CN102384932B - Formaldehyde gas sensor, making method and formaldehyde monitoring and treatment device - Google Patents
Formaldehyde gas sensor, making method and formaldehyde monitoring and treatment device Download PDFInfo
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- CN102384932B CN102384932B CN 201110349595 CN201110349595A CN102384932B CN 102384932 B CN102384932 B CN 102384932B CN 201110349595 CN201110349595 CN 201110349595 CN 201110349595 A CN201110349595 A CN 201110349595A CN 102384932 B CN102384932 B CN 102384932B
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Abstract
The invention discloses a formaldehyde gas sensor and a making method thereof and a formaldehyde monitoring and treatment device with the formaldehyde gas sensor. The formaldehyde gas sensor is an electrochemical two-electrode system, a Pd-Ni/SiNWs formaldehyde catalytic electrode is used as a working electrode, a Ni/SiNWs electrode is used as a counter electrode, and the formaldehyde gas sensor is made by electrolyte encapsulation. Each SiNWs of the Pd-Ni/SiNWs electrode in the designed formaldehyde gas sensor can be regarded as a micro electrode with a micro/nano-scale curvature radius tip,so that catalytic reaction of formaldehyde gas molecules on the surface of the Pd-Ni/SiNWs electrode is promoted. The clearances among numerous SiNWs also have micro or nano scale, so that the effective diffusion layer soaked into a solution is smaller, and meanwhile, the double-electrode layer of the solution/ electrode interface has stronger electric field effect. The formaldehyde monitoring and treatment device can be used for monitoring the formaldehyde concentration in the indoor air and treating the formaldehyde in real time, and has the advantages of low cost, simplicity in operation, easiness in implementation and the like.
Description
Technical field
The present invention relates to the manufacture method of a kind of formaldehyde gas sensor and this formaldehyde gas sensor, the invention still further relates to the formaldehyde monitoring treating apparatus of being made by this formaldehyde gas sensor.
Technical background
Formaldehyde another name is formalin, is a kind of colourless, gas that the intense stimulus smell is arranged, chemical formula CH
2O owing to its special chemical activity, purity height, low price, be widely used in production and the interior decoration, but its also is a kind of noxious material simultaneously, is endangering health.Therefore significant with processing to the detection of indoor formaldehyde.On the one hand, formaldehyde is the material than high toxicity, preferentially controls on the list formaldehyde at China's toxic chemical and is in second.Formaldehyde is defined as carcinogenic and teratogenesis shape material by the World Health Organization (WHO), is the allergen of generally acknowledging, also is one of potential strong mutagen.Studies show that formaldehyde has strong carcinogenic and short cancer effect.Formaldehyde mainly shows aspects such as allotriosmia, stimulation, allergy, abnormal pulmonary function, dysfunction of liver and immunologic dysfunction to health effects.When its concentration reached 0.06～0.07 mg in every cubic metres of air, slight asthma will take place in children.When formaldehyde in indoor air content is 0.1mg m
-3The time, peculiar smell and sense of discomfort are just arranged; Reach 0.5mg m
-3The time, can stimulate eyes, cause and shed tears; Reach 0.6mg m
-3, can cause throat discomfort or pain.When concentration was higher, the vomiting cough that can cause nausea was uncomfortable in chest, asthma even pulmonary edema; Reach 30 mg m
-3The time, meeting is the causing death immediately.On the other hand, long-term contact low dosage formaldehyde can cause chronic respiratory disease, cause nasopharyngeal carcinoma, colon cancer, brain tumor, paramenia, nuclear gene mutation, in the dna single chain commissure and DNA and protein commissure and suppress dna damage reparation, pregnancy syndrome, cause neonatal chromosome disorder, leukaemia, cause the decline of teenager's memory and intelligence.In all contactees, children and pregnant woman's PARA FORMALDEHYDE PRILLS(91,95) are particularly responsive, and harm is also just bigger.Show according to related data statistics: the mankind have 70% illness relevant with indoor environment, and China has 120,000 people to die from indoor pollution every year, and the child leukaemic more than 90% lives in new clothes and repairs the house ill in 1 year.So formaldehyde is the important raw and processed materials in the production, be again the serious polluter of indoor environment, it is healthy to endanger people, therefore, develops and design a kind of low cost, formaldehyde gas detection easily and real-time treating apparatus, significant.
