CN103439309A - Preparation method for high-sensitivity CO gas spectrum sensor - Google Patents
Preparation method for high-sensitivity CO gas spectrum sensor Download PDFInfo
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- CN103439309A CN103439309A CN2013103598760A CN201310359876A CN103439309A CN 103439309 A CN103439309 A CN 103439309A CN 2013103598760 A CN2013103598760 A CN 2013103598760A CN 201310359876 A CN201310359876 A CN 201310359876A CN 103439309 A CN103439309 A CN 103439309A
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Abstract
The invention discloses a preparation method for a high-sensitivity CO gas spectrum sensor. The preparation method comprises the following steps: taking n-hexane as an oil phase, adding the n-hexane into a gold sol solution, and forming a gold nanoparticle film on an oil water liquid/liquid phase interface; pulling the gold nanoparticle film onto ITO (Indium Tin Oxide) conductive glass through a pulling method to prepare a monodispersed a solid-phase gold film substrate with an SERS (Surface-Enhanced Raman Scattering) enhancement effect; depositing Pt particles to the solid-phase gold film substrate with constant current by chronovoltammetry. According to the preparation method, proper deposition conditions are selected for depositing the Pt particles through an electrochemical method, and through the surface enhancement effect of the gold film and good chemical adsorption effect of Pt and CO molecules, the characteristics of extremely-high sensitivity and high resolution of a surface-enhanced Raman spectrum are brought into full play and CO gas molecules are detected in real time on line. The preparation method has the characteristics of high sensitivity, convenience for preparation, high selectivity, excellent performance and the like.
Description
Technical field
The present invention relates to environmental gas detection technique field, is a kind of preparation method of highly sensitive CO gaseous spectrum sensor.
Background technology
Traditional CO gas sensor mainly is based on after CO gas enters sensing element oxidation reaction generation CO occurs
2gas, the electron stream that chemical reaction forms carry out signal amplification, conditioning through the rear end amplifying circuit, then sending processor carries out acquisition process after being drawn by electrode.But it is complicated that this type of detection method has the design preparation, is unfavorable for the shortcomings such as Site Detection.At present, a kind of optical fiber CO sensor-based system that also had research and development, it is from molecular structure and molecular spectrum theory, pass through infrared spectrum, according to Lambert-Beer's law and optical information processing technique, analyzed and adopted the spectral absorption method to detect mechanism by the CO gas concentration of optical signal transmission fiber.But this method also has corresponding shortcoming, a little less than CO absorption, the detection sensitivity of infrared spectrum is not high.
Meanwhile, Surface enhanced raman spectroscopy (SERS) has little by little obtained application in each field as a kind of spectral detection means with high detection sensitivity, thisly take the Surface enhanced raman spectroscopy that noble metal nano particles is substrate and become one of effective means of molecular detection and identification, current monomolecular SERS detects and has become possibility, thereby has obtained extensive concern and the research of scientific circles.
Summary of the invention
The object of the present invention is to provide a kind of effectively CO absorption gas molecule, can utilize fully Surface enhanced raman spectroscopy highly sensitive again, the preparation method of the highly sensitive CO gaseous spectrum sensor of good resolution advantage.
Technical solution of the present invention is:
A kind of preparation method of highly sensitive CO gaseous spectrum sensor, is characterized in that: comprise the following steps:
(1) take normal hexane as oil phase, normal hexane is joined in aurosol solution, the gold nano particle diameter is 30nm, and the volume of the normal hexane added is 1/5-1/6 of aurosol liquor capacity, on oil-water fluid/liquid two-phase interface, forms Au nanoparticles films; By czochralski method, golden film is dragged for to the ITO electro-conductive glass, be prepared into monodispersed and there is the golden film solid phase substrate of SERS enhancement effect;
(2) adopt timing voltammetry galvanostatic deposition Pt particle to golden film solid phase substrate, deposit solution is 1 mM H
2ptCl
6+ 0.1mM H
2sO
4, deposition current is 1 * 10
-4a, sedimentation time is 10s.
