaker of dimethyl formamide, described chloride is palladium bichloride or platinum chloride, obtain dark brown solution, dark brown solution is transferred in reactor, then by step 1) in metal oxide after annealing in process to join in reactor and to carry out ultrasonic disperse, after dispersion completely, reactor sealed and place under the growth temperature of setting, react complete be cooled to room temperature after, products therefrom is centrifugal and with absolute ethanol washing, in a solvent by product dispersion finally, obtain the metal oxide room temperature hydrogen sensitive material having palladium or Pt nanoparticle at surface deposition,
3) by step 2) the metal oxide room temperature hydrogen sensitive material ultrasonic disperse that obtains is in absolute ethyl alcohol, then the suspension after dispersion is dropped in cleaned golden interdigital electrode, air-sensitive chip is obtained after ethanol volatilization completely, then air-sensitive chip is connected with peripheral circuit, obtains room-temperature hydrogen sensor.
In step 1) in, described metal oxide can be the tin ash (SnO of granularity at 100 ~ 1000nm
2), tungstic acid (WO
3) or indium oxide (In
2o
3) etc.; The temperature of described annealing in process can be 400 ~ 600 DEG C, and the time of annealing in process can be 2h, can remove organic dirt that metal oxide surface may adhere to and improve its crystallinity after annealing in process.
In step 2) in, chloride, polyvinylpyrrolidone, NaI2H
2the mass ratio of O, deionized water, dimethyl formamide is 1: (10 ~ 20): (20 ~ 30): (100 ~ 200): (500 ~ 1000); Reactant packing ratio in a kettle. can be 40% ~ 60%;
The growth temperature of described setting can be 120 ~ 160 DEG C, and the time of described placement can be 6 ~ 10h; Volatile organic solvent preferably selected by described solvent, as absolute ethyl alcohol, cyclohexane etc.; Described surface deposition has in the metal oxide room temperature hydrogen sensitive material of palladium or Pt nanoparticle, and by mass percentage, the content of palladium or platinum can be 1% ~ 15%.
Compared with prior art, the present invention has following outstanding advantages:
1, with thermal evaporation, be sputtered to representative physical method compared with, production efficiency significantly promotes, and cost declines to a great extent, and is applicable to synthesis in enormous quantities.
2, compared with other wet chemistry synthetic methods, one is by selecting suitable solvent (dimethyl formamide) to enable palladium or platinum directly grow on oxide-base bottom material, catalyst granules be combined with base material than mechanical mix techniques obtain tightr, be conducive to the electronics in the response process of hydrogen between catalyzer and base material and ion transmission, two is the crystal faces utilizing the synergy of polyvinylpyrrolidone and iodide ion to control product, the crystal face major part that palladium or Pt catalyst granule are finally exposed is { 100} crystal face, catalytic performance is more all even stable.
3, the room-temperature hydrogen sensor fast response time made of the present invention, highly sensitive, homogeneity is good, and make simple, cost is low.The situation needing to detect hydrogen leak can be widely used in, be particularly suitable for the place that density of hydrogen is higher, easily cause security incident with traditional pyrostat.
Accompanying drawing explanation
The WO that be modified with palladium nano-particles of Fig. 1 prepared by the embodiment of the present invention 1
3the SEM photo of nanometer sheet.
The WO that be modified with palladium nano-particles of Fig. 2 prepared by the embodiment of the present invention 1
3the TEM photo of nanometer sheet.
The WO that be modified with Pt nanoparticle of Fig. 3 prepared by the embodiment of the present invention 2
3the SEM photo of nanometer sheet.
The WO that be modified with Pt nanoparticle of Fig. 4 prepared by the embodiment of the present invention 2
3the TEM photo of nanometer sheet.
The In that be modified with Pt nanoparticle of Fig. 5 prepared by the embodiment of the present invention 3
2o
3the cubical SEM photo of nanocube.
The In that be modified with Pt nanoparticle of Fig. 6 prepared by the embodiment of the present invention 3
2o
3the cubical TEM photo of nanocube.
The WO that be modified with palladium nano-particles of Fig. 7 prepared by the embodiment of the present invention 1
3nanometer sheet is at ambient temperature to the response diagram of hydrogen.Horizontal ordinate is the time (s), and ordinate is conductance (S).
The WO that be modified with Pt nanoparticle of Fig. 8 prepared by the embodiment of the present invention 2
3nanometer sheet is at ambient temperature to the response diagram of hydrogen.Horizontal ordinate is the time (s), and ordinate is conductance (S).
