CN101907595B - Electrochemical CO gas sensor - Google Patents
Electrochemical CO gas sensor Download PDFInfo
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- CN101907595B CN101907595B CN 201010231671 CN201010231671A CN101907595B CN 101907595 B CN101907595 B CN 101907595B CN 201010231671 CN201010231671 CN 201010231671 CN 201010231671 A CN201010231671 A CN 201010231671A CN 101907595 B CN101907595 B CN 101907595B
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Abstract
The invention relates to an electrochemical CO gas sensor which comprises a shell (6), a porous film (7), a reference electrode (1), a working electrode (2) and an auxiliary electrode (3). The reference electrode (1), the working electrode (2) and the auxiliary electrode (3) are encapsulated in the shell (6). The electrochemical CO gas sensor is characterized in that a composite catalyst film (5)is coated on the working electrode (2), hydrogel (4) is simultaneously coated on the reference electrode (1), the auxiliary electrode (3) and the composite catalyst film (5) which is formed by mixinga mixed catalyst and N-octyl pyridinium hexafluorophosphate in a mass ratio of 1-20 to 1, the mixed catalyst is formed by mixing nano Pt/carbon nanotubes and nano nickel / carbon nanotubes in a mass ratio of 10-40 to 1, and the hydrogel is gel formed in a way that superabsorbent absorbs water which contains dissolved lithium perchlorate and polyvinyl alcohol. The sensor is watertight and has the service life of 3-5 years and stable performance, and the decorative film on the working electrode is replaceable.
Description
One, technical field
The present invention relates to carbon monoxide (CO) gas sensor, exactly is a kind of CO gas eletrochemistry sensor.
Two, background technology
The content of environment harmful gas CO is one of important indicator of estimating the gaseous environment quality always, how to monitor its content accurately, rapidly and sensitively and has great significance.Airborne CO concentration reaches 10ppm, will cause the nerve system of human body reaction behind the 10min, makes human action slow, unconsciousness; Concentration reaches 30ppm, will cause people's vision and dysaudia; Concentration reaches 35ppm, will produce infringement to human body, causes health anoxic and fatal (D.Gorman, A.Drewry, Y.L.Huang, C.Sames, Toxicology, 2003,187,25).
The CO gas sensor that generally uses both at home and abroad has two classes at present, one class is based on Beer law and gas to ultrared selectivity principle of absorption, adopt gas filtering correlation technique and infrared eye to design (Shi Deheng, Liu Jianxin, Xu Qifu, optical technology, 2000,27,91), but its sensitivity and selectivity are subjected to the restriction of gas filtering sheet.The another kind of sensor that is based on electrochemical principle, usually with precious metal as working electrode.Both compare, latter's sensitivity higher (1ppm), and shortcoming is to use the life-span short.Reason be the latter in use, the oxidation product of gas and other interference gas are adsorbed on and cause on the avtive spot of working electrode that working electrode poisons, and reduce its catalytic activity and sensitivity (N.W.Cant gradually, P.W.Fredrickson, J.Catal.1975,37,531).In addition, electric chemical formula CO sensor adopts liquid electrolyte (C.G.Chen, J.B.He, D.Xu, X.L.Tan, et al, Sens.Actuators B, 2005,107,866) more, and sensor need seal to prevent electrolyte leakage.For this reason, the detection (Yan Heqing that has adopted solid polymer electrolyte to be used for carbon monoxide is waited in tight river clearly; Lu Juntao; Wang Efeng; Lin Fang; The money Jianping; The solid polymer electrolyte carbon monoxide transducer, application number: 01252229.5).The Pd-Nafion composite membrane solid state electrode of applied chemistry reducing process such as grandson roc preparation has catalytic activity (grandson roc, Yang Ming, Bai Shouli preferably to the electrocatalysis oxidation reaction of carbon monoxide, Chen Aifan, Luo Ruixian, Beijing University of Chemical Technology's journal, 2002,29,59).But the sensitivity of the sensor, response time and detectability still remain to be improved.Therefore, guaranteeing to prolong its serviceable life under easy, the quick and sensitive prerequisite of electrochemical sensor, be the manufacturing institute urgent problem of present CO gas eletrochemistry sensor.