Summary of the invention
The technical problem to be solved in the present invention first provides a kind of formaldehyde gas sensor, and this formaldehyde gas sensor has high sensitivity for formaldehyde gas.Second provides a kind of method for making of this formaldehyde gas sensor, and the 3rd provides a kind of formaldehyde monitoring treating apparatus of being made by this formaldehyde gas sensor.The present invention has the advantage that cost is low, use is convenient to operation.
Formaldehyde gas sensor of the present invention is galvanochemistry type two electrode systems, and its working electrode is Pd-Ni/SiNWs formaldehyde catalysis electrode, is the Ni/SiNWs electrode to electrode, makes the preferred 2ML of described electrolytic solution by the electrolytic solution encapsulation
-1The KOH solution of concentration.
The character express of above-mentioned " Pd-Ni/SiNWs formaldehyde catalysis electrode " is palladium-nickel/silicon nanowires formaldehyde catalysis electrode, and " Ni/SiNWs electrode " is nickel/silicon nanowires electrode.
Electrode in the above-mentioned formaldehyde gas sensor is to adopt following method to make: the SiNWs skeleton is that N-type silicon substrate obtains by normal temperature wet chemical etching; The electrode of Ni/SiNWs is to adopt electroless plating techniques to obtain in 300～400 ℃ of rapid thermal annealing 10 min under the ar gas environment protection after SiNWs surface deposition skim metal Ni; The Pd-Ni/SiNWs working electrode is to obtain in 300～400 ℃ of rapid thermal annealing 10 min under the ar gas environment protection behind SiNWs skeleton surface electroless plating codeposition metallic nickel and the trace palladium.
Above-mentioned formaldehyde gas sensor electrode method for making more specifically is:
1) the Ni/SiNWs formaldehyde gas sensor is got the about 1.0 * 0.5cm of surface area to the preparation method of electrode
2The SiNWs thin slice be prefabricated electrode substrate, use washed with de-ionized water, in 1～5% TritonX-100 wetting agent, soak 30～60s and carry out surface active, make SiNWs surface generate the H key and stop the surface.
Prepare the used electroless plating plating bath of electrod-array by following raw material and proportioning preparation: nickel source 1mol L
-1, buffering agent 0.5 mol L
-1, palladium source 0.005 ~ 0.010mol L
-1, stabilizing agent 2.5mol L
-1, surfactant 0.001mol L
-1, promoter 0.2mol L
-1Sodium succinate, sequestrant 0.2mol L
-1Put into 100 mL deionized water for ultrasonic after above-mentioned plating bath mixed and dissolve 20 min, the constant temperature water bath of putting into temperature-controlled precision again and be 0.1 ℃ is warming up to 80～90 ℃, by dripping 8.0～9.0mol L
-1Ammoniacal liquor is adjusted bath pH value to 8.0-9.0, puts into the SiNWs array substrate and carries out the electroless plating codeposition, and plating time is 10～20 min.
2) manufacture craft of Pd-Ni/SiNWs formaldehyde gas sensor working electrode is the same, just the middle PdCl that adds 1-5 mmol before the plating bath ultrasonic dissolution
2Reagent.
3) in RTA rapid thermal annealing system, under the hydrogen shield atmosphere, 300～400 ℃ of rapid thermal annealing 300s with the physical stability of further intensifier electrode, promote that Ni or the Pd distribution of particles in the thin layer is more even.Simultaneously, part Ni particle is understood the NiSi layer that forms low-resistivity in Si body phase diffusion process.