The preparation of aurosol solution is to reduce and obtain by sodium citrate, the synthesis step of 30nmAu nano particle: by 100 mL concentration, be 1.0 * 10
-4gmL
-1hAuCl
4aqueous solution is heated to boiling under magnetic agitation, when stirring, adds freshly prepared 1 mL 1.0 * 10
-2gmL
-1trisodium citrate aqueous solution, within 3 minutes, solution is by the transparent faint yellow black that becomes, and after 5 minutes, solution graduates into the slightly aubergine of the colour of loess, continues stirring and refluxing 15 minutes, treats that colloidal sol naturally cools to room temperature.
Step (1), after adding normal hexane, also drips ethanol, plays the golden film of compression, makes its finer and close effect.
The present invention selects suitable mode of deposition deposition Pt particle by electrochemical method, utilize the extensive chemical suction-operated of surface enhanced effect and Pt and the CO molecule of golden film, give full play to the high sensitivity of Surface enhanced raman spectroscopy (SERS) and the high characteristics of spectral resolution, the CO gas molecule is realized to real-time online detects.The method has highly sensitive, easy to prepare, and selectivity is high, the characteristics such as excellent performance.And, under noble potential, the CO molecule of absorption can pass through the electrochemical method desorption again, can realize that the circulation that detects substrate repeatedly utilizes.
The accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described.
Fig. 1 is the process flow diagram of one embodiment of the invention.
Fig. 2 is electro-conductive glass solid phase gold film substrate schematic diagram.
Fig. 3 is timing voltammetry deposition platinum schematic diagram.
Fig. 4 is the solid phase substrate Surface enhanced raman spectroscopy figure of deposition platinum grain.
Fig. 5 is the surface increasing Raman spectrum figure that solid phase detects the substrate CO absorption.
Embodiment
A kind of preparation method of highly sensitive CO gaseous spectrum sensor, is characterized in that: comprise the following steps:
(1) take normal hexane as oil phase, normal hexane is joined in aurosol solution, the gold nano particle diameter is 30nm, the volume of the normal hexane added is 1/5-1/6 of aurosol liquor capacity, also drip the ethanol (also can not adding) that is equivalent to aurosol liquor capacity 0.5-5%, play the golden film of compression, make its finer and close effect, on oil-water fluid/liquid two-phase interface, form Au nanoparticles films; By czochralski method, golden film is dragged for to the tin indium oxide to ITO(Indium tin oxide) on electro-conductive glass, be prepared into monodispersed and there is the golden film solid phase substrate of SERS enhancement effect;
The preparation of aurosol solution is to reduce and obtain by sodium citrate, the synthesis step of 30nmAu nano particle: by 100 mL concentration, be 1.0 * 10
-4gmL
-1hAuCl
4aqueous solution is heated to boiling under magnetic agitation, when stirring, adds freshly prepared 1 mL 1.0 * 10
-2gmL
-1trisodium citrate aqueous solution, within 3 minutes, solution is by the transparent faint yellow black that becomes, and after 5 minutes, solution graduates into the slightly aubergine of the colour of loess, continues stirring and refluxing 15 minutes, treats that colloidal sol naturally cools to room temperature.
(2) adopt timing voltammetry galvanostatic deposition Pt particle to golden film solid phase substrate, deposit solution is 1 mM H
2ptCl
6+ 0.1mM H
2sO
4, deposition current is 1 * 10
-4a, sedimentation time is 10s.Deposition current is excessive, can cause obvious hydrogen evolution phenomenon occurring, and deposition current is too small, easily forms and takes as the leading factor with the electrode surface diffusion control, and surperficial Pt particle is prone to three-dimensional island spiral dislocation growth pattern, causes the uniformity decreases of deposition.
Before can seeing CO absorption gas, at high wave number district (2000-2100 cm
-1) without any SERS spectrum peak-to-peak signal (as Fig. 4).