Nanometer platinum (Pt) (L.H.Leung, A.Wieckowski, M.J.Weaver, J.Phy.Chem., 1988,92,6985), CO is converted into CO
2Has stronger catalytic action; But when adopting single nanometer Pt as catalyzer, excessive CO irreversibly is adsorbed on catalyst surface, causes catalyzer easily to be poisoned; If use composite material can effectively suppress the poisoning of catalyzer, studies show that as Acres etc. Pt/Ru electrode pair CO has tolerance (G.J.K.Acres, J.C.Frost, G.A.Hards preferably, R.J.Potter, et al, Cataly.Today, 1997,38,393).In applicant's early-stage Study, nanometer platinum-nickel/carbon nano-tube (Pt-Ni/MWCNT) modified electrode of preparation shows good contamination resistance (G.P.Jin, X.Peng, Q.Z.Chen, Electroanal., 2008,20,907) to CO.
Research has found that CNT has unique adsorption desorption performance, good electronic conductivity, vestibule space multistory selectivity, big specific surface area, high mechanical tenacity (R.H.Baughman, A.A.Zakhidov, W.A.Heer, Science, 2007,297,787).These particular performances make CNT when becoming a kind of good catalyzer, are expected to become a kind of good catalyst carrier material.Ungroomed carbon nano-tube has been used to detect CO and the H of ppm level concentration range
2Common gas such as S, but advantage is not obvious, has just accelerated the response speed that detects, and has been subjected to humidity, CO
2, NH
3Deng influence (O.K.Varghese, P.D.Kichambre, D.Gong, K.G.Ong, E.C.Dickey, C.A.Grimes, Sens.Actuators, B, 2001,81,32).Carbon nano-tube is through after the strong acid treatment, and oxy radicals such as carboxyl, hydroxyl are contained on its surface, easy and precious metal ion generation bonding, and can make with the carbon nano-tube is the nano-noble metal composite catalyst of carrier.As: nanometer palladium/carbon nano-tube and platinum-nickel/carbon nano tube composite catalyst can be used as the sensitive membrane of oxygen and carbon monoxide transducer respectively, has improved sensitivity (Y.Lin, X.Gui, X.Ye, Electrochem.Commun., 2005,7,267 detected; G.P.Jin, X.Peng, Q.Z.Chen, Electroanal., 2008,20,907).
Ionic liquid at room temperature (RTIL) commonly used is that fusing point is lower than 100 ℃ liquid electrolyte, formed by ion fully, it has under high physics, chemical stability and the normal temperature almost negligible vapour pressure, and has a wide electrochemical window, high conductivity, can promote characteristics (M.C.Buzzeo such as electronics transmission, R.G.Evans, R.G.Compton, Chem.Phys.Chem., 2004,5,1106), its characteristic that not only can make solvent but also can be used as supporting electrolyte has caused analytical chemistry, special Electroanalytical Chemistry worker's interest.Compton etc. have studied O among the RTIL
2, CO
2, H
2Electrochemical behavior (A.M.O ' Mahony, E.J.F.Dickinson, L.Aldous, C.Hardacre, R.G.Compton, J.Physical Chemistry C., 2009,113,10997 of S gas on platinum electrode; L.E.Barrosse-Antle, R.G.Compton, Chemical Communications., 2009,3744; X.J.Huang, E.I..Rogers, C.Hardacre, R.G.Compton, J.Physical Chemistry B., 113,2009,8953.), but be not used for the preparation of actual electrical chemical sensor as yet.RTIL can produce strong interaction (T.Fukushima, A.Kosaka, Y.Ishimura, T.Yamamoto, et al, Science, 2003,300,2072 by " cation-π " power with carbon nano-tube; H.B.Kim, J.S.Choi, S.T.Lim, H.J.Choi, H.S.Kim, Synth.Matals, 2005,154,189; Z.W.Zhao, Z.P.Guo, J.Ding, Z.F.Ma, D.Y.Zhang, H.K.Liu, Electrochem.Commun., 2006,8,245), RTIL/ carbon nano-tube composite modified electrode has better chemical property (Q.Zhao, D.Zhan than the electrode of the two independent modification, H.Ma, H.Zhang, Y.Zhao, et al, Front.Biosci., 2005,10,326) and littler background current (R.T.Kachoosangi, M.M.Musameh, I.Abu-Yousef, J.M.Yousef, et al, Anal.Chem., 2009,81,435), but be used for gas sensor and also do not see bibliographical information as yet.Because the ionic liquid of mentioned kind at room temperature is liquid, but still not portable.