The In that be modified with Pt nanoparticle of Fig. 9 prepared by the embodiment of the present invention 3
2o
3cube is at ambient temperature to the response diagram of hydrogen.Horizontal ordinate is the time (s), and ordinate is conductance (S).
Embodiment
Embodiment 1
The preparation method of room-temperature hydrogen sensor described in the present embodiment, comprises the following steps:
1) to the WO of routine
3nanometer sheet carries out pre-service, at ambient temperature by 1gWO
3nanometer sheet loads in silica crucible, then puts it in muffle furnace.Start the heating schedule of muffle furnace, be heated to 500 DEG C with the rate of heat addition of 5 DEG C/min from room temperature, keep 2h at 500 DEG C, then close muffle furnace heating schedule, make its Temperature fall, after being down to room temperature, by WO
3nanometer sheet loads in sample bottle stand-by.
Described conventional tungstic trioxide nano-slice is average side length is 150nm, and average thickness is the thin slice of 30nm.Can synthesize with simple hydrothermal method in the lab, also can buy business-like similar clause.
2) 0.12g palladium bichloride, 1.6g polyvinylpyrrolidone, 3.6g sodium iodide and 20 ml deionized water are added in the beaker containing 100 milliliters of dimethyl formamides, at room temperature use magnetic stirrer 10min, obtain the potpourri of brownish black, in the reactor then said mixture being transferred to 250ml and by step 1) 1gWO of gained
3nanometer sheet adds, and is ultrasonic process 30min in the supersonic cleaning machine of 100W at rated power.Then reactor is sealed, in the air dry oven of 150 DEG C, place 8h.After room temperature is down to by reactor, the solid product dimethyl formamide obtained and absolute ethyl alcohol are washed three times respectively.Obtain the WO being modified with palladium nano-particles shown in Fig. 1 and 2
3nanometer sheet (namely surface deposition has the metal oxide room temperature hydrogen sensitive material of palladium nano-particles).
Described palladium bichloride, polyvinylpyrrolidone, sodium iodide and dimethyl formamide are general analysis pure reagent.
3) 10mg step 2 is got) WO being modified with palladium nano-particles that obtains
3nanometer sheet is scattered in 5ml absolute ethyl alcohol, then the suspension after 2.5 microlitre dispersions is dropped in golden interdigital electrode cleaned in advance, after ethanol volatilization completely, obtain air-sensitive chip, then air-sensitive chip is connected with peripheral circuit, obtains room-temperature hydrogen sensor.
4) with NS ?4003 type sense instrument measurements be modified with the WO of palladium nano-particles
3nanometer sheet is to the response of hydrogen.
Test condition is normal temperature and pressure, and measurement atmosphere is air, hydrogen is expelled to the test gas obtaining respective concentration in the glass air chamber of 10L.See Fig. 7, the quick conductance of hydrogen increases with the increase of density of hydrogen.
Embodiment 2
The preparation method of room-temperature hydrogen sensor described in the present embodiment, comprises the following steps:
1) to the WO of routine
3nanometer sheet carries out pre-service, at ambient temperature by 1gWO
3nanometer sheet loads in silica crucible, then puts it in muffle furnace.Start the heating schedule of muffle furnace, be heated to 600 DEG C with the rate of heat addition of 5 DEG C/min from room temperature, keep 2h at 600 DEG C, then close muffle furnace heating schedule, make its Temperature fall, after being down to room temperature, by WO
3nanometer sheet loads in sample bottle stand-by.
Described conventional tungstic trioxide nano-slice is average side length is 150nm, and average thickness is the thin slice of 30nm.Can synthesize with simple hydrothermal method in the lab, also can buy business-like similar clause.
2) 0.15g platinum chloride, 2.0g polyvinylpyrrolidone, 4.5g sodium iodide and 20 ml deionized water are added in the beaker containing 100 milliliters of dimethyl formamides, at room temperature use magnetic stirrer 10min, obtain the potpourri of brownish black, in the reactor then said mixture being transferred to 250ml and by step 1) 1gWO of gained
3nanometer sheet adds, and is ultrasonic process 30min in the supersonic cleaning machine of 100W at rated power.Then reactor is sealed, in the air dry oven of 120 DEG C, place 6h.After room temperature is down to by reactor, the solid product dimethyl formamide obtained and absolute ethyl alcohol are washed three times respectively.Obtain the WO being modified with Pt nanoparticle shown in Fig. 3 and 4
3nanometer sheet.