Nickel sulfate hexahydrate, nickel chloride can be adopted in above-mentioned nickel source, and buffering agent can adopt sulfate of ammoniac, and palladium bichloride, palladium sulfate can be adopted in the palladium source, and stabilizing agent can adopt ammonium fluoride, surfactant
1Can adopt lauryl sodium sulfate, promoter can be adopted sodium succinate, and sequestrant can adopt sodium citrate.
The formaldehyde monitoring treating apparatus of being made by above-mentioned formaldehyde gas sensor is made up of the demonstration follower that the formaldehyde sensor that connects in turn, single-chip microcomputer that model is STC12C5410AD, peak current retainer that model is PKD01 and model are LCD1602.
Advantage of the present invention is: in the design's formaldehyde gas sensor, every SiNWs of Pd-Ni/SiNWs electrode can be considered the microelectrode with micro/nano-scale radius-of-curvature tip, is conducive to promote the formaldehyde gas molecule in its surperficial catalytic reaction.Gap between numerous SiNWs also has micron or nanoscale, makes the effective diffusion layer that immerses solution littler, has stronger electric field action on the electrostatic double layer of solution/electrode interface simultaneously.Therefore, compare other traditional noble metal electrodes such as Pt electrode etc., Pd-Ni/SiNWs electrode pair formaldehyde has better catalytic action.This Pd-Ni/SiNWs formaldehyde through catalytic oxidation anode PARA FORMALDEHYDE PRILLS(91,95) has low catalysis opening point position (1.1 V), high sensitivity (7 mA mmol-1L cm
-2), (signal-to-noise-ratio=3, concentration of formaldehyde S/N=3) detect and are limited to 10 μ mol L based on three times of signal noise ratios
-1
The present invention utilizes the STC12C5410AD Single-chip Controlling to produce triangular wave scan round voltage, and then can drive the work of galvanochemistry type formaldehyde sensor, and by PKD01 peak current retainer loop formaldehyde through catalytic oxidation electric current is monitored, as the detection foundation that detects concentration of formaldehyde, and then by the calculating on the program voltage is scaled current value and shows by LCD1602.The present invention can Control Room in air formaldehyde concentration, and can handle in real time.It is low to have cost, simple to operate, realizes advantages such as easy.The present invention is Heilongjiang Province's natural science fund project, item number: F201008; The young science fund project in Heilongjiang Province, item number: QC2011C092; Also belong to the young teacher of Qiqihar University scientific research simultaneously and start project, item number: 2010k-Z02; Qiqihaer City's science and technology planning item, item number: GYGG2010-03-1.
Description of drawings
Below in conjunction with the drawings and specific embodiments the present invention is described in detail.
Fig. 1 is the structural representation of the embodiment of the invention 1.
Fig. 2 is Ni/SiNWs array cathode SEM figure.
Fig. 3 is Pd-Ni/SiNWs anode-array SEM figure.
Fig. 4 is the structural representation of embodiment 3.
Fig. 5 is indoor formaldehyde monitoring and real-time treating apparatus circuit for generating triangular wave output voltage waveform.
Fig. 6 detects the corresponding relation figure of concentration of formaldehyde and loop peak point current for indoor formaldehyde monitoring and real-time treating apparatus cyclic voltammetric method.
Number in the figure:
1, formaldehyde gas sensor 2, working electrode 3, to electrode 4, sensor housing
5, limb 6, electrolytic solution 7, ventilated membrane 8, filtrator 9, bleeder vent
10, single-chip microcomputer 11, peak current retainer 12, demonstration follower.