A kind of ionic liquid at room temperature N-octyl group pyridine hexafluorophosphate (OPFP) is solid electrolyte when temperature is lower than 130 ℃, formed by ion fully, it not only has under the normal temperature characteristic of the ionic liquid (RTIL) that is liquid state, as: high physics, chemical stability, wide electrochemical window, high conductivity can promote characteristics such as electronics transmission; Have lower background current and superior galvanochemistry operability (N.Maleki, A.Safavi, F.Tajabadi, Anal.Chem., 2006,78,3820 with respect to carbon paste electrode; Can significantly reduce the oxidizing potential of bio-electrical activity material, accelerate the speed (A.Safavi, N.Maleki, O.Moradlou, M.Sorouri, Electrochem.Commun., 2008,10,420) of electric transmission; When changing electrode microstructure, it can be used as coupling agent and the solid supporting electrolyte of electrode surface.But still its research as the electrode material of gas sensor of no use is reported both at home and abroad.Claim that in the following description OPFP is solid-state ionic liquid at room temperature.
The hydrogel electrolyte is under the prerequisite that keeps the solid phase dimensional stability, characteristics with similar liquids ionic conductivity, hydrogel is made up of water and super absorbent material, the super water-absorbent material has very high water-intake rate and water-retaining property, the supporting electrolyte (Wen Xiaoyan, the chemical progress that can be used as the gas eletrochemistry sensor; Progress in Chemistry; 2008,21 phases), solve the leakage problem of sensor effectively, but gas is slower in the adsorption/desorption speed of electrode, the response time that reaches 90% response needs several minutes, contact once but also exist with high concentration gas, and output needs could return for a long time shortcomings such as zero.
Three, summary of the invention
The present invention is directed to defectives such as existing CO electrochemical sensor electrolyte solution is volatile, unstable properties, life-span weak point, aim to provide a kind of CO gas eletrochemistry sensor of long service life, technical matters to be solved is that the working electrode to sensor improves.
Described improvement mainly is that design preparation a kind of nanometer platinum-nickel/CNT/solid-state ionic liquid at room temperature/hydrogel composite material constitutes the CO gas sensitive membrane at working electrode.
Technical scheme of the present invention comprises contrast electrode 1, working electrode 2 and the auxiliary electrode 3 of shell 6 and perforated membrane 7 and interior encapsulation thereof, difference with the prior art is to be coated with composite catalyst film 5 at working electrode 2, applies hydrogel 4 simultaneously on contrast electrode 1, auxiliary electrode 3 and composite catalyst film 5.Like this, at contrast electrode 1 and auxiliary electrode 3 the hydrogel electrolyte is arranged, at working electrode 2 CO gas sensitization film is arranged.
Described composite catalyst film 5 is 1～20: 1 mixed catalyst and solid-state ionic liquid at room temperature mixing formation by mass ratio.Described mixed catalyst by nanometer platinum/carbon nano-tube (Pt/MWCNT) and nanometer nickel/carbon nano-tube (Ni/MWCNT) by 10～40: 1 mass ratio mixes forms nanometer platinum-nickel/carbon nano-tube (Pt-Ni/MWCNT).
The mass ratio of mixed catalyst and solid-state ionic liquid at room temperature preferred 3～10: 1.
Described solid-state ionic liquid at room temperature is selected from N-octyl group pyridine hexafluorophosphate (OPFP).
Described hydrogel 4 is dissolved with the formed gel of water of lithium perchlorate and polyvinyl alcohol (PVA) by high hydroscopic resin absorption.