Described platinum chloride, polyvinylpyrrolidone, sodium iodide and dimethyl formamide are general analysis pure reagent.
3) 10mg step 2 is got) WO being modified with Pt nanoparticle that obtains
3nanometer sheet is scattered in 5ml absolute ethyl alcohol, then the suspension after 2.5 microlitre dispersions is dropped in golden interdigital electrode cleaned in advance, after ethanol volatilization completely, obtain air-sensitive chip, then air-sensitive chip is connected with peripheral circuit, obtains room-temperature hydrogen sensor.
4) with NS ?4003 type sense instrument measurements be modified with the WO of Pt nanoparticle
3nanometer sheet is to the response of hydrogen.
Test condition is normal temperature and pressure, and measurement atmosphere is air, a certain amount of hydrogen is expelled to the test gas obtaining respective concentration in the glass air chamber of 10L.See Fig. 8, the quick conductance of hydrogen increases with the increase of density of hydrogen.
Embodiment 3
The preparation method of room-temperature hydrogen sensor described in the present embodiment, comprises the following steps:
1) to the In of routine
2o
3nanocube carries out pre-service, at ambient temperature by 1gIn
2o
3nanocube loads in silica crucible, then puts it in muffle furnace.Start the heating schedule of muffle furnace, be heated to 400 DEG C with the rate of heat addition of 5 DEG C/min from room temperature, keep 2h at 400 DEG C, then close muffle furnace heating schedule, make its Temperature fall, after being down to room temperature, by In
2o
3nanocube loads in sample bottle stand-by.
Described conventional In
2o
3the indium oxide nanocube of nanocube to be average side length be 200nm.In the lab with simple solvent structure, also can buy business-like similar clause.
2) 0.15g platinum chloride, 1.6g polyvinylpyrrolidone, 3.2g sodium iodide and 20 ml deionized water are added in the beaker containing 100 milliliters of dimethyl formamides, at room temperature use magnetic stirrer 10min, obtain the potpourri of brownish black, in the reactor then said mixture being transferred to 250ml and by step 1) In of gained
2o
3nanocube adds, and is ultrasonic process 30min in the supersonic cleaning machine of 100W at rated power.Then reactor is sealed, in the air dry oven of 160 DEG C, place 10h.After room temperature is down to by reactor, the solid product dimethyl formamide obtained and absolute ethyl alcohol are washed three times respectively.Finally product is dispersed in 100 milliliters of absolute ethyl alcohols.Obtain the In being modified with Pt nanoparticle shown in Fig. 5 and 6
2o
3nanocube.
Described platinum chloride, polyvinylpyrrolidone, sodium iodide and dimethyl formamide are general analysis pure reagent.
3) 10mg step 2 is got) In being modified with Pt nanoparticle that obtains
2o
3nanocube is scattered in 5ml absolute ethyl alcohol, then the suspension after 2.5 microlitre dispersions is dropped in golden interdigital electrode cleaned in advance, after ethanol volatilization completely, obtain air-sensitive chip, then air-sensitive chip is connected with peripheral circuit, obtains room-temperature hydrogen sensor.
4) with NS ?4003 type sense instrument measurements be modified with the In of Pt nanoparticle
2o
3nanocube is to the response of hydrogen.
Test condition is normal temperature and pressure, and measurement atmosphere is air, a certain amount of hydrogen is expelled to the test gas obtaining respective concentration in the glass air chamber of 10L.See Fig. 9, the quick conductance of hydrogen increases with the increase of density of hydrogen.
Claims (9)
1. a preparation method for room-temperature hydrogen sensor, is characterized in that comprising the following steps:
1) annealing in process is carried out to metal oxide;
2) by chloride, polyvinylpyrrolidone, NaI2H
2o and deionized water add simultaneously and fill in the beaker of dimethyl formamide, described chloride is palladium bichloride or platinum chloride, obtain dark brown solution, dark brown solution is transferred in reactor, then by step 1) in metal oxide after annealing in process to join in reactor and to carry out ultrasonic disperse, after dispersion completely, reactor sealed and place under the growth temperature of setting, react complete be cooled to room temperature after, products therefrom is centrifugal and with absolute ethanol washing, in a solvent by product dispersion finally, obtain the metal oxide room temperature hydrogen sensitive material having palladium or Pt nanoparticle at surface deposition,
3) by step 2) the metal oxide room temperature hydrogen sensitive material ultrasonic disperse that obtains is in absolute ethyl alcohol, then the suspension after dispersion is dropped in cleaned golden interdigital electrode, air-sensitive chip is obtained after ethanol volatilization completely, then air-sensitive chip is connected with peripheral circuit, obtains room-temperature hydrogen sensor.