(3) absorption of CO and highly sensitive SERS detect
The golden film solid phase substrate of deposition Pt is inserted in closed container, pass into CO gas, at sedimentation time seldom the time, because the amount of the Pt of deposition is less, the CO molecule of absorption is less, SERS spectrum peak-to-peak signal a little less than, along with the increase of sedimentation time, the Pt deposition increases thereupon, and in high wavenumber region, the stretching vibration spectral strength of CO molecule increases gradually, when sedimentation time is 10 s, can see that the CO gas molecule is positioned at 2086 cm
-1the linear absorption of the C-O at place stretching vibration spectral strength reaches best, continues to increase the sedimentation time of Pt, and the spectrum peak-to-peak signal weakens again gradually, and this is that the Pt number of plies due to deposition increases, and the humidification of gold weakens gradually, the long-range effect of SERS be affected (as Fig. 5).
Described " czochralski method ", " timing voltammetry galvanostatic deposition Pt particle is to golden film solid phase substrate " are approach well known.
Czochralski method: czochralski method is by among the previously prepared good colloidal sol of whole clean substrate immersion, then with the even speed of accurately controlling, substrate is lifted out reposefully from colloidal sol, form the uniform liquid film of one deck in viscosity and Action of Gravity Field infrabasal plate surface, and then solvent evaporates rapidly, so be attached to the rapid gelation of the colloidal sol of substrate surface, forms the layer of gel film
Timing volt-ampere (current potential) method: the electrochemical techniques of a kind of electrochemical methods and Electrode process.Its ultimate principle is electrolysis, more close with polarography (seeing polarography and voltammetry).This method is under a certain fixed current, and the E-t curve of the relation in the measurement electrolytic process between electrode potential (seeing electrode potential) and time t, therefore claim chronoptentiometry.
Claims (3)
1. the preparation method of a highly sensitive CO gaseous spectrum sensor, is characterized in that: comprise the following steps:
(1) take normal hexane as oil phase, normal hexane is joined in aurosol solution, the gold nano particle diameter is 30nm, and the volume of the normal hexane added is 1/5-1/6 of aurosol liquor capacity, on oil-water fluid/liquid two-phase interface, forms Au nanoparticles films; By czochralski method, golden film is dragged for to the ITO electro-conductive glass, be prepared into monodispersed and there is the golden film solid phase substrate of SERS enhancement effect;
(2) adopt timing voltammetry galvanostatic deposition Pt particle to golden film solid phase substrate, deposit solution is 1 mM H
2ptCl
6+ 0.1mM H
2sO
4, deposition current is 1 * 10
-4a, sedimentation time is 10s.
2. the preparation method of highly sensitive CO gaseous spectrum sensor according to claim 1, it is characterized in that: the preparation of aurosol solution is to reduce and obtain by sodium citrate, the synthesis step of 30nmAu nano particle: by 100 mL concentration, be 1.0 * 10
-4gmL
-1hAuCl
4aqueous solution is heated to boiling under magnetic agitation, when stirring, adds freshly prepared 1 mL 1.0 * 10
-2gmL
-1trisodium citrate aqueous solution, within 3 minutes, solution is by the transparent faint yellow black that becomes, and after 5 minutes, solution graduates into the slightly aubergine of the colour of loess, continues stirring and refluxing 15 minutes, treats that colloidal sol naturally cools to room temperature.
3. the preparation method of highly sensitive CO gaseous spectrum sensor according to claim 1 and 2, it is characterized in that: step (1), after adding normal hexane, also drips ethanol, plays the golden film of compression, makes its finer and close effect.