In the sensitive membrane on working electrode, Pt-Ni/MWCNT is catalyzer, and solid-state ionic liquid at room temperature and hydrogel are composite electrolytes.This sensor has the advantage of no leakage, life-span length, stable performance.In addition, Tu Chu advantage is as follows:
1, the poisoning of catalyzer is suppressed
Adopt nanometer platinum-nickel (Pt-Ni) bimetallic catalyst, be that the sensor of catalyzer is compared with single Pt, because a spot of nanometer Ni can prevent that too much CO is adsorbed on the avtive spot of nanometer Pt in the catalyzer, and the nanometer Ni particle of contiguous nanometer Pt can transfer reaction intermediate product, thereby avoided nanometer Pt by embedding, suppressed the poisoning of catalyzer.
2, catalyzer can be produced in batches
Adopting the ultrasonic method preparation is nanometer platinum (nickel) catalyzer of carrier with the carbon nano-tube, and this method adopts the method for electrochemical preparation nanometer platinum (nickel)/carbon nano-tube catalyst to compare (G..P.Jin, X.Peng with the applicant in earlier stage, Q.Z.Chen, Electroanal., 2008,20,907; G P.Jin, Y.F.Ding, P.P.Zheng, J.Power.Sources., 2007,166,80), simple to operate, the capacity usage ratio height can be produced in batches, has more actual application value.
3, the stability of working electrode improves
Replaced traditional dielectric adhesive with solid-state ionic liquid at room temperature, the solid-state ionic liquid at room temperature modified electrode of nanometer Pt-Ni/MWCNT/ is had good electronic conduction performance, and has less background current, is conducive to improve the sensitivity of sensor.Solid-state ionic liquid at room temperature and MWCNT form stable " cation-π " effect, on the one hand MWCNT are evenly disperseed, and have improved the stability of working electrode on the other hand.
4, sensor aneroid leakage, life-span prolong, are easy to carry
Supporting electrolyte is formed jointly with solid-state ionic liquid at room temperature and hydrogel.The intervention of hydrogel has been avoided nanocatalyst because solvation comes off from electrode surface, has good moisture retention, for the oxidation of CO provides stable water source.Be 1～2 year the serviceable life that existing market is sold the CO sensor, and the present invention can use 3 to 5 years, and the modified membrane of sensor is removable simultaneously, can provide trim together with instrument, has reduced the cost of sensor.
The applicant selects commercially available three kinds of CO gas eletrochemistry sensors and this sensor to compare, and every performance sees the following form.
Four, description of drawings
Fig. 1 is this CO gas eletrochemistry sensor construction synoptic diagram.Among the figure, 1, contrast electrode (Ag, Φ 1mm), 2, working electrode (graphite, Φ 2.5mm), hydrogel (thick 1mm) 3, auxiliary electrode (Pt, Φ 1mm), 4,, 5, nanometer Pt-Ni/MWCNT/OPFP composite catalyst film, 6, the teflon shell, 7, voided polytetrafluoroethylene film.
Fig. 2 is type looks field emission scanning electron microscope (FE-SEM) figure of nanometer Ni/MWCNT (A) and Pt/MWCNT (B) catalyzer.By figure A as seen, obviously adhere to nano metal on the MWCNT; Further amplify, by illustration as seen, be deposited on nanometer Ni particle diameter on the MWCNT at 40 ± 25nm.By the particle diameter of figure B visible Pt nanometer at 60 ± 30nm.
Fig. 3 is X-crystal diffraction (XRD) figure of Ni/MWCNT and Pt/MWCNT mixed catalyst.Be illustrated as Ni/MWCNT and Pt/MWCNT catalyzer by 10: 1 mixed XRD figure.Rein in equation by seat and can calculate nanometer Ni particle diameter at 30 ± 10nm.The particle diameter of nanometer Pt is at 40 ± 20nm, and the nanometer particle size among the figure is less than the size among Fig. 2, show actual observation among Fig. 2 to nano particle may be to be reunited together by little nano particle.The clear composite catalyst of this chart is made up of Ni/MWCNT and Pt/MWCNT.
Shown in Figure 4 is this sensor current signal and CO concentration linear relationship chart when detecting CO gas.