2. the preparation method of a kind of room-temperature hydrogen sensor as claimed in claim 1, is characterized in that in step 1) in, described metal oxide is granularity at the tin ash of 100 ~ 1000nm, tungstic acid or indium oxide.
3. the preparation method of a kind of room-temperature hydrogen sensor as claimed in claim 1, is characterized in that in step 1) in, the temperature of described annealing in process is 400 ~ 600 DEG C, and the time of annealing in process is 2h.
4. the preparation method of a kind of room-temperature hydrogen sensor as claimed in claim 1, is characterized in that in step 2) in, described chloride, polyvinylpyrrolidone, NaI2H
2the mass ratio of O, deionized water, dimethyl formamide is 1: (10 ~ 20): (20 ~ 30): (100 ~ 200): (500 ~ 1000).
5. the preparation method of a kind of room-temperature hydrogen sensor as claimed in claim 1, is characterized in that in step 2) in, the growth temperature of described setting is 120 ~ 160 DEG C.
6. the preparation method of a kind of room-temperature hydrogen sensor as claimed in claim 1, is characterized in that in step 2) in, the time of described placement is 6 ~ 10h.
7. the preparation method of a kind of room-temperature hydrogen sensor as claimed in claim 1, is characterized in that in step 2) in, volatile organic solvent selected by described solvent.
8. the preparation method of a kind of room-temperature hydrogen sensor as claimed in claim 7, is characterized in that described volatile organic solvent is selected from absolute ethyl alcohol or cyclohexane.
9. the preparation method of a kind of room-temperature hydrogen sensor as claimed in claim 1, it is characterized in that in step 2) in, described surface deposition has in the metal oxide room temperature hydrogen sensitive material of palladium or Pt nanoparticle, and by mass percentage, the content of palladium or platinum is 1% ~ 15%.
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| CN104569051A (en) * | 2014-11-13 | 2015-04-29 | 无锡信大气象传感网科技有限公司 | Method for manufacturing hydrogen sensor |
| CN105891126A (en) * | 2015-06-30 | 2016-08-24 | 四川智立方博导科技有限责任公司 | Low-cost portable hydrogen optical sensor |
| KR101745128B1 (en) * | 2015-09-01 | 2017-06-08 | 현대자동차주식회사 | Chemochromic nanoparticles, method for manufacturing the same, and hydrogen sensor comprising the same |
| CN106198648B (en) * | 2016-09-14 | 2020-12-01 | 扬州大学 | Preparation method of room temperature hydrogen sensor |
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| CN111855756B (en) * | 2019-04-28 | 2023-11-21 | 中国科学院上海微系统与信息技术研究所 | Hydrogen sensor based on Pd-Ag alloy nanocrystalline and preparation method thereof |
| CN110346421A (en) * | 2019-06-27 | 2019-10-18 | 重庆大学 | A kind of gas sensitive and its preparation method and application |
| CN113249685A (en) * | 2021-04-09 | 2021-08-13 | 杭州电子科技大学 | Preparation method of silver sulfide film gas sensor |
| CN115711713B (en) * | 2021-08-19 | 2023-09-12 | 中国石油化工股份有限公司 | Hydrogen leakage detection material and preparation method and application thereof |
| CN114965594A (en) * | 2022-04-12 | 2022-08-30 | 中国科学技术大学 | Au-modified hollow spherical SnO 2 Nano composite material and preparation method of hydrogen sensor thereof |
| CN115015331A (en) * | 2022-05-20 | 2022-09-06 | 浙江工业大学 | WO with hydrogen gas sensitivity x Pd nano-assembly material hydrogen sensor and preparation method thereof |
| CN115032240A (en) * | 2022-06-09 | 2022-09-09 | 中国科学技术大学 | ZIF-8-derived Pd-ZnO nanocomposite material, preparation method thereof, sensor and preparation method thereof |
| CN118090837A (en) * | 2024-04-23 | 2024-05-28 | 大连理工大学 | Room-temperature hydrogen-sensitive cube material and preparation method thereof |
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