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|---|---|---|---|
| CN201410647638.4A Division CN104359891A (en) | 2013-08-19 | 2013-08-19 | Applications of CO gas spectral sensor with detection substrate repeatedly utilized in recycling manner |
| CN201410647637.XA Division CN104359890A (en) | 2013-08-19 | 2013-08-19 | Applications of CO gas spectral sensor for realizing real-time online detection |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103983632A (en) * | 2014-06-09 | 2014-08-13 | 哈尔滨工业大学 | Preparation method of liquid/liquid interface self-assembled silver nanoparticle surface enhanced raman spectroscopy filter paper base |
| CN104101591A (en) * | 2014-07-24 | 2014-10-15 | 江西农业大学 | Fast detection method for surface enhanced Raman scattering of trace pesticide residues in oranges |
| CN104280438A (en) * | 2014-09-15 | 2015-01-14 | 苏州健雄职业技术学院 | Electrochemical biosensor and application thereof |
| CN115096871A (en) * | 2022-07-22 | 2022-09-23 | 香港科技大学深圳研究院 | Detection device applied to multichannel SERS micro-fluidic chip |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060251874A1 (en) * | 2005-05-04 | 2006-11-09 | 3M Innovative Properties Company | Microporous article having metallic nanoparticle coating |
| CN102153287A (en) * | 2010-11-26 | 2011-08-17 | 吉林大学 | Method for self-assembling nanoparticles by means of patterned polyelectrolyte membrane |
| CN102352049A (en) * | 2011-07-25 | 2012-02-15 | 中国人民解放军国防科学技术大学 | Preparation method of noble metal nanoparticle-cellulose hybrid membrane |
| CN103180726A (en) * | 2010-06-25 | 2013-06-26 | 帝国革新有限公司 | Miniature hplc device |
-
2013
- 2013-08-19 CN CN2013103598760A patent/CN103439309A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060251874A1 (en) * | 2005-05-04 | 2006-11-09 | 3M Innovative Properties Company | Microporous article having metallic nanoparticle coating |
| CN103180726A (en) * | 2010-06-25 | 2013-06-26 | 帝国革新有限公司 | Miniature hplc device |
| CN102153287A (en) * | 2010-11-26 | 2011-08-17 | 吉林大学 | Method for self-assembling nanoparticles by means of patterned polyelectrolyte membrane |
| CN102352049A (en) * | 2011-07-25 | 2012-02-15 | 中国人民解放军国防科学技术大学 | Preparation method of noble metal nanoparticle-cellulose hybrid membrane |
Non-Patent Citations (3)
| Title |
|---|
| LAM-WING H 等: "Extending Surface-Enhanced Raman Spectroscopy to Transition-Metal Surface:Carbon Monoxide Adsorption and Electrooxidation on Platinum- and Palladium-Coated Gold Electrodes", 《J.AM.CHEM.SOC》, vol. 109, 31 December 1987 (1987-12-31), pages 5113 - 5119 * |
| 张彩萍 等: "Au@Pt纳米粒子单层膜对甲醇氧化的电催化性能及SERS研究", 《化学学报》, vol. 70, no. 12, 31 December 2012 (2012-12-31), pages 1327 - 1331 * |
| 肖方竹: "纳米膜基底型生物芯片载体制备及应用研究", 《中国优秀硕士学位论文全文数据库》, 31 December 2008 (2008-12-31), pages 26 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103983632A (en) * | 2014-06-09 | 2014-08-13 | 哈尔滨工业大学 | Preparation method of liquid/liquid interface self-assembled silver nanoparticle surface enhanced raman spectroscopy filter paper base |
| CN104101591A (en) * | 2014-07-24 | 2014-10-15 | 江西农业大学 | Fast detection method for surface enhanced Raman scattering of trace pesticide residues in oranges |
| CN104280438A (en) * | 2014-09-15 | 2015-01-14 | 苏州健雄职业技术学院 | Electrochemical biosensor and application thereof |
| CN104280438B (en) * | 2014-09-15 | 2018-01-23 | 苏州健雄职业技术学院 | A kind of electrochemica biological sensor and its application |
| CN115096871A (en) * | 2022-07-22 | 2022-09-23 | 香港科技大学深圳研究院 | Detection device applied to multichannel SERS micro-fluidic chip |
| CN115096871B (en) * | 2022-07-22 | 2022-12-23 | 香港科技大学深圳研究院 | Detection device applied to multichannel SERS micro-fluidic chip |
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Application publication date: 20131211 |