Five, embodiment
1, sensor construction
The structure of CO sensor of the present invention as shown in Figure 1.The housing that sensor uses and base are high hard teflon, have been coated with the potassium permanganate/NaOH potpourri that can absorb interference gas (sulfide, oxides of nitrogen) on the housing.Working electrode is substrate with graphite, is modified with the sensitive membrane that hydrogel/nanometer platinum-nickel/carbon nano-tube/solid-state ionic liquid at room temperature (SPA/Pt-Ni/MWCNT/OPTP) constitutes on it.Reference and auxiliary electrode are respectively filamentary silver and platinum filament, are coated with hydrogel on it.Electrolyte is conductive hydrogel and solid-state ionic liquid at room temperature.The porous Teflon filter membrane plays and prevents that dust, impurity from entering the effect of sensor.
2, Pt/MWCNT, the Ni/MWCNT Preparation of catalysts
With the 10mg MWCNT 7h that in the mixed liquor of 10mL perchloric acid and red fuming nitric acid (RFNA) (volume ratio 3: 7), refluxes, with secondary water MWCNT is washed till neutrality again, at room temperature drying for standby.
Preparation H
2PtCl
6, MWCNT, sodium citrate (the massfraction ratio is 2: 2: 1) aqueous solution, regulate pH=7.0 with NaOH, in 60 ℃ of water-baths ultrasonic 1 to 2 hour.Add the reductive agent ascorbic acid again (with H
2PtCl
6The massfraction ratio be 1: 3 to 1: 8), 60 ℃ ultrasonic 10 to 60 minutes down.After reaction is finished, leach thing and wash to the neutrality again with the acetonitrile flushing with secondary water washing, at 60～70 ℃ of down dry 5～12h, obtain the Pt/MWCNT catalyzer.
Preparation NiSO
4, MWCNT (the massfraction ratio is 1: 1 to 1: 10) acetonitrile solution, in 65 ℃ of water-baths ultrasonic 1 to 2 hour.Regulate pH=2 to 7 with NaOH again, add ascorbic acid (with NiSO
4The massfraction ratio be 1: 1 to 10: 1), 65 ℃ ultrasonic 10 to 60 minutes down.After reaction is finished, leach thing and wash to the neutrality with secondary water washing and clean with acetonitrile again, at 60～70 ℃ of down dry 5～12h, obtain the Ni/MWCNT catalyzer.The mechanism of action: after carbon nano tube surface is pretreated in strong acid solution, produce pendant carboxylic group and carbonyl functional group.Nickel chloride, perchloric acid platinum and carbon nano-tube are formed in suspending liquid carry out ultrasonic mixing, make active function groups effect on nickel ion and chloroplatinic acid root and the CNT, thereby be enriched in carbon nano tube surface.The metallic ion of ascorbic acid on carbon nano-tube that adds is reduced into nano metal.
3, the preparation of CO gas sensitive membrane
With Pt/MWCNT, Ni/MWCNT is by 10～40: 1 mass ratio is made mixed catalyst; With this mixed catalyst, solid-state ionic liquid at room temperature N-octyl group pyridine hexafluorophosphate (OPFP) by 1～20: 1 mass ratio grinds 5-30min in mortar, make thick slurry.OPFP at room temperature is solid state powder, but its viscosity is big, is easy to MWCNT strong effect takes place, and MWCNT is evenly disperseed, and mixes the solid state composite that the back forms stable mechanical performance.
Graphite electrode (WGE) is polished as mirror at 2000 and 4000 purpose abrasive paper for metallograph respectively, and difference ultrasonic cleaning 10min dries naturally in absolute ethyl alcohol and secondary water.Above-mentioned thick slurry is coated on graphite electrode surface equably constitutes the composite catalyst film, the hydrogel (SPA) of the following preparation of coating constitutes sensitive membrane again, and compacting is standby, is designated as SPA/Pt-Ni/MWCNT/OPFP/WGE.As a comparison, get a certain amount of Pt-Ni/MWCNT powder and be dispersed in an amount of acetonitrile, drop in the WGE surface, acetonitrile is volatilized naturally, dry standbyly, be designated as Pt-Ni/WMCNT/WGE.