Embodiment
Example 1
As shown in Figure 1, the working electrode 2 of this formaldehyde gas sensor 1 is a kind of Pd-Ni/SiNWs formaldehyde catalysis electrode, be installed in middle part in the sensor housing 4, be a kind of Ni/SiNWs formaldehyde gas sensor electrode to electrode 3, be installed in sensor housing 4 inner bottom parts, working electrode 2 with electrode 3 is connected by the lead limb 5 corresponding with sensor housing 4 bottoms respectively, working electrode 2 and to being filled with electrolytic solution 6 between the electrode 3, the space is connected with the bleeder vent 9 at sensor housing 4 tops by ventilated membrane 7, filtrator 8 in the shell of working electrode 2 tops.Described electrolytic solution 6 is 2 M L for concentration
-1KOH solution.Fig. 2 is Ni/SiNWs array cathode SEM figure, and Fig. 3 is Pd-Ni/SiNWs anode-array SEM figure.
The method for making of example 2 formaldehyde gas sensor electrodes
1) Ni/SiNWs formaldehyde gas sensor cathode preparation method is: get the about 1.0 * 0.5cm of surface area
2The SINWs thin slice be prefabricated electrode substrate, use washed with de-ionized water, in 1～5% TritonX-100 wetting agent, soak 30～60s and carry out surface active, make SiNWs surface generate the H key and stop the surface.
Prepare following polarizing electrode array electroless plating plating bath: 1mol L
-1Nickel sulfate hexahydrate, 0.5 mol L
-1Sulfate of ammoniac, 0.005 ~ 0.010mol L
-1Lead chloride, 2.5mol L
-1Ammonium fluoride, 0.001mol L
-1Lauryl sodium sulfate, 0.2mol L
-1Sodium succinate, 0.2mol L
-1Sodium citrate.Dissolve 20 min with putting into 100 mL deionized water for ultrasonic after the above-mentioned plating bath mixing, the constant temperature water bath of putting into temperature-controlled precision again and be 0.1 ℃ is warming up to 80～90 ℃, adjust bath pH value to 8.0-9.0 by dropping ammonia, put into the SiNWs array substrate and carry out the electroless plating codeposition, plating time is 10～20 min.
2) Pd-Ni/SiNWs formaldehyde gas sensor anode manufacture craft is the same, just the middle PdCl that adds 1-5 mmol before the plating bath ultrasonic dissolution
2Reagent.
3) in RTA rapid thermal annealing system, under the hydrogen shield atmosphere, 400 ℃ of rapid thermal annealing 300 s further to increase the physical stability of electrode, promote that Ni or the Pd distribution of particles in the thin layer is more even.Simultaneously, part Ni particle is understood the NiSi layer that forms low-resistivity in Si body phase diffusion process.
Formaldehyde monitoring and real-time treating apparatus that example 3 is made by formaldehyde gas sensor
As shown in Figure 4, this device is by stretching the formaldehyde sensor 1 that connects in turn, and model is the single-chip microcomputer 10 of STC12C5410, and model is the peak point current retainer 11 of PKD01; Model is that the demonstration follower 12 of LCD1602 constitutes.
This apparatus system is in dormant state at ordinary times, when room air does not have the formaldehyde gas molecule, does not have voltage on the electrode and generates; If when containing formaldehyde gas in the air, formaldehyde molecule can and discharge electric charge in the oxidation of Pd-Ni/SiNWs electrode catalyst, cause producing on the electrode catalysis voltage of-0.7 V approximately, this voltage can be by interrupting waking up single-chip microcomputer STC12C5410 work, export cyclic voltammetry scan voltage according to program at the triangular wave output circuit afterwards, this voltage can impel the formaldehyde molecule catalytic oxidation on the electrode and discharge electric current, this current value is corresponding with air formaldehyde concentration, and it is by peak current retainer sampling in the loop and send display circuit output; This current value, then starts the interior formaldehyde gas of single-chip microcomputer and handles subroutine in real time if concentration exceeds threshold value by comparing with predetermined threshold simultaneously, i.e. anode output-0.2 V constant potential, and PARA FORMALDEHYDE PRILLS(91,95) carries out catalytic oxidation, makes it generate carbon dioxide and water.