4, the preparation of hydrogel
Add the 0.9g lithium perchlorate in 100mL secondary water, add 3.75g polyvinyl alcohol (PVA) (PVA) after the dissolving therein, 60～80 ℃ of following sonic oscillations make its dissolving; In PVA solution, add water-absorbing resin sodium polyacrylate (SPA), continue to add thermal oscillation, make that solute evenly mixes in the solution, produce weak crosslinkedly, be cooled to room temperature, be the gel composite of conduction; This gel composite is uniformly coated on respectively on three electrodes, and thickness is 0.5 to 3mm, places a moment, seals up gland bonnet after making hydrogel and electrode fully contacting, and namely makes CO gas eletrochemistry sensor.
5, to the detection of CO gas
Under indoor temperature and damp condition, the SPA/Pt-Ni/MWCNT/OPFP/WGE that utilizes the present invention to prepare is, and CO gas detects.Experiment shows that the mass ratio of Pt-Ni/MWCNT mixed catalyst and N-octyl group pyridine hexafluorophosphate (OPFP) is in the sensitive membrane at 10: 1 to 3: 1 o'clock, and the background current of not only good catalytic activity, and electrode is less, and response is fast.
Adopt constant potentiometric electrolysis that CO is detected.At electrolysis 100-300 under the current potential of 1.3V-1.6V after second, the power taking flow valuve.As shown in Figure 4: along with the rising of CO content, the polarization of electrode electric current reduces gradually; Current signal presents good linear relationship in CO concentration is the scope of 1～90ppm, the linear fit equation is: i (μ A)=3.94 * 10-5-0.14c (ppm), and linearly dependent coefficient is 0.99, detects and is limited to 0.04ppm, sensitivity is 0.5ppm.
Claims (1)
1. CO gas eletrochemistry sensor, the contrast electrode (1), working electrode (2) and the auxiliary electrode (3) that comprise shell (6) and perforated membrane (7) and interior encapsulation thereof, it is characterized in that: be coated with composite catalyst film (5) at working electrode (2), on contrast electrode (1), auxiliary electrode (3) and composite catalyst film (5), apply hydrogel (4) simultaneously; Described composite catalyst film (5) is pressed 3～10: 1 mass ratio mixing formation by mixed catalyst and N-octyl group pyridine hexafluorophosphate; Described mixed catalyst by nanometer platinum/multi-walled carbon nano-tubes and nanometer nickel/multi-walled carbon nano-tubes by 10～40: 1 mass ratio mixes and forms; Described multi-walled carbon nano-tubes be in 3: 7 perchloric acid of volume ratio and red fuming nitric acid (RFNA) mixed liquor, reflux 7 hours, wash with secondary water washing that drying obtains to neutral, the room temperature again; Described hydrogel is to add the 0.9g lithium perchlorate in 100mL secondary water, adds the 3.75g polyvinyl alcohol (PVA) after the dissolving therein, and 60～80 ℃ of following sonic oscillations make its dissolving; In poly-vinyl alcohol solution, add the water-absorbing resin sodium polyacrylate, continue to add thermal oscillation, make that solute evenly mixes in the solution, be cooled to room temperature.
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| CN105466052B (en) * | 2016-01-13 | 2017-12-08 | 泰兴市东城水处理工程有限公司 | A kind of solar water heater with high duplication detection function |
| CN105738452B (en) * | 2016-02-04 | 2019-12-10 | 中国科学院烟台海岸带研究所 | Method and device for detecting ammonia nitrogen by using all-solid-state ammonia nitrogen sensor |
| CN107865637B (en) * | 2016-09-28 | 2019-12-20 | 中国科学院化学研究所 | Living body assay H2S electrode, preparation method and in vivo detection H2S device |
| CN108169109A (en) * | 2017-12-20 | 2018-06-15 | 河海大学 | A kind of Ag/AgCl solid state reference electrodes and preparation method |
| CN111982982A (en) * | 2020-08-31 | 2020-11-24 | 国网重庆市电力公司电力科学研究院 | Method and system for analyzing platinum-doped carbon nanotube sensor |
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