Microcontroller adopts single-chip microcomputer STC12C5410AD single-chip microcomputer, and loop current monitoring device uses PKD01 peak current retainer.When having formaldehyde in the room air, the formaldehyde gas molecule can discharge electric charge by catalytic oxidation on the Pd-Ni/SiNWs electrode, produce the voltage about-0.7 V, can wake single-chip microcomputer work up.After the single-chip microcomputer work, output-0.7 V is to the triangular voltage sweep voltage of 0.2 V, sweep speed 100 mV s
-1, the formaldehyde through catalytic oxidation current value that produces in the scanning process can be used for marking the concentration of formaldehyde in the room air.If the indoor formaldehyde gas concentration surpasses pre-set threshold, can be embodied in the sampled value of the PKD01 of system peak current retainer, trigger the constant potential of single-chip microcomputer output-0.2 V, catalytic oxidation is handled airborne formaldehyde; At interval behind the certain hour, again by single-chip microcomputer output triangular voltage sweep voltage detecting indoor formaldehyde gas concentration, until the threshold value that is reduced to of indoor formaldehyde concentration.
Example 4 indoor formaldehyde gas concentration test results
The triangle wave voltage of exporting in the real-time treating apparatus control circuit of indoor formaldehyde gas among the present invention as shown in Figure 5; Loop peak point current and formaldehyde gas concentration corresponding relation are as shown in Figure 6 in the indoor formaldehyde gas testing process.The about 7 mA mmol of the galvanochemistry sensitivity of system's PARA FORMALDEHYDE PRILLS(91,95) gas concentration
-1L cm
-2, indoor formaldehyde gas concentration detectability is assigned 10 μ mol L three times of signal to noise ratio (S/N ratio) conditions
-1
Claims (2)
1. a formaldehyde gas is monitored and real-time treating apparatus, it is characterized in that: these integrated apparatus PARA FORMALDEHYDE PRILLS(91,95) gas sensitization parts are the Pd-Ni/SiNWs catalysis electrode, be the Ni/SiNWs electrode to electrode, PARA FORMALDEHYDE PRILLS(91,95) gas-monitoring and handle and can finish with same Pd-Ni/SiNWs catalysis electrode; This apparatus system is in dormant state at ordinary times, whether contains the monitoring of formaldehyde gas in the environment by whether the perception of catalysis voltage is arranged on the Pd-Ni/SiNWs electrode; Formaldehyde gas concentration is the loop peak current size detection that produces under the triangle wave voltage effect by Pd-Ni/SiNWs electrode and Ni/SiNWs electrode in the environment; The processing of formaldehyde gas applies fixing-0.2 V voltage by Pd-Ni/SiNWs electrode and Ni/SiNWs electrode two ends and handles through electrochemical catalysis and make it generate carbon dioxide and water is handled in the environment; Above step is can finish in proper order in integrated apparatus of the present invention.
2. according to described formaldehyde gas monitoring and the real-time treating apparatus of claim 1, it is characterized in that: whether formaldehyde gas exists corresponding to the catalysis voltage that whether detects-0.7 V on the Pd-Ni/SiNWs electrode in the environment; The detection of formaldehyde gas concentration is to produce-0.7 V to the triangular voltage sweep voltage of 0.2 V by single-chip microcomputer in the environment, and formaldehyde molecule catalytic oxidation peak current obtains in the simulation loop volt-ampere detection method observation circuit loop.
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| CN102809634B (en) * | 2012-08-28 | 2013-12-11 | 济南大学 | Gas-sensitive sensor made of palladium hybridization ferroferric oxide nanometer material |
| CN104267079B (en) * | 2014-10-09 | 2017-03-22 | 无锡百灵传感技术有限公司 | Electrochemical sensor based on modified Ni(OH)2 (Nickel Hydroxide) electrode |
| WO2019056159A1 (en) * | 2017-09-19 | 2019-03-28 | Honeywell International Inc. | Improved electrochemical sensor and method for detecting formaldehyde by regulating voltage to reduce cross-sensitivity |
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